The prospects for hydrogen as an energy carrier: an overview of hydrogen energy and hydrogen energy systems

Energy Technology Data Exchange (ETDEWEB)

Rosen, Marc A.; Koohi-Fayegh, Seama [Ontario Univ., Oshawa, ON (Canada). Inst. of Technology

2016-02-15

Hydrogen is expected to play a key role as an energy carrier in future energy systems of the world. As fossil-fuel supplies become scarcer and environmental concerns increase, hydrogen is likely to become an increasingly important chemical energy carrier and eventually may become the principal chemical energy carrier. When most of the world's energy sources become non-fossil based, hydrogen and electricity are expected to be the two dominant energy carriers for the provision of end-use services. In such a ''hydrogen economy,'' the two complementary energy carriers, hydrogen and electricity, are used to satisfy most of the requirements of energy consumers. A transition era will bridge the gap between today's fossil-fuel economy and a hydrogen economy, in which non-fossil-derived hydrogen will be used to extend the lifetime of the world's fossil fuels - by upgrading heavy oils, for instance - and the infrastructure needed to support a hydrogen economy is gradually developed. In this paper, the role of hydrogen as an energy carrier and hydrogen energy systems' technologies and their economics are described. Also, the social and political implications of hydrogen energy are examined, and the questions of when and where hydrogen is likely to become important are addressed. Examples are provided to illustrate key points. (orig.)

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.

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.

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)

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.

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

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.

The energy carrier hydrogen

International Nuclear Information System (INIS)

Anon.

1992-01-01

The potential of hydrogen to be used as a clean fuel for the production of heat and power, as well as for the propulsion of aeroplanes and vehicles, is described, in particular for Germany. First, attention is paid to the application of hydrogen as a basic material for the (petro)chemical industry, as an indirect energy source for (petro)chemical processes, and as a direct energy source for several purposes. Than the importance of hydrogen as an energy carrier in a large-scale application of renewable energy sources is discussed. Next an overview is given of new and old hydrogen production techniques from fossil fuels, biomass, or the electrolysis of water. Energetic applications of hydrogen in the transportation sector and the production of electric power and heat are mentioned. Brief descriptions are given of techniques to store hydrogen safely. Finally attention is paid to hydrogen research in Germany. Two hydrogen projects, in which Germany participates, are briefly dealt with: the Euro-Quebec project (production of hydrogen by means of hydropower), and the HYSOLAR project (hydrogen production by means of solar energy). 18 figs., 1 tab., 7 refs

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

DEFF Research Database (Denmark)

Olsen, Esben Paul Krogh; Madsen, Robert

2012-01-01

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

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.

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.

Some aspects of hydrogen as a long-term energy carrier

International Nuclear Information System (INIS)

Quakernaat, J.; De Jong, K.P.; Van Wechem, H.M.H.; Okken, P.A.; Lako, P.; Ybema, J.R.

1994-11-01

Hydrogen as a secondary energy carrier received extensive and worldwide attention some ten to fifteen years ago. The developments in the energy market since then have reduced the interest in hydrogen. However, the increased concern for the environment and new technical options have brought hydrogen to the centre of attention once again. These considerations led to the organization of the National Hydrogen Seminar, held on 19 November 1993 at ECN, Petten, Netherlands. Eight experts in the field of hydrogen illustrated the possibilities and prospects of the production, storage and use of hydrogen as an energy carrier. In this report three of these contributions are presented, for which separate abstracts have been prepared. The first paper is on hydrogen in a global long-term perspective, in the second paper carbon is considered as a hydrogen carrier or as a disappearing skeleton, and in the third paper attention is paid to the cost effective integration of hydrogen in energy systems with CO 2 constraints

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

Hydrogen storage using borohydrides

International Nuclear Information System (INIS)

