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Sample records for include dehydrogenation hydrogenation

  1. Using ceramic membranes for the separation of hydrogen produced by dehydrogenation of perhydro- m-terphenyl

    Science.gov (United States)

    Kalenchuk, A. N.; Bogdan, V. I.; Kustov, L. M.

    2015-01-01

    The efficiency of a variety of ceramic membranes for the purification of hydrogen obtained by dehydrogenation of perhydro- m-terphenyl in a catalytic flow reactor from vapors of initial hydrocarbons and dehydrogenation products is investigated.

  2. Catalytic Dehydrogenation of Ethane in Hydrogen Membrane Reactor

    Science.gov (United States)

    Galuszka, Jan; Giddings, Terry; Clelland, Ian

    The effect of a hydrogen permselective membrane (H-membrane) reactor on catalytic dehydrogenation of ethane was assessed using a fixed bed conventional reactor and a double tubular H-membrane reactor. A 5.0wt.% Cr2O3/γ-Al2O3 catalyst prepared by incipient wetness impregnation of a γ-Al2O3 (BET surface area = 50 m2/g) support was used at 555°C and 600°C. Although about 40% of H2 produced during dehydrogenation of ethane in the membrane reactor passed through the membrane, only moderate enhancement in ethane conversion was observed. The slow processes on the catalyst surface are thought to counterbalance the positive effect of membrane assisted hydrogen removal. Also, decreased selectivity to ethylene due to enhanced carbon formation in the membrane reactor led to faster deactivation of the catalyst. A strategy for commercialization of catalytic dehydrogenation of ethane through the development of a better hydrogen membrane might require a reevaluation.

  3. Kinetics with deactivation of methylcyclohexane dehydrogenation for hydrogen energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Maria, G.; Marin, A.; Wyss, C.; Mueller, S.; Newson, E. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The methylcyclohexane dehydrogenation step to recycle toluene and release hydrogen is being studied as part of a hydrogen energy storage project. The reaction is performed catalytically in a fixed bed reactor, and the efficiency of this step significantly determines overall system economics. The fresh catalyst kinetics and the deactivation of the catalyst by coke play an important role in the process analysis. The main reaction kinetics were determined from isothermal experiments using a parameter sensitivity analysis for model discrimination. An activation energy for the main reaction of 220{+-}11 kJ/mol was obtained from a two-parameter model. From non-isothermal deactivation in PC-controlled integral reactors, an activation energy for deactivation of 160 kJ/mol was estimated. A model for catalyst coke content of 3-17 weight% was compared with experimental data. (author) 3 figs., 6 refs.

  4. Hydrogen bonding-mediated dehydrogenation in the ammonia borane combined graphene oxide systems

    Science.gov (United States)

    Kuang, Anlong; Liu, Taijuan; Kuang, Minquan; Yang, Ruifeng; Huang, Rui; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong; Yang, Xiaolan

    2018-03-01

    The dehydrogenation of ammonia borane (AB) adsorbed on three different graphene oxide (GO) sheets is investigated within the ab initio density functional theory. The energy barriers to direct combination the hydrogens of hydroxyl groups and the hydridic hydrogens of AB to release H2 are relatively high, indicating that the process is energetically unfavorable. Our theoretical study demonstrates that the dehydrogenation mechanism of the AB-GO systems has undergone two critical steps, first, there is the formation of the hydrogen bond (O-H-O) between two hydroxyl groups, and then, the hydrogen bond further react with the hydridic hydrogens of AB to release H2 with low reaction barriers.

  5. Understanding the mechanisms of cobalt-catalyzed hydrogenation and dehydrogenation reactions.

    Science.gov (United States)

    Zhang, Guoqi; Vasudevan, Kalyan V; Scott, Brian L; Hanson, Susan K

    2013-06-12

    Cobalt(II) alkyl complexes of aliphatic PNP pincer ligands have been synthesized and characterized. The cationic cobalt(II) alkyl complex [(PNHP(Cy))Co(CH2SiMe3)]BAr(F)4 (4) (PNHP(Cy) = bis[(2-dicyclohexylphosphino)ethyl]amine) is an active precatalyst for the hydrogenation of olefins and ketones and the acceptorless dehydrogenation of alcohols. To elucidate the possible involvement of the N-H group on the pincer ligand in the catalysis via a metal-ligand cooperative interaction, the reactivities of 4 and [(PNMeP(Cy))Co(CH2SiMe3)]BAr(F)4 (7) were compared. Complex 7 was found to be an active precatalyst for the hydrogenation of olefins. In contrast, no catalytic activity was observed using 7 as a precatalyst for the hydrogenation of acetophenone under mild conditions. For the acceptorless dehydrogenation of 1-phenylethanol, complex 7 displayed similar activity to complex 4, affording acetophenone in high yield. When the acceptorless dehydrogenation of 1-phenylethanol with precatalyst 4 was monitored by NMR spectroscopy, the formation of the cobalt(III) acetylphenyl hydride complex [(PNHP(Cy))Co(III)(κ(2)-O,C-C6H4C(O)CH3)(H)]BAr(F)4 (13) was detected. Isolated complex 13 was found to be an effective catalyst for the acceptorless dehydrogenation of alcohols, implicating 13 as a catalyst resting state during the alcohol dehydrogenation reaction. Complex 13 catalyzed the hydrogenation of styrene but showed no catalytic activity for the room temperature hydrogenation of acetophenone. These results support the involvement of metal-ligand cooperativity in the room temperature hydrogenation of ketones but not the hydrogenation of olefins or the acceptorless dehydrogenation of alcohols. Mechanisms consistent with these observations are presented for the cobalt-catalyzed hydrogenation of olefins and ketones and the acceptorless dehydrogenation of alcohols.

  6. Rapid PMR determination of hydrogen in titanium hydride and dehydrogenated titanium powders

    International Nuclear Information System (INIS)

    Il'enko, V.S.; Demidenko, L.M.

    1987-01-01

    Proton magnetic resonance (PMR) enables determining hydrogen quantitatively in titanium hydride and dehydrogenated titanium powders without destroying the specimen and is also more informative than high-temperature extraction methods. PMR provides data on the electron-nuclear interactions and the activation energies for hydrogen diffusion while also providing conclusions on the forms and positives of the hydrogen in the lattice and the binding to the metal atoms. The authors have developed a rapid method for determining hydrogen in titanium hydride and dehydrogenated titanium powders which reduces the analysis time and improves the metrological characteristics. The authors use a YaMR-5535 spectrometer working at 40 MHz upgraded for use with hydrogen in solids. The authors used specimens of mass about 2 g ground to 0.1 mm powder

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

    Science.gov (United States)

    Zell, Thomas; Milstein, David

    2015-07-21

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

  8. Influence of Particle Size on Reaction Selectivity in Cyclohexene Hydrogenation and Dehydrogenation over Silica-Supported Monodisperse Pt Particles

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, R. M.; Hsu, B. B.; Grass, M. E.; Song, H.; Somorjai, Gabor A.

    2008-07-11

    The role of particle size during the hydrogenation/dehydrogenation of cyclohexene (10 Torr C{sub 6}H{sub 10}, 200-600 Torr H{sub 2}, and 273-650 K) was studied over a series of monodisperse Pt/SBA-15 catalysts. The conversion of cyclohexene in the presence of excess H{sub 2} (H{sub 2}:C{sub 6}H{sub 10} ratio = 20-60) is characterized by three regimes: hydrogenation of cyclohexene to cyclohexane at low temperature (< 423 K), an intermediate temperature range in which both hydrogenation and dehydrogenation occur; and a high temperature regime in which the dehydrogenation of cyclohexene dominates (> 573 K). The rate of both reactions demonstrated maxima with temperature, regardless of Pt particle size. For the hydrogenation of cyclohexene, a non-Arrhenius temperature dependence (apparent negative activation energy) was observed. Hydrogenation is structure insensitive at low temperatures, and apparently structure sensitive in the non-Arrhenius regime; the origin of the particle-size dependent reactivity with temperature is attributed to a change in the coverage of reactive hydrogen. Small particles were more active for dehydrogenation and had lower apparent activation energies than large particles. The selectivity can be controlled by changing the particle size, which is attributed to the structure sensitivity of both reactions in the temperature regime where hydrogenation and dehydrogenation are catalyzed simultaneously.

  9. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide.

    Science.gov (United States)

    Nielsen, Martin; Alberico, Elisabetta; Baumann, Wolfgang; Drexler, Hans-Joachim; Junge, Henrik; Gladiali, Serafino; Beller, Matthias

    2013-03-07

    Hydrogen produced from renewable resources is a promising potential source of clean energy. With the help of low-temperature proton-exchange membrane fuel cells, molecular hydrogen can be converted efficiently to produce electricity. The implementation of sustainable hydrogen production and subsequent hydrogen conversion to energy is called "hydrogen economy". Unfortunately, its physical properties make the transport and handling of hydrogen gas difficult. To overcome this, methanol can be used as a material for the storage of hydrogen, because it is a liquid at room temperature and contains 12.6 per cent hydrogen. However, the state-of-the-art method for the production of hydrogen from methanol (methanol reforming) is conducted at high temperatures (over 200 degrees Celsius) and high pressures (25-50 bar), which limits its potential applications. Here we describe an efficient low-temperature aqueous-phase methanol dehydrogenation process, which is facilitated by ruthenium complexes. Hydrogen generation by this method proceeds at 65-95 degrees Celsius and ambient pressure with excellent catalyst turnover frequencies (4,700 per hour) and turnover numbers (exceeding 350,000). This would make the delivery of hydrogen on mobile devices--and hence the use of methanol as a practical hydrogen carrier--feasible.

  10. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions.

    Science.gov (United States)

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter

    2015-02-17

    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  11. Computational Design of Cobalt Catalysts for Hydrogenation of Carbon Dioxide and Dehydrogenation of Formic Acid.

    Science.gov (United States)

    Ge, Hongyu; Jing, Yuanyuan; Yang, Xinzheng

    2016-12-05

    A series of cobalt complexes with acylmethylpyridinol and aliphatic PNP pincer ligands are proposed based on the active site structure of [Fe]-hydrogenase. Density functional theory calculations indicate that the total free energy barriers of the hydrogenation of CO 2 and dehydrogenation of formic acid catalyzed by these Co complexes are as low as 23.1 kcal/mol in water. The acylmethylpyridinol ligand plays a significant role in the cleavage of H 2 by forming a strong Co-H δ- ···H δ+ -O dihydrogen bond in a fashion of frustrated Lewis pairs.

  12. In-situ TEM on (de)hydrogenation of Pd at 0.5-4.5 bar hydrogen pressure and 20-400°C.

    Science.gov (United States)

    Yokosawa, Tadahiro; Alan, Tuncay; Pandraud, Gregory; Dam, Bernard; Zandbergen, Henny

    2012-01-01

    We have developed a nanoreactor, sample holder and gas system for in-situ transmission electron microscopy (TEM) of hydrogen storage materials up to at least 4.5 bar. The MEMS-based nanoreactor has a microheater, two electron-transparent windows and a gas inlet and outlet. The holder contains various O-rings to have leak-tight connections with the nanoreactor. The system was tested with the (de)hydrogenation of Pd at pressures up to 4.5 bar. The Pd film consisted of islands being 15 nm thick and 50-500 nm wide. In electron diffraction mode we observed reproducibly a crystal lattice expansion and shrinkage owing to hydrogenation and dehydrogenation, respectively. In selected-area electron diffraction and bright/dark-field modes the (de)hydrogenation of individual Pd particles was followed. Some Pd islands are consistently hydrogenated faster than others. When thermally cycled, thermal hysteresis of about 10-16°C between hydrogen absorption and desorption was observed for hydrogen pressures of 0.5-4.5 bar. Experiments at 0.8 bar and 3.2 bar showed that the (de)hydrogenation temperature is not affected by the electron beam. This result shows that this is a fast method to investigate hydrogen storage materials with information at the nanometer scale. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. In-situ TEM on (de)hydrogenation of Pd at 0.5–4.5 bar hydrogen pressure and 20–400°C

    International Nuclear Information System (INIS)

    Yokosawa, Tadahiro; Alan, Tuncay; Pandraud, Gregory; Dam, Bernard; Zandbergen, Henny

    2012-01-01

    We have developed a nanoreactor, sample holder and gas system for in-situ transmission electron microscopy (TEM) of hydrogen storage materials up to at least 4.5 bar. The MEMS-based nanoreactor has a microheater, two electron-transparent windows and a gas inlet and outlet. The holder contains various O-rings to have leak-tight connections with the nanoreactor. The system was tested with the (de)hydrogenation of Pd at pressures up to 4.5 bar. The Pd film consisted of islands being 15 nm thick and 50–500 nm wide. In electron diffraction mode we observed reproducibly a crystal lattice expansion and shrinkage owing to hydrogenation and dehydrogenation, respectively. In selected-area electron diffraction and bright/dark-field modes the (de)hydrogenation of individual Pd particles was followed. Some Pd islands are consistently hydrogenated faster than others. When thermally cycled, thermal hysteresis of about 10–16 °C between hydrogen absorption and desorption was observed for hydrogen pressures of 0.5–4.5 bar. Experiments at 0.8 bar and 3.2 bar showed that the (de)hydrogenation temperature is not affected by the electron beam. This result shows that this is a fast method to investigate hydrogen storage materials with information at the nanometer scale. -- Highlights: ► In-situ TEM experiments up to 4.5 bar. ► In-situ TEM on a hydrogen storage material at pressures used in practice. ► No electron beam effect on (de)hydrogenation. ► In-situ TEM allows for fast screening of hydrogen storage materials.

  14. Hydrogen Production by Homogeneous Catalysis: Alcohol Acceptorless Dehydrogenation

    DEFF Research Database (Denmark)

    Nielsen, Martin

    2015-01-01

    , and are fundamental for the thrive of almost all business fields. The latter include the industries of agriculture, food additives, pharmaceuticals, electronics, plastic, fragrances, and more. Today, the major source of both energy and bulk chemicals is fossil fuels, being responsible for more than 80 % of the energy...... supplies. The large amounts of CO2 release owing to fossil fuel usage is believed to cause global warming on the long term, a highly undesired environmental consequence. Hence, it is of critical importance that alternative sources are developed and implemented in the society. One suggested solution...

  15. Study of the hydrogenation/dehydrogenation process in the Mg–Ni–C–Al system

    Energy Technology Data Exchange (ETDEWEB)

    Palumbo, O. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Research Center Hydro-Eco, Sapienza University of Rome, Via A. Scarpa 14, 00161 Roma (Italy); Trequattrini, F. [Physics Department, Sapienza University of Rome, Piazzale A. Moro 5, 00185 Roma (Italy); Vitucci, F.M. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Bianchin, A. [MBN Nanomaterialia S.p.A., Via G. Bortolan 42, 31040 Vascon di Carbonera-TV (Italy); Paolone, A., E-mail: annalisa.paolone@roma1.infn.it [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Research Center Hydro-Eco, Sapienza University of Rome, Via A. Scarpa 14, 00161 Roma (Italy)

    2015-10-05

    Highlights: • A Mg–Ni–C–Al mixture synthesized for application as pellets in a tank is studied. • It is the combination of a hydrogen storing composite with a binding phase. • The storage properties are studied by PCI curves, TGA–DSC and XRD. • The hydrogen absorbtion/desorption occurs in two steps. • The thermodynamics of the first more massive step is improved compared to MgH{sub 2}. - Abstract: In this work we present a detailed study of the hydrogenation and dehydrogenation processes of a nanostructured Mg–Ni–C–Al mixture. The sample has been characterized by means of X-ray diffraction, concomitant thermogravimetric and differential scanning calorimetry measurements and pressure-composition isothermal analyses. The hydrogenation takes place in two steps and is compatible with the formation of MgH{sub 2} and Mg{sub 2}NiH{sub 4}. The enthalpy and the activation energy measured for the main hydrogen desorption are lower than those ones reported for magnesium hydride.

  16. Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

    KAUST Repository

    Shaikh Ali, Anaam

    2017-01-18

    Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

  17. Decarbonylation and dehydrogenation of carbohydrates

    Science.gov (United States)

    Andrews, Mark A.; Klaeren, Stephen A.

    1991-01-01

    Carbohydrates, especially aldose or ketose sugars, including those whose carbonyl group is masked by hemi-acetal or hemi-ketal formation, are decarbonylated by heating the feed carbohydrate together with a transition metal complex in a suitable solvent. Also, primary alcohols, including sugar alditols are simultaneously dehydrogenated and decarbonylated by heating a mixture of rhodium and ruthenium complexes and the alcohol and optionally a hydrogen acceptor in an acceptable solvent. Such defarbonylation and/or dehydrogenation of sugars provides a convenient procedure for the synthesis of certain carbohydrates and may provide a means for the conversion of biomass into useful products.

  18. Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

    Science.gov (United States)

    Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

    2018-05-01

    In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

  19. 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.

  20. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

    Science.gov (United States)

    Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao

    2014-10-01

    In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  1. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  2. Thermochemical Energy Storage through De/Hydrogenation of Organic Liquids: Reactions of Organic Liquids on Metal Hydrides.

    Science.gov (United States)

    Ulmer, Ulrich; Cholewa, Martin; Diemant, Thomas; Bonatto Minella, Christian; Dittmeyer, Roland; Behm, R Jürgen; Fichtner, Maximilian

    2016-06-08

    A study of the reactions of liquid acetone and toluene on transition metal hydrides, which can be used in thermal energy or hydrogen storage applications, is presented. Hydrogen is confined in TiFe, Ti0.95Zr0.05Mn1.49V0.45Fe0.06 ("Hydralloy C5"), and V40Fe8Ti26Cr26 after contact with acetone. Toluene passivates V40Fe8Ti26Cr26 completely for hydrogen desorption while TiFe is only mildly deactivated and desorption is not blocked at all in the case of Hydralloy C5. LaNi5 is inert toward both organic liquids. Gas chromatography (GC) investigations reveal that CO, propane, and propene are formed during hydrogen desorption from V40Fe8Ti26Cr26 in liquid acetone, and methylcyclohexane is formed in the case of liquid toluene. These reactions do not occur if dehydrogenated samples are used, which indicates an enhanced surface reactivity during hydrogen desorption. Significant amounts of carbon-containing species are detected at the surface and subsurface of acetone- and toluene-treated V40Fe8Ti26Cr26 by X-ray photoelectron spectroscopy (XPS). The modification of the surface and subsurface chemistry and the resulting blocking of catalytic sites is believed to be responsible for the containment of hydrogen in the bulk. The surface passivation reactions occur only during hydrogen desorption of the samples.

  3. Hydrogen peroxide modified Mg-Al-O oxides supported Pt-Sn catalysts for paraffin dehydrogenation

    NARCIS (Netherlands)

    Lai, Y.; He, Songbo; Luo, S.; Bi, W.; Li, XianRu; Sun, Chenglin; Seshan, Kulathuiyer

    2015-01-01

    In this work, a new method to prepare Mg–Al–O oxide by co-precipitation method with addition of H2O2 was developed. The application of Mg–Al–O as a support of Pt–Sn catalysts for paraffin dehydrogenation was investigated. Characterization results indicated that modification of H2O2 (i) enlarged the

  4. Synergic catalytic effect of Ti hydride and Nb nanoparticles for improving hydrogenation and dehydrogenation kinetics of Mg-based nanocomposite

    Directory of Open Access Journals (Sweden)

    Xiujuan Ma

    2017-02-01

    Full Text Available The Mg-9.3 wt% (TiH1.971-TiH−0.7 wt% Nb nanocomposite has been synthesized by hydrogen plasma-metal reaction (HPMR approach to enhance the hydrogen sorption kinetics of Mg at moderate temperatures by providing nanosizing effect of increasing H “diffusion channels” and adding transition metallic catalysts. The Mg nanoparticles (NPs were in hexagonal shape range from 50 to 350 nm and the average size of the NPs was 177 nm. The small spherical TiH1.971, TiH and Nb NPs of about 25 nm uniformly decorated on the surface of the big Mg NPs. The Mg-TiH1.971-TiH-Nb nanocomposite could quickly absorb 5.6 wt% H2 within 5 min at 573 K and 4.5 wt% H2 within 5 min at 523 K, whereas the pure Mg prepared by HPMR could only absorb 4 and 1.5 wt% H2 at the same temperatures. TiH1.971, TiH and Nb NPs transformed into TiH2 and NbH during hydrogenation and recovered after dehydrogenation process. The apparent activation energies of the nanocomposite for hydrogenation and dehydrogenation were 45.0 and 50.7 kJ mol−1, which are much smaller than those of pure Mg NPs, 123.8 and 127.7 kJ mol−1. The improved sorption kinetics of the Mg-based nanocomposite at moderate temperatures and the small activation energy can be interpreted by the nanostructure of Mg and the synergic catalytic effects of Ti hydrides and Nb NPs.

  5. Dehydrogenation of liquid fuel in microchannel catalytic reactor

    Science.gov (United States)

    Toseland, Bernard Allen [Allentown, PA; Pez, Guido Peter [Allentown, PA; Puri, Pushpinder Singh [Emmaus, PA

    2009-02-03

    The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

  6. The influence of surface oxygen and hydroxyl groups on the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate on pure Pd(1 0 0): A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yanping [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072 (China); Dong, Xiuqin [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Zhang, Minhua, E-mail: mhzhangtj@163.com [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China)

    2016-12-01

    Highlights: • All dehydrogenation reactions in vinyl acetate synthesis on Pd(1 0 0) were studied. • The energy barriers of the transition state of the three reactions were calculated. • The influence of surface Os and OHs on all dehydrogenation actions was discussed. - Abstract: On the basis of a Langmuir–Hinshelwood-type mechanism, the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate (VAH) on pure Pd(1 0 0) with surface oxygen atoms (Os) and hydroxyl groups (OHs) was studied with density functional theory (DFT) method. Our calculation results show that both Os and OHs can consistently reduce the activation energies of dehydrogenation of ethylene, acetic acid and VAH to some degree with only one exception that OHs somehow increase the activation energy of VAH. Based on Langmuir–Hinshelwood mechanism, the three dehydrogenation reactions in presence of surface Os and OHs are almost consistently favored, compared with the corresponding processes on clean Pd(1 0 0) surfaces, and thus a Langmuir–Hinshelwood-type mechanism may not be excluded beforehand when investigating the microscopic performance of the oxygen-assisted vinyl acetate synthesis on Pd(1 0 0) catalysts.

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

    Science.gov (United States)

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

    2016-01-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation. PMID:27849033

  8. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni{sub 2}P supported on active carbon

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yanli [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Sang, Huanxin [Tianjin Academy of Environmental Sciences, Tianjin 300191 (China); Wang, Kang [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wang, Xitao, E-mail: wangxt@tju.edu.cn [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science and Technology, College of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2014-10-15

    Graphical abstract: - Highlights: • Ni{sub 2}P catalyst is tested in dehydrogenation of isobutane for the first time. • The effects of Cs promoter on catalytic performance of Ni2P/AC were investigated. • Cs-Ni2P/AC exhibits high activity and selectivity for isobutane dehydrogenation. - Abstract: In this article, an environmentally friendly non-noble-metal class of Cs-Ni{sub 2}P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H{sub 2}-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni{sub 2}P particles, which decreases the strength of Ni-C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni{sub 2}P/AC catalysts display much higher catalytic performance as compared to Ni{sub 2}P/AC catalyst. Cs-Ni{sub 2}P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni{sub 2}P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

  9. Metallic glassy Zr70Ni20Pd10 powders for improving the hydrogenation/dehydrogenation behavior of MgH2

    Science.gov (United States)

    El-Eskandarany, M. Sherif

    2016-01-01

    Because of its low density, storage of hydrogen in the gaseous and liquids states possess technical and economic challenges. One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides. Magnesium hydride (MgH2) remains the best hydrogen storage material due to its high hydrogen capacity and low cost of production. Due to its high activation energy and poor hydrogen sorption/desorption kinetics at moderate temperatures, the pure form of MgH2 is usually mechanically treated by high-energy ball mills and catalyzed with different types of catalysts. These steps are necessary for destabilizing MgH2 to enhance its kinetics behaviors. In the present work, we used a small mole fractions (5 wt.%) of metallic glassy of Zr70Ni20Pd10 powders as a new enhancement agent to improve its hydrogenation/dehydrogenation behaviors of MgH2. This short-range ordered material led to lower the decomposition temperature of MgH2 and its activation energy by about 121 °C and 51 kJ/mol, respectively. Complete hydrogenation/dehydrogenation processes were successfully achieved to charge/discharge about 6 wt.%H2 at 100 °C/200 °C within 1.18 min/3.8 min, respectively. In addition, this new nanocomposite system shows high performance of achieving continuous 100 hydrogen charging/discharging cycles without degradation. PMID:27220994

  10. for Isobutane Dehydrogenation

    OpenAIRE

    DOGAN, Meltem; KILICARSLAN, Saliha

    2012-01-01

    Isobutene is used as a raw material in the production of ethers for increasing the octane rating and reducing exhaust emissions in gasoline. Dehydrogenation of isobutane is an endothermic equilibrium-limited reaction. Recent studies have focused on overcoming equilibrium limitations by removing the product hydrogen through a membrane. In this study, alumina-modified porous glass supports were plated with Pd using electroless plating (ELP). Plating studies were carried out at 35°C and pH 10-11...

  11. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    Science.gov (United States)

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  12. CuCo2O4 nanoplate film as a low-cost, highly active and durable catalyst towards the hydrolytic dehydrogenation of ammonia borane for hydrogen production

    Science.gov (United States)

    Liu, Quanbing; Zhang, Shengjie; Liao, Jinyun; Feng, Kejun; Zheng, Yuying; Pollet, Bruno G.; Li, Hao

    2017-07-01

    Catalytic dehydrogenation of ammonia borane is one of the most promising routes for the production of clean hydrogen as it is seen as a highly efficient and safe method. However, its large-scale industrial application is either limited by the high cost of the catalyst (usually a noble metal based catalyst) or by the low activity and poor reusability (usually a non-noble metal catalyst). In this study, we have successfully prepared three low-cost CuCo2O4 nanocatalysts, namely: (i) Ti supported CuCo2O4 film made of CuCo2O4 nanoplates, (ii) Ti supported CuCo2O4 film made of CuCo2O4 nanosheets, and (iii) unsupported CuCo2O4 nanoparticles. Among the three catalysts used for the hydrolytic dehydrogeneration of ammonia borane, the CuCo2O4 nanoplate film exhibits the highest catalytic activity with a turnover frequency (TOF) of ∼44.0 molhydrogen min-1 molcat-1. This is one of the largest TOF value for noble-metal-free catalysts ever reported in the literature. Moreover, the CuCo2O4 nanoplate film almost keeps its original catalytic activity after eight cycles, indicative of its high stability and good reusability. Owing to its advantages, the CuCo2O4 nanoplate film can be a promising catalyst for the hydrolytic dehydrogenation of ammonia borane, which may find important applications in the field of hydrogen energy.

  13. Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

    International Nuclear Information System (INIS)

    Zahmakiran, Mehmet

    2012-01-01

    Highlights: ► Ru(0)NPs-ZK-4 were prepared and characterized by advanced analytical techniques. ► They achieve the hydrolysis of ammonia-borane with TOF = 5410 h −1 and TTO = 36700. ► They maintain 85% of their activity even at the fifth catalytic run. - Abstract: The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH 3 BH 3 ) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h −1 ), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.

  14. Size and Structure Effects Controlling the Stability of the Liquid Organic Hydrogen Carrier Dodecahydro-N-ethylcarbazole during Dehydrogenation over Pt Model Catalysts.

    Science.gov (United States)

    Amende, Max; Gleichweit, Christoph; Schernich, Stefan; Höfert, Oliver; Lorenz, Michael P A; Zhao, Wei; Koch, Marcus; Obesser, Katharina; Papp, Christian; Wasserscheid, Peter; Steinrück, Hans-Peter; Libuda, Jörg

    2014-04-17

    Hydrogen can be stored conveniently using so-called liquid organic hydrogen carriers (LOHCs), for example, N-ethylcarbazole (NEC), which can be reversibly hydrogenated to dodecahydro-N-ethylcarbazole (H12-NEC). In this study, we focus on the dealkylation of H12-NEC, an undesired side reaction, which competes with dehydrogenation. The structural sensivity of dealkylation was studied by high-resolution X-ray photoelectron spectroscopy (HR-XPS) on Al2O3-supported Pt model catalysts and Pt(111) single crystals. We show that the morphology of the Pt deposit strongly influences LOHC degradation via C-N bond breakage. On smaller, defect-rich Pt particles, the onset of dealkylation is shifted by 90 K to lower temperatures as compared to large, well-shaped particles and well-ordered Pt(111). We attribute these effects to a reduced activation barrier for C-N bond breakage at low-coordinated Pt sites, which are abundant on small Pt aggregates but are rare on large particles and single crystal surfaces.

  15. Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 : Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra

    NARCIS (Netherlands)

    Marashdeh, A.; Frankcombe, T.J.

    2008-01-01

    The dehydrogenation enthalpies of Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski’s direct method. The

  16. Long-term storage and long-distance transportation of hydrogen by use of catalyst-addisted decalin dehydrogenation/naphthalene hydrogenation pair; Dekarin dassuiso/nafutarensuisoka shokubai hannotai wo mochiiru suiso no chokikan chozo/chokyori yuso

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C.; Sakaguchi, M.; Saito, Y. [Scince Univ.of Tokyo, Tokyo (Japan)

    1997-06-01

    To enable taking in and out hydrogen with little energy consumption, it is sufficient if decalin is dehydrogenated to naphthalene under moderate heating condition. It is found that carbon supporting metal catalyst in liquid film state shows extremely high dehydrogeno-aromatization activity of decalin. The result of comparison with liquid hydrogen or metal hydride as media for hydrogen storage and transportation media is reported. The platinum-tungsten composite metal catalyst is prepared from an aqueous solution of K2PtC16 and Li2WO4 in the ratio of 1 to 1 so as to achieve 5wt-metal% carbon supporting. When hydrogen and naphthalene are discharged from the liquid phase reaction medium to the vapor phase and solid phase, respectively, under boiling and refluxing conditions, hydrogen is produced steadily by heating at 200 to 210degC. If economical efficiency is ignored, development of an inter-season energy storage system is desired to be developed which can be used in the season between summertime when sufficient hydrogen is obtained by photovoltaic power generation and electrolysis of water and wintertime when heat source is obtained by catalytic combustion of hydrogen. 11 refs., 4 figs., 4 tabs.

  17. Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis.

    Science.gov (United States)

    Crabtree, Robert H

    2017-07-12

    The different types of acceptorless alcohol dehydrogenation (AAD) reactions are discussed, followed by the catalysts and mechanisms involved. Special emphasis is put on the common appearance in AAD of pincer ligands, of noninnocent ligands, and of outer sphere mechanisms. Early work emphasized precious metals, mainly Ru and Ir, but interest in nonprecious metal AAD catalysis is growing. Alcohol-amine combinations are discussed to the extent that net oxidation occurs by loss of H 2 . These reactions are of potential synthetic interest because they can lead to N heterocycles such as pyrroles and pyridines. AAD also has green chemistry credentials in that an oxidation occurs without the need for an oxidizing agent and hence without the waste formation that would result from its use.

  18. The hydrogenation and dehydrogenation of C2-C4 hydrocarbons on Pt(111) monitored in situ over 13 orders of magnitude in pressure with infrared-visible sum frequency generation

    Energy Technology Data Exchange (ETDEWEB)

    Cremer, Paul Samuel [Univ. of California, Berkeley, CA (United States)

    1996-05-01

    The hydrogenation and dehydrogenation of ethylene, propylene, and isobutene were monitored in situ during heterogeneous catalysis over Pt(111) between 10-10 Torr and 1000 Torr with infrared-visible sum frequency generation (SFG). SFG is a surface specific vibrational spectroscopy capable of achieving submonolayer sensitivity under reaction conditions in the presence of hundreds of Toff of reactants and products. Olefin dehydrogenation experiments were carried out with SFG under ultra high vacuum (UHV) conditions on the (111) crystal face of platinum Ethylene chemisorbed on Pt(111) below 230 K in the di-σ bonded conformation (Pt-CH2CH2-Pt). Upon annealing the system to form the dehydrogenation product, ethylidyne (M=CCH3), evidence was found for an ethylidene intermediate (M=CHCH3) from its characteristic vas(CH3) near 2960 cm-1. Hydrogenation of ethylene was carried out between 1 Toff and 700 Torr of H2 while the vibrational spectrum of surface species was monitored with SFG. Simultaneously, gas chromatography was used to obtain the turnover rate for the catalytic reaction, which could be correlated with the adsorbed intermediate concentration to determine the reaction rate per surface intermediate. Di-σ bonded ethylene, π-bonded ethylene, ethyl groups and ethylidyne resided on the surface during reaction. The mechanistic pathway for ethylene hydrogenation involved the stepwise hydrogenation of π-bonded ethylene through an ethyl intermediate to ethane. The hydrogenation of propylene was carried out under the same conditions as ethylene. It was found that propylene hydrogenates from π-bonded propylene through a 2-propyl intermediate to propane on Pt(111). The rate of reaction was approximately 50% slower than that of ethylene hydrogenation. Isobutene, however, was found to hydrogenate almost two order of magnitude slower than propylene on Pt(111).

  19. Theoretical investigation of the selective dehydration and dehydrogenation of ethanol catalyzed by small molecules.

    Science.gov (United States)

    Wang, Yanqun; Tang, Yizhen; Shao, Youxiang

    2017-09-01

    Catalytic dehydration and dehydrogenation reactions of ethanol have been investigated systematically using the ab initio quantum chemistry methods The catalysts include water, hydrogen peroxide, formic acid, phosphoric acid, hydrogen fluoride, ammonia, and ethanol itself. Moreover, a few clusters of water and ethanol were considered to simulate the catalytic mechanisms in supercritical water and supercritical ethanol. The barriers for both dehydration and dehydrogenation can be reduced significantly in the presence of the catalysts. It is revealed that the selectivity of the catalytic dehydration and dehydrogenation depends on the acidity and basicity of the catalysts and the sizes of the clusters. The acidic catalyst prefers dehydration while the basic catalysts tend to promote dehydrogenation more effectively. The calculated water-dimer catalysis mechanism supports the experimental results of the selective oxidation of ethanol in the supercritical water. It is suggested that the solvent- and catalyst-free self-oxidation of the supercritical ethanol could be an important mechanism for the selective dehydrogenation of ethanol on the theoretical point of view. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Base metal dehydrogenation of amine-boranes

    Science.gov (United States)

    Blacquiere, Johanna Marie [Ottawa, CA; Keaton, Richard Jeffrey [Pearland, TX; Baker, Ralph Thomas [Los Alamos, NM

    2009-06-09

    A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

  1. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    Science.gov (United States)

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol.

  2. Process, including membrane separation, for separating hydrogen from hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Baker, Richard W. (Palo Alto, CA); Lokhandwala, Kaaeid A. (Union City, CA); He, Zhenjie (Fremont, CA); Pinnau, Ingo (Palo Alto, CA)

    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.

  3. Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier.

    Science.gov (United States)

    Ventura-Espinosa, David; Carretero-Cerdán, Alba; Baya, Miguel; García, Hermenegildo; Mata, Jose A

    2017-08-10

    The compound [Ru(p-cym)(Cl) 2 (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  5. Dehydrogenation in large ingot casting process

    International Nuclear Information System (INIS)

    Ubukata, Takashi; Suzuki, Tadashi; Ueda, Sou; Shibata, Takashi

    2009-01-01

    Forging components (for nuclear power plants) have become larger and larger because of decreased weld lines from a safety point of view. Consequently they have been manufactured from ingots requirement for 200 tons or more. Dehydrogenation is one of the key issues for large ingot manufacturing process. In the case of ingots of 200 tons or heavier, mold stream degassing (MSD) has been applied for dehydrogenation. Although JSW had developed mold stream degassing by argon (MSD-Ar) as a more effective dehydrogenating practice, MSD-Ar was not applied for these ingots, because conventional refractory materials of a stopper rod for the Ar blowing hole had low durability. In this study, we have developed a new type of stopper rod through modification of both refractory materials and the stopper rod construction and have successfully expanded the application range of MSD-Ar up to ingots weighting 330 tons. Compared with the conventional MSD, the hydrogen content in ingots after MSD-Ar has decreased by 24 percent due to the dehydrogenation rate of MSD-Ar increased by 34 percent. (author)

  6. Buckyball-, carbon nanotube-, graphite-, and graphene-enhanced dehydrogenation of lithium aluminum hydride.

    Science.gov (United States)

    Hsu, Chih-Ping; Jiang, De-hao; Lee, Sheng-Long; Horng, Jain-Long; Ger, Ming-Der; Chang, Jeng-Kuei

    2013-10-09

    Compared to C60, carbon nanotubes, and graphite, graphene more effectively lowers the dehydrogenation temperature and improves the dehydrogenation kinetics of LiAlH4. With 15 wt% graphene incorporation, the initial hydrogen release temperature is ~80 °C (60 °C lower than that of pristine LiAlH4).

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

    Science.gov (United States)

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

    2017-01-17

    One of the greatest challenges in using H 2 as a fuel source is finding a safe, efficient, and inexpensive method for its storage. Ammonia borane (AB) is a solid hydrogen storage material that has garnered attention for its high hydrogen weight density (19.6 wt %) and ease of handling and transport. Hydrogen release from ammonia borane is mediated by either hydrolysis, thus giving borate products that are difficult to rereduce, or direct dehydrogenation. Catalytic AB dehydrogenation has thus been a popular topic in recent years, motivated both by applications in hydrogen storage and main group synthetic chemistry. This Account is a complete description of work from our laboratory in ruthenium-catalyzed ammonia borane dehydrogenation over the last 6 years, beginning with the Shvo catalyst and resulting ultimately in the development of optimized, leading catalysts for efficient hydrogen release. We have studied AB dehydrogenation with Shvo's catalyst extensively and generated a detailed understanding of the role that borazine, a dehydrogenation product, plays in the reaction: it is a poison for both Shvo's catalyst and PEM fuel cells. Through independent syntheses of Shvo derivatives, we found a protective mechanism wherein catalyst deactivation by borazine is prevented by coordination of a ligand that might otherwise be a catalytic poison. These studies showed how a bidentate N-N ligand can transform the Shvo into a more reactive species for AB dehydrogenation that minimizes accumulation of borazine. Simultaneously, we designed novel ruthenium catalysts that contain a Lewis acidic boron to replace the Shvo -OH proton, thus offering more flexibility to optimize hydrogen release and take on more general problems in hydride abstraction. Our scorpionate-ligated ruthenium species (12) is a best-of-class catalyst for homogeneous dehydrogenation of ammonia borane in terms of its extent of hydrogen release (4.6 wt %), air tolerance, and reusability. Moreover, a

  8. Shaking table test study on seismic performance of dehydrogenation fan for nuclear power plants

    International Nuclear Information System (INIS)

    Liu Kaiyan; Shi Weixing; Cao Jialiang; Wang Yang

    2011-01-01

    Seismic performance of the dehydrogenation fan for nuclear power plants was evaluated based on the shaking table test of earthquake simulation. Dynamic characteristics including the orthogonal tri-axial fundamental frequencies and equivalent damping ratios were measured by the white noise scanning method. Artificial seismic waves were generated corresponding to the floor acceleration response spectra for nuclear power plants. Furthermore, five OBE and one SSE shaking table tests for dehydrogenation fan were performed by using the artificial seismic waves as the seismic inputs along the orthogonal axis simultaneity. Operating function of dehydrogenation fan was monitored and observed during all seismic tests, and performance indexes of dehydrogenation fan were compared before and after seismic tests. The results show that the structural integrity and operating function of the dehydrogenation fan are perfect during all seismic tests; and the performance indexes of the dehydrogenation fan can remain consistent before and after seismic tests; the seismic performance of the dehydrogenation fan can satisfy relevant technical requirements. (authors)

  9. 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.

  10. Concept and progress in coupling of dehydrogenation and ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 2 ... This review focuses on the importance of coupling of catalytic reactions which involves dehydrogenation and hydrogenation simultaneously and the study of ... Structural and textural properties also play a decisive role in this kind of coupled reactions.

  11. Chromium oxide catalysts in the dehydrogenation of alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Airaksinen, S.

    2005-07-01

    Light alkenes, such as propene and butenes, are important intermediates in the manufacture of fuel components and chemicals. The direct catalytic dehydrogenation of the corresponding alkanes is a selective way to produce these alkenes and is frequently carried out using chromia/alumina catalysts. The aim of this work was to obtain structure-activity information, which could be utilised in the optimisation of this catalytic system. The properties of chromia/alumina catalysts were investigated by advanced in situ and ex situ spectroscopic methods, and the activities were measured in the dehydrogenation of isobutane. The dehydrogenation activity of chromia/alumina was attributed to coordinatively unsaturated redox and non- redox Cr{sup 3+} ions at all chromium loadings. In addition, the oxygen ions in the catalyst appeared to participate in the reaction. The reduction of chromia/alumina resulted in formation of adsorbed surface species: hydroxyl groups bonded to chromia and alumina were formed in reduction by hydrogen and alkanes, and carbon- containing species in reduction by carbon monoxide and alkanes. Prereduction with hydrogen or carbon monoxide decreased the dehydrogenation activity. The effect by hydrogen was suggested to be related to the amount of OH/H species on the reduced surface affecting the number of coordinatively unsaturated chromium sites, and the effect by carbon monoxide to the formation of unselective chromium sites and carboncontaining species. The chromia/alumina catalysts were deactivated with time on stream and in cycles of (pre)reduction- dehydrogenation-regeneration. The deactivation with time on stream was caused mainly by coke formation. The nature of the coke species changed during dehydrogenation. Carboxylates and aliphatic hydrocarbon species formed at the beginning of the reaction and unsaturated/aromatic hydrocarbons and graphite- like species with increasing time on stream. The deactivation in several dehydrogenation- regeneration

  12. Dehydrogenation of goethite in Earth's deep lower mantle

    Science.gov (United States)

    Hu, Qingyang; Kim, Duck Young; Liu, Jin; Meng, Yue; Yang, Liuxiang; Zhang, Dongzhou; Mao, Wendy L.; Mao, Ho-kwang

    2017-02-01

    The cycling of hydrogen influences the structure, composition, and stratification of Earth’s interior. Our recent discovery of pyrite-structured iron peroxide (designated as the P phase) and the formation of the P phase from dehydrogenation of goethite FeO2H implies the separation of the oxygen and hydrogen cycles in the deep lower mantle beneath 1,800 km. Here we further characterize the residual hydrogen, x, in the P-phase FeO2Hx. Using a combination of theoretical simulations and high-pressure-temperature experiments, we calibrated the x dependence of molar volume of the P phase. Within the current range of experimental conditions, we observed a compositional range of P phase of 0.39 hydrogen and lower x, suggesting that dehydrogenation could be approaching completion at the high-temperature conditions of the lower mantle over extended geological time. Our observations indicate a fundamental change in the mode of hydrogen release from dehydration in the upper mantle to dehydrogenation in the deep lower mantle, thus differentiating the deep hydrogen and hydrous cycles.

  13. Investigation of the kinetics and mechanism of the dehydrogenation of isobutane on platinum and platinum-indium catalysts

    International Nuclear Information System (INIS)

    Loc, L.K.; Gaidai, N.A.; Gudkov, B.S.; Kostyukovskii, M.M.; Kiperman, S.L.; Podkletnova, N.M.; Kogan, S.B.; Bursian, N.R.

    1987-01-01

    The kinetics and mechanism of isobutane dehydrogenation on platinum and platinum-indium catalysts have been investigated. The kinetic isotopic effects have been measured during exchange of hydrogen by deuterium in reactions for isobutane dehydrogenation and isobutylene hydrogenation, and the isotopic distribution has been studied for exchange of isobutane and isobutylene with deuterium. A kinetic equation has been proposed for isobutane dehydrogenation, describing the experimental data over wide ranges of reagent concentration and degree of conversion. A stagewise scheme for the reaction mechanism has been substantiated, from which a kinetic equation results which is in accordance with experimental data

  14. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Nederlof, C.

    2012-01-01

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  15. Gasochromic property of dehydrogenation-catalyst loaded tungsten trioxide

    Science.gov (United States)

    Hakoda, Teruyuki; Igarashi, Hidetoshi; Isozumi, Yukihiro; Yamamoto, Shunya; Aritani, Hirofumi; Yoshikawa, Masahito

    2013-02-01

    The gasochromic property of dehydrogenation-catalyst loaded tungsten trioxide (M/WO3) powders was examined in exposure to gaseous cyclohexane under different kinds and contents of catalysts, catalyst temperatures, and cyclohexane concentrations. The change in the intensity of visible lights reflected from the M/WO3 powders was in situ obtained using a portable visible-light spectrometer associating with the analysis of dehydrogenation products when M/WO3 powders were exposed to cyclohexane gas. The catalyst of Pt was a catalyst initiating dehydrogenation and change of reflected light intensity at lower temperatures in comparison with the catalysts of Pd and Rh. Among 0.1, 0.5, and 1 wt% Pt/WO3 powders, 0.5 wt% Pt/WO3 powders demonstrated large change of reflected 640-nm lights, 5.4%, to visually detect their coloration at lower temperatures. The heating of 0.5 wt% Pt/WO3 powders at temperatures higher than 130 °C was required to visually detect cyclohexane at a concentration of 1 vol%, lower than the combustion lower limit (1.3 vol%). The quantitative analysis of hydrogen species such as hydrogen atoms and ions absorbed in 0.1-1 wt% Pt/WO3 powders demonstrated that Pt/WO3 powders would absorb the same amount of hydrogen species independent of loaded-Pt contents.

  16. Lead-containing solid "oxygen reservoirs" for selective hydrogen combustion

    NARCIS (Netherlands)

    Beckers, J.; Rothenberg, G.

    2009-01-01

    Lead-containing catalysts can be applied as solid "oxygen reservoirs" in a novel process for propane oxidative dehydrogenation. The catalyst lattice oxygen selectively burns hydrogen from the dehydrogenation mixture at 550 degrees C. This shifts the dehydrogenation equilibrium to the desired

  17. A prolific catalyst for dehydrogenation of neat formic acid.

    Science.gov (United States)

    Celaje, Jeff Joseph A; Lu, Zhiyao; Kedzie, Elyse A; Terrile, Nicholas J; Lo, Jonathan N; Williams, Travis J

    2016-04-14

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

  18. A prolific catalyst for dehydrogenation of neat formic acid

    Science.gov (United States)

    Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A.; Terrile, Nicholas J.; Lo, Jonathan N.; Williams, Travis J.

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  19. Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis.

    Science.gov (United States)

    West, Julian G; Huang, David; Sorensen, Erik J

    2015-12-11

    The dehydrogenation of unactivated alkanes is an important transformation both in industrial and biological systems. Recent efforts towards this reaction have revolved around high temperature, organometallic C-H activation by noble metal catalysts that produce alkenes and hydrogen gas as the sole products. Conversely, natural desaturase systems proceed through stepwise hydrogen atom transfer at physiological temperature; however, these transformations require a terminal oxidant. Here we show combining tetra-n-butylammonium decatungstate (TBADT) and cobaloxime pyridine chloride (COPC) can catalytically dehydrogenate unactivated alkanes and alcohols under near-UV irradiation at room temperature with hydrogen as the sole by-product. This noble metal-free process follows a nature-inspired pathway of high- and low-energy hydrogen atom abstractions. The hydrogen evolution ability of cobaloximes is leveraged to render the system catalytic, with cooperative turnover numbers up to 48 and yields up to 83%. Our results demonstrate how cooperative base metal catalysis can achieve transformations previously restricted to precious metal catalysts.

  20. Oxidative dehydrogenation of propane over niobia supported vanadium oxide catalysts

    NARCIS (Netherlands)

    Watling, T.C.; Watling, T.C.; Deo, G.; Seshan, Kulathuiyer; Wachs, I.E.; Lercher, J.A.

    1996-01-01

    Oxidative dehydrogenation (ODH) of propane is examined over a series of catalysts, which include Nb2O5 supported monolayer V2O5 catalysts, bulk vanadia-niobia with different vanadium oxide loadings and prepared by four different methods, V2O5and Nb2O5. The intrinsic activity (TOF) of the samples

  1. Catalysts for Dehydrogenation of ammonia boranes

    Energy Technology Data Exchange (ETDEWEB)

    Heinekey, Dennis M. [Univ. of Washington, Seattle, WA (United States)

    2009-10-31

    Several effective homogeneous catalysts for the dehydrogenation of amine boranes have been developed. The best catalyst uses an iridium complex, and is capable of dehydrogenating H3NBH3 (AB) and CH3NH2BH3 (MeAB) at comparable rates. Thermodynamic measurements using this catalyst demonstrate that the dehydrogenation of AB and MeAB is substantially exothermic, which has important implications for regeneration.

  2. Improved magnetic properties and fracture strength of NdFeB by dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Yan, M. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China)]. E-mail: mse_yanmi@dial.zju.edu.cn; Yu, L.Q. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Wu, J.M. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Cui, X.G. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China)

    2006-11-15

    Effects of the dehydrogenation of the hydrogen decrepitated (HD) powders on the magnetic properties and the fracture strength of sintered NdFeB magnets were studied. It was found that the lattice parameters and the crystal phase of NdFeB changed significantly with the various hydrogen contents of the resultant HD powders due to the different degrees of dehydrogenation. The magnetic properties and fracture strength increased with decreasing hydrogen content, reaching the maximum increases of 200% for both intrinsic coercivity and bending strength, which can be ascribed to the improved microstructure of the sintered NdFeB magnets. The hydrogen remaining in the HD powders diffused out and affected drastically the grain and grain boundaries by the hydrogen out-take channel during the subsequent sintering process.

  3. Improved magnetic properties and fracture strength of NdFeB by dehydrogenation

    International Nuclear Information System (INIS)

    Yan, M.; Yu, L.Q.; Wu, J.M.; Cui, X.G.

