Hydrogen/Chlorine exchange reactions of gaseous carbanions.

Science.gov (United States)

Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

2005-12-01

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

Nuclear reaction analysis of hydrogen in materials: Principals and applications

International Nuclear Information System (INIS)

Lanford, W.A.

1991-01-01

Analysis for hydrogen in materials is difficult by most traditional analytic methods. Because hydrogen has no Auger transitions, no X-ray transitions, does not neutron activate, and does not backscatter ions, it is invisible in analytical methods based on these effects. In addition, since hydrogen is a universal contaminant in vacuum systems, techniques based on mass spectrometry are difficult unless extreme measures are taken to reduce hydrogen backgrounds. Because of this situation, methods have been developed for analyzing for hydrogen in solid materials based on nuclear reactions between bombarding ions and hydrogen atoms (protons) in the samples. The nuclear reaction methods are now practiced at laboratories around the world. The basic principals of nuclear reaction analysis will be briefly presented. This method will be illustrated by applications to problems ranging from basic physics, to geology, to materials science, and to art history and archeology

Diels-Alder reactions onto fluorinated and hydrogenated graphene

Science.gov (United States)

Denis, Pablo A.

2017-09-01

We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

The reactions of oxygen and hydrogen with liquid sodium

International Nuclear Information System (INIS)

Ullmann, H.

1981-01-01

Results so far available as to the reactions and chemical equilibrium of oxygen and hydrogen with liquid sodium have been analyzed critically. The enthalpy values of the reactions have been discussed and supplemented on the basis of corresponding BORN-HABER cycles. The concentration and temperature functions of the hydrogen equilibrium pressure were deduced from experimental results. In relation to the solubility data the solid phases coexisting with liquid sodium in the ternary system Na-O-H have been discussed. The reaction of oxygen with hydrogen in diluted solution in liquid sodium has been investigated in more detail. Interaction coefficients, and the temperature functions of the free energy of formation and the equilibrium constant have been determined. (orig.)

Kinetics of Hydrogen Radical Reactions with Toluene Including Chemical Activation Theory Employing System-Specific Quantum RRK Theory Calibrated by Variational Transition State Theory.

Science.gov (United States)

Bao, Junwei Lucas; Zheng, Jingjing; Truhlar, Donald G

2016-03-02

Pressure-dependent reactions are ubiquitous in combustion and atmospheric chemistry. We employ a new calibration procedure for quantum Rice-Ramsperger-Kassel (QRRK) unimolecular rate theory within a chemical activation mechanism to calculate the pressure-falloff effect of a radical association with an aromatic ring. The new theoretical framework is applied to the reaction of H with toluene, which is a prototypical reaction in the combustion chemistry of aromatic hydrocarbons present in most fuels. Both the hydrogen abstraction reactions and the hydrogen addition reactions are calculated. Our system-specific (SS) QRRK approach is adjusted with SS parameters to agree with multistructural canonical variational transition state theory with multidimensional tunneling (MS-CVT/SCT) at the high-pressure limit. The new method avoids the need for the usual empirical estimations of the QRRK parameters, and it eliminates the need for variational transition state theory calculations as a function of energy, although in this first application we do validate the falloff curves by comparing SS-QRRK results without tunneling to multistructural microcanonical variational transition state theory (MS-μVT) rate constants without tunneling. At low temperatures, the two approaches agree well with each other, but at high temperatures, SS-QRRK tends to overestimate falloff slightly. We also show that the variational effect is important in computing the energy-resolved rate constants. Multiple-structure anharmonicity, torsional-potential anharmonicity, and high-frequency-mode vibrational anharmonicity are all included in the rate computations, and torsional anharmonicity effects on the density of states are investigated. Branching fractions, which are both temperature- and pressure-dependent (and for which only limited data is available from experiment), are predicted as a function of pressure.

F/Cl + C2H2 reactions: Are the addition and hydrogen abstraction direct processes?

International Nuclear Information System (INIS)

Li Jilai; Geng Caiyun; Huang Xuri; Zhan Jinhui; Sun Chiachung

2006-01-01

The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition-elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition-elimination reactions, the halogen atoms approach C 2 H 2 , perpendicular to the C≡C triple bond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C 2 H 2 F/C 2 H 2 Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry

Hydrogen desorption reactions of Li-N-H hydrogen storage system: Estimation of activation free energy

International Nuclear Information System (INIS)

Matsumoto, Mitsuru; Haga, Tetsuya; Kawai, Yasuaki; Kojima, Yoshitsugu

2007-01-01

The dehydrogenation reactions of the mixtures of lithium amide (LiNH 2 ) and lithium hydride (LiH) were studied under an Ar atmosphere by means of temperature programmed desorption (TPD) technique. The dehydrogenation reaction of the LiNH 2 /LiH mixture was accelerated by addition of 1 mol% Ti(III) species (k = 3.1 x 10 -4 s -1 at 493 K), and prolonged ball-milling time (16 h) further enhanced reaction rate (k = 1.1 x 10 -3 s -1 at 493 K). For the hydrogen desorption reaction of Ti(III) doped samples, the activation energies estimated by Kissinger plot (95 kJ mol -1 ) and Arrhenius plot (110 kJ mol -1 ) were in reasonable agreement. The LiNH 2 /LiH mixture without Ti(III) species, exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of the LiNH 2 /LiH mixture

Theoretical studies of the reactions of HCN with atomic hydrogen

International Nuclear Information System (INIS)

Bair, R.A.; Dunning, T.H. Jr.

1985-01-01

A comprehensive theoretical study has been made of the energetics of the important pathways involved in the reaction of hydrogen atoms with hydrogen cyanide. For each reaction ab initio GVB-CI calculations were carried out to determine the structures and vibrational frequencies of the reactants, transition states, and products; then POL-CI calculations were carried out to more accurately estimate the electronic contribution to the energetics of the reactions. The hydrogen abstraction reaction is calculated to be endoergic by 24 kcal/mol [expt. ΔH (0 K) = 16--19 kcal/mol] with a barrier of 31 kcal/mol in the forward direction and 6 kcal/mol in the reverse direction. For the hydrogen addition reactions, addition to the carbon atom is calculated to be exoergic by 19 kcal/mol with a barrier of 11 kcal/mol, while addition to the nitrogen center is essentially thermoneutral with a barrier of 17 kcal/mol. Calculations were also carried out on the isomerization reactions of the addition products. The cis→trans isomerization of HCNH has a barrier of only 10 kcal/mol with the trans isomer being more stable by 5 kcal/mol. The (1,2)-hydrogen migration reaction, converting H 2 CN to trans-HCNH, is endoergic by only 14 kcal/mol, but the calculated barrier for the transfer is 52 kcal/mol. The energy of the migration pathway thus lies above that of the dissociation--recombination pathway

Reaction of Aluminum with Water to Produce Hydrogen - 2010 Update

Energy Technology Data Exchange (ETDEWEB)

Petrovic, John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Thomas, George [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2011-06-01

A Study of Issues Related to the Use of Aluminum for On-Board Vehicular Hydrogen Storage The purpose of this White Paper is to describe and evaluate the potential of aluminum-water reactions for the production of hydrogen for on-board hydrogen-powered vehicle applications. Although the concept of reacting aluminum metal with water to produce hydrogen is not new, there have been a number of recent claims that such aluminum-water reactions might be employed to power fuel cell devices for portable applications such as emergency generators and laptop computers, and might even be considered for possible use as the hydrogen source for fuel cell-powered vehicles.

Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules

International Nuclear Information System (INIS)

Garrett, B.C.; Truhlar, D.G.

1979-01-01

Canonical variational transition state theory, microcanonical variational transition state theory, and Miller's unified statistical theory were used in an attempt to correct two major deficiencies of the conventional transition state theory. These are: (1) the necessity of extra assumptions to include quantum mechanical tunneling effects and (2) the fundamental assumption that trajectories crossing a dividing surface in phase space proceed directly to products. The accuracy of these approximate methods were tested by performing calculations for several collinear reactions of hydrogen, deuterium, chlorine, or iodine, with five isotopes of hydrogen molecules and comparison of these results with those from accurate quantitative calculations of the reaction probabilities as functions of energy and of the thermal rate constants as functions of temperature. 49 references, 28 figures, 17 tables

Destruction of oxalate by reaction with hydrogen peroxide. [Hydrazine oxalate

Energy Technology Data Exchange (ETDEWEB)

Mailen, J.C.; Tallent, O.K.; Arwood, P.C.

1981-09-01

The destruction of oxalate by oxidation to carbon dioxide using hydrogen peroxide was studied as an alternative method for the disposal of oxalate in connection with the possible use of an aqueous hydrazine oxalate solution as a scrubbing agent for solvent cleanup in processes for the recovery of uranium, plutonium, and thorium by solvent extraction. The rate of oxidation of oxalate by hydrogen peroxide in acid solution at the reflux temperature was adequate for process application; reaction half-times at 100/sup 0/C were less than one hour when the hydrogen peroxide concentration was greater than 0.5 M. The reaction was first order with respect to both the oxalate and hydrogen peroxide concentrations and had an activation energy of 58.7 kJ/g-mol. The rate increased with the hydrogen ion concentration as (H/sup +/)/sup 0/ /sup 3/ but was not significantly affected by the presence of 100 ppM of uranium or copper in solution. In the near-neutral hydrazine oxalate solutions, the reaction of either component with hydrogen peroxide was too slow for process application.

Advances of zeolite based membrane for hydrogen production via water gas shift reaction

Science.gov (United States)

Makertihartha, I. G. B. N.; Zunita, M.; Rizki, Z.; Dharmawijaya, P. T.

2017-07-01

Hydrogen is considered as a promising energy vector which can be obtained from various renewable sources. However, an efficient hydrogen production technology is still challenging. One technology to produce hydrogen with very high capacity with low cost is through water gas shift (WGS) reaction. Water gas shift reaction is an equilibrium reaction that produces hydrogen from syngas mixture by the introduction of steam. Conventional WGS reaction employs two or more reactors in series with inter-cooling to maximize conversion for a given volume of catalyst. Membrane reactor as new technology can cope several drawbacks of conventional reactor by removing reaction product and the reaction will favour towards product formation. Zeolite has properties namely high temperature, chemical resistant, and low price makes it suitable for membrane reactor applications. Moreover, it has been employed for years as hydrogen selective layer. This review paper is focusing on the development of membrane reactor for efficient water gas shift reaction to produce high purity hydrogen and carbon dioxide. Development of membrane reactor is discussed further related to its modification towards efficient reaction and separation from WGS reaction mixture. Moreover, zeolite framework suitable for WGS membrane reactor will be discussed more deeply.

N-Alkylation by Hydrogen Autotransfer Reactions.

Science.gov (United States)

Ma, Xiantao; Su, Chenliang; Xu, Qing

2016-06-01

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

Hydrogen electrode reaction: A complete kinetic description

International Nuclear Information System (INIS)

Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

2007-01-01

The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

Two dimensional simulation of hydrogen iodide decomposition reaction using fluent code for hydrogen production using nuclear technology

Energy Technology Data Exchange (ETDEWEB)

Chi, Jung Sik [The Institute of Machinery and Electronic Technology, Mokpo National Maritime University, Mokpo (Korea, Republic of); Shin, Young Joon; Lee, Ki Young [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Jae Hyuk [Division of Marine Engineering System, Korea Maritime and Ocean University, Busan (Korea, Republic of)

2015-06-15

The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen production were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribution, were studied to compare device performance with that expected for device development. Hydrogen production increased with an increase of the surface-to-volume (STV) ratio. With an increase of hydrogen production, the reaction heat increased. The internal pressure and velocity of the HI decomposer were estimated through pressure drop and reducing velocity from the preheating zone. The mass of H2O was independent of the STV ratio, whereas that of HI decreased with increasing STV ratio.

Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

Science.gov (United States)

Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

2002-04-23

In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional

Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

Energy Technology Data Exchange (ETDEWEB)

Weres, Oleh; Tsao, Leon

1983-01-01

Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

Reaction of hydrogen sulfide with oxygen in the presence of sulfite

Energy Technology Data Exchange (ETDEWEB)

Weres, O.; Tsao, L.

1983-01-14

Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

Applications of heavy-ion reactions on hydrogen isotopes

International Nuclear Information System (INIS)

Evers, E.J.

1987-01-01

This thesis describes various aspects of 'inverse' reactions between the lightest nuclides, hydrogen and deuterium, and heavy ions in the range from carbon to phosphorus. The reactions studied in this thesis always result in one light ejectile and one excited heavy nucleus. Coincidence experiments have been performed in which both the emitted light particle and the gamma radiation emitted by the excited heavy nucleus produced, are detected. Ch. 1 describes the system built for the acquisition of data obtained in such coincidence experiments. Ch. 2 describes precision measurements of nuclear lifetimes and stopping powers. Coincident Doppler shift attenuation (DSA) experiments were performed with the reaction 2 H( 31 P,pγ) 32 P at E( 31 P 7+ )=50 MeV and thin Ti 2 H targets on Au, Ag and Cu backings. Mean lifetimes of the E x =513, 1150, 1323 and 1755 levels were determined with experimental stopping powers of Forster et al. These lifetimes were used as input in further analysis of the experimental data and of an additional experiment with a target on Mg backing to determine a consistent set of stopping power data for P ions with a velocity in the range 0-8(c/137) in the four materials mentioned. Ch.'s 3 and 4 deal with narrow resonances in reactions of nitrogen and fluorine beams with hydrogen targets. In Ch. 3 a method is described for the calibration of analyzing-magnet systems of heavy-ions accelerators. Ch. 4 describes an experiment to investigate the hydrogen concentration in silicon nitride films using a resonant inverse nuclear reaction. This method turns out to be a very suitable one for determining hydrogen concentration profiles with a good depth resolution over a large depth. 69 refs.; 23 figs.; 7 tabs

Reaction-diffusion modeling of hydrogen in beryllium

Energy Technology Data Exchange (ETDEWEB)

Wensing, Mirko; Matveev, Dmitry; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

2016-07-01

Beryllium will be used as first-wall material for the future fusion reactor ITER as well as in the breeding blanket of DEMO. In both cases it is important to understand the mechanisms of hydrogen retention in beryllium. In earlier experiments with beryllium low-energy binding states of hydrogen were observed by thermal desorption spectroscopy (TDS) which are not yet well understood. Two candidates for these states are considered: beryllium-hydride phases within the bulk and surface effects. The retention of deuterium in beryllium is studied by a reaction rate approach using a coupled reaction diffusion system (CRDS)-model relying on ab initio data from density functional theory calculations (DFT). In this contribution we try to assess the influence of surface recombination.

Purification of free hydrogen or hydrogen combined in a gaseous mixture by chemical reactions with uranium

International Nuclear Information System (INIS)

Caron-Charles, M.; Gilot, B.

1989-01-01

Within the framework of the European fusion program, the authors are dealing with the tritium technology aspect. Hydrogen, free or under a combined form within a H 2 , N 2 , NH 3 , O 2 , gaseous mixture, can be purified by chemical reactions with uranium metal. The resulting reactions consist in absorbing the impurities without holding back H 2 . Working conditions have been defined according to two main goals: the formation of stable solid products, especially under hydrogenated atmosphere and the optimization of the material quantities to be used. Thermodynamical considerations have shown that the 950-1300 K temperature range should be suitable for this chemical process. Experiments performed with massive uranium set in a closed reactor at 973 K, have produced hydrogen according to the predicted reactions rates. But they have also pointed out the importance of interferences that might occur in the uranium-gas system, on the gases conversion rates. The comparison between the chemical kinetic ratings of the reactions of pure gases and the chemical kinetic ratings of the reactions of the same gases in mixture, has been set up. It proves that simultaneous reactions can modify the working conditions of the solid products formation, and particularly modify their structure. In this case, chemical kinetic ratings are increased up to their maximal value; that means surface phenomena are favoured as with uranium powder gases reactions. (orig.)

A light water excess heat reaction suggests that cold fusion may be alkali-hydrogen fusion

International Nuclear Information System (INIS)

Bush, R.T.

1992-01-01

This paper reports that Mills and Kneizys presented data in support of a light water excess heat reaction obtained with an electrolytic cell highly reminiscent of the Fleischmann-Pons cold fusion cell. The claim of Mills and Kneizys that their excess heat reaction can be explained on the basis of a novel chemistry, which supposedly also explains cold fusion, is rejected in favor of their reaction being, instead, a light water cold fusion reaction. It is the first known light water cold fusion reaction to exhibit excess heat, it may serve as a prototype to expand our understanding of cold fusion. From this new reactions are deduced, including those common to past cold fusion studies. This broader pattern of nuclear reactions is typically seen to involve a fusion of the nuclides of the alkali atoms with the simplest of the alkali-type nuclides, namely, protons, deuterons, and tritons. Thus, the term alkali-hydrogen fusion seems appropriate for this new type of reaction with three subclasses: alkali-hydrogen fusion, alkali-deuterium fusion, and alkali-tritium fusion. A new three-dimensional transmission resonance model (TRM) is sketched. Finally, preliminary experimental evidence in support of the hypothesis of a light water nuclear reaction and alkali-hydrogen fusion is reported. Evidence is presented that appears to strongly implicate the transmission resonance phenomenon of the new TRM

Measurement of hydrogen in BCN films by nuclear reaction analysis

Energy Technology Data Exchange (ETDEWEB)

Yasui, Haruyuki; Hirose, Yukio; Sasaki, Toshihiko [Kanazawa Univ. (Japan); Awazu, Kaoru [Industrial Research Inst., of Ishikawa, Kanazawa (Japan); Naramoto, Hiroshi [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Chemistry Research Establishment

2001-07-01

Hydrogen is a very common contaminant in carbon films. It can strongly influence on mechanical, physical and chemical properties of the films. The analysis of hydrogen is therefore a crucial problem produce the films with the properties required. Ion beam techniques using nuclear reactions are effective for the quantitative determination of hydrogen concentration. A specially designed spectrometer is employed for the detailed determination of hydrogen concentrations by detecting 4.43MeV {gamma}-rays from the resonant nuclear reactions {sup 1}H({sup 15}N, {alpha}{gamma}){sup 12}C at the 6.385MeV. In this study, the BCN films were formed on silicon substrate by ion beam assisted deposition (IBAD), in which boron and carbon were deposited by electron beam heating of B{sub 4}C solid and nitrogen was supplied by ion implantation simultaneously. The concentrations of hydrogen in BCN films were measured using RNRA. The mechanical properties of BCN films were evaluated using an ultra-micro-hardness tester. It was confirmed that the hardness of BCN films increased with increasing the concentration of hydrogen. (author)

Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

Science.gov (United States)

Alghamdi, Abdulaziz

2009-12-01

The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391°C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas

Ternary alloy nanocatalysts for hydrogen evolution reaction

Indian Academy of Sciences (India)

Generation of hydrogen through water splitting is an impor- tant area of research. ... Splitting of water using electricity makes this reaction feasible, but requires a catalyst to overcome .... The obtained product was dried in air and heated at 700.

GaN CVD Reactions: Hydrogen and Ammonia Decomposition and the Desorption of Gallium

International Nuclear Information System (INIS)

Bartram, Michael E.; Creighton, J. Randall

1999-01-01

Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N 15 H 3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N 2 of mixed isotopes below the onset of GaN sublimation, This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence G-aN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

Energy Technology Data Exchange (ETDEWEB)

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.

2017-01-18

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

International Nuclear Information System (INIS)

Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

2006-04-01

Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load

Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

Energy Technology Data Exchange (ETDEWEB)

Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

2006-04-15

Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load.

A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

Directory of Open Access Journals (Sweden)

Maria Michela Dell’Anna

2010-05-01

Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

International Nuclear Information System (INIS)

Iwaki, T.; Katsuta, K.; Miura, M.

1981-01-01

The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yun [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China); Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, Troy, NY (United States); Liu, Yinhe, E-mail: yinheliu@mail.xjtu.edu.cn [School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an (China)

2017-11-20

Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C{sub hydrogen} < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C{sub hydrogen} > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

Numerical Simulation of Hydrogen Combustion: Global Reaction Model and Validation

International Nuclear Information System (INIS)

Zhang, Yun; Liu, Yinhe

2017-01-01

Due to the complexity of modeling the combustion process in nuclear power plants, the global mechanisms are preferred for numerical simulation. To quickly perform the highly resolved simulations with limited processing resources of large-scale hydrogen combustion, a method based on thermal theory was developed to obtain kinetic parameters of global reaction mechanism of hydrogen–air combustion in a wide range. The calculated kinetic parameters at lower hydrogen concentration (C hydrogen < 20%) were validated against the results obtained from experimental measurements in a container and combustion test facility. In addition, the numerical data by the global mechanism (C hydrogen > 20%) were compared with the results by detailed mechanism. Good agreement between the model prediction and the experimental data was achieved, and the comparison between simulation results by the detailed mechanism and the global reaction mechanism show that the present calculated global mechanism has excellent predictable capabilities for a wide range of hydrogen–air mixtures.

Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

International Nuclear Information System (INIS)

Wiesener, K.; Winkler, E.; Schneider, W.

1985-01-01

The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

International Nuclear Information System (INIS)

Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

1993-01-01

Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

Decarbonylation and hydrogenation reactions of allyl alcohol and acrolein on Pd(110)

Science.gov (United States)

Shekhar, Ratna; Barteau, Mark A.

1994-11-01

Allyl alcohol and acrolein reactions on the Pd(110) surface were investigated using temperature programmed desorption. For both unsaturated oxygenates, three coverage-dependent reaction pathways were observed. At low coverages, allyl alcohol decomposed completely to CO, hydrogen and carbonaceous species on the surface. For θ > 0.15 monolayer, ethylene (and small amounts of ethane) desorbed at ca. 295 K. Near saturation coverages, desorption of propanal was detected at ca. 235 K. The parent molecule, allyl alcohol, desorbed only after exposures sufficient to saturate these channels. Acrolein decomposition spectra were similar to those observed for allyl alcohol decomposition on the clean surface. Additional experiments with allyl alcohol on hydrogen- and deuterium-precoveredPd(110) surfaces demonstrated increased hydrogenation of the C 2-hydrocarbon products along with hydrogenation of allyl alcohol to 1-propanol. However, in contrast to previous results for allyl alcohol on the Pd(111) surface, there was no evidence for C-O scission reactions of any C 3 oxygenate on Pd(110).

Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

Energy Technology Data Exchange (ETDEWEB)

Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol [Pusan National University, Busan (Korea, Republic of)

2015-03-15

An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

Numerical comparison of hydrogen-air reaction mechanisms for unsteady shockinduced combustion applications

International Nuclear Information System (INIS)

Kumar, P. Pradeep; Kim, Kui Soon; Oh, Se Jong; Choi, Jeong Yeol

2015-01-01

An unsteady shock-induced combustion (SIC) is characterized by the regularly oscillating combustion phenomenon behind the shock wave supported by the blunt projectile flying around the speed of Chapman-Jouguet detonation wave. The SIC is the coupling phenomenon between the hypersonic flow and the chemical kinetics, but the effects of chemical kinetics have been rarely reported. We compared hydrogen-air reaction mechanisms for the shock-induced combustion to demonstrate the importance of considering the reaction mechanisms for such complex flows. Seven hydrogen-air reaction mechanisms were considered, those available publically and used in other researches. As a first step in the comparison of the hydrogen combustion, ignition delay time of hydrogen-oxygen mixtures was compared at various initial conditions. Laminar premixed flame speed was also compared with available experimental data and at high pressure conditions. In addition, half-reaction length of ZND (Zeldovich-Neumann-Doering) detonation structure accounts for the length scale in SIC phenomena. Oscillation frequency of the SIC is compared by running the time-accurate 3rd-order Navier-Stokes CFD code fully coupled with the detailed chemistry by using four levels of grid resolutions.

Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

Science.gov (United States)

Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

2015-01-01

Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

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

International Nuclear Information System (INIS)

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

1985-01-01

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-01-29

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

Sum Frequency Generation Studies of Hydrogenation Reactions on Platinum Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

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

2013-08-31

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

Reaction of dimethyl hydrogen phosphite with acecyclone

International Nuclear Information System (INIS)

Arbuzov, B.A.; Fuzhenkova, A.V.; Tyryshkin, N.I.

1987-01-01

In the presence of bases acecyclone reacts with dimethyl hydrogen phosphite with the formation of gamma-keto phosphonates with conjugated and unconjugated structures, and also an enol phosphate, a product containing a bond between oxygen of the cyclone and phosphorus. In the absence of bases, as well as the beta-keto phosphonate, gamma-keto phosphonates of cis and trans structure are formed; they are products of the 1,4 addition of dimethyl hydrogen phosphite to the conjugated fragment C=C-C=O of the cyclone. The compositions of the reaction mixture were determined by IR and NMR spectroscopy and TLC. Full-scale analysis of chemical shifts and spin-spin coupling constants was performed

Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

Science.gov (United States)

Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

2013-09-01

In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

Hydrogen abstraction reactions by amide electron adducts

International Nuclear Information System (INIS)

Sevilla, M.D.; Sevilla, C.L.; Swarts, S.

1982-01-01

Electron reactions with a number of peptide model compounds (amides and N-acetylamino acids) in aqueous glasses at low temperature have been investigated using ESR spectroscopy. The radicals produced by electron attachment to amides, RC(OD)NDR', are found to act as hydrogen abstracting agents. For example, the propionamide electron adduct is found to abstract from its parent propionamide. Electron adducts of other amides investigated show similar behavior except for acetamide electron adduct which does not abstract from its parent compound, but does abstract from other amides. The tendency toward abstraction for amide electron adducts are compared to electron adducts of several carboxylic acids, ketones, aldehydes and esters. The comparison suggests the hydrogen abstraction tendency of the various deuterated electron adducts (DEAs) to be in the following order: aldehyde DEA > acid DEA = approximately ester DEA > ketone DEA > amide DEA. In basic glasses the hydrogen abstraction ability of the amide electron adducts is maintained until the concentration of base is increased sufficiently to convert the DEA to its anionic form, RC(O - )ND 2 . In this form the hydrogen abstracting ability of the radical is greatly diminished. Similar results were found for the ester and carboxylic acid DEA's tested. (author)

Reaction of O+, CO+, and CH+ ions with atomic hydrogen

International Nuclear Information System (INIS)

Federer, W.; Villinger, H.; Howorka, F.; Lindinger, W.; Tosis, P.; Bassi, D.; Ferguson, E.

1984-01-01

Rate coefficients for reactions of the ions O + , CO + , and CH + with atomic hydrogen have been measured for the first time at 300 K. This provides basic data for the ion chemistry of planetary atmospheres, cometary atmospheres, and interstellar molecular clouds. The O + +H measurement supports quantal calculations of this reaction. The CO + +H reaction provides an example of partial spin nonconservation in a charge-transfer reaction occurring in a deep potential well. Reactions of the same ions with H 2 that have been measured elsewhere are also reported

Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals

DEFF Research Database (Denmark)

Knap, Hasse Christian; Jørgensen, Solvejg

2017-01-01

-shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1...... with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H......We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H...

Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

International Nuclear Information System (INIS)

De Hollander, W.R.; Nivas, Y.

1975-01-01

Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

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

Science.gov (United States)

Ganesh, Karthik

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

The electrochemical Peltier heat of the standard hydrogen electrode reaction

International Nuclear Information System (INIS)

Fang Zheng; Wang Shaofen; Zhang Zhenghua; Qiu Guanzhou

2008-01-01

A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on φ 0 * = 0 and ΔS 0 * = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN) 6 3- /Fe(CN) 6 4- system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied

Diels-Alder reactions in water : Enforced hydrophobic interaction and hydrogen bonding

NARCIS (Netherlands)

Engberts, Jan B.F.N.

1995-01-01

Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

DIELS-ALDER REACTIONS IN WATER - ENFORCED HYDROPHOBIC INTERACTION AND HYDROGEN-BONDING

NARCIS (Netherlands)

Engberts, J.B.F.N.

Second-order rate constants have been measured for the Diels-Alder (DA) reactions of cyclopentadiene with dienophiles of varying hydrophobicity and hydrogen-bond acceptor capacity in water, in a series of organic solvents and in alcohol-water mixtures. The intramolecular DA reaction of

Selected specific rates of reactions of transients from water in aqueous solution. II. Hydrogen atom

International Nuclear Information System (INIS)

Anbar, M.; Farhataziz; Ross, A.B.

1975-05-01

Rates of reactions of hydrogen atoms (from radiolysis of water and other sources) with organic and inorganic molecules, ions, and transients in aqueous solution were tabulated. Directly measured rates obtained by kinetic spectroscopy or conductimetric methods, and relative rates determined by competition kinetics are included. (U.S.)

Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

Energy Technology Data Exchange (ETDEWEB)

Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

2015-10-05

Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

Science.gov (United States)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

International Nuclear Information System (INIS)

Santos, Elizabeth; Schmickler, Wolfgang

2008-01-01

A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

Zinc electrodeposition from flowing alkaline zincate solutions: Role of hydrogen evolution reaction

Science.gov (United States)

Dundálek, Jan; Šnajdr, Ivo; Libánský, Ondřej; Vrána, Jiří; Pocedič, Jaromír; Mazúr, Petr; Kosek, Juraj

2017-12-01

The hydrogen evolution reaction is known as a parasitic reaction during the zinc electrodeposition from alkaline zincate solutions and is thus responsible for current efficiency losses during the electrolysis. Besides that, the rising hydrogen bubbles may cause an extra convection within a diffusion layer, which leads to an enhanced mass transport of zincate ions to an electrode surface. In this work, the mentioned phenomena were studied experimentally in a flow through electrolyzer and the obtained data were subsequently evaluated by mathematical models. The results prove the indisputable influence of the rising hydrogen bubbles on the additional mixing of the diffusion layer, which partially compensates the drop of the current efficiency of the zinc deposition at higher current flows. Moreover, the results show that the current density ratio (i.e., the ratio of an overall current density to a zinc limiting current density) is not suitable for the description of the zinc deposition, because the hydrogen evolution current density is always involved in the overall current density.

Hydrogen release from irradiated elastomers measured by Nuclear Reaction Analysis

Energy Technology Data Exchange (ETDEWEB)

Jagielski, J., E-mail: jacek.jagielski@itme.edu.pl [Institute for Electronic Materials Technology, Wolczynska 133, 01-926 Warszawa (Poland); National Centre for Nuclear Research, A. Soltana 7, 05-400 Swierk/Otwock (Poland); Ostaszewska, U. [Institute for Engineering of Polymer Materials & Dyes, Division of Elastomers & Rubber Technology, Harcerska 30, 05-820 Piastow (Poland); Bielinski, D.M. [Technical University of Lodz, Institute of Polymer & Dye Technology, Stefanowskiego 12/16, 90-924 Lodz (Poland); Grambole, D. [Institute of Ion Beam Physics and Materials Research, Helmholtz Zentrum Dresden Rossendorf, PO Box 51 01 19, D-01314 Dresden (Germany); Romaniec, M.; Jozwik, I.; Kozinski, R. [Institute for Electronic Materials Technology, Wolczynska 133, 01-926 Warszawa (Poland); Kosinska, A. [National Centre for Nuclear Research, A. Soltana 7, 05-400 Swierk/Otwock (Poland)

2016-03-15

Ion irradiation appears as an interesting method of modification of elastomers, especially friction and wear properties. Main structural effect caused by heavy ions is a massive loss of hydrogen from the surface layer leading to its smoothening and shrinking. The paper presents the results of hydrogen release from various elastomers upon irradiation with H{sup +}, He{sup +} and Ar{sup +} studied by using Nuclear Reaction Analysis (NRA) method. The analysis of the experimental data indicates that the hydrogen release is controlled by inelastic collisions between ions and target electrons. The last part of the study was focused on preliminary analysis of mechanical properties of irradiated rubbers.

Reaction path sampling of the reaction between iron(II) and hydrogen peroxide in aqueous solution

NARCIS (Netherlands)

Ensing, B.; Baerends, E.J.

2002-01-01

Previously, we have studied the coordination and dissociation of hydrogen peroxide with iron(II) in aqueous solution by Car-Parrinello molecular dynamics at room temperature. We presented a few illustrative reaction events, in which the ferryl ion ([Fe(IV)O

Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

Science.gov (United States)

Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2014-03-01

In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

Reactions of oxygen and hydrogen with liquid sodium - a critical survey

International Nuclear Information System (INIS)

Ullmann, H.

1982-01-01

The fundamentals of solvation chemistry are presented with appropriate components formulated. Methods of investigation and kinetics of the reactions are described. The hydrogen equilibrium pressure and saturation solubilities are described. The chemical equilibrium between O and H in solution is presented with detailed tabulation of the saturation solutions of oxygen, hydrogen and hydroxide in liquid sodium. Agreements and differences with the literature are presented

Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

International Nuclear Information System (INIS)

Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

1979-01-01

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

The solvation reaction field for a hydrogen atom in a dielectric continuum

International Nuclear Information System (INIS)

Chipman, D.M.

1996-01-01

A reaction field exists even for a nonpolar solute embedded in a spherical cavity within a surrounding homogeneous dielectric continuum. This arises from the tail of the electronic wave function that penetrates beyond the cavity boundary into the dielectric region. This effect, which is neglected or treated only in cursory fashion in most reaction field implementations, is examined in detail for the simple case of a ground state hydrogen atom, where very accurate solutions of the relevant equations can be obtained. Properties considered include the penetration of the electron outside the cavity, the electronic density at the nucleus, the electron binding energy, the electrostatic free energy of solvation, the polarizability, and the vertical 1s→2p excitation energy. Also, the effect of the common approximation of neglecting the volume polarization and treating only the surface polarization contribution to the reaction field is critically evaluated. copyright 1996 American Institute of Physics

Hydrogenation of Phenol over Pt/CNTs: The Effects of Pt Loading and Reaction Solvents

OpenAIRE

Feng Li; Bo Cao; Wenxi Zhu; Hua Song; Keliang Wang; Cuiqin Li

2017-01-01

Carbon nanotubes (CNTs)-supported Pt nanoparticles were prepared with selective deposition of Pt nanoparticles inside and outside CNTs (Pt–in/CNTs and Pt–out/CNTs). The effects of Pt loading and reaction solvents on phenol hydrogenation were investigated. The Pt nanoparticles in Pt–in/CNTs versus Pt–out/CNTs are smaller and better dispersed. The catalytic activity and reuse stability toward phenol hydrogenation both improved markedly. The dichloromethane–water mixture as the reaction solvent,...