Bernard BONNETOT; Laetitia LAVERSENNE

2006-01-01

The possibilities of hydrogen storage using borohydrides are presented and discussed specially in regard of the recoverable hydrogen amount and related to the recovering conditions. A rapid analysis of storage possibilities is proposed taking in account the two main ways for hydrogen evolution: the dehydrogenation obtained through thermal decomposition or the hydrolysis of solids or solutions. The recoverable hydrogen is related to the dehydrogenation conditions and the real hydrogen useful percentage is determined for each case of use. The high temperature required for dehydrogenation even when using catalyzed compounds lead to poor outlooks for this storage way. The hydrolysis conditions direct the chemical yield of the water consuming, and this must be related to the experimental conditions which rule the storage capacity of the 'fuel' derived from the borohydride. (authors)

New efficient hydrogen process production from organosilane hydrogen carriers derivatives

Energy Technology Data Exchange (ETDEWEB)

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

2010-04-15

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

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

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.

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

Science.gov (United States)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: tanzhaoyi@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

2015-06-15

Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

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.

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.

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

Science.gov (United States)

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

DEFF Research Database (Denmark)

Ghalehshahi, Hajar Golshadi; Madsen, Robert

2017-01-01

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

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.

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)

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.

Formic Acid as a Hydrogen Energy Carrier

KAUST Repository

Eppinger, Jö rg; Huang, Kuo-Wei

2016-01-01

The high volumetric capacity (S3 g H-2/L) and its low toxicity and flammability under ambient conditions make formic acid a promising hydrogen energy carrier. Particularly, in the past decade, significant advancements have been achieved in catalyst development for selective hydrogen generation from formic acid. This Perspective highlights the advantages of this approach with discussions focused on potential applications in the transportation sector together with analysis of technical requirements, limitations, and costs.

Formic Acid as a Hydrogen Energy Carrier

KAUST Repository

Eppinger, Jorg

2016-12-15

The high volumetric capacity (S3 g H-2/L) and its low toxicity and flammability under ambient conditions make formic acid a promising hydrogen energy carrier. Particularly, in the past decade, significant advancements have been achieved in catalyst development for selective hydrogen generation from formic acid. This Perspective highlights the advantages of this approach with discussions focused on potential applications in the transportation sector together with analysis of technical requirements, limitations, and costs.

Reversible hydrogen storage in Ti-Zr-codoped NaAlH4 under realistic operation conditions: Part 2

International Nuclear Information System (INIS)

Schmidt, Thomas; Roentzsch, Lars; Weissgaerber, Thomas; Kieback, Bernd

2011-01-01

Research highlights: → The dehydrogenation kinetics of NaAlH 4 , codoped with TiCl 4 and Zrcl 3 are studied with respect to hydrogen back-pressure and catalyst concentration. → A strong pressure dependency is found in the second dehydrogenation step, whereas the first step shows little influence by hydrogen pressure. → The influence of the catalyst concentration is strong for both dehydrogenation steps. → Rate constants and activation energies are calculated from isothermal measurements. - Abstract: Recently, we have demonstrated that the dehydrogenation of NaAlH 4 can be carried out with sufficient kinetics even at a hydrogen back pressure of 4 bar, which is needed for a proton exchange membrane (PEM) fuel cell . In this contribution the influence of hydrogen back pressure in the range of 0.2 up to 5 bar and catalyst concentration in the range between 1 and 5 wt.% overall catalyst concentration on the dehydrogenation of Zr-Ti codoped NaAlH 4 is investigated in detail. The influence of the hydrogen back-pressure is significant in the 2nd dehydrogenation step. The catalyst concentration influences both kinetics and storage capacity. Rate constants as a function of the temperature and hydrogen back-pressure and activation energies of the dehydrogenation of NaAlH 4 to Na 3 AlH 6 at 1 bar and 4 bar hydrogen pressure are calculated from isothermal dehydrogenation experiments.

Hydrogen and Biofuels - A Modeling Analysis of Competing Energy Carriers for Western Europe

Energy Technology Data Exchange (ETDEWEB)

Guel, Timur; Kypreos, Socrates; Barreto, Leonardo

2007-07-01

This paper deals with the prospects of hydrogen and biofuels as energy carriers in the Western European transportation sector. The assessment is done by combining the US hydrogen analysis H2A models for the design of hydrogen production and delivery chains, and the Western European Hydrogen Markal Model EHM with a detailed representation of biofuels, and the European electricity and transportation sector. The paper derives policy recommendations to support the market penetration of hydrogen and biofuels, and investigates learning interactions between the different energy carriers. (auth)

The influence of ball-milling time on the dehydrogenation properties of the NaAlH4-MgH2 composite

NARCIS (Netherlands)

Bendyna, J.K.; Dyjak, S.M.; Notten, P.H.L.