    2006-01-01

    Effects of the dehydrogenation of the hydrogen decrepitated (HD) powders on the magnetic properties and the fracture strength of sintered NdFeB magnets were studied. It was found that the lattice parameters and the crystal phase of NdFeB changed significantly with the various hydrogen contents of the resultant HD powders due to the different degrees of dehydrogenation. The magnetic properties and fracture strength increased with decreasing hydrogen content, reaching the maximum increases of 200% for both intrinsic coercivity and bending strength, which can be ascribed to the improved microstructure of the sintered NdFeB magnets. The hydrogen remaining in the HD powders diffused out and affected drastically the grain and grain boundaries by the hydrogen out-take channel during the subsequent sintering process

  4. A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Ebru Ünel Barın

    2015-06-01

    Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

  5. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  6. Group 4 metallocene catalysed full dehydrogenation of hydrazine borane.

    Science.gov (United States)

    Thomas, Johannes; Klahn, Marcus; Spannenberg, Anke; Beweries, Torsten

    2013-10-01

    A study of the full dehydrogenation of hydrazine borane (H2N-NH2·BH3) to give H2 and N2 as gaseous products catalysed by a variety of group 4 metallocene alkyne complexes of the type CpM(L)(η(2)-Me3SiC2SiMe3) (Cp' = substituted or unsubstituted η(5)-cyclopentadienyl; M = Ti, no L; M = Zr, L = pyridine) and group 4 metallocene hydrides is presented. Volumetric data show that the amount of hydrogen released is strongly dependent on both, the metal and the cyclopentadienyl ligand.

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

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert

    2017-01-01

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

  8. Formation of carbon-containing deposits on chromia/alumina during isobutane dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Airaksinen, S.M.K.; Krause, A.O.I. [Helsinki Univ. of Technology, Lab. of Industrial Chemistry, Espoo (Finland)

    2004-07-01

    The formation of carbon-containing species during isobutane dehydrogenation was studied for a chromia/alumina catalyst with 13.5 wt-% chromium. Measurements were done by in situ DRIFT spectroscopy combined with on line mass spectrometry both as a function of temperature and of time on stream. Oxygen-containing carbon species formed on the catalyst during reduction by isobutane, whereas hydrocarbon species (aliphatic, unsaturated/aromatic) appeared under conditions where dehydrogenation of isobutane took place. Hydrogen prereduction of the catalyst decreased the formation of oxygen-containing and aliphatic species, but it did not have an observable effect on the unsaturated/aromatic species. (orig.)

  9. Dehydrogenation in lithium borohydride/conventional metal hydride composite based on a mutual catalysis

    DEFF Research Database (Denmark)

    Yu, X.B.; Shi, Qing; Vegge, Tejs

    2009-01-01

    The dehydrogenation of LiBH4 ball-milled with hydrogenated 40Ti–15Mn–15Cr–30V alloy was investigated. It was found that there is a mutual catalysis between the two hydrides, lowering the temperature of hydrogen release from both hydrides. In the case of 1h milled LiBH4/40Ti–15Mn–15Cr–30V...

  10. Dehydrogenation and Sintering of TiH2: An In Situ Study

    Science.gov (United States)

    Chen, Gang; Liss, Klaus D.; Auchterlonie, Graeme; Tang, Huiping; Cao, Peng

    2017-06-01

    This first-ever study investigated dehydrogenation and microstructural evolution of TiH2 during sintering under vacuum using in situ neutron diffraction, in situ transmission electron microscopy, and ex situ neutron tomography. The densification behavior, microstructure, hydrogen concentration, and in situ phase transformation were reported. The shrinkage, weight loss percentage, and densification of the TiH2 powder compact monotonically increase with sintering temperature, while the open porosity behaves differently; porosity first increases at the initial sintering stage and then decreases during further sintering. The in situ phase transformation observations reveal that dehydrogenation starts from the outer area of either a particle or a powder compact and progressively carries forward into the interior of the particle or the compact. A shrinking core model was proposed to elucidate the dehydrogenation process for a single particle and a powder compact.

  11. Study on catalytic properties and carbon deposition of Ni-Cu/SBA-15 for cyclohexane dehydrogenation

    Science.gov (United States)

    Xia, Zhijun; Liu, Huayan; Lu, Hanfeng; Zhang, Zekai; Chen, Yinfei

    2017-11-01

    A series of Ni-Cu supported on SBA-15 were prepared by impregnation, and used as catalysts in cyclohexane dehydrogenation for hydrogen production. The results indicated that the addition of Cu into Ni changes the crystal structure of metal Ni, and forms Ni-Cu alloy. Thus, Cu improves the reduction properties of Ni. Conversely, Ni stables and disperses metal Cu. With the space limitation of the ordered channels and high surface area of SBA-15, the bimetallic Ni-Cu/SBA-15 catalysts expose large amounts of selective active sites composed uniformly with Ni and Cu. Therefore, they present not only excellent catalytic performance for cyclohexane dehydrogenation, but also low coke formation. The in-situ DRIFT studies have shown the vinyl species, indicating the existence of alkenes in the reactive intermediates. Additionally, the strong absorption of benzene on the metal could induce benzene was dehydrogenated further to carbon.

  12. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille

    2015-01-01

    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...... cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment......, IrHCl2(CO)(rac-BINAP) was detected from the release of HCl in the dehydrogenation and subsequent reaction with IrCl(CO)(rac-BINAP). This indicated a substitution of chloride with the alcohol to form a square planar iridium alkoxo complex that could undergo a beta-hydride elimination. A KIE of 1...

  13. Improvement of the dehydrogenating kinetics of the Mg(NH{sub 2}){sub 2}/LiH materials by inducing LiBH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingchuan, E-mail: wangjingchuan@caep.cn; Song, Jiangfeng; Chen, Changan; Luo, Deli

    2016-12-15

    Highlights: • This work indicates that inducing 10 wt.% LiBH{sub 4} into the Mg(NH{sub 2}){sub 2}/LiH mixture significantly improves the dehydrogenating kinetics. It has a near 40 times as large as the effect of the Ti{sub 3}Cr{sub 3}V{sub 4} nanoparticles catalyst under the 200 °C and 0.1 MPa dehydrogenating environment. • Based on diffusion model, the dehydrogenating kinetic curve was fitted for illuminating the mechanism of dehydrogenation improvement. • The mechanism is proposed that the eutectic reaction takes a big role in the catalysis process as the arising of nanorods inside of the matrix after several re-/dehydrogenation cycles. - Abstract: The lightweight high-capacity Li-Mg-N-H system is a promising candidate for the hydrogen energy storage materials. Nevertheless, the slow dehydrogenating process limits its application. This work is focusing on the effect of LiBH{sub 4} on the dehydrogenating kinetics of the Mg(NH{sub 2}){sub 2}/LiH mixture. It indicates that inducing 10 wt.% LiBH{sub 4} into the Mg(NH{sub 2}){sub 2}/LiH mixture significantly improves the dehydrogenating kinetics. As a result, it has a near 40 times as large as the effect of the Ti alloy nanoparticles catalyst, under the 200 °C and 0.1 MPa dehydrogenating environment. Based on our previous dehydrogenating kinetics model, the mechanism of this improving effect of LiBH{sub 4} is discussed as well, which shows that the eutectic reaction takes a big role in the catalysis process as the arising of nanorods inside of the matrix after several re-/dehydrogenation cycles.

  14. Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M.

    1943-02-19

    A transcript is presented of a speech on the history of the development of hydrogenation of coal and tar. Apparently the talk had been accompanied by the showing of photographic slides, but none of the pictures were included with the report. In giving the history, Dr. Pier mentioned the dependence of much of the development of hydrogenation upon previous development in the related areas of ammonia and methanol syntheses, but he also pointed out several ways in which equipment appropriate for hydrogenation differed considerably from that used for ammonia and methanol. Dr. Pier discussed the difficulties encountered with residue processing, design of the reaction ovens, manufacture of ovens and preheaters, heating of reaction mixtures, development of steels, and development of compressor pumps. He described in some detail his own involvement in the development of the process. In addition, he discussed the development of methods of testing gasolines and other fuels. Also he listed some important byproducts of hydrogenation, such as phenols and polycyclic aromatics, and he discussed the formation of iso-octane fuel from the butanes arising from hydrogenation. In connection with several kinds of equipment used in hydrogenation (whose pictures were being shown), Dr. Pier gave some of the design and operating data.

  15. Supported organoiridium catalysts for alkane dehydrogenation

    Science.gov (United States)

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  16. Incorporation of catalytic dehydrogenation into Fischer-Tropsch synthesis to lower carbon dioxide emissions

    Science.gov (United States)

    Huffman, Gerald P

    2012-09-18

    A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbon monoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

  17. Reversible hydrogen storage materials

    Science.gov (United States)

    Ritter, James A [Lexington, SC; Wang, Tao [Columbia, SC; Ebner, Armin D [Lexington, SC; Holland, Charles E [Cayce, SC

    2012-04-10

    In accordance with the present disclosure, a process for synthesis of a complex hydride material for hydrogen storage is provided. The process includes mixing a borohydride with at least one additive agent and at least one catalyst and heating the mixture at a temperature of less than about 600.degree. C. and a pressure of H.sub.2 gas to form a complex hydride material. The complex hydride material comprises MAl.sub.xB.sub.yH.sub.z, wherein M is an alkali metal or group IIA metal, Al is the element aluminum, x is any number from 0 to 1, B is the element boron, y is a number from 0 to 13, and z is a number from 4 to 57 with the additive agent and catalyst still being present. The complex hydride material is capable of cyclic dehydrogenation and rehydrogenation and has a hydrogen capacity of at least about 4 weight percent.

  18. Dehydrogenation of Surface-Oxidized Mixtures of 2LiBH4 + Al/Additives (TiF3 or CeO2

    Directory of Open Access Journals (Sweden)

    Juan Luis Carrillo-Bucio

    2017-11-01

    Full Text Available Research for suitable hydrogen storage materials is an important ongoing subject. LiBH4–Al mixtures could be attractive; however, several issues must be solved. Here, the dehydrogenation reactions of surface-oxidized 2LiBH4 + Al mixtures plus an additive (TiF3 or CeO2 at two different pressures are presented. The mixtures were produced by mechanical milling and handled under welding-grade argon. The dehydrogenation reactions were studied by means of temperature programmed desorption (TPD at 400 °C and at 3 or 5 bar initial hydrogen pressure. The milled and dehydrogenated materials were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, and Fourier transformed infrared spectroscopy (FT-IR The additives and the surface oxidation, promoted by the impurities in the welding-grade argon, induced a reduction in the dehydrogenation temperature and an increase in the reaction kinetics, as compared to pure (reported LiBH4. The dehydrogenation reactions were observed to take place in two main steps, with onsets at 100 °C and 200–300 °C. The maximum released hydrogen was 9.3 wt % in the 2LiBH4 + Al/TiF3 material, and 7.9 wt % in the 2LiBH4 + Al/CeO2 material. Formation of CeB6 after dehydrogenation of 2LiBH4 + Al/CeO2 was confirmed.

  19. Improved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

    Directory of Open Access Journals (Sweden)

    Shujun Qiu

    2017-01-01

    Full Text Available Doping with additives in a Li-Mg-N-H system has been regarded as one of the most effective methods of improving hydrogen storage properties. In this paper, we prepared Li3AlH6 and evaluated its effect on the dehydrogenation properties of 2LiNH2-MgH2. Our studies show that doping with Li3AlH6 could effectively lower the dehydrogenation temperatures and increase the hydrogen content of 2LiNH2-MgH2. For example, 2LiNH2-MgH2-0.1Li3AlH6 can desorb 6.43 wt % of hydrogen upon heating to 300 °C, with the onset dehydrogenation temperature at 78 °C. Isothermal dehydrogenation testing indicated that 2LiNH2-MgH2-0.1Li3AlH6 had superior dehydrogenation kinetics at low temperature. Moreover, the release of byproduct NH3 was successfully suppressed. Measurement of the thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the fact that doping with Li3AlH6 could improve the heat transfer for solid–solid reaction.

  20. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  1. 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.

  2. Hydrogen separation membranes annual report for FY 2008.

    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

    2009-03-17

    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. HTMs 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 progress that was made during Fy 2008 on the development of HTM materials.

  3. Hydrogen storage materials with focus on main group I-II elements

    Energy Technology Data Exchange (ETDEWEB)

    Andreasen, Anders

    2005-07-01

    A future hydrogen based society, viz. a society in which hydrogen is the primary energy carrier, is viewed by many as a solution to many of the energy related problems of the world {integral} the ultimate problem being the eventual depletion of fossil fuels. Although, for the hydrogen based society to become realizable, several technical difficulties must be dealt with. Especially, the transport sector relies on a cheap, safe and reliable way of storing hydrogen with high storage capacity, fast kinetics and favourable thermodynamics. No potential hydrogen storage candidate has been found yet, which meets all the criteria just summarized. The hydrogen storage solution showing the greatest potential in fulfilling the hydrogen storage criteria with respect to storage capacity, is solid state storage in light metal hydrides e.g. alkali metals and alkali earth metals. The remaining issues to be dealt with mainly concerns the kinetics of hydrogen uptake/release and the thermal stability of the formed hydride. In this thesis the hydrogen storage properties of some magnesium based hydrides and alkali metal tetrahydridoaluminates, a subclass of the so called complex hydrides, are explored in relation to hydrogen storage. After briefly reviewing the major energy related problems of the world, including some basic concepts of solid state hydrogen storage the dehydrogenation kinetics of various magnesium based hydrides are investigated. By means of time resolved in situ X-ray powder diffraction, quantitative phase analysis is performed for air exposed samples of magnesium, magnesium-copper, and magnesium-aluminum based hydrides. From kinetic analysis of the different samples it is generally found that the dehydrogenation kinetics of magnesium hydride is severely hampered by the presence of oxide impurities whereas alloying with both Cu and Al creates compounds significantly less sensitive towards contamination. This leads to a phenomenological explanation of the large

  4. Synthesis of Pd Composite Tubes by Electroless Plating for Isobutane Dehydrogenation

    OpenAIRE

    DOGAN, Meltem; KILICARSLAN, Saliha

    2011-01-01

    Isobutene is used as a raw material in the production of ethers for increasing the octane rating and reducing exhaust emissions in gasoline. Dehydrogenation of isobutane is an endothermic equilibrium-limited reaction. Recent studies have focused on overcoming equilibrium limitations by removing the product hydrogen through a membrane. In this study, alumina-modified porous glass supports were plated with Pd using electroless plating (ELP). Plating studies were carried out at 35°C and ...

  5. Synthesis of Pd Composite Tubes by Electroless Plating for Isobutane Dehydrogenation

    OpenAIRE

    DOGAN, Meltem; KILICARSLAN, Saliha

    2012-01-01

    Isobutene is used as a raw material in the production of ethers for increasing the octane rating and reducing exhaust emissions in gasoline. Dehydrogenation of isobutane is an endothermic equilibrium-limited reaction. Recent studies have focused on overcoming equilibrium limitations by removing the product hydrogen through a membrane. In this study, alumina-modified porous glass supports were plated with Pd using electroless plating (ELP). Plating studies were carried out at 35°C and pH 1...

  6. A new perspective on catalytic dehydrogenation of ethylbenzene: the influence of side-reactions on catalytic performance

    OpenAIRE

    Gomez Sanz, S.; McMillan, L.; McGregor, J.; Zeitler, J.A.; Al-Yassir, N.; Al-Khattaf, S.; Gladden, L.F.

    2015-01-01

    The dehydrogenation of ethylbenzene to styrene is a highly important industrial reaction and the focus of significant research in order to optimise the selectivity to styrene and minimise catalyst deactivation. The reaction itself is a complex network of parallel and consecutive processes including cracking, steam-reforming and reverse water-gas shift (RWGS) in addition to dehydrogenation. The goal of this investigation is to decouple the major processes occurring and analyse how side-reactio...

  7. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

    Science.gov (United States)

    Metin, Önder; Sun, Xiaolian; Sun, Shouheng

    2013-02-07

    Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives.

  8. Ce0.95Cr0.05O2 and Ce0.97Cu0.03O2: Active, selective and stable catalysts for selective hydrogen combustion

    NARCIS (Netherlands)

    Beckers, J.; Rothenberg, G.

    2009-01-01

    Ceria-based materials are promising solid oxygen reservoirs for propane oxidative dehydrogenation. The ceria lattice oxygen can selectively combust hydrogen from the dehydrogenation mixture at 550 °C. This shifts the dehydrogenation equilibrium to the desired products side, generates heat aiding the

  9. 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

  10. Theoretical Study of Palladium Membrane Reactor Performance During Propane Dehydrogenation Using CFD Method

    Directory of Open Access Journals (Sweden)

    Kamran Ghasemzadeh

    2017-04-01

    Full Text Available This study presents a 2D-axisymmetric computational fluid dynamic (CFD model to investigate the performance Pd membrane reactor (MR during propane dehydrogenation process for hydrogen production. The proposed CFD model provided the local information of temperature and component concentration for the driving force analysis. After investigation of mesh independency of CFD model, the validation of CFD model results was carried out by other modeling data and a good agreement between CFD model results and theoretical data was achieved. Indeed, in the present model, a tubular reactor with length of 150 mm was considered, in which the Pt-Sn-K/Al2O3 as catalyst were filled in reaction zone. Hence, the effects of the important operating parameter (reaction temperature on the performances of membrane reactor (MR were studied in terms of propane conversion and hydrogen yield. The CFD results showed that the suggested MR system during propane dehydrogenation reaction presents higher performance with respect to once obtained in the conventional reactor (CR. In particular, by applying Pd membrane, was found that propane conversion can be increased from 41% to 49%. Moreover, the highest value of propane conversion (X = 91% was reached in case of Pd-Ag MR. It was also established that the feed flow rate of the MR is to be the one of the most important factors defining efficiency of the propane dehydrogenation process.

  11. Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts.

    Science.gov (United States)

    Wakizaka, Masanori; Matsumoto, Takeshi; Tanaka, Ryota; Chang, Ho-Chol

    2016-07-26

    Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH2), o-aminophenolate (apH(-)) and the non-precious metal complex trans-[Fe(II)(apH)2(MeOH)2]. Under excitation at 289±10 nm and in the absence of additional photosensitizers, these photocatalysts generate hydrogen and formaldehyde from anhydrous methanol with external quantum yields of 2.9±0.15%, 3.7±0.19% and 4.8±0.24%, respectively, which are the highest values reported so far to the best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of hydrogen radicals triggers the reaction.

  12. Incorporation of catalytic dehydrogenation into fischer-tropsch synthesis to significantly reduce carbon dioxide emissions

    Science.gov (United States)

    Huffman, Gerald P.

    2012-11-13

    A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO.sub.2 emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H.sub.2 level of coal-derived syngas for FTS. Additionally, the FTS-CDH process saves large amounts of water used by the WGS reaction and produces a valuable by-product, MWCNT.

  13. Reduced Toxicity Fuel Satellite Propulsion System Including Catalytic Decomposing Element with Hydrogen Peroxide

    Science.gov (United States)

    Schneider, Steven J. (Inventor)

    2002-01-01

    A reduced toxicity fuel satellite propulsion system including a reduced toxicity propellant supply for consumption in an axial class thruster and an ACS class thruster. The system includes suitable valves and conduits for supplying the reduced toxicity propellant to the ACS decomposing element of an ACS thruster. The ACS decomposing element is operative to decompose the reduced toxicity propellant into hot propulsive gases. In addition the system includes suitable valves and conduits for supplying the reduced toxicity propellant to an axial decomposing element of the axial thruster. The axial decomposing element is operative to decompose the reduced toxicity propellant into hot gases. The system further includes suitable valves and conduits for supplying a second propellant to a combustion chamber of the axial thruster, whereby the hot gases and the second propellant auto-ignite and begin the combustion process for producing thrust.

  14. Subnanometer-sized Pt/Sn alloy cluster catalysts for the dehydrogenation of linear alkanes.

    Science.gov (United States)

    Hauser, Andreas W; Gomes, Joseph; Bajdich, Michal; Head-Gordon, Martin; Bell, Alexis T

    2013-12-21

    The reaction pathways for the dehydrogenation of ethane, propane, and butane, over Pt are analyzed using density functional theory (DFT). Pt nanoparticles are represented by a tetrahedral Pt4 cluster. The objectives of this work were to establish which step is rate limiting and which one controls the selectivity for forming alkenes as opposed to causing further dehydrogenation of adsorbed alkenes to produce precursors responsible for catalyst deactivation due to coking. Further objectives of this work are to identify the role of adsorbed hydrogen, derived from H2 fed together with the alkane, on the reaction pathway, and the role of replacing one of the four Pt atoms by a Sn atom. A comparison of Gibbs free energies shows that in all cases the rate-determining step is cleavage of a C-H bond upon alkane adsorption. The selectivity to alkene formation versus precursors to coking is dictated by the relative magnitudes of the activation energies for alkene desorption and dehydrogenation of the adsorbed alkene. The presence of an adsorbed H atom on the cluster facilitates alkene desorption relative to dehydrogenation of the adsorbed alkene. Substitution of a Sn atom in the cluster to produce a Pt3Sn cluster leads to a downward shift of the potential energy surface for the reaction and causes an increase of the activity of the catalyst as suggested by recent experiments due to the lower net activation barrier for the rate limiting step. However, the introduction of Sn does not alter the relative activation barriers for gas-phase alkene formation versus loss of hydrogen from the adsorbed alkene, the process leading to the formation of coke precursors.

  15. Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

    KAUST Repository

    Chen, Tao

    2016-05-31

    In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

  16. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    DEFF Research Database (Denmark)

    Christensen, Rasmus Bjerregaard; Lu, Jing Tao; Hedegard, Per

    2016-01-01

    We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from...

  17. Catalytic dehydrogenation of light alkanes on metals and metal oxides

    NARCIS (Netherlands)

    Sattler, Jesper J H B|info:eu-repo/dai/nl/328235601; Ruiz-Martinez, Javier|info:eu-repo/dai/nl/341386405; Santillan-Jimenez, Eduardo|info:eu-repo/dai/nl/323171958; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2014-01-01

    A study is conducted to demonstrate catalytic dehydrogenation of light alkanes on metals and metal oxides. The study provides a complete overview of the materials used to catalyze this reaction, as dehydrogenation for the production of light olefins has become extremely relevant. Relevant factors,

  18. Investigation of the kinetics and mechanism of the dehydrogenation of isobutane on platinum-tin catalysts

    International Nuclear Information System (INIS)

    Lok, L.K.; Gaidai, N.A.; Gudkov, B.S.; Kiperman, S.L.; Kogan, S.B.

    1987-01-01

    An investigation has been made of the kinetics and mechanism for the dehydrogenation of isobutane on platinum-tin catalysts having different tin concentrations. It has been shown that the maximum activity is possessed by a catalyst containing 2% tin. On this catalyst the kinetic isotopic effect has been measured, in which the hydrogen was replaced by deuterium and the isotopic distribution has been measured for the exchange products between isobutane, isobutylene and deuterium. A stagewise system for the mechanism of the process and kinetic equations, proposed previously for the reaction on platinum and platinum-indium catalysts are fully applicable also to reactions on catalysts containing tin

  19. Hydrogen.

    Science.gov (United States)

    Bockris, John O'M

    2011-11-30

    The idea of a "Hydrogen Economy" is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO₂ in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H₂ from the electrolyzer. Methanol made with CO₂ from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  20. Accurate Bond Lengths to Hydrogen Atoms from Single?Crystal X?ray Diffraction by Including Estimated Hydrogen ADPs and Comparison to Neutron and QM/MM Benchmarks

    OpenAIRE

    Dittrich, Birger; L?bben, Jens; Mebs, Stefan; Wagner, Armin; Luger, Peter; Flaig, Ralf

    2017-01-01

    Abstract Amino acid structures are an ideal test set for method?development studies in crystallography. High?resolution X?ray diffraction data for eight previously studied genetically encoding amino acids are provided, complemented by a non?standard amino acid. Structures were re?investigated to study a widely applicable treatment that permits accurate X?H bond lengths to hydrogen atoms to be obtained: this treatment combines refinement of positional hydrogen?atom parameters with aspherical s...

  1. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris

    2011-11-01

    Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

  2. THE MATHEMATICAL MODEL DEVELOPMENT OF THE ETHYLBENZENE DEHYDROGENATION PROCESS KINETICS IN A TWO-STAGE ADIABATIC CONTINUOUS REACTOR

    Directory of Open Access Journals (Sweden)

    V. K. Bityukov

    2015-01-01

    Full Text Available The article is devoted to the mathematical modeling of the kinetics of ethyl benzene dehydrogenation in a two-stage adiabatic reactor with a catalytic bed functioning on continuous technology. The analysis of chemical reactions taking place parallel to the main reaction of styrene formation has been carried out on the basis of which a number of assumptions were made proceeding from which a kinetic scheme describing the mechanism of the chemical reactions during the dehydrogenation process was developed. A mathematical model of the dehydrogenation process, describing the dynamics of chemical reactions taking place in each of the two stages of the reactor block at a constant temperature is developed. The estimation of the rate constants of direct and reverse reactions of each component, formation and exhaustion of the reacted mixture was made. The dynamics of the starting material concentration variations (ethyl benzene batch was obtained as well as styrene formation dynamics and all byproducts of dehydrogenation (benzene, toluene, ethylene, carbon, hydrogen, ect.. The calculated the variations of the component composition of the reaction mixture during its passage through the first and second stages of the reactor showed that the proposed mathematical description adequately reproduces the kinetics of the process under investigation. This demonstrates the advantage of the developed model, as well as loyalty to the values found for the rate constants of reactions, which enable the use of models for calculating the kinetics of ethyl benzene dehydrogenation under nonisothermal mode in order to determine the optimal temperature trajectory of the reactor operation. In the future, it will reduce energy and resource consumption, increase the volume of produced styrene and improve the economic indexes of the process.

  3. New Gateways to the Platinum Group Metal-Catalyzed Direct Deuterium-Labeling Method Utilizing Hydrogen as a Catalyst Activator.

    Science.gov (United States)

    Sawama, Yoshinari; Park, Kwihwan; Yamada, Tsuyoshi; Sajiki, Hironao

    2018-01-01

    Deuterium-labeled compounds are widely utilized in various scientific fields. We summarize the recent advances in the direct deuteration of sugar, saturated fatty acid, and arene derivatives using heterogeneous platinum group metal on carbon catalysts by our research group. Hydrogen gas is a key catalyst-activator to facilitate the present H-D exchange reactions. In this review, the direct activation method of catalysts using in situ-generated hydrogen based on the dehydrogenation of alcohols is introduced. The obtained multiple deuterium-labeled products, including bioactive compounds, are expected to contribute to the development of many scientific investigations.

  4. Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States)

    2017-01-06

    An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources such as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.

  5. Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

    DEFF Research Database (Denmark)

    Bebensee, Fabian; Svane, K.; Bombis, Christian

    2013-01-01

    Adsorption of tetrahydroxybenzene (THB) on Cu(111) and Au(111) surfaces is studied using a combination of STM, XPS, and DFT. THB is deposited intact, but on Cu(111) it undergoes gradual dehydrogenation of the hydroxyl groups as a function of substrate temperature, yielding a pure dihydroxy......-benzoquinone phase at 370 K. Subtle changes to the adsorption structure upon dehydrogenation are explained from differences in molecule–surface bonding....

  6. Oxidative dehydrogenation of isobutane over a titanium pyrophosphate catalyst

    OpenAIRE

    IOAN-CEZAR MARCU; JEAN-MARC M. MILLET; IOAN SĂNDULESCU

    2005-01-01

    The catalytic properties of titanium pyrophosphate in the oxidative dehydrogenation of isobutane to isobutylene were investigated in the 400 – 550 ºC temperature range. Asignificant change of the product distribution and of the apparent activation energy of the reactionwas observed at about 490 ºC. This phenomenon, already observed in the oxidative dehydrogenation of n-butane, has been interpreted by the existence of two reaction mechanisms depending upon the reaction temperature. Comparison ...

  7. Accurate Bond Lengths to Hydrogen Atoms from Single-Crystal X-ray Diffraction by Including Estimated Hydrogen ADPs and Comparison to Neutron and QM/MM Benchmarks.

    Science.gov (United States)

    Dittrich, Birger; Lübben, Jens; Mebs, Stefan; Wagner, Armin; Luger, Peter; Flaig, Ralf

    2017-04-03

    Amino acid structures are an ideal test set for method-development studies in crystallography. High-resolution X-ray diffraction data for eight previously studied genetically encoding amino acids are provided, complemented by a non-standard amino acid. Structures were re-investigated to study a widely applicable treatment that permits accurate X-H bond lengths to hydrogen atoms to be obtained: this treatment combines refinement of positional hydrogen-atom parameters with aspherical scattering factors with constrained "TLS+INV" estimated hydrogen anisotropic displacement parameters (H-ADPs). Tabulated invariom scattering factors allow rapid modeling without further computations, and unconstrained Hirshfeld atom refinement provides a computationally demanding alternative when database entries are missing. Both should incorporate estimated H-ADPs, as free refinement frequently leads to over-parameterization and non-positive definite H-ADPs irrespective of the aspherical scattering model used. Using estimated H-ADPs, both methods yield accurate and precise X-H distances in best quantitative agreement with neutron diffraction data (available for five of the test-set molecules). This work thus solves the last remaining problem to obtain such results more frequently. Density functional theoretical QM/MM computations are able to play the role of an alternative benchmark to neutron diffraction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Operando Raman spectroscopy study on the deactivation of Pt/Al2O3 and Pt-Sn/Al2O3 propane dehydrogenation catalysts.

    Science.gov (United States)

    Sattler, Jesper J H B; Beale, Andrew M; Weckhuysen, Bert M

    2013-08-07

    The deactivation of 0.5 wt% Pt/Al2O3 and 0.5 wt% Pt-1.5 wt% Sn/Al2O3 catalysts has been studied by operando Raman spectroscopy during the dehydrogenation of propane and subsequent regeneration in air for 10 successive dehydrogenation-regeneration cycles. Furthermore, the reaction feed was altered by using different propane/propene/hydrogen ratios. It was found that the addition of hydrogen to the feed increases the catalyst performance and decreases the formation of coke deposits, as was revealed by thermogravimetrical analysis. The positive effect of hydrogen on the catalyst performance is comparable to the addition of Sn, a promoter element which increases both the propane conversion and propene selectivity. Operando Raman spectroscopy showed that hydrogen altered the nature of the coke deposits formed during propane dehydrogenation. Due to this approach it was possible to perform a systematic deconvolution procedure on the Raman spectra. By analysing the related intensity, band position and bandwidth of the different Raman features, it was determined that smaller graphite crystallites, which have less defects, are formed when the partial pressure of hydrogen in the feed was increased.

  9. Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry.

    Science.gov (United States)

    Haibach, Michael C; Kundu, Sabuj; Brookhart, Maurice; Goldman, Alan S

    2012-06-19

    Methods for the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels that are both efficient and economically viable could greatly enhance global security and prosperity. Currently, the major route to convert natural gas and coal to liquids is Fischer-Tropsch catalysis, which is potentially applicable to any source of synthesis gas including biomass and nonconventional fossil carbon sources. The major desired products of Fischer-Tropsch catalysis are n-alkanes that contain 9-19 carbons; they comprise a clean-burning and high combustion quality diesel, jet, and marine fuel. However, Fischer-Tropsch catalysis also results in significant yields of the much less valuable C(3) to C(8)n-alkanes; these are also present in large quantities in oil and gas reserves (natural gas liquids) and can be produced from the direct reduction of carbohydrates. Therefore, methods that could disproportionate medium-weight (C(3)-C(8)) n-alkanes into heavy and light n-alkanes offer great potential value as global demand for fuel increases and petroleum reserves decrease. This Account describes systems that we have developed for alkane metathesis based on the tandem operation of catalysts for alkane dehydrogenation and olefin metathesis. As dehydrogenation catalysts, we used pincer-ligated iridium complexes, and we initially investigated Schrock-type Mo or W alkylidene complexes as olefin metathesis catalysts. The interoperability of the catalysts typically represents a major challenge in tandem catalysis. In our systems, the rate of alkane dehydrogenation generally limits the overall reaction rate, whereas the lifetime of the alkylidene complexes at the relatively high temperatures required to obtain practical dehydrogenation rates (ca. 125 -200 °C) limits the total turnover numbers. Accordingly, we have focused on the development and use of more active dehydrogenation catalysts and more stable olefin-metathesis catalysts. We have used thermally

  10. Fabrication of hollow silica–zirconia composite spheres and their activity for hydrolytic dehydrogenation of ammonia borane

    International Nuclear Information System (INIS)

    Umegaki, Tetsuo; Hosoya, Tatsuya; Toyama, Naoki; Xu, Qiang; Kojima, Yoshiyuki

    2014-01-01

    Highlights: • Hollow silica–zirconia composite spheres were fabricated on polystyrene templates by the sol–gel method. • We study the effect of preparation conditions on the activity for hydrolytic dehydrogenation of ammonia borane. • The activity of hollow silica–zirconia composite spheres depends on wall thickness. - Abstract: In this paper, we report fabrication of hollow silica–zirconia composite spheres by polystyrene (PS) template method and control of wall thickness of the hollow spheres in nanoscale. Both the hollow spheres before and after calcination were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and powder X-ray diffraction analysis (XRD). Morphology of the hollow spheres does not significantly change after calcination from the results of SEM and TEM images, while the amount of residual PS templates drastically decreases via the calcination procedure from the results of FTIR and elemental analysis. The sample after calcination mainly includes amorphous silica from the results of XRD, indicating that the hollow silica–zirconia composite spheres consist of amorphous phases and/or fine particles. Wall thicknesses of the samples after calcination are controlled by adjusting the amount of PS template suspension, and hollow silica–zirconia composite spheres with the wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm are obtained using the PS template suspension of 25.0, 33.5, 100.0, and 400.0 g, respectively. The activities of the hollow spheres for hydrolytic dehydrogenation of ammonia borane (NH 3 BH 3 ) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0 mL hydrogen from aqueous NH 3 BH 3 solution were finished in about 4, 5, 3, and 7 min in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm, respectively. The molar ratios of the hydrolytically generated hydrogen to the initial NH 3

  11. Note on the chemical composition of the asphalts of bituminous coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Boente, L.

    1942-10-13

    This report was written not as a result of extensive unified experiments, but as a result of collected observations during the course of various investigations. It interpreted two of the major groups of constituents of the asphalts from hydrogenation of bituminous coal as the following: (1) highly condensed aromatics (including heterocyclic compounds with oxygen, nitrogen, or sulfur in the rings) (a) in dehydrogenated form, or (b) in partially hydrogenated form, and (2) reaction products from labile, partially hydrogenated highly condensed aromatics (a) through oxidation reactions, or (b) through condensation and polymerization reactions. These types of compounds seemed to come from rather symmetric precursors that were not split during pressure hydrogenation, as were most constituents of coal, but were dehydrogenated instead. The types of compounds mentioned above shared several properties with the asphalts, including precipitation and adsorption properties. Some examples given of Group 1 compounds were coronene and several derived from it, as well as napthoxanthene, carbazole, and diphenylene sulfide. One example given to illustrate Group 2 was some hypothetical reactions of a proposed hexakeideca-hydrocoronene.

  12. A comparative DFT study on the dehydrogenation of methanol on Rh(100) and Rh(110)

    Science.gov (United States)

    Zhang, Minhua; Wu, Xingyu; Yu, Yingzhe

    2018-04-01

    Numerous density functional theory calculations have been performed to investigate the complete mechanisms of methanol dehydrogenation on Rh(100) and Rh(110) surfaces. The adsorption properties of relevant species were discussed in details. In addition, a comprehensive reaction network including four reaction pathways was built and analyzed. It is found that the initial Osbnd H bond scission of CH3OH seems to be more favorable than Csbnd H bond cleavage on both Rh(100) and Rh(110) surfaces from the perspective of activation barriers. It is also concluded that path1 (CH3OH → CH3O → CH2O → CHO → CO) is the predominant pathway on both Rh(100) and Rh (110) surfaces. On the whole, in most of the dehydrogenation reactions investigated, the energy barriers on Rh(100) are lower than those on Rh (110). Remarkable differences in the activity and predominant reaction pathway on Rh(100), Rh(110) and Rh(111) indicate that the dehydrogenation of methanol might be structure-sensitive.

  13. Microstructures and Dehydrogenation Properties of Ball-milled MgH2-K2Ti6O13-Ni Composite Systems

    Directory of Open Access Journals (Sweden)

    ZHANG Jian

    2016-11-01

    Full Text Available The K2Ti6O13 whisker separate-doped and K2Ti6O13 whisker and Ni powder multi-doped MgH2 hydrogen storage composite systems were prepared by mechanical milling method. The microstructures and dehydrogenation properties of the prepared samples were characterized by some testing methods such as X-ray diffraction (XRD, scanning electron microscope (SEM and differential scanning calorimeter (DSC. The results show that the K2Ti6O13 whisker not only plays the roles in refining the MgH2 crystalline grain, but also inhibit the agglomeration of MgH2 particles in K2Ti6O13 whisker separate-doped system, which results in the decreased dehydrogenation temperature of MgH2 matrix. When the mass ratio of K2Ti6O13 to MgH2 is 3:7, the improvement effect on dehydrogenation properties of MgH2 is the most remarkable. As compared with pure ball-milled MgH2, the dehydrogenation temperature of MgH2 in K2Ti6O13 whisker separate-doped system is decreased by nearly 75℃. For K2Ti6O13 whisker and Ni powder multi-dopedsystem, the dehydrogenation temperature of MgH2 matrix is further decreased compared to K2Ti6O13 whisker separate-doped one due to the dual effects of refined MgH2 crystalline grain by K2Ti6O13 whisker and destabilized MgH2 lattice by Ni solution. As compared with pure ball-milled MgH2, the dehydrogenation temperature of MgH2 in K2Ti6O13 whisker and Ni powder multi-doped system is decreased by nearly 87℃.

  14. ENHANCEMENT OF EQUILIBRIUMSHIFT IN DEHYDROGENATION REACTIONS USING A NOVEL MEMBRANE REACTOR; FINAL

    International Nuclear Information System (INIS)

    Shamsuddin Ilias, Ph.d., P.E.; Franklin G. King, D.Sc.

    2001-01-01

    With the advances in new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Inorganic and composite membranes are being considered as potential candidates for use in membrane-reactor configuration for effectively increasing reaction rate, selectivity and yield of equilibrium limited reactions. To investigate the usefulness of a palladium-ceramic composite membrane in a membrane reactor-separator configuration, we investigated the dehydrogenation of cyclohexane by equilibrium shift. A two-dimensional pseudo-homogeneous reactor model was developed to study the dehydrogenation of cyclohexane by equilibrium shift in a tubular membrane reactor. Radial diffusion was considered to account for the concentration gradient in the radial direction due to permeation through the membrane. For a dehydrogenation reaction, the feed stream to the reaction side contained cyclohexane and argon, while the separation side used argon as the sweep gas. Equilibrium conversion for dehydrogenation of cyclohexane is 18.7%. The present study showed that 100% conversion could be achieved by equilibrium shift using Pd-ceramic membrane reactor. For a feed containing cyclohexane and argon of 1.64 x 10(sup -6) and 1.0 x 10(sup -3) mol/s, over 98% conversion could be readily achieved. The dehydrogenation of cyclohexane was also experimentally investigated in a palladium-ceramic membrane reactor. The Pd-ceramic membrane was fabricated by electroless deposition of palladium on ceramic substrate. The performance of Pd-ceramic membrane was compared with a commercially available hydrogen-selective ceramic membrane. From limited experimental data it was observed that by appropriate choice of feed flow rate and sweep gas rate, the conversion of cyclohexane to benzene and hydrogen can increased to 56% at atmospheric pressure and 200 C in a Pd-ceramic membrane reactor. In the commercial ceramic membrane

  15. Bismuth-doped ceria, Ce0.90Bi0.10O2: A selective and stable catalyst for clean hydrogen combustion

    NARCIS (Netherlands)

    Beckers, J.; Lee, A.F.; Rothenberg, G.

    2009-01-01

    Bismuth-doped cerias are successfully applied as solid oxygen reservoirs in the oxidative dehydrogenation of propane. The lattice oxygen of the ceria is used to selectively combust hydrogen from the dehydrogenation mixture at 550 °C. This process has three key advantages: it shifts the

  16. A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal

    Science.gov (United States)

    Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi; Carroll, Patrick J.; Manor, Brian C.; Baik, Mu-Hyun; Mindiola, Daniel J.

    2017-11-01

    Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2-), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

  17. Fullerene hydride - A potential hydrogen storage material

    International Nuclear Information System (INIS)

    Nai Xing Wang; Jun Ping Zhang; An Guang Yu; Yun Xu Yang; Wu Wei Wang; Rui long Sheng; Jia Zhao

    2005-01-01

    Hydrogen, as a clean, convenient, versatile fuel source, is considered to be an ideal energy carrier in the foreseeable future. Hydrogen storage must be solved in using of hydrogen energy. To date, much effort has been put into storage of hydrogen including physical storage via compression or liquefaction, chemical storage in hydrogen carriers, metal hydrides and gas-on-solid adsorption. But no one satisfies all of the efficiency, size, weight, cost and safety requirements for transportation or utility use. C 60 H 36 , firstly synthesized by the method of the Birch reduction, was loaded with 4.8 wt% hydrogen indicating [60]fullerene might be as a potential hydrogen storage material. If a 100% conversion of C 60 H 36 is achieved, 18 moles of H 2 gas would be liberated from each mole of fullerene hydride. Pure C 60 H 36 is very stable below 500 C under nitrogen atmosphere and it releases hydrogen accompanying by other hydrocarbons under high temperature. But C 60 H 36 can be decomposed to generate H 2 under effective catalyst. We have reported that hydrogen can be produced catalytically from C 60 H 36 by Vasks's compound (IrCl(CO)(PPh 3 ) 2 ) under mild conditions. (RhCl(CO)(PPh 3 ) 2 ) having similar structure to (IrCl(CO)(PPh 3 ) 2 ), was also examined for thermal dehydrogenation of C 60 H 36 ; but it showed low catalytic activity. To search better catalyst, palladium carbon (Pd/C) and platinum carbon (Pt/C) catalysts, which were known for catalytic hydrogenation of aromatic compounds, were tried and good results were obtained. A very big peak of hydrogen appeared at δ=5.2 ppm in 1 H NMR spectrum based on Evans'work (fig 1) at 100 C over a Pd/C catalyst for 16 hours. It is shown that hydrogen can be produced from C 60 H 36 using a catalytic amount of Pd/C. Comparing with Pd/C, Pt/C catalyst showed lower activity. The high cost and limited availability of Vaska's compounds, Pd and Pt make it advantageous to develop less expensive catalysts for our process based on

  18. Hydrogen separation membranes annual report for FY 2006.

    Energy Technology Data Exchange (ETDEWEB)

    Balachandran, U.; Chen, L.; Ciocco, M.; Doctor, R. D.; Dorris, S.E.; Emerson, J. E.; Fisher, B.; Lee, T. H.; Killmeyer, R. P.; Morreale,B.; Picciolo, J. J.; Siriwardane, R. V.; Song, S. J.

    2007-02-05

    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. This goal of this project is to develop two types of dense ceramic membrane for producing hydrogen nongalvanically, i.e., without electrodes or external power supply, at commercially significant fluxes under industrially relevant operating conditions. The first type of membrane, hydrogen transport membranes (HTMs), 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. The second type of membrane, oxygen transport membranes (OTMs), will produce hydrogen by nongalvanically removing oxygen that is generated when water dissociates at elevated temperatures. This report describes progress that was made during FY 2006 on the development of OTM and HTM materials.

  19. Acceleration of small, light projectiles (including hydrogen isotopes) to high speeds using a two-stage light gas gun

    International Nuclear Information System (INIS)

    Combs, S.K.; Foust, C.R.; Gouge, M.J.; Milora, S.L.

    1989-01-01

    Small, light projectiles have been accelerated to high speeds using a two-stage light gas gun at Oak Ridge National Laboratory. With 35-mg plastic projectiles (4 mm in diameter), speeds of up to 4.5 km/s have been recorded. The ''pipe gun'' technique for freezing hydrogen isotopes in situ in the gun barrel has been used to accelerate deuterium pellets (nominal diameter of 4 mm) to velocities of up to 2.85 km/s. The primary application of this technology is for plasma fueling of fusion devices via pellet injection of hydrogen isotopes. Conventional pellet injectors are limited to pellet speeds in the range 1-2 km/s. Higher velocities are desirable for plasma fueling applications, and the two-stage pneumatic technique offers performance in a higher velocity regime. However, experimental results indicate that the use of sabots to encase the cryogenic pellets and protect them for the high peak pressures will be required to reliably attain intact pellets at speeds of ∼3 km/s or greater. In some limited tests, lithium hydride pellets were accelerated to speeds of up to 4.2 km/s. Also, repetitive operation of the two-stage gun (four plastic pellets fired at ∼0.5 Hz) was demonstrated for the first time in preliminary tests. The equipment and operation are described, and experimental results and some comparisons with a theoretical model are presented. 17 refs., 6 figs., 2 tabs

  20. Long-Term Cycling of the Magnesium Hydrogen System

    DEFF Research Database (Denmark)

    Pedersen, Allan Schrøder; Kjøller, John; Larsen, Bent

    1984-01-01

    Magnesium powder with a grain size of approximately 50γm was hydrogenated for 30 min and dehydrogenated the same time at 390°C, 515 times. A moderate loss in hydrogen storage capacity was observed and was ascribed to a measured decrease in reaction kinetics as the cycle number increased. The time...

  1. Oxidative dehydrogenation of isobutane over a titanium pyrophosphate catalyst

    Directory of Open Access Journals (Sweden)

    IOAN-CEZAR MARCU

    2005-06-01

    Full Text Available The catalytic properties of titanium pyrophosphate in the oxidative dehydrogenation of isobutane to isobutylene were investigated in the 400 – 550 ºC temperature range. Asignificant change of the product distribution and of the apparent activation energy of the reactionwas observed at about 490 ºC. This phenomenon, already observed in the oxidative dehydrogenation of n-butane, has been interpreted by the existence of two reaction mechanisms depending upon the reaction temperature. Comparison with the n-butane reaction allowed different activation pathways for the activation of alkanes to be proposed. The catalytic properties of TiP2O7 in the oxidative dehydrogenation of isobutane was also compared to those obtained previously with several other pyrophosphates and TiP2O7 was found to be less active and selective for this reaction.

  2. Solid-Solid heterogeneous catalysis: the role of potassium in promoting the dehydrogenation of the Mg(NH(2))(2)/2 LiH composite.

    Science.gov (United States)

    Wang, Jianhui; Chen, Ping; Pan, Hongge; Xiong, Zhitao; Gao, Mingxia; Wu, Guotao; Liang, Chu; Li, Cao; Li, Bo; Wang, Jieru

    2013-11-01

    Considerable efforts have been devoted to the catalytic modification of hydrogen storage materials. The K-modified Mg(NH2 )2 /2 LiH composite is a typical model for such studies. In this work, we analyze the origin of the kinetic barrier in the first step of the dehydrogenation and investigate how K catalyzes this heterogeneous solid-state reaction. Our results indicate that the interface reaction of Mg(NH2 )2 and LiH is the main source of the kinetic barrier at the early stage of the dehydrogenation for the intensively ball-milled Mg(NH2 )2 /2 LiH sample. K can effectively activate Mg(NH2 )2 as well as promote LiH to participate in the dehydrogenation. Three K species of KH, K2 Mg(NH2 )4 , and Li3 K(NH2 )4 likely transform circularly in the dehydrogenation (KH↔K2 Mg(NH2 )4 ↔KLi3 (NH2 )4 ), which creates a more energy-favorable pathway and thus leads to the overall kinetic enhancement. This catalytic role of K in the amide/hydride system is different from the conventional catalysis of transition metals in the alanate system. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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.

  4. Oxidative dehydrogenation of isobutane over molybdenum and chromium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Nekrasov, N.V.; Gaidai, N.A.; Kasanzev, R.V.; Botavina, M.A. [N. D. Zelinsky Inst. of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    2004-07-01

    Effective molybdenum and chromium catalysts were found for oxidative dehydrogenation (ODH) of isobutane in the presence of O{sub 2}. Cobalt molybdate is the most active and selective catalyst in isobutane ODH. Kinetics and mechanism of the process was studied on it. The data obtained in nonstationary and stationary regions showed that lattice oxygen takes part in dehydrogenation reactions. Carbon oxides formation proceed by the interaction with adsorbed oxygen. The step-schemes for all reactions proceeding in the system are proposed. (orig.)

  5. Integration of catalyst design and reactor engineering in paraffins dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Sanfilippo, D.; Miracca, I. [Snamprogetti S.p.A., S. Donato Milanese (Italy)

    2005-07-01

    Unfortunately, olefins are not a natural fossil resource. Their production requires sophisticated and costly technologies, highly demanding in terms of investments and energy. Dehydrogenations are applied industrially to light alkanes (propane to propylene for polymers and isobutane to iso-butylene for gasoline and polymers) as well as long linear ones (C{sub 10}-C{sub 14} to linear-alkyl-benzenes) and for the production of styrene from ethylbenzene. The light paraffins dehydrogenation sustains a network of technologies allowing an integrated approach to create value from Natural Gas. (orig.)

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

    Science.gov (United States)

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

    2018-05-02

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

  7. 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

  8. Studies on dehydrogenation of cyclohexanol to cyclohexanone over ...

    Indian Academy of Sciences (India)

    B SRIDEVI

    be obtained from cyclohexanone.4,5 Copper-based cat- alysts have been reported for the dehydrogenation of cyclohexanol in liquid or vapour phase.6,7 A number of investigations have focused on the influence of support, method of preparation, and amount of copper loading on the activity, with the goal of enhancing the ...