Nuclear reaction analysis of hydrogen in amorphous silicon and silicon carbide films

International Nuclear Information System (INIS)

Guivarc'h, A.; Le Contellec, M.; Richard, J.; Ligeon, E.; Fontenille, J.; Danielou, R.

1980-01-01

The 1 H( 11 B, α)αα nuclear reaction is used to determine the H content and the density of amorphous semiconductor Si 1 -sub(x)Csub(x)H 2 and SiHsub(z) thin films. Rutherford backscattering is used to determine the x values and infrared transmission to study the hydrogen bonds. We have observed a transfer or/and a release of hydrogen under bombardment by various ions and we show that this last effect must be taken into account for a correct determination of the hydrogen content. An attempt is made to correlate the hydrogen release with electronic and nuclear energy losses. (orig.)

Hydrogen-Bonding Catalysis of Tetraalkylammonium Salts in an Aza-Diels-Alder Reaction.

Science.gov (United States)

Kumatabara, Yusuke; Kaneko, Shiho; Nakata, Satoshi; Shirakawa, Seiji; Maruoka, Keiji

2016-08-05

A piperidine-derived tetraalkylammonium salt with a non-coordinating counteranion worked as an effective hydrogen-bonding catalyst in an aza-Diels-Alder reaction of imines and a Danishefsky diene. The hydrogen-bonding interaction between the ammonium salt and an imine was observed as part of a (1) H NMR titration study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

Energy Technology Data Exchange (ETDEWEB)

Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

1978-05-01

Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

Sorption Enhanced Reaction Process (SERP) for production of hydrogen

Energy Technology Data Exchange (ETDEWEB)

Anand, M.; Hufton, J.; Mayorga, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)] [and others

1996-10-01

Sorption Enhanced Reaction Process (SERP) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The key consequences of SERP are: (i) reformation reaction is carried out at a significantly lower temperature (300-500{degrees}C) than that in a conventional SMR reactor (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (ii) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 98+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (iii) downstream hydrogen purification step is either eliminated or significantly reduced in size. The first phase of the program has focused on the development of a sorbent for CO{sub 2} which has (a) reversible CO{sub 2} capacity >0.3 mmol/g at low partial pressures of CO{sub 2} (0.1 - 1.0 atm) in the presence of excess steam (pH{sub 2}O/pCO{sub 2}>20) at 400-500{degrees}C and (b) fast sorption-desorption kinetics for CO{sub 2}, at 400-500{degrees}C. Several families of supported sorbents have been identified that meet the target CO{sub 2} capacity. A few of these sorbents have been tested under repeated sorption/desorption cycles and extended exposure to high pressure steam at 400-500{degrees}C. One sorbent has been scaled up to larger quantities (2-3 kg) and tested in the laboratory process equipment for sorption and desorption kinetics of CO{sub 2}. The CO{sub 2}, sorption and desorption kinetics are desirably fast. This was a critical path item for the first phase of the program and now has been successfully demonstrated. A reactor has been designed that will allow nearly isothermal operation for SERP-SMR. This reactor was integrated into an overall process flow diagram for the SERP-SMR process.

Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

Directory of Open Access Journals (Sweden)

Xiaoqing Zhang

2013-01-01

Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

2016-08-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

Science.gov (United States)

Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

2006-03-22

The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-12-12

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

Reactions of butadiyne. 1: The reaction with hydrogen atoms

Science.gov (United States)

Schwanebeck, W.; Warnatz, J.

1984-01-01

The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

Hydrogen evolution reaction on electrodes with different PT/C loadings by electrochemical impedance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Ortega-Chavez, L. [Inst. Tecnologico de Chihuahua 2, Chihuahua, Chih (Mexico); Ortega-Chavez, L.; Herrera-Peraza, E. [Centro de Investigacion en Materiales Avanzados, Chiuahua, Chih (Mexico); Verde, Y. [Inst. Tecnologico de Cancun, Cancun, Quintana Roo (Mexico)

2008-04-15

One of the most widely studied reactions in electrochemistry is the hydrogen evolution reaction (HER). HER is important for the development of water hydrolysis and fuel cell technologies. Because hydrogen-substrate interaction determines oxygen reduction efficiency, an understanding of the chemical and electronic state of hydrogen adsorbed on the electrocatalyst surface is required. Electrochemical impedance spectroscopy (EIS) is a proven highly efficient technique for interface characterization and kinetic parameter determination for different reactions carried out on interfaces. This article presented a study that utilized EIS for characterizing electrodes under HER by implementing a rotating disc electrode with different carbon supported platinum nanoparticles loadings and different potentials in acidic solutions. The results collected by EIS were analyzed in terms of equivalent circuits to calculate different parameters which were compared by statistical analysis. The study also considered the Volmer, Heyrovsky and Tafel steps in the HER reaction as well as a single electro-absorbed intermediate species. The article discussed the experimental set-up with reference to measurements, simulation and fitting. Parameters analysis using ANOVA were reviewed. It was concluded that an increase in impedance occurs when platinum loading decreases in both high and low frequencies. 22 refs., 1 tab., 5 figs.

Evaluation of a commercial packed bed flow hydrogenator for reaction screening, optimization, and synthesis

Directory of Open Access Journals (Sweden)

Marian C. Bryan

2011-08-01

Full Text Available The performance of the ThalesNano H-Cube®, a commercial packed bed flow hydrogenator, was evaluated in the context of small scale reaction screening and optimization. A model reaction, the reduction of styrene to ethylbenzene through a 10% Pd/C catalyst bed, was used to examine performance at various pressure settings, over sequential runs, and with commercial catalyst cartridges. In addition, the consistency of the hydrogen flow was indirectly measured by in-line UV spectroscopy. Finally, system contamination due to catalyst leaching, and the resolution of this issue, is described. The impact of these factors on the run-to-run reproducibility of the H-Cube® reactor for screening and reaction optimization is discussed.

Incident angle dependence of reactions between graphene and hydrogen atom by molecular dynamics simulation

International Nuclear Information System (INIS)

Saito, Seiki; Nakamura, Hiroaki; Ito, Atsushi

2010-01-01

Incident angle dependence of reactions between graphene and hydrogen atoms are obtained qualitatively by classical molecular dynamics simulation under the NVE condition with modified Brenner reactive empirical bond order (REBO) potential. Chemical reaction depends on two parameters, i.e., polar angle θ and azimuthal angle φ of the incident hydrogen. From the simulation results, it is found that the reaction rates strongly depend on polar angle θ. Reflection rate becomes larger with increasing θ, and the θ dependence of adsorption rate is also found. The θ dependence is caused by three dimensional structure of the small potential barrier which covers adsorption sites. φ dependence of penetration rate is also found for large θ. (author)

Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

Science.gov (United States)

Yuan, Heyang; He, Zhen

2017-07-01

Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

International Nuclear Information System (INIS)

Li, Lin; Borry, Richard W.; Iglesia, Enrique

2000-01-01

Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

Positron scattering by atomic hydrogen including positronium formation

International Nuclear Information System (INIS)

Higgins, K.; Burke, P.G.

1993-01-01

Positron scattering by atomic hydrogen including positronium formation has been formulated using the R-matrix method and a general computer code written. Partial wave elastic and ground state positronium formation cross sections have been calculated for L ≤ 6 using a six-state approximation which includes the ground state and the 2s and 2p pseudostates of both hydrogen and positronium. The elastic scattering results obtained are in good agreement with those derived from a highly accurate calculation based upon the intermediate energy R-matrix approach. As in a previous coupled-channel static calculation, resonance effects are observed at intermediate energies in the S-wave positronium formation cross section. However, in the present results, the dominant resonance arises in the P-wave cross sections at an energy of 2.73 Ryd and with a width of 0.19 Ryd. (author)

Gas storage materials, including hydrogen storage materials

Science.gov (United States)

Mohtadi, Rana F; Wicks, George G; Heung, Leung K; Nakamura, Kenji

2013-02-19

A material for the storage and release of gases comprises a plurality of hollow elements, each hollow element comprising a porous wall enclosing an interior cavity, the interior cavity including structures of a solid-state storage material. In particular examples, the storage material is a hydrogen storage material such as a solid state hydride. An improved method for forming such materials includes the solution diffusion of a storage material solution through a porous wall of a hollow element into an interior cavity.

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

Science.gov (United States)

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

2016-03-01

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

Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

International Nuclear Information System (INIS)

Zamfirescu, C.; Naterer, G.F.; Dincer, I.

2009-01-01

The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

Filtration and Hydrogen Reaction Modeling in a Depleted Uranium Bed

Energy Technology Data Exchange (ETDEWEB)

Jung, Kwang Jin; Kim, Yean Jin; Ahn, Do Hee; Chung, Hong Suk [UST, Daejeon (Korea, Republic of); Kang, Hee Seok [KAERI, Daejeon (Korea, Republic of); Yun, Sei Hun [NFRI, Daejeon (Korea, Republic of)

2016-05-15

The storage and delivery system (SDS) stores the hydrogen isotopes and delivers them to the fuel injection system. Depleted uranium (DU) was chosen as a hydrogen isotope storage material. The hydrogen isotopes stored in the SDS are in the form of DU hydride confined in the primary and secondary containment within a glove box with an argon atmosphere. In this study, we performed a modeling study of the SDS. A modeling study is practically important because an experimental study requires comparatively more money and time. We estimated the hydrogen atomic ratio in DU hydride by two empirical equations we formulated. Two empirical equations are used to determine Pressure-Composition-Temperature (PCT) curves and the hydrogen atomic ratio in DU hydride. In addition, we present the effect of pressure and temperature in the hydriding and dehydriding. A modeling study of the SDS was performed in this study. It is practically important to save more money and time. The hydrogen atomic ratio in the DU hydride was estimated using two empirical equations. The two empirical equations are modified and reformulated to determine PCT curves and the hydrogen atomic ratio in DU hydride. All parameters that are required to solve two empirical equations are obtained from the experimental data. The derived parameters are utilized for the numerical simulations. In the numerical simulations, the effects of pressure and temperature on both the hydriding and dehydriding reaction rates are confirmed.

Ion cyclotron resonance study of reactions of ions with hydrogen atoms

International Nuclear Information System (INIS)

Karpas, Z.; Anicich, V.; Huntress, W.T. Jr.

1979-01-01

Reactions of H 2 + , HeH + , and CO 2 + ions with hydrogen atoms, and the reactions of D 2 + , CO 2 + , CO + , N 2 + and HCN + with deuterium atoms, were studied using ion cyclotron resonance techniques. These reactions proceed predominantly via a charge transfer mechanism. The rate constants measured are: 6.4, 9.1, 1.1, 5.0, 0.84, 0.90, 1.2, and 0.37 x 10 -10 cm 3 /sec, respectively. Hydrocarbon ions of the types CH/sub n/ + and C 2 H/sub n/ + , where n=2--4, do not react with H or D atoms

A kinetic study of the electrochemical hydrogenation of ethylene

International Nuclear Information System (INIS)

Sedighi, S.; Gardner, C.L.

2010-01-01

In this study, we have examined the kinetics of the electrochemical hydrogenation of ethylene in a PEM reactor. While in itself this reaction is of little industrial interest, this reaction can be looked upon as a model reaction for many of the important hydrogenation processes including the refining of heavy oils and the hydrogenation of vegetable oils. To study the electrochemical hydrogenation of ethylene, several experimental techniques have been used including polarization measurements, measurement of the composition of the exit gases and potential step, transient measurements. The results show that the hydrogenation reaction proceeds rapidly and essentially to completion. By fitting the experimental transient data to the results from a zero-dimensional mathematical model of the process, a set of kinetic parameters for the reactions has been obtained that give generally good agreement with the experimental results. It seems probable that similar experimental techniques could be used to study the electrochemical hydrogenation of other unsaturated organic molecules of more industrial significance.

Rydberg phases of Hydrogen and low energy nuclear reactions

Science.gov (United States)

Olafsson, Sveinn; Holmlid, Leif

2016-03-01

For over the last 26 years the science of cold fusion/LENR has been researched around the world with slow pace of progress. Modest quantity of excess heat and signatures of nuclear transmutation and helium production have been confirmed in experiments and theoretical work has only resulted in a large flora of inadequate theoretical scenarios. Here we review current state of research in Rydberg matter of Hydrogen that is showing strong signature of nuclear processes. In the presentation experimental behavior of Rydberg matter of hydrogen is described. An extensive collaboration effort of surface physics, catalysis, atomic physics, solid state physics, nuclear physics and quantum information is need to tackle the surprising experimental results that have so far been obtained. Rydberg matter of Hydrogen is the only known state of matter that is able to bring huge collection of protons to so short distances and for so long time that tunneling becomes a reasonable process for making low energy nuclear reactions. Nuclear quantum entanglement can also become realistic process at theses conditions.

MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction

International Nuclear Information System (INIS)

Raoof, Jahan-Bakhsh; Hosseini, Sayed Reza; Ojani, Reza; Mandegarzad, Sakineh

2015-01-01

In this work, metal-organic framework Cu_3(BTC)_2 [BTC = 1,3,5-benzenetricarboxylate] (commonly known as MOF-199 or HKUST-1), is used as porous template for preparation of a Cu/nanoporous carbon composite. The MOF-derived Cu/nanoporous carbon composite (Cu/NPC composite) is synthesized by direct carbonization of the MOF-199 without any carbon precursor additive. The physical characterization of the solid catalyst is achieved by using a variety of different techniques, including XRD (X-ray powder diffraction), scanning electron microscopy, thermo-gravimetric analysis, and nitrogen physisorption measurements. The electrochemical results have shown that the Cu/NPC composite modified glassy carbon electrode (Cu/NPC/GCE) as a non-platinum electrocatalyst exhibited favorable catalytic activity for hydrogen evolution reaction, in spite of high resistance to faradic process. This behavior can be attributed to existence of Cu metal confirmed by XRD and/or high effective pore surface area (1025 m"2 g"−"1) in the Cu/NPC composite. The electron transfer coefficient and exchange current density for the Cu/NPC/GCE is calculated by Tafel plot at about 0.34 and 1.2 × 0"−"3 mAcm"−"2, respectively. - Graphical abstract: Metal organic framework-derived Cu/nanoporous carbon composite (Cu/NPC composite) was prepared by direct carbonization of MOF-199 without addition of any carbon source at 900 °C. The Cu/NPC/GCE demonstrated an excellent electrocatalytic activity towards hydrogen evolution reaction compared with bare GCE. - Highlights: • MDNPC (MOF-199 derived nanoporous carbon) is prepared by direct carbonization. • MOF-199 is utilized as a template without addition of carbon resource. • The MDNPC has a good electrocatalytic activity in hydrogen evolution reaction. • High BET surface area and hydrogen adsorption property improved catalyst activity.

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

International Nuclear Information System (INIS)

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

1998-01-01

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

Sulfur tolerance of Pt/mordenites for benzene hydrogenation. Do Bronsted acid sites participate in hydrogenation?

NARCIS (Netherlands)

Simon, L.; van Ommen, J.G.; Jentys, A.; Lercher, J.A.

2002-01-01

The comparison of Pt electronic properties studied by in situ XANES and the kinetic study of benzene hydrogenation strongly suggests that the hydrogenation of benzene on Pt/mordenites occurs along two parallel reaction pathways. The routes proposed include (i) the monofunctional hydrogenation of

Facile Hydrogen Evolution Reaction on WO3Nanorods

Directory of Open Access Journals (Sweden)

Rajeswari Janarthanan

2007-01-01

Full Text Available AbstractTungsten trioxide nanorods have been generated by the thermal decomposition (450 °C of tetrabutylammonium decatungstate. The synthesized tungsten trioxide (WO3 nanorods have been characterized by XRD, Raman, SEM, TEM, HRTEM and cyclic voltammetry. High resolution transmission electron microscopy and X-ray diffraction analysis showed that the synthesized WO3nanorods are crystalline in nature with monoclinic structure. The electrochemical experiments showed that they constitute a better electrocatalytic system for hydrogen evolution reaction in acid medium compared to their bulk counterpart.

Measure of hydrogen concentration profile in materials by resonant nuclear reactions

International Nuclear Information System (INIS)

Livi, R.P.; Zawislak, F.C.; Acquadro, J.C.

1986-01-01

The technique for determining the profile of hydrogen concentration in proximities of the surface of materials, is presented. The preliminary measurements were done, using the Pelletron accelerator at Sao Paulo University (USP), in Brazil, for the resonant-nuclear reaction 1 H( 19 F, α γ) 16 O. By using this reaction the technique is sensitive for concentrations above 500 ppm, which could be reduced to 100 ppm through special shieldings and other techniques to reduce the background radiation. (M.C.K.) [pt

Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons

Science.gov (United States)

Baker, Richard W.; Lokhandwala, Kaaeid A.; He, Zhenjie; Pinnau, Ingo

2001-01-01

An improved process for separating hydrogen from hydrocarbons. The process includes a pressure swing adsorption step, a compression/cooling step and a membrane separation step. The membrane step relies on achieving a methane/hydrogen selectivity of at least about 2.5 under the conditions of the process.

Regularities of catalytic reactions of hydrogen, ethane and ethylene with elementary sulfur

International Nuclear Information System (INIS)

Zazhigalov, V.A.

1978-01-01

Shown is the decisive role of metal-sulfur bond stability for activity determination of metal sulfides (WS 2 , MoS 2 , CdS) in interaction reactions of elementary sulfur and hydrogen, ethane and ethylene. Found is the regularity of changing the relative reactiveness of the given substances and a conclusion is made about uniformity of the investigated catalyst processes. The results of hydrogen, ethane and ethylene oxidation by oxygen and sulfur are compared, the semilarity of these processes being pointed out

The influence of reaction time on hydrogen sulphide removal from air by means of Fe(III)-EDTA/Fiban catalysts

Science.gov (United States)

Wasag, H.; Cel, W.; Chomczynska, M.; Kujawska, J.

2018-05-01

The paper deals with a new method of hydrogen sulphide removal from air by its filtration and selective catalytic oxidation with the use of fibrous carriers of Fe(III)-EDTA complex. The basis of these filtering materials includes fibrous ion exchangers with the complex immobilized on their functional groups. It has been established that the degree of catalytic hydrogen sulphide decomposition depends on the reaction time. Thus, the required degree of hydrogen sulphide removal from air could be easily controlled by applying appropriate thickness of the filtering layer under a given filtering velocity. It allows applying very thin filtering layers of the Fe(III)-EDTA/Fiban AK-22 or Fiban A-6 catalysts. The obtained results of the research confirm the applicability of these materials for deep air purification from hydrogen sulphide.

Effect of hydrogen coverage on hydrogenation of o-cresol on Pt(111)

Science.gov (United States)

Li, Yaping; Liu, Zhimin; Crossley, Steven P.; Jentoft, Friederike C.; Wang, Sanwu

2018-06-01

The conversion of phenolics over metal catalysts is an important process for upgrading biofuels. With density functional calculations, hydrogenation of o-cresol on the hydrogen-covered Pt(111) surface was investigated. The results show that the coverage of hydrogen plays a significant role in the reaction rate while it does not affect the reaction selectivity. The reaction barriers of the hydrogenation process leading to the formation of both 2-methyl-cyclohexanone (the intermediate product) and 2-methyl-cyclohexanol (the final product) at high H coverages (∼1 ML) are found to be smaller by 0.14-0.69 eV than those at lower H coverages (∼1/25 ML). After both hydrogen and cresol are adsorbed on Pt(111) from their initial gas phase state, the reaction energy of each hydrogenation step on the surface is also dependent on the hydrogen coverage. On the H-covered Pt(111) surface, most steps of hydrogenation involve exothermic reactions when the hydrogen coverage is high while they are endothermic reactions at low hydrogen coverages. The differences in reaction rate and reaction energy between high and low H coverages can be understood with the coverage-dependent bonding strength and configurations.

MIS-based sensors with hydrogen selectivity

Energy Technology Data Exchange (ETDEWEB)

Li,; Dongmei, [Boulder, CO; Medlin, J William [Boulder, CO; McDaniel, Anthony H [Livermore, CA; Bastasz, Robert J [Livermore, CA

2008-03-11

The invention provides hydrogen selective metal-insulator-semiconductor sensors which include a layer of hydrogen selective material. The hydrogen selective material can be polyimide layer having a thickness between 200 and 800 nm. Suitable polyimide materials include reaction products of benzophenone tetracarboxylic dianhydride 4,4-oxydianiline m-phenylene diamine and other structurally similar materials.

Production of hydrogen through the carbonation-calcination reaction applied to CH4/CO2 mixtures

International Nuclear Information System (INIS)

Barelli, L.; Bidini, G.; Corradetti, A.; Desideri, U.

2007-01-01

The production of hydrogen combined with carbon capture represents a possible option for reducing CO 2 emissions in atmosphere and anthropogenic greenhouse effect. Nowadays the worldwide hydrogen production is based mainly on natural gas reforming, but the attention of the scientific community is focused also on other gas mixtures with significant methane content. In particular mixtures constituted mainly by methane and carbon dioxide are extensively used in energy conversion applications, as they include land-fill gas, digester gas and natural gas. The present paper addresses the development of an innovative system for hydrogen production and CO 2 capture starting from these mixtures. The plant is based on steam methane reforming, coupled with the carbonation and calcination reactions for CO 2 absorption and desorption, respectively. A thermodynamic approach is proposed to investigate the plant performance in relation to the CH 4 content in the feeding gas. The results suggest that, in order to optimize the hydrogen purity and the efficiency, two different methodologies can be adopted involving both the system layout and operating parameters. In particular such methodologies are suitable for a methane content, respectively, higher and lower than 65%

Silicon Nano wires with MoS_x and Pt as Electrocatalysts for Hydrogen Evolution Reaction

International Nuclear Information System (INIS)

Hsieh, S.H.; Ho, S.T.; Chen, W.J.

2016-01-01

A convenient method was used for synthesizing Pt-nanoparticle//silicon nano wires nano composites. Obtained Pt-/silicon nano wires electrocatalysts were characterized by transmission electron microscopy (TEM). The hydrogen evolution reaction efficiency of the Pt-/silicon nano wire nano composite catalysts was assessed by examining polarization and electrolysis measurements under solar light irradiations. The electrochemical characterizations demonstrate that Pt-/silicon nano wire electrodes exhibited an excellent catalytic activity for hydrogen evolution reaction in an acidic electrolyte. The hydrogen production capability of Pt-/silicon nano wires is also comparable to /silicon nano wires and Pt/silicon nano wires. Electrochemical impedance spectroscopy experiments suggest that the enhanced performance of Pt-/silicon nano wires can be attributed to the fast electron transfer between Pt-/silicon nano wire electrodes and electrolyte interfaces.

MoS2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions.

Science.gov (United States)

Wang, Chengli; Su, Yingchun; Zhao, Xiaole; Tong, Shanshan; Han, Xiaojun

2018-01-24

A novel MoS 2 -based flower-like nanohybrid for hydrogen evolution was fabricated through coating the Cu-containing metal-organic framework (HKUST-1) onto MoS 2 nanosheets. It is the first time that MoS 2 @HKUST-1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS 2 @HKUST-1 flower-like nanohybrids were characterized by scanning electron microscopy, X-ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS 2 , the MoS 2 @HKUST-1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of -99 mV, a smaller Tafel slope of 69 mV dec -1 , and a Faradaic efficiency of nearly 100 %. The MoS 2 @HKUST-1 flower-like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non-noble metal catalysts with high performance for the hydrogen evolution reaction (HER). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aerosol simulation including chemical and nuclear reactions

International Nuclear Information System (INIS)

Marwil, E.S.; Lemmon, E.C.

1985-01-01

The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs

The effect of urea on microstructures of Ni{sub 3}S{sub 2} on nickel foam and its hydrogen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Jinlong, Lv, E-mail: ljltsinghua@126.com [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China); Tongxiang, Liang, E-mail: txliang@mail.tsinghua.edu.cn [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China)

2016-11-15

The effects of urea concentration on microstructures of Ni{sub 3}S{sub 2}formed on nickel foam and its hydrogen evolution reaction were investigated. The Ni{sub 3}S{sub 2} nanosheets with porous structure were formed on nickel foam during hydrothermal process due to low urea concentration. While high urea concentration facilitated the forming of Ni{sub 3}S{sub 2} nanotube arrays. The resulting Ni{sub 3}S{sub 2} nanotube arrays exhibited higher catalytic activity than Ni3S2nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction. - Graphical abstract: The resulting Ni{sub 3}S{sub 2} nanotube arrays exhibited higher catalytic activity than Ni{sub 3}S{sub 2} nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni{sub 3}S{sub 2} nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction and hydrogen evolution. - Highlights: • Urea promoted to forming more Ni{sub 3}S{sub 2} nanotube arrays on nickel foam. • Ni{sub 3}S{sub 2} nanotube arrays showed higher catalytic activity in alkaline solution. • Ni{sub 3}S{sub 2} nanotube arrays promoted electron transport and reaction during the HER.

Learning about Regiochemistry from a Hydrogen-Atom Abstraction Reaction in Water

Science.gov (United States)

Sears-Dundes, Christopher; Huon, Yoeup; Hotz, Richard P.; Pinhas, Allan R.

2011-01-01

An experiment has been developed in which the hydrogen-atom abstraction and the coupling of propionitrile, using Fenton's reagent, are investigated. Students learn about the regiochemistry of radical formation, the stereochemistry of product formation, and the interpretation of GC-MS data, in a safe reaction that can be easily completed in one…

Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

Science.gov (United States)

Lueking, Angela [State College, PA; Narayanan, Deepa [Redmond, WA

2011-03-08

A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

Tritium-tracer study of catalytic hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt

International Nuclear Information System (INIS)

Matsuyama, M.; Yasuda, Y.; Takeuchi, T.

1978-01-01

The influence of the pressure of tritiated hydrogen on the rate of the formation of tritiated ethylene, X, and that of tritiated ethane, Z, in the hydrogenation reaction of ethylene on Ni, Pt and Ni-Pt (1:1) alloy catalysts was investigated. The ratio of the rate of the exchange to that of the hydrogenation, selectivity X/Z, decreased markedly with the increase in the pressure of the tritiated hydrogen and the order of X/Z was Ni>Ni-Pt>Pt. These results were interpreted in terms of the difference in the amount of chemisorbed tritium on each metal catalyst. (orig.) [de

Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions

International Nuclear Information System (INIS)

Strozier, J.A.

1977-01-01

The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt

A Simple, Low-cost, and Robust System to Measure the Volume of Hydrogen Evolved by Chemical Reactions with Aqueous Solutions.

Science.gov (United States)

Brack, Paul; Dann, Sandie; Wijayantha, K G Upul; Adcock, Paul; Foster, Simon

2016-08-17

There is a growing research interest in the development of portable systems which can deliver hydrogen on-demand to proton exchange membrane (PEM) hydrogen fuel cells. Researchers seeking to develop such systems require a method of measuring the generated hydrogen. Herein, we describe a simple, low-cost, and robust method to measure the hydrogen generated from the reaction of solids with aqueous solutions. The reactions are conducted in a conventional one-necked round-bottomed flask placed in a temperature controlled water bath. The hydrogen generated from the reaction in the flask is channeled through tubing into a water-filled inverted measuring cylinder. The water displaced from the measuring cylinder by the incoming gas is diverted into a beaker on a balance. The balance is connected to a computer, and the change in the mass reading of the balance over time is recorded using data collection and spreadsheet software programs. The data can then be approximately corrected for water vapor using the method described herein, and parameters such as the total hydrogen yield, the hydrogen generation rate, and the induction period can also be deduced. The size of the measuring cylinder and the resolution of the balance can be changed to adapt the setup to different hydrogen volumes and flow rates.

Experimental determination of reaction rates of water. Hydrogen exchange of tritium with hydrophobic catalysts

International Nuclear Information System (INIS)

Bixel, J.C.; Hartzell, B.W.; Park, W.K.

1976-01-01

This study was undertaken to obtain data needed for further development of a process for the enrichment and removal of tritium from the water associated with light-water reactors, fuel-reprocessing plants, and tritium-handling laboratories. The approach is based on the use of antiwetting, hydrophobic catalysts which permit the chemical exchange reactions between liquid water and gaseous hydrogen in direct contact, thus eliminating problems of catalyst deactivation and the complexity of reactor design normally associated with current catalytic-detritiation techniques involving gas-phase catalysis. An apparatus and procedure were developed for measuring reaction rates of water-hydrogen chemical exchange with hydrophobic catalysts. Preliminary economic evaluations of the process were made as it might apply to the AGNS fuel reprocessing plant

Modeling of Syngas Reactions and Hydrogen Generation Over Sulfides

Energy Technology Data Exchange (ETDEWEB)

Kamil Klier; Jeffery A. Spirko; Michael L. Neiman

2002-09-17

The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. In this first year of study, adsorption reactions of H atoms and H{sub 2} molecules with MoS{sub 2}, both in molecular and solid form, have been modeled using high-level density functional theory. The geometries and strengths of the adsorption sites are described and the methods used in the study are described. An exposed MO{sup IV} species modeled as a bent MoS{sub 2} molecule is capable of homopolar dissociative chemisorption of H{sub 2} into a dihydride S{sub 2}MoH{sub 2}. Among the periodic edge structures of hexagonal MoS{sub 2}, the (1{bar 2}11) edge is most stable but still capable of dissociating H{sub 2}, while the basal plane (0001) is not. A challenging task of theoretically accounting for weak bonding of MoS{sub 2} sheets across the Van der Waals gap has been addressed, resulting in a weak attraction of 0.028 eV/MoS{sub 2} unit, compared to the experimental value of 0.013 eV/MoS{sub 2} unit.

The effect of moderators on the reactions of hot hydrogen atoms with methane

CERN Document Server

Estrup, Peder J.

1960-01-01

The reaction of recoil tritium with methane has been examined in further detail. The previous hypothesis that this system involves a hot displacement reaction of high kinetic energy hydrogen to give CH$_{3}$T, CH$_{2}$T and HT is confirmed. The effect of moderator on this process is studied by the addition of noble gases. As predicted these gases inhibit the hot reaction action, their efficiency in this respect being He > Ne > A > Se. The data are quantitatively in accord with a theory of hot atom kinetics. The mechanism of the hot displacement process is briefly discussed.

Industrial applications of plasma, microwave and ultrasound techniques : nitrogen-fixation and hydrogenation reactions

NARCIS (Netherlands)

Hessel, V.; Cravotto, G.; Fitzpatrick, P.; Patil, B.S.; Lang, J.; Bonrath, W.

2013-01-01

The MAPSYN project (Microwave, Acoustic and Plasma assisted SYNtheses) aims at nitrogen-fixation reactions intensified by plasma catalysis and selective hydrogenations intensified by microwaves, possibly assisted by ultrasound. Energy efficiency is the key motif of the project and the call of the

New method for the hydrogen isotope exchange reaction in a hydrophobic catalyst bed

International Nuclear Information System (INIS)

Asakura, Y.; Kikuchi, M.; Yusa, H.

1982-01-01

To improve the isotope exchange reaction efficiency between water and hydrogen, a new reactor in which water mists and hydrogen gas react cocurrently was studied. To apply this to the enrichment of tritium in heavy water, a dual temperature isotope exchange reactor which is composed of cocurrent low temperature reactors and the usual countercurrent high temperature reactor was proposed and analyzed using a McCabe-Thiele diagram. By utilizing cocurrent reactors, in combination, the necessary catalyst volume can be reduced to one-tenth as compared with the usual countercurrent low temperature reactor. 17 refs

Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

NARCIS (Netherlands)

Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

2000-01-01

We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

International Nuclear Information System (INIS)

Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

1998-01-01

The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

Quasiclassical trajectory study of the molecular beam kinetics of the deuterium atom--hydrogen halide exchange reactions

International Nuclear Information System (INIS)

Raff, L.M.; Suzukawa, H.H. Jr.; Thompson, D.L.

1975-01-01

Unadjusted quasiclassical trajectory computations have been carried out to simulate the molecular beam scattering of thermal D atom beams at 2800 degreeK crossed with beams of HCl and HI at 250 degreeK. Total reaction cross sections, energy partitioning distributions, and differential scattering cross sections have been computed for the exchange reactions D+HCl → DCl+H and D+HI → DI+H while total reaction cross sections are reported for the corresponding abstractions, i.e., D+HCl → HD+Cl and D+HI → HD+I. For the exchange reactions, the computed reaction cross sections are within the range estimated from the crossed beam experiments. The calculated average energy partitioned into relative translational motion of products is in near quantitative agreement with the beam results, and the predicted differential scattering cross sections appear to be in qualitative accord with the beam experiments. The over-all agreement between theory and experiment indicates that previously computed values for the thermal rate coefficients for the exchange reactions are of the right order and that a systematic error exists in the interpretation of photolysis data in the hydrogen--hydrogen halide systems

Low alloy steels that minimize the hydrogen-carbide reaction. Final technical report, October 1, 1978-September 30, 1979. Part I

Energy Technology Data Exchange (ETDEWEB)

Kar, R. J.; Parker, E. R.; Zackay, V. F.

1979-01-01

This report presents results obtained during the first year of a research program to investigate important metallurgical parameters that control the reactions of hydrogen with carbides in steels. Preliminary work included a detailed literature review of th phenomenon of decarburization and methane bubble formation in steels and a suitable experimental technique for investigating hydrogen attack in laboratory conditions was established. Detailed microstructural-mechanical property evaluations were carried out on two series of alloys; the first was based on a plain carbon steel to which binary and ternary alloy additions were made to vary the carbide structure and morphology and assess these effects on the observed hydrogen attack resistance. The second group of steels consisted of commercial Mn-Mo-Ni (A 533 B) and Cr-Mo (A 542 type) steels and their alloy modifications, with a view towards developing steels with improved hydrogen attack resistance.

Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

International Nuclear Information System (INIS)

Briere, M.A.

1993-07-01

Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.

Science.gov (United States)

Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier

2018-04-25

Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

Liquid composition having ammonia borane and decomposing to form hydrogen and liquid reaction product

Science.gov (United States)

Davis, Benjamin L; Rekken, Brian D

2014-04-01

Liquid compositions of ammonia borane and a suitably chosen amine borane material were prepared and subjected to conditions suitable for their thermal decomposition in a closed system that resulted in hydrogen and a liquid reaction product.

On line determination of deuterium in hydrogen water exchange reaction by mass spectrometry. IRP-10

International Nuclear Information System (INIS)

Sharma, J.D.; Alphonse, K.P.; Mishra, Sushama; Prabhu, S.A.; Mohan, Sadhana; Tangri, V.K.