2015-01-01

The recently developed NaAlH4eMgH2 composite shows improved hydrogen-storage properties compared to MgH2 and NaAlH4. However, the dehydrogenation reaction rates are still too limited, hampering practical applications. Mechanical ball milling is broadly used to improve the dehydrogenation reaction

Hydrogen, an energy carrier with a future

International Nuclear Information System (INIS)

Zimmer, K.H.

1975-01-01

The inefficient use, associated with pollutants, of the fossil energy carriers coal, crude oil and natural gas, will deplete resources, if the energy demand increases exponentially, in the not-too-distant future. That is the reason why the hydrogen-energy concept gains in importance. This requires drastic changes in structure in a lot of technological fields. This task is only to be mastered if there is cooperation between all special fields, in order to facilitate the economical production, distribution and utilization of hydrogen. (orig.) [de

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.

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

KAUST Repository

Jang, Ji-Wook

2017-08-25

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

Fundamental analysis of thermally regenerative fuel cell utilizing solar heat; Taiyonetsu wo riyosuru netsu saiseigata nenryo denchi no kiso tokusei no kaiseki

Energy Technology Data Exchange (ETDEWEB)

Ando, Y; Tanaka, T; Takashima, T; Doi, T [Electrotechnical Laboratory, Tsukuba (Japan); Aosawa, T; Kogoshi, S [Science University of Tokyo, Tokyo (Japan)

1997-11-25

Study was made on a thermally regenerative fuel cell using solar heat. The thermally regenerative fuel cell was devised which is composed of 2-propanol liquid-phase endothermic dehydrogenation at nearly 100degC, and acetone liquid- phase exothermic hydrogenation at nearly 30degC as reverse reaction. This low-temperature dehydrogenation can relatively easily utilize a flat solar heat concentrator. 2-propanol dehydrogenation generates acetone and hydrogen. Generated acetone generates electric power in hydrogenation, generating propanol. This propanol regenerates acetone and hydrogen in dehydrogenation. The activity of Ru and Pt composite catalyst was considerably higher than that of Ru or Pt single catalyst. The activity was also higher in carbon felt or carbon cloth carrier than carbon plate carrier. The open circuit voltage of the fuel cell was estimated to be 110-120mV, nearly consisting with theoretical values. Short circuit current was also estimated to be 9-11mA, suggesting reduction of its internal resistance as an important subject. 4 refs., 5 figs., 2 tabs.

Seasonal storage and alternative carriers: A flexible hydrogen supply chain model

International Nuclear Information System (INIS)

Reuß, M.; Grube, T.; Robinius, M.; Preuster, P.; Wasserscheid, P.; Stolten, D.

2017-01-01

Highlights: •Techno-economic model of future hydrogen supply chains. •Implementation of liquid organic hydrogen carriers into a hydrogen mobility analysis. •Consideration of large-scale seasonal storage for fluctuating renewable hydrogen production. •Implementation of different technologies for hydrogen storage and transportation. -- Abstract: A viable hydrogen infrastructure is one of the main challenges for fuel cells in mobile applications. Several studies have investigated the most cost-efficient hydrogen supply chain structure, with a focus on hydrogen transportation. However, supply chain models based on hydrogen produced by electrolysis require additional seasonal hydrogen storage capacity to close the gap between fluctuation in renewable generation from surplus electricity and fuelling station demand. To address this issue, we developed a model that draws on and extends approaches in the literature with respect to long-term storage. Thus, we analyse Liquid Organic Hydrogen Carriers (LOHC) and show their potential impact on future hydrogen mobility. We demonstrate that LOHC-based pathways are highly promising especially for smaller-scale hydrogen demand and if storage in salt caverns remains uncompetitive, but emit more greenhouse gases (GHG) than other gaseous or hydrogen ones. Liquid hydrogen as a seasonal storage medium offers no advantage compared to LOHC or cavern storage since lower electricity prices for flexible operation cannot balance the investment costs of liquefaction plants. A well-to-wheel analysis indicates that all investigated pathways have less than 30% GHG-emissions compared to conventional fossil fuel pathways within a European framework.