  9. Propane Dehydrogenation on Metal and Metal Oxide Catalysts

    NARCIS (Netherlands)

    Sattler, Jesper

    2014-01-01

    In this PhD thesis, the catalytic performance and deactivation of various propane dehydrogenation catalysts is studied. First of all, a literature study is performed, where the three most commonly used formulations, namely Pt-, CrOx- and GaOx-based catalysts are compared in terms of yield relative

  10. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert

    2017-01-01

    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...

  11. Studies on ethylbenzene dehydrogenation with CO2 as soft oxidant ...

    Indian Academy of Sciences (India)

    Abstract. Oxidative dehydrogenation of ethylbenzene to styrene has been studied over Co3O4 supported on mesoporous silica (COK-12) with CO2 as soft oxidant in a fixed bed reactor at atmospheric pressure in the temperature range of 723 to 923K. While COK-12 has been prepared by self-assembly method using long.

  12. Interactions of hydrogen with ethylene and ethane on iridium

    Energy Technology Data Exchange (ETDEWEB)

    Mahaffy, Paul Robert [Iowa State Univ., Ames, IA (United States)

    1977-06-01

    In an effort to determine the details of reaction mechanisms, kinetic parameters are obtained for the following two catalytic reactions, C2Hsub>4+ Hsub>2 → Csub>2Hsub>6 and Csub>2Hsub>6+ Hsub>2 → 2 CHsub>4. The first reaction is carried out, for the most part, under reaction conditions (e.g. 110-200 K) which prevent complications caused by a side reaction, the surface dehydrogenation of adsorbed ethylene. The second reaction is carried out at somewhat higher temperatures (80 to 200°C). Both reactions are studied in the pressure range 0.5 to 1000 μ Extensive isotope labeling experiments are also carried out, which together with the kinetic measurements support in a self-consistent way the following mechanisms of hydrogen addition. The adsorbed species Csub>2Hsub>5(a) and H(a) are found to be intermediates in both the hydrogenation and hydrogenolysis reactions. In the case of the hydrogenation reaction, the rate limiting step is found to be the irreversible addition of an adsorbed hydrogen atom to an adsorbed ethylene molecule to produce Csub>2Hsub>5(a) which is further hydrogenated to produce ethane. The hydrogenolysis occurs by dissociative adsorption of ethane to produce Csub>2Hsub>5(a) and H(a). In this case the final kinetically significant elementary step is the reaction of an adsorbed hydrogen atom with one of the methyl hydrogen atoms of Csub>2Hsub>5(a), which produces a hydrogen molecule and is accompanied by the breaking of the carbon-carbon bond. Other processes which are kinetically significant for the hydrogenolysis reaction include slow (the sticking coefficient approximately 10-5) ethane adsorption, slow ethane desorption (by reaction of Csub>2Hsub>5(a) with H(a)), the reversible dehydrogenation of Csub>2Hsub>5(a) to produce Csub>2Hsub>4(a) and competition of hydrogen for the surface sites on

  13. Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free Hydrogen Economy.

    Science.gov (United States)

    Preuster, Patrick; Papp, Christian; Wasserscheid, Peter

    2017-01-17

    The need to drastically reduce CO 2 emissions will lead to the transformation of our current, carbon-based energy system to a more sustainable, renewable-based one. In this process, hydrogen will gain increasing importance as secondary energy vector. Energy storage requirements on the TWh scale (to bridge extended times of low wind and sun harvest) and global logistics of renewable energy equivalents will create additional driving forces toward a future hydrogen economy. However, the nature of hydrogen requires dedicated infrastructures, and this has prevented so far the introduction of elemental hydrogen into the energy sector to a large extent. Recent scientific and technological progress in handling hydrogen in chemically bound form as liquid organic hydrogen carrier (LOHC) supports the technological vision that a future hydrogen economy may work without handling large amounts of elemental hydrogen. LOHC systems are composed of pairs of hydrogen-lean and hydrogen-rich organic compounds that store hydrogen by repeated catalytic hydrogenation and dehydrogenation cycles. While hydrogen handling in the form of LOHCs allows for using the existing infrastructure for fuels, it also builds on the existing public confidence in dealing with liquid energy carriers. In contrast to hydrogen storage by hydrogenation of gases, such as CO 2 or N 2 , hydrogen release from LOHC systems produces pure hydrogen after condensation of the high-boiling carrier compounds. This Account highlights the current state-of-the-art in hydrogen storage using LOHC systems. It first introduces fundamental aspects of a future hydrogen economy and derives therefrom requirements for suitable LOHC compounds. Molecular structures that have been successfully applied in the literature are presented, and their property profiles are discussed. Fundamental and applied aspects of the involved hydrogenation and dehydrogenation catalysis are discussed, characteristic differences for the catalytic conversion of

  14. Dehydrogenation of Formic Acid over a Homogeneous Ru-TPPTS Catalyst: Unwanted CO Production and Its Successful Removal by PROX

    Directory of Open Access Journals (Sweden)

    Vera Henricks

    2017-11-01

    Full Text Available Formic acid (FA is considered as a potential durable energy carrier. It contains ~4.4 wt % of hydrogen (or 53 g/L which can be catalytically released and converted to electricity using a proton exchange membrane (PEM fuel cell. Although various catalysts have been reported to be very selective towards FA dehydrogenation (resulting in H2 and CO2, a side-production of CO and H2O (FA dehydration should also be considered, because most PEM hydrogen fuel cells are poisoned by CO. In this research, a highly active aqueous catalytic system containing Ru(III chloride and meta-trisulfonated triphenylphosphine (mTPPTS as a ligand was applied for FA dehydrogenation in a continuous mode. CO concentration (8–70 ppm in the resulting H2 + CO2 gas stream was measured using a wide range of reactor operating conditions. The CO concentration was found to be independent on the reactor temperature but increased with increasing FA feed. It was concluded that unwanted CO concentration in the H2 + CO2 gas stream was dependent on the current FA concentration in the reactor which was in turn dependent on the reaction design. Next, preferential oxidation (PROX on a Pt/Al2O3 catalyst was applied to remove CO traces from the H2 + CO2 stream. It was demonstrated that CO concentration in the stream could be reduced to a level tolerable for PEM fuel cells (~3 ppm.

  15. A liquid-based eutectic system: LiBH4·NH 3-nNH3BH3 with high dehydrogenation capacity at moderate temperature

    KAUST Repository

    Tan, Yingbin

    2011-01-01

    A novel eutectic hydrogen storage system, LiBH4·NH 3-nNH3BH3, which exists in a liquid state at room temperature, was synthesized through a simple mixing of LiBH 4·NH3 and NH3BH3 (AB). In the temperature range of 90-110 °C, the eutectic system showed significantly improved dehydrogenation properties compared to the neat AB and LiBH 4·NH3 alone. For example, in the case of the LiBH4·NH3/AB with a mole ratio of 1:3, over 8 wt.% hydrogen could be released at 90 °C within 4 h, while only 5 wt.% hydrogen released from the neat AB at the same conditions. Through a series of experiments it has been demonstrated that the hydrogen release of the new system is resulted from an interaction of AB and the NH3 group in the LiBH4·NH3, in which LiBH4 works as a carrier of ammonia and plays a crucial role in promoting the interaction between the NH3 group and AB. The enhanced dehydrogenation of LiBH 4·NH3/AB may result from the polar liquid state reaction environments and the initially promoted formation of the diammoniate of diborane, which will facilitate the B-H⋯H-N interaction between LiBH4·NH3 and AB. Kinetics analysis revealed that the rate-controlling steps of the dehydrogenation process are three-dimensional diffusion of hydrogen at temperatures ranging from 90 to 110 °C. This journal is © The Royal Society of Chemistry.

  16. Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

    Science.gov (United States)

    Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

    2018-04-26

    An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

  17. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons.

    Science.gov (United States)

    Christensen, Rasmus Bjerregaard; Lü, Jing-Tao; Hedegård, Per; Brandbyge, Mads

    2016-01-01

    We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from the rest of carbon atoms. The electrical current can couple the dimer motion in a coherent fashion. The coupling, which is mediated by nonconservative and pseudo-magnetic current-induced forces, change the atomic dynamics, and thereby show their signature in this simple system. We study the atomic dynamics and current-induced vibrational instabilities using a simplified eigen-mode analysis. Our study illustrates how armchair nanoribbons can serve as a possible testbed for probing the current-induced forces.

  18. Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts

    KAUST Repository

    Atanda, Luqman

    2011-07-01

    Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.

  19. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    Directory of Open Access Journals (Sweden)

    Rasmus Bjerregaard Christensen

    2016-01-01

    Full Text Available We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from the rest of carbon atoms. The electrical current can couple the dimer motion in a coherent fashion. The coupling, which is mediated by nonconservative and pseudo-magnetic current-induced forces, change the atomic dynamics, and thereby show their signature in this simple system. We study the atomic dynamics and current-induced vibrational instabilities using a simplified eigen-mode analysis. Our study illustrates how armchair nanoribbons can serve as a possible testbed for probing the current-induced forces.

  20. Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts

    OpenAIRE

    Wakizaka, Masanori; Matsumoto, Takeshi; Tanaka, Ryota; Chang, Ho-Chol

    2016-01-01

    Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH2), o-aminophenola...

  1. Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Santacesaria, E.; Carotenuto, G.; Tesser, R.; Di Serio, M. [Naples Univ. (Italy). Dept. of Chemistry

    2011-07-01

    The oxidative dehydrogenation (ODH) of propane has been investigated by using many different vanadia based catalysts, prepared by grafting technique and containing variable amounts of active phase supported on SiO{sub 2} previously coated, by grafting in three different steps, with multilayer of TiO{sub 2}. A depth catalytic screening, conducted in a temperature range of 400-600 C, at atmospheric pressure and in a range of residence time W/F=0.08-0.33 ghmol{sub -1}, has shown that the vanadium oxide catalysts on TiO{sub 2}-SiO{sub 2} support, prepared by grafting have good performances in the ODH of propane. In particular, a preliminary study has demonstrated that higher selectivities can be obtained employing catalysts having a well dispersed active phase that can be achieved with a V{sub 2}O{sub 5} content lower than 10%{sub w}t. It is well known that, in the case of redox catalysts, an increase of the selectivity can be achieved not only by using an adequate catalytic system but also via engineering routes like decoupling catalytic steps of reduction and re-oxidation. In fact it has been observed that by operating in dehydrogenating mode, on the same catalysts, a higher selectivity is obtained although the catalyst is poisoned by the formation of coke on the surface. As consequence of the results obtained in dehydrogenation, in this work has been explored the possibility to feed low amounts of oxygen, below the stoichiometric level with the aim to keep clean the surface from coke but maintaining high the selectivity, because, dehydrogenation reaction prevails. In this work, the behavior of catalysts containing different amounts of V2O5 has been studied in the propane-propene reaction by using different ratios C{sub 3}H{sub 8}/O{sub 2} included in the range 0-2. (orig.)

  2. Effect of alloying on carbon formation during ethane dehydrogenation

    DEFF Research Database (Denmark)

    Rovik, Anne; Kegnæs, Søren; Dahl, Søren

    2009-01-01

    The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested in the c...... by covering the steps sites by Ag. This important information can be used in designing new catalysts with improved selectivity and stability....

  3. Study of the niobium dehydrogenation process by transmission electron microscopy

    International Nuclear Information System (INIS)

    Bulhoes, I.A.M.; Akune, K.

    1983-01-01

    The evolution of the micro-structure of Nb-H, during the dehydrogenation process through thermal treatment, has been studied by Transmission Electron Microscopy. The results are used in order to interpret the variation of the line resolution of Electron Channeling Pattern (ECP) of Nb-H as a function of isochronous annealing temperature. It is concluded that the improvement of the ECP line resolution is enhanced of β hydrate in Nb. (Author) [pt

  4. Chromium oxide catalysts in the dehydrogenation of alkanes

    OpenAIRE

    Airaksinen, Sanna

    2005-01-01

    Light alkenes, such as propene and butenes, are important intermediates in the manufacture of fuel components and chemicals. The direct catalytic dehydrogenation of the corresponding alkanes is a selective way to produce these alkenes and is frequently carried out using chromia/alumina catalysts. The aim of this work was to obtain structure–activity information, which could be utilised in the optimisation of this catalytic system. The properties of chromia/alumina catalysts were investigated ...

  5. Bimetallic catalysts for CO.sub.2 hydrogenation and H.sub.2 generation from formic acid and/or salts thereof

    Science.gov (United States)

    Hull, Jonathan F.; Himeda, Yuichiro; Fujita, Etsuko; Muckeman, James T.

    2015-08-04

    The invention relates to a ligand that may be used to create a catalyst including a coordination complex is formed by the addition of two metals; Cp, Cp* or an unsubstituted or substituted .pi.-arene; and two coordinating solvent species or solvent molecules. The bimetallic catalyst may be used in the hydrogenation of CO.sub.2 to form formic acid and/or salts thereof, and in the dehydrogenation of formic acid and/or salts thereof to form H.sub.2 and CO.sub.2.

  6. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    OpenAIRE

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker th...

  7. Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    None

    2014-09-01

    This 2-page fact sheet provides a brief introduction to hydrogen production technologies. Intended for a non-technical audience, it explains how different resources and processes can be used to produce hydrogen. It includes an overview of research goals as well as “quick facts” about hydrogen energy resources and production technologies.

  8. 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.

  9. Ballmilling of metal borohydrides for hydrogen storage

    DEFF Research Database (Denmark)

    Sommer, Sanna

    2014-01-01

    is to hydrogenate simple compounds such as metalborides and hydrides with the intention of forming a new and more hydrogen rich borohydride. In contrast to mainstream research, the method of synthesis has been based on reactants that are expected to be found in the metal borohydride’s dehydrogenated state....... Specifically, the research undertaken targets CaB6 whose boron is in a octahedral network, or AlB2 whose boron is layered. These compounds were then reactive ball milled with alkali and alkaline earth metal under hydrogen pressure, with the intention of forming metal borohydrides. For CaB6, no clear sign...

  10. Structures of the dehydrogenation products of methane activation by 5d transition metal cations

    NARCIS (Netherlands)

    Lapoutre, V. J. F.; Redlich, B.; van der Meer, A. F. G.; Oomens, J.; Bakker, J. M.; Sweeney, A.; Mookherjee, A.; Armentrout, P. B.

    2013-01-01

    The activation of methane by gas-phase transition metal cations (M +) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H]+ and H2. However, the structure of the dehydrogenation

  11. A liquid organic carrier of hydrogen as a fuel for automobiles

    International Nuclear Information System (INIS)

    Taube, M.; Taube, P.

    1979-09-01

    A system of storing energy in a hydrogen containing fuel for the motor car is discussed. The recyclable liquid chemical carrier is: (Methylcyclohexane (liquid)) dehydrogenation (Toluene (liquid)) + (hydrogen (gas)). The reverse reaction, the hydrogenation of toluene, occurs in a regional plant connected to a source of hydrogen (electrolysis of water) with a significant by-product being heat at 200 0 C for district heating. The system is able to store hydrogen in liquid form under ambient temperature and pressure even in a small motor car. The concentration of hydrogen is 6.1 % by weight. The release of gaseous hydrogen from the liquid methylcyclohexane needs a chemical catalytic reactor having a temperature of 300 0 C and a pressure of some bars. This reaction has been well studied. The thermal energy for the dehydrogenation is taken from the exhaust gases at 780 0 C. A layout of the most important processes of the system is given. (Auth.)

  12. Report on visit to Poelitz Hydrogenation Plant

    Energy Technology Data Exchange (ETDEWEB)

    Schwab

    1943-07-31

    Poelitz was operating two DHD (dehydrogenation under pressure) chambers, each with 5 reaction ovens and 3 heat exchangers. One of the chambers had been operating for 18 months without any trouble and without having the catalyst changed. Data are presented on operation of this chamber, including the types of tubes in the preheater and heat exchangers, the pressure drop through each piece of apparatus, the temperature at each measuring location, the times required for the regeneration cycle, the throughputs, heats of reaction, etc. For example, the chamber was processing 15.5 tons/hr of petroleum residues and 12,500 m/sup 3//hr of hydrogen gas. The other chamber had been showing excessive wall temperatures at various measuring spots because of irregularities in the inner insulation bricks of the oven. The report mentioned that Leuna had had better results by using a different material (alumina cement thinned with fire clay dust) for the bricks. Finally, the report described the Poelitz procedure used in the coal-hydrogenation ovens of heating gas and thin coal paste in heat exchangers, thus leaving thick coal paste as the only material really to be heated in a preheater. Also, Poelitz was currently trying a change in the way the cold paste passed through the heat exchangers, in order to prevent deposition of some of the catalyst in the heat exchanger.

  13. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

    OpenAIRE

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2015-01-01

    Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based ...

  14. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...... to the aldehyde, which stays coordinated to ruthenium. Nucleophilic attack of the amine affords the hemiaminal, which is released from ruthenium and converted into the imine....

  15. CO impurities effect on LaNi4∙ 7Al0∙ 3 hydrogen storage alloy ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 37; Issue 4. CO impurities effect on LaNi4.7Al0.3 hydrogen storage alloy hydrogenation/dehydrogenation properties. Qi Wan Ping Li Yunlong Li Fuqiang Zhai Weina Zhang Liqun Cui Alex A Volinsky Xuanhui Qu. Volume 37 Issue 4 June 2014 pp 837-842 ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Carl R. Evenson; Shane E. Roark

    2006-03-31

    The objective of this project was to develop an environmentally benign, inexpensive, and efficient method for separating hydrogen from gas mixtures produced during industrial processes, such as coal gasification. A family of hydrogen separation membranes was developed including single phase mixed conducting ceramics, ceramic/ceramic composites, cermet membranes, cermet membranes containing a hydrogen permeable metal, and intermediate temperature composite layered membranes. Each membrane type had different operating parameters, advantages, and disadvantages that were documented over the course of the project. Research on these membranes progressed from ceramics to cermets to intermediate temperature composite layered membranes. During this progression performance was increased from 0.01 mL x min{sup -1} x cm{sup -2} up to 423 mL x min{sup -1} x cm{sup -2}. Eltron and team membranes not only developed each membrane type, but also membrane surface catalysis and impurity tolerance, creation of thin film membranes, alternative applications such as membrane promoted alkane dehydrogenation, demonstration of scale-up testing, and complete engineering documentation including process and mechanical considerations necessary for inclusion of Eltron membranes in a full scale integrated gasification combined cycle power plant. The results of this project directly led to a new $15 million program funded by the Department of Energy. This new project will focus exclusively on scale-up of this technology as part of the FutureGen initiative.

  17. An overview—Functional nanomaterials for lithium rechargeable batteries, supercapacitors, hydrogen storage, and fuel cells

    International Nuclear Information System (INIS)

    Liu, Hua Kun

    2013-01-01

    Graphical abstract: Nanomaterials play important role in lithium ion batteries, supercapacitors, hydrogen storage and fuel cells. - Highlights: • Nanomaterials play important role for lithium rechargeable batteries. • Nanostructured materials increase the capacitance of supercapacitors. • Nanostructure improves the hydrogenation/dehydrogenation of hydrogen storage materials. • Nanomaterials enhance the electrocatalytic activity of the catalysts in fuel cells. - Abstract: There is tremendous worldwide interest in functional nanostructured materials, which are the advanced nanotechnology materials with internal or external dimensions on the order of nanometers. Their extremely small dimensions make these materials unique and promising for clean energy applications such as lithium ion batteries, supercapacitors, hydrogen storage, fuel cells, and other applications. This paper will highlight the development of new approaches to study the relationships between the structure and the physical, chemical, and electrochemical properties of functional nanostructured materials. The Energy Materials Research Programme at the Institute for Superconducting and Electronic Materials, the University of Wollongong, has been focused on the synthesis, characterization, and applications of functional nanomaterials, including nanoparticles, nanotubes, nanowires, nanoporous materials, and nanocomposites. The emphases are placed on advanced nanotechnology, design, and control of the composition, morphology, nanostructure, and functionality of the nanomaterials, and on the subsequent applications of these materials to areas including lithium ion batteries, supercapacitors, hydrogen storage, and fuel cells

  18. Phase transition and hydrogen storage properties of Mg–Ga alloy

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Daifeng [School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Ouyang, Liuzhang, E-mail: meouyang@scut.edu.cn [School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Wu, Cong [School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Wang, Hui; Liu, Jiangwen [School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Sun, Lixian [Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, Guilin 541004 (China); Zhu, Min [School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China)

    2015-09-05

    Highlights: • A fully reversible transformation in Mg–Ga–H system with reduced dehydrogenation enthalpy is realized. • The mechanism of phase transformation in the de/hydrogenation of Mg–Ga alloy is revealed. • The de/hydrogenation process of Mg{sub 5}Ga{sub 2} compound is expressed as: Mg{sub 5}Ga{sub 2} + H{sub 2} ↔ 2Mg{sub 2}Ga + MgH{sub 2}. - Abstract: Mg-based alloys are viewed as one of the most promising candidates for hydrogen storage; however, high desorption temperature and the sluggish kinetics of MgH{sub 2} hinder their practical application. Alloying and changing the reaction pathway are effective methods to solve these issues. As the solid solubility of Ga in Mg is 5 wt% at 573 K, the preparation of a Mg(Ga) solid solution at relatively high temperatures was designed in this paper. The phase transition and hydrogen storage properties of the MgH{sub 2} and Mg{sub 5}Ga{sub 2} composite (hereafter referred to as Mg–Ga alloy) were investigated by X-ray diffraction (XRD), pressure–composition-isotherm (PCI) measurements, and differential scanning calorimetry (DSC). The reversible hydrogen storage capacity of Mg–Ga alloy is 5.7 wt% H{sub 2}. During the dehydrogenation process of Mg–Ga alloy, Mg{sub 2}Ga reacts with MgH{sub 2}, initially releasing H{sub 2} and forming Mg{sub 5}Ga{sub 2}; subsequently, MgH{sub 2} decomposes into Mg with further release of H{sub 2}. The phase transition mechanism of the Mg{sub 5}Ga{sub 2} compound during the dehydrogenation process was also investigated by using in situ XRD analysis. In addition, the dehydrogenation enthalpy and entropy changes, and the apparent activation energy were also calculated.

  19. Structural Dynamics of the GW182 Silencing Domain Including its RNA Recognition motif (RRM) Revealed by Hydrogen-Deuterium Exchange Mass Spectrometry

    Science.gov (United States)

    Cieplak-Rotowska, Maja K.; Tarnowski, Krzysztof; Rubin, Marcin; Fabian, Marc R.; Sonenberg, Nahum; Dadlez, Michal; Niedzwiecka, Anna

    2018-01-01

    The human GW182 protein plays an essential role in micro(mi)RNA-dependent gene silencing. miRNA silencing is mediated, in part, by a GW182 C-terminal region called the silencing domain, which interacts with the poly(A) binding protein and the CCR4-NOT deadenylase complex to repress protein synthesis. Structural studies of this GW182 fragment are challenging due to its predicted intrinsically disordered character, except for its RRM domain. However, detailed insights into the properties of proteins containing disordered regions can be provided by hydrogen-deuterium exchange mass spectrometry (HDX/MS). In this work, we applied HDX/MS to define the structural state of the GW182 silencing domain. HDX/MS analysis revealed that this domain is clearly divided into a natively unstructured part, including the CCR4-NOT interacting motif 1, and a distinct RRM domain. The GW182 RRM has a very dynamic structure, since water molecules can penetrate the whole domain in 2 h. The finding of this high structural dynamics sheds new light on the RRM structure. Though this domain is one of the most frequently occurring canonical protein domains in eukaryotes, these results are - to our knowledge - the first HDX/MS characteristics of an RRM. The HDX/MS studies show also that the α2 helix of the RRM can display EX1 behavior after a freezing-thawing cycle. This means that the RRM structure is sensitive to environmental conditions and can change its conformation, which suggests that the state of the RRM containing proteins should be checked by HDX/MS in regard of the conformational uniformity. [Figure not available: see fulltext.

  20. An efficient strategy for designing ambipolar organic semiconductor material: Introducing dehydrogenated phosphorus atoms into pentacene core

    Science.gov (United States)

    Tang, Xiao-Dan

    2017-09-01

    The charge transport properties of phosphapentacene (P-PEN) derivatives were systematically explored by theoretical calculation. The dehydrogenated P-PENs have reasonable frontier molecular orbital energy levels to facilitate both electron and hole injection. The reduced reorganization energies of dehydrogenated P-PENs could be intimately connected to the bonding nature of phosphorus atoms. From the idea of homology modeling, the crystal structure of TIPSE-4P-2p is constructed and fully optimized. Fascinatingly, TIPSE-4P-2p shows the intrinsic property of ambipolar transport in both hopping and band models. Thus, introducing dehydrogenated phosphorus atoms into pentacene core could be an efficient strategy for designing ambipolar material.

  1. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene

  2. Ce0.95Cr0.05O2 and Ce0.97Cu0.03O2: active, selective and stable catalysts for selective hydrogen combustion.

    Science.gov (United States)

    Beckers, Jurriaan; Rothenberg, Gadi

    2009-08-07

    Ceria-based materials are promising solid "oxygen reservoirs" for propane oxidative dehydrogenation. The ceria lattice oxygen can selectively combust hydrogen from the dehydrogenation mixture at 550 degrees C. This shifts the dehydrogenation equilibrium to the desired products side, generates heat aiding the endothermic dehydrogenation, and simplifies product separation. The process is also safer, since it avoids mixing O(2) and H(2) at high temperatures. While ceria itself is unselective, its catalytic properties can be tuned by doping. We study the effects of dopant type, concentration and the crystallite size on the catalytic properties. Doping with Cr or Cu increases both the selectivity and activity of the ceria, albeit that propane combustion also increases linearly with the Cu-concentration. The Cu-doped catalysts give selectivities up to 95% and combust up to 8% of the hydrogen feed. The best results are obtained with Cr-doped ceria, with selectivities up to 98%, and combustion of up to 15% of the hydrogen feed. The Cr-doped catalysts are stable in the reductive gas feed, and no extra coke is formed when the catalyst is subjected to an extra 10 min in the dehydrogenation mixture, after the hydrogen combustion reaction has stopped. This robustness is essential for industrial dehydrogenation applications.

  3. Selective and Stable Ethylbenzene Dehydrogenation to Styrene over Nanodiamonds under Oxygen-lean Conditions.

    Science.gov (United States)

    Diao, Jiangyong; Feng, Zhenbao; Huang, Rui; Liu, Hongyang; Hamid, Sharifah Bee Abd; Su, Dang Sheng

    2016-04-07

    For the first time, significant improvement of the catalytic performance of nanodiamonds was achieved for the dehydrogenation of ethylbenzene to styrene under oxygen-lean conditions. We demonstrated that the combination of direct dehydrogenation and oxidative dehydrogenation indeed occurred on the nanodiamond surface throughout the reaction system. It was found that the active sp(2)-sp(3) hybridized nanostructure was well maintained after the long-term test and the active ketonic carbonyl groups could be generated in situ. A high reactivity with 40% ethylbenzene conversion and 92% styrene selectivity was obtained over the nanodiamond catalyst under oxygen-lean conditions even after a 240 h test, demonstrating the potential of this procedure for application as a promising industrial process for the ethylbenzene dehydrogenation to styrene without steam protection. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    Science.gov (United States)

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  5. A Moessbauer spectroscopic study of an industrial catalyst for dehydrogenation of etylbenzene to styrene

    International Nuclear Information System (INIS)

    Jiang, K. Y.; Fan, Q.; Zhao, Z. J.; Mao, L. S.; Yang, X. L.

    2006-01-01

    Iron oxide catalyst with spinel structure used for dehydrogenation of ethylbenzene is one kind of important catalyst in petrochemical industry. In this work several series of industrial catalyst were prepared with different components and different manufacturing processes. Moessbauer Spectroscopy has been used to determine the optimal components and the better manufacturing process for spinel structure formation. The results may prove useful for producing the industrial dehydrogenation catalyst with better catalytic property.

  6. Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

    Science.gov (United States)

    Bower, John F.; Krische, Michael J.

    2011-01-01

    The formation of C–C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C–C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile–nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C–H bonds. PMID:21822399

  7. A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

    Science.gov (United States)

    Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

    2016-09-01

    Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at -1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier.

  8. Stepwise dehydrogenation of ammonia on Fcc-Co surfaces: A DFT study

    International Nuclear Information System (INIS)

    Ma, F.F.; Ma, S.H.; Jiao, Z.Y.; Dai, X.Q.

    2017-01-01

    Highlights: • On Co surfaces, oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation on the Co surfaces. • Pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. • The dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces. • The species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom. - Abstract: The stepwise dehydrogenation of ammonia on clean and O-covered Co surfaces have been studied by performing density functional theory (DFT) calculations. It is found that the interaction of species NH x (x = 0–3) with the Co surfaces become stronger with its further dehydrogenation, and oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation. Specifically, pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. In contrast, the dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces, due to the high energy barriers. And present results demonstrate that the species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom.

  9. Hydrogen millennium

    International Nuclear Information System (INIS)

    Bose, T.K.; Benard, P.

    2000-05-01

    The 10th Canadian Hydrogen Conference was held at the Hilton Hotel in Quebec City from May 28 to May 31, 2000. The topics discussed included current drivers for the hydrogen economy, the international response to these drivers, new initiatives, sustainable as well as biological and hydrocarbon-derived production of hydrogen, defense applications of fuel cells, hydrogen storage on metal hydrides and carbon nanostructures, stationary power and remote application, micro-fuel cells and portable applications, marketing aspects, fuel cell modeling, materials, safety, fuel cell vehicles and residential applications. (author)

  10. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Greeley, Jeffrey Philip; Studt, Felix

    2007-01-01

    with the adsorption energy of the central, C, N, O, or S atom, the scaling constant depending only on x. A model is proposed to understand this behavior. The scaling model is developed into a general framework for estimating the reaction energies for hydrogenation and dehydrogenation reactions....

  11. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane

    Directory of Open Access Journals (Sweden)

    Tetsuo Umegaki

    2015-07-01

    Full Text Available Hydrogen storage is still one of the most significant issues hindering the development of a “hydrogen energy economy”. Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane.

  12. Porous Materials for Hydrolytic Dehydrogenation of Ammonia Borane.

    Science.gov (United States)

    Umegaki, Tetsuo; Xu, Qiang; Kojima, Yoshiyuki

    2015-07-21

    Hydrogen storage is still one of the most significant issues hindering the development of a "hydrogen energy economy". Ammonia borane is notable for its high hydrogen densities. For the material, one of the main challenges is to release efficiently the maximum amount of the stored hydrogen. Hydrolysis reaction is a promising process by which hydrogen can be easily generated from this compound. High purity hydrogen from this compound can be evolved in the presence of solid acid or metal based catalyst. The reaction performance depends on the morphology and/or structure of these materials. In this review, we survey the research on nanostructured materials, especially porous materials for hydrogen generation from hydrolysis of ammonia borane.

  13. In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

    2012-03-20

    The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

  14. Reversible Hydrogen Storage Materials – Structure, Chemistry, and Electronic Structure

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, Ian M. [University of Wisconsin-Madison; Johnson, Duane D. [Ames Lab., Iowa

    2014-06-21

    To understand the processes involved in the uptake and release of hydrogen from candidate light-weight metal hydride storage systems, a combination of materials characterization techniques and first principle calculation methods have been employed. In addition to conventional microstructural characterization in the transmission electron microscope, which provides projected information about the through thickness microstructure, electron tomography methods were employed to determine the three-dimensional spatial distribution of catalyst species for select systems both before and after dehydrogenation. Catalyst species identification as well as compositional analysis of the storage material before and after hydrogen charging and discharging was performed using a combination of energy dispersive spectroscopy, EDS, and electron energy loss spectroscopy, EELS. The characterization effort was coupled with first-principles, electronic-structure and thermodynamic techniques to predict and assess meta-stable and stable phases, reaction pathways, and thermodynamic and kinetic barriers. Systems studied included:NaAlH4, CaH2/CaB6 and Ca(BH4)2, MgH2/MgB2, Ni-Catalyzed Magnesium Hydride, TiH2-Catalyzed Magnesium Hydride, LiBH4, Aluminum-based systems and Aluminum

  15. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst.

    Science.gov (United States)

    Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

    2013-05-14

    Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500-575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol-1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors.

  16. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst

    Directory of Open Access Journals (Sweden)

    Miguel Menéndez

    2013-05-01

    Full Text Available Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR, where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500–575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol−1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB. The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen, the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors.

  17. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  18. Heat transfer and thermographic analysis of catalyst surface during multiphase phenomena under spray-pulsed conditions for dehydrogenation of cyclohexane over Pt catalysts.

    Science.gov (United States)

    Biniwale, Rajesh B; Kariya, N; Yamashiro, H; Ichikawa, Masaru

    2006-02-23

    Dehydrogenation of cyclohexane over Pt/alumite and Pt/activated carbon catalysts has been carried out for hydrogen storage and supply to fuel cell applications. An unsteady state has been created using spray pulsed injection of cyclohexane over the catalyst surface to facilitate the endothermic reaction to occur efficiently. Higher temperature of the catalyst surface is more favorable for the reaction, thus the heat transfer phenomena and temperature profile under alternate wet and dry conditions created using spray pulsed injection becomes important. IR thermography has been used for monitoring of temperature profile of the catalyst surface simultaneously with product analysis. The heat flux from the plate-type heater to the catalyst has been estimated using a rapid temperature recording and thermocouple arrangement. The estimated heat flux under transient conditions was in the range of 10-15 kW/m(2), which equates the requirement for endothermic reactions to the injection frequency of 0.5 Hz, as used in this study. The analysis of temperature profiles, reaction products over two different supports namely activated carbon cloth and alumite, reveals that the more conductive support such as alumite is more suitable for dehydrogenation of cyclohexane.

  19. Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

    Directory of Open Access Journals (Sweden)

    Romain Moury

    2015-04-01

    Full Text Available Hydrazine borane N2H4BH3 and alkali derivatives (i.e., lithium, sodium and potassium hydrazinidoboranes MN2H3BH3 with M = Li, Na and K have been considered as potential chemical hydrogen storage materials. They belong to the family of boron- and nitrogen-based materials and the present article aims at providing a timely review while focusing on fundamentals so that their effective potential in the field could be appreciated. It stands out that, on the one hand, hydrazine borane, in aqueous solution, would be suitable for full dehydrogenation in hydrolytic conditions; the most attractive feature is the possibility to dehydrogenate, in addition to the BH3 group, the N2H4 moiety in the presence of an active and selective metal-based catalyst but for which further improvements are still necessary. However, the thermolytic dehydrogenation of hydrazine borane should be avoided because of the evolution of significant amounts of hydrazine and the formation of a shock-sensitive solid residue upon heating at >300 °C. On the other hand, the alkali hydrazinidoboranes, obtained by reaction of hydrazine borane with alkali hydrides, would be more suitable to thermolytic dehydrogenation, with improved properties in comparison to the parent borane. All of these aspects are surveyed herein and put into perspective.

  20. Industrial development of long chain paraffin (n-C10-C13) dehydrogenation catalysts and the deactivation characterization

    NARCIS (Netherlands)

    He, Songbo; Wang, Bin; Dai, Xihai; Sun, Chenglin; Bai, Ziwu; Wang, Xiao; Guo, Qi

    2015-01-01

    Pt–Sn–K–Mg/Al2O3 catalysts for the dehydrogenation of long chain paraffins (n-C100–C130) were successfully developed and applied in the industry. The catalysts were tested on both the industrial side fixed bed reactor and the industrial PACOL dehydrogenation plant. The industrially deactivated

  1. Highly Ordered Mesoporous Metal Oxides as Catalysts for Dehydrogenation of Cyclohexanol

    International Nuclear Information System (INIS)

    Lee, Eunok; Jin, Mingshi; Kim, Ji Man

    2013-01-01

    Cyclohexanone is important intermediate for the manufacture of caprolactam which is monomer of nylron. Cyclohexanone is generally produced by dehydrogenation reaction of cyclohexanol. In this study, highly mesoporous metal oxides such as meso-WO 3 , meso-TiO 2 , meso-Fe 2 O 3 , meso-CuO, meso-SnO 2 and meso-NiO were synthesized using mesoporous silica KIT-6 as a hard template via nano-replication method for dehydrogenation of cyclohexanol. The overall conversion of cyclohexanol followed a general order: meso-WO 3 >> meso-Fe 2 O 3 > meso-SnO 2 > meso-TiO 2 > meso-NiO > meso-CuO. In particular, meso-WO 3 significantly showed higher activity than the other mesoporous metal oxides. Therefore, the meso-WO 3 has wide range of application possibilities for dehydrogenation of cyclohexanol

  2. Improved hydrogen absorption and desorption kinetics of magnesium-based alloy via addition of yttrium

    Science.gov (United States)

    Yang, Tai; Li, Qiang; Liu, Ning; Liang, Chunyong; Yin, Fuxing; Zhang, Yanghuan

    2018-02-01

    Yttrium (Y) is selected to modify the microstructure of magnesium (Mg) to improve the hydrogen storage performance. Thereby, binary alloys with the nominal compositions of Mg24Yx (x = 1-5) are fabricated by inexpensive casting technique. Their microstructure and phase transformation during hydriding and dehydriding process are characterized by using X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy analysis. The isothermal hydrogen absorption and desorption kinetics are also measured by a Sievert's-type apparatus at various temperatures. Typical multiphase structures of binary alloy can be clearly observed. All of these alloys can reversibly absorb and desorb large amount of hydrogen at proper temperatures. The addition of Y markedly promotes the hydrogen absorption kinetics. However, it results in a reduction of reversible hydrogen storage capacity. A maximum value of dehydrogenation rate is observed with the increase of Y content. The Mg24Y3 alloy has the optimal desorption kinetic performance, and it can desorb about 5.4 wt% of hydrogen at 380 °C within 12 min. Combining Johnson-Mehl-Avrami kinetic model and Arrhenius equation, the dehydrogenation activation energy of the alloys are evaluated. The Mg24Y3 alloy also has the lowest dehydrogenation activation energy (119 kJ mol-1).

  3. Hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Donath, E.

    1942-10-16

    This report mentioned that not very severe demands for purity were made on the hydrogen used in hydrogenation of coal or similar raw materials, because the catalysts were not very sensitive to poisoning. However, the hydrogenation plants tried to remove most impurities anyway by means of oil washes. The report included a table giving the amount of wash oil used up and the amount of hydrogen lost by dissolving into the wash oil used up and the amount of hydrogen lost by dissolving into the wash oil in order to remove 1% of various impurities from 1000 m/sup 3/ of the circulating gas. The amounts of wash oil used up were 1.1 m/sup 3/ for removing 1% nitrogen, 0.3 m/sup 3/ for 1% carbon monoxide, 0.03 m/sup 3/ for 1% methane. The amount of hydrogen lost was 28 m/sup 3/ for 1% nitrogen, 9 m/sup 3/ for 1% methane and ranged from 9 m/sup 3/ to 39 m/sup 3/ for 1% carbon monoxide and 1 m/sup 3/ to 41 m/sup 3/ for carbon dioxide depending on whether the removal was done in liquid phase or vapor phase and with or without reduction of the oxide to methane. Next the report listed and described the major processes used in German hydrogenation plants to produce hydrogen. Most of them produced water gas, which then had its carbon monoxide changed to carbon dioxide, and the carbon oxides washed out with water under pressure and copper hydroxide solution. The methods included the Winkler, Pintsch-Hillebrand, and Schmalfeldt-Wintershall processes, as well as roasting of coke in a rotating generator, splitting of gases formed during hydrogenation, and separation of cokery gas into its components by the Linde process.

  4. Ni/La2O3 catalyst containing low content platinum-rhodium for the dehydrogenation of N2H4·H2O at room temperature

    Science.gov (United States)

    O, Song-Il; Yan, Jun-Min; Wang, Hong-Li; Wang, Zhi-Li; Jiang, Qing

    2014-09-01

    Ni/La2O3 nanocatalyst with Pt and Rh content as low as 5 mol%, respectively, is successfully synthesized by a facile co-reduction method in the presence of hexadecyl trimethyl ammonium chloride aqueous solution under ambient atmosphere. Interestingly, the resulted Ni/La2O3 catalyst with low cost exhibits excellent catalytic activity to dehydrogenation of hydrous hydrazine (N2H4·H2O), producing hydrogen with 100% selectivity at room temperature (298 K), which represents a promising step toward the practical application for N2H4·H2O system on fuel cells.

  5. Enhancing hydrogen spillover and storage

    Science.gov (United States)

    Yang, Ralph T [Ann Arbor, MI; Li, Yingwel [Ann Arbor, MI; Lachawiec, Jr., Anthony J.

    2011-05-31

    Methods for enhancing hydrogen spillover and storage are disclosed. One embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the hydrogen receptor to ultrasonification as doping occurs. Another embodiment of the method includes doping a hydrogen receptor with metal particles, and exposing the doped hydrogen receptor to a plasma treatment.

  6. Preparation of bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Liu, Yang; Zhang, Jun; Guan, Huijuan; Zhao, Yafei; Yang, Jing-He; Zhang, Bing

    2018-01-01

    In present work, we prepared the bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes (Cu-Co/PDDA-HNTs) by a deposition-reduction technique at room temperature. The analysis of XRD, SEM, TEM, HAADF-STEM and XPS were employed to systematically investigate the morphology, particle size, structure and surface properties of the nanocomposite. The results reveal that the PDDA coating with thickness of ∼15 nm could be formed on the surface of HNTs, and the existence of PDDA is beneficial to deposit Cu and Co nanoparticles (NPs) with high dispersibility on the surface. While the cost-effective nanocomposite was used for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), the nanocatalyst showed extraordinary catalytic properties with high total turnover frequency of 30.8 molH2/(molmetal min), low activation energy of 35.15 kJ mol-1 and high recycling stability (>90% conversion at 10th reuse). These results indicate that the bimetallic Cu-Co nanocatalysts on PDDA functionalized HNTs have particular potential for application in release hydrogen process.

  7. Revisiting the Hydrogen Storage Behavior of the Na-O-H System

    Directory of Open Access Journals (Sweden)

    Jianfeng Mao

    2015-04-01

    Full Text Available Solid-state reactions between sodium hydride and sodium hydroxide are unusual among hydride-hydroxide systems since hydrogen can be stored reversibly. In order to understand the relationship between hydrogen uptake/release properties and phase/structure evolution, the dehydrogenation and hydrogenation behavior of the Na-O-H system has been investigated in detail both ex- and in-situ. Simultaneous thermogravimetric-differential thermal analysis coupled to mass spectrometry (TG-DTA-MS experiments of NaH-NaOH composites reveal two principal features: Firstly, an H2 desorption event occurring between 240 and 380 °C and secondly an additional endothermic process at around 170 °C with no associated weight change. In-situ high-resolution synchrotron powder X-ray diffraction showed that NaOH appears to form a solid solution with NaH yielding a new cubic complex hydride phase below 200 °C. The Na-H-OH phase persists up to the maximum temperature of the in-situ diffraction experiment shortly before dehydrogenation occurs. The present work suggests that not only is the inter-phase synergic interaction of protic hydrogen (in NaOH and hydridic hydrogen (in NaH important in the dehydrogenation mechanism, but that also an intra-phase Hδ+… Hδ– interaction may be a crucial step in the desorption process.

  8. Structures of the Dehydrogenation Products of Methane Activation by 5d Transition Metal Cations

    NARCIS (Netherlands)

    Lapoutre, V.J.F.; Redlich, B.; Meer, A.F.G.; Oomens, J.; Bakker, J.M.; Sweeney, A.; Mookherjee, A.; Armentrout, P.B.

    2013-01-01

    The activation of methane by gas-phase transition metal cations (M+) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H](+) and H-2. However, the structure of the

  9. Dehydrogenation of light alkanes over rhenium catalysts on conventional and mesoporous MFI supports

    DEFF Research Database (Denmark)

    Rovik, Anne Krogh; Hagen, Anke; Schmidt, I.

    2006-01-01

    Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time...

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

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  11. Oxidative dehydrogenation of ethylbenzene using nitrous oxide over vanadia-magnesia catalysts

    NARCIS (Netherlands)

    Shiju, N.R.; Anilkumar, M.; Gokhale, S.P.; Rao, B.S.; Satyanarayana, C.V.V.

    2011-01-01

    A series of V-Mg-O catalysts with different loadings of vanadia were prepared by the wet impregnation method and the effect of the local structure of these catalysts on the oxidative dehydrogenation of ethylbenzene with N2O was investigated. High styrene selectivity (97%) was obtained at 773 K. The

  12. Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

    Science.gov (United States)

    Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

    2016-01-01

    In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

  13. Kinetics of Hydrogen Absorption and Desorption in Titanium

    Directory of Open Access Journals (Sweden)

    Suwarno Suwarno

    2017-10-01

    Full Text Available Titanium is reactive toward hydrogen forming metal hydride which has a potential application in      energy storage and conversion. Titanium hydride has been widely studied for hydrogen storage, thermal storage, and battery electrodes applications. A special interest is using titanium for hydrogen production in a hydrogen sorption-enhanced steam reforming of natural gas. In the present work, non-isothermal dehydrogenation kinetics of titanium hydride and kinetics of hydrogenation in gaseous flow at isothermal conditions were investigated. The hydrogen desorption was studied using temperature desorption spectroscopy (TDS while the hydrogen absorption and desorption in gaseous flow were studied by temperature programmed desorption (TPD. The present work showed that the path of dehydrogenation of the TiH2 is d®b®a hydride phase with possible overlapping steps occurred. The fast hydrogen desorption rate observed at the TDS main peak temperature were correlated with the fast transformation of the d-TiH1.41 to b-TiH0.59. In the gaseous flow, hydrogen absorption and desorption were related to the transformation of b-TiH0.59 Û d-TiH1.41 with 2 wt.% hydrogen reversible content. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 20th March 2017; Accepted: 9th April 2017; Available online: 27th October 2017; Published regularly: December 2017 How to Cite: Suwarno, S., Yartys, V.A. (2017. Kinetics of Hydrogen Absorption and Desorption in Titanium. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3: 312-317  (doi:10.9767/bcrec.12.3.810.312-317

  14. CHARACTERIZING THE INFRARED SPECTRA OF SMALL, NEUTRAL, FULLY DEHYDROGENATED POLYCYCLIC AROMATIC HYDROCARBONS

    Energy Technology Data Exchange (ETDEWEB)

    Mackie, C. J.; Peeters, E.; Cami, J. [Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7 (Canada); Bauschlicher, C. W. Jr., E-mail: mackie@strw.leidenuniv.nl [NASA Ames Research Center, MS 245-6, Moffett Field, CA 94035 (United States)

    2015-02-01

    We present the results of a computational study to investigate the infrared spectroscopic properties of a large number of polycyclic aromatic hydrocarbon (PAH) molecules and their fully dehydrogenated counterparts. We constructed a database of fully optimized geometries for PAHs that is complete for eight or fewer fused benzene rings, thus containing 1550 PAHs and 805 fully dehydrogenated aromatics. A large fraction of the species in our database have clearly non-planar or curved geometries. For each species, we determined the frequencies and intensities of their normal modes using density functional theory calculations. Whereas most PAH spectra are fairly similar, the spectra of fully dehydrogenated aromatics are much more diverse. Nevertheless, these fully dehydrogenated species show characteristic emission features at 5.2 μm, 5.5 μm, and 10.6 μm; at longer wavelengths, there is a forest of emission features in the 16-30 μm range that appears as a structured continuum, but with a clear peak centered around 19 μm. We searched for these features in Spitzer-IRS spectra of various positions in the reflection nebula NGC 7023. We find a weak emission feature at 10.68 μm in all positions except that closest to the central star. We also find evidence for a weak 19 μm feature at all positions that is not likely due to C{sub 60}. We interpret these features as tentative evidence for the presence of a small population of fully dehydrogenated PAHs, and discuss our results in the framework of PAH photolysis and the formation of fullerenes.

  15. Hydrogen from formic acid through its selective disproportionation over sodium germanate--a non-transition-metal catalysis system.

    Science.gov (United States)

    Amos, Ruth I J; Heinroth, Falk; Chan, Bun; Zheng, Sisi; Haynes, Brian S; Easton, Christopher J; Masters, Anthony F; Radom, Leo; Maschmeyer, Thomas

    2014-10-13

    A robust catalyst for the selective dehydrogenation of formic acid to liberate hydrogen gas has been designed computationally, and also successfully demonstrated experimentally. This is the first such catalyst not based on transition metals, and it exhibits very encouraging performance. It represents an important step towards the use of renewable formic acid as a hydrogen-storage and transport vector in fuel and energy applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Recent Progress in Metal Borohydrides for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Craig M. Jensen

    2011-01-01

    Full Text Available The prerequisite for widespread use of hydrogen as an energy carrier is the development of new materials that can safely store it at high gravimetric and volumetric densities. Metal borohydrides M(BH4n (n is the valence of metal M, in particular, have high hydrogen density, and are therefore regarded as one such potential hydrogen storage material. For fuel cell vehicles, the goal for on-board storage systems is to achieve reversible store at high density but moderate temperature and hydrogen pressure. To this end, a large amount of effort has been devoted to improvements in their thermodynamic and kinetic aspects. This review provides an overview of recent research activity on various M(BH4n, with a focus on the fundamental dehydrogenation and rehydrogenation properties and on providing guidance for material design in terms of tailoring thermodynamics and promoting kinetics for hydrogen storage.

  17. Hydrogenation of passivated contacts

    Energy Technology Data Exchange (ETDEWEB)

    Nemeth, William; Yuan, Hao-Chih; LaSalvia, Vincenzo; Stradins, Pauls; Page, Matthew R.

    2018-03-06

    Methods of hydrogenation of passivated contacts using materials having hydrogen impurities are provided. An example method includes applying, to a passivated contact, a layer of a material, the material containing hydrogen impurities. The method further includes subsequently annealing the material and subsequently removing the material from the passivated contact.