2007-01-01

The Deuterium (D)/Hydrogen (H) analysis at low Concentration is generally carried out by Mass Spectrometry. Mass Spectrometer is specially designed for the measurement of Mass 2 and 3 ratio. The Deuterium analysis of water and hydrogen in concentration range of a few ppm to about 1% plays an important role in the Heavy Water Production Plants. For the enrichment of the Deuterium concentration in H 2 O by H 2 - H 2 O exchange a catalyst is essential as reaction is relatively slow. Heavy Water Division has developed in house Platinum based catalyst for the isotopic exchange of Hydrogen and Water

Evidence of 9Be  +  p nuclear reactions during 2ω CH and hydrogen minority ICRH in JET-ILW hydrogen and deuterium plasmas

Science.gov (United States)

Krasilnikov, A. V.; Kiptily, V.; Lerche, E.; Van Eester, D.; Afanasyev, V. I.; Giroud, C.; Goloborodko, V.; Hellesen, C.; Popovichev, S. V.; Mironov, M. I.; contributors, JET

2018-02-01

The intensity of 9Be  +  p nuclear fusion reactions was experimentally studied during second harmonic (2ω CH) ion-cyclotron resonance heating (ICRH) and further analyzed during fundamental hydrogen minority ICRH of JET-ILW hydrogen and deuterium plasmas. In relatively low-density plasmas with a high ICRH power, a population of fast H+ ions was created and measured by neutral particle analyzers. Primary and secondary nuclear reaction products, due to 9Be  +  p interaction, were observed with fast ion loss detectors, γ-ray spectrometers and neutron flux monitors and spectrometers. The possibility of using 9Be(p, d)2α and 9Be(p, α)6Li nuclear reactions to create a population of fast alpha particles and study their behaviour in non-active stage of ITER operation is discussed in the paper.

Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

Directory of Open Access Journals (Sweden)

Yasuharu Kanda

2018-04-01

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

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

Energy Technology Data Exchange (ETDEWEB)

Stoerzinger, Kelsey A. [Physical; Favaro, Marco [Advanced; Joint; Chemical; Ross, Philip N. [Materials; Yano, Junko [Joint; Molecular; Liu, Zhi [State; Division; Hussain, Zahid [Advanced; Crumlin, Ethan J. [Advanced; Joint Center

2017-11-02

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.

Magnetic field effects on geminate reactions. Study of anthraquinone - hydrogen donors systems

International Nuclear Information System (INIS)

Vidal, Marie-Helene

1987-01-01

This study is devoted to magnetic field effects on chemical reactions which involve a radical pair with correlated spins (radical in a 'cage'). In the first part, the radical pair theory is described: mechanisms of singlet-triplet mixing, the different interactions inside the pair and a quantum mechanical treatment of the radical pair. The details of the experimental method (nanosecond laser flash photolysis) are reported in the second part. In the third part are shown experimental results obtained on Anthraquinone (AQ) - Hydrogen donors systems: - There is no magnetic field effect in homogeneous solution even at a high viscosity. The absorption spectra of the different reaction intermediates are obtained. - However a magnetic field effect is put forward when AQ is introduced in SDS micelles which are hydrogen donors. The absorption spectrum of the AQH · . semi-quinone radical in 'cage' is shown and a mechanism is proposed for its disappearance to generate the AQH-S and AQH 2 species. - The addition of 9, 10 Dihydroanthracene (DH2) inside the micelle near AQ induces an increase of the magnetic field effect by creation of (AQH · . - DH · . ) pairs which diffuse slowly. - Fixed radical pairs in a protein matrix were studied in reaction centers of photosynthetic bacteria: in that case, the half effect field is shifted to low fields when compared to the previously described systems. (author) [fr

Influence of sodium dodecyl sulfate on the reaction between Nile Blue A and hydrogen peroxide

Directory of Open Access Journals (Sweden)

IVANA A. JANKOVIC

1999-05-01

Full Text Available The influence of the anionic surfactant sodium dodecyl sulfate on the rate of the reaction between the cationic form of Nile Blue A and hydrogen peroxide was investigated in the pH range from 5 to 8.5. A retardation of the oxidation of Nile Blue A with hydrogen peroxide of three orders of magnitude was observed at pH 8.5 in the presence of anionic micelles compared to the kinetic data in water. The retardation effect was less pronounced at lower pH values. These effects were explained by the electrostatic interaction of the species involved in the reaction with the negatively charged micellar surface and their effective separation in the vicinity of the micellar surface.

Production of Hydrogen from Bio-ethanol

International Nuclear Information System (INIS)

Fabrice Giroudiere; Christophe Boyer; Stephane His; Robert Sanger; Kishore Doshi; Jijun Xu

2006-01-01

IFP and HyRadix are collaborating in the development of a new hydrogen production system from liquid feedstock such as bio-ethanol. Reducing greenhouse gas (GHG) emissions along with high hydrogen yield are the key objectives. Market application of the system will be hydrogen refueling stations as well as medium scale hydrogen consumers including the electronics, metals processing, and oils hydrogenation industries. The conversion of bio-ethanol to hydrogen will be performed within a co-developed process including an auto-thermal reformer working under pressure. The technology will produce high-purity hydrogen with ultralow CO content. The catalytic auto-thermal reforming technology combines the exothermic and endothermic reaction and leads to a highly efficient heat integration. The development strategy to reach a high hydrogen yield target with the bio-ethanol hydrogen generator is presented. (authors)

Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

International Nuclear Information System (INIS)

Caron Charles, M.

1988-03-01

Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H 2 , N 2 , NH 3 , CH 4 , O 2 , gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K [fr

Hydrogen bonds in the vicinity of the special pair of the bacterial reaction center probed by hydrostatic high-pressure absorption spectroscopy.

Science.gov (United States)

Kangur, Liina; Jones, Michael R; Freiberg, Arvi

2017-12-01

Using the native bacteriochlorophyll a pigment cofactors as local probes, we investigated the response to external hydrostatic high pressure of reaction center membrane protein complexes from the photosynthetic bacterium Rhodobacter sphaeroides. Wild-type and engineered complexes were used with a varied number (0, 1 or 2) of hydrogen bonds that bind the reaction center primary donor bacteriochlorophyll cofactors to the surrounding protein scaffold. A pressure-induced breakage of hydrogen bonds was established for both detergent-purified and membrane-embedded reaction centers, but at rather different pressures: between 0.2 and 0.3GPa and at about 0.55GPa, respectively. The free energy change associated with the rupture of the single hydrogen bond present in wild-type reaction centers was estimated to be equal to 13-14kJ/mol. In the mutant with two symmetrical hydrogen bonds (FM197H) a single cooperative rupture of the two bonds was observed corresponding to an about twice stronger bond, rather than a sequential rupture of two individual bonds. Copyright © 2017 Elsevier B.V. All rights reserved.

Performance test results of mock-up model test facility with a full-scale reaction tube for HTTR hydrogen production system. Contract research

Energy Technology Data Exchange (ETDEWEB)

Inagaki, Yoshiyuki; Hayashi, Koji; Kato, Michio [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment] [and others

2003-03-01

Research on a hydrogen production system by steam reforming of methane, chemical reaction; CH{sub 4} + H{sub 2}O {yields} 3H{sub 2}O + CO, has been carried out to couple with the HTTR for establishment of high-temperature nuclear heat utilization technology and contribution to hydrogen energy society in future. The mock-up test facility with a full-scale reaction tube test facility, a model simulating one reaction tube of a steam reformer of the HTTR hydrogen production system in full scale, was fabricated to perform tests on controllability, hydrogen production performance etc. under the same pressure and temperature conditions as those of the HTTR hydrogen production system. The design and fabrication of the test facility started from 1997, and the all components were installed until September in 2001. In a performance test conducted from October in 2001 to February in 2002, performance of each component was examined and hydrogen of 120m{sup 3}{sub N}/h was successfully produced with high-temperature helium gas. This report describes the performance test results on components performance, hydrogen production characteristics etc., and main troubles and countermeasures. (author)

Performance test results of mock-up model test facility with a full-scale reaction tube for HTTR hydrogen production system. Contract research

International Nuclear Information System (INIS)

Inagaki, Yoshiyuki; Hayashi, Koji; Kato, Michio

2003-03-01

Research on a hydrogen production system by steam reforming of methane, chemical reaction; CH 4 + H 2 O → 3H 2 O + CO, has been carried out to couple with the HTTR for establishment of high-temperature nuclear heat utilization technology and contribution to hydrogen energy society in future. The mock-up test facility with a full-scale reaction tube test facility, a model simulating one reaction tube of a steam reformer of the HTTR hydrogen production system in full scale, was fabricated to perform tests on controllability, hydrogen production performance etc. under the same pressure and temperature conditions as those of the HTTR hydrogen production system. The design and fabrication of the test facility started from 1997, and the all components were installed until September in 2001. In a performance test conducted from October in 2001 to February in 2002, performance of each component was examined and hydrogen of 120m 3 N /h was successfully produced with high-temperature helium gas. This report describes the performance test results on components performance, hydrogen production characteristics etc., and main troubles and countermeasures. (author)

Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

Science.gov (United States)

Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

Tungsten deposition by hydrogen-atom reaction with tungsten hexafluoride

International Nuclear Information System (INIS)

Lee, W.W.

1991-01-01

Using gaseous hydrogen atoms with WF 6 , tungsten atoms can be produced in a gas-phase reaction. The atoms then deposit in a near-room temperature process, which results in the formation of tungsten films. The W atoms (10 10 -10 11 /cm 3 ) were measured in situ by atomic absorption spectroscopy during the CVD process. Deposited W films were characterized by Auger electron spectroscopy, Rutherford backscattering, and X-ray diffraction. The surface morphology of the deposited films and filled holes was studied using scanning electron microscopy. The deposited films were highly adherent to different substrates, such as Si, SiO 2 , Ti/Si, TiN/Si and Teflon. The reaction mechanism and kinetics were studied. The experimental results indicated that this method has three advantages compared to conventional CVD or PECVD: (1) film growth occurs at low temperatures; (2) deposition takes place in a plasma-free environment; and (3) a low level of impurities results in high-quality adherent films

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

Science.gov (United States)

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

2015-07-14

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

Thermal and combined thermal and radiolytic reactions involving nitrous oxide, hydrogen, nitrogen, and ammonia in contact with tank 241-SY-101 simulated waste

International Nuclear Information System (INIS)

Bryan, S.A.; Pederson, L.R.

1996-02-01

Work described in this report was conducted at Pacific Northwest National Laboratory (PNNL) for the Flammable Gas Safety Project, the purpose of which is to develop information needed to support Westinghouse Hanford Company (WHC) in their efforts to ensure the safe interim storage of wastes at the Hanford Site. Described in this report are the results of tests to evaluate the rates of thermal and combined thermal and radiolytic reactions involving flammable gases in the presence of Tank 241-SY-101 simulated waste. Flammable gases generated by the radiolysis of water and by the thermal and radiolytic decomposition of organic waste constituents may themselves participate in further reactions. Examples include the decomposition of nitrous oxide to yield nitrogen and oxygen, the reaction of nitrous oxide and hydrogen to produce nitrogen and water, and the reaction of nitrogen and hydrogen to produce ammonia. The composition of the gases trapped in bubbles in the wastes might therefore change continuously as a function of the time that the gas bubbles are retained

Hydrogen Transfer during Liquefaction of Elbistan Lignite to Biomass; Total Reaction Transformation Approach

Science.gov (United States)

Koyunoglu, Cemil; Karaca, Hüseyin

2017-12-01

Given the high cost of the tetraline solvent commonly used in liquefaction, the use of manure with EL is an important factor when considering the high cost of using tetraline as a hydrogen transfer source. In addition, due to the another cost factor which is the catalyst prices, red mud (commonly used, produced as a byproduct in the production of aluminium) is reduced cost in the work of liquefaction of coal, biomass, even coal combined biomass, corresponding that making the EL liquefaction an agenda for our country is another important factor. Conditions for liquefaction experiments conducted for hydrogen transfer from manure to coal; Catalyst concentration of 9%, liquid/solid ratio of 3/1, reaction time of 60 min, fertilizer/lignite ratio of 1/3, and the reaction temperature of 400 °C, the stirred speed of 400 rpm and the initial nitrogen pressure of 20 bar was fixed. In order to demonstrate the hydrogen, transfer from manure to coal, coal is used solely, by using tetraline (also known as a hydrogen carrier) and distilled water which is not hydrogen donor as a solvent in the co-liquefaction of experiments, and also the liquefaction conditions are carried out under an inert (N2) gas atmosphere. According to the results of the obtained liquefaction test; using tetraline solvent the total liquid product conversion percentage of the oil + gas conversion was 38.3 %, however, the results of oil+gas conversion obtained using distilled water and EL combined with manure the total liquid product conversion percentage was 7.4 %. According to the results of calorific value and elemental analysis, only the ratio of (H/C)atomic of coal obtained by using tetraline increased with the liquefaction of manure and distilled water. The reason of the increase in the amount of hydrogen due to hydrogen transfer from the manure on the solid surface of the coal, and also on the surface of the inner pore of the coal during the liquefaction, brings about the evaluation of the coal as a

High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

KAUST Repository

Coy, Emerson; Yate, Luis; Valencia, Drochss P; Aperador, Willian; Siuzdak, Katarzyna; Torruella, Pau; Azanza, Eduardo; Estrade, Sonia; Iatsunskyi, Igor; Peiró , Francesca; Zhang, Xixiang; Tejada, Javier; Ziolo, Ronald F.

2017-01-01

Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced

Electrocatalysis of the hydrogen evolution reaction by rhenium oxides electrodeposited by pulsed-current

International Nuclear Information System (INIS)

Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis

2015-01-01

Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.

Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

Science.gov (United States)

DeGregorio, Nicole; Iyengar, Srinivasan S

2018-01-09

We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

Hydrogen evolution reaction at Ru-modified nickel-coated carbon fibre in 0.1 M NaOH

Directory of Open Access Journals (Sweden)

Pierożyński Bogusław

2015-03-01

Full Text Available The electrochemical activity towards hydrogen evolution reaction (HER was studied on commercially available (Toho-Tenax and Ru-modified nickel-coated carbon fibre (NiCCF materials. Quality and extent of Ru electrodeposition on NiCCF tows were examined by means of scanning electron microscopy (SEM. Kinetics of the hydrogen evolution reaction were investigated at room temperature, as well as over the temperature range: 20-50°C in 0.1 M NaOH solution for the cathodic overpotential range: -100 to -300 mV vs. RHE. Corresponding values of charge-transfer resistance, exchange current-density for the HER and other electrochemical parameters for the examined fibre tow composites were recorded.

Lattice-enabled nuclear reactions in the nickel and hydrogen gas system

International Nuclear Information System (INIS)

Nagel, David J.

2015-01-01

Thousands of lattice-enabled nuclear reaction (LENR) experiments involving electrochemical loading of deuterium into palladium have been conducted and reported in hundreds of papers. But, it appears that the first commercial LENR power generators will employ gas loading of hydrogen onto nickel. This article reviews the scientific base for LENR in the gas-loaded Ni-H system, and some of the tests of pre-commercial prototype generators based on this combination. (author)

Effect of addition of water-soluble salts on the hydrogen generation of aluminum in reaction with hot water

International Nuclear Information System (INIS)

Razavi-Tousi, S.S.; Szpunar, J.A.

2016-01-01

Aluminum powder was ball milled for different durations of time with different weight percentages of water-soluble salts (NaCl and KCl). The hydrogen generation of each mixture in reaction with hot water was measured. A scanning electron microscope (SEM) as well as energy-dispersive spectroscopy (EDS) were used to investigate the morphology, surfaces and cross sections of the produced particles. The results show that the presence of salts in the microstructure of the aluminum considerably increases the hydrogen generation rate. At shorter milling times, the salt covers the aluminum particles and becomes embedded in layers within the aluminum matrix. At higher milling durations, salt and aluminum phases form composite particles. A higher percentage of the second phase significantly decreases the milling time needed for activation of the aluminum particles. Based on the EDS results from cross sections of the milled particles, a mechanism for improvement of the hydrogen generation rate in the presence of salts is suggested. - Highlights: • Milling and water soluble salts have a synergic effect on hydrogen generation. • Salt and aluminum form composite particles by milling. • Salt is dissolved in water leaving aluminum with much fresh surfaces for the reaction. • The chemical effect of salt on the reaction is negligible compared to its structural effect.

Hydrogen-Etched TiO2−x as Efficient Support of Gold Catalysts for Water–Gas Shift Reaction

Directory of Open Access Journals (Sweden)

Li Song

2018-01-01

Full Text Available Hydrogen-etching technology was used to prepare TiO2−x nanoribbons with abundant stable surface oxygen vacancies. Compared with traditional Au-TiO2, gold supported on hydrogen-etched TiO2−x nanoribbons had been proven to be efficient and stable water–gas shift (WGS catalysts. The disorder layer and abundant stable surface oxygen vacancies of hydrogen-etched TiO2−x nanoribbons lead to higher microstrain and more metallic Au0 species, respectively, which all facilitate the improvement of WGS catalytic activities. Furthermore, we successfully correlated the WGS thermocatalytic activities with their optoelectronic properties, and then tried to understand WGS pathways from the view of electron flow process. Hereinto, the narrowed forbidden band gap leads to the decreased Ohmic barrier, which enhances the transmission efficiency of “hot-electron flow”. Meanwhile, the abundant surface oxygen vacancies are considered as electron traps, thus promoting the flow of “hot-electron” and reduction reaction of H2O. As a result, the WGS catalytic activity was enhanced. The concept involved hydrogen-etching technology leading to abundant surface oxygen vacancies can be attempted on other supported catalysts for WGS reaction or other thermocatalytic reactions.

Signatures of a quantum diffusion limited hydrogen atom tunneling reaction.

Science.gov (United States)

Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T

2017-12-20

We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

The evolution of hydrogen and iodine by the decomposition of ammonium iodide and hydrogen iodide

International Nuclear Information System (INIS)

Ishikawa, Hiroshi; Nakane, Masanori; Ishii, Eiichi; Uehara, Itsuki; Miyake, Yoshizo

1977-01-01

As a fundamental study on thermochemical production of hydrogen from water, the evolution of hydrogen and iodine from ammonium iodide and hydrogen iodide was investigated. Hydrogen was evolved by the reaction of nickel with ammonium iodide or with hydrogen iodide, and the resulting nickel(II) iodide was decomposed thermally at 600 -- 700 0 C to form nickel. First, the iodination of powdered nickel with ammonium iodide was studied by heating their powder mixture. The maximum yield of hydrogen was obtained at a temperature near 430 0 C. The iodination of powdered nickel with gaseous ammonium iodide or with dry hydrogen iodide gas was also investigated. In this case, coating of nickel particles with a layer of resulting nickel(II) iodide prevented further conversion of nickel and lowered the reaction rate. Such a retardation effect was appreciably lessened by use of carrier. When nickel was supported on such a carrier as ''isolite'', the nickel was converted into nickel(II) iodide easily. In a reaction temperature from 400 to 500 0 C, the rate of reaction between nickel and hydrogen iodide increased slightly with the elevation of the reaction temperature. In the case of ammonium iodide, the reaction rate was higher than that for hydrogen iodide and decreased apparently with the elevation of the reaction temperature, because ammonium iodide decomposed to ammonia and hydrogen iodide. Tests using a fixed bed reactor charged with 8 -- 10 mesh ''isolite''-nickel (30 wt%) were also carried out. The maximum yield of hydrogen was about 80% for ammonium iodide at 430 0 C of reaction temperature and 60% for hydrogen iodide at 500 0 C. (auth.)

Unusual Intramolecular Hydrogen Transfer in 3,5-Di(triphenylethylenyl) BODIPY Synthesis and 1,2-Migratory Shift in Subsequent Scholl Type Reaction

KAUST Repository

Chua, Ming Hui; Huang, Kuo-Wei; Xu, Jianwei; Wu, Jishan

2015-01-01

The straightforward synthesis of 3,5-di(triphenylethylenyl) BODIPYs 1–3 from the condensation of 2-(triphenylethylenyl) pyrrole with aryl aldehydes are surprisingly found to produce side products that are hydrogenated at one of the two triphenylethylene substituents. It was also observed that the subsequent Scholl type reaction of 1 resulted in a “1,2-migratory shift” of one triphenylethylene substituent in addition to a ring closing reaction. Preliminary investigations, including DFT calculations and isolation of intermediates, were conducted to study these unusual observations on BODIPY chemistry.

Unusual Intramolecular Hydrogen Transfer in 3,5-Di(triphenylethylenyl) BODIPY Synthesis and 1,2-Migratory Shift in Subsequent Scholl Type Reaction

KAUST Repository

Chua, Ming Hui

2015-08-17

The straightforward synthesis of 3,5-di(triphenylethylenyl) BODIPYs 1–3 from the condensation of 2-(triphenylethylenyl) pyrrole with aryl aldehydes are surprisingly found to produce side products that are hydrogenated at one of the two triphenylethylene substituents. It was also observed that the subsequent Scholl type reaction of 1 resulted in a “1,2-migratory shift” of one triphenylethylene substituent in addition to a ring closing reaction. Preliminary investigations, including DFT calculations and isolation of intermediates, were conducted to study these unusual observations on BODIPY chemistry.

Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

Energy Technology Data Exchange (ETDEWEB)

Larsson, L G; Moeller, E; Purohit, S N

1966-03-15

The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

Energy Technology Data Exchange (ETDEWEB)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

2012-01-15

The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

International Nuclear Information System (INIS)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

2012-01-01

The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

Polyallylamine-Rh nanosheet nanoassemblies-carbon nanotubes organic-inorganic nanohybrids: A electrocatalyst superior to Pt for the hydrogen evolution reaction

Science.gov (United States)

Bai, Juan; Xing, Shi-Hui; Zhu, Ying-Ying; Jiang, Jia-Xing; Zeng, Jing-Hui; Chen, Yu

2018-05-01

Rationally tailoring the surface/interface structures of noble metal nanostructures emerges as a highly efficient method for improving their electrocatalytic activity, selectivity, and long-term stability. Recently, hydrogen evolution reaction is attracting more and more attention due to the energy crisis and environment pollution. Herein, we successfully synthesize polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids via a facile one-pot hydrothermal method. Three-dimensionally branched rhodium nanosheet nanoassemblies are consisted of two dimensionally atomically thick ultrathin rhodium nanosheets. The as-prepared polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids show the excellent electrocatalytic activity for the hydrogen evolution reaction in acidic media, with a low onset reduction potential of -1 mV, a small overpotential of 5 mV at 10 mA cm-2, which is much superior to commercial platinum nanocrystals. Two dimensionally ultrathin morphology of rhodium nanosheet, particular rhodium-polyallylamine interface, and three-dimensionally networks induced by carbon nanotube are the key factors for the excellent hydrogen evolution reaction activity in acidic media.

Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

KAUST Repository

Chen, Tao

2012-08-01

Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

Directory of Open Access Journals (Sweden)

Carmen Moreno-Marrodan

2017-04-01

Full Text Available The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible.

Hydrogenation/Deoxygenation (H/D Reaction of Furfural-Acetone Condensation Product using Ni/Al2O3-ZrO2 Catalyst

Directory of Open Access Journals (Sweden)

Adam Mahfud

2016-08-01

Full Text Available The catalytic hydrogenation/deoxygenation (H/D reaction was carried out using Ni/Al2O3-ZrO2 catalyst. The 10% (wt/wt of Ni were impregnated on Al2O3-ZrO2 (10NiAZ by wet impregnation method followed by calcination and reduction. X-Ray diffraction analysis showed that Nideposited on the surface, with specific surface areas (SBET was 48.616 m2/g. Catalyst performance were evaluated for H/D reaction over furfural-acetone condensation products, mixture of 2-(4-furyl-3-buten-2-on and 1,5-bis-(furan-2-yl-pentan-3-one. The reaction was carried out in a batch, performed at 150°C for 8 hours. The H/D reaction gave alkane derivatives C8 and C10 by hydrogenation process followed by ring opening of furan in 15.2% yield. While, oxygenated product C10-C13 were also detected in 17.2% yield. The increasing of pore volume of 10NiAZ might enhance catalyst activity over H/D reaction. The alkene C=C bond was easy to hydrogenated under this condition by the lower bond energy gap.

Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural.

Science.gov (United States)

Brentzel, Zachary J; Barnett, Kevin J; Huang, Kefeng; Maravelias, Christos T; Dumesic, James A; Huber, George W

2017-04-10

A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84 % yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. 2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the selective abstration reaction of the hydrogen atom in the radiolysis and photolysis of alkane mixture at 77 K

International Nuclear Information System (INIS)

Guedes, S.M.L.

1979-01-01

The occurence of the selective abstraction reaction of the solute hydrogen atom by hydrogen atom produced during radiolysis or photolysis of the systems such as neopentane/cyclo-hexane/HI, neopentane/2,3 dimethylbutane, n-pentane/HI/cyclo-hexane and cyclo-hexane/HI/n-pentane, at 77 K is studied. Experiments have been undertaken on the kinetics nature of the active species, the H atom, during radiolysis and photolysis of the neopentane/cyclo-hexane/HI system at 77 K, presenting competitive reactions. Studies have also been made on the occurrence of the selective abstraction reaction in inverted systems, in which the concentrations of the components of a system are so much altered that the solute becomes the solvent and vice-versa, in the other system. By means of photolysis at 77 K, it has been observed that for the two systems constitued by the cyclo-hexane and n-pentane the selective abstraction reaction occurs. However, for radiolysis of that same two systems it has been observed that only the hydrogen atom abstraction reaction corresponding to the solvent occurs. (Author) [pt

Alkyl hydrogen atom abstraction reactions of the CN radical with ethanol

Science.gov (United States)

Athokpam, Bijyalaxmi; Ramesh, Sai G.

2018-04-01

We present a study of the abstraction of alkyl hydrogen atoms from the β and α positions of ethanol by the CN radical in solution using the Empirical Valence Bond (EVB) method. We have built separate 2 × 2 EVB models for the Hβ and Hα reactions, where the atom transfer is parameterized using ab initio calculations. The intra- and intermolecular potentials of the reactant and product molecules were modelled with the General AMBER Force Field, with some modifications. We have carried out the dynamics in water and chloroform, which are solvents of contrasting polarity. We have computed the potential of mean force for both abstractions in each of the solvents. They are found to have a small and early barrier along the reaction coordinate with a large energy release. Analyzing the solvent structure around the reaction system, we have found two solvents to have little effect on either reaction. Simulating the dynamics from the transition state, we also study the fate of the energies in the HCN vibrational modes. The HCN molecule is born vibrationally hot in the CH stretch in both reactions and additionally in the HCN bends for the Hα abstraction reaction. In the early stage of the dynamics, we find that the CN stretch mode gains energy at the expense of the energy in CH stretch mode.

Proceedings of the 1996 U.S. DOE hydrogen program review. Volume 1

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-10-01

The 29 papers contained in Volume 1 are related to systems analysis and hydrogen production. Papers in the systems analysis section discuss utility markets, comparison of hydrogen with other alternative fuels, hydrogen vehicles, renewable hydrogen production, storage, and detection, and hydrogen storage systems development. Hydrogen production methods include the use of algae, photosynthesis, glucose dehydrogenase, syngas, photoelectrochemical reactions, photovoltaics, water electrolysis, solar photochemical reactions, pyrolysis, catalytic steam reforming, municipal solid wastes, thermocatalytic cracking of natural gas, and plasma reformers. Selected papers are indexed separately for inclusion in the Energy Science and Technology Database.

Modeling Electric Double-Layers Including Chemical Reaction Effects

DEFF Research Database (Denmark)

Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

2014-01-01

A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...... for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration...

Coal reactions during shock heating in a hydrogen atmosphere. Reaktionsverhalten von Kohlen bei schockartiger Aufheizung in Wasserstoffatmosphaere

Energy Technology Data Exchange (ETDEWEB)

Sperling, R

1987-04-30

The study deals with the hydropyrolysis of coal under shock heating in order to learn more about the elementary reactions, which take place on the coal surface or in the interior of the carbon grain and which determine the product range and product yield. For recording the factors influencing primary cracking of products and the secondary reactions of the crack products, investigations were carried out by varying the particle diameter of the coals used (3 coals of different carbonization degrees) and the hydrogen pressure. For further recording of secondary reactions and thus the mechanism of the hydropyrolysis, typical crack products with primary character were presented on or in the coal; this was done by the absorption of a defined quantity of model compounds from the gas phase. For shock heating, the Curie point method (inductive heating) was used. It turned out that, with increasing H/sub 2/ pressure, the formation of H-transporting compounds and the availability of the molecular hydrogen from the gas phase is increased but the volatility of the reaction products is inhibited by cross-linking reactions of radicals with high-molecular crack products. High temperatures in shock heating can compensate this negative effect.

Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

Directory of Open Access Journals (Sweden)

Yongki Choi

2011-12-01

Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

Development of a Hydrogen Uptake-Release Mg-Based Alloy by Adding a Polymer CMC (Carboxymethylcellulose, Sodium Salt) via Reaction-Accompanying Milling

Science.gov (United States)

Kwak, Young Jun; Choi, Eunho; Song, Myoung Youp

2018-03-01

The addition of carboxymethylcellulose, sodium salt (CMC) might improve the hydrogen uptake and release properties of Mg since it has a relatively low melting point and the melting of CMC during milling in hydrogen (reaction-accompanying milling) may make the milled samples be in good states to absorb and release hydrogen rapidly and to have a large hydrogen-storage capacity. Samples with compositions of 95 w/o Mg + 5 w/o CMC (named Mg-5CMC) and 90 w/o Mg + 10 w/o CMC (named Mg-10CMC) were prepared by adding CMC via reaction-accompanying milling. Activation of Mg-10CMC was completed after about 3 hydrogen uptake-release cycles. Mg-10CMC had a higher initial hydrogen uptake rate and a larger amount of hydrogen absorbed in 60 min, U (60 min), than Mg-5CMC before and after activation. At the cycle number of three (CN = 3), Mg-10CMC had a very high initial hydrogen uptake rate (1.56 w/o H/min) and a large U (60 min) (5.57 w/o H) at 593 K in hydrogen of 12 bar, showing that the activated Mg-10CMC has an effective hydrogen-storage capacity of about 5.6 w/o at 593 K in hydrogen of 12 bar at CN = 3. At CN = 2, Mg-10CMC released 1.00 w/o H in 2.5 min, 4.67 w/o H in 10 min, and 4.76 w/o H in 60 min at 648 K in hydrogen of 1.0 bar. The milling in hydrogen of Mg with CMC is believed to generate imperfections and cracks and reduce the particle size. The addition of 10 w/o CMC was more effective on the initial hydrogen uptake rate and U (60 min) compared with the 10 w/o additions of NbF5, TaF5, Fe2O3, and MnO, and the 10 w/o simultaneous addition of Ni, Fe, and Ti. To the best of our knowledge, this study is the first in which a polymer CMC is added to Mg by reaction-accompanying milling to improve the hydrogen storage properties of Mg.

Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

KAUST Repository

Michalak, William D.

2013-01-31

The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

Studies of reaction difference between γ-ray and glow discharge on hydrogenation of unsaturated fatty acid esters

International Nuclear Information System (INIS)

Sakoda, Tatsuya; Nieda, Hiroshi; Kitahara, Kazuta; Ando, Kiyomi

2000-01-01

Hydrogenation of unsaturated fatty acid esters using an inductively coupled plasma at low pressure was performed, and electron temperature and density were measured using a double-probe in order to investigate the reaction difference between γ-ray and glow discharge on hydrogenation. In this experiment, unsaturated fatty acid esters were partly hydrogenated by the hydrogen plasma that had electron temperature of 3.5 eV, which was more efficient than γ-ray irradiation method. As a result, it was found that the plasma can effectively supply electrons that had the optimum energy for hydrogenation at the interface of fatty acids as well as excited atoms and ions. Also, the plasma generated at low pressure would be possible to convert unsaturated fatty acids into saturated fatty acids without breaking the starting monomer. (author)

Process, including membrane separation, for separating hydrogen from hydrocarbons

Science.gov (United States)

Baker, Richard W.; Lokhandwala, Kaaeid A.; He, Zhenjie; Pinnau, Ingo

2001-01-01

Processes for providing improved methane removal and hydrogen reuse in reactors, particularly in refineries and petrochemical plants. The improved methane removal is achieved by selective purging, by passing gases in the reactor recycle loop across membranes selective in favor of methane over hydrogen, and capable of exhibiting a methane/hydrogen selectivity of at least about 2.5 under the process conditions.

Exchange reaction between hydrogen and deuterium. II - Proposal for an heterogeneous initiation mechanism of gaseous phase reactions

Energy Technology Data Exchange (ETDEWEB)

Marteau, Chantal; Gaillard-Cusin, Francoise; James, Henri [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

1978-05-01

Investigation of experimental data related to evolution period exhibited by H/sub 2/-D/sub 2/ exchange process requires to take into account the variation against time of every atomic species -adsorbed or not- implied in the reaction mechanism. The formation of first chain carriers involves: - chemisorption of either gaseous reactant on the surface active centres (..sigma..), e.g.: ..sigma.. + 1/2 H/sub 2/ reversible ..sigma..H; - consecutive generation of atomic species through hetero-homogeneous transfer between chemisorbed species (..sigma..H) and gaseous molecules: ..sigma..H+H/sub 2/..--> sigma..+H/sub 2/+H/sup 0/, ..sigma..H+D/sub 2/..--> sigma..+HD+D/sup 0/. Therefore, it can be shown that the heterogeneous initiation process of a gas phase reaction identifies to a chain linear mechanism. Such an heterogeneous sequence conditions the further proceeding of the homogeneous chain reaction; both evolutions being kinematically connected. Rate constant of hydrogen adsorption on silica glass: ksub(a1) approximately 10/sup 14/ exp(-47/RT)Isup(0,5).molesup(-0,5).S/sup -1/ has been evaluated.

Hydrogen/deuterium exchange in mass spectrometry.