Development of a Practical Hydrogen Storage System Based on Liquid Organic Hydrogen Carriers and a Homogeneous Catalyst

Energy Technology Data Exchange (ETDEWEB)

Jensen, Craig [Hawaii Hydrogen Carriers, LLC, Honolulu, HI (United States); Brayton, Daniel [Hawaii Hydrogen Carriers, LLC, Honolulu, HI (United States); Jorgensen, Scott W. [General Motors, LLC, Warren, MI (United States). Research and Development Center. Chemical and Material Systems Lab.; Hou, Peter [General Motors, LLC, Warren, MI (United States). Research and Development Center. Chemical and Material Systems Lab.

2017-03-24

The objectives of this project were: 1) optimize a hydrogen storage media based on LOC/homogeneous pincer catalyst (carried out at Hawaii Hydrogen Carriers, LLC) and 2) develop space, mass and energy efficient tank and reactor system to house and release hydrogen from the media (carried out at General Motor Research Center).

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.

Hydrogen as an energy carrier. 2. rev. and enlarged ed.

International Nuclear Information System (INIS)

Winter, C.J.; Nitsch, J.

1991-01-01

This book deals with the possibilities of an energetic utilisation of hydrogen. This energy carrier can be produced from the unlimited energy sources - solar energy, wind energy and hydropower - and from nuclear energy. It is also capable of one day supplementing or superseding the fossil energy carriers oil, coal and gas. What is special about the book is that it goes beyond a mere physical/technical description to discuss the economic and political aspects and ecological effects and requirements that are an essential part of sound energy planning today. Thus, the authors and editors outline the step-by-step development of a hydrogen economy, mainly based on solar energy, providing a solution to both the pollution problems caused by the use of fossil energy carriers and the energy requirements of the third world. (orig.) With 197 figs., 71 tabs

Sodium tetra-hydro-borate as energy/hydrogen carrier, its history

International Nuclear Information System (INIS)

Demirci, U.B.; Miele, Ph.

2009-01-01

Sodium tetra-hydro-borate NaBH 4 is considered as being a promising energy/hydrogen carrier. NaBH 4 is not a new compound. It has been discovered in 1940's by Prof. H.C. Brown, Nobel Laureate in Chemistry in 1979. NaBH 4 has thus a history and this history distinguishes the NaBH 4 utilisation as hydrogen carrier from that as energy carrier. In fact, the history of NaBH 4 (for both utilizations) can be divided into three periods, each period being characterised by specific societal challenges. Whereas during the first period the challenges were military and political, the challenges in the third period (i.e. at present) are energetic, environmental, civilian, social and political. The second period was rather calm for NaBH 4 even if it was intensively used as a reducing agent in organic chemistry. (authors)

Hydrogen storage via polyhydride complexes

Energy Technology Data Exchange (ETDEWEB)

Jensen, C.M.; Zidan, R.A. [Univ. of Hawaii, Honolulu, HI (United States)

1998-08-01

The reversible dehydrogenation of NaAlH{sub 4} is catalyzed in toluene slurries of the NaAlH{sub 4} containing the pincer complex, IrH{sub 4} {l_brace}C{sub 6}H{sub 3}-2,6-(CH{sub 2}PBu{sup t}{sub 2}){sub 2}{r_brace}. The rates of the pincer complex catalyzed dehydrogenation are about five times greater those previously found for NaAlH{sub 4} that was doped with titanium through a wet chemistry method. Homogenization of NaAlH{sub 4} with 2 mole % Ti(OBu{sup n}){sub 4} under an atmosphere of argon produces a novel titanium containing material. TPD measurements show that the dehydrogenation of this material occurs about 30 C lower than that previously found for wet titanium doped NaAlH{sub 4}. In further contrast to wet doped NaAlH{sub 4}, the dehydrogenation kinetics and hydrogen capacity of the novel material are undiminished over several dehydriding/hydriding cycles. Rehydrogenation of the titanium doped material occurs readily at 170 C under 150 atm of hydrogen. TPD measurements show that about 80% of the original hydrogen content (4.2 wt%) can be restored under these conditions.