  18. Constant rate thermal analysis of a dehydrogenation reaction

    Czech Academy of Sciences Publication Activity Database

    Perejon, A.; Perez-Maqueda, L. A.; Sanchez-Jimenez, P.E.; Criado, J. M.; Murafa, Nataliya; Šubrt, Jan

    2016-01-01

    Roč. 6, č. 84 (2016), s. 81454-81460 ISSN 2046-2069 Institutional support: RVO:61388980 Keywords : solid-state reactions * hydrogen storage properties * milled magnesium hydride Subject RIV: CA - Inorganic Chemistry Impact factor: 3.108, year: 2016

  19. Hydrogen energy

    International Nuclear Information System (INIS)

    2005-03-01

    This book consists of seven chapters, which deals with hydrogen energy with discover and using of hydrogen, Korean plan for hydrogen economy and background, manufacturing technique on hydrogen like classification and hydrogen manufacture by water splitting, hydrogen storage technique with need and method, hydrogen using technique like fuel cell, hydrogen engine, international trend on involving hydrogen economy, technical current for infrastructure such as hydrogen station and price, regulation, standard, prospect and education for hydrogen safety and system. It has an appendix on related organization with hydrogen and fuel cell.

  20. 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

  1. Solid Aluminum Borohydrides for Prospective Hydrogen Storage.

    Science.gov (United States)

    Dovgaliuk, Iurii; Safin, Damir A; Tumanov, Nikolay A; Morelle, Fabrice; Moulai, Adel; Černý, Radovan; Łodziana, Zbigniew; Devillers, Michel; Filinchuk, Yaroslav

    2017-12-08

    Metal borohydrides are intensively researched as high-capacity hydrogen storage materials. Aluminum is a cheap, light, and abundant element and Al 3+ can serve as a template for reversible dehydrogenation. However, Al(BH 4 ) 3 , containing 16.9 wt % of hydrogen, has a low boiling point, is explosive on air and has poor storage stability. A new family of mixed-cation borohydrides M[Al(BH 4 ) 4 ], which are all solid under ambient conditions, show diverse thermal decomposition behaviors: Al(BH 4 ) 3 is released for M=Li + or Na + , whereas heavier derivatives evolve hydrogen and diborane. NH 4 [Al(BH 4 ) 4 ], containing both protic and hydridic hydrogen, has the lowest decomposition temperature of 35 °C and yields Al(BH 4 ) 3 ⋅NHBH and hydrogen. The decomposition temperatures, correlated with the cations' ionic potential, show that M[Al(BH 4 ) 4 ] species are in the most practical stability window. This family of solids, with convenient and versatile properties, puts aluminum borohydride chemistry in the mainstream of hydrogen storage research, for example, for the development of reactive hydride composites with increased hydrogen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Hydrogen in semiconductors

    CERN Document Server

    Pankove, Jacques I

    1991-01-01

    Hydrogen plays an important role in silicon technology, having a profound effect on a wide range of properties. Thus, the study of hydrogen in semiconductors has received much attention from an interdisciplinary assortment of researchers. This sixteen-chapter volume provides a comprehensive review of the field, including a discussion of hydrogenation methods, the use of hydrogen to passivate defects, the use of hydrogen to neutralize deep levels, shallow acceptors and shallow donors in silicon, vibrational spectroscopy, and hydrogen-induced defects in silicon. In addition to this detailed cove

  3. Metastable hydrogen

    International Nuclear Information System (INIS)

    Dose, V.

    1982-01-01

    This paper deals with the basic physical properties of the metastable 2 2 sub(1/2) state of atomic hydrogen. Applications relying on its special properties, including measurement of the Lamb shift, production of spin-polarized protons and the measurement of molecular electric moments, are discussed. (author)

  4. Influence of preparation conditions of hollow silica–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Seki, Ayano [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-03-05

    Highlights: • We study influence of preparation conditions on activity of hollow silica–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Si+Ni content. • The particle size distribution affects the activity and reducibility of active nickel species. • The amount of PS residue in the hollow spheres decreases by treatment of as-prepared sample in toluene. -- Abstract: In this paper, we investigated influence of preparation conditions of hollow silica–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane. In the preparation method of this study, when silica–nickel composite shells were coated on polystyrene templates by the sol–gel method using L(+)-arginine as the promoter for the reaction to form silica–nickel composite shell, the polystyrene templates were dissolved subsequently, even synchronously, in the same medium to form hollow spheres. The as-prepared silica–nickel composite spheres were characterized by transmission electron microscopy and scanning electron microscopy. The effects of Si+Ni content on the morphology were systematically evaluated. All the as-prepared hollow silica–nickel composite spheres have the similar morphology as identified by SEM and TEM measurement. Homogeneity of the hollow silica–nickel composite spheres increases with the increase in the Si+Ni content as shown by the laser diffraction particle size analysis. The catalytic activities of the hollow silica–nickel composite spheres for hydrolytic dehydrogenation of ammonia borane prepared with different Si+Ni contents were compared. The catalytic activity for the hydrogen evolution in the presence of the hollow spheres increases with the increase of Si+Ni content. The results of FTIR spectra of the hollow silica–nickel composite spheres indicate that a certain amount of residual PS templates exists in hollow silica

  5. Production of high-octane, unleaded motor fuel by alkylation of isobutane with isoamylenes obtained by dehydrogenation of isopentane

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.; Hann, P.D.

    1981-01-31

    A process combination, with inter-cooperation, for producing high-octane alkylates comprising (a) dehydrogenating isopentane to isopentenes (amylenes), (b) introducing the mixture of said amylenes and unconverted isopentane into an HF alkylation unit for reaction with fresh or recycled isobutane, (c) separating the alkylation products into high octane alkylates, isopentane (for recycling to the dehydrogenation reactor) and isobutane (for recycling to the alkylation reactor).

  6. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    Science.gov (United States)

    Agarwal, Pradeep K.

    2007-01-16

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

  7. Effect of support material on the performance of chromia dehydrogenation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Korhonen, S.

    2008-07-01

    The effect of support material on the dehydrogenation performance of chromia catalysts was studied with zirconium oxide (zirconia), aluminum oxide (alumina), and zirconia/alumina as the support materials. The dehydrogenation performance of the supports and chromia catalysts was studied by in situ infrared and Raman spectroscopies and activity measurements. The active surface sites of the supports and catalysts were characterized by in situ infrared and Raman spectroscopies using probe molecules, and the surface of zirconia was studied in more depth by modeling with density functional theory (DFT). The characterization experiments and DFT calculations revealed the amphoteric character of the hydroxyl groups of zirconia and the presence of coordinatively unsaturated (c.u.s.) acid-base pairs. The hydroxyls of alumina exhibited similar basicity to those of zirconia, but their acidity was lower. Lewis acid and Lewis base sites were observed for alumina, but they did not form c.u.s. acid-base pairs as on zirconia. The deposition of zirconia on alumina decreased the Lewis acidity of the c.u.s. sites and the acidity of the hydroxyls, while the total basicity of the material appeared to increase. The addition of chromium also appeared to increase the basicity. Zirconia was the most active and selective support material in the dehydrogenation of isobutane. The high activity was suggested to originate from the acid - base pairs that were present only on the zirconia surface. The performance of zirconia/alumina resembled that of alumina more than that of zirconia. The benefit of zirconia deposition on alumina was a lower coke deposition rate than on alumina due to the lower Lewis acidity of the zirconia/alumina. However, the cracking activity of alumina was not influenced by zirconia deposition and this was attributed to the presence of similar hydroxyls. The chromia/zirconia catalyst was the most active dehydrogenation catalyst. The deposition of zirconia on alumina decreased

  8. First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

    Energy Technology Data Exchange (ETDEWEB)

    J. Karl Johnson

    2011-05-20

    The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. New materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.

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

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

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

  10. Mechanical and Thermal Dehydrogenation of Lithium Alanate (LiAlH4 and Lithium Amide (LiNH2 Hydride Composites

    Directory of Open Access Journals (Sweden)

    Leszek Zbroniec

    2012-04-01

    Full Text Available Hydrogen storage properties of the (nLiAlH4 + LiNH2 hydride composite where n = 1, 3, 11.5 and 30, synthesized by high energy ball milling have been investigated. The composite with the molar ratio n = 1 releases large quantities of H2 (up to ~5 wt.% during ball milling up to 100–150 min. The quantity of released H2 rapidly decreases for the molar ratio n = 3 and is not observed for n = 11.5 and 30. The XRD studies indicate that the H2 release is a result of a solid state decomposition of LiAlH4 into (1/3Li3AlH6 + (2/3Al + H2 and subsequently decomposition of (1/3Li3AlH6 into LiH + (1/3Al + 0.5H2. Apparently, LiAlH4 is profoundly destabilized during ball milling by the presence of a large quantity of LiNH2 (37.7 wt.% in the n = 1 composite. The rate of dehydrogenation at 100–170 °C (at 1 bar H2 is adversely affected by insufficient microstructural refinement, as observed for the n = 1 composite, which was milled for only 2 min to avoid H2 discharge during milling. XRD studies show that isothermal dehydrogenation of (nLiAlH4 + LiNH2 occurs by the same LiAlH4 decomposition reactions as those found during ball milling. The ball milled n = 1 composite stored under Ar at 80 °C slowly discharges large quantities of H2 approaching 3.5 wt.% after 8 days of storage.

  11. Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co3O4) Nanoparticles: The Effect of Particle Size on Activity and Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Tyo, Eric C.; Yin, Chunrong; Di Vece, Marcel; Qian, Qiang; Kwon, Gihan; Lee, Sungsik; Lee, Byeongdu; DeBartolo, Janae E.; Seifert, Sönke; Winans, Randall E.; Si, Rui; Ricks, Brian; Goergen, Simone; Rutter, Matthew; Zugic, Branko; Flytzani-Stephanopoulos, Maria; Wang, Zhi Wei; Palmer, Richard E.; Neurock, Matthew; Vajda, Stefan

    2012-10-02

    The oxidative dehydrogenation of cyclohexane by cobalt oxide nanoparticles was studied via temperature programmed reaction combined with in situ grazing incidence X-ray absorption spectroscopy and grazing incidence small-angle X-ray scattering and theoretical calculations on model Co3O4 substrates. Both 6 and 12 nm Co3O4 nanoparticles were made through a surfactant-free preparation and dispersed on an Al2O3 surface formed by atomic layer deposition. Under reaction conditions the nanoparticles retained their oxidation state and did not sinter. They instead underwent an assembly/disassembly process and could reorganize within their assemblies. The selectivity of the catalyst was found to be size- and temperature-dependent, with larger particles preferentially producing cyclohexene at lower temperatures and smaller particles predominantly resulting in benzene at higher temperatures. The mechanistic features thought to control the oxidative dehydrogenation of cyclohexane and other light alkanes on cobalt oxide were established by carrying out density functional theory calculations on the activation of propane, a surrogate model alkane, over model Co3O4 surfaces. The initial activation of the alkane (propane) proceeds via hydrogen abstraction over surface oxygen sites. The subsequent activation of the resulting alkoxide intermediate occurs at a second surface oxygen site to form the alkene (propene) which then desorbs from the surface. Hydroxyl recombination results in the formation of water which desorbs from the surface. Finally, oxygen is necessary to regenerate the surface oxygen sites, catalyze C–H activation steps, and minimize catalyst degradation.

  12. New nitrogen-containing materials for hydrogen storage and their characterization by high-pressure microbalance

    DEFF Research Database (Denmark)

    Vestbø, Andreas Peter

    -called complex hydrides, which contain hydrogen bound covalently often in very light materials involving elements such as lithium, sodium, nitrogen and aluminum. While these materials typically have high decomposition temperatures, the combination with other compounds helps to destabilize the material resulting...... in lowered effective dehydrogenation temperatures. From the discovery in 1996 by Borislav Bogdanović and his group that catalyzed sodium alanate, NaAlH4, can release hydrogen reversibly below 200 °C relatively fast, hydrogen storage in nitrogen-containing compounds beginning with lithium nitride, Li3N...

  13. Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

    Science.gov (United States)

    Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

    2014-06-01

    A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2)  g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Properties of Mg-Al alloys in relation to hydrogen storage

    DEFF Research Database (Denmark)

    Andreasen, A.

    2005-01-01

    Magnesium theoretically stores 7.6 wt. % hydrogen, although it requires heating to above 300 degrees C in order to release hydrogen. This limits its use for mobile application. However, due to its low price and abundance magnesium should still beconsidered as a potential candidate for hydrogen st...... properties (lower desorption temperature), and kinetics of hydrogenation/dehydrogenation are improved. In addition to this, the low price of the hydride isretained along with improved heat transfer properties and improved resistance towards oxygen contamination.......Magnesium theoretically stores 7.6 wt. % hydrogen, although it requires heating to above 300 degrees C in order to release hydrogen. This limits its use for mobile application. However, due to its low price and abundance magnesium should still beconsidered as a potential candidate for hydrogen...

  15. Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Chunling Wei

    2016-10-01

    Full Text Available A series of vanadia catalysts supported on SBA-15 (V/SBA with a vanadia (V content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, and temperature-programmed reduction (TPR. It was found that these catalysts were effective for the dehydrogenation reaction, and the catalytic activity is correlated with the amount of dispersed vanadium species on the SBA-15 support. The 7% V/SBA catalyst shows the highest activity, which gives 40.8% isobutane conversion and 84.8% isobutene selectivity. The SBA-15-supported vanadia exhibits higher isobutane conversion and isobutene selectivity than the MCM-41-supported one.

  16. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

    DEFF Research Database (Denmark)

    Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation of benz...... dehydrogenation of benzyl alcohols to be proposed. The use of CuO as an inexpensive and efficient heterogeneous catalyst under aerobic conditions provides a new noble metal-free and green reaction protocol for carbonyl compound synthesis....... of benzylic, alicyclic and unsaturated alcohols to their corresponding carbonyl compounds with excellent selectivities. The observed trend in activity for conversion of substituted alcohols suggested a β-H elimination step to be involved, thus enabling a possible reaction mechanism for oxidative...

  17. Synthesis of octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals and their structure-activity relationship for the decomposition of hydrazine in aqueous solution to hydrogen

    Science.gov (United States)

    Li, Chun; Wang, Tao; Chu, Wei; Wu, Ping; Tong, Dong Ge

    2016-03-01

    We developed a co-reduction method to synthesize octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals. The shape/size distribution, structural characteristics, and composition of the Rh2Ni nanocrystals are investigated, and their possible formation mechanism at high temperatures in margaric acid/1-aminoheptadecane solution in the presence of tetraethylgermanium and borane trimethylamine complexes is proposed. A preliminary probing of the structure-activity dependence of the surface ``clean'' Rh2Ni nanocrystals supported on carbon towards hydrazine (N2H4) in aqueous solution dehydrogenation revealed that the higher the percentage of {111} facets, the higher is the activity and H2 selectivity of the nanocrystals. This result was attributed to the {111} facets not only introducing more basic sites, but also weakening the interaction between the produced adspecies (including H2 and NHx) and surface metal atoms in comparison with those of {100} facets. Furthermore, the as-prepared Rh2Ni nanooctahedra exhibited 100% H2 selectivity and high activity at room temperature for H2 generation via N2H4 decomposition. The activation energy of the Rh2Ni nanooctahedra was 41.6 +/- 1.2 kJ mol-1. The Rh2Ni nanooctahedra were stable catalysts for the hydrolytic dehydrogenation of N2H4, providing 27 723 total turnovers in 30 h. Our work provides a new perspective concerning the possibility of constructing hydrogen-producing systems based on N2H4 and surface ``clean'' Rh2Ni nanocrystal catalysts with defined shapes supported on carbon that possess a competitive performance in comparison with NaBH4 and NH3BH3 hydrogen-producing systems for fuel cell applications.We developed a co-reduction method to synthesize octahedral, truncated octahedral, and cubic Rh2Ni nanocrystals. The shape/size distribution, structural characteristics, and composition of the Rh2Ni nanocrystals are investigated, and their possible formation mechanism at high temperatures in margaric acid/1

  18. Boron-Based Hydrogen Storage: Ternary Borides and Beyond

    Energy Technology Data Exchange (ETDEWEB)

    Vajo, John J. [HRL Laboratories, LLC, Malibu, CA (United States)

    2016-04-28

    DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slow rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.

  19. Titania-catalysed oxidative dehydrogenation of ethyl lactate: effective yet selective free-radical oxidation

    NARCIS (Netherlands)

    Ramos-Fernandez, E.V.; Geels, N.J.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    We research here the catalytic oxidative dehydrogenation of ethyl lactate, as an alternative route to ethyl pyruvate. Testing various solid catalysts (Fe2O3, TiO2, V2O5/MgO-Al2O3, ZrO2, CeO2 and ZnO), we find that simple and inexpensive TiO2 efficiently catalyses this reaction under mild conditions.

  20. Selection of mixed conducting oxides for oxidative dehydrogenation of propane with pulse experiments

    NARCIS (Netherlands)

    Crapanzano, S.D.; Babych, Igor V.; Lefferts, Leonardus

    2010-01-01

    In this study, propane pulse experiments at 550 °C are used as a method to select suitable oxides for further operation of catalytic dense membrane reactor (CDMR) for oxidative dehydrogenation of propane. Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF), La2NiO4+δ (LN) and PrBaCo2O5+δ (PBC) powders were used as

  1. Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

    OpenAIRE

    Chunling Wei; Fangqi Xue; Changxi Miao; Yinghong Yue; Weimin Yang; Weiming Hua; Zi Gao

    2016-01-01

    A series of vanadia catalysts supported on SBA-15 (V/SBA) with a vanadia (V) content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and temperature-programmed reduction (TPR). It was found that these catalysts were effective for the dehydrogenati...

  2. Chlorific efficiency of coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Schappert, H.

    1942-10-20

    In studies on the calorific efficiency of coal hydrogenation, the efficiency for H/sub 2/ production was calculated to be 26%, the efficiency for hydrogenation was calculated to be 49%, and the efficiency of hydrogenation including H/sub 2/ production was 27.2%. The efficiency of hydrogenation plus hydrogen production was almost equal to the efficiency of hydrogen production alone, even though this was not expected because of the total energy calculated in the efficiency of hydrogenation proper. It was entirely possible, but did not affect computations, that the efficiency of one or the other components of hydrogenation process differed somewhat from 49%. The average efficiency for all cases was 49%. However, when hydrogen was not bought, but was produced--(efficiency of hydrogen production was 26%, not 100%-- then the total energy changed and the efficiency of hydrogen production and combination was not 26%, but 13%. This lower value explained the drop of hydrogenation efficiency to 27.2%.

  3. Adsorption and dehydrogenation of ethane, propane and butane on Rh13 clusters supported on unzipped graphene oxide and TiO2(110) - a DFT study.

    Science.gov (United States)

    Chang, Chun-Chih; Liu, Chi-You; Wu, Shiuan-Yau; Tsai, Ming-Kang

    2017-02-15

    The catalytic activity for the adsorption and dehydrogenation of alkanes (C n H 2n+2 , n = 2, 3, 4) on a low-symmetry Rh 13 cluster (Rh 13 -L s ) is compared with a system consisting of the same cluster (Rh 13 -L s ) supported on either an unzipped graphene-oxide (UGO) sheet (Rh 13 -L s /UGO) or a TiO 2 (110) surface (Rh 13 -L s /TiO 2 ). The adsorption energies of these alkanes, calculated using density-functional theory, follow the order Rh 13 -L s /TiO 2 ≈ Rh 13 -L s /UGO > Rh 13 -L s . Our proposed reaction path for the dehydrogenation of ethane, propane and butane on Rh 13 -L s /UGO has first barrier heights of 0.21, 0.22 and 0.16 eV for the dissociation of a terminal C-H bond to form -C 2 H 5 , -C 3 H 7 and -C 4 H 9 , respectively. Compared with the barriers on Rh 13 -L s and Rh 13 -L s /TiO 2 , the barrier on Rh 13 -L s /UGO is the lowest for all alkanes. The calculated data, including the electronic distribution and the density of states of alkanes adsorbed on Rh 13 -L s /UGO, Rh 13 -L s and Rh 13 -L s /TiO 2 , to support our results are presented.

  4. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst

    Directory of Open Access Journals (Sweden)

    M. Toghyani

    2015-07-01

    Full Text Available The Pt/γ-Al2O3 catalyst life time was limited by the formation of coke on the external and internal surfaces of catalyst in dehydrogenation reactors. The kinetics of decoking of dehydrogenation catalyst was studied in a pilot scale fixed bed reactor experimentally. The effects of temperature, oxygen concentration and other operating conditions on decoking process were investigated. A kinetic model was deve-loped to describe the decoking of mentioned catalyst. An objective function was defined as the sum of squares of the deviations among the calculated and plant data. Accordingly the appropriate values were found in order to minimize this function. It was concluded that there was a good agreement between simulation results and experimental data.  © 2015 BCREC UNDIP. All rights reservedReceived: 18th September 2014; Revised: 28th February 2015; Accepted: 9th March 2015How to Cite: Toghyani, M., Rahimi, A., Mamanpoush, M., Kazemian, R., Harandizadeh, A.H. (2015. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 155-161. (doi:10.9767/bcrec.10.2.7357.155-161 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7357.155-161  

  5. Highly Ordered Mesoporous Metal Oxides as Catalysts for Dehydrogenation of Cyclohexanol

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eunok; Jin, Mingshi; Kim, Ji Man [Sungkyunkwan University, Suwon (Korea, Republic of)

    2013-08-15

    Cyclohexanone is important intermediate for the manufacture of caprolactam which is monomer of nylron. Cyclohexanone is generally produced by dehydrogenation reaction of cyclohexanol. In this study, highly mesoporous metal oxides such as meso-WO{sub 3}, meso-TiO{sub 2}, meso-Fe{sub 2}O{sub 3}, meso-CuO, meso-SnO{sub 2} and meso-NiO were synthesized using mesoporous silica KIT-6 as a hard template via nano-replication method for dehydrogenation of cyclohexanol. The overall conversion of cyclohexanol followed a general order: meso-WO{sub 3} >> meso-Fe{sub 2}O{sub 3} > meso-SnO{sub 2} > meso-TiO{sub 2} > meso-NiO > meso-CuO. In particular, meso-WO{sub 3} significantly showed higher activity than the other mesoporous metal oxides. Therefore, the meso-WO{sub 3} has wide range of application possibilities for dehydrogenation of cyclohexanol.

  6. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

  7. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  8. Hydrogen production by Cyanobacteria

    Directory of Open Access Journals (Sweden)

    Chaudhuri Surabhi

    2005-12-01

    Full Text Available Abstract The limited fossil fuel prompts the prospecting of various unconventional energy sources to take over the traditional fossil fuel energy source. In this respect the use of hydrogen gas is an attractive alternate source. Attributed by its numerous advantages including those of environmentally clean, efficiency and renew ability, hydrogen gas is considered to be one of the most desired alternate. Cyanobacteria are highly promising microorganism for hydrogen production. In comparison to the traditional ways of hydrogen production (chemical, photoelectrical, Cyanobacterial hydrogen production is commercially viable. This review highlights the basic biology of cynobacterial hydrogen production, strains involved, large-scale hydrogen production and its future prospects. While integrating the existing knowledge and technology, much future improvement and progress is to be done before hydrogen is accepted as a commercial primary energy source.

  9. Model Catalytic Studies of Novel Liquid Organic Hydrogen Carriers: Indole, Indoline and Octahydroindole on Pt(111).

    Science.gov (United States)

    Schwarz, Matthias; Bachmann, Philipp; Silva, Thais Nascimento; Mohr, Susanne; Scheuermeyer, Marlene; Späth, Florian; Bauer, Udo; Düll, Fabian; Steinhauer, Johann; Hohner, Chantal; Döpper, Tibor; Noei, Heshmat; Stierle, Andreas; Papp, Christian; Steinrück, H-P; Wasserscheid, Peter; Görling, Andreas; Libuda, Jörg

    2017-10-20

    Indole derivatives were recently proposed as potential liquid organic hydrogen carriers (LOHC) for storage of renewable energies. In this work, we have investigated the adsorption, dehydrogenation and degradation mechanisms in the indole/indoline/octahydroindole system on Pt(111). We have combined infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS) and DFT calculations. Indole multilayers show a crystallization transition at 200 K, in which the molecules adopt a strongly tilted orientation, before the multilayer desorbs at 220 K. For indoline, a less pronounced restructuring transition occurs at 150 K and multilayer desorption is observed at 200 K. Octahydroindole multilayers desorb already at 185 K, without any indication for restructuring. Adsorbed monolayers of all three compounds are stable up to room temperature and undergo deprotonation at the NH bond above 300 K. For indoline, the reaction is followed by partial dehydrogenation at the 5-membered ring, leading to the formation of a flat-lying di-σ-indolide in the temperature range from 330-390 K. Noteworthy, the same surface intermediate is formed from indole. In contrast, the reaction of octahydroindole with Pt(111) leads to the formation of a different intermediate, which originates from partial dehydrogenation of the 6-membered ring. Above 390 K, all three compounds again form the same strongly dehydrogenated and partially decomposed surface species. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Comparison of the hydrogenating capacities of Pt. Re and Pt-Re/Al/sub 2/O/sub 3/ in n-hexane reforming

    Energy Technology Data Exchange (ETDEWEB)

    Parera, J.M.; Beltramini, J.N.; Querini, C.A.; Figoli, N.S.

    1986-09-01

    The introduction of rhenium as a second metal and its sulfidation increase the stability and selectivity of Pt Al/sub 2/O/sub 3/ catalyst for naphtha reforming. The addition of Re and S affects the metallic function of the catalyst but not the acidic one. One proposed cause of the improvement of the catalyst by addition of Re and S is higher resistance to deactivation by coking. Others stated that Pt-Re has a greater capacity than Pt to hydrogenate cyclopentadiene, one of the most important coke precursors. Others ascribed to Re the capacity to destroy by hydrogenolysis the coke precursors without necessity of an intimate contact between Pt and Re. Others stated that Re reduces the dehydrogenating capacity of Pt, thereby increasing the dehydrogenation of coke precursors and, in the case of methylcyclopentadiene reforming, decreasing its condensation-dehydrogenation to produce heavy aromatics and poly-ring coke. This paper presents information about the hydrogenation-dehydrogenation capacity of the metallic component of Pt/Al/sub 2/O/sub 3/ reforming catalyst, comparing the activity of Pt, Re and Pt-Re for hydrogenating their own coke and for recovering the activity of metallic-catalyzed reactions.

  11. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  12. C1 Chemistry for the Production of Ultra-Clean Liquid Transportation Fuels and Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Gerald P. Huffman

    2006-03-30

    Professors and graduate students from five universities--the University of Kentucky, University of Pittsburgh, University of Utah, West Virginia University, and Auburn University--are collaborating in a research program to develop C1 chemistry processes to produce ultra-clean liquid transportation fuels and hydrogen, the zero-emissions transportation fuel of the future. The feedstocks contain one carbon atom per molecular unit. They include synthesis gas (syngas), a mixture of carbon monoxide and hydrogen produced by coal gasification or reforming of natural gas, methane, methanol, carbon dioxide, and carbon monoxide. An important objective is to develop C1 technology for the production of liquid transportation fuel and hydrogen from domestically plentiful resources such as coal, coalbed methane, and hydrocarbon gases and liquids produced from coal. An Advisory Board with representatives from Chevron-Texaco, Eastman Chemical, Conoco-Phillips, the Air Force Research Laboratory, the U.S. Army National Automotive Center, and Tier Associates provides guidance on the practicality of the research. The current report summarizes the results obtained in this program during the period October 1, 2002 through March 31, 2006. The results are presented in detailed reports on 16 research projects headed by professors at each of the five CFFS Universities and an Executive Summary. Some of the highlights from these results are: (1) Small ({approx}1%) additions of acetylene or other alkynes to the Fischer-Tropsch (F-T) reaction increases its yield, causes chain initiation, and promotes oxygenate formation. (2) The addition of Mo to Fe-Cu-K/AC F-T catalysts improves catalyst lifetime and activity. (3) The use of gas phase deposition to place highly dispersed metal catalysts on silica or ceria aerogels offers promise for both the F-T and the water-gas shift WGS reactions. (4) Improved activity and selectivity are exhibited by Co F-T catalysts in supercritical hexane. (5) Binary Fe

  13. Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers.

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2018-01-28

    La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C 4 H 6 ) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C 4 H 6 ) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH 2 ) 3 ] (Iso A) and La(CH 2 CHCHCH 2 ) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2 A 1 (C 3v ) for Iso A and 2 A' (C s ) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1 A 1 ion of Iso A and the 1 A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp 3 )-H bonds, and H 2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C-H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C-H bond activation.

  14. Lanthanum-mediated dehydrogenation of butenes: Spectroscopy and formation of La(C4H6) isomers

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2018-01-01

    La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH2)3] (Iso A) and La(CH2CHCHCH2) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2A1 (C3v) for Iso A and 2A' (Cs) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1A1 ion of Iso A and the 1A' ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp3)—H bonds, and H2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C—H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C—H bond activation.

  15. Recent Advances in the Use of Sodium Borohydride as a Solid State Hydrogen Store

    Directory of Open Access Journals (Sweden)

    Jianfeng Mao

    2015-01-01

    Full Text Available The development of new practical hydrogen storage materials with high volumetric and gravimetric hydrogen densities is necessary to implement fuel cell technology for both mobile and stationary applications. NaBH4, owing to its low cost and high hydrogen density (10.6 wt%, has received extensive attention as a promising hydrogen storage medium. However, its practical use is hampered by its high thermodynamic stability and slow hydrogen exchange kinetics. Recent developments have been made in promoting H2 release and tuning the thermodynamics of the thermal decomposition of solid NaBH4. These conceptual advances offer a positive outlook for using NaBH4-based materials as viable hydrogen storage carriers for mobile applications. This review summarizes contemporary progress in this field with a focus on the fundamental dehydrogenation and rehydrogenation pathways and properties and on material design strategies towards improved kinetics and thermodynamics such as catalytic doping, nano-engineering, additive destabilization and chemical modification.

  16. Properties of MgAl alloys in relation to hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Andreasen, Anders

    2005-08-01

    Magnesium theoretically stores 7.6 wt. % hydrogen, although it requires heating to above 300 degrees C in order to release hydrogen. This limits its use for mobile application. However, due to its low price and abundance magnesium should still be considered as a potential candidate for hydrogen storage e.g. in stationary applications. In this report the properties of Mg-Al alloys are reviewed in relation to solid state hydrogen storage Alloying with Al reduces the hydrogen capacity since Al does not form a hydride under conventional hydriding conditions, however both the thermodynamical properties (lower desorption temperature), and kinetics of hydrogenation/dehydrogenation are improved. In addition to this, the low price of the hydride is retained along with improved heat transfer properties and improved resistance towards oxygen contamination. (au)

  17. Amineborane Based Chemical Hydrogen Storage - Final Report

    International Nuclear Information System (INIS)

    Sneddon, Larry G.

    2011-01-01

    The development of efficient and safe methods for hydrogen storage is a major hurdle that must be overcome to enable the use of hydrogen as an alternative energy carrier. The objectives of this project in the DOE Center of Excellence in Chemical Hydride Storage were both to develop new methods for on-demand, low temperature hydrogen release from chemical hydrides and to design high-conversion off-board methods for chemical hydride regeneration. Because of their reactive protic (N-H) and hydridic (B-H) hydrogens and high hydrogen contents, amineboranes such as ammonia borane, NH 3 BH 3 (AB), 19.6-wt% H 2 , and ammonia triborane NH 3 B 3 H 7 (AT), 17.7-wt% H 2 , were initially identified by the Center as promising, high-capacity chemical hydrogen storage materials with the potential to store and deliver molecular hydrogen through dehydrogenation and hydrolysis reactions. In collaboration with other Center partners, the Penn project focused both on new methods to induce amineborane H 2 -release and on new strategies for the regeneration the amineborane spent-fuel materials. The Penn approach to improving amineborane H 2 -release focused on the use of ionic liquids, base additives and metal catalysts to activate AB dehydrogenation and these studies successfully demonstrated that in ionic liquids the AB induction period that had been observed in the solid-state was eliminated and both the rate and extent of AB H2-release were significantly increased. These results have clearly shown that, while improvements are still necessary, many of these systems have the potential to achieve DOE hydrogen-storage goals. The high extent of their H 2 -release, the tunability of both their H 2 materials weight-percents and release rates, and their product control that is attained by either trapping or suppressing unwanted volatile side products, such as borazine, continue to make AB/ionic-liquid based systems attractive candidates for chemical hydrogen storage applications. These

  18. Amineborane Based Chemical Hydrogen Storage - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sneddon, Larry G.

    2011-04-21

    The development of efficient and safe methods for hydrogen storage is a major hurdle that must be overcome to enable the use of hydrogen as an alternative energy carrier. The objectives of this project in the DOE Center of Excellence in Chemical Hydride Storage were both to develop new methods for on-demand, low temperature hydrogen release from chemical hydrides and to design high-conversion off-board methods for chemical hydride regeneration. Because of their reactive protic (N-H) and hydridic (B-H) hydrogens and high hydrogen contents, amineboranes such as ammonia borane, NH3BH3 (AB), 19.6-wt% H2, and ammonia triborane NH3B3H7 (AT), 17.7-wt% H2, were initially identified by the Center as promising, high-capacity chemical hydrogen storage materials with the potential to store and deliver molecular hydrogen through dehydrogenation and hydrolysis reactions. In collaboration with other Center partners, the Penn project focused both on new methods to induce amineborane H2-release and on new strategies for the regeneration the amineborane spent-fuel materials. The Penn approach to improving amineborane H2-release focused on the use of ionic liquids, base additives and metal catalysts to activate AB dehydrogenation and these studies successfully demonstrated that in ionic liquids the AB induction period that had been observed in the solid-state was eliminated and both the rate and extent of AB H2-release were significantly increased. These results have clearly shown that, while improvements are still necessary, many of these systems have the potential to achieve DOE hydrogen-storage goals. The high extent of their H2­-release, the tunability of both their H2 materials weight-percents and release rates, and their product control that is attained by either trapping or suppressing unwanted volatile side products, such as borazine, continue to make AB/ionic­-liquid based systems attractive candidates for chemical hydrogen storage applications. These studies also

  19. Pt0.02Sn0.003Mg0.06 on γ-alumina: a stable catalyst for oxidative dehydrogenation of ethane

    NARCIS (Netherlands)

    de Graaff, E.A.; Rothenberg, G.; Kooyman, P.J.; Andreini, A.; Bliek, A.

    2005-01-01

    The advantages of two-step oxidative dehydrogenation as an alternative method for manufacturing small alkenes are outlined. In a nutshell, the process is based on separating the gaseous oxygen and hydrocarbon feeds in time. In the first step, alkanes are dehydrogenated in the presence of a solid

  20. Hydrogenation apparatus

    Science.gov (United States)

    Friedman, Joseph [Encino, CA; Oberg, Carl L [Canoga Park, CA; Russell, Larry H [Agoura, CA

    1981-01-01

    Hydrogenation reaction apparatus comprising a housing having walls which define a reaction zone and conduits for introducing streams of hydrogen and oxygen into the reaction zone, the oxygen being introduced into a central portion of the hydrogen stream to maintain a boundary layer of hydrogen along the walls of the reaction zone. A portion of the hydrogen and all of the oxygen react to produce a heated gas stream having a temperature within the range of from 1100.degree. to 1900.degree. C., while the boundary layer of hydrogen maintains the wall temperature at a substantially lower temperature. The heated gas stream is introduced into a hydrogenation reaction zone and provides the source of heat and hydrogen for a hydrogenation reaction. There also is provided means for quenching the products of the hydrogenation reaction. The present invention is particularly suitable for the hydrogenation of low-value solid carbonaceous materials to provide high yields of more valuable liquid and gaseous products.

  1. Hydrogen Storage In Nanostructured Materials

    OpenAIRE

    Assfour, Bassem

    2011-01-01

    Hydrogen is an appealing energy carrier for clean energy use. However, storage of hydrogen is still the main bottleneck for the realization of an energy economy based on hydrogen. Many materials with outstanding properties have been synthesized with the aim to store enough amount of hydrogen under ambient conditions. Such efforts need guidance from material science, which includes predictive theoretical tools. Carbon nanotubes were considered as promising candidates for hydrogen storag...

  2. Resin-derived hierarchical porous carbon spheres with high catalytic performance in the oxidative dehydrogenation of ethylbenzene.

    Science.gov (United States)

    Wang, Lifeng; Delgado, Juan J; Frank, Benjamin; Zhang, Zhe; Shan, Zhichao; Su, Dang Sheng; Xiao, Feng-Shou

    2012-04-01

    Pre-shaped hierarchical porous carbon (HPC) spheres have been synthesized through a facile anion exchanged route. An industrial polymeric anion-exchange resin with a hierarchical pore structure was used as the carbon precursor. Its high porosity was conserved using an aluminate/silicate precursor forming a hard support to prevent the structural collapse during the carbonization process. Physicochemical bulk and surface properties of the obtained HPC spheres were characterized by X-ray diffraction, scanning and transmission electron microscopy, N(2) physisorption, and X-ray photoemission spectroscopy. Results obtained indicate that HPC keeps the abundant hierarchical porosity including meso- and macropores as well as the high surface area of the resin precursor. The as-synthesized HPC spheres were tested as a catalyst for oxidative dehydrogenation of ethylbenzene to styrene. The oxygen-rich catalyst surface formed under reaction conditions shows a high catalytic performance and stability, making HPC to a potential catalyst for this type of reaction. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Mechanistic Investigations of C-H Activations on Silica-Supported Co(ii) Sites in Catalytic Propane Dehydrogenation.

    Science.gov (United States)

    Estes, Deven P

    2017-04-26

    Catalytic reactions involving C-H bond activations are central to the chemical industry. One such example, alkane dehydrogenation, has recently become very important due to shortfalls in propene production and a large supply of cheap propane. However, current technologies are inefficient and have only moderate selectivity. In order to understand how to improve currently used catalysts, we must know more about the mechanism by which propane is dehydrogenated. We show here that Co(ii) sites on silica are good catalysts for the dehydrogenation of propane, having high activity and selectivity that is reasonably stable over the course of 10 h. Mechanistic investigations of this catalyst show that the main activation mechanism is most likely C-H activation by 1,2 addition.

  4. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    Science.gov (United States)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

  5. Cobalt-promoted Iron Oxide Nanoparticles for the Selective Oxidative Dehydrogenation of Cyclohexane

    Science.gov (United States)

    Rutter, Matthew

    Recent work has shown that both cobalt and iron oxide nanoparticles are active for the oxidative dehydrogenation (ODH) of cyclohexane to benzene, the former more active than the latter. Further study has shown that the addition of gold species as a minority component into iron oxide nanocrystals increases the selectivity of the reaction to benzene. Since a primary motivation for this work is the addition of catalysts in jet fuels to facilitate the dehydrogenation and cracking reactions preceding their combustion, a low-cost, sacrificial catalyst is sought after. In this application, catalyst nanoparticles suspended in the fuel stream will dehydrogenate cyclic alkanes (cyclohexane) to their aromatic counterparts (benzene). Alkenes and aromatics have a much higher rate of combustion, which decreases the amount of uncombusted fuel in the exhaust, thereby increasing performance. As these catalysts are not recyclable, there is significant impetus to substitute cheaper base metals for expensive noble metals. In this work, iron oxide nanoparticles are doped with varying levels of cobalt to examine the effect of cobalt content and oxidation state on the selectivity and activity of the iron oxide for the oxidative dehydrogenation of cyclohexane, used as a model cyclic alkane in jet fuel. We have shown previously that small (˜5nm) cobalt oxide nanoparticles favor the production of benzene over the partial dehydrogenation products cyclohexene and cyclohexadiene, or the complete oxidation product carbon dioxide. It is the aim of this work to examine the surface of these cobalt-iron oxide nanoparticles to determine the conditions most favorable for this selective oxidative dehydrogenation. Cobalt-doped iron nanoparticles were prepared by a surfactant-free hydrothermal co-precipitation technique that enabled a high degree of composition control and size control. These samples were characterized via Transmission Electron Microscopy (TEM), powder X-Ray Diffraction (XRD), X

  6. Organic chemical hydrides as storage medium of hydrogen on the basis of superheated liquid-film concept

    International Nuclear Information System (INIS)

    Shinya Hodoshima; Atsushi Shono; Kazumi Satoh; Yasukazu Saito

    2006-01-01

    A catalysis pair of tetralin dehydrogenation / naphthalene hydrogenation has been proposed in the present paper as an organic chemical hydride for operating stationary fuel cells. Catalytic naphthalene hydrogenation, having been commercialized since the 1940's, proceeds to generate decalin via tetralin as an intermediate. The storage capacities of tetralin (3.0 wt%, 28.2 kg-H 2 / m 3 ) are lower than decalin (7.3 wt%, 64.8 kg-H 2 / m 3 ) but both tetralin dehydrogenation and naphthalene hydrogenation are much faster than the decalin / naphthalene pair. Moreover, existing infrastructures, e.g., gas station and tank lorry, are available for storage, transportation and supply of hydrogen. As for the stationary fuel cells with large space for hydrogen storage, tetralin as a hydrogen carrier is superior to decalin in terms of fast hydrogen supply. Rapid hydrogen supply from tetralin under mild conditions was only accomplished with the carbon supported metal catalysts in the 'superheated liquid-film states' under reactive distillation conditions. In contrast to the ordinary suspended states, the catalyst layer superheated in the liquid-film state gave high catalytic performances at around 250 C. As a result, serious coke formation over the catalyst surface and excessive exergy consumption were prevented simultaneously. (authors)

  7. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry

    1998-12-31

    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  8. Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2011-07-01

    Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

  9. Mechanistic insights on ethanol dehydrogenation on Pd-Au model catalysts: a combined experimental and DFT study.

    Science.gov (United States)

    Evans, E J; Li, H; Yu, Wen-Yueh; Mullen, G M; Henkelman, G; Mullins, C Buddie

    2017-11-22

    In this study, we have combined ultra-high vacuum (UHV) experiments and density functional theory (DFT) calculations to investigate ethanol (EtOH) dehydrogenation on Pd-Au model catalysts. Using EtOH reactive molecular beam scattering (RMBS), EtOH temperature-programmed desorption (TPD), and DFT calculations, we show how different Pd ensemble sizes on Au(111) can affect the mechanism for EtOH dehydrogenation and H 2 production. The Au(111) surface with an initial coverage of 2 monolayers of Pd (2 ML Pd-Au) had the highest H 2 yield. However, the 1 ML Pd-Au catalyst showed the highest selectivity and stability, yielding appreciable amounts of only H 2 and acetaldehyde. Arrhenius plots of H 2 production confirm that the mechanisms for EtOH dehydrogenation differed between 1 and 2 ML Pd-Au, supporting the perceived difference in selectivity between the two surfaces. DFT calculations support this difference in mechanism, showing a dependence of the initial dehydrogenation selectivity of EtOH on the size of Pd ensemble. DFT binding energies and EtOH TPD confirm that EtOH has increasing surface affinity with increasing Pd ensemble size and Pd coverage, indicating that surfaces with more Pd are more likely to induce an EtOH reaction instead of desorb. Our theoretical results show that the synergistic influence of atomic ensemble and electronic effects on Pd/Au(111) can lead to different H 2 association energies and EtOH dehydrogenation capacities at different Pd ensembles. These results provide mechanistic insights into ethanol's dehydrogenation interactions with different sites on the Pd-Au surface and can potentially aid in bimetallic catalyst design for applications such as fuel cells.

  10. Catalytic dehydrogenation of dimethylamine borane by group 4 metallocene alkyne complexes and homoleptic amido compounds.

    Science.gov (United States)

    Beweries, Torsten; Hansen, Sven; Kessler, Monty; Klahn, Marcus; Rosenthal, Uwe

    2011-08-14

    Dehydrogenation of Me(2)NH·BH(3) (1) by group 4 metallocene alkyne complexes of the type Cp(2)M(L)(η(2)-Me(3)SiC(2)SiMe(3)) [Cp = η(5)-cyclopentadienyl; M = Ti, no L (2Ti); M = Zr, L = pyridine (2Zr)] and group 4 metal amido complexes of the type M(NMe(2))(4) [M = Ti (8Ti), Zr (8Zr)] is presented. This journal is © The Royal Society of Chemistry 2011

  11. Reactivity of oxygen ions in mixed oxides in dehydrogenation of propane

    NARCIS (Netherlands)

    Crapanzano, S.D.

    2010-01-01

    Propane pulse experiments are used as a method to select suitable oxides as oxygen supplier for operation of catalytic dense membrane reactor (CDMR) in oxidative dehydrogenation of propane. Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF), La2NiO4+d (LN), La2Ni0.9V0.1O4.15+d (LNV-10) and PrBaCo2O5+d (PBC) powders

  12. Novel Sol-Gel Based Pt Nanocluster Catalysts for Propane Dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Boespflug, Elaine; Kawola, Jeffrey S.; Martino, Anthony; Sault, Allen G.

    1999-08-09

    We report propane dehydrogenation behavior of catalysts prepared using two novel synthesis strategies that combine inverse micelle Pt nanocluster technology with silica and alumina sol-gel processing. Unlike some other sol-gel catalyst preparations. Pt particles in these catalysts are not encapsulated in the support structure and the entire Pt particle surface is accessible for reaction. Turnover frequencies (TOF) for these catalysts are comparable to those obtained over Pt catalysts prepared by traditional techniques such as impregnation, yet the resistance to deactivation by carbon poisoning is much greater in our catalysts. The deactivation behavior is more typical of traditionally prepared PtSn catalysts than of pure Pt catalysts.

  13. Synthesis of Versatile Chemicals through Oxidative Dehydrogenation on Solid Catalysts of Non-Petroleum Resource

    OpenAIRE

    Sugiyama, Shigeru; Nagai, Yuya; Sakamoto, Naotaka; Ohtake, Naotaka; Katoh, Masahiro

    2016-01-01

    To prepare 1,3-butadiene, one of versatile chemicals, from 1-butene, one of the main components in liquefied petroleum gas (LPG), the oxidative dehydrogenation of 1-butene on α-Bi2Mo3O12 doped with cerium was examined. Regardless to the doped amount of cerium, the conversion of 1-butene was constant while the selectivity to 1,3-butadiene decreased with the doped amount of cerium, while the selectivities to 2-butenes, CO and CO2 increased. It is concluded that the introduction of cerium into α...

  14. Hail hydrogen

    International Nuclear Information System (INIS)

    Hairston, D.

    1996-01-01

    After years of being scorned and maligned, hydrogen is finding favor in environmental and process applications. There is enormous demand for the industrial gas from petroleum refiners, who need in creasing amounts of hydrogen to remove sulfur and other contaminants from crude oil. In pulp and paper mills, hydrogen is turning up as hydrogen peroxide, displacing bleaching agents based on chlorine. Now, new technologies for making hydrogen have the industry abuzz. With better capabilities of being generated onsite at higher purity levels, recycled and reused, hydrogen is being prepped for a range of applications, from waste reduction to purification of Nylon 6 and hydrogenation of specialty chemicals. The paper discusses the strong market demand for hydrogen, easier routes being developed for hydrogen production, and the use of hydrogen in the future

  15. Future hydrogen markets for large-scale hydrogen production systems

    International Nuclear Information System (INIS)

    Forsberg, Charles W.

    2007-01-01

    The cost of delivered hydrogen includes production, storage, and distribution. For equal production costs, large users (>10 6 m 3 /day) will favor high-volume centralized hydrogen production technologies to avoid collection costs for hydrogen from widely distributed sources. Potential hydrogen markets were examined to identify and characterize those markets that will favor large-scale hydrogen production technologies. The two high-volume centralized hydrogen production technologies are nuclear energy and fossil energy with carbon dioxide sequestration. The potential markets for these technologies are: (1) production of liquid fuels (gasoline, diesel and jet) including liquid fuels with no net greenhouse gas emissions and (2) peak electricity production. The development of high-volume centralized hydrogen production technologies requires an understanding of the markets to (1) define hydrogen production requirements (purity, pressure, volumes, need for co-product oxygen, etc.); (2) define and develop technologies to use the hydrogen, and (3) create the industrial partnerships to commercialize such technologies. (author)

  16. Hydrogen-Mediated Nitrogen Clustering in Dilute III-V Nitrides

    Science.gov (United States)

    Du, Mao-Hua; Limpijumnong, Sukit; Zhang, S. B.

    2006-08-01

    First-principles calculation reveals multi-N clusters to be the ground states for hydrogenated N in dilute III-V nitrides. While hydrogenation of a single N, forming H2*(N), can relax the large strain induced by the size-mismatched N, formation of the clusters will relax the strain even more effectively. This suppresses the formation of H2*(N), the existence of which has recently been debated. More importantly, postgrowth dehydrogenation of the N-H clusters provides an explanation to the observed metastable bare N clusters in GaAsN grown by gas-source molecular beam epitaxy or metal-organic chemical vapor deposition.

  17. Metal salt catalysts for enhancing hydrogen spillover

    Science.gov (United States)

    Yang, Ralph T; Wang, Yuhe

    2013-04-23

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

  18. Synthesis of carbon-supported copper catalyst and its catalytic performance in methanol dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Shelepova, Ekaterina V. [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); National Research Tomsk Polytechnic University, Lenin av., 30, Tomsk, 634050 (Russian Federation); Vedyagin, Aleksey A., E-mail: vedyagin@catalysis.ru [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); National Research Tomsk Polytechnic University, Lenin av., 30, Tomsk, 634050 (Russian Federation); Ilina, Ludmila Yu.; Nizovskii, Alexander I. [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); Tsyrulnikov, Pavel G. [Institute of Hydrocarbon Processing SB RAS, Neftezavodskaya st., 54, Omsk, 644040 (Russian Federation)

    2017-07-01

    Highlights: • Carbon-supported copper catalyst was studied in dehydrogenation of methanol. • Reduction temperature affected size of Cu particles and Cu{sup 0}/Cu{sup 2+} ratio. • Reduction at 400 °C was required to obtain high methyl formate yield. - Abstract: Carbon-supported copper catalyst was prepared by incipient wetness impregnation of Sibunit with an aqueous solution of copper nitrate. Copper loading was 5 wt.%. Temperature of reductive pretreatment was varied within a range of 200–400 °C. The samples were characterized by transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron and X-ray absorption spectroscopies. Catalytic activity of the samples was studied in a reaction of methanol dehydrogenation. Silica-based catalyst with similar copper loading was used as a reference. It was found that copper is distributed over the surface of support in the form of metallic and partially oxidized particles of about 12–17 nm in size. Diminished interaction of copper with support was supposed to be responsible for high catalytic activity.