Science.gov (United States)

Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

2018-03-30

The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

2015-01-01

Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

Molybdenum acetate like precursor of molybdenum carburized supported on alumina: a catalyst for hydrogenation reactions

International Nuclear Information System (INIS)

Petkovic, Lucia M; Parra, Ruben D; Marquez Manuel; Larsen, Gustavo

1994-01-01

The stability of the Al203 supported dimers under relatively high temperatures and hydrocarbon/H2 (carburizing) atmospheres is reported also, it has been developed a new method for Mo2 loading of the support based on the wet impregnation of the latter. Since carbided Mo is active for hydrogenations, the isobutene/H2 has been chosen as the probe reaction. Al203 supported Mo2(Ac)4 results in a catalyst active for isobutene hydrogenation after treatment with a H2/C2H6 2:1 mixture at 753 k

Symmetrical synergy of hybrid Co9S8-MoSx electrocatalysts for hydrogen evolution reaction

KAUST Repository

Zhou, Xiaofeng; Yang, Xiulin; Hedhili, Mohamed N.; Li, Henan; Min, Shixiong; Ming, Jun; Huang, Kuo-Wei; Zhang, Wenjing; Li, Lain-Jong

2017-01-01

There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

Science.gov (United States)

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

A Fluorescent Molecular Probe for the Detection of Hydrogen Based on Oxidative Addition Reactions with Crabtree-Type Hydrogenation Catalysts.

Science.gov (United States)

Kos, Pavlo; Plenio, Herbert

2015-11-02

A Crabtree-type Ir(I) complex tagged with a fluorescent dye (bodipy) was synthesized. The oxidative addition of H2 converts the weakly fluorescent Ir(I) complex (Φ=0.038) into a highly fluorescent Ir(III) species (Φ=0.51). This fluorogenic reaction can be utilized for the detection of H2 and to probe the oxidative addition step in the catalytic hydrogenation of olefins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

Directory of Open Access Journals (Sweden)

F. Keppler

2018-05-01

Full Text Available Chloromethane (CH3Cl is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4 as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

Energy Technology Data Exchange (ETDEWEB)

Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H. [KAERI, Taejon (Korea, Republic of)

2005-11-15

Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities.

Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

International Nuclear Information System (INIS)

Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H.

2005-01-01

Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

Science.gov (United States)

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

Chemical interesterification of soybean oil and fully hydrogenated soybean oil: Influence of the reaction time

International Nuclear Information System (INIS)

Ribeiro, Ana Paula Badan; Masuchi, Monise Helen; Grimaldi, Renato; Goncalves, Lireny Aparecida Guaraldo

2009-01-01

Chemical interesterification is an important alternative to produce zero trans fats. In practice, however, excessive reaction times are used to ensure complete randomization. This work evaluated the influence of the reaction time on the interesterification of soybean oil/fully hydrogenated soybean oil blend, carried out in the following conditions: 100 deg C, 500 rpm stirring speed, 0.4% (w/w) sodium methoxide catalyst. The triacylglycerol composition, solid fat content and melting point analysis showed that the reaction was very fast, reaching the equilibrium within 5 min. This result suggests the interesterification can be performed in substantially lower times, with reduction in process costs. (author)

Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

Science.gov (United States)

Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

2017-01-25

The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

Theoretical investigation of molecular hydrogen reactions with active centres in B6H5- and AlB6H5- clusters

International Nuclear Information System (INIS)

Mebel', A.M.; Charkin, O.P.

1991-01-01

Nonempirical calculations of sections of potential surface (PS) along the shortest way of reaction of hydrogen interaction with different active centres in AlB 5 H 5 - cluster were conducted. Mechanisms of reactions of valent-saturated hydrides (BH, AlH) and clusters (B 6 H 5 - , AlB 5 H 5 - ) with molecular hydrogen are correlated. Qualitative model enabling to form an opinion about the presence or the absence of barrier on PS of the shortest way of reactions of breaking σ-bond of H-H type on the active centre of cluster, is suggested. The model is based on analysis of the character of canonical MO reagents and products

Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine.

Science.gov (United States)

Madsen, Henrik T; Søgaard, Erik G

2012-01-01

To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry was used to investigate the nature of unknown peaks in the mass spectra. The reaction was found to proceed as expected from theory with the triazine reacting with hydrogen sulphide to form the corresponding thiadiazine. This species subsequently reacted with a second hydrogen sulphide molecule to form the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution, and possible pathways and structures were suggested to describe the observed fragments. In these, thiadiazine fragmented to 2-(methylidene amino)-ethanol and 2-(1,3-thiazetidin-3-yl)-ethanol and N-(2-hydroxyethyl)-N-(sulfanylmethyl)-ethaniminium, which underwent a further fragmentation to N-methyl-N-(2-oxoethyl)-methaniminium. Dithiazine fragmented to N-methyl-N-(2-oxoethyl)-methaniminium as well. The by-product from this reaction is methanedithiol, which was not detected due to its low polarity.

Dodecahedral W@WC Composite as Efficient Catalyst for Hydrogen Evolution and Nitrobenzene Reduction Reactions.

Science.gov (United States)

Chen, Zhao-Yang; Duan, Long-Fa; Sheng, Tian; Lin, Xiao; Chen, Ya-Feng; Chu, You-Qun; Sun, Shi-Gang; Lin, Wen-Feng

2017-06-21

Core-shell composites with strong phase-phase contact could provide an incentive for catalytic activity. A simple, yet efficient, H 2 O-mediated method has been developed to synthesize a mesoscopic core-shell W@WC architecture with a dodecahedral microstructure, via a one-pot reaction. The H 2 O plays an important role in the resistance of carbon diffusion, resulting in the formation of the W core and W-terminated WC shell. Density functional theory (DFT) calculations reveal that adding W as core reduced the oxygen adsorption energy and provided the W-terminated WC surface. The W@WC exhibits significant electrocatalytic activities toward hydrogen evolution and nitrobenzene electroreduction reactions, which are comparable to those found for commercial Pt/C, and substantially higher than those found for meso- and nano-WC materials. The experimental results were explained by DFT calculations based on the energy profiles in the hydrogen evolution reactions over WC, W@WC, and Pt model surfaces. The W@WC also shows a high thermal stability and thus may serve as a promising more economical alternative to Pt catalysts in these important energy conversion and environmental protection applications. The current approach can also be extended or adapted to various metals and carbides, allowing for the design and fabrication of a wide range of catalytic and other multifunctional composites.

Hydrogen production from water gas shift reaction in a high gravity (Higee) environment using a rotating packed bed

Energy Technology Data Exchange (ETDEWEB)

Chen, Wei-Hsin; Syu, Yu-Jhih [Department of Greenergy, National University of Tainan, Tainan 700 (China)

2010-10-15

Hydrogen production via the water gas shift reaction (WGSR) was investigated in a high gravity environment. A rotating packed bed (RPB) reactor containing a Cu-Zn catalyst and spinning in the range of 0-1800 rpm was used to create high centrifugal force. The reaction temperature and the steam/CO ratio ranged from 250 to 350 C and 2 to 8, respectively. A dimensionless parameter, the G number, was derived to account for the effect of centrifugal force on the enhancement of the WGSR. With the rotor speed of 1800 rpm, the induced centrifugal force acting on the reactants was as high as 234 g on average in the RPB. As a result, the CO conversion from the WGSR was increased up to 70% compared to that without rotation. This clearly revealed that the centrifugal force was conducive to hydrogen production, resulting from intensifying mass transfer and elongating the path of the reactants in the catalyst bed. From Le Chatelier's principle, a higher reaction temperature or a lower steam/CO ratio disfavors CO conversion; however, under such a situation the enhancement of the centrifugal force on hydrogen production from the WGSR tended to become more significant. Accordingly, a correlation between the enhancement of CO conversion and the G number was established. As a whole, the higher the reaction temperature and the lower the steam/CO ratio, the higher the exponent of the G number function and the better the centrifugal force on the WGSR. (author)

Kinetics and mechanism of the furan peroxide formation in the reaction of furfural with hydrogen peroxide in the presence and absence of sodium molybdate

International Nuclear Information System (INIS)

Grunskaya, E.P.; Badovskaya, L.A.; Kaklyugina, T.Ya.; Poskonin, V.V.

2000-01-01

Kinetics of the initial stage of the reaction of furfural with hydrogen peroxide are studied in the presence of Na 2 MoO 4 in water and without catalytic additions in n-butanol. Organic peroxide having in its disposal Mo(6), which is the only product on the initial stage of the reaction, is formed since the first minutes of oxidation of furfural by hydrogen peroxide with the presence of Na 2 MoO 4 . The mechanisms of conversion of furfural in the Na 2 MoO 4 - H 2 O system and its oxidation by peroxide without sodium molybdate are discussed. Schemes of formation of furfural complexes based on the results of kinetic studies are suggested. Comparison of obtained data demonstrates that presence of the sodium molybdates in the reaction medium trends to change of reaction procedure in the hydrogen peroxide [ru

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan

2016-07-18

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

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

International Nuclear Information System (INIS)

Hu Sheng; Wang Heyi; Luo Shunzhong

2009-04-01

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

Determination of the Molar Volume of Hydrogen from the Metal-Acid Reaction: An Experimental Alternative.

Science.gov (United States)

de Berg, Kevin; Chapman, Ken

1996-01-01

Describes an alternative technique for determining the molar volume of hydrogen from the metal-acid reaction in which the metal sample is encased in a specially prepared cage and a pipette filler is used to fill an inverted burette with water. Eliminates some difficulties encountered with the conventional technique. (JRH)

Biological hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Benemann, J.R. [Univ. of California, Berkeley, CA (United States)

1995-11-01

Biological hydrogen production can be accomplished by either thermochemical (gasification) conversion of woody biomass and agricultural residues or by microbiological processes that yield hydrogen gas from organic wastes or water. Biomass gasification is a well established technology; however, the synthesis gas produced, a mixture of CO and H{sub 2}, requires a shift reaction to convert the CO to H{sub 2}. Microbiological processes can carry out this reaction more efficiently than conventional catalysts, and may be more appropriate for the relatively small-scale of biomass gasification processes. Development of a microbial shift reaction may be a near-term practical application of microbial hydrogen production.

On the influence of hydronium and hydroxide ion diffusion on the hydrogen and oxygen evolution reactions in aqueous media

DEFF Research Database (Denmark)

Wiberg, Gustav Karl Henrik; Arenz, Matthias

2015-01-01

We present a study concerning the influence of the diffusion of H+ and OH- ions on the hydrogen and oxygen evolution reactions (HER and OER) in aqueous electrolyte solutions. Using a rotating disk electrode (RDE), it is shown that at certain conditions the observed current, i.e., the reaction rate...

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

Energy Technology Data Exchange (ETDEWEB)

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

2002-05-01

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

Relation between Hydrogen Evolution and Hydrodesulfurization Catalysis

DEFF Research Database (Denmark)

Šaric, Manuel; Moses, Poul Georg; Rossmeisl, Jan

2016-01-01

A relation between hydrogen evolution and hydrodesulfurization catalysis was found by density functional theory calculations. The hydrogen evolution reaction and the hydrogenation reaction in hydrodesulfurization share hydrogen as a surface intermediate and, thus, have a common elementary step...

Method for the enzymatic production of hydrogen

Science.gov (United States)

Woodward, J.; Mattingly, S.M.

1999-08-24

The present invention is an enzymatic method for producing hydrogen comprising the steps of: (a) forming a reaction mixture within a reaction vessel comprising a substrate capable of undergoing oxidation within a catabolic reaction, such as glucose, galactose, xylose, mannose, sucrose, lactose, cellulose, xylan and starch; the reaction mixture also comprising an amount of glucose dehydrogenase in an amount sufficient to catalyze the oxidation of the substrate, an amount of hydrogenase sufficient to catalyze an electron-requiring reaction wherein a stoichiometric yield of hydrogen is produced, an amount of pH buffer in an amount sufficient to provide an environment that allows the hydrogenase and the glucose dehydrogenase to retain sufficient activity for the production of hydrogen to occur and also comprising an amount of nicotinamide adenine dinucleotide phosphate sufficient to transfer electrons from the catabolic reaction to the electron-requiring reaction; (b) heating the reaction mixture at a temperature sufficient for glucose dehydrogenase and the hydrogenase to retain sufficient activity and sufficient for the production of hydrogen to occur, and heating for a period of time that continues until the hydrogen is no longer produced by the reaction mixture, wherein the catabolic reaction and the electron-requiring reactions have rates of reaction dependent upon the temperature; and (c) detecting the hydrogen produced from the reaction mixture. 8 figs.

Nuclear Reactor/Hydrogen Process Interface Including the HyPEP Model

International Nuclear Information System (INIS)

Steven R. Sherman

2007-01-01

The Nuclear Reactor/Hydrogen Plant interface is the intermediate heat transport loop that will connect a very high temperature gas-cooled nuclear reactor (VHTR) to a thermochemical, high-temperature electrolysis, or hybrid hydrogen production plant. A prototype plant called the Next Generation Nuclear Plant (NGNP) is planned for construction and operation at the Idaho National Laboratory in the 2018-2021 timeframe, and will involve a VHTR, a high-temperature interface, and a hydrogen production plant. The interface is responsible for transporting high-temperature thermal energy from the nuclear reactor to the hydrogen production plant while protecting the nuclear plant from operational disturbances at the hydrogen plant. Development of the interface is occurring under the DOE Nuclear Hydrogen Initiative (NHI) and involves the study, design, and development of high-temperature heat exchangers, heat transport systems, materials, safety, and integrated system models. Research and development work on the system interface began in 2004 and is expected to continue at least until the start of construction of an engineering-scale demonstration plant

A CFD Simulation of Hydrogen Production in Microreactors

Directory of Open Access Journals (Sweden)

Javad Sabziani

2015-01-01

Full Text Available In this study, the modeling of hydrogen production process in microreactors by methanol-steam reforming reaction is investigated. The catalytic reaction of methanol-steam reforming producing hydrogen is simulated considering a 3D geometry for the microreactor. To calculate diffusion among species, mixture average correlations are compared to Stephan-Maxwell equations. The reactions occurring inside the microreactor include reforming of methanol with steam, methanol decomposition, and a reaction between carbon dioxide and hydrogen. The main objectives of this study are the prediction of temperature profile along the microreactor using either mixture average method or Stephan-Maxwell one and the comparison between the present predictions and some existing experimental data. The simulation results indicate that Stephan-Maxwell method conforms more suitably to the experimental results. The difference is more at lower feed flow rates since, when the flow rate increases, mass transfer mechanism changes from diffusion to convection, which in turn reduces the difference.

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

International Nuclear Information System (INIS)

Trasatti, S.

1975-01-01

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

Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

Science.gov (United States)

Niyitanga, Theophile; Jeong, Hae Kyung

2017-10-01

Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

Applications of nuclear reaction analysis for determining hydrogen and deuterium distribution in metals

International Nuclear Information System (INIS)

Altstetter, C.J.

1981-01-01

The use of ion beams for materials analysis has made a successful transition from the domain of the particle physicist to that of the materials scientist. The subcategory of this field, nuclear reaction analysis, is just now undergoing the transition, particularly in applications to hydrogen in materials. The materials scientist must locate the nearest accelerator, because now he will find that using it can solve mysteries that do not yield to other techniques. 9 figures

Dehydriding reaction of Mg(NH2)2-LiH system under hydrogen pressure

International Nuclear Information System (INIS)

Aoki, M.; Noritake, T.; Kitahara, G.; Nakamori, Y.; Towata, S.; Orimo, S.

2007-01-01

The dehydriding and structural properties of the 3Mg(NH 2 ) 2 + 12LiH system under hydrogen pressure were investigated using the pressure-composition (p-c) isotherm measurement and X-ray diffraction (XRD) analysis. Two distinct regions, a plateau region and a sloping region, can be seen on the p-c isotherms and the amount of the desorbed hydrogen at 523 K was 4.9 mass%. The enthalpy of hydrogenation calculated using a van't Hoff plot was -46 kJ/mol H 2 . The dehydriding reaction was proposed for the 3Mg(NH 2 ) 2 + 12LiH system based on the obtained p-c isotherms and XRD profiles and chemical valences of Li, Mg, N, and H. In the plateau region on the p-c isotherm, Mg(NH 2 ) 2 , Li 4 Mg 3 (NH 2 ) 2 (NH) 4 (tetragonal), and LiH phases coexist and the molar ratio of the Li 4 Mg 3 (NH 2 ) 2 (NH) 4 phase increases (while those of Mg(NH 2 ) 2 and LiH phases decrease) with the amount of the desorbed hydrogen. On the other hand, the mixture of Li 4+x Mg 3 (NH 2 ) 2-x (NH) 4+x + (8-x)LiH (0 ≤ x ≤ 2) is formed and the lattice volume of the Li 4+x Mg 3 (NH 2 ) 2-x (NH) 4+x phase continuously increases with the amount of the desorbed hydrogen in the sloping region on the p-c isotherm

Thermometric titration of cadmium with sodium diethyldithiocarbamate, with oxidation by hydrogen peroxide as indicator reaction.

Science.gov (United States)

Hattori, T; Yoshida, H

1987-08-01

A new method of end-point indication is described for thermometric titration of cadmium with sodium diethyldithiocarbamate (DDTC). It is based on the redox reaction between hydrogen peroxide added to the system before titration, and the first excess of DDTC. Amounts of cadmium in the range 10-50 mumoles are titrated within 1% error.

Prediction of thermodynamically reversible hydrogen storage reactions utilizing Ca-M(M = Li, Na, K)-B-H systems: a first-principles study.

Science.gov (United States)

Guo, Yajuan; Ren, Ying; Wu, Haishun; Jia, Jianfeng

2013-12-01

Calcium borohydride is a potential candidate for onboard hydrogen storage because it has a high gravimetric capacity (11.5 wt.%) and a high volumetric hydrogen content (∼130 kg m(-3)). Unfortunately, calcium borohydride suffers from the drawback of having very strongly bound hydrogen. In this study, Ca(BH₄)₂ was predicted to form a destabilized system when it was mixed with LiBH₄, NaBH₄, or KBH₄. The release of hydrogen from Ca(BH₄)₂ was predicted to proceed via two competing reaction pathways (leading to CaB₆ and CaH₂ or CaB₁₂H₁₂ and CaH₂) that were found to have almost equal free energies. Using a set of recently developed theoretical methods derived from first principles, we predicted five new hydrogen storage reactions that are among the most attractive of those presently known. These combine high gravimetric densities (>6.0 wt.% H₂) with have low enthalpies [approximately 35 kJ/(mol(-1) H₂)] and are thermodynamically reversible at low pressure within the target window for onboard storage that is actively being considered for hydrogen storage applications. Thus, the first-principles theoretical design of new materials for energy storage in future research appears to be possible.

Reaction of intermetallic compounds of the ScT composition (T=Ag, Cu, Zn, Ni) with hydrogen

International Nuclear Information System (INIS)

Shilkin, S.P.; Volkova, L.S.; Tarasov, B.P.

1995-01-01

Reaction of intermetallic compounds of ScT composition (T=Ag, Cu, Zn, Ni), crystallized in CsCl structural type, with hydrogen at 0.2-10 MPa pressure and 293-673 K temperature is studied by chemical, x-ray phase and complex thermogravimetry analysis methods. It is shown that under such conditions hydrogen absorption by ScAg and ScCu is accompanied by the decay of their source matrices into scandium dihydride and metal silver and copper respectively. For ScZn a fine-dispersion mixture of scandium dihydride with zinc and hydride phase of a new zinc-containing intermetallic compound appears to be the finite reaction product. In case of ScNi a hydride phase of ScNiH 2.6 composition is produced, which is crystallized in a rhombic syngony with the lattice periods: a=0.5281±0.0007, b=0.7393±0.0009 and c=0.3327±0.0004 nm. 9 refs.; 2 tabs

Deuterium exchange reaction between hydrogen and water in a trickle-bed column packed with novel catalysts

International Nuclear Information System (INIS)

Ahn, D. H.; Baek, S. W.; Lee, H. S.; Kim, K. R.; Kang, H. S.; Lee, S. H.; Jeong, H. S.

1998-01-01

The activity of a novel catalyst (Pt/SDBC) for deuterium exchange reaction between water and hydrogen streams in a trickle bed was measured. The performance of the catalyst was compared with a commercial catalyst with same metal content. The catalytic activity for the bed of wet-proofed catalyst diluted with hydrophillic packing material also measured. The Pt/SDBC catalyst shows higher activity in the liquid phase reaction than the commercial catalyst as measured in the vapor phase reaction. The performance for 50% dilution of the Pt/SDBC catalyst bed with hydrophillic packing material is better than that of the 100% bed due to more liquid holdup and better water distribution

Reaction rates and electrical resistivities of the hydrogen isotopes with, and their solubilities in, liquid lithium

International Nuclear Information System (INIS)

Pulham, R.J.; Adams, P.F.; Hubberstey, P.; Parry, G.; Thunder, A.E.

1976-01-01

The rate of reaction, k, of hydrogen and of deuterium with liquid lithium have been determined up to pressures of 20kNm -2 and at temperatures between 230 and 270 0 C. The reaction is first order with an apparent activation energy of 52.8 and 55.2 kJmol -1 for hydrogen and deuterium, respectively. The deuterium isotope effect, k/sub H/k/sub D/, decreases from 2.95 at 230 to 2.83 at 270 0 C. Tritium is predicted to react even more slowly than deuterium. The freezing point of lithium is depressed by 0.082 and 0.075 0 C, respectively, by dissolved hydride and deuteride giving eutectics at 0.016 mol percent H and 0.012 mol percent D in the metal-salt phase diagrams. The depression and eutectic concentration are expected to be less for tritium. The increase in the resistivity of liquid lithium caused by dissolved hydrogen isotopes is linear and relatively large, 5 x 10 -8 Ωm (mol percent H or D) -1 . The solubility of lithium hydride and deuteride was determined from the marked change in resistivity on saturation. The liquidus of the metal-salt phase diagram rises steeply from the eutectic point to meet the two-immiscible liquid region. Tritium is expected to be less soluble than deuterium. The partial molar enthalpies of solution are 44.2 and 55.0 kJmol -1 for hydrogen and deuterium, respectively. These values are used to calculate the solvation enthalpies of the isotope anions in the metal

Magnesium for Hydrogen Storage

DEFF Research Database (Denmark)

Vigeholm, B.; Kjøller, John; Larsen, Bent

1980-01-01

The reaction of hydrogen with commercially pure magnesium powder (above 99.7%) was investigated in the temperature range 250–400 °C. Hydrogen is readily sorbed above the dissociation pressure. During the initial exposure the magnesium powder sorbs hydrogen slowly below 400 °C but during the second...... that the particles do not disintegrate is explained by a sintering process at the working temperatures. Exposure to air does not impair the sorption ability; on the contrary, it appears that surface oxidation plays an important role in the reaction. Some handling problems, e.g. the reaction of the hydride with water...

Research on Liquid Management Technology in Water Tank and Reactor for Propulsion System with Hydrogen Production System Utilizing Aluminum and Water Reaction

Science.gov (United States)

Imai, Ryoji; Imamura, Takuya; Sugioka, Masatoshi; Higashino, Kazuyuki

2017-12-01

High pressure hydrogen produced by aluminum and water reaction is considered to be applied to space propulsion system. Water tank and hydrogen production reactor in this propulsion system require gas and liquid separation function under microgravity condition. We consider to install vane type liquid acquisition device (LAD) utilizing surface tension in the water tank, and install gas-liquid separation mechanism by centrifugal force which swirling flow creates in the hydrogen reactor. In water tank, hydrophilic coating was covered on both tank wall and vane surface to improve wettability. Function of LAD in water tank and gas-liquid separation in reaction vessel were evaluated by short duration microgravity experiments using drop tower facility. In the water tank, it was confirmed that liquid was driven and acquired on the outlet due to capillary force created by vanes. In addition of this, it was found that gas-liquid separation worked well by swirling flow in hydrogen production reactor. However, collection of hydrogen gas bubble was sometimes suppressed by aluminum alloy particles, which is open problem to be solved.

Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values

Czech Academy of Sciences Publication Activity Database

Zou, X.; Huang, X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, Eliška; Asefa, T.

2014-01-01

Roč. 53, č. 17 (2014), s. 4372-4376 ISSN 1433-7851 R&D Projects: GA MŠk(CZ) LO1212 Institutional support: RVO:68081731 Keywords : carbon nanotubes * cobalt nanoparticles * electrocatalysis * hydrogen evolution reaction * water splitting Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 11.261, year: 2014

Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

Science.gov (United States)

Stolbov, Sergey; Alcántara Ortigoza, Marisol

2012-02-01

The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

Hydrogen yield from low temperature steam reforming of ethanol

Energy Technology Data Exchange (ETDEWEB)

Das, N.K.; Dalai, A.K. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemical Engineering, Catalysis and Chemical Reaction Engineering Laboratories; Ranganathan, R. [Saskatchewan Research Council, Saskatoon, SK (Canada)

2007-02-15

Interest in the use of ethanol for fuel cell hydrogen production was discussed with particular reference to a study in which the production of hydrogen was maximized through low temperature steam reforming of ethanol in the temperature range of 200 to 360 degrees C. The primary objective of this study was to determine the effect of Mn concentration on a Cu/Al{sub 2}O{sub 3} catalyst for steam reforming of ethanol to produce hydrogen. The purpose was to maximize ethanol conversion and hydrogen selectivity in the lowest possible reaction temperature for the ideal catalyst activity. The optimum reaction conditions in the presence of a suitable catalyst can produce the desired products of hydrogen and carbon dioxide. Cu/Al{sub 2}O{sub 3} catalysts with six different concentrations ranging from 0 to 10 weight per cent Mn, were prepared, characterized and studied for the ethanol-steam reforming reaction. The effects of different process variables were studied, including water-to-ethanol feed ratio, space time and catalyst reduction temperatures on ethanol conversion and hydrogen yield. Maximum ethanol conversion of 60.7 per cent and hydrogen yield of 3.74 (mol of hydrogen per mol of ethanol converted) were observed at 360 degrees C for a catalyst with 2.5 weight per cent Mn loading. 29 refs., 3 tabs., 12 figs.

Factors affecting hydrogen-tunneling contribution in hydroxylation reactions promoted by oxoiron(IV) porphyrin π-cation radical complexes.

Science.gov (United States)

Cong, Zhiqi; Kinemuchi, Haruki; Kurahashi, Takuya; Fujii, Hiroshi

2014-10-06

Hydrogen atom transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by examining the kinetics of hydroxylation reactions at the benzylic positions of xanthene and 1,2,3,4-tetrahydronaphthalene by oxoiron(IV) 5,10,15,20-tetramesitylporphyrin π-cation radical complexes ((TMP(+•))Fe(IV)O(L)) under single-turnover conditions. The Arrhenius plots for these hydroxylation reactions of H-isotopomers have upwardly concave profiles. The Arrhenius plots of D-isotopomers, clear isosbestic points, and product analysis rule out the participation of thermally dependent other reaction processes in the concave profiles. These results provide evidence for the involvement of H-tunneling in the rate-limiting H-transfer process. These profiles are simulated using an equation derived from Bell's tunneling model. The temperature dependence of the KIE values (k(H)/k(D)) determined for these reactions indicates that the KIE value increases as the reaction temperature becomes lower, the bond dissociation energy (BDE) of the C-H bond of a substrate becomes higher, and the reactivity of (TMP(+•))Fe(IV)O(L) decreases. In addition, we found correlation of the slope of the ln(k(H)/k(D)) - 1/T plot and the bond strengths of the Fe═O bond of (TMP(+•))Fe(IV)O(L) estimated from resonance Raman spectroscopy. These observations indicate that these factors modulate the extent of the H-tunneling contribution by modulating the ratio of the height and thickness of the reaction barrier.

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

Science.gov (United States)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

Gas-phase ion/molecule isotope-exchange reactions: methodology for counting hydrogen atoms in specific organic structural environments by chemical ionization mass spectrometry

International Nuclear Information System (INIS)

Hunt, D.F.; Sethi, S.K.

1980-01-01

Ion/molecule reactions are described which facilitate exchange of hydrogens for deuteriums in a variety of different chemical environments. Aromatic hydrogens in alkylbenzenes, oxygenated benzenes, m-toluidine, m-phenylenediamine, thiophene, and several polycyclic aromatic hydrocarbons and metallocenes are exchanged under positive ion CI conditions by using either D 2 O, EtOD, or ND 3 as the reagent gas. Aromatic hydrogens, benzylic hydrogens, and hydrogens on carbon adjacent to carbonyl groups suffer exchange under negative ion CI conditions in ND 3 , D 2 O, and EtOD, respectively. A possible mechanism for the exchange process is discussed. 1 figure, 2 tables

Simulation of an industrial pyrolysis gasoline hydrogenation unit

Energy Technology Data Exchange (ETDEWEB)

Mostoufi, N.; Sotudeh-Gharebagh, R.; Ahmadpour, M.; Eyvani, J. [Process Design and Simulation Research Centre, Department of Chemical Engineering, Faculty of Engineering, University of Tehran, P.O. Box 11365/4563, Tehran (Iran)

2005-02-01

A model is developed based on a two-stage hydrogenation of pyrolysis gasoline to obtain a C{sub 6}-C{sub 8} cut suitable for extraction of aromatics. In order to model the hydrogenation reactors, suitable hydrodynamic and reaction submodels should be solved simultaneously. The first stage hydrogenation takes place in a trickle bed reactor. The reaction rates of different di-olefines as well as hydrodynamic parameters of the trickle bed (i.e., catalyst wetting efficiency, pressure drop, mass transfer coefficient and liquid hold-up) have been combined to derive the equations to model this reactor. The second stage hydrogenation takes place in a two compartment fixed bed reactor. Hydrogenation of olefines takes place in the first compartment while sulfur is eliminated from the flow in the second compartment. These reactions occur at relatively higher temperature and pressure compared to the first stage. The key component in this stage is considered to be cyclohexene, of which the hydrogenation was found to be the most difficult of the olefines present in the feed. The Langmuir-Hinshelwood kinetic expression was adopted for the hydrogenation of cyclohexene and its kinetic parameters were determined experimentally in a micro-reactor in the presence of the industrial catalyst. The model was solved for the whole process of hydrogenation, including hydro-desulfurization. The predictions of the model were compared with actual plant data from an industrial scale pyrolysis gasoline hydrogenation unit and satisfactory agreement was found between the model and plant data. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

Science.gov (United States)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

A study of the electrochemical hydrogenation of o-xylene in a PEM hydrogenation reactor

International Nuclear Information System (INIS)

Fonocho, R.; Gardner, C.L.; Ternan, M.

2012-01-01

In this study, we investigate the electrochemical hydrogenation of o-xylene in a proton exchange membrane hydrogenation reactor (PEMHR). The reactor was operated isothermally over the temperature range 20–68 °C and at a pressure of 1 atm in a semi-batch mode. Hydrogen was fed into the anode compartment and o-xylene into the cathode. The hydrogenation efficiency was investigated at different current densities and temperatures. Results obtained show that the hydrogenation efficiency increases with temperature but decreases with current density. At low current densities the hydrogenation efficiency approaches 100%. A zero dimensional model was used to fit the data and extract a rate constant for the hydrogenation reaction. The activation energy for this reaction was found to be 28 kJ/mole.

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine

DEFF Research Database (Denmark)

Madsen, Henrik Tækker; Søgaard, Erik Gydesen

2012-01-01

To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)- hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry...... the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution...

Experimental and Theoretical Studies in Hydrogen-Bonding Organocatalysis

Directory of Open Access Journals (Sweden)

Matej Žabka

2015-08-01

Full Text Available Chiral thioureas and squaramides are among the most prominent hydrogen-bond bifunctional organocatalysts now extensively used for various transformations, including aldol, Michael, Mannich and Diels-Alder reactions. More importantly, the experimental and computational study of the mode of activation has begun to attract considerable attention. Various experimental, spectroscopic and calculation methods are now frequently used, often as an integrated approach, to establish the reaction mechanism, the mode of activation or explain the stereochemical outcome of the reaction. This article comprises several case studies, sorted according to the method used in their study. The aim of this review is to give the investigators an overview of the methods currently utilized for mechanistic investigations in hydrogen-bonding organocatalysis.

Reaction of hydrogen atoms produced by radiolysis and photolysis in solid phase at 4 and 77 K

International Nuclear Information System (INIS)

Miyazaki, Tetsuo

1991-01-01

The behavior of H atoms in the solid phase has been reviewed with special attention to comparison of H atoms produced by radiolysis with those produced by photolysis. The paper consists of three parts. I -Production of H atoms: (1) the experimental results which indicate H-atom formation in the radiolysis of solid alkane are summarized; (2) ESR saturation behavior of trapped H atoms depends upon the method of H-atom-production, i.e. photolysis or radiolysis, and upon the initial energy of H atoms in the photolysis. II - Diffusion of H atoms: (1) activation energies for thermally-activated diffusion of H atoms are shown; (2) quantum diffusion of H atoms in solid H 2 is explained in terms of repetition of tunneling reaction H 2 + H → H + H 2 . III -Reaction of H atoms: (1) reactions and trapping processes of hot H atoms have been shown in solid methane and argon by use of hot H atoms with specified initial energy; (2) when H atoms are produced by the radiolysis of solvent alkane or by the photolysis of HI in the alkane mixtures at 77 K, the H atoms react very selectively with solute alkane at low concentration. The selective reaction of the H atom has been found in eight matrices; (3) activation energy for a hydrogen-atom-abstraction reaction by thermal H atoms at low temperatures is less than than several kJ mol -1 because of quantum tunneling. The absolute rate constants for H 2 (D 2 , HD) + H(D) tunneling reactions have been determined experimentally in solid hydrogen at 4.2K; (4) theoretical studies for tunneling reactions H 2 (D 2 ,HD) + H(D) at ultralow temperatures were reviewed. The calculated rate constants were compared with the rate constants obtained experimentally. (author)

Use of Heterogenized Metal Complexes in Hydrogenation Reactions: Comparison of Hydrogenation and CTH Reactions.