  19. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  20. Preparation, characterisation and activity of chromia-zirconia catalysts for propane dehydrogenation

    International Nuclear Information System (INIS)

    Cutrufello, M.G.; De Rossi, S.; Ferino, I.; Monaci, R.; Rombi, E.; Solinas, V.

    2005-01-01

    Dehydrogenation catalysts based on chromia supported on ZrO 2 , containing about 10 wt.% of chromium and increasing amounts of potassium (up to 4 wt.%), were prepared and characterised by chemical analysis, N 2 adsorption-desorption at 77 K, X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), temperature programmed reduction (TPR) and adsorption microcalorimetry of ammonia. Increasing K amounts deeply modify the ammonia adsorption behaviour, with a progressive decrease in the acidic features, which are completely lost when the K content attains 1 wt.%. Reduction of Cr species seems rather easy for chromia-zirconia and K-containing chromia-zirconia samples with K contents up to 0.5 wt.%. The onset of reduction shifts to higher temperatures as the K concentration increases. Catalytic testing was performed under atmospheric pressure at 813 K. Pure zirconia is very poorly active in propane dehydrogenation; also virtually inactive are the samples with a K content ≥1 wt.%. Conversion decreases as the K amount increases up to 0.5 wt.%, propene selectivity being close to 100 mol%. An induction period is observed for all the active samples, which attains a maximum in conversion before being deactivated by coking

  1. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Luma M. Ahmed

    2014-01-01

    Full Text Available Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100. The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, atomic force microscopy (AFM, and UV-visible diffuse spectrophotometry (UV-Vis. XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

  2. Process economics and safety considerations for the oxidative dehydrogenation of ethane using the M1 catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Baroi, Chinmoy; Gaffney, Anne M.; Fushimi, Rebecca

    2017-12-01

    Olefins or unsaturated hydrocarbons play a vital role as feedstock for many industrially significant processes. Ethylene is the simplest olefin and a key raw material for consumer products. Oxidative Dehydrogenation (ODH) is one of the most promising new routes for ethylene production that can offer a significant advantage in energy efficiency over the conventional steam pyrolysis process. This study is focused on the ODH chemistry using the mixed metal oxide MoVTeNbOx catalysts, generally referred to as M1 for the key phase known to be active for dehydrogenation. Using performance results from the patent literature a series of process simulations were conducted to evaluate the effect of feed composition on operating costs, profitability and process safety. The key results of this study indicate that the ODH reaction can be made safer and more profitable without use of an inert diluent and furthermore by replacing O2 with CO2 as an oxidant. Modifications of the M1 catalyst composition in order to adopt these changes are discussed.

  3. Modification by SiO2 of Alumina Support for Light Alkane Dehydrogenation Catalysts

    Directory of Open Access Journals (Sweden)

    Giyjaz E. Bekmukhamedov

    2016-10-01

    Full Text Available Due to the continuously rising demand for C3–C5 olefins it is important to improve the performance of catalysts for dehydrogenation of light alkanes. In this work the effect of modification by SiO2 on the properties of the alumina support and the chromia-alumina catalyst was studied. SiO2 was introduced by impregnation of the support with a silica sol. To characterize the supports and the catalysts the following techniques were used: low-temperature nitrogen adsorption; IR-spectroscopy; magic angle spinning 29Si nuclear magnetic resonance; temperature programmed desorption and reduction; UV-Vis-, Raman- and electron paramagnetic resonance (EPR-spectroscopy. It was shown that the modifier in amounts of 2.5–7.5 wt % distributed on the support surface in the form of SiOx-islands diminishes the interaction between the alumina support and the chromate ions (precursor of the active component. As a result, polychromates are the compounds predominantly stabilized on the surface of the modified support; under thermal activation of the catalyst and are reduced to the amorphous Cr2O3. This in turn leads to an increase in the activity of the catalyst in the dehydrogenation of isobutane.

  4. Hydrogen Filling Station

    Energy Technology Data Exchange (ETDEWEB)

    Boehm, Robert F; Sabacky, Bruce; Anderson II, Everett B; Haberman, David; Al-Hassin, Mowafak; He, Xiaoming; Morriseau, Brian

    2010-02-24

    future. Project partners also conducted a workshop on hydrogen safety and permitting. This provided an opportunity for the various permitting agencies and end users to gather to share experiences and knowledge. As a result of this workshop, the permitting process for the hydrogen filling station on the Las Vegas Valley Water District’s land was done more efficiently and those who would be responsible for the operation were better educated on the safety and reliability of hydrogen production and storage. The lessons learned in permitting the filling station and conducting this workshop provided a basis for future hydrogen projects in the region. Continuing efforts to increase the working pressure of electrolysis and efficiency have been pursued. Research was also performed on improving the cost, efficiency and durability of Proton Exchange Membrane (PEM) hydrogen technology. Research elements focused upon PEM membranes, electrodes/catalysts, membrane-electrode assemblies, seals, bipolar plates, utilization of renewable power, reliability issues, scale, and advanced conversion topics. Additionally, direct solar-to-hydrogen conversion research to demonstrate stable and efficient photoelectrochemistry (PEC) hydrogen production systems based on a number of optional concepts was performed. Candidate PEC concepts included technical obstacles such as inefficient photocatalysis, inadequate photocurrent due to non-optimal material band gap energies, rapid electron-hole recombination, reduced hole mobility and diminished operational lifetimes of surface materials exposed to electrolytes. Project Objective 1: Design, build, operate hydrogen filling station Project Objective 2: Perform research and development for utilizing solar technologies on the hydrogen filling station and convert two utility vehicles for use by the station operators Project Objective 3: Increase capacity of hydrogen filling station; add additional vehicle; conduct safety workshop; develop a roadmap for

  5. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    Science.gov (United States)

    Kawasaki, Shin-ichiro; Suzuki, Akira

    2013-01-01

    Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  6. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    Directory of Open Access Journals (Sweden)

    Rahat Javaid

    2013-06-01

    Full Text Available The inner surface of a metallic tube (i.d. 0.5 mm was coated with a palladium (Pd-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2 was observed during the reaction, although hydrogen (H2 was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid.

  7. Hydrogen Fuelling Stations

    DEFF Research Database (Denmark)

    Rothuizen, Erasmus Damgaard

    station has been developed in Dymola. The models include the fuelling protocol (J2601) for hydrogen vehicles made by Society of Automotive Engineers (SAE) and the thermodynamic property library CoolProp is used for retrieving state point. The components in the hydrogen fuelling library are building up...

  8. Hydrogen evolution reaction catalyst

    Science.gov (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

    2016-02-09

    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

  9. Spectroscopic characterization of the on-surface induced (cyclo) dehydrogenation of a N-heteroaromatic compound on noble metal surfaces

    Czech Academy of Sciences Publication Activity Database

    Palacio, I.; Pinardi, A. L.; Martínez, J. I.; Preobrajenski, A.; Cossaro, A.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Méndez, J.; Martín-Gago, J.A.; López, M.F.

    2017-01-01

    Roč. 19, č. 33 (2017), s. 22454-22461 ISSN 1463-9076 Institutional support: RVO:61388963 Keywords : dibenzohelicene * on-surface (cyclo)dehydrogenation * spectroscopic characterization Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.123, year: 2016

  10. The oxidative dehydrogenation of methanol to formaldehyde over silver catalysts in relation to the oxygen-silver interaction

    NARCIS (Netherlands)

    Lefferts, Leonardus; van Ommen, J.G.; Ross, J.R.H.

    1986-01-01

    The properties of silver in the oxidative dehydrogenation of methanol were studied in a flow reactor under near industrial conditions. The influences of temperature, concentration of both reactants, gas velocity, space velocity, the form of the silver catalyst and surface composition of the catalyst

  11. Towards real-time spectroscopic process control for the dehydrogenation of propane over supported chromium oxide catalysts

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Nijhuis, T.A.; Tinnemans, S.J.; Visser, T.

    2004-01-01

    UV–Vis and Raman spectroscopy are applied under realistic reaction conditions to investigate the changes occurring to an industrial-like supported chromium oxide catalyst during the dehydrogenation of propane. Linking the catalytic activity to the simultaneously collected spectroscopic data has

  12. DNA-based prenatal diagnosis for severe and variant forms of multiple acyl-CoA dehydrogenation deficiency

    DEFF Research Database (Denmark)

    Olsen, Rikke K J; Andresen, Brage S; Christensen, Ernst

    2005-01-01

    OBJECTIVES: Multiple acyl-CoA dehydrogenation deficiency (MADD) is a clinically heterogeneous disorder of mitochondrial fatty acid, amino acid, and choline oxidation due to mutations in the genes encoding electron transfer flavoprotein (ETF) or ETF ubiquinone oxidoreductase (ETFQO). So far...

  13. Thermally Stable and Regenerable Platinum-Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

    NARCIS (Netherlands)

    Xiong, Haifeng; Lin, Sen; Goetze, Joris; Pletcher, Paul; Guo, Hua; Kovarik, Libor; Artyushkova, Kateryna; Weckhuysen, Bert M.; Datye, Abhaya K.

    2017-01-01

    Ceria (CeO2) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single-atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single-atom

  14. Making coke a more efficient catalyst in the oxidative dehydrogenation of ethylbenzene using wide-pore transitional aluminas

    NARCIS (Netherlands)

    Zarubina, V.; Nederlof, C.; Linden, B. van der; Kapteijn, F.; Heeres, H.J.; Makkee, M.; Melián-Cabrera, I.

    The thermal activation of a silica-stabilized gamma-alumina impacts positively on the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST). A systematic thermal study reveals that the transition from gamma-alumina into transitional phases at 1050 degrees C leads to an optimal enhancement

  15. The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Li, X.; Seshan, Kulathuiyer; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

    1993-01-01

    The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production

  16. Tailored Formation of N-Doped Nanoarchitectures by Diffusion-Controlled on-Surface (Cyclo)-Dehydrogenation of Heteroaromatics

    Czech Academy of Sciences Publication Activity Database

    Pinardi, A. L.; Otero-Irurueta, G.; Palacio, I.; Martinez, J. I.; Sánchez-Sánchez, C.; Tello, M.; Rogero, C.; Cossaro, A.; Preobrajenski, A.; Gomez-Lor, B.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Lopez, M. F.; Méndez, J.; Martin-Gago, J. A.

    2013-01-01

    Roč. 7, č. 4 (2013), s. 3676-3684 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GAP207/10/2207 Institutional support: RVO:61388963 Keywords : surface-assisted dehydrogenation * dibenzo[5]helicene * N-doped nanographene * heteroaromatic polymer Subject RIV: CC - Organic Chemistry Impact factor: 12.033, year: 2013

  17. Rhenium-catalyzed dehydrogenative olefination of C(sp(3))-H bonds with hypervalent iodine(III) reagents.

    Science.gov (United States)

    Gu, Haidong; Wang, Congyang

    2015-06-07

    A dehydrogenative olefination of C(sp(3))-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

  18. Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite Catalysts: A Review

    KAUST Repository

    Hong, Eunpyo

    2015-11-02

    1,3-Butadiene, an important raw material for a variety of chemical products, can be produced via the oxidative dehydrogenation (ODH) of n-butenes over multicomponent oxide catalysts based on bismuth molybdates and ferrites. In this review, the basic concept, reaction mechanism, and catalysts typically used in an ODH reaction are discussed. © 2015, Springer Science+Business Media New York.

  19. Hydrogen highway

    International Nuclear Information System (INIS)

    Anon

    2008-01-01

    The USA Administration would like to consider the US power generating industry as a basis ensuring both the full-scale production of hydrogen and the widespread use of the hydrogen related technological processes into the economy [ru

  20. SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS

    Energy Technology Data Exchange (ETDEWEB)

    Shamsuddin Ilias

    2005-02-03

    Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation to the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application of this new development. A two-dimensional, pseudo-homogeneous membrane-reactor model was developed to investigate the steam-methane reforming (SMR) reactions in a Pd-based membrane reactor. Radial diffusion was taken into consideration to account for the concentration gradient in the radial direction due to hydrogen permeation through the membrane. With appropriate reaction rate expressions, a set of partial differential equations was derived using the continuity equation for the reaction system. The equations were

  1. Versatile Hydrogen

    Indian Academy of Sciences (India)

    H m . Some of these compounds have fascinating structures (1,2,3). However the most interesting interaction of hydrogen, is the hydrogen bond. When a hydrogen atom is bound to an electronegative element it acquires a slight positive charge. As a result, it is attracted to other atoms such as nitrogen or oxygen in the ...

  2. Surface characterizations of TiH{sub 2} powders before and after dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yeguang [School of Aeronautics & Astronautics, Sichuan University, Chengdu, 610065 (China); Wang, Chunming; Liu, Yang; Liu, Shaopeng; Xiao, Sufen [College of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Chen, Yungui, E-mail: ygchen60@aliyun.com [School of Aeronautics & Astronautics, Sichuan University, Chengdu, 610065 (China); College of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China)

    2017-07-15

    Highlights: • Oxides characteristics of TiH{sub 2} and HDH-Ti are investigated by XPS depth profiles. • The relative contents of TiO{sub 2}, Ti{sub 2}O{sub 3} and TiO are lower after dehydrogenation. • The decrease of Ti{sub 2}O{sub 3} is more remarkable followed by TiO{sub 2}, TiO after dehydrogenation. • The H atoms of TiH{sub 2} react preferentially with Ti{sub 2}O{sub 3} followed by TiO{sub 2}, TiO. - Abstract: The oxide film of TiH{sub 2} and HDH-Ti powder are investigated using X-ray photoelectron spectroscopy (XPS). The XPS depth profiles indicate that there exists mainly Ti{sup 2+}, Ti{sup 3+}, Ti{sup 4+} and Ti{sup 0} on TiH{sub 2} and HDH-Ti surface. The intensities of Ti 2p decrease for Ti{sup 4+}, first increase and then decrease for Ti{sup 3+} and Ti{sup 2+}, and increase all the time for Ti{sup 0} in the surface layer of TiH{sub 2} and HDH-Ti with the sputtering depth increasing. The relative fractions of TiO{sub 2}, Ti{sub 2}O{sub 3} and TiO for the Ti 2p of TiH{sub 2} and HDH-Ti first decrease and then slow down with the sputtering depth increasing. Meanwhile, the relative fractions of TiO{sub 2} and TiO of HDH-Ti are lower than that of TiH{sub 2} after the sputtering depth of about 5 nm, and the fraction of Ti{sub 2}O{sub 3} of HDH-Ti is always lower that of TiH{sub 2}. In addition, the decrease of Ti{sub 2}O{sub 3} is much pronounced, followed by TiO{sub 2} and TiO before and after dehydrogenation when the sputtering depth is more than 5 nm. The XPS depth profiles and calculation results suggest that the release of H atoms removes the part of oxygen on TiH{sub 2} surface, which results in the thinner oxide layer and low oxygen content of HDH-Ti powder.

  3. Effect of MoS2 on hydrogenation storage properties of LiBH4

    International Nuclear Information System (INIS)

    Liang, Dan; Han, Shumin; Wang, Jiasheng; Zhang, Wei; Zhao, Xin; Zhao, Ziyang

    2014-01-01

    The hydrogen storage properties of LiBH 4 ball milled with 20 wt% MoS 2 have been investigated. It shows that the LiBH 4 doped with MoS 2 exhibits favorable hydrogenation and dehydrogenation properties in terms of decomposition temperature and hydriding/dehydriding reversibility. The sample with MoS 2 starts to release hydrogen at 230 °C and has a decrease of 80 °C in contrast with pristine LiBH 4 . Furthermore, for the second cycle, the LiBH 4 with MoS 2 maintains a reversible hydrogen storage capacity of about 8.0 wt% which is almost identical with the first cycle under 5 MPa at 550 °C. Analyzed by the XRD and the FTIR results, LiBH 4 can be regenerated after re-hydrogenation under a relatively mild condition by adding MoS 2 . The improvement of the hydrogenation and dehydrogenation properties mainly results from the formation of Li 2 S and MoB 2 during ball milling. -- Graphical abstract: Hydrogen absorption curves of LiBH 4 doped with MoS 2 for five cycles at 400 °C. Highlights: • The hydrogen absorption capacity is nearly the same for 5 cycles at 400 °C. • The sample with MoS 2 starts to release hydrogen at 230 °C. • The coexistence of MoB 2 and Li 2 S catalyzes the decomposition of LiBH 4

  4. Hydrogen economy

    Energy Technology Data Exchange (ETDEWEB)

    Pahwa, P.K.; Pahwa, Gulshan Kumar

    2013-10-01

    In the future, our energy systems will need to be renewable and sustainable, efficient and cost-effective, convenient and safe. Hydrogen has been proposed as the perfect fuel for this future energy system. The availability of a reliable and cost-effective supply, safe and efficient storage, and convenient end use of hydrogen will be essential for a transition to a hydrogen economy. Research is being conducted throughout the world for the development of safe, cost-effective hydrogen production, storage, and end-use technologies that support and foster this transition. This book discusses hydrogen economy vis-a-vis sustainable development. It examines the link between development and energy, prospects of sustainable development, significance of hydrogen energy economy, and provides an authoritative and up-to-date scientific account of hydrogen generation, storage, transportation, and safety.

  5. Hydrogen effects in stainless steel

    International Nuclear Information System (INIS)

    Caskey, G.R. Jr.

    1983-01-01

    The effects of hydrogen on stainless steels have been reviewed and are summarized in this paper. Discussion covers hydrogen solution and transport in stainless steels as well as the effects of hydrogen on deformation and fracture under various loading conditions. Damage is caused also by helium that arises from decay of the hydrogen isotope tritium. Austenitic, ferritic, martensite, and precipitation-hardenable stainless steels are included in the discussion. 200 references

  6. Hydrogen fuel cells in chemical industry: The assemini project

    Energy Technology Data Exchange (ETDEWEB)

    Caserza, G.; Bozzoni, T.; Porcino, G.; Pasquinucci, A. [Ansaldo CLC s.r.l., Genova (Italy)] [and others

    1996-12-31

    Chemical and petrochemical industries generate large quantities of hydrogen-rich streams, in the range 50%-100% H{sub 2} concentration by volume, as by-products of electrochemical or dehydrogenation processes, or exhausts/purging in hydrogenation processes. Due to safety aspects, and because of the low density, which makes difficult transportation and storage, such streams often constitute a problem for plant managers. In most cases recycling within the plant processes is not possible, and transportation to other sites, generally by truck after compression in cylinders, is not economical. Many of these streams arc therefore simply co-burned in plant boilers, and in some cases even wasted by venting or flaring. Their value ranges from zero (if vented), to the value of the fuel used in the boiler, where they are co-burned.

  7. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  8. Influence of promoters and oxidants on propane dehydrogenation over chromium-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Shaporeva, N.Yu.; Trushin, D.V.; Gaidai, N.A.; Nekrasov, N.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2010-12-30

    Possibilities for increasing the efficiency of supported on SiO{sub 2} chromium-oxide catalysts in propane oxidative dehydrogenation in CO{sub 2} presence are investigated: the introduction of Li, Na, K, Ca in catalysts and the addition of O{sub 2} in the reaction mixture. It was been found that the positive role of K - the increase of the selectivity to propene and stability of catalysts at long-duration tests - appeared at the relation of Cr:K=20. It was shown that the presence of little amount of O{sub 2} (2%) in the reaction mixtures of propane and carbon dioxide resulted in the increase of propene yield and catalyst stability. (orig.)

  9. Combining CO2 reduction with propane oxidative dehydrogenation over bimetallic catalysts.

    Science.gov (United States)

    Gomez, Elaine; Kattel, Shyam; Yan, Binhang; Yao, Siyu; Liu, Ping; Chen, Jingguang G

    2018-04-11

    The inherent variability and insufficiencies in the co-production of propylene from steam crackers has raised concerns regarding the global propylene production gap and has directed industry to develop more on-purpose propylene technologies. The oxidative dehydrogenation of propane by CO 2 (CO 2 -ODHP) can potentially fill this gap while consuming a greenhouse gas. Non-precious FeNi and precious NiPt catalysts supported on CeO 2 have been identified as promising catalysts for CO 2 -ODHP and dry reforming, respectively, in flow reactor studies conducted at 823 K. In-situ X-ray absorption spectroscopy measurements revealed the oxidation states of metals under reaction conditions and density functional theory calculations were utilized to identify the most favorable reaction pathways over the two types of catalysts.

  10. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2015-03-05

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

  11. Effects of Ti-Based Additives on the Hydrogen Storage Properties of a LiBH4/CaH2 Destabilized System

    Directory of Open Access Journals (Sweden)

    Hongwei Yang

    2010-01-01

    Full Text Available The hydrogen storage properties of a destabilized LiBH4/CaH2 system ball-milled with TiCl3, TiF3, and TiO2 additives have been investigated. It is found that the system with TiCl3 additive has a lower dehydrogenation temperature than the ones with other additives. Further study shows that a higher amount of TiCl3 is more effective in reducing the desorption temperature of the LiBH4/CaH2 system, since it leads to a lower activation energy of dehydrogenation. The activations energies for mixtures containing 4, 10, and 25 mol% of TiCl3 are 141, 126, and 110 kJ/mol, respectively. However, the benefits of higher amounts of TiCl3 are offset by a larger reduction in hydrogen capacity of the mixtures.

  12. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  13. Modeling of ethylbenzene dehydrogenation kinetics process taking into account deactivation of catalyst bed of the reactor

    Directory of Open Access Journals (Sweden)

    V. K. Bityukov

    2017-01-01

    Full Text Available Styrene synthesis process occurring in a two-stage continuous adiabatic reactor is a complex chemical engineering system. It is characterized by indeterminacy, nonstationarity and occurs in permanent uncontrolled disturbances. Therefore, the task of developing the predictive control system of the main product concentration of the dehydrogenation reaction - styrene to maintain this value within a predetermined range throughout the period of operation is important. This solution is impossible without the development of the process model on the basis of the kinetic revised scheme, taking into account the drop of the reactor catalytic bed activity due to coke formation on the surface. The article justifies and proposes: the drop changes dependence of catalyst bed activity as a time of reactor block operation function and improved model of chemical reactions kinetics. The synthesized mathematical model of the process is a system of ordinary differential equations and allows you: to calculate the concentration profiles of reaction mixture components during the passage of the charge through the adiabatic reactor stage, to determine the contact gas composition at the outlet of the reactor stages throughout the cycle of catalytic system, taking into account temperature changes and drop of the catalyst bed activity. The compensation of the decreased catalyst bed activity is carried out by raising the temperature in the reactor block for the duration of the operation. The estimation of the values of chemical reactions rate constants, as well as the calculation and analysis of the main and by-products concentrations of dehydrogenation reactions at the outlet of the reactor plant is curried out. Simulation results show that the change of temperature of the reactor, carried out by the exponential law considering deactivation of the catalyst bed allows the yield in a given range of technological regulations throughout the operation cycle of the reactor block.

  14. A study of the isobutane dehydrogenation in a porous membrane catalytic reactor: design, use and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Casanave, D.

    1996-01-26

    The aim of this study was to set up and model a catalytic fixed-bed membrane reactor for the isobutane dehydrogenation. The catalyst, developed at Catalysis Research Institute (IRC), was a silicalite-supported Pt-based catalyst. Their catalytic performances (activity, selectivity, stability) where found better adapted to the membrane reactor, when compared with commercial Pt or Cr based catalysts. The kinetic study of the reaction has been performed in a differential reactor and led to the determination of a kinetic law, suitable when the catalyst is used near thermodynamic equilibrium. The mass transfer mechanisms were determined in meso-porous and microporous membranes through both permeability and gas mixtures (iC{sub 4}/H{sub 2}/N{sub 2}) separation measurements. For the meso-porous {gamma}-alumina, the mass transfer is ensured by a Knudsen diffusion mechanism which can compete with surface diffusion for condensable gas like isobutane. The resulting permselectivity H{sub 2}/iC4 of this membrane is low ({approx} 4). For the microporous zeolite membrane, molecular sieving occurs due to steric hindrance, leading to higher permselectivity {approx}14. Catalyst/membrane associations were compared in terms of isobutane dehydrogenation performances, for both types of membranes (meso-porous and microporous) and for two different reactor configurations (co-current and counter-current sweep gas flow). The best experimental results were obtained with the zeolite membrane, when sweeping the outer compartment in a co-current flow. The equilibrium displacement observed with the {gamma}-alumina membrane was lower and mainly due to a dilution effect of the reaction mixture by the sweep gas. A mathematical model was developed, which correctly describes all the experimental results obtained with the zeolite membrane, when the co-current mode is used. (Abstract Truncated)

  15. Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

    Science.gov (United States)

    2015-01-01

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  16. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    KAUST Repository

    Balasamy, Rabindran J.

    2010-12-20

    A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

  17. Unexpected dehydrogenation behaviors of the 2LiBH4-MgH2 composite confined in a mesoporous carbon scaffold

    CSIR Research Space (South Africa)

    Wang, K

    2014-11-01

    Full Text Available Nanoconfinement has been widely employed as a promising strategy to improve dehydrogenation kinetics, reversibility, and equilibrium pressure of complex metal hydrides. In this paper, we report a careful study of the influence of nanoconfinement...

  18. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters

    Science.gov (United States)

    Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J.; Schweinberger, Florian F.; Heiz, Ueli; Yoon, Bokwon; Landman, Uzi

    2016-01-01

    The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8–15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the hydrogenation occurs for Ptn (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity. PMID:26817713

  19. Hydrogen safety

    International Nuclear Information System (INIS)

    Frazier, W.R.

    1991-01-01

    The NASA experience with hydrogen began in the 1950s when the National Advisory Committee on Aeronautics (NACA) research on rocket fuels was inherited by the newly formed National Aeronautics and Space Administration (NASA). Initial emphasis on the use of hydrogen as a fuel for high-altitude probes, satellites, and aircraft limited the available data on hydrogen hazards to small quantities of hydrogen. NASA began to use hydrogen as the principal liquid propellant for launch vehicles and quickly determined the need for hydrogen safety documentation to support design and operational requirements. The resulting NASA approach to hydrogen safety requires a joint effort by design and safety engineering to address hydrogen hazards and develop procedures for safe operation of equipment and facilities. NASA also determined the need for rigorous training and certification programs for personnel involved with hydrogen use. NASA's current use of hydrogen is mainly for large heavy-lift vehicle propulsion, which necessitates storage of large quantities for fueling space shots and for testing. Future use will involve new applications such as thermal imaging

  20. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    Lipp, Ludwig [FuelCell Energy, Inc., Torrington, CT (United States)

    2016-01-21

    Conventional compressors have not been able to meet DOE targets for hydrogen refueling stations. They suffer from high capital cost, poor reliability and pose a risk of fuel contamination from lubricant oils. This project has significantly advanced the development of solid state hydrogen compressor technology for multiple applications. The project has achieved all of its major objectives. It has demonstrated capability of Electrochemical Hydrogen Compression (EHC) technology to potentially meet the DOE targets for small compressors for refueling sites. It has quantified EHC cell performance and durability, including single stage hydrogen compression from near-atmospheric pressure to 12,800 psi and operation of EHC for more than 22,000 hours. Capital cost of EHC was reduced by 60%, enabling a path to meeting the DOE cost targets for hydrogen compression, storage and delivery ($2.00-2.15/gge by 2020).

  1. Hydrogen production methods

    International Nuclear Information System (INIS)

    Hammerli, M.

    1982-07-01

    Old, present and new proceses for producing hydrogen are assessed critically. The emphasis throughout is placed on those processes which could be commercially viable before the turn of the century for large-scale hydrogen manufacture. Electrolysis of water is the only industrial process not dependent on fossil resources for large-scale hydrogen production and is likely to remain so for the next two or three decades. While many new processes, including those utilizing sunlight directly or indirectly, are presently not considered to be commercially viable for large-scale hydrogen production, research and development effort is needed to enhance our understanding of the nature of these processes. Water vapour electrolysis is compared with thermochemical processes: the former has the potential for displacing all other processes for producing hydrogen and oxygen from water

  2. A first-principles study of the electronic structure and stability of a lithium aluminum hydride for hydrogen storage.

    Science.gov (United States)

    Song, Y; Singh, R; Guo, Z X

    2006-04-06

    LiAlH4 holds great promise for reversible hydrogen storage, where a fundamental understanding of hydrogen interaction with the metal elements is essential to further improve its properties. The present paper reports a first-principles study of its stability and electronic structure, using a full potential linearized augmented plane wave (FLAPW) method within the generalized gradient approximation (GGA) for high accuracy. The theoretically calculated heat of formation agrees well with experiment. The electronic structures show that the H atoms bond nonequivalently with the Al in the [AlH4]- ligand, which leads to complex dehydrogenation characteristics of LiAlH4.

  3. Cooperative catalysis: electron-rich Fe-H complexes and DMAP, a successful "joint venture" for ultrafast hydrogen production.

    Science.gov (United States)

    Rommel, Susanne; Hettmanczyk, Lara; Klein, Johannes E M N; Plietker, Bernd

    2014-08-01

    A series of defined iron-hydrogen complexes was prepared in a straightforward one-pot approach. The structure and electronic properties of such complexes were investigated by means of quantum-chemical analysis. These new complexes were then applied in the dehydrogenative silylation of methanol. The complex (dppp)(CO)(NO)FeH showed a remarkable activity with a TOF of more than 600 000 h(-1) of pure hydrogen gas within seconds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Hydrogen Embrittlement

    Science.gov (United States)

    Woods, Stephen; Lee, Jonathan A.

    2016-01-01

    Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of

  5. Efficient hydrogen storage in up-scale metal hydride tanks as possible metal hydride compression agents equipped with aluminium extended surfaces

    OpenAIRE

    Gkanas, Evangelos I.; Grant, David M.; Khzouz, Martin; Stuart, Alastair D.; Manickam, Kandavel; Walker, Gavin S.

    2016-01-01

    In the current work, a three-dimensional computational study regarding coupled heat and mass transfer during both the hydrogenation and dehydrogenation process in upscale cylindrical metal hydride reactors is presented, analysed and optimized. Three different heat management scenarios were examined at the degree to which they provide improved system performance. The three scenarios were: 1) plain embedded cooling/heating tubes, 2) transverse finned tubes and 3) longitudinal finned tubes. A de...

  6. KINETIC STUDIES OF ISOBUTANE DEHYDROGENATION AND ISOBUTENE HYDROGENATION OVER PT/SN-BASED CATALYSTS. (R825370C056)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  7. Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols.

    Science.gov (United States)

    Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K; Junge, Henrik; Dyson, Paul J; Beller, Matthias; Laurenczy, Gábor

    2018-01-24

    Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO 2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels. However, to bring about a paradigm change in our energy infrastructure, efficient catalytic processes that release the hydrogen from these molecules, as well as catalysts that regenerate these molecules from CO 2 and hydrogen, are required. In this review, we describe the considerable progress that has been made in homogeneous catalysis for these critical reactions, namely, the hydrogenation of CO 2 to formic acid and methanol and the reverse dehydrogenation reactions. The dehydrogenation of higher alcohols available from renewable feedstocks is also described. Key structural features of the catalysts are analyzed, as is the role of additives, which are required in many systems. Particular attention is paid to advances in sustainable catalytic processes, especially to additive-free processes and catalysts based on Earth-abundant metal ions. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field but also offers insights into how superior catalytic systems can be obtained in the future.

  8. Electrical Characterization of Irradiated Semiconducting Amorphous Hydrogenated Boron Carbide

    Science.gov (United States)

    Peterson, George Glenn

    Semiconducting amorphous partially dehydrogenated boron carbide has been explored as a neutron voltaic for operation in radiation harsh environments, such as on deep space satellites/probes. A neutron voltaic device could also be used as a solid state neutron radiation detector to provide immediate alerts for radiation workers/students, as opposed to the passive dosimetry badges utilized today. Understanding how the irradiation environment effects the electrical properties of semiconducting amorphous partially dehydrogenated boron carbide is important to predicting the stability of these devices in operation. p-n heterojunction diodes were formed from the synthesis of semiconducting amorphous partially dehydrogenated boron carbide on silicon substrates through the use of plasma enhanced chemical vapor deposition (PECVD). Many forms of structural and electrical measurements and analysis have been performed on the p-n heterojunction devices as a function of both He+ ion and neutron irradiation including: transmission electron microscopy (TEM), selected area electron diffraction (SAED), current versus voltage I(V), capacitance versus voltage C(V), conductance versus frequency G(f), and charge carrier lifetime (tau). In stark contrast to nearly all other electronic devices, the electrical performance of these p-n heterojunction diodes improved with irradiation. This is most likely the result of bond defect passivation and resolution of degraded icosahedral based carborane structures (icosahedral molecules missing a B, C, or H atom(s)).

  9. Why hydrogen

    International Nuclear Information System (INIS)

    2004-02-01

    The energy consumption increase and the associated environmental risks, led to develop new energy sources. The authors present the potentialities of the hydrogen in this context of energy supply safety. They detail the today market and the perspectives, the energy sources for the hydrogen production (fossils, nuclear and renewable), the hydrogen transport, storage, distribution and conversion, the application domains, the associated risks. (A.L.B.)

  10. Efficient Discovery of Novel Multicomponent Mixtures for Hydrogen Storage: A Combined Computational/Experimental Approach

    Energy Technology Data Exchange (ETDEWEB)

    Wolverton, Christopher [Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering; Ozolins, Vidvuds [Univ. of California, Los Angeles, CA (United States). Dept. of Materials Science and Engineering; Kung, Harold H. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering; Yang, Jun [Ford Scientific Research Lab., Dearborn, MI (United States); Hwang, Sonjong [California Inst. of Technology (CalTech), Pasadena, CA (United States). Dept. of Chemistry and Chemical Engineering; Shore, Sheldon [The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry

    2016-11-28

    The objective of the proposed program is to discover novel mixed hydrides for hydrogen storage, which enable the DOE 2010 system-level goals. Our goal is to find a material that desorbs 8.5 wt.% H2 or more at temperatures below 85°C. The research program will combine first-principles calculations of reaction thermodynamics and kinetics with material and catalyst synthesis, testing, and characterization. We will combine materials from distinct categories (e.g., chemical and complex hydrides) to form novel multicomponent reactions. Systems to be studied include mixtures of complex hydrides and chemical hydrides [e.g. LiNH2+NH3BH3] and nitrogen-hydrogen based borohydrides [e.g. Al(BH4)3(NH3)3]. The 2010 and 2015 FreedomCAR/DOE targets for hydrogen storage systems are very challenging, and cannot be met with existing materials. The vast majority of the work to date has delineated materials into various classes, e.g., complex and metal hydrides, chemical hydrides, and sorbents. However, very recent studies indicate that mixtures of storage materials, particularly mixtures between various classes, hold promise to achieve technological attributes that materials within an individual class cannot reach. Our project involves a systematic, rational approach to designing novel multicomponent mixtures of materials with fast hydrogenation/dehydrogenation kinetics and favorable thermodynamics using a combination of state-of-the-art scientific computing and experimentation. We will use the accurate predictive power of first-principles modeling to understand the thermodynamic and microscopic kinetic processes involved in hydrogen release and uptake and to design new material/catalyst systems with improved properties. Detailed characterization and atomic-scale catalysis experiments will elucidate the effect of dopants and nanoscale catalysts in achieving fast kinetics and reversibility. And

  11. and BN-doped C60 in lowering dehydrogenation of MXH4

    Indian Academy of Sciences (India)

    2017-11-23

    Nov 23, 2017 ... fossil fuel base, towards renewable, sustainable clean source of energy such as hydrogen [1]. Hydrogen has the highest energy density by mass and is therefore a potential future fuel option for on-board usage [2]. Among various scientific and technological challenges, search for hydrogen storage material ...

  12. 2010 Annual Progress Report DOE Hydrogen Program

    Energy Technology Data Exchange (ETDEWEB)

    None, None

    2011-02-01

    This report summarizes the hydrogen and fuel cell R&D activities and accomplishments in FY2009 for the DOE Hydrogen Program, including the Hydrogen, Fuel Cells, and Infrastructure Technologies Program and hydrogen-related work in the Offices of Science; Fossil Energy; and Nuclear Energy, Science, and Technology. It includes reports on all of the research projects funded by the DOE Hydrogen Program between October 2009 and September 2010.

  13. Hydrogen diffusion and effect on degradation in welded microstructures of creep-resistant low-alloyed steels

    Energy Technology Data Exchange (ETDEWEB)

    Rhode, Michael

    2016-04-04

    with the permeation technique at room temperature and at elevated temperature ranges up to 400 C - It was investigated by interpreting the hydrogen effusion behavior with carrier gas hot extraction technique (CGHE). For realistic determination of the hydrogen diffusion coefficients, an improved method was developed encompassing accelerated specimen heating and hydrogen determination via mass spectrometer (MS). Simultaneously, the corresponding temperature dependent trapped and total hydrogen concentrations were determined. The determined experimental results showed increased susceptibility to the hydrogen affected degradation of the HAZ compared to the base material, which is independent of the investigated alloy composition. In particular, the martensitic coarse grain HAZ is the most susceptible microstructure to hydrogen-affected degradation. The results of the tensile tests allowed the definition of consistent microstructure specific failure criteria (envelope curves) versus quantified hydrogen concentrations for the reactor pressure vessel 16MND5 steel (20MnMoNi-5-5) and the creep-resistant T24 steel (7CrMoVTiB10-10). The procedure of quantifying hydrogen concentrations in HAZ microstructures is novel and supports a new method of analysis for hydrogen degradation effects. Further investigations with the T22 steel (10CrMo9-10), as compared to the creep-resistant T24 steel (7CrMoVTiB10-10), confirmed the beneficial effect of Vanadium as an alloying element to improve the resistance to degradation. In general, Mn-Mo-Ni base material grades show a higher resistance compared to Cr-Mo steels that do not include Vanadium alloying. The investigations showed the decreased diffusion coefficient of the HAZ microstructure compared to the base material microstructure. This is caused by the stronger trapping effects that are present which simultaneously increase the hydrogen solubility as well. In general, trapping effects above 100 C are negligible. It is noted that after

  14. Hydrogen diffusion and effect on degradation in welded microstructures of creep-resistant low-alloyed steels

    International Nuclear Information System (INIS)

    Rhode, Michael

    2016-01-01

    the permeation technique at room temperature and at elevated temperature ranges up to 400 C - It was investigated by interpreting the hydrogen effusion behavior with carrier gas hot extraction technique (CGHE). For realistic determination of the hydrogen diffusion coefficients, an improved method was developed encompassing accelerated specimen heating and hydrogen determination via mass spectrometer (MS). Simultaneously, the corresponding temperature dependent trapped and total hydrogen concentrations were determined. The determined experimental results showed increased susceptibility to the hydrogen affected degradation of the HAZ compared to the base material, which is independent of the investigated alloy composition. In particular, the martensitic coarse grain HAZ is the most susceptible microstructure to hydrogen-affected degradation. The results of the tensile tests allowed the definition of consistent microstructure specific failure criteria (envelope curves) versus quantified hydrogen concentrations for the reactor pressure vessel 16MND5 steel (20MnMoNi-5-5) and the creep-resistant T24 steel (7CrMoVTiB10-10). The procedure of quantifying hydrogen concentrations in HAZ microstructures is novel and supports a new method of analysis for hydrogen degradation effects. Further investigations with the T22 steel (10CrMo9-10), as compared to the creep-resistant T24 steel (7CrMoVTiB10-10), confirmed the beneficial effect of Vanadium as an alloying element to improve the resistance to degradation. In general, Mn-Mo-Ni base material grades show a higher resistance compared to Cr-Mo steels that do not include Vanadium alloying. The investigations showed the decreased diffusion coefficient of the HAZ microstructure compared to the base material microstructure. This is caused by the stronger trapping effects that are present which simultaneously increase the hydrogen solubility as well. In general, trapping effects above 100 C are negligible. It is noted that after testing

  15. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

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

  16. Synthetic nanocomposite MgH2/5 wt. % TiMn2powders for solid-hydrogen storage tank integrated with PEM fuel cell.

    Science.gov (United States)

    El-Eskandarany, M Sherif; Shaban, Ehab; Aldakheel, Fahad; Alkandary, Abdullah; Behbehani, Montaha; Al-Saidi, M

    2017-10-16

    Storing hydrogen gas into cylinders under high pressure of 350 bar is not safe and still needs many intensive studies dedic ated for tank's manufacturing. Liquid hydrogen faces also severe practical difficulties due to its very low density, leading to larger fuel tanks three times larger than traditional gasoline tank. Moreover, converting hydrogen gas into liquid phase is not an economic process since it consumes high energy needed to cool down the gas temperature to -252.8 °C. One practical solution is storing hydrogen gas in metal lattice such as Mg powder and its nanocomposites in the form of MgH 2 . There are two major issues should be solved first. One related to MgH 2 in which its inherent poor hydrogenation/dehydrogenation kinetics and high thermal stability must be improved. Secondly, related to providing a safe tank. Here we have succeeded to prepare a new binary system of MgH 2 /5 wt. % TiMn 2 nanocomposite powder that show excellent hydrogenation/dehydrogenation behavior at relatively low temperature (250 °C) with long cycle-life-time (1400 h). Moreover, a simple hydrogen storage tank filled with our synthetic nanocomposite powders was designed and tested in electrical charging a battery of a cell phone device at 180 °C through a commercial fuel cell.

  17. Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols and Hydroxide Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Santilli, Carola; Makarov, Ilya; Fristrup, Peter

    2016-01-01

    Primary alcohols have been reacted with hydroxide and the ruthenium complex [RuCl2(IiPr)(p-cymene)] to afford carboxylic acids and dihydrogen. The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation and extraction. The transformat......Primary alcohols have been reacted with hydroxide and the ruthenium complex [RuCl2(IiPr)(p-cymene)] to afford carboxylic acids and dihydrogen. The dehydrogenative reaction is performed in toluene, which allows for a simple isolation of the products by precipitation and extraction....... The transformation can be applied to a range of benzylic and saturated aliphatic alcohols containing halide and (thio)ether substituents, while olefins and ester groups are not compatible with the reaction conditions. Benzylic alcohols undergo faster conversion than other substrates, and a competing Cannizzaro...

  18. Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones.

    Science.gov (United States)

    Yoshii, Daichi; Jin, Xiongjie; Yatabe, Takafumi; Hasegawa, Jun-Ya; Yamaguchi, Kazuya; Mizuno, Noritaka

    2016-12-06

    In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O 2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.

  19. Iodine-Catalyzed Direct Olefination of 2-Oxindoles and Alkenes via Cross-Dehydrogenative Coupling (CDC) in Air.

    Science.gov (United States)

    Huang, Hong-Yan; Wu, Hong-Ru; Wei, Feng; Wang, Dong; Liu, Li

    2015-08-07

    A direct intermolecular olefination of sp(3) C-H bond between 2-oxindoles and simple alkenes via a Cross-Dehydrogenative Coupling (CDC) strategy has been developed. In the absence of additional base, moderate to excellent yields have been obtained by using a catalytic amount of iodine with atmospheric oxygen as the reoxidant. Based on the observation of a radical capture experiment, the transformation is proposed to proceed via a radical process.

  20. A Novel and Efficient Synthesis of Hexanitrostilbene by N-Hydroxyphthalimide/FeCl2-Catalyzed Aerobic Dehydrogenation of Hexanitrobibenzyl

    Science.gov (United States)

    Lu, Tingting; Yao, Kai; Mao, Yang; Xu, Jian; Wang, Pengcheng; Lu, Ming

    2013-07-01

    A novel and effective catalytic system containing N-hydroxyphthalimide (NHPI) and FeCl2 is described for the preparation of hexanitrostilbene (HNS) by the dehydrogenation of hexanitrobibenzyl (HNBB) under an oxygen atmosphere. The reaction conditions, such as reaction time, and the amount of NHPI were discussed. The efficient and more environmentally friendly method proved to be a better selection when compared to other previous methods, such as Shipp and Kaplan's method [1].

  1. Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

    KAUST Repository

    Tope, Balkrishna B.

    2011-11-01

    Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni2+ in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co3+/Co2+ in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe3+ active sites by forming Fe3+-O-Co 3+/2+(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and π-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe3+ acid sites via π-bonding and the dehydrogenation was initiated by α-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg2+) base couple and the Fe 3+/Fe2+ reduction-oxidation cycle was further assisted by Co3+/Co2+, leading to a good catalytic activity for the dehydrogenation of ethylbenzene. © 2011 Elsevier B.V. All rights reserved.

  2. Sequential decarboxylative azide–alkyne cycloaddition and dehydrogenative coupling reactions: one-pot synthesis of polycyclic fused triazoles

    Directory of Open Access Journals (Sweden)

    Kuppusamy Bharathimohan

    2014-12-01

    Full Text Available Herein, we describe a one-pot protocol for the synthesis of a novel series of polycyclic triazole derivatives. Transition metal-catalyzed decarboxylative CuAAC and dehydrogenative cross coupling reactions are combined in a single flask and achieved good yields of the respective triazoles (up to 97% yield. This methodology is more convenient to produce the complex polycyclic molecules in a simple way.

  3. Effects of Acid Treatment on the Acidic Properties and Catalytic Activity of MCM-41 for the Oxidative Dehydrogenation of Isobutane

    OpenAIRE

    Ehiro, Takuya; Itagaki, Ai; Misu, Hisanobu; Nakagawa, Keizo; Katoh, Masahiro; Katou, Yuuki; Ninomiya, Wataru; Sugiyama, Shigeru

    2016-01-01

    Mesoporous silicas have shown promise as materials for solid catalysts or catalyst supports due to their unique characteristics. Metal-doped mesoporous silicas are known to be catalytically active in the oxidative dehydrogenation (ODH) of isobutane. However, heavy-metal-free mesoporous silicas have not been studied closely for their use as catalysts. In the present study, MCM-41 (#41 Mobil composition of matter) was acid-treated to enhance its catalytic activity, although pure MCM-41 was conf...

  4. Hydrogen Bibliography

    Energy Technology Data Exchange (ETDEWEB)

    1991-12-01

    The Hydrogen Bibliography is a compilation of research reports that are the result of research funded over the last fifteen years. In addition, other documents have been added. All cited reports are contained in the National Renewable Energy Laboratory (NREL) Hydrogen Program Library.

  5. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  6. Hydrogen energy.

    Science.gov (United States)

    Edwards, P P; Kuznetsov, V L; David, W I F

    2007-04-15

    The problem of anthropogenically driven climate change and its inextricable link to our global society's present and future energy needs are arguably the greatest challenge facing our planet. Hydrogen is now widely regarded as one key element of a potential energy solution for the twenty-first century, capable of assisting in issues of environmental emissions, sustainability and energy security. Hydrogen has the potential to provide for energy in transportation, distributed heat and power generation and energy storage systems with little or no impact on the environment, both locally and globally. However, any transition from a carbon-based (fossil fuel) energy system to a hydrogen-based economy involves significant scientific, technological and socio-economic barriers. This brief report aims to outline the basis of the growing worldwide interest in hydrogen energy and examines some of the important issues relating to the future development of hydrogen as an energy vector.

  7. Effects of Al{sub 2}O{sub 3} phase and Cl component on dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jie; Liu, Changcheng; Ma, Aizeng; Rong, Junfeng; Da, Zhijian, E-mail: dazhijianripp@163.com; Zheng, Aiguo; Qin, Ling

    2016-04-15

    Graphical abstract: - Highlights: • Comparative study of Al{sub 2}O{sub 3} phase on dehydrogenation of propane was implemented. • Pore structures and acid properties of Pt-Al{sub 2}O{sub 3} are correlated to the activities. • Pt-θ-Al{sub 2}O{sub 3} with abundant Cl content shows the highest activity and stability. - Abstract: The effects of two Al{sub 2}O{sub 3} phases, γ- and θ-Al{sub 2}O{sub 3}, and Cl component on the performances of Pt-Al{sub 2}O{sub 3} catalysts in the dehydrogenation of propane were investigated in this work. The catalysts were systematically characterized by various techniques, such as scanning transmission electron microscopy (STEM), temperature-programmed desorption with ammonia as probe molecules (NH{sub 3}-TPD) and temperature-programmed oxidation (TPO). The characterizations and catalytic results show that: (i) the pore structures and acid properties of the two Al{sub 2}O{sub 3} phases can change the quantity, location and property of the carbon deposition, (ii) the existence of Cl plays a significant role on the agglomeration of Pt particles and carbon deposition, which further influence the catalytic performances of Pt-Al{sub 2}O{sub 3} catalysts with different support phases for propane dehydrogenation.

  8. NH NMR shifts of new structurally characterized fac-[Re(CO)3(polyamine)]n+ complexes probed via outer-sphere hydrogen-bonding interactions to anions, including the paramagnetic [Re(IV)Br6]2- anion.