Czech Academy of Sciences Publication Activity Database

Bata, P.; Zsigmond, A.; Gyémánt, M.; Czeglédi, A.; Klusoň, Petr

2015-01-01

Roč. 41, č. 12 (2015), s. 9281-9294 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] Institutional support: RVO:67985858 Keywords : catalytic transfer hydrogenation * iron-phthalocyanine catalyst * chemoselectivity Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

Science.gov (United States)

Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

2014-12-08

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bond cleavage reactions of the bridge structure in coal in the presence of hydrogen donating compounds; Suiso kyoyosei kagobutsu sonzaika deno sekitanchu no kakyo kozo no kairetsu hanno

Energy Technology Data Exchange (ETDEWEB)

Bando, N.; Kidena, K.; Murata, S.; Nomura, M. [Osaka University, Osaka (Japan). Faculty of Engineering

1996-10-28

In this paper, bond cleavage reactions are discussed in relation to the softening and solubilization of coal. Were used 9,10-dihydroanthracene (DHA) and 9,10-dihydrophenanthrene (DHP) as models of hydrogen donating compounds in coal, and bibenzyl, 1,2-diethane, benzylphenylether, and 1,5-dibenzylnaphthalene were used as models of bridge structure compounds. They were compared mutually, as to reactivity of coal against DHA and DHP. For the homolytic cleavage of bridges, DHA with excellent radical supplement performance provided excellent hydrogen donating performance. While, for the ipso-position cleavage of bridges, it was found that DHP can act as an effective hydrogen donor. For the reaction between coal and hydrogenated aromatic compounds, cleavage of relatively weak bonds, such as ether linkage and dimethylene linkage, occurred at about 380{degree}C, and hydrogen from DHA or DHP was consumed. On the other hand, the results suggested that the cleavage reaction at ipso-position affected by hydrogen donating solvent is also important at temperature range around 420{degree}C. 2 refs., 3 figs., 1 tab.

Dual-level direct dynamics studies for the hydrogen abstraction reaction of 1,1-difluoroethane with O( 3P)

Science.gov (United States)

Liu, Jing-yao; Li, Ze-sheng; Dai, Zhen-wen; Zhang, Gang; Sun, Chia-chung

2004-01-01

We present dual-level direct dynamics calculations for the CH 3CHF 2 + O( 3P) hydrogen abstraction reaction in a wide temperature range, based on canonical variational transition-state theory including small curvature tunneling corrections. For this reaction, three distinct transition states, one for α-abstraction and two for β-abstraction, have been located. The potential energy surface information is obtained at the MP2(full)/6-311G(d,p) level of theory, and higher-level single-point calculations for the stationary points are preformed at several levels, namely QCISD(T)/6-311+G(3df,3pd), G2, and G3 using the MP2 geometries, as well as at the G3//MP4SDQ/6-311G(d,p) level. The energy profiles are further refined with the interpolated single-point energies method at the G3//MP2(full)/6-311G(d,p) level. The total rate constants match the experimental data reasonable well in the measured temperature range 1110-1340 K. It is shown that at low temperature α-abstraction may be the major reaction channel, while β-abstraction will have more contribution to the whole reaction rate as the temperature increases.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Science.gov (United States)

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Production From Water By Thermo-Chemical Methods (UT-3): Evaluation of Side Reactions By Simulation Process

International Nuclear Information System (INIS)

Rusli, A.

1997-01-01

Hydogen fuel with its advantages will be able to replace all the positions of fossil fuels post o il and gas or migas . Among the advantages of hydrogen fuel are pollution free, abundant of raw material in the form of water molecule, flexible in application, able to stroge and transport as well as fossil energy sources (oil and gas). Hydogen could be produced from water by means of thermochemical, thermolysis, photolysis and electrolysis. Nuclear heat (HTGR), solar heat or waste heat from steel industry can be used as energy source for these processes. In case of thermochemical method, some problems realated to production process should be studied and evaluated. Simulation is considered can be applied to study the effects of side reactions and also to resolve its problems in hydrogen production process. In this paper is reported the evalution results of hydrogen production process by thermochemical (UT-3) through both of the experimental and computer simulation. It has been proposed a new flow chart of hydrogen production to achieve the hydrogen production continuously. A simulator has been developed based on experimental data and related mathematical equations. This simulator can be used to scle-up the UT-3 thermochemical cycle for hydrogen production process

Autothermal hydrogen storage and delivery systems

Science.gov (United States)

Pez, Guido Peter [Allentown, PA; Cooper, Alan Charles [Macungie, PA; Scott, Aaron Raymond [Allentown, PA

2011-08-23

Processes are provided for the storage and release of hydrogen by means of dehydrogenation of hydrogen carrier compositions where at least part of the heat of dehydrogenation is provided by a hydrogen-reversible selective oxidation of the carrier. Autothermal generation of hydrogen is achieved wherein sufficient heat is provided to sustain the at least partial endothermic dehydrogenation of the carrier at reaction temperature. The at least partially dehydrogenated and at least partially selectively oxidized liquid carrier is regenerated in a catalytic hydrogenation process where apart from an incidental employment of process heat, gaseous hydrogen is the primary source of reversibly contained hydrogen and the necessary reaction energy.

Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: An efficient electrocatalyst for the hydrogen evolution reaction

Science.gov (United States)

Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei

2018-02-01

The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.

Electrodeposition of Nickel Nanoparticles for the Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition.

Science.gov (United States)

Tao, Shasha; Yang, Florent; Schuch, Jona; Jaegermann, Wolfram; Kaiser, Bernhard

2018-03-09

Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH) 2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm -2 as well as a small Tafel slope of 88 mV dec -1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH) 2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni 0 , NiO, and Ni(OH) 2 into the less active Ni(OH) 2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar Hydrogen Production

Energy Technology Data Exchange (ETDEWEB)

Koval, C. [Univ. of Colorado, Boulder (United States); Sutin, N. [Brookhaven National Lab., Upton, NY (United States); Turner, J. [National Renewable Energy Lab., Golden, CO (United States)

1996-09-01

This panel addressed different methods for the photoassisted dissociation of water into its component parts, hydrogen and oxygen. Systems considered include PV-electrolysis, photoelectrochemical cells, and transition-metal based microheterogeneous and homogeneous systems. While none of the systems for water splitting appear economically viable at the present time, the panel identified areas of basic research that could increase the overall efficiency and decrease the costs. Common to all the areas considered was the underlying belief that the water-to-hydrogen half reaction is reasonably well characterized, while the four-electron oxidation of water-to-oxygen is less well understood and represents a significant energy loss. For electrolysis, research in electrocatalysis to reduce overvoltage losses was identified as a key area for increased efficiency. Non-noble metal catalysts and less expensive components would reduce capital costs. While potentially offering higher efficiencies and lower costs, photoelectrochemical-based direct conversion systems undergo corrosion reactions and often have poor energetics for the water reaction. Research is needed to understand the factors that control the interfacial energetics and the photoinduced corrosion. Multi-photon devices were identified as promising systems for high efficiency conversion.

Sorption-enhanced water gas shift reaction for high-purity hydrogen production: Application of a Na-Mg double salt-based sorbent and the divided section packing concept

International Nuclear Information System (INIS)

Lee, Chan Hyun; Lee, Ki Bong

2017-01-01

Highlights: •Na-Mg double salt-based sorbent was used for high-temperature CO 2 sorption. •Divided section packing concept was applied to the SE-WGS reaction. •High-purity H 2 was produced from the SE-WGS reaction with divided section packing. •High-purity H 2 productivity could be further enhanced by modifying packing method. -- Abstract: Hydrogen is considered a promising environmentally benign energy carrier because it has high energy density and produces no pollutants when it is converted into other types of energy. The sorption-enhanced water gas shift (SE-WGS) reaction, where the catalytic WGS reaction and byproduct CO 2 removal are carried out simultaneously in a single reactor, has received considerable attention as a novel method for high-purity hydrogen production. Since the high-purity hydrogen productivity of the SE-WGS reaction is largely dependent on the performance of the CO 2 sorbent, the development of sorbents having high CO 2 sorption capacity is crucial. Recently, a Na-Mg double salt-based sorbent has been considered for high-temperature CO 2 capture since it has been reported to have a high sorption capacity and fast sorption kinetics. In this study, the SE-WGS reaction was experimentally demonstrated using a commercial catalyst and a Na-Mg double salt-based sorbent. However, the SE-WGS reaction with a one-body hybrid solid, a physical admixture of catalyst and sorbent, showed poor reactivity and reduced CO 2 sorption uptake. As a result, a divided section packing concept was suggested as a solution. In the divided section packing method, the degree of mixing for the catalyst and sorbent in a column can be controlled by the number of sections. High-purity hydrogen (<10 ppm CO) was produced directly from the SE-WGS reaction with divided section packing, and the hydrogen productivity was further improved when the reactor column was divided into more sections and packed with more sorbent.

Process for hydrogenating coal and coal solvents

Science.gov (United States)

Tarrer, Arthur R.; Shridharani, Ketan G.

1983-01-01

A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260.degree. C. to 315.degree. C. in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275.degree. C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350.degree. C.

Hydrogen detector

International Nuclear Information System (INIS)

Kumagaya, Hiromichi; Yoshida, Kazuo; Sanada, Kazuo; Chigira, Sadao.

1994-01-01

The present invention concerns a hydrogen detector for detecting water-sodium reaction. The hydrogen detector comprises a sensor portion having coiled optical fibers and detects hydrogen on the basis of the increase of light transmission loss upon hydrogen absorption. In the hydrogen detector, optical fibers are wound around and welded to the outer circumference of a quartz rod, as well as the thickness of the clad layer of the optical fiber is reduced by etching. With such procedures, size of the hydrogen detecting sensor portion can be decreased easily. Further, since it can be used at high temperature, diffusion rate is improved to shorten the detection time. (N.H.)

Flow injection determination of hydrogen peroxide using catalytic effect of cobalt(II) ion on a dye formation reaction.

Science.gov (United States)

Kurihara, Makoto; Muramatsu, Miyuki; Yamada, Mari; Kitamura, Naoya

2012-07-15

A novel flow injection photometric method was developed for the determination of hydrogen peroxide in rainwater. This method is based on a cobalt(II)-catalyzed oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3,5-dimethoxyaniline (DAOS) as a modified Trinder's reagent to produce intensely colored dye (λ(max)=530nm) in the presence of hydrogen peroxide at pH 8.4. In this method, 1,2-dihydroxy-3,5-benzenedisulfonic acid (Tiron) acted as an activator for the cobalt(II)-catalyzed reaction and effectively increased the peak height for hydrogen peroxide. The linear calibration graphs were obtained in the hydrogen peroxide concentration range 5×10(-8) to 2.2×10(-6)mol dm(-3) at a sampling rate of 20h(-1). The relative standard deviations for ten determinations of 2.2×10(-6) and 2×10(-7)mol dm(-3) hydrogen peroxide were 1.1% and 3.7%, respectively. The proposed method was successfully applied to the determination of hydrogen peroxide in rainwater samples and the analytical results agreed fairly well with the results obtained by different two reference methods; peroxidase method and hydrogen peroxide electrode method. Copyright © 2012 Elsevier B.V. All rights reserved.

Hydrogen considerations in light-water power reactons

International Nuclear Information System (INIS)

Keilholtz, G.W.

1976-02-01

A critical review of the literature now available on hydrogen considerations in light-water power reactors (LWRs) and a bibliography of that literature are presented. The subject matter includes mechanisms for the generation of hydrogen-oxygen mixtures, a description of the fundamental properties of such mixtures, and their spontaneous ignition in both static and dynamic systems. The limits for hydrogen flammability and flame propagation are examined in terms of the effects of pressure, temperature, and additives; the emphasis is on the effects of steam and water vapor. The containment systems for pressurized-water reactors (PWRs) and boiling-water reactors (BWRs) are compared, and methods to control hydrogen and oxygen under the conditions of both normal operation and postulated accidents are reviewed. It is concluded that hydrogen can be controlled so that serious complications from the production of hydrogen will not occur. The bibliography contains abstracts from the computerized files of the Nuclear Safety Information Center. Key-word, author, and permuted-title indexes are provided. The bibliography includes responses to questions asked by the U. S. Nuclear Regulatory Commission (NRC) which relate to hydrogen, as well as information on normal operations and postulated accidents including generation of hydrogen from core sprays. Other topics included in the ten sections of the bibliography are metal-water reactions, containment atmosphere, radiolytic gas, and recombiners

Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.

2015-10-20

Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction

KAUST Repository

Muralikrishna, S.; Manjunath, K.; Samrat, D.; Reddy, Viswanath; Ramakrishnappa, T.; Nagaraju, Doddahalli H.

2015-01-01

Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.

A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

Science.gov (United States)

Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

2017-04-05

The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

Energy Technology Data Exchange (ETDEWEB)

Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M., E-mail: fattah@cnu.edu

2016-11-01

Highlights: • Co films deposition via aqueous and ionic liquid Precursors. • Hydrogen evolution produced from reactive surfaces. • Co deposited films characterized by SEM, AFM, EDX and XRD techniques. - Abstract: Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH{sub 4}) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm{sup 2} catalytic surface with aqueous NaBH{sub 4} solutions generated rate constants (K) = equal to 4.9 × 10{sup −3} min{sup −1}, 4.6 × 10{sup −3} min{sup −1}, and 3.3 × 10{sup −3} min{sup −1} for ACoF, NCoF, and copper substrate respectively.

Hydrolysis reactor for hydrogen production

Science.gov (United States)

Davis, Thomas A.; Matthews, Michael A.

2012-12-04

In accordance with certain embodiments of the present disclosure, a method for hydrolysis of a chemical hydride is provided. The method includes adding a chemical hydride to a reaction chamber and exposing the chemical hydride in the reaction chamber to a temperature of at least about 100.degree. C. in the presence of water and in the absence of an acid or a heterogeneous catalyst, wherein the chemical hydride undergoes hydrolysis to form hydrogen gas and a byproduct material.

Methanol from biomass and hydrogen

International Nuclear Information System (INIS)

Anon.

1989-01-01

For Hawaii in the near term, the only liquid fuels indigenous sources will be those that can be made from biomass, and of these, methanol is the most promising. In addition, hydrogen produced by electrolysis can be used to markedly increase the yield of biomass methanol. This paper calculates cost of producing methanol by an integrated system including a geothermal electricity facility plus a plant producing methanol by gasifying biomass and adding hydrogen produced by electrolysis. Other studies cover methanol from biomass without added hydrogen and methanol from biomass by steam and carbon dioxide reforming. Methanol is made in a two-step process: the first is the gasification of biomass by partial oxidation with pure oxygen to produce carbon oxides and hydrogen, and the second is the reaction of gases to form methanol. Geothermal steam is used to generate the electricity used for the electrolysis to produce the added hydrogen

Factors determining the activity of catalysts of various chemical types in the oxidation of hydrogen. I. Oxidation and isotope exchange of hydrogen on cobalt monoxide-oxide

International Nuclear Information System (INIS)

Polgikh, L.Y.; Golodets, G.I.; Il'chenko, N.I.

1985-01-01

On the basis of data on the kinetics of the reaction 2H 2 + O 2 = 2H 2 O isotope exchange H 2 + D 2 = 2HD under the conditions of oxidative catalysis, and the kinetic isotope effect, a mechanism is proposed for the oxidation of hydrogen on cobalt monoxide-oxide. At low temperatures the reaction proceeds according to a mechanism of alternating reduction-reoxidation of the surface with the participation of hydrogen adsorbed in molecular form; at increased temperature and low P 02 /P /SUB H2/ ratios, a significant contribution to the observed rate is made by a mechanism including dissociative chemisorption of hydrogen

Selective hydrogen atom abstraction by hydrogen atoms in photolysis and radiolysis of alkane mixtures at 770 K

International Nuclear Information System (INIS)

Miyazaki, T.; Kinugawa, K.; Eguchi, M.; Guedes, S.M.L.

1977-01-01

Selective hydrogen atom abstraction reaction by H atoms, has been found in Isobutane, 2,2,3,3-tetramethylbutane(TMB), cyclopropane matrices besides neopentane matrix. The selective hydrogen atom abstraction reaction in neopentane-isobutane mixture is affected by the difference of kinetic energies of H atoms. The reaction occurs more favorably with decreasing the kinetic energy of H atoms. Competitive reaction between c-C 6 H 12 and Hi for H atoms has been studied in the radiolysis and photolysis of neo-C 5 H 12 HI mixture at 77 K. The rate constants of these reactions in neopentane matrix are quite different from these of thermal H atom reaction, but similar to those of hot H atom reaction. Importance of the selective hydrogen atom abstraction reaction by H atoms is pointed out in the radical formation in the radiolysis of pure TMB at 77 K [pt

Production of hydrogen in the reaction between aluminum and water in the presence of NaOH and KOH

Directory of Open Access Journals (Sweden)

C. B. Porciúncula

2012-06-01

Full Text Available The objective of this work is to investigate the production of hydrogen as an energy source by means of the reaction of aluminum with water. This reaction only occurs in the presence of NaOH and KOH, which behave as catalysts. The main advantages of using aluminum for indirect energy storage are: recyclability, non-toxicity and easiness to shape. Alkali concentrations varying from 1 to 3 mol.L-1 were applied to different metallic samples, either foil (0.02 mm thick or plates (0.5 and 1 mm thick, and reaction temperatures between 295 and 345 K were tested. The results show that the reaction is strongly influenced by temperature, alkali concentration and metal shape. NaOH commonly promotes faster reactions and higher real yields than KOH.

Hydrogen-deuterium exchange reaction of 2-methylpyridine catalyzed by several fatty acids

International Nuclear Information System (INIS)

Hirata, Hirohumi; Fukuzumi, Kazuo.

1976-01-01

Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several fatty acids as catalysts. The reaction was carried out in a sealed pyrex tube at 120 0 C, and the contents of the products were determined by mass spectrometry. Reaction of 2-methylpyridine with monodeuteroacetic acid (1 : 1, mol/mol) arrived at a equilibrium (d 0 reversible d 1 reversible d 2 reversible d 3 ) in 2 hr (d 0 41%, d 1 42%, d 2 15%, d 3 2%). No exchange was observed for the reaction of pyridine with monodeuteroacetic acid. The conversion-time curves of typical series reactions (d 0 → d 1 → d 2 → d 3 ) were obtained for the fatty acid catalyzed exchange in deuterium oxide. The effect of the fatty acid RCO 2 H (substrate : fatty acid : D 2 O=1 : 0.86 : 27.6, mol/mol/mol) on the conversion was in the order of R; C 1 --C 3 4 --C 10 , where the reaction mixtures were homogeneous in the case of C 1 --C 3 and were heterogeneous in the case of C 4 --C 10 . The effects of the initial concentration of the substrates and the catalysts (RCO 2 H) on the total conversion were studied by using some fatty acids (R; C 2 , C 4 and C 9 ) in deuterium oxide (for 2 hr). The total conversion of the substrate increases with increasing the concentration of the acids. The total conversion decreases in the case of R=C 9 , but, increases in the case of R=C 2 with increasing the concentration of the substrate. In the case of reactions with low concentrations of the substrate, the reactivity was in the order of C 9 >C 4 >C 2 , while with high concentrations, the reactivity was in the order of C 4 >C 2 >C 9 and C 9 >C 4 >C 2 with high and low concentrations of the acids, respectively. A possible reaction mechanism was proposed and discussed. (auth.)

Process for hydrogenating coal and coal solvents

Energy Technology Data Exchange (ETDEWEB)

Shridharani, K.G.; Tarrer, A.R.

1983-02-15

A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260/sup 0/ C to 315/sup 0/ C in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275/sup 0/ C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350/sup 0/ C.

Process for exchanging hydrogen isotopes between gaseous hydrogen and water

International Nuclear Information System (INIS)

Hindin, S.G.; Roberts, G.W.

1977-01-01

A process is described for exchanging isotopes (particularly tritium) between water and gaseous hydrogen. Isotope depleted gaseous hydrogen and water containing a hydrogen isotope are introduced into the vapour phase in a first reaction area. The steam and gaseous hydrogen are brought into contact with a supported metal catalyst in this area in a parallel flow at a temperature range of around 225 and 300 0 C. An effluent flow comprising a mixture of isotope enriched gaseous hydrogen and depleted steam is evacuated from this area and the steam condensed into liquid water [fr

Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

Science.gov (United States)

Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

2018-03-01

Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

Gas-phase hydrogenation of benzene on supported nickel catalyst

Energy Technology Data Exchange (ETDEWEB)

Franco, H.A.; Phillips, M.J.

1980-06-01

The reaction of 22.66-280 Pa benzene with 72.39-122.79 Pa hydrogen on kieselguhr-supported nickel at 392.2/sup 0/-468.2/sup 0/K yielded only cyclohexane and was independent of 5.33-40 Pa cyclohexane added to the feed of the differential flow reactor. Best fit for the kinetic data was obtained with a rate equation developed by van Meerten and Coenen which assumed that all hydrogen addition steps have the same rate constant and are slow. An observed rate maximum at 458/sup 0/K may be the result of an increasing rate constant and decreasing cyclohexyl surface coverage as the temperature increases. Temperature-programed hydrogen desorption showed a series of desorption peaks at 358/sup 0/-600/sup 0/K, including one at 453/sup 0/K, which may be due to the hydrogen involved in the surface reaction.

Understanding the reaction between muonium atoms and hydrogen molecules: zero point energy, tunnelling, and vibrational adiabaticity

Science.gov (United States)

Aldegunde, J.; Jambrina, P. G.; García, E.; Herrero, V. J.; Sáez-Rábanos, V.; Aoiz, F. J.

2013-11-01

The advent of very precise measurements of rate coefficients in reactions of muonium (Mu), the lightest hydrogen isotope, with H2 in its ground and first vibrational state and of kinetic isotope effects with respect to heavier isotopes has triggered a renewed interests in the field of muonic chemistry. The aim of the present article is to review the most recent results about the dynamics and mechanism of the reaction Mu+H2 to shed light on the importance of quantum effects such as tunnelling, the preservation of the zero point energy, and the vibrational adiabaticity. In addition to accurate quantum mechanical (QM) calculations, quasiclassical trajectories (QCT) have been run in order to check the reliability of this method for this isotopic variant. It has been found that the reaction with H2(v=0) is dominated by the high zero point energy (ZPE) of the products and that tunnelling is largely irrelevant. Accordingly, both QCT calculations that preserve the products' ZPE as well as those based on the Ring Polymer Molecular Dynamics methodology can reproduce the QM rate coefficients. However, when the hydrogen molecule is vibrationally excited, QCT calculations fail completely in the prediction of the huge vibrational enhancement of the reactivity. This failure is attributed to tunnelling, which plays a decisive role breaking the vibrational adiabaticity when v=1. By means of the analysis of the results, it can be concluded that the tunnelling takes place through the ν1=1 collinear barrier. Somehow, the tunnelling that is missing in the Mu+H2(v=0) reaction is found in Mu+H2(v=1).

Uranium/water vapor reactions in gaseous atmospheres

International Nuclear Information System (INIS)

Jackson, R.L.; Condon, J.B.; Steckel, L.M.

1977-07-01

Experiments have been performed to determine the effect of varying humidities, gaseous atmospheres, and temperatures on the uranium/water vapor reaction. A balance, which allowed continuous in-system weighings, was used to determine the rates of the uranium/water vapor reactions at water vapor pressures of 383, 1586, and 2853 Pa and at temperatures of 80, 100, and 150 0 C in atmospheres of hydrogen, argon, or argon/oxygen mixtures. Based on rate data, the reactions were characterized as hydriding or nonhydriding. Hydriding reactions were found to be preferred in moist hydrogen systems at the higher temperatures and the lower humidities. The presence of hydrogen in hydriding systems was found to initially inhibit the reaction, but causes an acceleration of the rate in the final stages. In general, reaction rates of hydriding systems approached the hydriding rates calculated and observed in dry hydrogen. Hydriding and nonhydriding reaction rates showed a positive correlation to temperature and water vapor pressure. Final reaction rates in moist argon/oxygen mixtures of 1.93, 4.57, and 9.08 mole percent oxygen were greater than the rates observed in moist hydrogen or argon. Final reaction rates were negatively correlated to the oxygen concentration

Storage of hydrogen in metals

International Nuclear Information System (INIS)

Wiswall, R.

1981-01-01

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

Gaseous anion chemistry. Hydrogen-deuterium exchange in mono- and dialcohol alkoxide ions: ionization reactions in dialcohols

International Nuclear Information System (INIS)

Lloyd, J.R.; Agosta, W.C.; Field, F.H.

1980-01-01

The subject of this work is H-D exchange in certain gaseous anions using D 2 as the exchanging agent. The anions involved are produced from ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethanol, 1-propanol, and 1-butanol. Spectra and postulated ionization reactions for these mono- and dialcohols are given. Hydrogen-deuterium exchange occurs in the (M - 1) - and (2M - 1) - ions of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The amount of exchange occurring is 3-8 times greater in (2M - 1) - than in (M - 1) - . The amount of H-D exchange occurring in ethanol, 1-propanol, and 1-butanol is small or zero in the (2M - 1) - ions and in the (M - 1) - ion for 1-butanol [the only (M - 1) - ion which could be examined experimentally]. The amount of exchange occurring in the (2M - 1) - and (M - 1) - ions from ethylene glycol is not affected by the total pressure or composition of the reaction mixture in the ionization chamber of the mass spectrometer. A novel hydrogen-bridging mechanism is suggested to account for the observed exchange occurring in the dialcohols

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

Science.gov (United States)

Tanabe, Katsuaki

2016-01-01

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

Adsorption of cadmium ions on nickel surface skeleton catalysts and its effect on reaction of cathodic hydrogen evolution

International Nuclear Information System (INIS)

Korovin, N.V.; Udris, E.Ya.; Savel'eva, O.N.

1986-01-01

Cadmium adsorption from different concentration CdSO 4 solutions on nickel surface skeleton catalysts (Ni ssc ) is studied by recording of polarization and potentiodynamic curves using electron microscopy and X-ray spectrometry. Main regularities of cadmium adsorption on Ni ssc are shown to be similar to those on smooth and skeleton nickel. A conclusion is drawn that increase of catalytic activity in reaction of cathodic hydrogen evolution from alkali solutions of Ni ssc base electrodes after their treatment in solutions containing Cd 2+ ions is due to irreversible desorption of strongly and averagely bound hydrogen from electrode surface at cadmium adsorption on them

Hydrogen fuel. Uses

International Nuclear Information System (INIS)

Darkrim-Lamari, F.; Malbrunot, P.

2006-01-01

Hydrogen is a very energetic fuel which can be used in combustion to generate heat and mechanical energy or which can be used to generate electricity and heat through an electrochemical reaction with oxygen. This article deals with the energy conversion, the availability and safety problems linked with the use of hydrogen, and with the socio-economical consequences of a generalized use of hydrogen: 1 - hydrogen energy conversion: hydrogen engines, aerospace applications, fuel cells (principle, different types, domains of application); 2 - hydrogen energy availability: transport and storage (gas pipelines, liquid hydrogen, adsorbed and absorbed hydrogen in solid materials), service stations; 3 - hazards and safety: flammability, explosibility, storage and transport safety, standards and regulations; 4 - hydrogen economy; 5 - conclusion. (J.S.)

Matrix effect on hydrogen-atom tunneling of organic molecules in cryogenic solids

International Nuclear Information System (INIS)

Ichikawa, Tsuneki

2000-01-01

Although the tunneling of atoms through potential energy barriers separating the reactant and reaction systems is not paid much attention in organic reactions, this plays an important role in reactions including the transfer of light atoms. Atomic tunneling is especially important for chemical reactions at low temperatures, since the thermal activation of reactant systems is very slow process in comparison with the tunneling. One of the typical reactions of atomic tunneling is hydrogen-atom abstraction from alkanes in cryogenic solids exposed to high-energy radiation. Irradiation of alkane molecules causes the homolytic cleavage of C-H bonds, which results in the pairwise formation of free hydrogen atoms and organic free radicals. Since the activation energies for the abstraction of hydrogen atoms from alkane molecules by free hydrogen atoms are higher than 5 kcal/mol, the lifetime of free hydrogen atoms at 77 K is estimated from the Arrhenius equation of k=vexp(-E a /RT) to be longer than 10 hrs. However, except for solid methane, free hydrogen atoms immediately convert to alkyl radicals even at 4.2 K by hydrogen-atom tunneling from alkane molecules to the free hydrogen atoms. The rate of hydrogen atom tunneling does not necessary increase with decreasing activation energy or the peak height of the potential energy barrier preventing the tunneling. Although the activation energy is the lowest at the tertiary carbon of alkanes, hydrogen atom tunneling from branched alkanes with tertiary carbon at the antepenultimate position of the carbon skeleton is the fastest at the secondary penultimate carbon. Based on our experimental results, we have proposed that the peculiarity of the hydrogen-atom abstraction in cryogenic solids comes from the steric hindrance by matrix molecules to the deformation of alkane molecules from the initial sp 3 to the final sp 2 configurations. The steric hindrance causes the increase of the height of the potential energy barrier for the

Enhanced Hydrogen Evolution Reactions on Nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS) Electrocatalyst

Energy Technology Data Exchange (ETDEWEB)

Digraskar, Renuka V.; Mulik, Balaji B. [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India); Walke, Pravin S. [National Centre for Nanosciences and Nanotechnology, University of Mumbai, Mumbai 400098, MH (India); Ghule, Anil V. [Department of Chemistry, Shivaji University, Kolhapur, 416004, MH (India); Sathe, Bhaskar R., E-mail: bhaskarsathe@gmail.com [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India)

2017-08-01

Graphical abstract: CZTS nano-electrocatalyst (2.6 ± 0.4 nm) for HER is synthesized by one step sonochemical method with uniform size distribution, which shows promisingly lower onset potential with higher current density and longer stability. - Highlights: • The nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS; ∼3 nm) based electrocatalytic systems were developed by facile sonochemical method. • The novel Cu{sub 2}ZnSnS{sub 4} based nanoclustered cathode improves the electrocatalytic performance toward hydrogen generation reaction (HER). • The electrocatalytic result exhibits lower Tafel slope, higher exchange current density, excellent current stability and lower charge transfer resistance. • The high activity due to synergetic effect of Cu, Zn, Sn and S from their internal cooperative supports. - Abstract: A novel and facile one-step sonochemical method is used to synthesize Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer−Emmett−Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density −130 mA/cm{sup 2}, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm{sup 2}, excellent

Kinetic Models Study of Hydrogenation of Aromatic Hydrocarbons in Vacuum Gas Oil and Basrah Crude Oil Reaction

Directory of Open Access Journals (Sweden)

Muzher M. Ibraheem

2013-05-01

Full Text Available             The aim of this research is to study the kinetic reaction models for catalytic hydrogenation of aromatic content for Basrah crude oil (BCO and vacuum gas oil (VGO derived from Kirkuk crude oil which has the boiling point rang of (611-833K.            This work is performed using a hydrodesulphurization (HDS pilot plant unit located in AL-Basil Company. A commercial (HDS catalyst cobalt-molybdenum (Co-Mo supported in alumina (γ-Al2O3 is used in this work. The feed is supplied by North Refinery Company in Baiji. The reaction temperatures range is (600-675 K over liquid hourly space velocity (LHSV range of (0.7-2hr-1 and hydrogen pressure is 3 MPa with H2/oil ratio of 300 of Basrah Crude oil (BCO, while the corresponding conditions for vacuum gas oil (VGO are (583-643 K, (1.5-3.75 hr-1, 3.5 MPa and 250  respectively .            The results showed that the reaction kinetics is of second order for both types of feed. Activation energies are found to be 30.396, 38.479 kJ/mole for Basrah Crude Oil (BCO and Vacuum Gas Oil (VGO respectively.

Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

Energy Technology Data Exchange (ETDEWEB)

Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

2006-07-01

Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

Recycling of chemical hydrogen storage materials

International Nuclear Information System (INIS)

Lo, C.F.; Davis, B.R.; Karan, K.

2004-01-01

'Full text:' Light weight chemical hydrides such as sodium borohydride (NaBH4) and lithium borohydride (LiBH4) are promising hydrogen storage materials. They offer several advantages including high volumetric storage density, safe storage, practical storage and operating condition, controlled and rapid hydrogen release kinetics in alkaline aqueous media in the presence of catalysts. In addition, borate or borax, the reaction by-product, is environmentally friendly and can be directly disposed or recycled. One technical barrier for utilizing borohydrides as hydrogen storage material is their high production cost. Sodium borohydride currently costs $90 per kg while lithium borohydride costs $8000 per kg. For commercialization, new and improved technology to manufacture borohydrides must be developed - preferably by recycling borates. We are investigating different inorganic recycling routes for regenerating borohydrides from borates. In this paper, the results of a chlorination-based recycling route, incorporating multi-step reactions, will be discussed. Experiments were conducted to establish the efficiency of various steps of the selected regeneration process. The yields of desired products as a function of reaction temperature and composition were obtained from multi-phase batch reactor. Separation efficiency of desired product was also determined. The results obtained so far appear to be promising. (author)

Renewable carbohydrates are a potential high-density hydrogen carrier

Energy Technology Data Exchange (ETDEWEB)

Zhang, Y.-H. Percival [Biological Systems Engineering Department, 210-A Seitz Hall, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States); Institute for Critical Technology and Applied Sciences (ICTAS), Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States); DOE BioEnergy Science Center (BESC), Oak Ridge, TN 37831 (United States)

2010-10-15

The possibility of using renewable biomass carbohydrates as a potential high-density hydrogen carrier is discussed here. Gravimetric density of polysaccharides is 14.8 H{sub 2} mass% where water can be recycled from PEM fuel cells or 8.33% H{sub 2} mass% without water recycling; volumetric densities of polysaccharides are >100 kg of H{sup 2}/m{sup 3}. Renewable carbohydrates (e.g., cellulosic materials and starch) are less expensive based on GJ than are other hydrogen carriers, such as hydrocarbons, biodiesel, methanol, ethanol, and ammonia. Biotransformation of carbohydrates to hydrogen by cell-free synthetic (enzymatic) pathway biotransformation (SyPaB) has numerous advantages, such as high product yield (12 H{sub 2}/glucose unit), 100% selectivity, high energy conversion efficiency (122%, based on combustion energy), high-purity hydrogen generated, mild reaction conditions, low-cost of bioreactor, few safety concerns, and nearly no toxicity hazards. Although SyPaB may suffer from current low reaction rates, numerous approaches for accelerating hydrogen production rates are proposed and discussed. Potential applications of carbohydrate-based hydrogen/electricity generation would include hydrogen bioreactors, home-size electricity generators, sugar batteries for portable electronics, sugar-powered passenger vehicles, and so on. Developments in thermostable enzymes as standardized building blocks for cell-free SyPaB projects, use of stable and low-cost biomimetic NAD cofactors, and accelerating reaction rates are among the top research and development priorities. International collaborations are urgently needed to solve the above obstacles within a short time. (author)

Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

KAUST Repository

Chang, Yunghuang

2014-10-22

Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

Photochemical hydrogen abstractions as radiationless transitions

International Nuclear Information System (INIS)

Burrows, H.D.; Formosinho, S.J.

1977-01-01

The tunnel-effect theory of radiationless transitions is applied to the quenching of the uranyl ion excited state by aliphatic compounds. The most important mechanism kinetically is suggested to involve chemical quenching via hydrogen abstraction, and rates for these reactions are analysed theoretically. Good agreement between theory and experiment is observed for a number of alcohols and ethers, and the reactions are suggested to possess considerable charge-transfer character. With t-butanol it is suggested that abstraction occurs preferentially from the hydroxylic hydrogen. Theoretical analysis of the rates of hydrogen abstraction from carboxylic acids suggests that the reaction geometry in this case may be different from the reaction with alcohols or ethers. The possibility that excited uranyl ion can abstract a hydrogen atom from water is examined, and theoretical evidence is presented to suggest that this is the main route for deactivation of uranyl ion lowest excited state in water at room temperature. (author)

Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

International Nuclear Information System (INIS)

Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

1987-01-01

A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

Hydrogen vacancies facilitate hydrogen transport kinetics in sodium hydride nanocrystallites

NARCIS (Netherlands)

Singh, S.; Eijt, S.W.H.

2008-01-01

We report ab initio calculations based on density-functional theory, of the vacancy-mediated hydrogen migration energy in bulk NaH and near the NaH(001) surface. The estimated rate of the vacancy mediated hydrogen transport, obtained within a hopping diffusion model, is consistent with the reaction

The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

KAUST Repository

Li, Zhengxing

2014-07-01

In the context of the future hydrogen economy, effective production of hydrogen (H2) from readily available and sustainable resources is of crucial importance. Hydrogen generation via water splitting by solar energy or electricity has attracted great attention in recent years. In comparison with photocatalytic water-splitting directly using solar light, which is ideal but the relevant technologies are not yet mature, electrolysis of water with catalyst is more practical at the current stage. The Pt-group noble metals are the most effective electrocatalysts for hydrogen evolution reaction (HER) from water, but their high costs limit their applications. Due to the earth-abundance and low price, MoS2 is expected to be a good alternative of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more investigations are still needed to better understand the structure-performance correlation in this system. In this thesis, we report a new strategy for fabricating MoS2 eletrocatalysts which gives rise to much improved HER performance and allows us to tune the electrocatalytic activity by varying the preparation conditions. Specifically, we sulfurized molybdenum oxide on the surface of a Ti foil electrode via a facile chemical vapor deposition (CVD) method, and directly used the electrode for HER testing. Depending on the CVD temperature, the MoO2-MoS2 nanocomposites show different HER activities. Under the optimal synthesis condition (400ºC), the resulting catalyst exhibited excellent HER activity: an onset potential (overpotential) of 0.095 V versus RHE and the Tafel slope of 40 mv/dec. Such a performance exceeds those of most reported MoS2 based HER electrocatalysts. We demonstrated that the CVD temperature has significant influence on the catalysts in crystallinity degree, particle

SPE (tm) regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications

Science.gov (United States)

Mcelroy, J. F.

1990-01-01

Viewgraphs on SPE regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications are presented. Topics covered include: hydrogen-oxygen regenerative fuel cell energy storage system; electrochemical cell reactions; SPE cell voltage stability; passive water removal SPE fuel cell; fuel cell performance; SPE water electrolyzers; hydrophobic oxygen phase separator; hydrophilic/electrochemical hydrogen phase separator; and unitized regenerative fuel cell.

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

Science.gov (United States)

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

2009-01-01

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

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

Science.gov (United States)

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

2010-05-25

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

Photo- and radiation-chemical stability of molecules. Reactions of monomolecular hydrogen atom splitting off

International Nuclear Information System (INIS)

Plotnikov, V.G.; Ovchinnikov, A.A.

1978-01-01

In the review of works published up to 1978 one of the main problems of radiation chemistry is discussed, namely the relationship between the structure of organic molecules and their resistance to the effect of ionizing radiation. Theoretical aspects of this problem are considered for reactions of monomolecular hydrogen atom splitting off. It is shown that the radical yield in low-temperature radiation-chemical experiments is connected with the position of lower triplet states of molecules, ionization potentials, polarity of medium and the energy of C-H bonds in cation radicals

Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

Science.gov (United States)

Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

2011-11-01

By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

Science.gov (United States)

Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

2016-03-29

Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

Storage characteristics of hydrogen by titanium

International Nuclear Information System (INIS)

Lee, S. H.; Kang, H. S.; Back, S. W.; Choi, H. J.; Kim, K. R.; An, D. H.; Lee, H. S.; Jung, H. S.

2000-01-01

Hydrogen absorption experiments were performed by the sponge, strip and rod types of titanium(Ti) for investigating the absorption characteristics of hydrogen. From experimental results, Ti sponge showed the high hydrogen absorption capacity inspite of low reaction temperature(25 .deg. C), the H/M, which mean the capacity of hydrogen absorption was measured 2.0 for Ti sponge at 25 .deg. C. However, in case of strip and rod type of Ti, the hydrogen absorption capacities were very low in the experimental condition of 25 .deg. C. The pulverizing phenomena after metal hydriding reaction was observed in both Ti strip and Ti rod. However, the pulverizing phenomena was not observed in the Ti sponges because of high surface area

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-11-15

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

Hydrogen problems related to reactor accidents

International Nuclear Information System (INIS)

Bujor, A.

1993-09-01

At reactor accidents, the combustion of hydrogen causes pressure and temperature transients which pose supplementary loads in containment. In certain conditions, they could reach hazardous levels and impair the integrity of the containment and the operability of the safety systems. The mechanisms of chemical reactions specific for the hydrogen-oxygen system are presented. Conditions in which combustion can occur and the various combustion modes, including the transition to detonation are also described. The related safety aspects and mitigation methods are discussed. Examples for particular applications and safety approaches for various types of reactors, included those promoted for the advanced reactors are also given. Presentation of the experimental research completed at AECL-Research, Whiteshell Laboratory is given, where the multi-point ignition effects for constant volume and for vented combustion of dry hydrogen-air mixtures in various geometries have been investigated. Various aspects of modelling and simulation of hydrogen combustion are discussed. The adaptations and the new models implemented in the codes VENT and CONTAIN, aimed to widen the simulation capabilities of hydrogen combustion models are described. The capabilities and limitations of the modelling assumptions of these two codes are also evaluated. (EG) (11 tabs., 39 ills., 82 refs.)

Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

Science.gov (United States)

Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

2009-12-31

Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

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

Directory of Open Access Journals (Sweden)

Katsuaki Tanabe

2016-01-01

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

Hydrogen separation membranes annual report for FY 2010.

Energy Technology Data Exchange (ETDEWEB)

Balachandran, U.; Dorris, S. E; Emerson, J. E.; Lee, T. H.; Lu, Y.; Park, C. Y.; Picciolo, J. J. (Energy Systems)

2011-03-14

The objective of this work is to develop dense ceramic membranes for separating hydrogen from other gaseous components in a nongalvanic mode, i.e., without using an external power supply or electrical circuitry. The goal of this project is to develop dense hydrogen transport membranes (HTMs) that nongalvanically (i.e., without electrodes or external power supply) separate hydrogen from gas mixtures at commercially significant fluxes under industrially relevant operating conditions. These membranes will be used to separate hydrogen from gas mixtures such as the product streams from coal gasification, methane partial oxidation, and water-gas shift reactions. Potential ancillary uses of HTMs include dehydrogenation and olefin production, as well as hydrogen recovery in petroleum refineries and ammonia synthesis plants, the largest current users of deliberately produced hydrogen. This report describes the results from the development and testing of HTM materials during FY 2010.

Reaction behaviour of DSD waste plastics in hydrogenating liquefaction with varied times of residue and reaction temperatures; Das Reaktionsverhalten von DSD-Kunststoffabfaellen in der hydrierenden Verfluessigung bei Variation von Verweilzeit und Reaktionstemperatur

Energy Technology Data Exchange (ETDEWEB)

Burgtorf, J; Meier zu Koecker, H [Technische Univ. Berlin (Germany). Inst. fuer Energietechnik

1997-12-31

Hydrogenation is an established process of waste plastics recycling. At the 1st DGMK Technical Meeting at Velen, the Energy Engineering Institute of Berlin Technical University presented studies on the reaction behaviour of waste plastics collected by the DSD (Duales System Deutschland) during hydrogenating liquefaction. The studies have been finished by now, and some results are presented, with particular regard to times of residue and reaction temperaperatures. (orig) [Deutsch] Die Hydrierung ist ein etabliertes Verfahren der rohstofflichen Verwertung von Kunststoffabfaellen. Die auf der 1. DGMK-Fachtagung in Velen vorgestellten Arbeiten des Instituts fuer Energietechnik der Technischen Universitaet Berlin zum Reaktionsverhalten von Kuststoffabfaellen aus der Sammlung des Dualen Systems Deutschland (DSD) in der hydrierenden Verfluessigung sind inzwischen abgeschlossen. Einige Ergebnisse werden hier unter besonderer Beruecksichtigung der Parameter Verweilzeit und Reaktionstemperatur dargestellt. (orig)

Reaction behaviour of DSD waste plastics in hydrogenating liquefaction with varied times of residue and reaction temperatures; Das Reaktionsverhalten von DSD-Kunststoffabfaellen in der hydrierenden Verfluessigung bei Variation von Verweilzeit und Reaktionstemperatur

Energy Technology Data Exchange (ETDEWEB)

Burgtorf, J.; Meier zu Koecker, H. [Technische Univ. Berlin (Germany). Inst. fuer Energietechnik

1996-12-31

Hydrogenation is an established process of waste plastics recycling. At the 1st DGMK Technical Meeting at Velen, the Energy Engineering Institute of Berlin Technical University presented studies on the reaction behaviour of waste plastics collected by the DSD (Duales System Deutschland) during hydrogenating liquefaction. The studies have been finished by now, and some results are presented, with particular regard to times of residue and reaction temperaperatures. (orig) [Deutsch] Die Hydrierung ist ein etabliertes Verfahren der rohstofflichen Verwertung von Kunststoffabfaellen. Die auf der 1. DGMK-Fachtagung in Velen vorgestellten Arbeiten des Instituts fuer Energietechnik der Technischen Universitaet Berlin zum Reaktionsverhalten von Kuststoffabfaellen aus der Sammlung des Dualen Systems Deutschland (DSD) in der hydrierenden Verfluessigung sind inzwischen abgeschlossen. Einige Ergebnisse werden hier unter besonderer Beruecksichtigung der Parameter Verweilzeit und Reaktionstemperatur dargestellt. (orig)

Use of portable analytical methods to determine the stoichiometry of reaction for hexahydrotriazine-based hydrogen sulfide scavenger operations.

Science.gov (United States)

Taylor, Grahame N; Matherly, Ron

2014-05-20

During the reaction between 1,3,5-tris(2-hydroxyethyl)hexahydro-s-triazine and hydrogen sulphide, the principle by-product is the organic sulphide 5-(2-hydroxyethyl)dithiazine. It can be determined by a novel, portable, field-capable ion mobility spectrometry method described herein and enables the "degree spent" to be determined. Dependant upon the level of carbon dioxide in the produced gas, a mixture of ethanolaminium bicarbonate and ethanolamine bisulphide is also produced. Using a field capable spectrophotometric method the level of inorganic sulphide can be determined, thus allowing the ethanolaminium bisulphide concentration to be calculated. Provided the fluid is only partially spent, and there is some unreacted 1,3,5-tris(2-hydroxyethyl)hexahydro-s-triazine remaining; the only source of inorganic sulphide is the amine salt. From a knowledge of the original fluid concentration, the combination of these two methods allows the effective stoichiometry, or observed molar reaction proportions between 1,3,5-tris(2-hydroxyethyl)hexahydro-s-triazine and hydrogen sulphide, to be measured for a specific field location.

Ligand iron catalysts for selective hydrogenation

Science.gov (United States)

Casey, Charles P.; Guan, Hairong

2010-11-16

Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

Reactions of dialkyl hydrogen phosphites with 2,3-diphenylindone

International Nuclear Information System (INIS)

Arbuzov, B.A.; Fuzhenkova, A.V.; Banderova, N.A.

1987-01-01

Dialkyl hydrogen phosphites are found to add to 2,3-diphenylindone at the carbonyl group with the formation of dialkyl 1-hydroxy-2,3-diphenylinden-1-yl phosphonates, which, under conditions of basic catalysis, are rearranged into diakyl 2,3-diphenylinden-1-yl phosphates, presumably as a result of phosphonate-phosphate rearrangement. Data derived by IR and NMR spectroscopy are included on the electronic and molecular structure of the resulting isomers. Electron density and spin-spin coupling constants are also determined

The hydrogen atom-deuterium molecule reaction: Experimental determination of product quantum state distributions

International Nuclear Information System (INIS)

Rinnen, K.

1989-01-01

The H + H 2 atom exchange reaction (and its isotopic analogs) is the simplest neutral bimolecular chemical reaction because of the small number of electrons in the system and the lightness of the nuclei. The H 3 potential energy surface (PES) is the most accurately known reactive surface (LSTH surface); there have been both quasiclassical trajectory (QCT) and quantal calculations performed on it. This is one of the few systems for which theory is ahead of experiment, and many theoretical predictions await experimental comparison. The H + D 2 → HD + D reaction is studied using thermal D 2 (∼298 K) and translationally hot hydrogen atoms. Photolysis of HI at 266 nm generates H atoms with center-of-mass collision energies of 1.3 and 0.55 eV, both of which are above the classical reaction barrier of 0.42 eV. The rovibrational population distribution of the molecular product is measured by (2+1) resonance-enhanced multiphoton ionization (REMPI). A major effort has been directed toward calibrating the (2+1) REMPI detection procedure, to determine quantitatively the relationship between ion signals and relative quantum state populations for HD. An effusive, high-temperature nozzle has been constructed to populate thermally the high rovibrational levels observed in the reaction. The results are compared to theoretical calculations of the E,F 1 Σ g + - X 1 Σ g + two-photon transition moments. For the H + D 2 reaction, the populations of all energetically accessible HD product levels are measured. Specifically, the following levels are observed: HD(v = 0, J = 0-15), HD(v = 1, J = 0-12), and HD(v = 2, J = 0-8). Of the available energy, 73% is partitioned into product translation, 18% into HD rotation, and 9% into HD vibration

Hydrogen storage by reaction between metallic amides and imides

International Nuclear Information System (INIS)

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

2007-01-01

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

Medium temperature reaction between lanthanide and actinide carbides and hydrogen; Reaction a temperature moyenne entre les monocarbures de lanthanides et d'actinides et l'hydrogene

Energy Technology Data Exchange (ETDEWEB)

Dean, G; Lorenzelli, R; Pascard, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1964-07-01

Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C{sub 1-x}, H{sub 2x}). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [French] Les monocarbures d'actinides et de lanthanides fixent reversiblement de l'hydrogene a temperature peu elevee, a peu pres dans les memes conditions que les metaux purs correspondants. L'hydrogene penetre dans le reseau des carbures par l'intermediaire des lacunes de carbone, et la quantite totale fixee est approximativement egale a deux atomes d'hydrogene par lacune initiale. Les produits obtenus peuvent donc etre consideres comme des carbohydrures de formule generale M(C{sub 1-x}, H{sub 2x}). La structure d'origine CFC, type NaCl est conservee, mais avec une forte expansion, dans le cas des carbures d'actinides. En revanche, l'hydrogenation entraine un changement de phase cristalline avec retour a la structure du metal (HC) pour les carbures de lanthanides. Tous les carbohydrures etudies ont des tensions de decomposition en hydrogene superieures a celles des dihydrures correspondants. (auteurs)

Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

DEFF Research Database (Denmark)

Knap, Hasse Christian; Jørgensen, Solvejg; Kjærgaard, Henrik Grum

2015-01-01

The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHand...

The Third Dimension of a More O'Ferrall-Jencks Diagram for Hydrogen Atom Transfer in the Isoelectronic Hydrogen Exchange Reactions of (PhX)(2)H(•) with X = O, NH, and CH(2).

Science.gov (United States)

Cembran, Alessandro; Provorse, Makenzie R; Wang, Changwei; Wu, Wei; Gao, Jiali

2012-11-13

A critical element in theoretical characterization of the mechanism of proton-coupled electron transfer (PCET) reactions, including hydrogen atom transfer (HAT), is the formulation of the electron and proton localized diabatic states, based on which a More O'Ferrall-Jencks diagram can be represented to determine the step-wise and concerted nature of the reaction. Although the More O'Ferrall-Jencks diabatic states have often been used empirically to develop theoretical models for PCET reactions, the potential energy surfaces for these states have never been determined directly based on first principles calculations using electronic structure theory. The difficulty is due to a lack of practical method to constrain electron and proton localized diabatic states in wave function or density functional theory calculations. Employing a multistate density functional theory (MSDFT), in which the electron and proton localized diabatic configurations are constructed through block-localization of Kohn-Sham orbitals, we show that distinction between concerted proton-electron transfer (CPET) and HAT, which are not distinguishable experimentally from phenomenological kinetic data, can be made by examining the third dimension of a More O'Ferrall-Jencks diagram that includes both the ground and excited state potential surfaces. In addition, we formulate a pair of effective two-state valence bond models to represent the CPET and HAT mechanisms. We found that the lower energy of the CPET and HAT effective diabatic states at the intersection point can be used as an energetic criterion to distinguish the two mechanisms. In the isoelectronic series of hydrogen exchange reaction in (PhX)(2)H(•), where X = O, NH, and CH(2), there is a continuous transition from a CPET mechanism for the phenoxy radical-phenol pair to a HAT process for benzyl radical and toluene, while the reaction between PhNH(2) and PhNH(•) has a mechanism intermediate of CPET and HAT. The electronically nonadiabatic

Medium temperature reaction between lanthanide and actinide carbides and hydrogen

International Nuclear Information System (INIS)

Dean, G.; Lorenzelli, R.; Pascard, R.

1964-01-01

Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C 1-x , H 2x ). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [fr

Exploring Hydrogen Evolution and the Overpotential

Science.gov (United States)

Lyon, Yana A.; Roberts, Adrienne A.; McMillin, David R.

2015-01-01

The laboratory experiment described provides insight into the energetics of hydrogen evolution at an electrode as well as the intrinsic barrier that typically impedes reaction. In the course of the exercise, students find that Sn(s) is thermodynamically capable of combining with protons to form hydrogen, but that the direct reaction occurs at a…

Influence of the concentration of borohydride towards hydrogen production and escape for borohydride oxidation reaction on Pt and Au electrodes - experimental and modelling insights

Science.gov (United States)

Olu, Pierre-Yves; Bonnefont, Antoine; Braesch, Guillaume; Martin, Vincent; Savinova, Elena R.; Chatenet, Marian

2018-01-01

The Borohydride Oxidation Reaction (BOR), the anode reaction in a Direct borohydride fuel cell (DBFC), is complex and still poorly understood, which impedes the development and deployment of the DBFC technology. In particular, no practical electrocatalyst is capable to prevent gaseous hydrogen generation and escape from its anode upon operation, which lowers the fuel-efficiency of the DBFC and raises safety issues in operation. The nature of the anode electrocatalysts strongly influences the hydrogen escape characteristics of the DBFC, which demonstrates how important it is to isolate the BOR mechanism in conditions relevant to DBFC operation. In this paper, from a selected literature review and BOR experiments performed in differential electrochemical mass spectrometry (DEMS) in a wide range of NaBH4 concentration (5-500 mM), a microkinetic model of the BOR for both Pt and Au surfaces is proposed; this model takes into account the hydrogen generation and escape.

In-situ investigation of hydrogen evolution behavior in vanadium redox flow batteries

International Nuclear Information System (INIS)

Wei, L.; Zhao, T.S.; Xu, Q.; Zhou, X.L.; Zhang, Z.H.

2017-01-01

Highlights: • An in-situ method to investigate hydrogen evolution in VRFBs is developed. • The rate of hydrogen evolution during battery operation is quantified. • The gas evolution behaviors in the charge process of VRFBs are observed. - Abstract: In this work, we conceived and fabricated a three-electrode electrochemical cell and transparent vanadium redox flow battery to in-situ investigate the hydrogen evolution reaction during battery operation. Experimental results show that operating temperature has a strong influence on the HER rate. In particular, compared with V"3"+ reduction reaction, HER is more sensitive to temperature variation. It is also found that, contrary to the conventional wisdom that side reactions occur at the late stage of the charge process, H_2 evolves at a relatively low SOC. About 0.26 and 1.94 mL H_2 were collected at an early (SOC lower than 20%) and end of the charge process, respectively, suggesting that attention to the hydrogen formation at the negative electrode in the early charge process should also be paid to during long-term battery operations. Moreover, the produced hydrogen gas at the negative side prefers to form macroscopically observable bubbles onto the electrode surface, covering the active sites for vanadium redox reactions, while oxygen evolution (including CO_2 production) at the positive side corrodes electrode surface and introduces certain oxygen-containing functional groups.

Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

International Nuclear Information System (INIS)

Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

1982-01-01

Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

Hydrogen Tunneling in Enzymes and Biomimetic Models

Energy Technology Data Exchange (ETDEWEB)

Layfield, Joshua P.; Hammes-Schiffer, Sharon

2014-04-09

Hydrogen transfer reactions play an important role throughout chemistry and biology. In general, hydrogen transfer reactions encompass proton and hydride transfer, which are associated with the transfer of a positively or negatively charged species, respectively, and proton-coupled electron transfer (PCET), which corresponds to the net transfer of one electron and one proton in the simplest case. Such PCET reactions can occur by either a sequential mechanism, in which the proton or electron transfers first, or a concerted mechanism, in which the electron and proton transfer in a single kinetic step with no stable intermediate. Furthermore, concerted PCET reactions can be subdivided into hydrogen atom transfer (HAT), which corresponds to the transfer of an electron and proton between the same donor and acceptor (i.e., the transfer of a predominantly neutral species), and electron-proton transfer (EPT), which corresponds to the transfer of an electron and proton between different donors and acceptors, possibly even in different directions. In all of these types of hydrogen transfer reactions, hydrogen tunneling could potentially play a significant role. The biomimetic portion was 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, Office of Basic Energy Sciences.

Process chemistry related to hydrogen isotopes

International Nuclear Information System (INIS)

Iwasaki, Matae; Ogata, Yukio

1991-01-01

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

Material Technologies Developments for Solar Hydrogen

International Nuclear Information System (INIS)

Agrafiotis, C.; Pagkoura, C.; Lorentzou, S.; Hoguet, J.C.; Konstandopoulos, A.G.

2006-01-01

The present work presents recent activities of our Laboratory in the field of solar-aided hydrogen production materials and reactor technologies that can be fully integrated into solar thermal power plants. Emphasis is given on structured monolithic solar reactors where ceramic supports optimized to absorb solar radiation and develop sufficiently high temperatures, are coated with active materials to perform a variety of 'solar-aided' reactions such as water splitting or natural gas reforming. Particular examples discussed include properties'' assessment of monolithic ceramic honeycombs used as volumetric solar thermal reactors/receivers, synthesis of active water-splitting redox materials for the production of hydrogen and their tailored deposition upon porous supports and design, operation simulation and performance optimization of structured monolithic solar hydrogen production reactors. (authors)

The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

DEFF Research Database (Denmark)

Knap, Hasse Christian

a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

Reactivity of hydrogen contained in Raney nickel for ethylene hydrogenation studied by means of a tritium tracer

International Nuclear Information System (INIS)

Miyatani, Daisaku; Takeuchi, Toyosaburo.

1979-01-01

Reactivity of hydrogen contained in Raney nickel with ethylene was studied by using a tritium tracer. Hydrogen in Raney nickel was previously labeled with tritium and distinguished from hydrogen introduced during the hydrogenation reaction. The reactivity of the contained hydrogen was determined by measurement of the radioactivity of ethane produced in the hydrogenation. Ethylene reacted with hydrogen in Raney nickel for no supply of hydrogen during the hydrogenation. However, when ethylene was hydrogenated by both hydrogen in Raney nickel and introduced hydrogen, over 99% of the ethylene reacted with the introduced hydrogen and hardly reacted with the contained hydrogen. (author)

Energetics of the lithium-magnesium imide-magnesium amide and lithium hydride reaction for hydrogen storage: An ab initio study

International Nuclear Information System (INIS)

Velikokhatnyi, Oleg I.; Kumta, Prashant N.

2007-01-01

An ab initio study within the density functional theory of the recently described reversible hydrogen storage reaction Mg(NH 2 ) 2 + 2LiH ↔ Li 2 Mg(NH) 2 + 2H 2 has been conducted. The electronic structure, structural parameters, vibrational spectra, and enthalpies of formation of all the reactants and products as well as the heat of the overall reaction at zero and finite temperature have been calculated in the generalized gradient approximation (GGA) to the exchange correlation potential. The heat of the overall reaction is calculated to be 53.4 kJ/mol H 2 in contrast to the experimentally obtained overall heat of reaction of ∼44.1 kJ/mol H 2 . The difference of ∼20% between the experimental and calculated values is discussed

Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

Science.gov (United States)

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

2003-07-01

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

The behavior of hydrogen in metals

International Nuclear Information System (INIS)

Hirabayashi, Makoto

1975-01-01

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

Poisoning by carbon monoxide in the hydrogen exchange reaction between deuterium gas and water preadsorbed on a platinum--alumina catalyst

International Nuclear Information System (INIS)

Iida, I.; Tamaru, K.

1979-01-01

Poisoning by carbon monoxide in the exchange reaction between deuterium and the water preadsorbed on a platinum--alumina catalyst was studied, by measuring not only the rate of reaction but also its kinetic behavior and the adsorption of reactants on the catalyst surface. The shape of the poisoning curve is closely associated with the kinetic behavior and exhibited an abrupt change on freezing the adsorbed water below 273 0 K. When the rate is proportional to deuterium pressure and independent of the amount of water adsorbed, the exchange rate dropped sharply by carbon monoxide adsorbed of a few percent coverage without any marked changes in the amount and the rate of hydrogen adsorption on the platinum surface. However, at temperatures lower than 273 0 K and at higher deuterium pressures, the rate depends not on the deuterium pressure but on the amount of water adsorbed. The migration of hydrogen in or through the adsorbed water is seemingly sufficiently suppressed by freezing to control the overall reaction rate. In this case, a small amount of adsorption of carbon monoxide did not show any toxicity, but then a steep poisoning started accompanying a change in the kinetic behavior. It was accordingly demonstrated that the mechanism of the reaction may be better understood by studying poisoning and measuring adsorption, overall rate, and kinetic behavior

Hydrogen. A small molecule with large impact

Energy Technology Data Exchange (ETDEWEB)

Gehrke, H.; Ruthardt, K.; Mathiak, J.; Roosen, C. [Uhde GmbH, Dortmund (Germany)

2010-12-30

The first section of the presentation will provide general information about hydrogen including physical data, natural abundance, production and consumption figures. This will be followed by detailed information about current industrial production routes for hydrogen. Main on-purpose production for hydrogen is by classical steam reforming (SR) of natural gas. A brief overview of most important steps in stream reforming is given including reforming section, CO conversion and gas purification. Also the use of heavier than methane feedstocks and refinery off-gases is discussed. Alternative routes for hydrogen production or production of synthesis gas are autothermal reforming (ATR) or partial oxidation (POX). Pros and Cons for each specific technology are given and discussed. Gasification, especially gasification of renewable feedstocks, is a further possibility to produce hydrogen or synthesis gas. New developments and current commercial processes are presented. Hydrogen from electrolysis plants has only a small share on the hydrogen production slate, but in some cases this hydrogen is a suitable feedstock for niche applications with future potential. Finally, production of hydrogen by solar power as a new route is discussed. The final section focuses on the use of hydrogen. Classical applications are hydrogenation reactions in refineries, like HDS, HDN, hydrocracking and hydrofinishing. But, with an increased demand for liquid fuels for transportation or power supply, hydrogen becomes a key player in future as an energy source. Use of hydrogen in synthesis gas for the production of liquid fuels via Fischer-Tropsch synthesis or coal liquefaction is discussed as well as use of pure hydrogen in fuel cells. Additional, new application for biomass-derived feedstocks are discussed. (orig.)

A Study on the Pressure-Composition Isotherm for the Reaction of ZrCo with Hydrogen

International Nuclear Information System (INIS)

Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Sihyung; Kim, Kwangrag; Ahn, Dohee; Sohn, Soonhwan; Song, Kyumin

2007-01-01

The intermetallic compound of ZrCo which is one of the promising getters for the handling, transport, and storage of tritium has been extensively studied and widely used due to its attractive properties as a tritium getter. At a typical storage temperature of room temperature, the ZrCo-H system has an equilibrium pressure of about 10 -3 Pa for an absorption. The immobilized gas can be recovered at a moderate temperature. Also, from the point of view of safety, the ZrCo and its hydrides have proven to be much less pyrophoric than uranium and its hydrides are the most widely used as a tritium getter. In the current study, the pressure-composition isotherm for the reaction of ZrCo with hydrogen was derived to evaluate its absorption and release characteristics. This provides useful information on the stability and the storage capabilities of ZrCo and the subsequent release of the hydrogen on a heating

A Study on the Pressure-Composition Isotherm for the Reaction of ZrCo with Hydrogen

Energy Technology Data Exchange (ETDEWEB)

Kim, Sunmi; Paek, Seungwoo; Lee, Minsoo; Kim, Sihyung; Kim, Kwangrag; Ahn, Dohee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Sohn, Soonhwan; Song, Kyumin [Electric Power Research Institute, Daejeon (Korea, Republic of)

2007-10-15

The intermetallic compound of ZrCo which is one of the promising getters for the handling, transport, and storage of tritium has been extensively studied and widely used due to its attractive properties as a tritium getter. At a typical storage temperature of room temperature, the ZrCo-H system has an equilibrium pressure of about 10{sup -3} Pa for an absorption. The immobilized gas can be recovered at a moderate temperature. Also, from the point of view of safety, the ZrCo and its hydrides have proven to be much less pyrophoric than uranium and its hydrides are the most widely used as a tritium getter. In the current study, the pressure-composition isotherm for the reaction of ZrCo with hydrogen was derived to evaluate its absorption and release characteristics. This provides useful information on the stability and the storage capabilities of ZrCo and the subsequent release of the hydrogen on a heating.

Superaerophobic Ultrathin Ni-Mo Alloy Nanosheet Array from In Situ Topotactic Reduction for Hydrogen Evolution Reaction.

Science.gov (United States)

Zhang, Qian; Li, Pengsong; Zhou, Daojin; Chang, Zheng; Kuang, Yun; Sun, Xiaoming

2017-11-01

Hydrogen evolution reaction (HER) has prospect to becoming clean and renewable technology for hydrogen production and Ni-Mo alloy is among the best HER catalysts in alkaline electrolytes. Here, an in situ topotactic reduction method to synthesize ultrathin 2D Ni-Mo alloy nanosheets for electrocatalytic hydrogen evolution is reported. Due to its ultrathin structure and tailored composition, the as-synthesized Ni-Mo alloy shows an overpotential of 35 mV to reach a current density of 10 mA cm -2 , along with a Tafel slope of 45 mV decade -1 , demonstrating a comparable intrinsic activity to state-of-art commercial Pt/C catalyst. Besides, the vertically aligned assemble structure of the 2D NiMo nanosheets on conductive substrate makes the electrode "superaerophobic," thus leading to much faster bubble releasing during HER process and therefore shows faster mass transfer behavior at high current density as compared with drop drying Pt/C catalyst on the same substrate. Such in situ topotactic conversion finds a way to design and fabricate low-cost, earth-abundant non-noble metal based ultrathin 2D nanostructures for electrocatalytic issues. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A contribution to the study of the hydrogen evolution reaction on tungsten under water electrolysis conditions

International Nuclear Information System (INIS)

Tanaka, A.A.; Avaca, L.A.; Gonzalez, E.R.

1984-01-01

Tungsten, electrodeposited on mild steel from aqueous solutions, has been shown to behave similarly to electroplated nickel when used as a cathode in 28% KOH at 60 0 C and current densities of the order of 135 mA cm -2 . When compared with bare mild steel the tungsten cathodes present an overpotential 50mV higher, but this is largely compensated by the extremely higher chemical stability of the deposits in the electrolyte. This is particularly important when the electrolyzer is going to be used in an intermittent fashion. In the present work, the hydrogen evolution reaction was studied on pure and electrodeposited tungsten electrodes in alkaline solutions through the recording of steady-state polarization curves. By comparison of the experimental electrochemical parameters with those predicted by theory, it was established that the mechanism of the reaction is of the type Volmer-Heyrowsky, with the electrochemical desorption reaction being the rate determining step

High capacity hydrogen storage nanocomposite materials

Science.gov (United States)

Zidan, Ragaiy; Wellons, Matthew S.

2017-12-12

A novel hydrogen absorption material is provided comprising a mixture of a lithium hydride with a fullerene. The subsequent reaction product provides for a hydrogen storage material which reversibly stores and releases hydrogen at temperatures of about 270.degree. C.

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

International Nuclear Information System (INIS)

Cohen, S.G.

1976-10-01

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

Dynamics of the reaction of the N+ ion with hydrogen isotopes and helium

International Nuclear Information System (INIS)

Ruska, W.E.W.

1976-01-01

Molecular beam techniques were used to study the reactive and non-reactive scattering of the nitrogen positive ion from hydrogen isotopes and helium, at energies above the stability limit for spectator stripping. Reactive scattering was observed from H 2 and HD targets. Non-reactive scattering was observed from H 2 and D 2 targets, and from He at one energy. A correlation diagram for the system is presented and compared with the available a priori calculations. Two surfaces are expected to lead to reaction. One is a 3 A 2 - 3 PI surface, the other, a 3 B 1 - 3 Σ - surface. Collinear approaches are expected to be most reactive on the 3 B 1 - 3 Σ - surface; noncollinear, on the 3 A 1 - 3 PI surface. Theoretical models are presented in which an incident hard sphere A, representing the projectile ion, strikes one of a pair of hard spheres B-C representing the B hydrogen molecule. After an impulsive A-B collision, an impulsive B-C collision may take place. The relative energy of A to B is then examined, and a reactive event is considered to have occurred if the energy is less than the dissociation energy for the A-B molecule. This model is treated both in the collinear case and in three dimensions. A graphical technique for the collinear case is summarized and applied to reaction on the 3 B 1 - 3 Σ - surface. An integral equation for the three-dimensional case is developed. A synthesis of two treatments, representing the behavior of the system on both reactive surfaces, and considering the charge-exchange channel, correctly predicts the observed product distribution. Predictions are also presented for the as yet unobserved case of reactive scattering from a D 2 target

Hydrogen gas getters: Susceptibility to poisoning

International Nuclear Information System (INIS)

Mroz, E.J.; Dye, R.C.; Duke, J.R.; Weinrach, J.