    Science.gov (United States)

    Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

    2010-06-21

    fac-[Re(I)(CO)(3)L](n) complexes serve as models for short-lived fac-[(99m)Tc(I)(CO)(3)L](n) imaging tracers (L = tridentate ligands forming two five-membered chelate rings defining the L face). Dangling groups on L, needed to achieve desirable biodistribution, complicate the NMR spectra, which are not readily understood. Using less complicated L, we found that NH groups (exo-NH) projecting toward the L face sometimes showed an upfield shift attributable to steric shielding of the exo-NH group from the solvent by the chelate rings. Our goal is to advance our ability to relate these spectral features to structure and solution properties. To investigate whether exo-NH groups in six-membered rings exhibit the same effect and whether the presence of dangling groups alters the effect, we prepared new fac-[Re(CO)(3)L](n+) complexes that allow direct comparisons of exo-NH shifts for six-membered versus five-membered chelate rings. New complexes were structurally characterized with the following L: dipn [N-3-(aminopropyl)-1,3-propanediamine], N'-Medipn (3,3'-diamino-N-methyldipropylamine), N,N-Me(2)dipn (N,N-dimethyldipropylenetriamine), aepn [N-2-(aminoethyl)-1,3-propanediamine], trpn [tris-(3-aminopropyl)amine], and tren [tris-(2-aminoethyl)amine]. In DMSO-d(6), the upfield exo-NH signals were exhibited by all complexes, indicating that the rings sterically shield the exo-NH groups from bulky solvent molecules. This interpretation was supported by exo-NH signal shift changes caused by added halide and [ReBr(6)](2-) anions, consistent with outer-sphere hydrogen-bond interactions between these anions and the exo-NH groups. For fac-[Re(CO)(3)(dipn)]PF(6) in acetonitrile-d(3), the exo-NH signal shifted further downfield in the series, Cl(-) > Br(-) > I(-), and the plateau in the shift change required a lower concentration for smaller anions. These results are consistent with steric shielding of the exo-NH groups by the chelate rings. Nevertheless, despite its size, the shape

  9. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

  10. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  11. Color Changing Hydrogen Sensors

    Science.gov (United States)

    Roberson, Luke B.; Williams, Martha; Captain, Janine E.; Mohajeri, Nahid; Raissi, Ali

    2015-01-01

    During the Space Shuttle Program, one of the most hazardous operation that occurred was the loading of liquid hydrogen (LH2) during fueling operations of the spacecraft. Due to hydrogen's low explosive limit, any amount leaked could lead to catastrophic event. Hydrogen's chemical properties make it ideal as a rocket fuel; however, the fuel is deemed unsafe for most commercial use because of the inability to easily detect the gas leaking. The increased use of hydrogen over traditional fossil fuels would reduce greenhouse gases and America's dependency on foreign oil. Therefore a technology that would improve safety at NASA and in the commercial sector while creating a new economic sector would have a huge impact to NASA's mission. The Chemochromic Detector for sensing hydrogen gas leakage is a color-changing detector that is useful in any application where it is important to know not only the presence but also the location of the hydrogen gas leak. This technology utilizes a chemochromicpigment and polymer matrix that can be molded or spun into rigid or pliable shapes useable in variable temperature environments including atmospheres of inert gas, hydrogen gas, or mixtures of gases. A change in color of the detector material indicates where gaseous hydrogen leaks are occurring. The irreversible sensor has a dramatic color change from beige to dark grey and remains dark grey after exposure. A reversible pigment changes from white to blue in the presence of hydrogen and reverts back to white in the presence of oxygen. Both versions of the sensor's pigments were comprised of a mixture of a metal oxide substrate and a hydro-chromic compound (i.e., the compound that changed color in the presence of hydrogen) and immediately notified the operator of the presence of low levels of hydrogen. The detector can be used in a variety of formats including paint, tape, caulking, injection molded parts, textiles and fabrics, composites, and films. This technology brings numerous

  12. A green hydrogen economy

    International Nuclear Information System (INIS)

    Clark, Woodrow W.; Rifkin, Jeremy

    2006-01-01

    This paper is the result of over a dozen scholars and practitioners who strongly felt that a hydrogen economy and hence the future is closer than some American politicians and bureaucrats state. Moreover, when seen internationally, there is strong evidence, the most recent and obvious ones are the proliferation of hybrid vehicles, that for any nation-state to be energy independent it must seek a renewable or green hydrogen future in the near term. The State of California has once again taken the lead in this effort for both an energy-independent future and one linked strongly to the hydrogen economy. Then why a hydrogen economy in the first instance? The fact is that hydrogen most likely will not be used for refueling of vehicles in the near term. The number of vehicles to make hydrogen commercially viable will not be in the mass market by almost all estimates until 2010. However, it is less than a decade away. The time frame is NOT 30-40 years as some argue. The hydrogen economy needs trained people, new ventures and public-private partnerships now. The paper points out how the concerns of today, including higher costs and technologies under development, can be turned into opportunities for both the public and private sectors. It was not too long ago that the size of a mobile phone was that of a briefcase, and then almost 10 years ago, the size of a shoe box. Today, they are not only the size of a man's wallet but also often given away free to consumers who subscribe or contract for wireless services. While hydrogen may not follow this technological commercialization exactly, it certainly will be on a parallel path. International events and local or regional security dictate that the time for a hydrogen must be close at hand

  13. Investigations into Chemical Hydrogen Storage and the anti-Markovnikov Hydroamination of Alkenes

    Science.gov (United States)

    St. John, Anthony J.

    The known carbon-boron-nitrogen (CBN) material ethylenediamine bisborane (EDBB) has been prepared and tested as a potential hydrogen storage material. Dehydrogenation of EDBB was achieved using the (t BuPOCOP)Ir(H)2 (t BuPOCOP = 2,6-bis(OPtBu2)C 6H3) catalyst. This reaction results in the release of two equivalents of hydrogen per molecule of EDBB. The product of this reaction is an insoluble, likely oligomeric, species. Heating the reaction mixture does not result in the release of additional equivalents of hydrogen. A new CBN material, 1,2-B,N-cyclohexane, was targeted as a potential hydrogen storage material. The enthalpy of dehydrogenation of 1,2-B,N-cyclohexane to 1,2-dihydro-1,2-azaborine was calculated to be 23.5 kcal/mol at 298 K using the B3LYP basis set. Ultimately, our collaborators at the University of Oregon prepared 1,2-B,N-cyclohexane. This molecule is a stable solid and undergoes thermal dehydrogenation of the B-N bond at 150 °C. The dehydrogenation of a variety of cyclic CBN materials was studied with the ( tBuPOCOP)Ir(H)2 catalyst. A number of cobalt-pincer complexes were tested as ammonia borane (AB) dehydrogenation catalysts. (PhPSiNSiP)CoCl (PhPSiNSiP = (N(SiMe2CH2PPh 2)2) was found to be a very active precatalyst for AB dehydrogenation, releasing 1 equivalent of hydrogen at 2.0 mol % catalyst loading within 5 minutes. The product of this reaction was characterized as cyclopentaborazane. The catalyst lifetime is limited and the identity of the active species remains unknown. A novel [(tBuPOCOP)Co] 2Hg complex was synthesized by reaction of (t BuPOCOP)CoI with Na/Hg. This complex was fully characterized by 1H NMR spectroscopy, elemental analysis, and X-ray crystallography. A new catalytic pathway for the anti-Markovnikov hydroamination of alkenes is proposed. The individual steps of this pathway were studied with the [(MTPA)Rh(propene)][BPh 4] (MTPA = tris((6-methyl-2-pyridyl)methyl)amine) complex. Protonation of this complex with anilinium

  14. Europe - the first hydrogen economy?

    International Nuclear Information System (INIS)

    Hart, D.

    1999-01-01

    An examination of the state of research relating to hydrogen production and utilization indicates that interest in hydrogen from major companies in Europe has increased by several orders of magnitude in recent years. Of the three major areas where a hydrogen economy could be expected to start, namely, Japan, the United States and Europe, the latter may have advantages in diversity of resources, attitudes towards environmental issues and specific fiscal and regulatory structures. Examples of ongoing research and development projects in Europe include Norway's hydrogen combustion turbine to run on hydrogen from decarbonised natural gas, a project in the Netherlands involving mixing hydrogen and methane in the natural gas grid and a variety of projects involving liquid hydrogen refuelling, hydrogen aircraft, hydrogen fuelling stations and fuel cell vehicle development. There are also ongoing projects in carbon sequestration and hydrogen production for power generation and vehicle use. The author's main contention is that the combination of natural surroundings, environmental problems and attitudes, and business and government frameworks strongly suggest that Europe may be the first to have a hydrogen-based economy. 8 refs

  15. Oxidative Dehydrogenation of Methanol on Chromium Oxide/Montmorillonite K10 Catalysts

    International Nuclear Information System (INIS)

    Chattas, M.S.

    2004-01-01

    Methanol conversion was carried out on one of meso porous materials, Chromia I Montmorillonite K10 (MK10) in a pulse micro catalytic system. Methanol was converted to formaldehyde and ethylene by two different mechanisms. Methanol dehydrogenation increases by reaction temperature (300-400 degree C) and as chromia loading decrease. In contradiction, the dehydration of methanol takes place at higher temperature (400-500 degree C) and as chromia loading increase, 3-18% Cr. Redox and exposed non-redox Cr 3+ are responsible for HCHO formation. There is relationship between increasing of C 2 H 4 production and the increase of Cr +6 phase (from TPR and UV-Vis) according to the acidity of chromia catalysts 34 and 76 μL tert-Butylamine /gram catalyst for 3% Cr and 18% Cr, respectively. Formaldehyde formation is diffusional controlled at high temperature (400-500 degree C) and kinetically controlled at lower reaction temperature (300-400 degree C) while methanol dehydration to ethylene is surface reaction controlled at 400-500 degree C

  16. Oxidative dehydrogenation reaction of short alkanes on nanostructured carbon catalysts: a computational account.

    Science.gov (United States)

    Sun, XiaoYing; Han, Peng; Li, Bo; Mao, ShanJun; Liu, TianFu; Ali, Sajjad; Lian, Zan; Su, DangSheng

    2018-01-23

    Recent progress from first principles computational studies is presented for catalytic properties of nanostructured carbon catalysts in the oxidative dehydrogenation (ODH) reaction of short alkanes. Firstly, a brief introduction is given on the development of carbon catalysts in ODH since 1970. Oxygen functional groups have pivotal importance for ODH on nanostructured carbon catalysts. We discuss the oxidation process by HNO 3 on pristine and defective carbon materials. The interactions between the oxygen molecule (oxidant) and the nanostructured carbon catalysts are quantitatively calibrated. Moreover the different nucleophilic abilities of oxygen functional groups are carefully compared and the strongest nucleophilic sites are proposed. The active sites and detailed reaction pathway are revealed from several computational studies. Diketone/quinone groups are generally considered to be the active centers in ODH. A reaction pathway via radical formation is considered as the favorable path. Furthermore, single ketone and carbon sites are verified to be active in ODH from the analysis of aromaticity. Heteroatom doping effects in ODH are examined. Nitrogen doping is found to be very reactive towards oxygen molecule activation. Other dopants such as boron, phosphorous and sulfur also have positive effects on the reactivity of ODH. Extensive calculations suggest that the BEP relation is applicable for the doped nanostructured carbon catalysts. In the end, an outlook for the future direction of the computational study is supplied.

  17. Palladium Nanoparticles Supported on Titanium-Doped Graphitic Carbon Nitride for Formic Acid Dehydrogenation.

    Science.gov (United States)

    Wu, Yongmei; Wen, Meicheng; Navlani-García, Miriam; Kuwahara, Yasutaka; Mori, Kohsuke; Yamashita, Hiromi

    2017-04-18

    Pd nanoparticles (NPs) supported on Ti-doped graphitic carbon nitride (g-C 3 N 4 ) were synthesized by a deposition-precipitation route and a subsequent reduction with NaBH 4 . The features of the NPs were studied by XRD, TEM, FTIR, XPS, EXAFS and N 2 -physisorption measurements. It was found that the NPs had an average size of 2.9 nm and presented a high dispersion on the surface of Ti-doped g-C 3 N 4 . Compared to Pd loaded on pristine g-C 3 N 4 , the Pd NPs supported on Ti-doped g-C 3 N 4 exhibited a high catalytic activity in formic acid dehydrogenation in water at room temperature. The enhanced activity could be attributed to the small Pd NPs size, as well as the strong interaction between Pd NPs and Ti-doped g-C 3 N 4 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Mineral-catalyzed dehydrogenation of C6 cyclic hydrocarbons: results from experimental studies under hydrothermal conditions

    Science.gov (United States)

    Venturi, S.; Tassi, F.; Gould, I.; Shock, E.; Lorance, E. D.; Bockisch, C.; Fecteau, K.

    2015-12-01

    Volatile organic compounds (VOCs) are ubiquitously present in volcanic and hydrothermal gases. Their relative abundances have been demonstrated to be sensitive to physical and chemical parameters, suggesting VOCs as potential tools for evaluating deep reservoir conditions. Nevertheless, reaction pathways for VOC production at hydrothermal conditions are still poorly understood. Reversible catalytic reforming may be responsible for the high abundance of benzene observed in hydrothermal gases relative to saturated hydrocarbons. The dehydrogenation of n-hexane to benzene could proceed with C6 cyclic hydrocarbons as intermediates, as suggested by the relative enrichment in cyclic hydrocarbons observed in gases originating at T production of benzene from cyclic hydrocarbons at 300°C and 85 bar. At these conditions in pure water, negligible benzene is produced from cyclohexane after 10 days. The presence of a mineral phase, especially sphalerite, favored the formation of both benzene and cyclohexene. The efficiency of dehydroaromatization reaction increased at increasing mineral/cyclohexane ratio, pointing to a surface catalyzed reaction. The catalytic action of sphalerite on the C-H bonds was confirmed by the large abundance of deuterated cyclohexane resulted in D2O experiments. The same experiment carried out using cyclohexene in pure water mainly produced methyl-cyclopentenes (via isomerization) and cyclohexanol (via oxygenation). In presence of sphalerite, the production of significant amounts of benzene confirmed the critical role of this mineral for the aromatization of cyclic compounds under hydrothermal conditions. Contrarily, products from cyclohexene solution phase oxidation using Cu(II) mainly consisted of oxygenated VOCs.

  19. Competition between Dehydrogenative Organometallic Bonding and Covalent Coupling of an Unfunctionalized Porphyrin on Cu(111).

    Science.gov (United States)

    Xiang, Feifei; Gemeinhardt, Anja; Schneider, M Alexander

    2018-02-27

    We studied the formation of linked porphyrin oligomers from 5,15-diphenylporphyrin (2H-DPP) by thermal, substrate-assisted organometallic and dehydrogenation coupling on Cu(111) by scanning tunneling microscopy. In the range of 300-620 K, we find three distinct stages, at 300 K, the intact 2H-DPP molecules self-assemble into linear structures held together by van der Waals forces. Increasing the substrate temperature, self-metalation and intramolecular ring-closing reactions result in planar and isolated DPP species on the surface. By C-H cleavage, porphyrin oligomers bonded by organometallic and covalent bonds between the modified DPP are formed. The amount of covalently bonded DPP oligomers increases strongly with annealing time and temperature, and they become the dominant species at 570 K. In contrast, the number of organometallically bonded DPP oligomers increases moderately even up to 620 K, indicating that in this case the organometallic bond is no precursor of the covalent bond.

  20. Questioning hydrogen

    International Nuclear Information System (INIS)

    Hammerschlag, Roel; Mazza, Patrick

    2005-01-01

    As an energy carrier, hydrogen is to be compared to electricity, the only widespread and viable alternative. When hydrogen is used to transmit renewable electricity, only 51% can reach the end user due to losses in electrolysis, hydrogen compression, and the fuel cell. In contrast, conventional electric storage technologies allow between 75% and 85% of the original electricity to be delivered. Even when hydrogen is extracted from gasified coal (with carbon sequestration) or from water cracked in high-temperature nuclear reactors, more of the primary energy reaches the end user if a conventional electric process is used instead. Hydrogen performs no better in mobile applications, where electric vehicles that are far closer to commercialization exceed fuel cell vehicles in efficiency, cost and performance. New, carbon-neutral energy can prevent twice the quantity of GHG's by displacing fossil electricity than it can by powering fuel cell vehicles. The same is true for new, natural gas energy. New energy resources should be used to displace high-GHG electric generation, not to manufacture hydrogen

  1. California Hydrogen Infrastructure Project

    Energy Technology Data Exchange (ETDEWEB)

    Heydorn, Edward C

    2013-03-12

    Air Products and Chemicals, Inc. has completed a comprehensive, multiyear project to demonstrate a hydrogen infrastructure in California. The specific primary objective of the project was to demonstrate a model of a real-world retail hydrogen infrastructure and acquire sufficient data within the project to assess the feasibility of achieving the nation's hydrogen infrastructure goals. The project helped to advance hydrogen station technology, including the vehicle-to-station fueling interface, through consumer experiences and feedback. By encompassing a variety of fuel cell vehicles, customer profiles and fueling experiences, this project was able to obtain a complete portrait of real market needs. The project also opened its stations to other qualified vehicle providers at the appropriate time to promote widespread use and gain even broader public understanding of a hydrogen infrastructure. The project engaged major energy companies to provide a fueling experience similar to traditional gasoline station sites to foster public acceptance of hydrogen. Work over the course of the project was focused in multiple areas. With respect to the equipment needed, technical design specifications (including both safety and operational considerations) were written, reviewed, and finalized. After finalizing individual equipment designs, complete station designs were started including process flow diagrams and systems safety reviews. Material quotes were obtained, and in some cases, depending on the project status and the lead time, equipment was placed on order and fabrication began. Consideration was given for expected vehicle usage and station capacity, standard features needed, and the ability to upgrade the station at a later date. In parallel with work on the equipment, discussions were started with various vehicle manufacturers to identify vehicle demand (short- and long-term needs). Discussions included identifying potential areas most suited for hydrogen fueling

  2. Hydrogen Storage Properties of Lithium Aluminohydride Modified by Dopants and Mechanochemistry

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-01-01

    Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al [1, 2] succeeded in the re-hydrogenation of NaAlH4 below 70 atm. They achieved 4 wt.% H2 reversible capacity by doping NaAlH4 with Ti and/or Fe organo-metalic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr27Ti9Ni38V5Mn16Cr5, LaNi4.85Sn0.15, Al3Ti, and PdCl2 were combined , LaNi4.85Sn0.15, Al3Ti, and PdCl2 were combined with LiAlH4 by ball-milling to study whether or not LiAlH4 is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH4 and Li3AlH6 by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

  3. Hydrogen Storage Properties of Lithium Aluminohydride modified by dopants and mechanochemistry

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-01-01

    Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al [1, 2] succeeded in the re-hydrogenation of NaAlH4 below 70 atm. They achieved 4 wt.% H2 reversible capacity by doping NaAlH4 with Ti and/or Fe organo-metalic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr27Ti9Ni38V5Mn16Cr5, LaNi4.85Sn0.15, Al3Ti, and PdCl2 were combined with LiAlH4 by ball-milling to study whether or not LiAlH4 is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH4 and Li3AlH6 by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

  4. Hydrogen Storage Properties of Lithium Aluminohydride Modified by Dopants and Mechanochemistry

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-01-01

    Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al succeeded in the re-hydrogenation of NaAlH4 below 70 atm. They achieved 4 wt.% H2 reversible capacity by doping NaAlH4 with Ti and/or Fe organo-metallic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr27Ti9Ni38V5Mn16Cr5, LaNi 4.85Sn0.15, Al3Ti, and PdCl2 were combined with LiAlH4 by ball-milling to study whether or not LiAlH4 is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH4 and Li3AlH6 by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

  5. Hydrogen isotope investigation of amphibole and biotite phenocrysts in silicic magmas erupted at Lassen Volcanic Center, California

    Science.gov (United States)

    Underwood, S.J.; Feeley, T.C.; Clynne, M.A.

    2012-01-01

    Hydrogen isotope ratio, water content and Fe3 +/Fe2 + in coexisting amphibole and biotite phenocrysts in volcanic rocks can provide insight into shallow pre- and syn-eruptive magmatic processes such as vesiculation, and lava drainback with mixing into less devolatilized magma that erupts later in a volcanic sequence. We studied four ~ 35 ka and younger eruption sequences (i.e. Kings Creek, Lassen Peak, Chaos Crags, and 1915) at the Lassen Volcanic Center (LVC), California, where intrusion of crystal-rich silicic magma mushes by mafic magmas is inferred from the varying abundances of mafic magmatic inclusions (MMIs) in the silicic volcanic rocks. Types and relative proportions of reacted and unreacted hydrous phenocryst populations are evaluated with accompanying chemical and H isotope changes. Biotite phenocrysts were more susceptible to rehydration in older vesicular glassy volcanic rocks than coexisting amphibole phenocrysts. Biotite and magnesiohornblende phenocrysts toward the core of the Lassen Peak dome are extensively dehydroxylated and reacted from prolonged exposure to high temperature, low pressure, and higher fO2 conditions from post-emplacement cooling. In silicic volcanic rocks not affected by alteration, biotite phenocrysts are often relatively more dehydroxylated than are magnesiohornblende phenocrysts of similar size; this is likely due to the ca 10 times larger overall bulk H diffusion coefficient in biotite. A simplified model of dehydrogenation in hydrous phenocrysts above reaction closure temperature suggests that eruption and quench of magma ascended to the surface in a few hours is too short a time for substantial H loss from amphibole. In contrast, slowly ascended magma can have extremely dehydrogenated and possibly dehydrated biotite, relatively less dehydrogenated magnesiohornblende and reaction rims on both phases. Eruptive products containing the highest proportions of mottled dehydrogenated crystals could indicate that within a few days

  6. 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

  7. 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

  8. Proceedings of a Canadian Hydrogen Association workshop : Building Canadian strength with hydrogen systems

    Energy Technology Data Exchange (ETDEWEB)

    Fairlie, M.; Laflamme, C. [Canadian Hydrogen Association, Ottawa, ON (Canada); Venter, R. [Canadian Hydrogen Association, Ottawa, ON (Canada)]|[Toronto Univ., ON (Canada); McMillan, R. [Natural Resources Canada, Ottawa, ON (Canada)] (comps.)

    2006-07-01

    The Canadian Hydrogen Association (CHA) promotes the development of a hydrogen infrastructure and the commercialization of new, efficient and economic methods that accelerate the adoption of hydrogen technologies that will eventually replace fossil-based energy systems to reduce greenhouse gas emissions. This workshop focused on defining the strategic direction of research and development that will define the future of hydrogen related energy developments across Canada. It provided a forum to strengthen the research, development and innovation linkages among government, industry and academia to build Canadian strength with hydrogen systems. The presentations described new technologies and the companies that are making small scale hydrogen and hydrogen powered vehicles. Other topics of discussion included storage issues, hydrogen safety, competition in the hydrogen market, hydrogen fuel cell opportunities, nuclear-based hydrogen production, and environmental impacts. The conference featured 54 presentations, of which 3 have been catalogued separately for inclusion in this database. refs., tabs., figs.

  9. BIG hydrogen: hydrogen technology in the oil and gas sector

    International Nuclear Information System (INIS)

    2006-01-01

    The BIG Hydrogen workshop was held in Calgary, Alberta, Canada on February 13, 2006. About 60 representatives of industry, academia and government attended this one-day technical meeting on hydrogen production for the oil and gas industry. The following themes were identified from the presentations and discussion: the need to find a BIG hydrogen replacement for Steam Methane Reformer (SMR) because of uncertainty regarding cost and availability of natural gas, although given the maturity of SMR process (reliability, known capital cost) how high will H2 prices have to rise?; need for a national strategy to link the near-term and the longer-term hydrogen production requirements, which can take hydrogen from chemical feedstock to energy carrier; and in the near-term Canada should get involved in demonstrations and build expertise in large hydrogen systems including production and carbon capture and sequestration

  10. 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)

  11. Importance of international standards on hydrogen technologies

    International Nuclear Information System (INIS)

    Bose, T.K.; Gingras, S.

    2001-01-01

    This presentation provided some basic information regarding standards and the International Organization for Standardization (ISO). It also explained the importance of standardization activities, particularly ISO/TC 197 which applies to hydrogen technologies. Standards are established by consensus. They define the minimum requirements that will ensure that products and services are reliable and effective. Standards contribute to the elimination of technical barriers to trade (TBT). The harmonization of standards around the world is desirable in a free trade environment. The influence of the TBT on international standardization was discussed with particular reference to the objectives of ISO/TC 197 hydrogen technologies. One of the priorities for ISO/TC 197 is a hydrogen fuel infrastructure which includes refuelling stations, fuelling connectors, and storage technologies for gaseous and liquid hydrogen. Other priorities include an agreement between the International Electrotechnical Commission (IEC) and the ISO, in particular the IEC/TC 105 and ISO/TC 197 for the development of fuel cell standards. The international standards that have been published thus far include ISO 13984:1999 for liquid hydrogen, land vehicle fuelling system interface, and ISO 14687:1999 for hydrogen fuel product specification. Standards are currently under development for: liquid hydrogen; airport hydrogen fuelling facilities; gaseous hydrogen blends; basic considerations for the safety of hydrogen systems; gaseous hydrogen and hydrogen blends; and gaseous hydrogen for land vehicle filling connectors. It was concluded that the widespread use of hydrogen is dependent on international standardization

  12. Hydrogen program overview

    Energy Technology Data Exchange (ETDEWEB)

    Gronich, S. [Dept. of Energy, Washington, DC (United States). Office of Utility Technologies

    1997-12-31

    This paper consists of viewgraphs which summarize the following: Hydrogen program structure; Goals for hydrogen production research; Goals for hydrogen storage and utilization research; Technology validation; DOE technology validation activities supporting hydrogen pathways; Near-term opportunities for hydrogen; Market for hydrogen; and List of solicitation awards. It is concluded that a full transition toward a hydrogen economy can begin in the next decade.

  13. Hydrogen energy for tomorrow: Advanced hydrogen production technologies

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-08-01

    The future vision for hydrogen is that it will be cost-effectively produced from renewable energy sources and made available for widespread use as an energy carrier and a fuel. Hydrogen can be produced from water and when burned as a fuel, or converted to electricity, joins with oxygen to again form water. It is a clean, sustainable resource with many potential applications, including generating electricity, heating homes and offices, and fueling surface and air transportation. To achieve this vision, researchers must develop advanced technologies to produce hydrogen at costs competitive with fossil fuels, using sustainable sources. Hydrogen is now produced primarily by steam reforming of natural gas. For applications requiring extremely pure hydrogen, production is done by electrolysis. This is a relatively expensive process that uses electric current to dissociate, or split, water into its hydrogen and oxygen components. Technologies with the best potential for producing hydrogen to meet future demand fall into three general process categories: photobiological, photoelectrochemical, and thermochemical. Photobiological and photoelectrochemical processes generally use sunlight to split water into hydrogen and oxygen. Thermochemical processes, including gasification and pyrolysis systems, use heat to produce hydrogen from sources such as biomass and solid waste.

  14. MIS-based sensors with hydrogen selectivity

    Science.gov (United States)

    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.

  15. Safety considerations for compressed hydrogen storage systems

    International Nuclear Information System (INIS)

    Gleason, D.

    2006-01-01

    An overview of the safety considerations for various hydrogen storage options, including stationary, vehicle storage, and mobile refueling technologies. Indications of some of the challenges facing the industry as the demand for hydrogen fuel storage systems increases. (author)

  16. Effects of metastability on hydrogen sorption in fluorine substituted hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Pinatel, E.R.; Corno, M.; Ugliengo, P.; Baricco, M., E-mail: marcello.baricco@unito.it

    2014-12-05

    Highlights: • Fluorine substitution in simple metal hydrides has been modelled. • The stability of the MH{sub (1−x)}F{sub x} solid solutions has been discussed. • Conditions for reversibility of sorption reactions have been suggested. - Abstract: In this work ab initio calculations and Calphad modelling have been coupled to describe the effect of fluorine substitution on the thermodynamics of hydrogenation–dehydrogenation in simple hydrides (NaH, AlH{sub 3} and CaH{sub 2}). These example systems have been used to discuss the conditions required for the formation of a stable hydride–fluoride solid solution necessary to obtain a reversible hydrogenation reaction.

  17. Hydrogen usage

    Energy Technology Data Exchange (ETDEWEB)

    1942-10-22

    This short tabular report listed the number of m/sup 3/ of hydrogen required for a (metric) ton of product for various combinations of raw material and product in a hydrogenation procedure. In producing auto gasoline, bituminous coal required 2800 m/sup 3/, brown coal required 2400 m/sup 3/, high-temperature-carbonization tar required 2100 m/sup 3/, bituminous coal distillation tar required 1300 m/sup 3/, brown-coal low-temperature-carbonization tar required 850 m/sup 3/, petroleum residues required 900 m/sup 3/, and gas oil required 500 m/sup 3/. In producing diesel oil, brown coal required 1900 m/sup 3/, whereas petroleum residues required 500 m/sup 3/. In producing diesel oil, lubricants, and paraffin by the TTH (low-temperature-hydrogenation) process, brown-coal low-temperature-carbonization tar required 550 m/sup 3/. 1 table.

  18. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Directory of Open Access Journals (Sweden)

    Ryo eWatanabe

    2013-10-01

    Full Text Available For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1–xSrxFeyMn1–yO3–d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8, perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst with that of an industrial potassium promoted iron (Fe–K catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d and the Fe–K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3–d was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d perovskite oxide.

  19. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2015-09-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

  20. Calcium-mediated coupling between mitochondrial substrate dehydrogenation and cardiac workload in single guinea-pig ventricular myocytes.

    Science.gov (United States)

    Jo, Hikari; Noma, Akinori; Matsuoka, Satoshi

    2006-03-01

    We measured mitochondrial NADH autofluorescence or Ca(2+) using Rhod-2, simultaneously with cell shortening in isolated guinea-pig ventricular myocytes. When both frequency and amplitude of twitch shortening (work intensity) were increased by raising stimulus frequency in incremental steps from 0.1 to 3.3 Hz, the steady level of NADH signal increased in a frequency-dependent manner. Mitochondrial Ca(2+) also increased with increasing work intensity. Applying Ru360, an inhibitor of mitochondrial Ca(2+) uniporter, largely attenuated the response of both NADH fluorescence and mitochondrial Ca(2+). The increase in mitochondrial Ca(2+) was slow with t(1/2)=~12 s and no obvious cyclic changes were observed in the NADH signal. When a step change from 0.1 to 3.3 Hz stimulation was applied, the NADH signal first decreased to 83% and then increased to 155% of the control level. Upon returning to 0.1 Hz, the NADH signal showed an overshoot before declining to the control level. The biphasic onset time course was well explained by the delayed Ca(2+) activation of the substrate dehydrogenation superimposed on the feedback control of the ATP synthesis, while the offset time course with a delayed deactivation of dehydrogenation. A computer simulation using an oxidative phosphorylation linked to the cardiac excitation contraction model well reconstructed the response of NADH. This model simulation predicts that the activation of substrate dehydrogenation provides ~23% of driving force of the ATP synthesis to meet the increased workload induced by the jump of stimulus from 0.1 to 3.3 Hz, and remaining ~77% is supplied by the feedback control.

  1. C1 CHEMISTRY FOR THE PRODUCTION OF ULTRA-CLEAN LIQUID TRANSPORTATION FUELS AND HYDROGEN

    Energy Technology Data Exchange (ETDEWEB)

    Gerald P. Huffman

    2003-09-30

    hydrogen and carbon nanotubes using binary Fe-based catalysts containing Mo, Ni, or Pd in a single step non-oxidative reaction. (7) Partial dehydrogenation of liquid hydrocarbons (cyclohexane and methyl cyclohexane) has been performed using catalysts consisting of Pt and other metals on stacked-cone carbon nanotubes. (8) An understanding of the catalytic reaction mechanisms of the catalysts developed in the CFFS C1 program is being achieved by structural characterization using multiple techniques, including XAFS and Moessbauer spectroscopy, XRD, TEM, NMR, ESR, and magnetometry.

  2. Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2012-01-01

    A method for the preparation of NiO and Nb-NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb-Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb 2O 6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb-NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3-4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb-NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst. © 2011 Elsevier Inc. All rights reserved.

  3. The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes

    Science.gov (United States)

    Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; Mikulas, Tanya C.; Dixon, David A.

    2015-01-01

    Abstract The coordination chemistry of the 1,2‐BN‐cyclohexanes 2,2‐R2‐1,2‐B,N‐C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid‐state (X‐ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal‐promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino‐borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino‐borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2‐H,Me‐1,2‐B,N‐C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF 4]. Using the initial rate method starting from this dimer, a first‐order relationship to [amine‐borane], but half‐order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating. PMID:26602704

  4. Hydrogen-selective membrane

    Science.gov (United States)

    Collins, J.P.; Way, J.D.

    1997-07-29

    A hydrogen-selective membrane comprises a tubular porous ceramic support having a palladium metal layer deposited on an inside surface of the ceramic support. The thickness of the palladium layer is greater than about 10 {micro}m but typically less than about 20 {micro}m. The hydrogen permeation rate of the membrane is greater than about 1.0 moles/m{sup 2} s at a temperature of greater than about 500 C and a transmembrane pressure difference of about 1,500 kPa. Moreover, the hydrogen-to-nitrogen selectivity is greater than about 600 at a temperature of greater than about 500 C and a transmembrane pressure of about 700 kPa. Hydrogen can be separated from a mixture of gases using the membrane. The method may include the step of heating the mixture of gases to a temperature of greater than about 400 C and less than about 1000 C before the step of flowing the mixture of gases past the membrane. The mixture of gases may include ammonia. The ammonia typically is decomposed to provide nitrogen and hydrogen using a catalyst such as nickel. The catalyst may be placed inside the tubular ceramic support. The mixture of gases may be supplied by an industrial process such as the mixture of exhaust gases from the IGCC process. 9 figs.

  5. Vanadium Oxide Supported on MSU-1 as a Highly Active Catalyst for Dehydrogenation of Isobutane with CO2

    OpenAIRE

    Guosong Sun; Qingze Huang; Shiyong Huang; Qiuping Wang; Huiquan Li; Haitao Liu; Shijie Wan; Xuewang Zhang; Jinshu Wang

    2016-01-01

    Vanadium oxide supported on MSU-1, with VOx loading ranging from 2.5 to 17.5 wt. %, was developed as a highly active catalyst in dehydrogenation of isobutane with CO2. The obtained catalysts of VOx/MSU-1 were characterized by X-ray diffraction (XRD), N2 adsorption-desorption, and H2-temperature programmed reduction (H2-TPR) methods and the results showed that the large surface area of MSU-1 was favorable for the dispersion of VOx species and the optimal loading of VOx was 12.0 wt. %. Meanwhil...

  6. Acidic Properties of Various Silica Catalysts Doped with Chromium for the Oxidative Dehydrogenation of Isobutane to Isobutene

    OpenAIRE

    Sugiyama, Shigeru; Ehiro, Takuya; Nitta, Yoshihisa; Itagaki, Ai; Nakagawa, Keizo; Katoh, Masahiro; Katou, Yuuki; Akihara, Shuji; Yasukawa, Toshiya; Ninomiya, Wataru

    2015-01-01

    Although previous researchers have found that FSM-16 (#16 Folded Sheet Mesoporous material) doped with chromium and related Cr-doped silica catalysts has shown great activity for the oxidative dehydrogenation of isobutane to isobutene, information on the nature of these catalysts is insufficient. For this study, three types of Cr-doped silica catalysts were prepared by applying the template ion exchange method. CrOx/FSM-16 and CrOx/SiO2 were used as references. These catalysts were used for o...

  7. Design and operation of an aluminium alloy tank using doped Na3AlH6 in kg scale for hydrogen storage

    Science.gov (United States)

    Urbanczyk, R.; Peinecke, K.; Meggouh, M.; Minne, P.; Peil, S.; Bathen, D.; Felderhoff, M.

    2016-08-01

    In this publication the authors present an aluminium alloy tank for hydrogen storage using 1921 g of Na3AlH6 doped with 4 mol% of TiCl3 and 8 mol% of activated carbon. The tank and the heat exchangers are manufactured by extrusion moulding of Al-Mg-Si based alloys. EN AW 6082 T6 alloy is used for the tank and a specifically developed alloy with a composition similar to EN AW 6060 T6 is used for the heat exchangers. The three heat exchangers have a corrugated profile to enhance the surface area for heat transfer. The doped complex hydride Na3AlH6 is densified to a powder density of 0.62 g cm-3. The hydrogenation experiments are carried out at 2.5 MPa. During one of the dehydrogenation experiments approximately 38 g of hydrogen is released, accounting for gravimetric hydrogen density of 2.0 mass-%. With this tank 15 hydrogenation and 16 dehydrogenation tests are carried out.

  8. Preparation and catalytic effect of porous Co3O4 on the hydrogen storage properties of a Li-B-N-H system

    Directory of Open Access Journals (Sweden)

    You Li

    2017-02-01

    Full Text Available A porous Co3O4 with a particle size of 1–3 µm was successfully prepared by heating Co-based metal organic frameworks MOF-74(Co up to 500 °C in air atmospheric conditions. The as-prepared porous Co3O4 significantly reduced the dehydrogenation temperatures of the LiBH4-2LiNH2 system and improved the purity of the released hydrogen. The LiBH4-2LiNH2-0.05/3Co3O4 sample started to release hydrogen at 140 °C and released hydrogen levels of approximately 9.7 wt% at 225 °C. The end temperature for hydrogen release was lowered by 125 °C relative to that of the pristine sample. Structural analyses revealed that the as-prepared porous Co3O4 is in-situ reduced to metallic Co, which functions as an active catalyst, reducing the kinetic barriers and lowering the dehydrogenation temperatures of the LiBH4-2LiNH2 system. More importantly, the porous Co3O4-containing sample exhibited partially improved reversibility for hydrogen storage in the LiBH4-2LiNH2 system.

  9. Performance of Existing Hydrogen Stations

    Energy Technology Data Exchange (ETDEWEB)

    Sprik, Samuel [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kurtz, Jennifer M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ainscough, Christopher D [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Saur, Genevieve [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Peters, Michael C [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2017-12-01

    In this presentation, the National Renewable Energy Laboratory presented aggregated analysis results on the performance of existing hydrogen stations, including performance, operation, utilization, maintenance, safety, hydrogen quality, and cost. The U.S. Department of Energy funds technology validation work at NREL through its National Fuel Cell Technology Evaluation Center (NFCTEC).

  10. Redox kinetics of ceria-based mixed oxides in selective hydrogen combustion.

    Science.gov (United States)

    Blank, Jan Hendrik; Beckers, Jurriaan; Collignon, Paul F; Rothenberg, Gadi

    2007-12-03

    Ceria-based mixed oxides, in which about 10 mol % of the cerium is replaced by another metal, catalyze the selective combustion of hydrogen from a mixture of hydrogen, propane, and propene at 550 degrees C. This makes them attractive catalysts for the oxidative dehydrogenation of propane. Hydrogen combustion shifts the equilibrium to the products side, supplies energy for the endothermic dehydrogenation, and simplifies product separation. The type of metal added has an important effect on the catalytic properties. To gain insight into the process, a set consisting of six mixed oxides was synthesized and the catalytic properties and redox behavior were tested. The mixed oxides generally release more oxygen than plain ceria. Mixed oxides containing Bi, Cu, Fe, Pd or Ca release between 1.6 and 2.0 mg of oxygen per 100 mg sample (compared to only 1.2 mg for plain ceria). This result is important for reactions in which the catalyst acts as an oxygen reservoir, such as selective hydrogen combustion. The temperature at which oxygen is released is generally lower for the mixed oxides, and varies from 110 degrees C (for Cu-CeO2) to 550 degrees C (for Ca-CeO2), which enables catalytic applications over a wide temperature range. The reduction rate at 550 degrees C is related to the reduction onset of the catalysts. Those catalysts with a relatively low reduction temperature, such as Cu-, Mn-, Bi-, and Pb-CeO2, show a high reduction rate, whereas those with a high reduction temperature, such as Ca-CeO2, Fe-CeO2, and plain ceria, reduce at a slower rate. The latter catalysts also have a low selectivity towards hydrogen combustion. The influence of the catalyst composition and crystallite size on the activity and selectivity is discussed.

  11. Carbon-supported platinum alloy catalysts for phenol hydrogenation for making industrial chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Srinivas, S.T.; Song, C.

    1999-07-01

    Phenol is available in large quantities in liquids derived from coal and biomass. Phenol hydrogenation is an industrially important reaction to produce cyclohexanone and cyclohexanol. Cyclohexane, cyclohexene and benzene are obtained as minor products in this reaction. Cyclohexanone is an important intermediate in the production of caprolactam for nylon 6 and cyclohexanol for adipic acid production. In USA, cyclohexanol and cyclohexanone are produced by benzene hydrogenation to cyclohexane over nickel or noble metal catalysts, followed by oxidation of cyclohexane to produce a mixture of cyclohexanol and cyclohexanone. Then cyclohexanol is dehydrogenated in the presence of Cu-Zn catalyst to cyclohexanone. Usually phenol hydrogenation is also carried out by using Ni catalyst in liquid phase. However, a direct single-step vapor phase hydrogenation of phenol to give cyclohexanone selectively is more advantageous in terms of energy savings and process economics, since processing is simplified and the endothermic step of cyclohexanol dehydrogenation can be avoided, as demonstrated by Montedipe and Johnson Matthey using promoted Pd/Al{sub 2}O{sub 3} catalyst. While it is not the purpose of this paper to dwell on the relative merits of these routes, it is necessary to mention that while using monometallic catalysts, generally the problem of catalyst deactivation of sintering as well as coking is frequently encountered. Addition and alloying of noble metal (e.g. Pt) with a second metal can result in a catalyst with better selectivity and activity in the reaction which is more resistant to deactivation. This paper presents the results on the single-step vapor phase hydrogenation of phenol over carbon-supported Pt-M (M=Cr, V, Zr) alloy catalysts to yield mainly cyclohexanone or cyclohexanol.

  12. Versatile Hydrogen

    Indian Academy of Sciences (India)

    Hydrogen is probably the most intriguing ele- ment in the periodic table. Although it is only the seventh most abundant element on earth, it is the most abundant element in the uni- verse. It combines with almost all the ele- ments of the periodic table, except for a few transition elements, to form binary compounds of the type E.

  13. Hydrogen storage in a combined M.sub.xAlH.sub.6/M'.sub.y(NH.sub.2).sub.z system and methods of making and using the same

    Science.gov (United States)

    Lu, Jun [Salt Lake City, UT; Fang, Zhigang Zak [Salt Lake City, UT; Sohn, Hong Yong [Salt Lake City, UT

    2012-04-03

    As a promising clean fuel for vehicles, hydrogen can be used for propulsion, either directly or in fuel cells. Hydrogen storage compositions having high storage capacity, good dehydrogenation kinetics, and hydrogen release and uptake reactions which are reversible are disclosed and described. Generally a hydrogen storage composition of a metal aluminum hexahydride and a metal amide can be used. A combined system (Li.sub.3AIH.sub.6/3LiNH.sub.2) with a very high inherent hydrogen capacity (7.3 wt %) can be carried out at moderate temperatures, and with approximately 95% of that inherent hydrogen storage capacity (7.0%) is reversible over repeated cycling of release and uptake.

  14. High stability of palladium/kieselguhr composites during absorption/desorption cycling for hydrogen isotope separation

    Energy Technology Data Exchange (ETDEWEB)

    Lei, Yang, E-mail: lei.y@outlook.com; Liu, Xiaopeng; Li, Shuo; Jiang, Lijun; Zhang, Chao; Li, Shuai; He, Di; Wang, Shumao

    2016-12-15

    Highlights: • Pd/K composites with as high as 57 wt.% of Pd have been successfully prepared. • Palladium particles can be effectively packed into the pores of kieselguhr substrates. • Variation of heat-treatment temperatures hardly affect hydrogen absorption capacity and hydrogen saturation time of the Pd/K. • Anti-pulverization property of Pd/K can be improved by packing palladium into the kieselguhr internal pores and heating at 1300 °C. - Abstract: Palladium/kieselguhr (Pd/K) composites with 57 wt.% of Pd were prepared by an improved dipping and thermal decomposition method and heated at elevated temperature to reduce breakdown during hydrogenation-dehydrogenation cycles. The hydrogen absorption kinetic properties of the samples heated at different temperatures were tested under the condition of 20 °C with 100 kPa hydrogen pressure. The 1300 °C heated Pd/K composites were repeated up to 4010 absorption and desorption cycles at temperature ranges between −40 °C and 200 °C. The results show that the phase structure, hydrogen absorption capacity and hydrogen saturation time of the Pd/K were not affected by the change of heat-treated temperatures. And after heat treatment at 1300 °C, the Pd/K particles were strengthened and fraction of larger than 80 mesh were as high as 93.4%.

  15. Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4Hydrogen Storage Composite.

    Science.gov (United States)

    Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

    2017-09-20

    The lightweight compound material NaNH 2 -NaBH 4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH 2 -NaBH 4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H 2 , NH 3 , B 2 H 6 , and N 2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B 6 H 12 also exists. The TG/DTA analyses show that the composite NaNH 2 -NaBH 4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na 3 (NH 2 ) 2 BH 4 hydride decomposes into Na 3 BN 2 and H 2 (200-350 °C); (2) remaining Na 3 (NH 2 ) 2 BH 4 reacts with NaBH 4 and Na 3 BN 2 , generating Na, BN, NH 3 , N 2 , and H 2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

  16. Industrial implications of hydrogen

    International Nuclear Information System (INIS)

    Pressouyre, G.M.

    1982-01-01

    Two major industrial implications of hydrogen are examined: problems related to the effect of hydrogen on materials properties (hydrogen embrittlement), and problems related to the use and production of hydrogen as a future energy vector [fr

  17. Thin film hydrogen sensor

    Science.gov (United States)

    Cheng, Yang-Tse; Poli, Andrea A.; Meltser, Mark Alexander

    1999-01-01

    A thin film hydrogen sensor, includes: a substantially flat ceramic substrate with first and second planar sides and a first substrate end opposite a second substrate end; a thin film temperature responsive resistor on the first planar side of the substrate proximate to the first substrate end; a thin film hydrogen responsive metal resistor on the first planar side of the substrate proximate to the fist substrate end and proximate to the temperature responsive resistor; and a heater on the second planar side of the substrate proximate to the first end.

  18. Magnetic liquefier for hydrogen

    International Nuclear Information System (INIS)

    1992-01-01

    This document summarizes work done at the Astronautics Technology Center of the Astronautics Corporation of America (ACA) in Phase 1 of a four phase program leading to the development of a magnetic liquefier for hydrogen. The project involves the design, fabrication, installation, and operation of a hydrogen liquefier providing significantly reduced capital and operating costs, compared to present liquefiers. To achieve this goal, magnetic refrigeration, a recently developed, highly efficient refrigeration technology, will be used for the liquefaction process. Phase 1 project tasks included liquefier conceptual design and analysis, preliminary design of promising configurations, design selection, and detailed design of the selected design. Fabrication drawings and vendor specifications for the selected design were completed during detailed design. The design of a subscale, demonstration magnetic hydrogen liquefier represents a significant advance in liquefaction technology. The cost reductions that can be realized in hydrogen liquefaction in both the subscale and, more importantly, in the full-scale device are expected to have considerable impact on the use of liquid hydrogen in transportation, chemical, and electronic industries. The benefits to the nation from this technological advance will continue to have importance well into the 21st century

  19. Magnetic liquefier for hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1992-12-31

    This document summarizes work done at the Astronautics Technology Center of the Astronautics Corporation of America (ACA) in Phase 1 of a four phase program leading to the development of a magnetic liquefier for hydrogen. The project involves the design, fabrication, installation, and operation of a hydrogen liquefier providing significantly reduced capital and operating costs, compared to present liquefiers. To achieve this goal, magnetic refrigeration, a recently developed, highly efficient refrigeration technology, will be used for the liquefaction process. Phase 1 project tasks included liquefier conceptual design and analysis, preliminary design of promising configurations, design selection, and detailed design of the selected design. Fabrication drawings and vendor specifications for the selected design were completed during detailed design. The design of a subscale, demonstration magnetic hydrogen liquefier represents a significant advance in liquefaction technology. The cost reductions that can be realized in hydrogen liquefaction in both the subscale and, more importantly, in the full-scale device are expected to have considerable impact on the use of liquid hydrogen in transportation, chemical, and electronic industries. The benefits to the nation from this technological advance will continue to have importance well into the 21st century.

  20. Hydrogen storage in carbon nanotubes.

    Science.gov (United States)

    Hirscher, M; Becher, M

    2003-01-01

    The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.

  1. Improving the Kinetics and Thermodynamics of Mg(BH4)2 for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Brandon [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Klebanoff, Lennie [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Stavila, Vitalie [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Heo, Tae Wook [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ray, Keith [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lee, Jonathan [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Baker, Alex [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Kang, ShinYoung [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Yu, Hui-Chia [Univ. of Michigan, Ann Arbor, MI (United States); Thornton, Katsuyo [Univ. of Michigan, Ann Arbor, MI (United States)

    2017-10-31

    The objective of this project is to (1) combine theory, synthesis, and characterization across multiple scales to understand the intrinsic kinetic and thermodynamic limitations in MgB2/Mg(BH4)2; (2) construct and apply a flexible, validated, multiscale theoretical framework for modeling (de)hydrogenation kinetics of the Mg-B-H system and related metal hydrides; and (3) devise strategies for improving kinetics and thermodynamics, particularly through nanostructuring and doping. The project has an emphasis on understanding and improving rehydrogenation of MgB2, which has generally been less explored and is key to enabling practical use.

  2. Experimental results of 2-propanol dehydrogenation with a falling-liquid film reactor for solar chemical heat pump; Solar chemical heat pump ni okeru ryuka ekimakushiki 2-propanol bunkai hanno jikken

    Energy Technology Data Exchange (ETDEWEB)

    Doi, T.; Tanaka, T.; Ando, Y.; Takashima, T. [Electrotechnical Laboratory, Tsukuba (Japan); Koike, M.; Kamoshida, J. [Shibaura Institute of Technology, Tokyo (Japan)

    1997-11-25

    A solar chemical heat pump is intended to attempt multi-purposed effective utilization of solar energy by raising low temperature solar heat of about 100 degC to 150 to 200 degC by utilizing chemical reactions. The chemical heat pump under the present study uses a 2-propanol (IPA)/acetone/hydrogen system which can utilize low-temperature solar heat and has large temperature rising degree. It was found from the result of experiments and analyses that IPA dehydrogenation reaction can improve more largely the heat utilization rate in using a falling-liquid film reactor than using a liquid phase suspended system. As an attempt to improve further the heat utilization rate, this paper reports the result of experimental discussions on inclination angles of a reaction vessel and feed liquid flow rate which would affect the fluid condition of the liquid film. As a result of the experiments, the initial deterioration in the catalyst has settled in about 15 hours, and its activity has decreased to about 60% of the initial activity. It was made clear that the influence of the inclination angle of the reaction vessel on the reaction is small. 5 refs., 7 figs.