1998-01-01

About 40% (∼9,000) of the ∼23,000 transuranic (TRU) waste drums at Los Alamos National Laboratory (LANL) are presently unshippable because conservative calculations suggest that the hydrogen concentration may exceed the lower explosive limit for hydrogen. This situation extends across nearly all DOE sites holding and generating TRU waste. The incorporation of a hydrogen getter such as DEB into the waste drums (or the TRUPACT II shipping containers) could substantially mitigate the explosion risk. The result would be to increase the number of drums that qualify for transportation to the Waste Isolation Pilot Plant (WIPP) without having to resort to expensive re-packaging or waste treatment technologies. However, before this approach can be implemented, key technical questions must be answered. Foremost among these is the question of whether the presence of other chemical vapors and gases in the drum might poison the catalytic reaction between hydrogen and DEB. This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of this project was to obtain fundamental information on the chemical mechanism of the catalytic reaction of hydrogen with one commonly used hydrogen getter, DEB. Experiments with these materials showed that the method of exposure affects the nature of the reaction products. The results of this work contributed to the development of a mechanistic model of the reaction

Ultrafine Iridium Oxide Nanorods Synthesized by Molten Salt Method toward Electrocatalytic Oxygen and Hydrogen Evolution Reactions

International Nuclear Information System (INIS)

Ahmed, Jahangeer; Mao, Yuanbing

2016-01-01

Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.

Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

Science.gov (United States)

Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

2017-10-19

An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interstellar hydrogen bonding

Science.gov (United States)

Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

2018-06-01

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

Science.gov (United States)

Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

2015-02-21

Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for

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

Science.gov (United States)

Dhooge, Patrick M.

1987-10-13

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

Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

International Nuclear Information System (INIS)

Liu Tong; Zhang Tongwen; Zhu Mu; Qin Chenggong

2012-01-01

Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al 3 Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi 3 were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.

Optimization of hydrogen production via coupling of the Fischer-Tropsch synthesis reaction and dehydrogenation of cyclohexane in GTL technology

International Nuclear Information System (INIS)

Rahimpour, M.R.; Bahmanpour, A.M.

2011-01-01

In this study, a thermally-coupled reactor containing the Fischer-Tropsch synthesis reaction in the exothermic side and dehydrogenation of cyclohexane in the endothermic side has been modified using a hydrogen perm-selective membrane as the shell of the reactor to separate the produced hydrogen from the dehydrogenation process. Permeated hydrogen enters another section called permeation side to be collected by Argon, known as the sweep gas. This three-sided reactor has been optimized using differential evolution (DE) method to predict the conditions at which the reactants' conversion and also the hydrogen recovery yield would be maximized. Minimizing the CO 2 and CH 4 yield in the reactor's outlet as undesired products is also considered in the optimization process. To reach this goal, optimal initial molar flow rate and inlet temperature of three sides as well as pressure of the exothermic side have been calculated. The obtained results have been compared with the conventional reactor data of the Research Institute of Petroleum Industry (RIPI), the membrane dual - type reactor suggested for Fischer-Tropsch synthesis, and the membrane coupled reactor presented for methanol synthesis. The comparison shows acceptable enhancement in the reactor's performance and that the production of hydrogen as a valuable byproduct should also be considered.

Hydrogen system (hydrogen fuels feasibility)

International Nuclear Information System (INIS)

Guarna, S.

1991-07-01

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

Low energy cross section data for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions with atoms and molecules

International Nuclear Information System (INIS)

Okuno, Kazuhiko

2007-04-01

Systematic cross section measurements for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions in low energy collisions with atoms and molecules have been performed continuously by the identical apparatus installed with an octo-pole ion beam guide (OPIG) since 1980 till 2004. Recently, all of accumulated cross section data for a hundred collision systems has been entered into CMOL and CHART of the NIFS atomic and molecular numerical database together with some related cross section data. In this present paper, complicated ion-molecule reactions in hydrogen systems are revealed and the brief outlines of specific properties in low energy charge transfer collisions of multiply charged ions with atoms and molecules are introduced. (author)

Electrochemical behavior of NixW1−x materials as catalyst for hydrogen evolution reaction in alkaline media

International Nuclear Information System (INIS)

Oliver-Tolentino, Miguel A.; Arce-Estrada, Elsa M.; Cortés-Escobedo, Claudia A.; Bolarín-Miro, Ana M.; Sánchez-De Jesús, Félix; González-Huerta, Rosa de G.; Manzo-Robledo, Arturo

2012-01-01

Highlights: ► The electrochemical techniques used in this study elucidated the Ni–W surface state. ► The Ni–W materials were effective for the hydrogen evolution reaction. ► The prepared alloys exhibited higher catalytic activity than their precursors. ► The preparation method is relatively simple and effective procedure. - Abstract: In the present work, results of electrochemical evaluation, as well as morphological and structural characterization of Ni x W 1−x materials with x = 0.77, 0.64, 0.4, 0.19 and 0.07 processed by means of high energy ball milling from high purity powders are presented. Also, the electrocatalytic performance on the hydrogen evolution reaction (HER) of the Ni x W 1−x materials evaluated by linear polarization and cyclic voltammetry techniques in alkaline media at room temperature is discussed. The structural and morphological characterization of the as-prepared materials was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated a small-particle clusters and solid solution formation. According to the kinetics parameters the best electrocatalytic activity was observed at Ni 64 W 36 .

Development of a new reduced hydrogen combustion mechanism with NO_x and parametric study of hydrogen HCCI combustion using stochastic reactor model

International Nuclear Information System (INIS)

Maurya, Rakesh Kumar; Akhil, Nekkanti

2017-01-01

Highlights: • PDF based stochastic reactor model used for study of hydrogen HCCI engine. • New reduced hydrogen combustion mechanism with NOx developed (30 species and 253 reactions). • Mechanism predicts cylinder pressure and captures NO_x emission trend with sufficient accuracy. • Parametric study of hydrogen HCCI engine over wide range of speed and load conditions. • Hydrogen HCCI operating range increases with compression ratio & decreases with engine speed. - Abstract: Hydrogen is a potential alternative and renewable fuel for homogenous charge compression ignition (HCCI) engine to achieve higher efficiency and zero emissions of CO, unburned hydrocarbons as well as other greenhouse gases such as CO_2 and CH_4. In this study, a detailed hydrogen oxidation mechanism with NO_x was developed by incorporating additional species and NO_x reactions to the existing hydrogen combustion mechanism (10 species and 40 reactions). The detailed hydrogen combustion mechanism used in this study consists of 39 species and 311 reactions. A reduced mechanism consisting 30 species and 253 reactions was also developed by using directed relation graph (DRG) method from detailed mechanism. Developed mechanisms were validated with experimental data by HCCI engine simulation using stochastic reactor model. Sensitivity analysis was performed to identify the most important reactions in hydrogen combustion and NO_x formation in HCCI engine. Pathway analysis was also performed to analyze the important reaction pathways at different temperatures. Results revealed that H2 + HO2 [=] H + H2O2 and O2 + NNH [=] N2 + HO2 are the most significant reactions in the hydrogen HCCI combustion and NO_x formation respectively. Detailed parametric study of HCCI combustion was conducted using developed chemical kinetic model. Numerical simulations are performed at different engine operating condition by varying engine speed (1000–3000 rpm), intake air temperature (380–460 K), and compression

Sorption enhanced reaction process (SERP) for the production of hydrogen

Energy Technology Data Exchange (ETDEWEB)

Hufton, J.; Mayorga, S.; Gaffney, T.; Nataraj, S.; Rao, M.; Sircar, S. [Air Products and Chemicals, Inc., Allentown, PA (United States)

1998-08-01

The novel Sorption Enhanced Reaction Process has the potential to decrease the cost of hydrogen production by steam methane reforming. Current effort for development of this technology has focused on adsorbent development, experimental process concept testing, and process development and design. A preferred CO{sub 2} adsorbent, K{sub 2}CO{sub 3} promoted hydrotalcite, satisfies all of the performance targets and it has been scaled up for process testing. A separate class of adsorbents has been identified which could potentially improve the performance of the H{sub 2}-SER process. Although this material exhibits improved CO{sub 2} adsorption capacity compared to the HTC adsorbent, its hydrothermal stability must be improved. Single-step process experiments (not cyclic) indicate that the H{sub 2}-SER reactor performance during the reaction step improves with decreasing pressure and increasing temperature and steam to methane ratio in the feed. Methane conversion in the H{sub 2}-SER reactor is higher than for a conventional catalyst-only reactor operated at similar temperature and pressure. The reactor effluent gas consists of 90+% H{sub 2}, balance CH{sub 4}, with only trace levels (< 50 ppm) of carbon oxides. A best-case process design (2.5 MMSCFD of 99.9+% H{sub 2}) based on the HTC adsorbent properties and a revised SER process cycle has been generated. Economic analysis of this design indicates the process has the potential to reduce the H{sub 2} product cost by 25--31% compared to conventional steam methane reforming.

An efficient route for catalytic activity promotion via hybrid electro-depositional modification on commercial nickel foam for hydrogen evolution reaction in alkaline water electrolysis

Energy Technology Data Exchange (ETDEWEB)

Ma, Guanshui; He, Yongwei; Wang, Mei; Zhu, Fuchun; Tang, Bin [Research Institute of Surface Engineering, Taiyuan University of Technology, Yingze West Road 79, Taiyuan 030024 (China); Wang, Xiaoguang, E-mail: wangxiaog1982@163.com [Research Institute of Surface Engineering, Taiyuan University of Technology, Yingze West Road 79, Taiyuan 030024 (China); International Iberian Nanotechnology Laboratory (INL), 4715-330 Braga (Portugal)

2014-09-15

Highlights: • Mono-Cu surface modification depress the HER activity of Ni-foam. • Hybrid Ni-foam/Cu0.01/Co0.05 exhibits superior HER performance. • Layer-by-layer structure may contribute to a synergistic promoting effect. - Abstract: In this paper, the single- and hybrid-layered Cu, Ni and Co thin films were electrochemically deposited onto the three-dimensional nickel foam as composite cathode catalyst for hydrogen evolution reaction in alkaline water electrolysis. The morphology, structure and chemical composition of the electrodeposited composite catalysts were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Electrochemical measurement depicted that, for the case of the monometallic layered samples, the general activity for hydrogen evolution reaction followed the sequence: Ni-foam/Ni > Ni-foam/Co > bare Ni-foam > Ni-foam/Cu. It is noteworthy that, the hybrid-layered Ni-foam/Cu0.01/Co0.05 exhibited the highest catalytic activity towards hydrogen evolution reaction with the current density as high as 2.82 times that of the bare Ni-foam. Moreover, both excellent electrochemical and physical stabilities can also be acquired on the Ni-foam/Cu0.01/Co0.05, making this hybrid-layered composite structure as a promising HER electro-catalyst.

The evaluation of the polarization resistance in a tubular electrode and its application to the hydrogen electrode reaction

International Nuclear Information System (INIS)

Montero, M.A.; Marozzi, C.A.; Chialvo, M.R. Gennero de; Chialvo, A.C.

2007-01-01

An alternative method for the determination of the kinetic parameters involved in the elementary steps of the reaction mechanism of the hydrogen electrode reaction is proposed. It is based on the determination of the variation of the polarization resistance in a tubular platinum electrode with a laminar flow of electrolyte as a function of the activity of protons of the electrolyte solution. A theoretical expression that relates the experimental variables and the equilibrium polarization resistance is developed, which takes into account the current distribution along the electrode surface. The results are compared with others obtained previously, contributing to the verification of the kinetic mechanism through a completely different experimental procedure

Magnesium for Hydrogen Storage

DEFF Research Database (Denmark)

Pedersen, Allan Schrøder; Kjøller, John; Larsen, B.

1983-01-01

A study of the hydrogenation characteristics of fine magnesium powder during repeated cycling has been performed using a high-pressure microbalance facility. No effect was found from the cycling regarding kinetics and storage capacity. The reaction rate of the absorption process was fast...... at temperatures around 600 K and above, but the reversed reaction showed somewhat slower kinetics around 600 K. At higher temperatures the opposite was found. The enthalpy and entropy change by the hydrogenation, derived from pressure-concentration isotherms, agree fairly well with those reported earlier....

Synthesis of Fe-Al nanoparticles by hydrogen plasma-metal reaction

CERN Document Server

Liu Tong; Li Xing Guo

2003-01-01

Fe-Al nanoparticles of eight kinds have been prepared by hydrogen plasma-metal reaction. The morphology, crystal structure, and chemical composition of the nanoparticles obtained were investigated by transmission electron microscopy (TEM), x-ray diffractometry (XRD), and induction-coupled plasma spectroscopy. The particle size was determined by TEM and Brunaumer-Emmet-Teller gas adsorption. It was found that all the nanoparticles have spherical shapes, with average particle size in the range of 29-46 nm. The oxide layer in nanoparticles containing Al after passivation is not observable by XRD and TEM. The Al contents in Fe-Al ultrafine particles are about 1.2-1.5 times those in the master alloys. The evaporation speeds of Al and Fe in Fe-Al alloys are mutually accelerated at a certain composition. The crystal structures of the Fe-Al nanoparticles vary with the composition of the master alloys. Pure Fe sub 3 Al (D0 sub 3) and FeAl (B2) structures are successfully produced with 15 and 25 at.% Al in bulks, respe...

Isotope exchange reactions in hydrogen mixtures

International Nuclear Information System (INIS)

Czaplinski, W.; Gula, A.; Kravtsov, A.; Mikhailov, A.; Popov, N.

1990-12-01

The rates of isotopic exchange for the excited states of muonic hydrogen are calculated as functions of collision energy. Ground state population q 1s for different collision energies, target densities and isotope concentrations is obtained. It is shown that for principal quantum numbers n > 5 the isotopic exchange still considerably influences the value of q 1s . (author)

Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

KAUST Repository

Michalak, William D.; Krier, James M.; Komvopoulos, Kyriakos; Somorjai, Gabor A.

2013-01-01

hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical

When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms.

Science.gov (United States)

Petković, Milena; Nakarada, Đura; Etinski, Mihajlo

2018-05-25

Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra-atomic and inter-atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange-correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange-correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Trapping and detrapping of hydrogen in graphite materials exposed to hydrogen gas

International Nuclear Information System (INIS)

Atsumi, Hisao; Iseki, Michio; Shikama, Tatsuo.

1994-01-01

Measurements of hydrogen solubility have been performed for several unirradiated and neutron-irradiated graphite (and CFC) samples at temperatures between 973 and 1323 K under a ∼10 kPa hydrogen atmosphere. The hydrogen dissolution process has been studied and it is discussed here. The values of hydrogen solubility vary substantially among the samples up to about a factor of 16. A strong correlation has been observed between the values of hydrogen solubility and the degrees of graphitization determined by X-ray diffraction technique. The relation can be extended even for the neutron irradiated samples. Hydrogen dissolution into graphite can be explained with the trapping of hydrogen at defect sites (e.g. dangling carbon bonds) considering an equilibrium reaction between hydrogen molecules and the trapping sites. The migration of hydrogen in graphite is speculated to result from a sequence of detrapping and retrapping events with high energy activation processes. (author)

Hydrogen management in nuclear reactor containment

International Nuclear Information System (INIS)

Iyer, Kannan

2014-01-01

The talk will present the systematic methodology evolved to assess the hydrogen management in nuclear reactor containment during a severe accident. The focus is on the methodology evolved as the full problem is yet to be solved completely. First, the method to quantify mixing of hydrogen is presented. It is demonstrated that buoyancy modified model is adequate to quantify the process satisfactorily. On noting that the hydrogen levels are higher than the safe limits, effort was directed towards mitigating the concentration. Passive Auto-catalytic Recombiners (PAR) were identified as the potential devices for mitigation. Efforts were then directed to model these and a satisfactory one-step reaction derived from a 12 reaction model was evolved. This model was satisfactory when compared with experimental results with hydrogen concentration below 4%. However, the same when extended to hydrogen concentration of 20%, predicts very high concentration thereby indicating the need for experiments at high hydrogen concentration. (author)

Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

Science.gov (United States)

Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

2017-02-01

Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

Design and construction of a photobioreactor for hydrogen production, including status in the field.

Science.gov (United States)

Skjånes, Kari; Andersen, Uno; Heidorn, Thorsten; Borgvang, Stig A

Several species of microalgae and phototrophic bacteria are able to produce hydrogen under certain conditions. A range of different photobioreactor systems have been used by different research groups for lab-scale hydrogen production experiments, and some few attempts have been made to upscale the hydrogen production process. Even though a photobioreactor system for hydrogen production does require special construction properties (e.g., hydrogen tight, mixing by other means than bubbling with air), only very few attempts have been made to design photobioreactors specifically for the purpose of hydrogen production. We have constructed a flat panel photobioreactor system that can be used in two modes: either for the cultivation of phototrophic microorganisms (upright and bubbling) or for the production of hydrogen or other anaerobic products (mixing by "rocking motion"). Special emphasis has been taken to avoid any hydrogen leakages, both by means of constructional and material choices. The flat plate photobioreactor system is controlled by a custom-built control system that can log and control temperature, pH, and optical density and additionally log the amount of produced gas and dissolved oxygen concentration. This paper summarizes the status in the field of photobioreactors for hydrogen production and describes in detail the design and construction of a purpose-built flat panel photobioreactor system, optimized for hydrogen production in terms of structural functionality, durability, performance, and selection of materials. The motivations for the choices made during the design process and advantages/disadvantages of previous designs are discussed.

Stand alone solution for generation and storage of hydrogen and electric energy

International Nuclear Information System (INIS)

Gany, Alon; Elitzur, Shani; Valery

2015-01-01

A novel method enabling safe, simple, and controllable production, storage, and use of hydrogen as well as compact electric energy storage and generation via hydrogen- oxygen fuel cells has been developed. The technology indicates, in our opinion, a significant milestone in the search for practical utilization of hydrogen as an alternative energy source. It consists of an original thermal-chemical treatment / activation of aluminum powders to react spontaneously with water to produce hydrogen at regular conditions according to the reaction Al+3H 2 O=Al (OH) 3 +3/2H 2 . Only about 1-2% of lithium, based activator is applied, and any type of water including tap water, sea water and waste water may be used, making the method attractive for variety of applications. 11% of hydrogen compared to the aluminum mass can be obtained, and our experiments reveal 90% reaction yield and more. The technology has a clear advantage over batteries, providing specific electric energy of over 2 kW h/kg Al, 5-10 times greater than that of commonly used lithium-ion batteries. Combined with a fuel cell it may be particularly beneficial for stand-alone electric power generators, where there is no access to the grid. Such applications include emergency generators (e.g., in hospitals), electricity backup systems, and power generation in remote communication posts. Automotive applications may be considered as well. The technology provides green electric energy and quiet operation as well as additional heat energy resulting mainly from the exothermic aluminum-water reaction. (full text)

Hydrogen production from water: Recent advances in photosynthesis research

Energy Technology Data Exchange (ETDEWEB)

Greenbaum, E.; Lee, J.W. [Oak Ridge National Lab., TN (United States). Chemical Technology Div.

1997-12-31

The great potential of hydrogen production by microalgal water splitting is predicated on quantitative measurement of the algae`s hydrogen-producing capability, which is based on the following: (1) the photosynthetic unit size of hydrogen production; (2) the turnover time of photosynthetic hydrogen production; (3) thermodynamic efficiencies of conversion of light energy into the Gibbs free energy of molecular hydrogen; (4) photosynthetic hydrogen production from sea water using marine algae; (5) the potential for research advances using modern methods of molecular biology and genetic engineering to maximize hydrogen production. ORNL has shown that sustained simultaneous photoevolution of molecular hydrogen and oxygen can be performed with mutants of the green alga Chlamydomonas reinhardtii that lack a detectable level of the Photosystem I light reaction. This result is surprising in view of the standard two-light reaction model of photosynthesis and has interesting scientific and technological implications. This ORNL discovery also has potentially important implications for maximum thermodynamic conversion efficiency of light energy into chemical energy by green plant photosynthesis. Hydrogen production performed by a single light reaction, as opposed to two, implies a doubling of the theoretically maximum thermodynamic conversion efficiency from {approx}10% to {approx}20%.

Storage and production of hydrogen for fuel cell applications

Science.gov (United States)

Aiello, Rita

The increased utilization of proton-exchange membrane (PEM) fuel cells as an alternative to internal combustion engines is expected to increase the demand for hydrogen, which is used as the energy source in these systems. The objective of this work is to develop and test new methods for the storage and production of hydrogen for fuel cells. Six ligand-stabilized hydrides were synthesized and tested as hydrogen storage media for use in portable fuel cells. These novel compounds are more stable than classical hydrides (e.g., NaBH4, LiAlH4) and react to release hydrogen less exothermically upon hydrolysis with water. Three of the compounds produced hydrogen in high yield (88 to 100 percent of the theoretical) and at significantly lower temperatures than those required for the hydrolysis of NaBH4 and LiAlH4. However, a large excess of water and acid were required to completely wet the hydride and keep the pH of the reaction medium neutral. The hydrolysis of the classical hydrides with steam can overcome these limitations. This reaction was studied in a flow reactor and the results indicate that classical hydrides can be hydrolyzed with steam in high yields at low temperatures (110 to 123°C) and in the absence of acid. Although excess steam was required, the pH of the condensed steam was neutral. Consequently, steam could be recycled back to the reactor. Production of hydrogen for large-scale transportation fuel cells is primarily achieved via the steam reforming, partial oxidation or autothermal reforming of natural gas or the steam reforming of methanol. However, in all of these processes CO is a by-product that must be subsequently removed because the Pt-based electrocatalyst used in the fuel cells is poisoned by its presence. The direct cracking of methane over a Ni/SiO2 catalyst can produce CO-free hydrogen. In addition to hydrogen, filamentous carbon is also produced. This material accumulates on the catalyst and eventually deactivates it. The Ni/SiO2 catalyst

Anomalous deuteron to hydrogen ratio in naturally occuring fission reactions and the possibility of deuteron disintegration

International Nuclear Information System (INIS)

Shaheen, M.; Ragheb, M.

1992-01-01

A hypothesis is presented for explaining the experimentally determined anomalous D/H ratio observed in the samples from the naturally occuring fission reaction in the Oklo phenomenon. No other explanation has been given, to the best knowledge, for the large difference between the measured D/H ratio in the Oklo samples and the expected values in a fission neutron spectrum. A multicomponent system consisting of hydrogen, deuterium, tritium and helium nuclei is considered. An analytical solution is derived and solved using as boundary conditions the experimentally determined value of the D/H ratio. The solution of the rate equations for hydrogen and deuteron concentrations, assuming a pure fission process without a deuteron sink term, yields a D/H ratio of 445 ppm for a reaction in which the fluence of neutrons is 10 21 n/cm 2 . This exceeds the experimentally observed value of 127 ppm, and the naturally occuring value of 150 ppm. Solving the same rate equations accounting for a deuterium sink term using a hypothesis of deuteron disintegration, and the experimentally observed value of 127 ppm yields a deuteron disintegration constant of 7.47*10 -14 s -1 . Deuteron disintegration would provide a neutron source, in addition to the fission neutrons, driving a subcritical chain reaction over an extended period of time. Relationship of the presented hypothesis to the Vlasov theory of an annihilation meteorite impact explosion explaining the experimentally observed anomalous 235 U/ 238 U ratio, and to the suggestion of deuteron disintegration as a possible explanation of some observations of deuterium dissociation in palladium and titanium electrodes is discussed. The tritium andhelium-3 rate equations are further solved under the deuteron disintegration hypothesis and the relationship of the present work to the work by JONES et al. is discussed. (author) 16 refs.; 7 figs.; 2 tabs

Noncatalytic hydrogenation of decene-1 with hydrogen accumulated in a hybrid carbon nanostructure in nanosized membrane reactors

Science.gov (United States)

Soldatov, A. P.

2014-08-01

Studies on the creation of nanosized membrane reactors (NMRs) of a new generation with accumulated hydrogen and a regulated volume of reaction zone were continued at the next stage. Hydrogenation was performed in the pores of ceramic membranes with hydrogen preliminarily adsorbed in mono- and multilayered orientated carbon nanotubes with graphene walls (OCNTGs)—a new hybrid carbon nanostructure formed on the inner pore surface. Quantitative determination of hydrogen adsorption in OCNTGs was performed using TRUMEM ultrafiltration membranes with D av = 50 and 90 nm and showed that hydrogen adsorption was up to ˜1.5% of the mass of OCNTG. The instrumentation and procedure for noncatalytic hydrogenation of decene-1 at 250-350°C using hydrogen accumulated and stored in OCNTG were developed. The conversion of decene-1 into decane was ˜0.2-1.8% at hydrogenation temperatures of 250 and 350°C, respectively. The rate constants and activation energy of hydrogenation were determined. The latter was found to be 94.5 kJ/mol, which is much smaller than the values typical for noncatalytic hydrogenations and very close to the values characteristic for catalytic reactions. The quantitative distribution of the reacting compounds in each pore regarded as a nanosized membrane reactor was determined. The activity of hydrogen adsorbed in a 2D carbon nanostructure was evaluated. Possible mechanisms of noncatalytic hydrogenation were discussed.

Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

DEFF Research Database (Denmark)

Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons

2012-01-01

Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved...... performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental...

Free-polymer controlling morphology of α-MoO3 nanobelts by a facile hydrothermal synthesis, their electrochemistry for hydrogen evolution reactions and optical properties

International Nuclear Information System (INIS)

Sinaim, Hathai; Ham, Dong Jin; Lee, Jae Sung; Phuruangrat, Anukorn; Thongtem, Somchai; Thongtem, Titipun

2012-01-01

Highlights: ► MoO 3 nanobelts as an n-type semiconducting material. ► It was successfully synthesized by a facile hydrothermal reaction. ► A promising material with 3.75 eV band gap for hydrogen evolution reaction (HER). - Abstract: Orthorhombic molybdenum oxide (α-MoO 3 ) nanobelts were successfully synthesized by the 100–180 °C and 2–20 h hydrothermal reactions of (NH 4 ) 6 Mo 7 O 24 ·4H 2 O solutions containing 15 ml 2 M acid (HNO 3 , H 2 SO 4 or HCl) with no surfactant and template adding. These products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopy, and electron microscopy (EM). In the present research, the product synthesized by the 180 °C and 20 h hydrothermal reaction of the solution containing HNO 3 was α-MoO 3 nanobelts with >10 μm long and 3 nanobelts were characterized by linear sweep voltammetry (LSV) and Tafel plot, including UV–vis and photoluminescence (PL) spectroscopy. These imply that α-MoO 3 nanobelts show satisfied performance for HER, with the 3.75 eV direct allowed band gap (E g ) due to the charged transition of O 2p → Mo 4d , including the emission of 437 nm wavelength at room temperature.

Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

DEFF Research Database (Denmark)

Kemppainen, Erno; Halme, Janne; Hansen, Ole

2016-01-01

is the evolution and transport of gaseous H2, since HER leads to the continuous formation of H2 bubbles near the electrode. We present a numerical model that includes the transport of both gaseous and dissolved H2, as well as mass exchange between them, and combine it with a kinetic model of HER at platinum (Pt......) nanoparticle electrodes. We study the effect of the diffusion layer thickness and H2 dissolution rate constant on the importance of gaseous transport, and the effect of equilibrium hydrogen coverage and Pt loading on the kinetic and mass transport overpotentials. Gaseous transport becomes significant when...

Some considerations of ''cold fusion'' including the calculation of fusion rates in molecules of hydrogen isotopes

International Nuclear Information System (INIS)

Cowley, S.C.; Kulsrud, R.M.

1989-11-01

We calculate the fusion reaction rates in molecules of hydrogen isotopes. The rates are calculated analytically (for the first time) as an asymptotic expansion in the ratio of the electron mass to the reduced mass of the nucleii. The fusion rates of the P-D, D-D, and D-T reactions are given for a variable electron mass by a simple analytic formula. However, we do not know any mechanism by which a sufficiently localized electron in solid can have an 'effective mass' large enough to explain the result of Fleischman and Pons (FP). This calculation indicates that P-D rates should exceed D-D rates for D-D fusion rates less than approximately 10 -23 per molecule per second. The D-D fusion rate is enhanced by a factor of 10 5 at 10,000 degree K if the excited vibrational states are populated with a Boltzmann distribution and the rotational excitations suppressed. The suggestion that experimental results could be explained by bombardment of cold deuterons by kilovolt deuterons is shown to be an unlikely from an energetic point of view. 12 refs., 3 figs., 1 tab

Hydrogen Tunneling in Enzymes and Biomimetic Models

Energy Technology Data Exchange (ETDEWEB)

Layfield, Joshua P.; Hammes-Schiffer, Sharon

2013-12-20

Hydrogen transfer reactions play an important role throughout chemistry and biology. In general, hydrogen transfer reactions encompass proton and hydride transfer, which are associated with the transfer of a positively or negatively charged species, respectively, and proton-coupled electron transfer (PCET), which corresponds to the net transfer of one electron and one proton in the simplest case. Such PCET reactions can occur by either a sequential mechanism, in which the proton or electron transfers first, or a concerted mechanism, in which the electron and proton transfer in a single kinetic step with no stable intermediate. Furthermore, concerted PCET reactions can be subdivided into hydrogen atom transfer (HAT), which corresponds to the transfer of an electron and proton between the same donor and acceptor (i.e., the transfer of a predominantly neutral species), and electron-proton transfer (EPT), which corresponds to the transfer of an electron and proton between different donors and acceptors, possibly even in different directions. In all of these types of hydrogen transfer reactions, hydrogen tunneling could potentially play a signficant role. The theoretical development portion of this Review was supported by the National Science Foundation under CHE-10-57875. The biological portion of this Review was funded by NIH Grant No. GM056207. The biomimetic portion was supported as part of the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

Salt-assisted clean transfer of continuous monolayer MoS2 film for hydrogen evolution reaction

Science.gov (United States)

Cho, Heung-Yeol; Nguyen, Tri Khoa; Ullah, Farman; Yun, Jong-Won; Nguyen, Cao Khang; Kim, Yong Soo

2018-03-01

The transfer of two-dimensional (2D) materials from one substrate to another is challenging but of great importance for technological applications. Here, we propose a facile etching and residue-free method for transferring a large-area monolayer MoS2 film continuously grown on a SiO2/Si by chemical vapor deposition. Prior to synthesis, the substrate is dropped with water- soluble perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt (PTAS). The as-grown MoS2 on the substrate is simply dipped in water to quickly dissolve PTAS to yield the MoS2 film floating on the water surface, which is subsequently transferred to the desired substrate. The morphological, optical and X-ray photoelectron spectroscopic results show that our method is useful for fast and clean transfer of the MoS2 film. Specially, we demonstrate that monolayer MoS2 film transferred onto a conducting substrate leads to excellent performance for hydrogen evolution reaction with low overpotential (0.29 V vs the reversible hydrogen electrode) and Tafel slope (85.5 mV/decade).

Line-emission cross sections for the charge-exchange reaction between fully stripped carbon and atomic hydrogen in tokamak plasma

International Nuclear Information System (INIS)

Ida, K.; Kato, T.

1992-01-01

Line-emission cross sections of the charge-exchange reaction between fully stripped carbon and atomic hydrogen are measured in the energy range of 18 - 38 keV/amu in tokamak plasmas. The energy dependence of the emission cross sections for the transition of Δn = 8 - 7 and Δn = 7 - 6 and their ratios are compared with theoretical calculations. (author)

Methylation reactions, the redox balance and atherothrombosis: the search for a link with hydrogen sulfide.

Science.gov (United States)

Lupoli, Roberta; Di Minno, Alessandro; Spadarella, Gaia; Franchini, Massimo; Sorrentino, Raffaella; Cirino, Giuseppe; Di Minno, Giovanni

2015-06-01

It is now clear that homocysteine (Hcy) is irreversibly degraded to hydrogen sulfide (H(2)S), an endogenous gasotransmitter that causes in vivo platelet activation via upregulation of phospholipase A2 and downstream boost of the arachidonate cascade. This mechanism involves a transsulfuration pathway. Based on these new data, clinical and experimental models on the relationships between Hcy and folate pathways in vascular disease and information on the Hcy controversy have been reanalyzed in the present review. Most interventional trials focused on Hcy lowering by folate administration did not exclude patients routinely taking the arachidonate inhibitor aspirin. This may have influenced the results of some of these trials. It is also clear that nutritional intake of folate affects several enzymatic reactions of the methionine-Hcy cycle and associated one-carbon metabolism and, thereby, both methylation reactions and redox balance. Hence, it is conceivable that the abnormally high Hcy levels seen in pathologic states reflect a poorly elucidated perturbation of such reactions and of such balance. While it is unknown whether there is an interplay between H2S, methylation reactions, and redox balance, measuring the sole reduction of blood Hcy that follows folate administration may well be an oversimplified approach to a complex biologic perturbation. The need to investigate this complex framework is thoroughly discussed in this article. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

A parametric investigation of hydrogen hcci combustion using a multi-zone model approach

International Nuclear Information System (INIS)

Komninos, N.P.; Hountalas, D.T.; Rakopoulos, C.D.

2007-01-01

The purpose of the present study is to examine the effect of various operating variables of a homogeneous charge compression ignition (HCCI) engine fueled with hydrogen, using a multi-zone model developed by the authors. The multi-zone model consists of zones, which are allotted spatial locations within the combustion chamber. The model takes into account heat transfer between the zones and the combustion chamber walls, providing a spatial temperature distribution during the closed part of the engine cycle, i.e. compression, combustion and expansion. Mass transfer between zones is also accounted for, based on the geometric configuration of the zones, and includes the flow of mass in and out of the crevice regions, represented by the crevice zone. Combustion is incorporated using chemical kinetics based on a chemical reaction mechanism for the oxidation of hydrogen. This chemical reaction mechanism also includes the reactions for nitrogen oxides formation. Using the multi-zone model a parametric investigation is conducted, in order to determine the effect of engine speed, equivalence ratio, compression ratio, inlet pressure and inlet temperature, on the performance, combustion characteristics and emissions of an HCCI engine fueled with hydrogen

First Principles Based Simulation of Reaction-Induced Phase Transition in Hydrogen Storage and Other Materials

Energy Technology Data Exchange (ETDEWEB)

Ge, Qingfeng [Southern Illinois Univ., Carbondale, IL (United States)

2014-08-31

This major part of this proposal is simulating hydrogen interactions in the complex metal hydrides. Over the period of DOE BES support, key achievements include (i) Predicted TiAl₃Hx as a precursor state for forming TiAl₃ through analyzing the Ti-doped NaAlH₄ and demonstrated its catalytic role for hydrogen release; (ii) Explored the possibility of forming similar complex structures with other 3d transition metals in NaAlH₄ as well as the impact of such complex structures on hydrogen release/uptake; (iii) Demonstrated the role of TiAl₃ in hydriding process; (iv) Predicted a new phase of NaAlH₄ that links to Na3AlH6 using first-principles metadynamics; (v) Examined support effect on hydrogen release from supported/encapsulated NaAlH₄; and (vi) Expanded research scope beyond hydrogen storage. The success of our research is documented by the peer-reviewed publications.

Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Yang, Lun [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Xinglong, E-mail: hkxlwu@nju.edu.cn [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Physics, NingBo University, NingBo 315001 (China); Zhu, Xiaoshu [Center for Analysis and Testing, Nanjing Normal University, Nanjing 210093 (China); He, Chengyu; Meng, Ming; Gan, Zhixing [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Chu, Paul K. [Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

2015-06-30

Graphical abstract: - Highlights: • Amorphous nickel/cobalt tungsten sulfides were synthesized by a thermolytic process. • Amorphous NiWS and CoWS could realize hydrogen evolution efficiently. • Ni/Co promotion and annealing alter the porous structure and chemical bonding states. • Active sites on the surface of amorphous WS{sub x} are increased with Ni or Co doping. • Amorphous NiWS and CoWS have immense potentials in water splitting devices. - Abstract: The hydrogen evolution reaction (HER), an appealing solution for future energy supply, requires efficient and inexpensive electrocatalysts with abundant active surface sites. Although crystalline MoS{sub 2} and WS{sub 2} are promising candidates, their activity is dominated by edge sites. Amorphous tungsten sulfide prepared so far lacks the required active sites and its application has thus been hampered. In this work, nickel and cobalt incorporated amorphous tungsten sulfide synthesized by a thermolytic process is demonstrated to enhance the HER efficiency dramatically. The amorphous nickel tungsten sulfide (amorphous NiWS) annealed at 210 °C delivers the best HER performance in this system boasting a Tafel slope of 55 mV per decade and current density of 8.6 mA cm{sup −2} at 250 mV overpotential in a sustained test for 24 h. The introduction of Ni or Co into the catalyst and subsequent thermal treatment alters the porous structure and chemical bonding states thereby increasing the density of active sites on the surface.

A Simple Method To Demonstrate the Enzymatic Production of Hydrogen from Sugar

Science.gov (United States)

Hershlag, Natalie; Hurley, Ian; Woodward, Jonathan

1998-10-01

There is current interest in and concern for the development of environmentally friendly bioprocesses whereby biomass and the biodegradable content of municipal wastes can be converted to useful forms of energy. For example, cellulose, a glucose polymer that is the principal component of biomass and paper waste, can be enzymatically degraded to glucose, which can subsequently be converted by fermentation or further enzymatic reaction to fuels such as ethanol or hydrogen. These products represent alternative energy sources to fossil fuels such as oil. Demonstration of the relevant reactions in high-school and undergraduate college laboratories would have value not only in illustrating environmentally friendly biotechnology for the utilization of renewable energy sources, such as cellulosic wastes, but could also be used to teach the principles of enzyme-catalyzed reactions. In the experimental protocol described here, it has been demonstrated that the common sugar glucose can be used to produce hydrogen using two enzymes, glucose dehydrogenase and hydrogenase. No sophisticated or expensive hydrogen detection equipment is required-only a redox dye, benzyl viologen, which turns purple when it is reduced. The color can be detected by a simple colorimeter. Furthermore, it is shown that the renewable resource cellulose, in its soluble derivative from carboxymethylcellulose, as well as aspen-wood waste, is also a source of hydrogen if the enzyme cellulase is included in the reaction mixture.

Hydrogen sensor

Science.gov (United States)

Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

2010-11-23

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

Hydrogen production by sodium borohydride in NaOH aqueous solution

Science.gov (United States)

Wang, Q.; Zhang, L. F.; Zhao, Z. G.

2018-01-01

The kinetics of hydrolysis reaction of NaBH4 in NaOH aqueous solution is studied. The influence of pH of the NaOH aqueous solution on the rate of hydrogen production and the hydrogen production efficiency are studied for the hydrolysis reaction of NaBH4. The results show that the activation energy of hydrolysis reaction of NaBH4 increased with the increase of the initial pH of NaOH aqueous solution.With the increasing of the initial pH of NaOH aqueous solution, the rate of hydrogen production and hydrogen production efficiency of NaBH4 hydrolysis decrease.

Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

International Nuclear Information System (INIS)

Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

2017-01-01

Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

Science.gov (United States)

Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

2017-05-01

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Electrochemical hydrogen Storage Systems

International Nuclear Information System (INIS)

Macdonald, Digby

2010-01-01

previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin halides. To enable a

Electrochemical hydrogen Storage Systems

Energy Technology Data Exchange (ETDEWEB)

Dr. Digby Macdonald

2010-08-09

described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin

Hydrogen production as a promising nuclear energy application

International Nuclear Information System (INIS)

Vanek, V.

2003-01-01

Hydrogen production from nuclear is a field of application which eventually can outweigh power production by nuclear power plants. There are two feasible routes of hydrogen production. The one uses heat to obtain hydrogen from natural gas through steam reforming of methane. This is an highly energy-consuming process requiring temperatures up to 900 deg C and producing carbon dioxide as a by-product. The other method includes direct thermochemical processes to obtain hydrogen, using sulfuric acid for instance. Sulfuric acid is decomposed thermally by the reaction: H 2 SO 4 -> H 2 O = SO 2 + (1/2) O 2 , followed by the processes I 2 + SO 2 + 2H O -> 2HI + H 2 SO 4 and 2HI -> H 2 + I 2 . The use of nuclear for this purpose is currently examined in Japan and in the US. (P.A.)

Identifying Reaction Pathways and their Environments

DEFF Research Database (Denmark)

Maronsson, Jon Bergmann

Finding the mechanisms and estimating the rate of chemical reactions is an essential part of modern research of atomic scale systems. In this thesis, the application of well established methods for reaction rates and paths to important systems for hydrogen storage is considered before developing...... extensions to further identify the reaction environment for a more accurate rate. Complex borohydrides are materials of high hydrogen storage capacity and high thermodynamic stability (too high for hydrogen storage). In an effort to gain insight into the structural transitions of two such materials, Ca(BH4......-interstitial defects. In good agreement with the experiments, C3-type rotations activate at lower temperature than C2-type rotations. In order to investigate the environment of reaction pathways, a method for finding the ridge between first order saddle points on a multidimensional surface was developed...

Design, construction and implementation of a packed reactor system to study the production of hydrogen by the catalytic reaction of reforming of oxygenated hydrocarbons

International Nuclear Information System (INIS)

Salas Aguilar, Cesar Augusto

2014-01-01

The Laboratorio de Quimica Inorganica of the Universidad de Costa Rica has evaluated the performance of several types of catalysts and supports in steam reforming reactions, using different conditions for synthesis of the same. The construction of a reaction system at laboratory scale is described to improve the conditions of the reforming process compared to previous projects. Catalysts synthesized and characterized are used but providing better disposal through a packed bed reactor. The system has had the necessary instrumentation for proper measurement of the temperature at the entrance and inside the reactor, proper feeding of reactants, flow measurement and sampling and measurement system. The conceptual design of the reactions system presented has taken into account the income of reactants through a peristaltic pump, preheating or vaporization of reagents, income and measurement of carrier gas sampling, take of sampling, flow measurement product, reactor packed and cooler product. The order of each stage is defined and positioning in the entire system. The design of a preheater and a tubular reactor is detailed, taking into account the dimensions and construction materials of each of the pieces. The design is presented in a series of diagrams and then the result of the construction is illustrated by photographs, all work done also has been described. The implementation of the system has described by the coupling of all parties and the respective tests. A basic experimental plan is presented to evaluate the performance of the reaction system, using glycerin as a reactant, demonstrating ability to react and take effective data. Four experiments are performed: vacuum reactor, packed reactor with two types of filling and reactor with an exposed surface cobalt oxide (II) reduced, the gases produced in the reaction are analyzed by gas chromatography. The results are discussed and analyzed, focusing on the overall selectivity of hydrogen relative to methane, and the

Hydrogenation of rapeseed oil for production of liquid bio-chemicals

International Nuclear Information System (INIS)

Pinto, F.; Martins, S.; Gonçalves, M.; Costa, P.; Gulyurtlu, I.; Alves, A.; Mendes, B.

2013-01-01

Highlights: ► Production of renewable liquid hydrocarbons through rapeseed oil hydrogenation. ► Hydrogenation at lower temperature and lower hydrogen pressures. ► Test of a catalyst commonly employed in petrochemical industry. ► Improve of hydrogenation process viability by decreasing operational costs. ► Analysis of hydrogenated product applications as bio-chemicals. -- Abstract: The main objective of rapeseed oil hydrogenation tests was the production of liquid bio-chemicals to be used as renewable raw material for the production of several chemicals and in chemical synthesis to substitute petroleum derived stuff. As, hydrogenation of vegetable oils is already applied for the production of biofuels, the work done focused in producing aromatic compounds, due to their economic value. The effect of experimental conditions on rapeseed oil hydrogenation was studied, namely, reaction temperature and time with the aim of selecting the most favourable conditions to convert rapeseed oil into liquid valuable bio-chemicals. Rapeseed oil was hydrogenated at a hydrogen initial pressure of 1.10 MPa. Reaction temperature varied in the range from 200 °C to 400 °C, while reaction times between 6 and 180 min were tested. The performance of a commercial cobalt and molybdenum catalyst was also studied. The highest hydrocarbons yields were obtained at the highest temperature and reaction times tested. At a temperature of 400 °C and at the reaction time of 120 min hydrocarbons yield was about 92% in catalyst presence, while in the absence of the catalyst this value decreased to 85%. Hydrocarbons yield was even higher when the reaction time of 180 min was used in the presence of catalyst, as the yield of 97% was observed. At these conditions hydrocarbons formed had a high content of aromatic compounds, around 50%. For this reason, the viscosity values of hydrogenated oils were lower than that established by EN590, which together with hydrogenated liquids composition

Kinetic Study of the Aroxyl-Radical-Scavenging Activity of Five Fatty Acid Esters and Six Carotenoids in Toluene Solution: Structure-Activity Relationship for the Hydrogen Abstraction Reaction.

Science.gov (United States)

Mukai, Kazuo; Yoshimoto, Maya; Ishikura, Masaharu; Nagaoka, Shin-Ichi

2017-08-17

A kinetic study of the reaction between an aroxyl radical (ArO • ) and fatty acid esters (LHs 1-5, ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) has been undertaken. The second-order rate constants (k s ) for the reaction of ArO • with LHs 1-5 in toluene at 25.0 °C have been determined spectrophotometrically. The k s values obtained increased in the order of LH 1 LHs 1-5. The k s value for LH 5 was 2.93 × 10 -3 M -1 s -1 . From the result, it has been clarified that the reaction of ArO • with LHs 1-5 was explained by an allylic hydrogen abstraction reaction. A similar kinetic study was performed for the reaction of ArO • with six carotenoids (Car-Hs 1-6, astaxanthin 1, β-carotene 2, lycopene 3, capsanthin 4, zeaxanthin 5, and lutein 6). The k s values obtained increased in the order of Car-H 1 LHs 1-5. The results of detailed analyses of the k s values for the above reaction indicated that the reaction was also explained by an allylic hydrogen abstraction reaction. Furthermore, the structure-activity relationship for the reaction was discussed by taking the result of density functional theory calculation reported by Martinez and Barbosa into account.

Research Progress on the Indirect Hydrogenation of Carbon Dioxide to Methanol.

Science.gov (United States)

Du, Xian-Long; Jiang, Zheng; Su, Dang Sheng; Wang, Jian-Qiang

2016-02-19

Methanol is a sustainable source of liquid fuels and one of the most useful organic chemicals. To date, most of the work in this area has focused on the direct hydrogenation of CO2 to methanol. However, this process requires high operating temperatures (200-250 °C), which limits the theoretical yield of methanol. Thus, it is desirable to find a new strategy for the efficient conversion of CO2 to methanol at relatively low reaction temperatures. This Minireview seeks to outline the recent advances on the indirect hydrogenation of CO2 to methanol. Much emphasis is placed on discussing specific systems, including hydrogenation of CO2 derivatives (organic carbonates, carbamates, formates, cyclic carbonates, etc.) and cascade reactions, with the aim of critically highlighting both the achievements and remaining challenges associated with this field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

Energy Technology Data Exchange (ETDEWEB)

Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

2011-06-30

Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

Annual report on experimental operations and maintenances of mock-up model test facility with a full-scale reaction tube for HTTR hydrogen production system in 2003 fiscal year (Contract research)

International Nuclear Information System (INIS)

Hayashi, Koji; Morisaki, Norihiro; Ohashi, Hirofumi; Kato, Michio; Aita, Hideki; Takeda, Tetsuaki; Nishihara, Tetsuo; Inaba, Yoshitomo; Takada, Shoji; Inagaki, Yoshiyuki

2006-03-01

This is a report on the experimental operations and maintenances of the mock-up test facility with a full-scale reaction tube for the HTTR hydrogen production system in 2003 fiscal year. The fourth and fifth experimental test operations were performed, from May to July and from October to December in 2003, for the following tests; (a) start-up and shutdown operation test, (b) process change test, (c) continuous hydrogen-production test and (d) chemical reaction shutdown test. From the results, a long time-range stability of the hydrogen production system was confirmed, a behavior of the helium-gas cooling system, consists of steam generator and radiator; during chemical reaction shutdown, was understood, and so on. Periodic inspections on boiler equipment and high-pressure gas production facilities were performed from end of July 2003. This report is summarized on outlines and results of the tests, outlines and results of the periodic inspections, and operation records of the mock-up test facility. (author)

Sensitivity analyses on in-vessel hydrogen generation for KNGR

International Nuclear Information System (INIS)

Kim, See Darl; Park, S.Y.; Park, S.H.; Park, J.H.

2001-03-01

Sensitivity analyses for the in-vessel hydrogen generation, using the MELCOR program, are described in this report for the Korean Next Generation Reactor. The typical accident sequences of a station blackout and a large LOCA scenario are selected. A lower head failure model, a Zircaloy oxidation reaction model and a B 4 C reaction model are considered for the sensitivity parameters. As for the base case, 1273.15K for a failure temperature of the penetrations or the lower head, an Urbanic-Heidrich correlation for the Zircaloy oxidation reaction model and the B 4 C reaction model are used. Case 1 used 1650K as the failure temperature for the penetrations and Case 2 considered creep rupture instead of penetration failure. Case 3 used a MATPRO-EG and G correlation for the Zircaloy oxidation reaction model and Case 4 turned off the B 4 C reaction model. The results of the studies are summarized below : (1) When the penetration failure temperature is higher, or the creep rupture failure model is considered, the amount of hydrogen increases for two sequences. (2) When the MATPRO-EG and G correlation for a Zircaloy oxidation reaction is considered, the amount of hydrogen is less than the Urbanic-Heidrich correlation (Base case) for both scenarios. (3) When the B 4 C reaction model turns off, the amount of hydrogen decreases for two sequences

Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

Science.gov (United States)

Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

2016-01-01

A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

Chemical hydrogen storage material property guidelines for automotive applications

Science.gov (United States)

Semelsberger, Troy A.; Brooks, Kriston P.

2015-04-01

Chemical hydrogen storage is the sought after hydrogen storage media for automotive applications because of the expected low pressure operation (0.05 kg H2/kgsystem), and system volumetric capacities (>0.05 kg H2/Lsystem). Currently, the primary shortcomings of chemical hydrogen storage are regeneration efficiency, fuel cost and fuel phase (i.e., solid or slurry phase). Understanding the required material properties to meet the DOE Technical Targets for Onboard Hydrogen Storage Systems is a critical knowledge gap in the hydrogen storage research community. This study presents a set of fluid-phase chemical hydrogen storage material property guidelines for automotive applications meeting the 2017 DOE technical targets. Viable material properties were determined using a boiler-plate automotive system design. The fluid-phase chemical hydrogen storage media considered in this study were neat liquids, solutions, and non-settling homogeneous slurries. Material properties examined include kinetics, heats of reaction, fuel-cell impurities, gravimetric and volumetric hydrogen storage capacities, and regeneration efficiency. The material properties, although not exhaustive, are an essential first step in identifying viable chemical hydrogen storage material properties-and most important, their implications on system mass, system volume and system performance.

Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

Science.gov (United States)

Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

2017-09-19

This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

Reaction between Hydrogen Sulfide and Limestone Calcines

Czech Academy of Sciences Publication Activity Database

Hartman, Miloslav; Svoboda, Karel; Trnka, Otakar; Čermák, Jiří

2002-01-01

Roč. 41, č. 10 (2002), s. 2392-2398 ISSN 0888-5885 R&D Projects: GA AV ČR IAA4072711; GA AV ČR IAA4072801 Keywords : hydrogen sulfide * limestone calcines * desulfurization Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.247, year: 2002

Study on hydrogen transfer in coal liquefaction by tritium and carbon-14 tracers

International Nuclear Information System (INIS)

Nitoh, Osamu; Kabe, Toshiaki; Kabe, Yaeko.

1985-01-01

For the analysis of mechanism of hydrogenation and cracking of coal, the liquefaction of Taiheiyo coal using tritium labeled gaseous hydrogen and tritium labeled tetralin with small amounts of carbon-14 labeled naphthalene has been studied. Taiheiyo coal(25g) was thermally decomposed in tetralin or naphthalene solvent(75g) at 400--440 0 C under the initial hydrogen pressure of 5.9MPa for 30min with Ni-Mo-Al 2 O 3 catalyst(0--5g). The reaction mixture in an autoclave was separated by filtration, distillation and solvent extraction. Produced gas, oils and the solvent were analyzed by gas chromatography. The tritium and carbon-14 contents of separated reaction products were measured with a liquid scintilation counter to study the hydrogen transfer mechanism. The distribution of reaction products and the amount of hydrogen transfer from gas or solvent to the products were also determined. In hydrogen donor solvent such as tetralin, the coal liquefaction yield was independent from the catalyst, but the catalyst was effective in hydrocracking of preasphaltene and asphaltene. In naphthalene solvent, the coal liquefaction reaction hardly occured in the absence of the catalyst, because hydrogen transfer from both the solvent and gaseous hydrogen was scarce. Tritium distribution in the reaction products showed that complicated hydrogen exchange reactions between gaseous hydrogen, coal liquids and solvent came out by the presence of coal liquids and catalyst. The very small amounts of carbon-14 transferred to the liquefaction products showed that carbon exchange or transfer between solvent and coal did not take place. (author)

High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

Science.gov (United States)

Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

2018-02-26

The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

Including lateral interactions into microkinetic models of catalytic reactions

DEFF Research Database (Denmark)

Hellman, Anders; Honkala, Johanna Karoliina

2007-01-01

In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

Destructive hydrogenation of carbonaceous materials, etc

Energy Technology Data Exchange (ETDEWEB)

1938-02-15

A process is described for the destructive hydrogenation continuously of solid and infusible carbonaceous substances, consisting of heating the charge to the same temperature as the added hydrogen, under a pressure essentially equal to that of the reaction, from the first to at least 300/sup 0/C, but not more than 440/sup 0/C, while passing the heated charge through a zone the contents of which are equal to about 20 per cent to 40 per cent of that of the reaction space, maintaining the charge for a certain time at the temperature without sensible change in the pressure, then reheating the charge to at least the temperature to prime the reaction and finally to introduce the charge into the reaction space.

Decomposition analysis of cupric chloride hydrolysis in the Cu-Cl cycle of hydrogen production

International Nuclear Information System (INIS)

Daggupati, V.N.; Naterer, G.F.; Gabriel, K.S.; Gravelsins, R.; Wang, Z.

2009-01-01

This paper examines cupric chloride solid conversion during hydrolysis in a thermochemical copper-chlorine (Cu-Cl) cycle for hydrogen production. The hydrolysis reaction is a challenging step, in terms of the excess steam requirement and the decomposition of cupric chloride (CuCl 2 ) into cuprous chloride (CuCl) and chlorine (Cl 2 ). The hydrolysis and decomposition reactions are analyzed with respect to the chemical equilibrium constant. The effects of operating parameters are examined, including the temperature, pressure, excess steam and equilibrium conversion. A maximization of yield and selectivity are very important. Rate constants for the simultaneous reaction steps are determined using a uniform reaction model. A shrinking core model is used to determine the rate coefficients and predict the solid conversion time, with diffusional and reaction control. These new results are useful for scale-up of the engineering equipment in the thermochemical Cu-Cl cycle for hydrogen production. (author)

Hydrogen, energy of the future?

International Nuclear Information System (INIS)

Alleau, Th.

2007-01-01

A cheap, non-polluting energy with no greenhouse gas emissions and unlimited resources? This is towards this fantastic future that this book brings us, analyzing the complex but promising question of hydrogen. The scientific and technical aspects of production, transport, storage and distribution raised by hydrogen are thoroughly reviewed. Content: I) Energy, which solutions?: 1 - hydrogen, a future; 2 - hydrogen, a foreseeable solution?; II) Hydrogen, an energy vector: 3 - characteristics of hydrogen (physical data, quality and drawbacks); 4 - hydrogen production (from fossil fuels, from water, from biomass, bio-hydrogen generation); 5 - transport, storage and distribution of hydrogen; 6 - hydrogen cost (production, storage, transport and distribution costs); III) Fuel cells and ITER, utopias?: 7 - molecular hydrogen uses (thermal engines and fuel cells); 8 - hydrogen and fusion (hydrogen isotopes, thermonuclear reaction, ITER project, fusion and wastes); IV) Hydrogen acceptability: 9 - risk acceptability; 10 - standards and regulations; 11 - national, European and international policies about hydrogen; 12 - big demonstration projects in France and in the rest of the world; conclusion. (J.S.)

A study on the reaction of Zircaloy-4 tube with hydrogen/steam mixture

Science.gov (United States)

Lee, Ji-Min; Kook, Dong-Hak; Cho, Il-Je; Kim, Yong-Soo

2017-08-01

In order to fundamentally understand the secondary hydriding mechanism of zirconium alloy cladding, the reaction of commercial Zircaloy-4 tubes with hydrogen and steam mixture was studied using a thermo-gravimetric analyser with two variables, H2/H2O ratio and temperature. Phenomenological analysis revealed that in the steam starvation condition, i.e., when the H2/H2O ratio is greater than 104, hydriding is the dominant reaction and the weight gain increases linearly after a short incubation time. On the other hand, when the gas ratio is 5 × 102 or 103, both hydriding and oxidation reactions take place simultaneously, leading to three distinct regimes: primary hydriding, enhanced oxidation, and massive hydriding. Microstructural changes of oxide demonstrate that when the weight gain exceeds a certain critical value, massive hydriding takes place due to the significant localized crack development within the oxide, which possibly simulates the secondary hydriding failure in a defective fuel operation. This study reveals that the steam starvation condition above the critical H2/H2O ratio is only a necessary condition for the secondary hydriding failure and, as a sufficient condition, oxide needs to grow sufficiently to reach the critical thickness that produces substantial crack development. In other words, in a real defective fuel operation incident, the secondary failure is initiated only when both steam starvation and oxide degradation conditions are simultaneously met. Therefore, it is concluded that the indispensable time for the critical oxide growth primarily determines the triggering time of massive hydriding failure.

Measuring hydrogen-isotope distribution profiles

International Nuclear Information System (INIS)

Poppe, C.H.

1977-01-01

A new nondestructive technique was developed for measuring the depth distribution of hydrogen isotopes absorbed or implanted near the surface of any material. The method allows real-time study of the inventory and diffusion of hydrogen, deuterium, and tritium. Briefly, the technique involves bombarding the surface with a monoenergetic beam of ions chosen for their ability to react with the hydrogen isotope in question and produce fast neutrons. The energy distribution of the neutrons is a sensitive indicator of the energy of the bombarding particles at the instant of reaction, and hence of the depth of the reaction sites below he surface of the material. A sensitivity of one part per million was obtained for tritium in copper. The technique is applicable to several energy-related materials problems. 5 figures

Study of hydrogen in metal and alloy by nuclear reaction channeling method

International Nuclear Information System (INIS)

Yagi, Eiichi

1998-01-01

The position of hydrogen in the lattice was determined by the combination method of 1 H( 11 B, α)αα with a channeling effect of 11 B ion in the crystal. When the concentration of hydrogen in V single crystal was VH 0.1 at the room temperature, hydrogen occupied T position in the body-centered cubic lattice. The position was shifted to the displaced-T by the thermal treatment. Hydrogen in V is oversensitive to a stress, so that it located the displaced-T or 4T state under 7 kg/mm 2 of compressive stress. Hydrogen in Nb and Ta located T position, too. But their displaced states were not observed by the thermal treatment. All hydrogen in Nb-3 at % Mo-2 at % H alloy were captured by Mo and they located the positions of 0.62A displaced from T in the direction of Mo. In Nb-3 at % Mo-5 at % H alloy, a part of hydrogen were captured by Mo, but the other located T positions. At 100degC, hydrogen was free from capture of Mo and moved to T position. (S.Y.)

Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction

International Nuclear Information System (INIS)

Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T.; Scheifers, Jan P.; Zhang, Yuemei

2017-01-01

Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo_2B, α-MoB, β-MoB, and MoB_2 by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB_2 and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo_2C phases, while the molybdenum richest phase Mo_2B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB_2 and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T. [Department of Chemistry, University of California, Riverside, CA (United States); Department of Chemical and Environmental Engineering, University of California, Riverside, CA (United States); Scheifers, Jan P.; Zhang, Yuemei [Department of Chemistry, University of California, Riverside, CA (United States)

2017-05-08

Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo{sub 2}B, α-MoB, β-MoB, and MoB{sub 2} by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB{sub 2} and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo{sub 2}C phases, while the molybdenum richest phase Mo{sub 2}B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB{sub 2} and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

KAUST Repository

Zhang, Junjun

2017-12-27

A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

KAUST Repository

Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang

2017-01-01

A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

Purdue Hydrogen Systems Laboratory

Energy Technology Data Exchange (ETDEWEB)

Jay P Gore; Robert Kramer; Timothee L Pourpoint; P. V. Ramachandran; Arvind Varma; Yuan Zheng

2011-12-28

The Hydrogen Systems Laboratory in a unique partnership between Purdue University's main campus in West Lafayette and the Calumet campus was established and its capabilities were enhanced towards technology demonstrators. The laboratory engaged in basic research in hydrogen production and storage and initiated engineering systems research with performance goals established as per the USDOE Hydrogen, Fuel Cells, and Infrastructure Technologies Program. In the chemical storage and recycling part of the project, we worked towards maximum recycling yield via novel chemical selection and novel recycling pathways. With the basic potential of a large hydrogen yield from AB, we used it as an example chemical but have also discovered its limitations. Further, we discovered alternate storage chemicals that appear to have advantages over AB. We improved the slurry hydrolysis approach by using advanced slurry/solution mixing techniques. We demonstrated vehicle scale aqueous and non-aqueous slurry reactors to address various engineering issues in on-board chemical hydrogen storage systems. We measured the thermal properties of raw and spent AB. Further, we conducted experiments to determine reaction mechanisms and kinetics of hydrothermolysis in hydride-rich solutions and slurries. We also developed a continuous flow reactor and a laboratory scale fuel cell power generation system. The biological hydrogen production work summarized as Task 4.0 below, included investigating optimal hydrogen production cultures for different substrates, reducing the water content in the substrate, and integrating results from vacuum tube solar collector based pre and post processing tests into an enhanced energy system model. An automated testing device was used to finalize optimal hydrogen production conditions using statistical procedures. A 3 L commercial fermentor (New Brunswick, BioFlo 115) was used to finalize testing of larger samples and to consider issues related to scale up

Purdue Hydrogen Systems Laboratory

International Nuclear Information System (INIS)

Gore, Jay P.; Kramer, Robert; Pourpoint, Timothee L.; Ramachandran, P.V.; Varma, Arvind; Zheng, Yuan

2011-01-01

The Hydrogen Systems Laboratory in a unique partnership between Purdue University's main campus in West Lafayette and the Calumet campus was established and its capabilities were enhanced towards technology demonstrators. The laboratory engaged in basic research in hydrogen production and storage and initiated engineering systems research with performance goals established as per the USDOE Hydrogen, Fuel Cells, and Infrastructure Technologies Program. In the chemical storage and recycling part of the project, we worked towards maximum recycling yield via novel chemical selection and novel recycling pathways. With the basic potential of a large hydrogen yield from AB, we used it as an example chemical but have also discovered its limitations. Further, we discovered alternate storage chemicals that appear to have advantages over AB. We improved the slurry hydrolysis approach by using advanced slurry/solution mixing techniques. We demonstrated vehicle scale aqueous and non-aqueous slurry reactors to address various engineering issues in on-board chemical hydrogen storage systems. We measured the thermal properties of raw and spent AB. Further, we conducted experiments to determine reaction mechanisms and kinetics of hydrothermolysis in hydride-rich solutions and slurries. We also developed a continuous flow reactor and a laboratory scale fuel cell power generation system. The biological hydrogen production work summarized as Task 4.0 below, included investigating optimal hydrogen production cultures for different substrates, reducing the water content in the substrate, and integrating results from vacuum tube solar collector based pre and post processing tests into an enhanced energy system model. An automated testing device was used to finalize optimal hydrogen production conditions using statistical procedures. A 3 L commercial fermentor (New Brunswick, BioFlo 115) was used to finalize testing of larger samples and to consider issues related to scale up. Efforts

Ion beam investigation of hydrogen implanted in magnesium

International Nuclear Information System (INIS)

Chami, A.-C.

1977-01-01

The diffusion mechanism for hydrogen implanted in magnesium was investigated by nuclear reaction analysis or channeling. The hydrogen introduced is then in the presence of radiation defects created by implantation. The H( 11 B,α) reaction used allowed the profiles of implanted hydrogen to be drawn. The Winterbon calculations derived from LSS theory (Lindhard, Scharff, Schiott) were used. LSS profiles folding and the excitation curve unfolding give very same results. An analysis of the profile of the defects and the evaluation of the total number of Frenkel pairs produced show that the defects are isolated when low energy light elements are implanted, and hydrogen interactions are effected through point defects. A channeling analysis shows that hydrogen occupies tetrahedral sites as far as the temperature remains lower that the migration temperature (about 100K). Beyonds this temperature, the hydrogen migrates and is trapped on motionless defects [fr

Factors responsible for activity of catalysts of different chemical types in the reaction of hydrogen oxidation

International Nuclear Information System (INIS)

Il'chenko, N.I.; Dolgikh, L.Yu.

1985-01-01

Reasons of differences in the kinetics and mechanism of the H 2 oxidation on optimum metallic (Pt), carbide (WC) and oxide (Co 3 O 4 ) catalysts are discussed. These differences lead to unequal specific activity. It is shown that the catalytic activity of the catalysts in question increases with respect to reactions of isotopic exchange and hydrogen oxidation with an increasing electron-donating ability of anat of the transition metal M on which H 2 is adsorbed. The possibility is considered of increasing the transition metal activity by introduction of additions to increase the electron-donating ability of M

Advanced Electrochemical Technologies for Hydrogen Production by Alternative Thermochemical Cycles

Energy Technology Data Exchange (ETDEWEB)

Lvov, Serguei; Chung, Mike; Fedkin, Mark; Lewis, Michele; Balashov, Victor; Chalkova, Elena; Akinfiev, Nikolay; Stork, Carol; Davis, Thomas; Gadala-Maria, Francis; Stanford, Thomas; Weidner, John; Law, Victor; Prindle, John

2011-01-06

reactions going to completion without side reactions, and lower demands on materials of construction. Three university research groups from PSU, USC, and TU as well as a group from ANL have been collaborating on the development of enabling technologies for the Cu-Cl cycle, including experimental work on the Cu-Cl cycle reactions, modeling and simulation, and particularly electrochemical reaction for hydrogen production using a CuCl electrolyzer. The Consortium research was distributed over the participants and organized in the following tasks: (1) Development of CuCl electrolyzer (PSU), (2) Thermodynamic modeling of anolyte solution (PSU), (3) Proton conductive membranes for CuCl electrolysis (PSU), (4) Development of an analytical method for online analysis of copper compounds in highly concentrated aqueous solutions (USC), (5) Electrodialysis as a means for separation and purification of the streams exiting the electrolyzer in the Cu-Cl cycle (USC), (6) Development of nanostructured electrocatalysts for the Cu-Cl electrolysis (USC), (7) Cu-Cl electrolyzer modeling (USC), (8) Aspen Plus modeling of the Cu-Cl thermochemical cycle (TU), (9) International coordination of research on the development of the Cu-Cl thermochemical cycle (ANL). The results obtained in the project clearly demonstrate that the Cu-Cl alternative thermochemical cycle is a promising and viable technology to produce hydrogen efficiently.

General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water

International Nuclear Information System (INIS)

Suarez, C.; Diaz, D.; Paz, D.

1991-01-01

Gentamicin C was labelled with tritium by means of a PtO2 catalyzed hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H2O-3H, and 50 mg of prereduced PtO2) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 degree celsius, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accomplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v) . Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95. Main exchange degradation products show biological activity. (Author) 12 refs

General Tritium labelling of gentamicin C by catalytic hydrogen exchange reaction with tritiated water

International Nuclear Information System (INIS)

Suarez, C.; Diaz, D.

1991-01-01

Gentamicin C was labelled with tritium by means of a PtO 2 catalized hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H 2 O- 3 H, and 50 mg of prereduced PtO 2 ) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 o C, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accoumplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v). Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95 % . Main exchange degradation products show biological activity. (Author). 12 refs