  3. Thermally Stable and Regenerable Platinum-Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Haifeng; Lin, Sen; Goetze, Joris G.; Pletcher, Paul; Guo, Hua; Kovarik, Libor; Artyushkova, Kateryna; Weckhuysen, Bert M.; Datye, Abhaya K.

    2017-06-28

    CeO2 supports are unique in their ability to trap ionic Pt, providing exceptional stability for isolated single atoms of Pt. Here, we explore the reactivity and stability of single atom Pt species for the industrially important reaction of light alkane dehydrogenation. The single atom Pt/CeO2 catalysts are stable during propane dehydrogenation, but we observe no selectivity towards propene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when Sn is added to ceria, the single atom Pt catalyst undergoes an activation phase where it transforms into Pt-Sn clusters under reaction conditions. Formation of small Pt-Sn clusters allows the catalyst to achieve high selectivity towards propene, due to facile desorption of the product. The CeO2-supported Pt-Sn clusters are very stable, even during extended reaction at 680 °C. By adding water vapor to the feed, coke formation can almost completely be suppressed. Furthermore, the Pt-Sn clusters can be readily transformed back to the atomically dispersed species on ceria via oxidation, making Pt-Sn/CeO2 a fully regenerable catalyst.

  4. Oxidative dehydrogenation of propane on the VO x /CeZrO/Al2O3 supported catalyst

    Science.gov (United States)

    Turakulova, A. O.; Kharlanov, A. N.; Levanov, A. V.; Lunin, V. V.

    2017-05-01

    The oxidative dehydrogenation of propane on a supported vanadium catalyst was studied (the support was a complex oxide system consisting of a ceria-zirconia solid solution deposited on γ-Al2O3 (CeZrO/γ-Al2O3)). A comparative analysis of the properties of the support and the catalyst prepared on its basis was performed. The support and catalyst were characterized by the BET method, scanning electron microscopy, X-ray diffraction analysis, and Raman spectroscopy. The catalytic properties of the catalyst and support were studied in propane oxidation at 450 and 500°C with pulse feeding of the reagent. The effect of propane on the support was found to improve the oxidative properties of the latter. This behavior of the support is related to the preparation procedure, which leads to the formation on its surface of the crystalline phase of the ceria-zirconia solid solution and amorphous ZrO2 and Al2O3 phases and/or their solid solution. Similar processes occur with the catalyst support during the oxidative dehydrogenation, giving rise to additional active centers (CeVO4).

  5. VO x /SiO 2 Catalyst Prepared by Grafting VOCl 3 on Silica for Oxidative Dehydrogenation of Propane

    KAUST Repository

    Zhu, Haibo

    2015-09-07

    The VOx/SiO2 catalysts for oxidative dehydrogenation of propane were synthesized by a simple grafting method. The VOCl3 was first grafted at the surface of SiO2, which was dehydrated at different temperature (from 200 to 1000°C). The formed grafted complexes were then calcined in air, leading to the formation of VOx/SiO2 catalysts. The synthesized catalysts were characterized by nitrogen adsorption, SEM, Raman spectroscopy, temperature-programmed reduction, and extended X-ray absorption fine structure analysis. The SiO2 pretreatment temperature has an evident effect on the loading and dispersion of VOx on SiO2, which finally affects their catalytic performance. High SiO2 treatment temperature is beneficial to dispersing the vanadium oxide species at the SiO2 surface. These materials are efficient catalysts for the catalytic oxidative dehydrogenation of propane to propylene. The best selectivity to propylene is achieved on the VOx/SiO2-(1000) catalyst. The high selectivity and activity are well maintained for three days catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations.

    Science.gov (United States)

    Armentrout, P B; Kuijpers, Stach E J; Lushchikova, Olga V; Hightower, Randy L; Boles, Georgia C; Bakker, Joost M

    2018-04-09

    The present work explores the structures of species formed by dehydrogenation of methane (CH 4 ) and perdeuterated methane (CD 4 ) by the 5d transition metal cation osmium (Os + ). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H] + and [Os,C,2D] + products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M + = Ta + , W + , Ir + , and Pt + ). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300-1800 cm -1 range. Photofragmentation was monitored by the loss of H 2 /D 2 . Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH + ( 2 A') as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH + ( 2 A'). Graphical Abstract ᅟ.

  7. Vanadium Oxide Supported on MSU-1 as a Highly Active Catalyst for Dehydrogenation of Isobutane with CO2

    Directory of Open Access Journals (Sweden)

    Guosong Sun

    2016-03-01

    Full Text Available Vanadium oxide supported on MSU-1, with VOx loading ranging from 2.5 to 17.5 wt. %, was developed as a highly active catalyst in dehydrogenation of isobutane with CO2. The obtained catalysts of VOx/MSU-1 were characterized by X-ray diffraction (XRD, N2 adsorption-desorption, and H2-temperature programmed reduction (H2-TPR methods and the results showed that the large surface area of MSU-1 was favorable for the dispersion of VOx species and the optimal loading of VOx was 12.0 wt. %. Meanwhile, the catalytic activity of VOx/MSU-1 was investigated, and VOx/MSU-1 with 12.0 wt. % VOx content was found to be the best one, with the conversion of isobutane (58.8% and the selectivity of isobutene (78.5% under the optimal reaction conditions. In contrast with the reaction in the absence of CO2, the presence of CO2 in the reaction stream could obviously enhance the isobutane dehydrogenation, which raised the conversion of reaction and the stability of VOx/MSU-1.

  8. Precipitation hardening and hydrogen embrittlement of aluminum ...

    Indian Academy of Sciences (India)

    AA7020 Al–Mg–Zn, a medium strength aluminium alloy, is used in welded structures in military and aerospace applications. As it may be subjected to extremes of environmental exposures, including high pressure liquid hydrogen, it could suffer hydrogen embrittlement. Hydrogen susceptibility of alloy AA7020 was ...

  9. Hydrogen: The Ultimate Fuel and Energy Carrier.

    Science.gov (United States)

    Dinga, Gustav P.

    1988-01-01

    Lists 24 frequently asked questions concerning hydrogen as a fuel with several responses given to each question. Emphasized are hydrogen production, storage, transmission, and application to various energy-consuming sectors. Summarizes current findings and research on hydrogen. An extensive bibliography is included. (ML)

  10. Support of a pathway to a hydrogen future

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, A.R. [Dept. of Energy, Washington, DC (United States). Office of Utility Technologies

    1997-12-31

    This paper consists of viewgraphs which outline the content of the presentation. Subjects addressed include: hydrogen research program vision; electricity industry restructuring -- opportunities and challenges for hydrogen; transportation sector -- opportunities for hydrogen; near-term and mid-term opportunities for hydrogen; and hydrogen production technologies from water. It is concluded that the global climate change challenge is the potential driver for the development of hydrogen systems.

  11. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

  12. Hydrogen Separation Membranes for Vision 21 Fossil Fuel Plants

    Energy Technology Data Exchange (ETDEWEB)

    Roark, Shane E.; Mackay, Richard; Sammells, Anthony F.

    2001-11-06

    Eltron Research and team members CoorsTek, McDermott Technology, Sued Chemie, Argonne National Laboratory, and Oak Ridge National Laboratory are developing an environmentally benign, inexpensive, and efficient method for separating hydrogen from gas mixtures produced during industrial processes, such as coal gasification. This objective is being pursued using dense membranes based in part on Eltron-patented ceramic materials with a demonstrated ability for proton and electron conduction. The technical goals are being addressed by modifying single-phase and composite membrane composition and microstructure to maximize proton and electron conductivity without loss of material stability. Ultimately, these materials must enable hydrogen separation at practical rates under ambient and high-pressure conditions, without deactivation in the presence of feedstream components such as carbon dioxide, water, and sulfur. This project was motivated by the Department of Energy (DOE) National Energy Technology Laboratory (NETL) Vision 21 initiative which seeks to economically eliminate environmental concerns associated with the use of fossil fuels. The proposed technology addresses the DOE Vision 21 initiative in two ways. First, this process offers a relatively inexpensive solution for pure hydrogen separation that can be easily incorporated into Vision 21 fossil fuel plants. Second, this process could reduce the cost of hydrogen, which is a clean burning fuel under increasing demand as supporting technologies are developed for hydrogen utilization and storage. Additional motivation for this project arises from the potential of this technology for other applications. By appropriately changing the catalysts coupled with the membrane, essentially the same system can be used to facilitate alkane dehydrogenation and coupling, aromatics processing, and hydrogen sulfide decomposition.

  13. Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

    2013-11-01

    The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

  14. Hydrogen uptake in vanadium first wall structures

    Energy Technology Data Exchange (ETDEWEB)

    Simonen, E.P.; Jones, R.H. [Pacific Northwest National Laboratory, Richland, WA (United States)

    1996-04-01

    Evaluation of hydrogen sources and transport are needed to assess the mechanical integrity of V structures. Two sources include implantation and transmutation. The proposed coatings for the DEMO and ITER first wall strongly influence retention of hydrogen isotopes. Upper limit calculations of hydrogen inventory were based on recycling to the plasma and an impermeable coolant-side coating. Hydrogen isotope concentrations in V approaching 1,000 appm may be activated.

  15. Hydrogen energy. A bibliography with abstracts

    Science.gov (United States)

    1978-01-01

    Hydrogen Energy is a continuing bibliographic summary with abstracts of research and projections on the subject of hydrogen as a secondary fuel and as an energy carrier. This update to Hydrogen Energy cites additional references identified during the fourth quarter of 1978. It is the fourth in a 1978 quarterly series intended to provide current awareness to those interested in hydrogen energy. A series of cross indexes are included which track directly with those of the cumulative volume.

  16. 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.

  17. Hydrogen isotope effect on storage behavior of U{sub 2}Ti and UZr{sub 2.3}

    Energy Technology Data Exchange (ETDEWEB)

    Jat, Ram Avtar; Sawant, S.G.; Rajan, M.B.; Dhanuskar, J.R. [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Kaity, Santu [Radiometallurgy Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Parida, S.C., E-mail: sureshp@barc.gov.in [Product Development Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

    2013-11-15

    U{sub 2}Ti and UZr{sub 2.3} alloys were prepared by arc melting method, vacuum annealed and characterized by XRD, SEM and EDX methods. Hydrogen isotope effect on the storage behavior of these alloys were studied by measuring the hydrogen/deuterium desorption pressure–composition–temperature (PCT) profiles in the temperature range of 573–678 K using a Sievert’s type volumetric apparatus. It was observed that, in the temperature and pressure range of investigation, all the isotherms show a single desorption plateau. The PCT data reveals that both U{sub 2}Ti and UZr{sub 2.3} alloys had normal isotope effects on hydrogen/deuterium desorption at all experimental temperatures. Thermodynamic parameters for dehydrogenation and dedeuteration reactions of the corresponding hydrides and deuterides of the above alloys were deduced from the PCT data.

  18. Reactions of Ti, Zr, and Hf atoms with hydrogen sulfide: argon matrix infrared spectra and theoretical calculations.

    Science.gov (United States)

    Wang, Qiang; Zhao, Jie; Wang, Xuefeng

    2015-03-19

    Laser-ablated Ti, Zr, and Hf atoms have been codeposited at 4 K with hydrogen sulfide in excess argon. The metal atoms insert into the S-H bond of hydrogen sulfide to form the HMSH, H2MS, and H2M(SH)2 molecules (M = Ti, Zr, Hf), which were identified on the basis of the D2S and H2(34)S isotopic substitutions. The observed vibrational frequencies of these species were reproduced by B3LYP functional calculations. The reaction mechanisms have been proposed on the potential energy surface of the studied system to account for the formation of these molecules. We have made a theoretical prediction about the H2MS complexes dehydrogenation, which can provide a novel proposal for generating hydrogen from H2S.

  19. Dehydrogenation and C-H Bond Insertion of Propene: La(η^2-C_3H_4) and HLa(η^3-C_3H_5)

    Science.gov (United States)

    Kumari, Sudesh; Yang, Dong-Sheng

    2011-06-01

    Dehydrogenation and C-H bond insertion are observed in the reaction of laser-ablated La atoms with propene (C_3H_6) in a pulsed molecular beam source. Several dehydrogenated and inserted products are identified by the time-of-flight mass spectrometry. La(C_3H_4) formed from H_2 elimination and HLa(C_3H_5) formed by C-H bond insertion are characterized by pulsed-field-ionization electron and ion spectroscopy, in combination with density functional theory. Two isomers of La(C_3H_4) are identified from 1,2- and 1,3-dehydrogenation. The adiabatic ionization energies of 1,2- and 1,3-dehydrogenated isomers are measured to be 40506(5) and 40941(5) Cm-1, respectively. For the inserted product HLa(C_3H_5), La atom is bound to the allyl radical in a three-fold binding mode (η^3). It is observed that the ionization energy of the HLa(η^3-C_3H_5) insertion complex (41130(5) Cm-1) is close to that of the 1,3-dehydrogented La(η^2-C_3H_4) species.

  20. Synergistic effect of Ti and F co-doping on dehydrogenation properties of MgH2 from first-principles calculations

    International Nuclear Information System (INIS)

    Zhang, J.; Huang, Y.N.; Mao, C.; Peng, P.

    2012-01-01

    Highlights: ► The co-incorporation of Ti and F into MgH 2 lattice is energetically favorable. ► The incorporated Ti and F in MgH 2 preferably generate TiH 2 and MgF 2 , respectively. ► The synergistic effect of Ti and F is superior to that of pure Ti. ► The weakened interactions of Mg–H explain enhanced dehydrogenation properties. - Abstract: The energetic and electronic properties of MgH 2 co-doped with Ti and F are investigated using first-principles calculations based on density functional theory. The calculation results show that incorporation of Ti combined with F atoms into MgH 2 lattice is energetically favorable relative to single incorporation of Ti atom. After dehydrogenation, the co-doped Ti and F in MgH 2 preferably generate TiH 2 and MgF 2 , respectively. Comparatively, the combined effect of Ti and F in improving the dehydrogenation properties of MgH 2 is superior to that of pure Ti. These results provide a reasonable explanation for experimental observations. Analysis of electronic structures suggests the enhanced dehydrogenation properties of doped MgH 2 can be attributed to the weakened bonding interactions between Mg and H due to foreign species doping.

  1. Real-Time Quantitative Operando Raman Spectroscopy of a CrOx/Al2O3 Propane Dehydrogenation Catalyst in a Pilot-Scale Reactor

    NARCIS (Netherlands)

    Sattler, Jesper J. H. B.|info:eu-repo/dai/nl/328235601; Mens, Ad M.; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2014-01-01

    Combined operando UV/vis-Raman spectroscopy has been used to study the deactivation of CrOx/Al2O3 catalyst extrudates in a pilot scale propane dehydrogenation reactor. For this purpose, UV/vis and Raman optical fiber probes have been designed, constructed and tested. The light absorption measured by

  2. Operando Raman spectroscopy study on the deactivation of Pt/Al2O3 and Pt–Sn/Al2O3 propane dehydrogenation catalysts

    NARCIS (Netherlands)

    Sattler, J.J.H.B.|info:eu-repo/dai/nl/328235601; Beale, A.M.|info:eu-repo/dai/nl/325802068; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2013-01-01

    The deactivation of 0.5 wt% Pt/Al2O3 and 0.5 wt% Pt–1.5 wt% Sn/Al2O3 catalysts has been studied by operando Raman spectroscopy during the dehydrogenation of propane and subsequent regeneration in air for 10 successive dehydrogenation–regeneration cycles. Furthermore, the reaction feed was altered by

  3. Synthesis, characterization and testing of a new V2O5/Al2O3−MgO catalyst for butane dehydrogenation and limonene oxidation

    NARCIS (Netherlands)

    Strassberger, Z.; Ramos-Fernandez, E.V.; Boonstra, A.; Jorna, R.; Tanase, S.; Rothenberg, G.

    2013-01-01

    We report the synthesis and characterization of new V2O5/Al2O3-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an

  4. Synthesis of bis- and tris(indolylmethanes catalyzed by an inorganic nano-sized catalyst followed by dehydrogenation to hyperconjugated products

    Directory of Open Access Journals (Sweden)

    Khorshidi Alireza

    2016-01-01

    Full Text Available A set of bis- and tris(indolylmethanes were prepared and dehydrogenated to their hyperconjugated products in a one-pot fashion. Nano-sized-SO3H functionalized mesoporous KIT-6 coated on magnetite nanoparticles (Fe3O4@SiO2@KIT-6-OSO3H was used as an efficient catalyst in the first step of synthesis, and dehydrogenation was performed by using (NH42S2O8 after removal of the catalyst. The catalyst was fully characterized by Fourier transform infrared spectroscopy (FT-IR, transmission electron microscopy (TEM and X-ray powder diffraction (XRD, as well as nitrogen adsorption-desorption isotherms. The bis- and tris(indolylmethanes were studied by UV-Vis spectroscopy before and after dehydrogenation, and effect of the ambient parameters on their spectra was investigated. It was found that bis- and tris(indolylmethanes have no considerable absorption in the visible range and what makes them colorful is partial dehydrogenation due to exposure to air. Our catalyst as a new combination of known materials, showed superiority in terms of yield, time, and mild reaction conditions in comparison with previous reports.

  5. Lipid-storage myopathy and respiratory insufficiency due to ETFQO mutations in a patient with late-onset multiple acyl-CoA dehydrogenation deficiency

    DEFF Research Database (Denmark)

    Olsen, R K J; Pourfarzam, M; Morris, A A M

    2004-01-01

    We report a patient with lipid-storage myopathy due to multiple acyl-CoA dehydrogenation deficiency (MADD). Molecular genetic analysis showed that she was compound heterozygous for mutations in the gene for electron transfer flavoprotein:ubiquinone oxidoreductase (ETFQO). Despite a good initial r...

  6. Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co3O4) Nanoparticles: The Effect of Particle Size on Activity and Selectivity

    NARCIS (Netherlands)

    Tyo, E.C.; Yin, C.; et al, [No Value; Di Vece, M.|info:eu-repo/dai/nl/248753355; Vajda, S.

    2013-01-01

    The oxidative dehydrogenation of cyclohexane by cobalt oxide nanoparticles was studied via temperature programmed reaction combined with in situ grazing incidence X-ray absorption spectroscopy and grazing incidence smallangle X-ray scattering and theoretical calculations on model Co3O4 substrates.

  7. Hydrogen-mediated Nitrogen Clustering in Dilute III-V Nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Du, M.-H.; Limpijumnong, S.; Zhang, S. B

    2006-01-01

    First-principles calculation reveals multi-N clusters to be the ground states for hydrogenated N in dilute III-V nitrides. While hydrogenation of a single N, forming H*{sub 2}(N), can relax the large strain induced by the size-mismatched N, formation of the clusters will relax the strain even more effectively. This suppresses the formation of H*{sub 2}(N), the existence of which has recently been debated. More importantly, postgrowth dehydrogenation of the N-H clusters provides an explanation to the observed metastable bare N clusters in GaAsN grown by gas-source molecular beam epitaxy or metal-organic chemical vapor deposition.

  8. Efficient and selective hydrogen generation from bioethanol using ruthenium pincer-type complexes.

    Science.gov (United States)

    Sponholz, Peter; Mellmann, Dörthe; Cordes, Christoph; Alsabeh, Pamela G; Li, Bin; Li, Yang; Nielsen, Martin; Junge, Henrik; Dixneuf, Pierre; Beller, Matthias

    2014-09-01

    Catalytic generation of hydrogen from aqueous ethanol solution proceeds in the presence of pincer-type transition metal catalysts. Optimal results are obtained applying a [Ru(H)(Cl)(CO)(iPr2PEtN(H)EtPiPr2)] complex (catalyst TON 80,000) in the presence of water and base. This dehydrogenation reaction provides up to 70% acetic acid in a selective manner. For the first time, it is shown that bioethanol obtained from fermentation processes can be used directly in this protocol without the need for water removal. The produced hydrogen can be directly utilized in proton exchange membrane (PEM) fuel cells, since very low amounts of CO are formed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Dynamics of hydrogen in hydrogenated amorphous silicon

    Indian Academy of Sciences (India)

    weak (strained) Si–Si bond thereby apparently enhancing the hydrogen diffusion and increasing the light-induced dangling bonds. Keywords. Hydrogenated amorphous silicon; metastable electronic states; hydrogen diffusion. PACS Nos 61.43.Dq; 66.30.-h; 71.23.Cq. 1. Introduction. Hydrogen passivation of dangling bonds ...

  10. Water reactive hydrogen fuel cell power system

    Science.gov (United States)

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

    2014-01-21

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  11. 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

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

    Science.gov (United States)

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

    2015-04-24

    Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. The hydrogen; L'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2004-07-01

    The hydrogen as an energy system represents nowadays a main challenge (in a scientific, economical and environmental point of view). The physical and chemical characteristics of hydrogen are at first given. Then, the challenges of an hydrogen economy are explained. The different possibilities of hydrogen production are described as well as the distribution systems and the different possibilities of hydrogen storage. Several fuel cells are at last presented: PEMFC, DMFC and SOFC. (O.M.)

  14. Final Report for the DOE-BES Program Mechanistic Studies of Activated Hydrogen Release from Amine-Boranes

    Energy Technology Data Exchange (ETDEWEB)

    Larry G. Sneddon; R. Thomas Baker

    2013-01-13

    Effective storage of hydrogen presents one of the most significant technical gaps to successful implementation of the hydrogen economy, particularly for transportation applications. Amine boranes, such as ammonia borane H3NBH3 and ammonia triborane H3NB3H7, have been identified as promising, high-capacity chemical hydrogen storage media containing potentially readily released protic (N-H) and hydridic (B-H) hydrogens. At the outset of our studies, dehydrogenation of ammonia borane had been studied primarily in the solid state, but our DOE sponsored work clearly demonstrated that ionic liquids, base-initiators and/or metal-catalysts can each significantly increase both the rate and extent of hydrogen release from amine boranes under moderate conditions. Our studies also showed that depending upon the activation method, hydrogen release from amine boranes can occur by very different mechanistic steps and yield different types of spent-fuel materials. The fundamental understanding that was developed during this grant of the pathways and controlling factors for each of these hydrogen-release mechanisms is now enabling continuing discovery and optimization of new chemical-hydride based hydrogen storage systems.

  15. Influence of thermo hydrogen treatment on microstructure and mechanical properties of Ti-5Al-2.5Sn ELI alloy

    Directory of Open Access Journals (Sweden)

    Ya-fei Ren

    2017-01-01

    Full Text Available Thermo hydrogen treatment (THT of titanium is a process in which hydrogen is used as a temporary alloying element in titanium alloys. It is an attractive approach for controlling the microstructure and thereby improving the final mechanical properties. In the present study, the microstructure of the original (non-hydrogenated sample has only α phase and the grains is coarse with an average size of ~ 650 μm. While the grain size of thermo hydrogen treated Ti-5Al-2.5Sn ELI alloy became finer and the mechanical properties were improved significantly. When the hydrogen content of the hydrogenated Ti-5Al-2.5Sn ELI alloy is 0.321wt.%, β phase and δ titanium hydride appear. Also the average grain size decreases to 450 μm. When the hydrogen content is 0.515wt.%, the grain size decreases to 220 μm. The mechanical properties were tested after dehydrogenation, and the mechanical properties improved significantly compared to the unhydrogenated specimens. The tensile strength of the Ti-5Al-2.5Sn ELI alloy improved by 17.7% when the hydrogen content increased to 0.920wt.%, at the same time the percentage reduction of area (Z increased by 33% and the impact toughness increased by 37%.

  16. Reactivity of a Ruthenium-Carbonyl Complex in the Methanol Dehydrogenation Reaction

    NARCIS (Netherlands)

    Van De Watering, Fenna F.; Lutz, Martin; Dzik, Wojciech I.; De Bruin, Bas; Reek, Joost N. H.

    2016-01-01

    Finding new catalysts for the release of molecular hydrogen from methanol is of high relevance in the context of the devel- opment of sustainable energy carriers. Herein, we report that the ruthenium complex Ru(salbinapht)(CO)(P i-Pr 3 ) {salbinapht = 2-[({2’-[(2-hydroxybenzyl)amino]-[1,1 ’

  17. Copper-based nanocatalysts for 2-butanol dehydrogenation: Screening and optimization of preparation parameters by response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Geravand, Elham; Shariatinia, Geravand; Yaripour, Fereydoon [Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Sahebdelfar, Saeed [National Iranian Petrochemical Company, P. O. Box 1493, Tehran (Iran, Islamic Republic of)

    2015-12-15

    Two types of copper-based dehydrogenation nanocatalysts (Cu/ZnO/Al{sub 2}O{sub 3} and Cu/SiO{sub 2}) were prepared from various precursors by impregnation (IM), sol-gel (SG) and co precipitation (COPRE) methods. The structures of samples were characterized by N{sub 2} adsorption-desorption, XRD, XRF, TPR, N{sub 2}O-Titration, FT-IR, FE-SEM and TEM techniques. The catalytic performance tests in vapor-phase dehydrogenation of 2-butanol to methyl ethyl ketone (MEK) were carried out in a fixed-bed reactor at a temperature of 260 .deg. C under atmospheric pressure and LHSV of 4mL/(h·g cat). The experimental results indicated that (i) the copper oxide over the COPRE nanocatalyst was reduced at a lower temperature (222 .deg. C) in comparison with the CuO reduced on the SG and IM samples (243 and 327 .deg. C, respectively). Also, the percentage of reduction of CuO species on COPRE catalyst was the highest (98.8%) in comparison with the two other samples, (ii) the COPRE nanocatalyst exhibited the highest activity for the dehydrogenation of 2-butanol to MEK, and (iii) co-precipitation method was selected as an optimum method for preparation of nanocatalyst. The central composite experimental design method was applied for investigation of the effects of four critical preparation factors on the MEK selectivity of Cu/ZnO/Al{sub 2}O{sub 3} nanocatalyst. The results showed that Cu/Zn molar ratio and precipitation pH are the most effective factors on the response and the optimum conditions for synthesis of Cu/ZnO/Al{sub 2}O{sub 3} nanocatalyst with maximum selectivity of MEK were T(pre)=67.5 .deg. C, T(aging)=68.8 .deg. C, pH(pre)=7.27 and Cu/Zn molar ratio=1.38. The performance of the prepared nanocatalyst at the optimum conditions was comparable to the commercially available nanocatalyst.

  18. Hydrogen Gas Production from Nuclear Power Plant in Relation to Hydrogen Fuel Cell Technologies Nowadays

    International Nuclear Information System (INIS)

    Yusibani, Elin; Kamil, Insan; Suud, Zaki

    2010-01-01

    Recently, world has been confused by issues of energy resourcing, including fossil fuel use, global warming, and sustainable energy generation. Hydrogen may become the choice for future fuel of combustion engine. Hydrogen is an environmentally clean source of energy to end-users, particularly in transportation applications because without release of pollutants at the point of end use. Hydrogen may be produced from water using the process of electrolysis. One of the GEN-IV reactors nuclear projects (HTGRs, HTR, VHTR) is also can produce hydrogen from the process. In the present study, hydrogen gas production from nuclear power plant is reviewed in relation to commercialization of hydrogen fuel cell technologies nowadays.

  19. Hydrogen fuel - Universal energy

    Science.gov (United States)

    Prince, A. G.; Burg, J. A.

    The technology for the production, storage, transmission, and consumption of hydrogen as a fuel is surveyed, with the physical and chemical properties of hydrogen examined as they affect its use as a fuel. Sources of hydrogen production are described including synthesis from coal or natural gas, biomass conversion, thermochemical decomposition of water, and electrolysis of water, of these only electrolysis is considered economicially and technologically feasible in the near future. Methods of production of the large quantities of electricity required for the electrolysis of sea water are explored: fossil fuels, hydroelectric plants, nuclear fission, solar energy, wind power, geothermal energy, tidal power, wave motion, electrochemical concentration cells, and finally ocean thermal energy conversion (OTEC). The wind power and OTEC are considered in detail as the most feasible approaches. Techniques for transmission (by railcar or pipeline), storage (as liquid in underwater or underground tanks, as granular metal hydride, or as cryogenic liquid), and consumption (in fuel cells in conventional power plants, for home usage, for industrial furnaces, and for cars and aircraft) are analyzed. The safety problems of hydrogen as a universal fuel are discussed, noting that they are no greater than those for conventional fuels.

  20. Economic data on hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    1943-07-22

    General information is recorded about hydrogenation plants and their operation up to July 1943. For 12 German plants, there is a table indicating date of beginning construction, start of operation, and production capacity, including gas. Another chart gives the same data for foreign plants, in the United States, England, Italy, Iran and Holland. Domestic and foreign partners and agreements are also listed, as well as license returns from hydrogenation. Extent of I.G. Farben patent ownership is given in a short list. Development of production costs for liquid products is indicated for the years 1927-1941. Data on test costs are also given. Production figures for hydrogenation are shown, as well as the share of Farben synthetics in total German fuel production. The report gives a breakdown for requirements of raw materials, manpower, capital, and construction steels for production of four million metric tons of fuels from hydrogenation. Finally, the report lists the special areas in which Farben was carrying on work related to synthetic fuels. The data are given mostly in tabular form.

  1. Mechanochemical hydrogenation of coal

    Science.gov (United States)

    Yang, Ralph T.; Smol, Robert; Farber, Gerald; Naphtali, Leonard M.

    1981-01-01

    Hydrogenation of coal is improved through the use of a mechanical force to reduce the size of the particulate coal simultaneously with the introduction of gaseous hydrogen, or other hydrogen donor composition. Such hydrogen in the presence of elemental tin during this one-step size reduction-hydrogenation further improves the yield of the liquid hydrocarbon product.

  2. Hydrogen storage and integrated fuel cell assembly

    Science.gov (United States)

    Gross, Karl J.

    2010-08-24

    Hydrogen is stored in materials that absorb and desorb hydrogen with temperature dependent rates. A housing is provided that allows for the storage of one or more types of hydrogen-storage materials in close thermal proximity to a fuel cell stack. This arrangement, which includes alternating fuel cell stack and hydrogen-storage units, allows for close thermal matching of the hydrogen storage material and the fuel cell stack. Also, the present invention allows for tailoring of the hydrogen delivery by mixing different materials in one unit. Thermal insulation alternatively allows for a highly efficient unit. Individual power modules including one fuel cell stack surrounded by a pair of hydrogen-storage units allows for distribution of power throughout a vehicle or other electric power consuming devices.

  3. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun

    2016-01-22

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  4. Nature of active tin species and promoting effect of nickle in silica supported tin oxide for dehydrogenation of propane

    Science.gov (United States)

    Wang, Haoren; Wang, Hui; Li, Xiuyi; Li, Chunyi

    2017-06-01

    Different with Wang et. al.'s study, we found that polymeric Si-O-Sn2+ rather than Ni-Sn alloy and metallic Sn are active species in silica-supported tin oxide catalysts for dehydrogenation of propane. The results showed that high surface area of mesoporous silica brought about high dispersion of tin oxide species, as a result, catalytic activity and stability were both improved. DRUV-vis, XPS, TPR and XRD studies of fresh and reduced catalysts indicated that the deactivation was related to the reduction of active species rather than the coke formation since active tin species cannot maintain its oxidation state at reaction conditions (high temperature and reducing atmosphere). The formed Ni3Sn2 alloy after reduction just functioned as promoter which accelerated the desorption of H2 and regeneration of active site. A synergy effect between active tin species and Ni3Sn2 alloy were observed.

  5. Preparation and characterization of Ni-Zr-O nanoparticles and its catalytic behavior for ethane oxidative dehydrogenation

    International Nuclear Information System (INIS)

    Wu Ying; Gao Jing; He Yiming; Wu Tinghua

    2012-01-01

    Ni-Zr-O nanoparticles with various Zr contents were prepared by a modified sol-gel method and characterized by X-ray diffraction (XRD), scanning/high-resolution transmission electron microscope (SEM/HRTEM), BET surface area analysis, H 2 temperature-programmed reduction (H 2 -TPR), X-ray photoelectron spectroscopy (XPS) and O 2 temperature-programmed desorption (O 2 -TPD). The oxidative dehydrogenation of ethane (ODHE) to ethylene was applied to evaluate catalytic performance of the samples. The results show that the doping of Zr affected the cell parameter and the chemical environment of the catalysts, indicating the existence of strong interaction between Ni and Zr. The interaction plays an important role in the lessened reducibility and the distribution of adsorbed oxygen species, consequently influence their catalytic performance. The best yield to ethylene was obtained over the 10% Ni-Zr-O catalyst with 60% ethane conversion and 66% ethylene selectivity.

  6. Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

    KAUST Repository

    Gallo, Alessandro

    2013-01-01

    Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for propane dehydrogenation to propene. Detailed CO-adsorption DRIFTS, XANES and EXAFS characterization studies have been performed on these systems in order to compare the structural and electronic evolution of systems in relation to the nature of the Ir-Sn bonds present in the precursor compounds and to propose a structural model of the Ir-Sn species present at the silica surface of the final catalyst. © 2013 The Royal Society of Chemistry.

  7. Ice method for production of hydrogen clathrate hydrates

    Science.gov (United States)

    Lokshin, Konstantin [Santa Fe, NM; Zhao, Yusheng [Los Alamos, NM

    2008-05-13

    The present invention includes a method for hydrogen clathrate hydrate synthesis. First, ice and hydrogen gas are supplied to a containment volume at a first temperature and a first pressure. Next, the containment volume is pressurized with hydrogen gas to a second higher pressure, where hydrogen clathrate hydrates are formed in the process.

  8. Incomplete Combustion of Hydrogen: Trapping a Reaction Intermediate

    Science.gov (United States)

    Mattson, Bruce; Hoette, Trisha

    2007-01-01

    The combustion of hydrogen in air is quite complex with at least 28 mechanistic steps and twelve reaction species. Most of the species involved are radicals (having unpaired electrons) in nature. Among the various species generated, a few are stable, including hydrogen peroxide. In a normal hydrogen flame, the hydrogen peroxide goes on to further…

  9. Application of gas chromatography in hydrogen isotope separation

    International Nuclear Information System (INIS)

    Ye Xiaoqiu; Sang Ge; Peng Lixia; Xue Yan; Cao Wei

    2008-01-01

    The principle of gas chromatographic separation of hydrogen isotopes was briefly introduced. The main technology and their development of separating hydrogen isotopes, including elution chromatography, hydrogen-displacement chromatography, self-displacement chromatography and frontal chromatography were discussed in detail. The prospect of hydrogen isotope separation by gas chromatography was presented. (authors)

  10. Systems and methods for selective hydrogen transport and measurement

    Science.gov (United States)

    Glatzmaier, Gregory C

    2013-10-29

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

  11. Lanthanum-mediated dehydrogenation of 1- and 2-butynes: Spectroscopy and formation of La(C4H4) isomers.

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2017-08-14

    La atom reactions with 1-butyne and 2-butyne are carried out in a laser-vaporization molecular beam source. Both reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butynes. The dehydrogenated species La(C 4 H 4 ) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of La(C 4 H 4 ) produced from the two reactions exhibit two identical transitions, each consisting of a strong origin band and several vibrational intervals. The two transitions are assigned to the ionization of two isomers: La(η 4 -CH 2 CCCH 2 ) (Iso A) and La(η 4 -CH 2 CHCCH) (Iso B). The ground electronic states are 2 A 1 (C 2v ) for Iso A and 2 A (C 1 ) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and results in a 1 A 1 ion of Iso A and a 1 A ion of Iso B. The formation of Iso A from 2-butyne and Iso B from 1-butyne involves the addition of La to the C≡C triple bond, the activation of two C(sp 3 )-H bonds, and concerted elimination of a H 2 molecule. The formation of Iso A from 1-butyne and Iso B from 2-butyne involves the isomerization of the two butynes to 1,2-butadiene in addition to the concerted H 2 elimination.

  12. Characterization of Industrial Pt-Sn/Al2O3 Catalyst and Transient Product Formations during Propane Dehydrogenation

    Directory of Open Access Journals (Sweden)

    Kah Sing Ho

    2013-06-01

    Full Text Available The major problem plaguing propane dehydrogenation process is the coke formation on the Pt-Sn/Al2O3 catalyst which leads to catalyst deactivation. Due to information paucity, the physicochemical characteristics of the commercially obtained regenerated Pt-Sn/Al2O3 catalyst (operated in moving bed reactor and coke formation at different temperatures of reaction were discussed. The physicochemical characterization of regenerated catalyst gave a BET surface area of 104.0 m2/g with graphitic carbon content of 8.0% indicative of incomplete carbon gasification during the industrial propylene production. Effect of temperatures on coke formation was identified by studying the product yield via temperature-programmed reaction carried out at 500oC, 600oC and 700oC. It was found that ethylene was precursor to carbon laydown while propylene tends to crack into methane. Post reaction, the spent catalyst possessed relatively lower surface area and pore radius whilst exhibited higher carbon content (31.80% at 700oC compared to the regenerated catalyst. Significantly, current studies also found that higher reaction temperatures favoured the coke formation. Consequently, the propylene yield has decreased with reaction temperature. © 2013 BCREC UNDIP. All rights reservedReceived: 10th March 2013; Revised: 28th April 2013; Accepted: 6th May 2013[How to Cite: Kah, S.H., Joanna Jo, E.C., Sim, Y.C., Chin, K.C. (2013. Characterization of Industrial Pt-Sn/Al2O3 Catalyst and Transient Product Formations during Propane Dehydrogenation. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 77-82. (doi:10.9767/bcrec.8.1.4569.77-82][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4569.77-82] | View in  |

  13. Sn surface-enriched Pt-Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation

    KAUST Repository

    Zhu, Haibo

    2014-12-01

    A new one pot, surfactant-free, synthetic route based on the surface organometallic chemistry (SOMC) concept has been developed for the synthesis of Sn surface-enriched Pt-Sn nanoparticles. Bu3SnH selectively reacts with [Pt]-H formed in situ at the surface of Pt nanoparticles, Pt NPs, obtained by reduction of K2PtCl4 by LiB(C2H5)3H. Chemical analysis, 1H MAS and 13C CP/MAS solid-state NMR as well as two-dimensional double-quantum (DQ) and triple-quantum (TQ) experiments show that organo-tin moieties Sn(n-C4H9) are chemically linked to the surface of Pt NPs to produce, in fine, after removal of most of the n-butyl fragment, bimetallic Pt-Sn nanoparticles. The Sn(n-CH2CH2CH2CH3) groups remaining at the surface are believed to stabilize the as-synthesized Pt-Sn NPs, enabling the bimetallic NPs to be well dispersed in THF. Additionally, the Pt-Sn nanoparticles can be supported on MgAl2O4 during the synthesis of the nanoparticles. Some of the Pt-Sn/MgAl2O4 catalyst thus prepared exhibits high activity in PROX of CO and an extremely high selectivity and stability in propane dehydrogenation to propylene. The enhanced activity in propane dehydrogenation is associated with the high concentration of inactive Sn at the surface of Pt nanoparticles which ”isolates” the active Pt atoms. This conclusion is confirmed by XRD, NMR, TEM, and XPS analysis.

  14. Lanthanum-mediated dehydrogenation of 1- and 2-butynes: Spectroscopy and formation of La(C4H4) isomers

    Science.gov (United States)

    Cao, Wenjin; Hewage, Dilrukshi; Yang, Dong-Sheng

    2017-08-01

    La atom reactions with 1-butyne and 2-butyne are carried out in a laser-vaporization molecular beam source. Both reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butynes. The dehydrogenated species La(C4H4) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of La(C4H4) produced from the two reactions exhibit two identical transitions, each consisting of a strong origin band and several vibrational intervals. The two transitions are assigned to the ionization of two isomers: La(η4-CH2CCCH2) (Iso A) and La(η4-CH2CHCCH) (Iso B). The ground electronic states are 2A1 (C2v) for Iso A and 2A (C1) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and results in a 1A1 ion of Iso A and a 1A ion of Iso B. The formation of Iso A from 2-butyne and Iso B from 1-butyne involves the addition of La to the C≡C triple bond, the activation of two C(sp3)-H bonds, and concerted elimination of a H2 molecule. The formation of Iso A from 1-butyne and Iso B from 2-butyne involves the isomerization of the two butynes to 1,2-butadiene in addition to the concerted H2 elimination.

  15. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    Science.gov (United States)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  16. Role of Ti doping and Al and B vacancies in the dehydrogenation of ...

    Indian Academy of Sciences (India)

    Å). (b) Electron density around the Al(BH4)3 unit (Isosurface value: 0.039 e.Å. −3. ). (c) Molecular structure of Al(BH4)3 with four pairs (HA, HB, HC and HD) of hydrogen atoms. (d) Total and partial density of states of pure aluminium borohydride. The Fermi level is set to zero and indicated by a black-dashed line.

  17. 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

  18. Destabilization of combined Ca(BH{sub 4}){sub 2} and Mg(AlH{sub 4}){sub 2} for improved hydrogen storage properties

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jingjun; Gao, Mingxia, E-mail: gaomx@zju.edu.cn; Li, Zhenglong; Cheng, Xuanbing; Gu, Jian; Liu, Yongfeng; Pan, Hongge

    2016-06-15

    A reactive hydride system of Ca(BH{sub 4}){sub 2}+Mg(AlH{sub 4}){sub 2} in a molar ratio of 1: 1 with improved dehydrogenation thermodynamics and kinetics compared with either initial constituent is obtained. The system shows a three-step dehydrogenation process, the temperature of which is lower than that of the main dehydrogenation of pure Ca(BH{sub 4}){sub 2}. There is 8.4 wt.% H{sub 2} released when the system is heated to 330 °C, significantly higher than the corresponding value of 2.6 wt.% H{sub 2} for pure Ca(BH{sub 4}){sub 2}. The rate of the main dehydrogenation of the Ca(BH{sub 4}){sub 2}+Mg(AlH{sub 4}){sub 2} system isothermally maintaining at 300 °C is 0.337 wt.% H{sub 2}/min, which is 10 times faster than that of pure Ca(BH{sub 4}){sub 2}. The reversibility of the combined system is also improved compared with either of the starting constituents. A mechanism study reveals that the initially decomposed MgH{sub 2} and Al from Mg(AlH{sub 4}){sub 2} prefer to react with each other, forming a Al(Mg) solid solution, which reacts further with Ca(BH{sub 4}){sub 2}, reducing the reaction enthalpy and activation energy of the system. Thus, the system is destabilized, resulting in improved overall hydrogen storage properties. - Highlights: • A Ca(BH{sub 4}){sub 2}+Mg(AlH{sub 4}){sub 2} system with improved hydrogen storage properties is described. • The decomposed MgH{sub 2} and Al from Mg(AlH{sub 4}){sub 2} destabilizes Ca(BH{sub 4}){sub 2} effectively. • The dehydrogenation pathway of Ca(BH{sub 4}){sub 2} is changed by combining with Mg(AlH{sub 4}){sub 2}. • The Ca(BH{sub 4}){sub 2}+Mg(AlH{sub 4}){sub 2} system shows improved reaction thermodynamics and kinetics.

  19. Hydrogen in metals

    CSIR Research Space (South Africa)

    Carter, TJ

    2001-04-01

    Full Text Available of hydrogen in metals processing and treatment identified, and mechanisms for hydrogen entry into a ferritic surface are discussed. The differences between hydrogen attack of ferritic steels and copper alloys are contrasted, and an unusual case study...

  20. In situ UV–Vis diffuse reflectance spectroscopy — on line activity measurements of supported chromium oxide catalysts: relating isobutane dehydrogenation activity with Cr-speciation via experimental design

    OpenAIRE

    Weckhuysen, B.M.; Verberckmoes, A.A.; Debaere, J.; Ooms, K.; Langhans, I.; Schoonheydt, R.A.

    2000-01-01

    The dehydrogenation of isobutane over supported chromium oxide catalysts was studied by a combination of in situ UV–Vis diffuse reflectance spectroscopy and on line GC analysis. A well-defined set of experiments, based on an experimental design, was carried out to develop mathematical models, which quantitatively relate Cr-speciation and dehydrogenation activity with reaction temperature and time, support composition, gas composition and Cr loading. It will be shown that: (1) the dehydrogenat...

  1. Photovoltaic Hydrogen Sensor

    Science.gov (United States)

    Daud, Taher; Janesick, James R.; Lambe, John

    1989-01-01

    Photovoltaic device senses hydrogen developed to test degradation of diodes with platinum flash gates on backs. Sensing element is p/n junction rather than conventional Schottky barrier or metal oxide/silicon field-effect transistor. Hydrogen-indicating electrical signal modulated optically rather than electrically. Layered structure of hydrogen detector and principle of operation resemble silicon solar photovoltaic cell. Hydrogen detector responds to hydrogen in atmosphere within minutes and recovers quickly when hydrogen removed.

  2. Hydrogen-based electrochemical energy storage

    Science.gov (United States)

    Simpson, Lin Jay

    2013-08-06

    An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

  3. [Study on the Emission Spectrum of Hydrogen Production with Microwave Discharge Plasma in Ethanol Solution].

    Science.gov (United States)

    Sun, Bing; Wang, Bo; Zhu, Xiao-mei; Yan, Zhi-yu; Liu, Yong-jun; Liu, Hui

    2016-03-01

    Hydrogen is regarded as a kind of clean energy with high caloricity and non-pollution, which has been studied by many experts and scholars home and abroad. Microwave discharge plasma shows light future in the area of hydrogen production from ethanol solution, providing a new way to produce hydrogen. In order to further improve the technology and analyze the mechanism of hydrogen production with microwave discharge in liquid, emission spectrum of hydrogen production by microwave discharge plasma in ethanol solution was being studied. In this paper, plasma was generated on the top of electrode by 2.45 GHz microwave, and the spectral characteristics of hydrogen production from ethanol by microwave discharge in liquid were being studied using emission spectrometer. The results showed that a large number of H, O, OH, CH, C2 and other active particles could be produced in the process of hydrogen production from ethanol by microwave discharge in liquid. The emission spectrum intensity of OH, H, O radicals generated from ethanol is far more than that generated from pure water. Bond of O-H split by more high-energy particles from water molecule was more difficult than that from ethanol molecule, so in the process of hydrogen production by microwave discharge plasma in ethanol solution; the main source of hydrogen was the dehydrogenation and restructuring of ethanol molecules instead of water decomposition. Under the definite external pressure and temperature, the emission spectrum intensity of OH, H, O radicals increased with the increase of microwave power markedly, but the emission spectrum intensity of CH, C2 active particles had the tendency to decrease with the increase of microwave power. It indicated that the number of high energy electrons and active particles high energy electron energy increased as the increase of microwave power, so more CH, C2 active particles were split more thoroughly.

  4. Technical Analysis of Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Ali T-Raissi

    2005-01-14

    The aim of this work was to assess issues of cost, and performance associated with the production and storage of hydrogen via following three feedstocks: sub-quality natural gas (SQNG), ammonia (NH{sub 3}), and water. Three technology areas were considered: (1) Hydrogen production utilizing SQNG resources, (2) Hydrogen storage in ammonia and amine-borane complexes for fuel cell applications, and (3) Hydrogen from solar thermochemical cycles for splitting water. This report summarizes our findings with the following objectives: Technoeconomic analysis of the feasibility of the technology areas 1-3; Evaluation of the hydrogen production cost by technology areas 1; and Feasibility of ammonia and/or amine-borane complexes (technology areas 2) as a means of hydrogen storage on-board fuel cell powered vehicles. For each technology area, we reviewed the open literature with respect to the following criteria: process efficiency, cost, safety, and ease of implementation and impact of the latest materials innovations, if any. We employed various process analysis platforms including FactSage chemical equilibrium software and Aspen Technologies AspenPlus and HYSYS chemical process simulation programs for determining the performance of the prospective hydrogen production processes.

  5. Hydrogen storage in nanostructured materials

    Energy Technology Data Exchange (ETDEWEB)

    Assfour, Bassem

    2011-02-28

    Hydrogen is an appealing energy carrier for clean energy use. However, storage of hydrogen is still the main bottleneck for the realization of an energy economy based on hydrogen. Many materials with outstanding properties have been synthesized with the aim to store enough amount of hydrogen under ambient conditions. Such efforts need guidance from material science, which includes predictive theoretical tools. Carbon nanotubes were considered as promising candidates for hydrogen storage applications, but later on it was found to be unable to store enough amounts of hydrogen under ambient conditions. New arrangements of carbon nanotubes were constructed and hydrogen sorption properties were investigated using state-of-the-art simulation methods. The simulations indicate outstanding total hydrogen uptake (up to 19.0 wt.% at 77 K and 5.52wt.% at 300 K), which makes these materials excellent candidates for storage applications. This reopens the carbon route to superior materials for a hydrogen-based economy. Zeolite imidazolate frameworks are subclass of MOFs with an exceptional chemical and thermal stability. The hydrogen adsorption in ZIFs was investigated as a function of network geometry and organic linker exchange. Ab initio calculations performed at the MP2 level to obtain correct interaction energies between hydrogen molecules and the ZIF framework. Subsequently, GCMC simulations are carried out to obtain the hydrogen uptake of ZIFs at different thermodynamic conditions. The best of these materials (ZIF-8) is found to be able to store up to 5 wt.% at 77 K and high pressure. We expected possible improvement of hydrogen capacity of ZIFs by substituting the metal atom (Zn{sup 2+}) in the structure by lighter elements such as B or Li. Therefore, we investigated the energy landscape of LiB(IM)4 polymorphs in detail and analyzed their hydrogen storage capacities. The structure with the fau topology was shown to be one of the best materials for hydrogen storage. Its

  6. Effect of cold rolling on the hydrogen absorption and desorption kinetics of Zircaloy-4

    International Nuclear Information System (INIS)

    Dupim, I.S.; Moreira, J.M.L.; Huot, J.; Santos, S.F.

    2015-01-01

    Metal matrix composites have been considered promising candidates as nuclear fuels for pressurized water reactors and also for nuclear waste management. Among others, Zircaloy is considered an excellent alternative for metallic matrix in such composites due to its excellent mechanical properties, high thermal conductivity and high corrosion resistance at operating temperatures. For manufacturing these fuels, a necessary step is the production of Zircaloy powder to be used as raw material. A feasible route to produce powders of refractory metals and alloys like Zircaloy is the hydriding and dehydriding process. For this type of processing route, hydrogen absorption and desorption should be performed at the lowest temperature and pressure possible in order to reduce the processing costs. In this paper, we investigated the hydrogen sorption kinetics of Zircaloy and the effect of cold rolling on the reaction rate. It was found that cold rolling greatly increases the hydrogenation kinetics and drastically reduces the dehydrogenation temperature. - Highlights: • The effects of temperature and pressure on the hydrogen reaction kinetics in Zircaloy-4 are analyzed. • The incubation time during absorption measurements increased for higher H2 pressures. • Changes in hydriding reaction kinetics at 1500 kPa of H 2 and 1.25 wt.% of absorption. • Cold rolling increased the hydrogen absorption kinetics and decreased the hydride decomposition temperature

  7. Hydrogen embrittlement in nickel-hydrogen cells

    Science.gov (United States)

    Gross, Sidney

    1989-01-01

    It was long known that many strong metals can become weakened and brittle as the result of the accumulation of hydrogen within the metal. When the metal is stretched, it does not show normal ductile properties, but fractures prematurely. This problem can occur as the result of a hydrogen evolution reaction such as corrosion or electroplating, or due to hydrogen in the environment at the metal surface. High strength alloys such as steels are especially susceptible to hydrogen embrittlement. Nickel-hydrogen cells commonly use Inconel 718 alloy for the pressure container, and this also is susceptible to hydrogen embrittlement. Metals differ in their susceptibility to embrittlement. Hydrogen embrittlement in nickel-hydrogen cells is analyzed and the reasons why it may or may not occur are discussed. Although Inconel 718 can display hydrogen embrittlement, experience has not identified any problem with nickel-hydrogen cells. No hydrogen embrittlement problem is expected with the 718 alloy pressure container used in nickel-hydrogen cells.

  8. Dynamics of hydrogen in hydrogenated amorphous silicon

    Indian Academy of Sciences (India)

    c0, c being the instantaneous concentration at a local point and c0, the average concentration of hydrogen in the hydrogenated amorphous silicon. If the system is both incompressible and isotropic, the change in Helmholtz free energy due to fluctuations in the local concentration of hydrogen is given as. 122. Pramana – J.

  9. Iron-catalyzed oxidative sp3carbon-hydrogen bond functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones.

    Science.gov (United States)

    Huo, Congde; Dong, Jie; Su, Yingpeng; Tang, Jing; Chen, Fengjuan

    2016-11-08

    A novel and efficient iron-catalyzed sp 3 carbon-hydrogen bond functionalization of benzoxazinone derivatives has been developed. For the first time, benzoxazin-2-ones were used as substrates in an oxidative dehydrogenative coupling reaction. The experiments were performed under mild reaction conditions to construct alkyl-aryl C(sp 3 )-C(sp 2 ) bonds. The application of this method to the gram-scale synthesis of natural product cephalandole A has been accomplished in a 3-step sequence. A plausible one electron oxidation involved mechanism is proposed.

  10. Solar hydrogen for urban trucks

    Energy Technology Data Exchange (ETDEWEB)

    Provenzano, J.: Scott, P.B.; Zweig, R. [Clean Air Now, Northridge, CA (United States)

    1997-12-31

    The Clean Air Now (CAN) Solar Hydrogen Project, located at Xerox Corp., El Segundo, California, includes solar photovoltaic powered hydrogen generation, compression, storage and end use. Three modified Ford Ranger trucks use the hydrogen fuel. The stand-alone electrolyzer and hydrogen dispensing system are solely powered by a photovoltaic array. A variable frequency DC-AC converter steps up the voltage to drive the 15 horsepower compressor motor. On site storage is available for up to 14,000 standard cubic feet (SCF) of solar hydrogen, and up to 80,000 SCF of commercial hydrogen. The project is 3 miles from Los Angeles International airport. The engine conversions are bored to 2.9 liter displacement and are supercharged. Performance is similar to that of the Ranger gasoline powered truck. Fuel is stored in carbon composite tanks (just behind the driver`s cab) at pressures up to 3600 psi. Truck range is 144 miles, given 3600 psi of hydrogen. The engine operates in lean burn mode, with nil CO and HC emissions. NO{sub x} emissions vary with load and rpm in the range from 10 to 100 ppm, yielding total emissions at a small fraction of the ULEV standard. Two trucks have been converted for the Xerox fleet, and one for the City of West Hollywood. A public outreach program, done in conjunction with the local public schools and the Department of Energy, introduces the local public to the advantages of hydrogen fuel technologies. The Clean Air Now program demonstrates that hydrogen powered fleet development is an appropriate, safe, and effective strategy for improvement of urban air quality, energy security and avoidance of global warming impact. Continued technology development and cost reduction promises to make such implementation market competitive.

  11. Hydrogen sorption and permeability of compacted LiBH4 nanoconfined into activated carbon nanofibers impregnated with TiO2

    Science.gov (United States)

    Sitthiwet, Chongsutthamani; Thiangviriya, Sophida; Thaweelap, Natthaporn; Meethom, Sukanya; Kaewsuwan, Dechmongkhon; Chanlek, Narong; Utke, Rapee

    2017-11-01

    Activated carbon nanofibers impregnated with titanium (IV) oxide (TiO2), denoted as ACNF-Ti are prepared by carbonization and activation of electrospun nanofibers of polyacrylonitrile (PAN)-titanium (IV) isopropoxide composite. Pristine LiBH4 and nanoconfined LiBH4 in ACNF-Ti, denoted as LiBH4-ACNF-Ti are compacted under the pressures of 434 and 868 MPa. Dehydrogenation temperature of compacted LiBH4 increases (up to 485 °C) with compaction pressure due to poor hydrogen permeability. In the case of compacted LiBH4-ACNF-Ti, major dehydrogenation temperature at 352-359 °C and hydrogen content liberated (74-76% of theoretical capacity) are obtained despite enhanced compaction pressure. Mechanical stability during cycling of compacted LiBH4-ACNF-Ti is achieved. Although hydrogen permeability of compacted LiBH4-ACNF-Ti improves with enhanced compaction pressure, detrimental kinetics and reversibility are detected. Since the fibrous structure of ACNF-Ti are brittle, the broken and/or shorten fibers are observed after compaction under high pressure. The latter results in not only inferior nanoconfinement of LiBH4 into ACNF-Ti, but also agglomeration of hydride materials upon cycling.

  12. Canadian Hydrogen Association workshop on building Canadian strength with hydrogen systems. Proceedings

    International Nuclear Information System (INIS)

    2006-01-01

    The Canadian Hydrogen Association workshop on 'Building Canadian Strength with Hydrogen Systems' was held in Montreal, Quebec, Canada on October 19-20, 2006. Over 100 delegates attended the workshop and there were over 50 presentations made. The Canadian Hydrogen Association (CHA) promotes the development of a hydrogen infrastructure and the commercialization of new, efficient and economic methods that accelerate the adoption of hydrogen technologies that will eventually replace fossil-based energy systems to reduce greenhouse gas emissions. This workshop focused on defining the strategic direction of research and development that will define the future of hydrogen related energy developments across Canada. It provided a forum to strengthen the research, development and innovation linkages among government, industry and academia to build Canadian strength with hydrogen systems. The presentations described new technologies and the companies that are making small scale hydrogen and hydrogen powered vehicles. Other topics of discussion included storage issues, hydrogen safety, competition in the hydrogen market, hydrogen fuel cell opportunities, nuclear-based hydrogen production, and environmental impacts

  13. Synthesis, characterization and spectroscopic studies of some boron-containing hydrogen storage materials

    Science.gov (United States)

    Jash, Panchatapa

    In this dissertation the synthesis and characterization of boron-related nanostructures and dehydrogenation studies of metal borohydrides using FTIR are reported. Boron-related nanostructures are of interest because of their potential applications in nanoelectronics and in hydrogen storage. A low pressure chemical vapor deposition (LPCVD) apparatus was built in order to grow boron nanostructures. Various techniques, namely, Auger electron spectroscopy (AES), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy were used to characterize the synthesized boron and boride nanostructures, and boron coated carbon nanotubes (CNTs). By the uncatalyzed pyrolysis of diborane, at relatively low temperature, crystalline boron nanoribbons were synthesized. Nickel-catalyzed growth also produced Ca, Sr and Y boride nanowires that were found to be crystalline. Amorphous boron coated CNTs were synthesized by LPCVD. Two growth mechanisms, vapor-liquid-solid (VLS) and vapor-solid (VS) were invoked to explain the observed nanostructures. A high vacuum apparatus for FTIR studies was built. The capabilities of the apparatus were first tested by acquiring low temperature and room temperature spectra of sodium and lithium borohydrides. The metal borohydrides are of high hydrogen content and dehydrogenation studies using FTIR were done. NaBH 4 and the K2B12H12 salt were studied. It was found that above its melting point (673 K), NaBH4 is probably converted to its B12H12-2 salt, which then loses all hydrogen to produce amorphous boron. This conversion of B 12H12-2 to boron clusters was confirmed through dehydrogenation studies of K2B12H12. Both SIMS and AES are surface sensitive techniques to study thin film surfaces and interfaces at nano-dimentions. Thin (9-10 mum) cadmium telluride films have application as the buffer layer on silicon substrates to form high

  14. 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.)

  15. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  16. Clean energy and the hydrogen economy.

    Science.gov (United States)

    Brandon, N P; Kurban, Z

    2017-07-28

    In recent years, new-found interest in the hydrogen economy from both industry and academia has helped to shed light on its potential. Hydrogen can enable an energy revolution by providing much needed flexibility in renewable energy systems. As a clean energy carrier, hydrogen offers a range of benefits for simultaneously decarbonizing the transport, residential, commercial and industrial sectors. Hydrogen is shown here to have synergies with other low-carbon alternatives, and can enable a more cost-effective transition to de-carbonized and cleaner energy systems. This paper presents the opportunities for the use of hydrogen in key sectors of the economy and identifies the benefits and challenges within the hydrogen supply chain for power-to-gas, power-to-power and gas-to-gas supply pathways. While industry players have already started the market introduction of hydrogen fuel cell systems, including fuel cell electric vehicles and micro-combined heat and power devices, the use of hydrogen at grid scale requires the challenges of clean hydrogen production, bulk storage and distribution to be resolved. Ultimately, greater government support, in partnership with industry and academia, is still needed to realize hydrogen's potential across all economic sectors.This article is part of the themed issue 'The challenges of hydrogen and metals'. © 2017 The Author(s).

  17. The hydrogen 700 project - 700 Bar Co

    International Nuclear Information System (INIS)

    Gambone, L.; Webster, C.

    2004-01-01

    'Full text:' Major automotive companies, including DaimlerChrysler, Ford, Hyundai, Nissan, PSA Peugeot-Citroen, and Toyota, are co-operating in the Hydrogen 700 project at Powertech to establish a global basis for high pressure hydrogen fuel systems for vehicles. The fuel systems will store compressed hydrogen on-board at pressures up to 700 bar (10,000psi). It is anticipated that the 700 bar storage pressure will provide hydrogen powered vehicles with a range comparable to the range of petroleum-fueled vehicles. The Hydrogen 700 project has contracted world leaders in high pressure technologies to provide 700 bar fuel system components for evaluation. The data from these tests will be used as the basis for the development of relevant standards and regulations. In a development that complements the Hydrogen 700 project, Powertech Labs has established the world's first 700 bar hydrogen station for fast filling operations. This prototype station will be used to evaluate the performance of the 700 bar vehicle fuel system components. The presentation will provide an overview of the Hydrogen 700 project. Safety issues surrounding the use of compressed hydrogen gas as a vehicle fuel, as well as the use of higher storage pressures, will be reviewed. Test data involving the fire testing of vehicles containing hydrogen fuel systems will be presented. The project is intended to result in the introduction of 700 bar fuel systems in the next generation of hydrogen powered vehicles. (author)

  18. Hydrogen converters

    International Nuclear Information System (INIS)

    Mondino, Angel V.

    2003-01-01

    The National Atomic Energy Commission of Argentina developed a process of 99 Mo production from fission, based on irradiation of uranium aluminide targets with thermal neutrons in the RA-3 reactor of the Ezeiza Atomic Centre. These targets are afterwards dissolved in an alkaline solution, with the consequent liberation of hydrogen as the main gaseous residue. This work deals with the use of a first model of metallic converter and a later prototype of glass converter at laboratory scale, adjusted to the requirements and conditions of the specific redox process. Oxidized copper wires were used, which were reduced to elementary copper at 400 C degrees and then regenerated by oxidation with hot air. Details of the bed structure and the operation conditions are also provided. The equipment required for the assembling in cells is minimal and, taking into account the operation final temperature and the purge with nitrogen, the procedure is totally safe. Finally, the results are extrapolated for the design of a converter to be used in a hot cell. (author)

  19. Transfer Hydrogenation of Alkenes Using Ethanol Catalyzed by a NCP Pincer Iridium Complex: Scope and Mechanism.

    Science.gov (United States)

    Wang, Yulei; Huang, Zhidao; Leng, Xuebing; Zhu, Huping; Liu, Guixia; Huang, Zheng

    2018-03-28

    The first general catalytic approach to effecting transfer hydrogenation (TH) of unactivated alkenes using ethanol as the hydrogen source is described. A new NCP-type pincer iridium complex ( BQ -NC O P)IrHCl containing a rigid benzoquinoline backbone has been developed for efficient, mild TH of unactivated C-C multiple bonds with ethanol, forming ethyl acetate as the sole byproduct. A wide variety of alkenes, including multisubstituted alkyl alkenes, aryl alkenes, and heteroatom-substituted alkenes, as well as O- or N-containing heteroarenes and internal alkynes, are suitable substrates. Importantly, the ( BQ -NC O P)Ir/EtOH system exhibits high chemoselectivity for alkene hydrogenation in the presence of reactive functional groups, such as ketones and carboxylic acids. Furthermore, the reaction with C 2 D 5 OD provides a convenient route to deuterium-labeled compounds. Detailed kinetic and mechanistic studies have revealed that monosubstituted alkenes (e.g., 1-octene, styrene) and multisubstituted alkenes (e.g., cyclooctene (COE)) exhibit fundamental mechanistic difference. The OH group of ethanol displays a normal kinetic isotope effect (KIE) in the reaction of styrene, but a substantial inverse KIE in the case of COE. The catalysis of styrene or 1-octene with relatively strong binding affinity to the Ir(I) center has ( BQ -NC O P)Ir I (alkene) adduct as an off-cycle catalyst resting state, and the rate law shows a positive order in EtOH, inverse first-order in styrene, and first-order in the catalyst. In contrast, the catalysis of COE has an off-cycle catalyst resting state of ( BQ -NC O P)Ir III (H)[O(Et)···HO(Et)···HOEt] that features a six-membered iridacycle consisting of two hydrogen-bonds between one EtO ligand and two EtOH molecules, one of which is coordinated to the Ir(III) center. The rate law shows a negative order in EtOH, zeroth-order in COE, and first-order in the catalyst. The observed inverse KIE corresponds to an inverse equilibrium

  20. Palladium-Catalyzed Selective Mono-/Tetraacetoxylation of o-Carboranes with Acetic Acid via Cross Dehydrogenative Coupling of Cage B-H/O-H Bonds.

    Science.gov (United States)

    Xu, Tao-Tao; Cao, Ke; Wu, Ji; Zhang, Cai-Yan; Yang, Junxiao

    2018-03-05

    A selective mono-/tetraacetoxylation of o-carboranes with acetic acid via cross dehydrogenative coupling of cage B-H/O-H bonds has been developed, and a series of mono- and tetraacetoxylated o-carboranes have been synthesized with moderate to good yields as well as good selectivity. Mechanistic studies indicate that the acetoxyl originates from acetic acid directly, and a nucleophilic addition of Pd IV -oxo species and dehydration process is proposed.

  1. Catalytic dehydrogenative N-((triisopropylsilyl)oxy)carbonyl (Tsoc) protection of amines using iPr3SiH and CO2.

    Science.gov (United States)

    Tanaka, S; Yamamura, T; Nakane, S; Kitamura, M

    2015-08-25

    A versatile method has been found to catalyze the dehydrogenative N-((triisopropylsilyl)oxy)carbonyl (Tsoc) protection of amines using Pd/C, volatile iPr3SiH and CO2 gas without the liberation of any salts. A simple filtration/evaporation process facilitates the easy isolation of the product, thereby enhancing the utility of Tsoc as an amine-protecting group in organic synthesis.

  2. Single-stage oxidative dehydrogenation of n-butaneand isopentane in adiabatic sectional reactors with supply of oxygene and water steam

    International Nuclear Information System (INIS)

    Azizov, A.G; Gadji-Kasumov, V.S

    2000-01-01

    Full text: The advanced technique of single-stage dehydrogenation of n-butane and iso-pentane in adiabatic sectional with separate supply of oxygen on every section is offered. The substance of the novel method consist in water metering for every section. Such technological technique considerably cut the specific energy expenses on high temperature water steam production, increase the yield and selectivity of main products formation at the expense of more complete partial oxidation of the correspondend olefins.

  3. Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds

    Science.gov (United States)

    Li, Zhiping; Bohle, D. Scott; Li, Chao-Jun

    2006-06-01

    Cu-catalyzed cross-dehydrogenative coupling (CDC) methodologies were developed based on the oxidative activation of sp3 C-H bonds adjacent to a nitrogen atom. Various sp, sp2, and sp3 C-H bonds of pronucleophiles were used in the Cu-catalyzed CDC reactions. Based on these results, the mechanisms of the CDC reactions also are discussed. C-H activation | catalysis | Baylis-Hillman reaction | Mannich reaction | Friedel-Crafts reaction

  4. Oxidative dehydrogenation of C{sub 3}-C{sub 4} paraffins in the presence of CO{sub 2} over chromium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Botavina, M.A.; Agafonov, A.A.; Trushin, D.V.; Makashov, A.V.; Nekrasov, N.V.; Gaidai, N.A. [N.D. Zelinsky Inst. of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    2005-07-01

    Supported chromium catalysts show good activity and selectivity in the reaction of propane and isobutane oxidative dehydrogenation in the presence of CO{sub 2}. The most active, selective and stable is the catalyst containing 5% (wt.%) of Cr supported on silica and prepared by impregnation method. It was found that the addition up to 5,0% (vol.) of oxygen results in a significant increase of catalyst activity and stability at little decrease of catalyst selectivity. (orig.)

  5. Iodine-Mediated Intramolecular Dehydrogenative Coupling: Synthesis of N-Alkylindolo[3,2-c]- and -[2,3-c]quinoline Iodides.

    Science.gov (United States)

    Volvoikar, Prajesh S; Tilve, Santosh G

    2016-03-04

    An I2/TBHP-mediated intramolecular dehydrogenative coupling reaction is developed for the synthesis of a library of medicinally important 5,11-dialkylindolo[3,2-c]quinoline salts and 5,7-dimethylindolo[2,3-c]quinoline salts. The annulation reaction is followed by aromatization to yield tetracycles in good yield. This protocol is also demonstrated for the synthesis of the naturally occurring isocryptolepine in salt form.

  6. A hydrogen ice cube

    NARCIS (Netherlands)

    Peters, C.J.; Schoonman, J.; Schrauwers, A.

    2004-01-01

    Hydrogen is considered to be a highly promising energy carrier. Nonetheless, before hydrogen can become the fuel of choice for the future a number of slight problems will have to be overcome. For example, how can hydrogen be safely stored? Motor vehicles running on hydrogen may be clean in concept

  7. Room Temperature Reactivity Of Silicon Nanocrystals With Solvents: The Case Of Ketone And Hydrogen Production From Secondary Alcohols: Catalysis?

    KAUST Repository

    El Demellawi, Jehad K.

    2015-05-29

    Although silicon nanoparticles dispersed in liquids are used in various applications ranging from bio-labeling to hydrogen production, their reactivities with their solvents and their catalytic properties re-main still unexplored. Here, we discovered that, because of their surface structures and mechanical strain, silicon nanoparticles react strongly with their solvents and may act as catalysts for the dehydrogenation, at room temperature, of secondary alcohols (e.g. isopropanol) to ketones and hydrogen. This catalytic reaction was followed by gas chromatography, pH measurements, mass spectroscopy and solidstate NMR. This discovery provides new understanding of the role played by silicon nanoparticles, and nanosilicon in general, in their stability in solvents in general as well as being candidates in catalysis.

  8. Comparative study on hydrogenation of propanal on Ni(111) and Cu(111) from density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    An, Wei, E-mail: weian@sues.edu.cn; Men, Yong; Wang, Jinguo

    2017-02-01

    Highlights: • Hydrogenation of propanal is kinetically much faster on Ni(111) than Cu(111). • Hydroxyl route is prefered over alkoxy route on Ni(111). • Alkoxy route is prefered over hydroxyl route on Cu(111). • Activation barrier for hydrogenation of carbonyl is lowered by H-tunneling effect. • η{sup 2}(C,O)-adsorption mode is beneficial for hydrogenation/dehydrogenation of aldehyde. - Abstract: Using propanal as a probe molecule, we have comparatively investigated hydrogenation of carbonyl (C=O) in short carbon-chain aldehyde on Ni(111) and Cu(111) by means of periodic density functional theory. Our focus is in particular on the differentiation of reaction route in sequential hydrogenation on Ni(111) and Cu(111) following Langmuir–Hinshelwood mechanism. Strong binding with alkoxy intermediates has great impact on altering reaction pathways on the two surfaces, where hydroxyl route via 1-hydroxyl propyl intermediate is dominant on Ni(111), but alkoxy route via propoxyl intermediate is more likely on Cu(111) due to a higher activiation barrier of initial hydrogenation in hydroxyl route. In comparison, hydrogenation of carbonyl on Ni(111) is kinetically much faster than that on Cu(111) as a result of much lower activation barrier in rate-determining step (i.e., 13.2 vs 26.8 kcal/mol) of most favorable reaction pathways. Furthermore, the discrepancy in calculated and experimental barriers can be well explained by using the concept of H-tunneling effect on bond forming with H atoms during sequential hydrogenation. The different features of electronic structure exhibited by the two metal surfaces provide insight into their catalytic behaviors.

  9. Suicide with hydrogen sulfide.

    Science.gov (United States)

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  10. Hydrogen and nuclear energy

    International Nuclear Information System (INIS)

    Duffey, R.B.; Miller, A.I.; Hancox, W.T.; Pendergast, D.R.

    1999-01-01

    The current world-wide emphasis on reducing greenhouse gas (GHG) emissions provides an opportunity to revisit how energy is produced and used, consistent with the need for human and economic growth. Both the scale of the problem and the efforts needed for its resolution are extremely large. We argue that GHG reduction strategies must include a greater penetration of electricity into areas, such as transportation, that have been the almost exclusive domain of fossil fuels. An opportunity for electricity to displace fossil fuel use is through electrolytic production of hydrogen. Nuclear power is the only large-scale commercially proven non-carbon electricity generation source, and it must play a key role. As a non-carbon power source, it can also provide the high-capacity base needed to stabilize electricity grids so that they can accommodate other non-carbon sources, namely low-capacity factor renewables such as wind and solar. Electricity can be used directly to power standalone hydrogen production facilities. In the special case of CANDU reactors, the hydrogen streams can be preprocessed to recover the trace concentrations of deuterium that can be re-oxidized to heavy water. World-wide experience shows that nuclear power can achieve high standards of public safety, environmental protection and commercially competitive economics, and must . be an integral part of future energy systems. (author)

  11. A study on hazard types occurring in hydrogen facilities

    International Nuclear Information System (INIS)

    Cho, Nam Chul; Jae, Moo Sung; Eon, Yang Joon

    2004-01-01

    Hydrogen has ideal characteristics as an energy carrier. Hydrogen can be used as a clean fuel in a variety of energy end-use sectors including the conversion to electricity. After combustion, it produces only water. Therefore, the concept of hydrogen energy system has attracted much interest worldwide. But hydrogen has a defect that the explosion risk is high to an inflammable gas of a colorless, tasteless and odorless. Therefore, to use the hydrogen to the source of energy, hydrogen accident sequences and causes analysis must be needed. For this, hazard types occurring in hydrogen facilities have been considered through the case of domestic and foreign hydrogen accident in this study and hazard types to be considered are ignition, leaks, hydrogen dispersion, fire an explosion, storage vessel failure, vent and exhaust system, purging, condensation of air, hydrogen embrittlement, physiological hazard, and collisions during transportation

  12. Electric arc hydrogen heaters

    International Nuclear Information System (INIS)

    Zasypin, I.M.

    2000-01-01

    The experimental data on the electric arc burning in hydrogen are presented. Empirical and semiempirical dependences for calculating the arc characteristics are derived. An engineering method of calculating plasma torches for hydrogen heating is proposed. A model of interaction of a hydrogen arc with a gas flow is outlined. The characteristics of plasma torches for heating hydrogen and hydrogen-bearing gases are described. (author)

  13. The deployment of projects of hydrogen-related innovative technologies in Japan and some topics in the project

    International Nuclear Information System (INIS)

    Sakata, K.; Mizutani, E.; Fukuda, K.

    2004-01-01

    The deployment of innovative technologies, which have the potentiality to make breakthroughs in the future but have been kept remained at early stages of development because of their uncertain technological values, is important in the course of introduction and dissemination of hydrogen energy into our society. In Japan, in the consecutive projects of 'World Energy Network' (WE-NET) and 'Development of Safe Utilization Technology and an Infrastructure for Hydrogen Use', both supported by New Energy and Industrial Technology Development Organization (NEDO), significant results have been achieved in the project of 'Research on Innovative Technologies'. The framework and characteristics of this project are outlined with several research topics. In the exploratory research on the alternative catalytic materials to Platinum group metals for fuel cells and hydrogen production, a series of Tantalum oxynitrides were found potentially applicable as new electrodes catalysts the development of magnetic refrigeration of hydrogen is under way with the finding of materials with feasible properties; in search of innovative hydrogen storage systems, a new process of decalin dehydrogenation / naphthalene hydrogenation based on superheated liquid-film-type catalysis was developed. (author)

  14. Hydrogenation of biomass-derived substrates

    Science.gov (United States)

    Gordon, John C.; Waidmann, Christopher R.

    2016-06-07

    The .alpha.,.beta.-unsaturated ketone moiety of a substrate representative of non-food based biomass was hydrogenated to the corresponding saturated alcohol moiety using a composition including (1) a copper salt; (2) a phosphine; (3) a polar aprotic solvent such as acetonitrile, and (4) a compound suitable for providing hydrogen for the hydrogenation, such as a suitable silane material or a suitable siloxane material.

  15. Homogeneous catalytic dehydrocoupling/dehydrogenation of amine-borane adducts by early transition metal, group 4 metallocene complexes.

    Science.gov (United States)

    Sloan, Matthew E; Staubitz, Anne; Clark, Timothy J; Russell, Christopher A; Lloyd-Jones, Guy C; Manners, Ian

    2010-03-24

    The efficient catalytic dehydrocoupling of a range of amine-borane adducts, R'RNH x BH(3) (R' = R = Me 1a; R' = R = (i)Pr 1b; R' = Me, R = CH(2)Ph 1c) by a series of group 4 metallocene type precatalysts has been demonstrated. A reduction in catalytic activity was detected upon descending the group and also on substitution of the cyclopentadienyl (Cp) ligands with sterically bulky or electron-donating substituents. Precatalysts Cp(2)TiCl(2)/2(n)BuLi and Cp(2)Ti(PMe(3))(2), which are believed to act as precursors to [Cp(2)Ti], were found to promote the transformation of 1a to [Me(2)N-BH(2)](2) (3a) in a homogeneous catalytic process. Mechanistic studies identified the linear dimer Me(2)NH-BH(2)-NMe(2)-BH(3) (2a) as a reaction intermediate, which subsequently undergoes further catalytic dehydrogenation to form cyclic dimer 3a. Synthesis of the (2)H-isotopologues of 1a allowed the extraction of phenomenological kinetic isotope effects for 1a --> 2a and 2a --> 3a from initial rate data, which permitted the proposal of a catalytic cycle with plausible intermediates. Support for the presence of an active Ti(II) catalyst was provided by the lack of reactivity of Ti(III) complexes TiCl(3) and Cp(2)TiCl or Ti(0) in the form of THF soluble colloids or bulk Ti powder toward 1a or 1b. Modeling of the rates of consumption of 1a and formation of 3a during catalysis by Cp(2)Ti(PMe(3))(2) supported this conclusion and allowed the proposal of a two cycle, four step reaction mechanism. The proposed first cycle generates 2a in a two step process. In the second cycle, interaction of 2a with the same catalyst then results in a catalytic dehydrogenative ring closing reaction to form 3a, also in a two step process.

  16. Hydrogenation of organic solid wastes

    Energy Technology Data Exchange (ETDEWEB)

    Wu, W.R.K.; Kawa, W.

    1980-02-01

    Eight organic solid wastes, six cellulosic and two noncellulosic, were hydrogenated batchwise with and without a catalyst. Conversions obtained range from 64 to 98 % of moisture- and ash-free (maf) raw material; oil yields, 10 to 59 %; and gaseous hydrocarbon yields, 7 to 16 %. Based on batch hydrogenation results, the oil production from large-scale hydrogenation of the wastes is projected to be 1.6 to 3.5 bbl/ton of maf raw material; the gaseous-hydrocarbon production, 2000 to 4100 standard cubic feet (scf). Activities of the two catalysts (SnCl/sub 2// and a combination of Fe/sub 2/O/sub 3/ and H/sub 2/S) used in the hydrogenation of the wastes are discussed. Also discussed are the chemical reactions and mechanisms involved in the hydrogenation, potential market for the product oil, and possible improvement of the oil yield. Elemental compositions of the hydrogenation oils and types of hydrocarbons including oxygenated hydrocarbons found in the oils are presented. The energy equivalent of the organic solid wastes generated in the United States in 1973 is shown to be 27 % of the nation's total 1972 energy production.

  17. Magnetic refrigerator for hydrogen liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, T [National Institute for Materials Science, Tsukuba (Japan); Kamlya, K. [Japan Atomic Energy Agency, Naka (Japan); Utaki, T. [Osaka University, Osaka (Japan); Matsumoto, K. [Kanazawa University, Kanazawa (Japan)

    2013-06-15

    This paper reviews the development status of magnetic refrigeration system for hydrogen liquefaction. There is no doubt that hydrogen is one of most important energy sources in the near future. In particular, liquid hydrogen can be utilized for infrastructure construction consisting of storage and transportation. Liquid hydrogen is in cryogenic temperatures and therefore high efficient liquefaction method must be studied. Magnetic refrigeration which uses the magneto-caloric effect has potential to realize not only the higher liquefaction efficiency > 50 %, but also to be environmentally friendly and cost effective. Our hydrogen magnetic refrigeration system consists of Carnot cycle for liquefaction stage and AMR (active magnetic regenerator) cycle for precooling stages. For the Carnot cycle, we develop the high efficient system > 80 % liquefaction efficiency by using the heat pipe. For the AMR cycle, we studied two kinds of displacer systems, which transferred the working fluid. We confirmed the AMR effect with the cooling temperature span of 12 K for 1.8 T of the magnetic field and 6 second of the cycle. By using the simulation, we estimate the total efficiency of the hydrogen liquefaction plant for 10 kg/day. A FOM of 0.47 is obtained in the magnetic refrigeration system operation temperature between 20 K and 77 K including LN2 work input.

  18. Microalgal hydrogen production - A review.

    Science.gov (United States)

    Khetkorn, Wanthanee; Rastogi, Rajesh P; Incharoensakdi, Aran; Lindblad, Peter; Madamwar, Datta; Pandey, Ashok; Larroche, Christian

    2017-11-01

    Bio-hydrogen from microalgae including cyanobacteria has attracted commercial awareness due to its potential as an alternative, reliable and renewable energy source. Photosynthetic hydrogen production from microalgae can be interesting and promising options for clean energy. Advances in hydrogen-fuel-cell technology may attest an eco-friendly way of biofuel production, since, the use of H 2 to generate electricity releases only water as a by-product. Progress in genetic/metabolic engineering may significantly enhance the photobiological hydrogen production from microalgae. Manipulation of competing metabolic pathways by modulating the certain key enzymes such as hydrogenase and nitrogenase may enhance the evolution of H 2 from photoautotrophic cells. Moreover, biological H 2 production at low operating costs is requisite for economic viability. Several photobioreactors have been developed for large-scale biomass and hydrogen production. This review highlights the recent technological progress, enzymes involved and genetic as well as metabolic engineering approaches towards sustainable hydrogen production from microalgae. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Hydrogen Energy Storage (HES) Activities at NREL; NREL (National Renewable Energy Laboratory)

    Energy Technology Data Exchange (ETDEWEB)

    Eichman, J.

    2015-04-21

    This presentation provides an overview of hydrogen and energy storage, including hydrogen storage pathways and international power-to-gas activities, and summarizes the National Renewable Energy Laboratory's hydrogen energy storage activities and results.

  20. Waste/By-Product Hydrogen

    Science.gov (United States)

    2011-01-13

    Biogas , including anaerobic digester gas, can be reformed to produce hydrogen and used in a fuel cell to produce significant amounts of electricity...Waste/By product Hydrogen Waste H2 sources include: � Waste bio‐mass: biogas to high temp fuel cells to produce H2 – there are over two dozen sites...and heat. � When biogas is produced and used on‐site in a fuel cell, fuel utilization or overall energy efficiency can reach 90% and can reduce

  1. Why hydrogen; Pourquoi l'hydrogene?

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2004-02-01

    The energy consumption increase and the associated environmental risks, led to develop new energy sources. The authors present the potentialities of the hydrogen in this context of energy supply safety. They detail the today market and the perspectives, the energy sources for the hydrogen production (fossils, nuclear and renewable), the hydrogen transport, storage, distribution and conversion, the application domains, the associated risks. (A.L.B.)

  2. Materials Engineering and Scale Up of Fluid Phase Chemical Hydrogen Storage for Automotive Applications

    Energy Technology Data Exchange (ETDEWEB)

    Westman, Matthew P.; Chun, Jaehun; Choi, Young Joon; Ronnebro, Ewa

    2016-01-25

    Among candidates for chemical hydrogen storage in PEM fuel cell automotive applications, ammonia borane (AB, NH3BH3) is considered to be one of the most promising materials due to its high hydrogen content of 14-16 wt% below 200°C and high volumetric density. In our previous paper, we selected AB in silicone oil as a role model for a slurry hydrogen storage system. Materials engineering properties were optimized by increasing solid loading by using an ultra-sonic process. In this paper, we proceeded to scale up to liter size batches with solid loadings up to 50 wt% (8 wt% H2) with dynamic viscosities less than 1000cP at 25°C. The use of a non-ionic surfactant, Triton X-15, shows significant promise in controlling the level of foaming produced during the thermal dehydrogenation of the AB. Through the development of new and efficient processing techniques and the ability to adequately control the foaming, stable homogenous slurries of high solid loading have been demonstrated as a viable hydrogen delivery source.

  3. 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.)

  4. Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

    Science.gov (United States)

    1997-04-01

    An experimental study of sulfur tolerant zeolite platinum catalysts for aormatics hydrogenation. Platinum catalysts supported on Y-zeolite have been prepared and characterized in various ways, including the hydrogenation of toluene in a high pressure...

  5. Green energy and hydrogen research at University of Waterloo

    International Nuclear Information System (INIS)

    Fowler, M.

    2006-01-01

    This paper summarises Green Energy and Hydrogen Research at the University of Waterloo in Canada. Green energy includes solar, wind, bio fuels, hydrogen economy and conventional energy sources with carbon dioxide sequestration

  6. Complex rare-earth aluminum hydrides: mechanochemical preparation, crystal structure and potential for hydrogen storage.

    Science.gov (United States)

    Weidenthaler, Claudia; Pommerin, André; Felderhoff, Michael; Sun, Wenhao; Wolverton, Christopher; Bogdanović, Borislav; Schüth, Ferdi

    2009-11-25

    A novel type of complex rare-earth aluminum hydride was prepared by mechanochemical preparation. The crystal structure of the REAlH(6) (with RE = La, Ce, Pr, Nd) compounds was calculated by DFT methods and confirmed by preliminary structure refinements. The trigonal crystal structure consists of isolated [AlH(6)](3-) octahedra bridged via [12] coordinated RE cations. The investigation of the rare-earth aluminum hydrides during thermolysis shows a decrease of thermal stability with increasing atomic number of the RE element. Rare-earth hydrides (REH(x)) are formed as primary dehydrogenation products; the final products are RE-aluminum alloys. The calculated decomposition enthalpies of the rare-earth aluminum hydrides are at the lower end for reversible hydrogenation under moderate conditions. Even though these materials may require somewhat higher pressures and/or lower temperatures for rehydrogenation, they are interesting examples of low-temperature metal hydrides for which reversibility might be reached.

  7. Photocatalytic Ethanol Oxidative Dehydrogenation over Pt/TiO2: Effect of the Addition of Blue Phosphors

    Directory of Open Access Journals (Sweden)

    J. J. Murcia

    2012-01-01

    Full Text Available Ethanol oxidative dehydrogenation over Pt/TiO2 photocatalyst, in the presence and absence of blue phosphors, was performed. The catalyst was prepared by photodeposition of Pt on sulphated TiO2. This material was tested in a gas-solid photocatalytic fluidized bed reactor at high illumination efficiency. The effect of the addition of blue phosphors into the fluidized bed has been evaluated. The synthesized catalysts were extensively characterized by different techniques. Pt/TiO2 with a loading of 0.5 wt% of Pt appeared to be an active photocatalyst in the selective partial oxidation of ethanol to acetaldehyde improving its activity and selectivity compared to pure TiO2. In the same way, a notable enhancement of ethanol conversion in the presence of the blue phosphors has been obtained. The blue phosphors produced an increase in the level of ethanol conversion over the Pt/TiO2 catalyst, keeping at the same time the high selectivity to acetaldehyde.

  8. Effect of additives to VPO system on its catalytic properties in oxidative dehydrogenation of propane and ethane

    International Nuclear Information System (INIS)

    Gasior, M.; Gressel, I.; Grzybowska, B.; Zazhigalov, V.A.

    2003-01-01

    Oxidative dehydrogenation (ODH) of propane and ethane has been studied on VPO catalysts with additives of Bi, La, Mo, and Zr. The catalysts show promising properties in the ethane ODH, with selectiveness of ethene of ∼ 85% at 10% conversion of ethane, but are poor in the propane ODH (maximal selectivities to propene of ∼40%). For both alkanes introduction of the additives leads to an increase in the overall rate of the reaction. The effect of the additives on the selectivity to olefins is complex and depends on the reaction temperature, the additive content and the type of alkane. The same additive has in several cases an inverse effect on the selectivity for the propane and ethane ODH. The Mo additive and higher amounts of the La additive increase the selectivity to propane, whereas they decrease the selectivity of ethane. Low content of La additive gives rise of the increase of selectivity to ethane and decrease in that to propane. The differences between the selectivities to olefins in ODH of propane and ethane are discussed as being due to different acidic-basic properties of the propene and ethene and their different strength of bonding to the catalyst surface. (author)

  9. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper

    Science.gov (United States)

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-08-01

    This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt-Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt-Cu interaction inhibits propylene adsorption and elevates the energy barrier of C-C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt-Cu/Al2O3, while a higher energy barrier for C-C bond cleavage suppresses the methane formation.

  10. Role of Sn in the Regeneration of Pt/γ-Al2O3 Light Alkane Dehydrogenation Catalysts.

    Science.gov (United States)

    Pham, Hien N; Sattler, Jesper J H B; Weckhuysen, Bert M; Datye, Abhaya K

    2016-04-01

    Alumina-supported Pt is one of the major industrial catalysts for light alkane dehydrogenation. This catalyst loses activity during reaction, with coke formation often considered as the reason for deactivation. As we show in this study, the amount and nature of carbon deposits do not directly correlate with the loss of activity. Rather, it is the transformation of subnanometer Pt species into larger Pt nanoparticles that appears to be responsible for the loss of catalytic activity. Surprisingly, a portion of the Sn remains atomically dispersed on the alumina surface in the spent catalyst and helps in the redispersion of the Pt. In the absence of Sn on the alumina support, the larger Pt nanoparticles formed during reaction are not redispersed during oxidative regeneration. It is known that Sn is added as a promoter in the industrial catalyst to help in achieving high propene selectivity and to minimize coke formation. This work shows that an important role of Sn is to help in the regeneration of Pt, by providing nucleation sites on the alumina surface. Aberration-corrected scanning transmission electron microscopy helps to provide unique insights into the operating characteristics of an industrially important catalyst by demonstrating the role of promoter elements, such as Sn, in the oxidative regeneration of Pt on γ-Al 2 O 3 .

  11. Carbon Dioxide Promotes Dehydrogenation in the Equimolar C2H2-CO2Reaction to Synthesize Carbon Nanotubes.

    Science.gov (United States)

    Shi, Wenbo; Peng, Yue; Steiner, Stephen A; Li, Junhua; Plata, Desiree L

    2018-01-16

    The equimolar C 2 H 2 -CO 2 reaction has shown promise for carbon nanotube (CNT) production at low temperatures and on diverse functional substrate materials; however, the electron-pushing mechanism of this reaction is not well demonstrated. Here, the role of CO 2 is explored experimentally and theoretically. In particular, 13 C labeling of CO 2 demonstrates that CO 2 is not an important C source in CNT growth by thermal catalytic chemical vapor deposition. Consistent with this experimental finding, the adsorption behaviors of C 2 H 2 and CO 2 on a graphene-like lattice via density functional theory calculations reveal that the binding energies of C 2 H 2 are markedly higher than that of CO 2 , suggesting the former is more likely to incorporate into CNT structure. Further, H-abstraction by CO 2 from the active CNT growth edge would be favored, ultimately forming CO and H 2 O. These results support that the commonly observed, promoting role of CO 2 in CNT growth is due to a CO 2 -assisted dehydrogenation mechanism. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

    KAUST Repository

    Takanabe, Kazuhiro

    2016-08-21

    The dehydrogenation of ethane to ethylene in the presence of oxygen and water was conducted using Na2WO4/SiO2 catalyst at high temperatures. At 923 K, the conversion rate without water was proportional to ethane pressure and a half order of oxygen pressure, consistent with a kinetically relevant step where an ethane molecule is activated with dissociated oxygen on the surface. When water was present, the ethane conversion rate was drastically enhanced. An additional term in the rate expression was proportional to a quarter of the oxygen pressure and a half order of the water pressure. This mechanism is consistent with the quasi-equilibrated OH radical formation with subsequent ethane activation. The attainable yield can be accurately described by taking the water contribution into consideration. At high conversion levels at 1073 K, the C2H4 yield exceeded 60% in a single-pass conversion. The C2H4 selectivity was almost insensitive to the C2H6 and O2 pressures. © 2016 American Institute of Chemical Engineers.

  13. The physicochemical properties and catalytic performance of carbon-covered alumina for oxidative dehydrogenation of ethylbenzene with CO2

    Science.gov (United States)

    Wang, Tehua; Chong, Siying; Wang, Tongtong; Lu, Huiyi; Ji, Min

    2018-01-01

    In order to correlate the physicochemical properties of carbon-covered alumina (CCA) materials with their catalytic performance for oxidative dehydrogenation of ethylbenzene with CO2 (CO2-ODEB), a series of CCA materials with diverse carbon contents (8.7-31.3 wt%) and pyrolysis temperatures (600-800 °C), which were synthesized via an impregnation method followed by pyrolysis, were applied. These catalytic materials were characterized by TGA, N2 physisorption, XRD, Raman spectroscopy and XPS techniques. It was found that the catalytic performance of these CCA materials highly depended on their physicochemical properties, and the optimum CCA catalyst exhibited much better catalytic stability than conventional hydroxyl carbon nanotubes. Below an optimum value of carbon content, the CCA catalyst preserved the main pore characteristics of the Al2O3 support and its catalytic activity increased with the carbon content. Excessive carbon loading resulted in significant textural alterations and thereby decreased both the ethylbenzene conversion and styrene selectivity. On the other hand, high pyrolysis temperature was detrimental to the ordered graphitic structure of the carbon species within the Al2O3 pore. The decreased ordered graphitic degree was found to be associated with the loss of the surface active carbonyl groups, consequently hampering the catalytic efficiency of the CCA catalyst.

  14. Primary energy sources for hydrogen production

    International Nuclear Information System (INIS)

    Hassmann, K.; Kuehne, H.M.

    1993-01-01

    The costs for hydrogen production through water electrolysis are estimated, assuming the electricity is produced from solar, hydro-, fossil, or nuclear power. The costs for hydrogen end-use in the power generation, heat and transportation sectors are also calculated, based on a state of the art technology and a more advanced technology expected to represent the state by the year 2010. The costs for hydrogen utilization (without energy taxes) are shown to be higher than current prices for fossil fuels (including taxes). Without restrictions imposed on fossil fuel consumption, hydrogen shall not gain a significant market share in either of the cases discussed. 2 figs., 3 tabs., 4 refs

  15. Primary energy sources for hydrogen production

    International Nuclear Information System (INIS)

    Hassmann, K.; Kuehne, H.-M.

    1993-01-01

    The cost of hydrogen from water electrolysis is estimated, assuming that the electricity was produced from solar, hydro-, fossil, or nuclear power. The costs for hydrogen end-use in the sectors of power generation, heat and transportation are calculated, based on a state-of-the-art technology and a more advanced technology expected to represent the state by the year 2010. The cost of hydrogen utilization (without energy taxes) is higher than the current price of fossil fuels (including taxes). Without restrictions imposed on fossil fuel consumption, hydrogen will not gain a significant market share in either of the cases discussed. (Author)

  16. Modelling of stationary bulk hydrogen storage systems

    Energy Technology Data Exchange (ETDEWEB)

    Venter, R.D.; Pucher, G. [Centre for Hydrogen and Electrochemical Studies (CHES), University of Toronto (Canada)

    1997-08-01

    The employment of bulk hydrogen storage systems within industry appears increasingly to be a near-term prospect given the steadily increasing levels of hydrogen production. The current study defines and outlines a cost model through which comparative and informative assessments of different stationary bulk hydrogen storage reservoir types can be made. The reservoir types investigated include: mined salt caverns, depleted natural gas reservoirs and liquid vessels. Using the model, cost of storage for these potential bulk hydrogen containment technologies is estimated and compared in qualitative terms. for similar storage applications. (Author)

  17. Cryogenic hydrogen-induced air liquefaction technologies

    Science.gov (United States)

    Escher, William J. D.

    1990-01-01

    Extensively utilizing a special advanced airbreathing propulsion archives database, as well as direct contacts with individuals who were active in the field in previous years, a technical assessment of cryogenic hydrogen-induced air liquefaction, as a prospective onboard aerospace vehicle process, was performed and documented. The resulting assessment report is summarized. Technical findings are presented relating the status of air liquefaction technology, both as a singular technical area, and also that of a cluster of collateral technical areas including: compact lightweight cryogenic heat exchangers; heat exchanger atmospheric constituents fouling alleviation; para/ortho hydrogen shift conversion catalysts; hydrogen turbine expanders, cryogenic air compressors and liquid air pumps; hydrogen recycling using slush hydrogen as heat sink; liquid hydrogen/liquid air rocket-type combustion devices; air collection and enrichment systems (ACES); and technically related engine concepts.

  18. Concentration of Hydrogen Peroxide

    Science.gov (United States)

    Parrish, Clyde F. (Inventor)

    2006-01-01

    Methods for concentrating hydrogen peroxide solutions have been described. The methods utilize a polymeric membrane separating a hydrogen peroxide solution from a sweep gas or permeate. The membrane is selective to the permeability of water over the permeability of hydrogen peroxide, thereby facilitating the concentration of the hydrogen peroxide solution through the transport of water through the membrane to the permeate. By utilizing methods in accordance with the invention, hydrogen peroxide solutions of up to 85% by volume or higher may be generated at a point of use without storing substantial quantities of the highly concentrated solutions and without requiring temperatures that would produce explosive mixtures of hydrogen peroxide vapors.

  19. Hydrogen, this hallucinogen

    International Nuclear Information System (INIS)

    Gay, Michel

    2013-01-01

    The author discusses the origin of hydrogen for energetic use (mainly by extraction from water), the possible uses of this cumbersome gas (in vehicles, in electricity storage), and outlines that hydrogen economy consumes a lot of other energies (nuclear, wind, sun, biomass, and so on) for a high cost, and that hydrogen is therefore not a solution for the future. Other elements are given in appendix: production methods and processes, figures of energy production, ways to use and to store hydrogen in vehicles, assessment of possibilities for a vehicle, techniques and figures for hydrogen packaging, transport and distribution, energy cost, energetic assessment of hydrogen production, problems associated with distribution (tank filling)

  20. Hydrogen and deuterium trapping in iron

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, H H; Lin, R W

    1981-02-01

    The research described is directed at present almost exclusively to hydrogen transport, including both chemical and physical trapping, in iron and iron-base alloys. Some attention is directed to isotope effects. Efforts are made to clarify and understand hydrogen-related phenomena which are believed to be of direct importance to practical performance.