Renewable carbohydrates are a potential high-density hydrogen carrier

Energy Technology Data Exchange (ETDEWEB)

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

2010-10-15

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

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...

Lactic acid and hydrogen from glycerol via acceptorless dehydrogenation using homogeneous catalysts

NARCIS (Netherlands)

Bottari, Giovanni; Barta, Katalin

2015-01-01

Acceptorless dehydrogenation of alcohols has emerged as a powerful methodology for the valorization of biomass derived platform chemicals and building blocks. In this review we provide a short overview of the advantages and possible product outcomes of this method. The main focus will be devoted to

Phase transition and hydrogen storage properties of Mg–Ga alloy

International Nuclear Information System (INIS)

Wu, Daifeng; Ouyang, Liuzhang; Wu, Cong; Wang, Hui; Liu, Jiangwen; Sun, Lixian; Zhu, Min

2015-01-01

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 5 Ga 2 compound is expressed as: Mg 5 Ga 2 + H 2 ↔ 2Mg 2 Ga + MgH 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 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 2 and Mg 5 Ga 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 2 . During the dehydrogenation process of Mg–Ga alloy, Mg 2 Ga reacts with MgH 2 , initially releasing H 2 and forming Mg 5 Ga 2 ; subsequently, MgH 2 decomposes into Mg with further release of H 2 . The phase transition mechanism of the Mg 5 Ga 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

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.

Development of the ReaxFFCBN reactive force field for the improved design of liquid CBN hydrogen storage materials.

Science.gov (United States)

Pai, Sung Jin; Yeo, Byung Chul; Han, Sang Soo

2016-01-21

Liquid CBN (carbon-boron-nitrogen) hydrogen-storage materials such as 3-methyl-1,2-BN-cyclopentane have the advantage of being easily accessible for use in current liquid-fuel infrastructure. To develop practical liquid CBN hydrogen-storage materials, it is of great importance to understand the reaction pathways of hydrogenation/dehydrogenation in the liquid phase, which are difficult to discover by experimental methods. Herein, we developed a reactive force field (ReaxFFCBN) from quantum mechanical (QM) calculations based on density functional theory for the storage of hydrogen in BN-substituted cyclic hydrocarbon materials. The developed ReaxFFCBN provides similar dehydrogenation pathways and energetics to those predicted by QM calculations. Moreover, molecular dynamics (MD) simulations with the developed ReaxFFCBN can predict the stability and dehydrogenation behavior of various liquid CBN hydrogen-storage materials. Our simulations reveal that a unimolecular dehydrogenation mechanism is preferred in liquid CBN hydrogen-storage materials. However, as the temperature in the simulation increases, the contribution of a bimolecular dehydrogenation mechanism also increases. Moreover, our ReaxFF MD simulations show that in terms of thermal stability and dehydrogenation kinetics, liquid CBN materials with a hexagonal structure are more suitable materials than those with a pentagonal structure. We expect that the developed ReaxFFCBN could be a useful protocol in developing novel liquid CBN hydrogen-storage materials.

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.

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; Zeng, Gaofeng; Lai, Zhiping; Huang, Kuo-Wei

2016-01-01

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.

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

KAUST Repository

Jang, Ji-Wook; Friedrich, Dennis; Mü ller, Sö nke; Lamers, Marlene; Hempel, Hannes; Lardhi, Sheikha F.; Cao, Zhen; Harb, Moussab; Cavallo, Luigi; Heller, René ; Eichberger, Rainer; van de Krol, Roel; Abdi, Fatwa F.

2017-01-01

and are relatively cheap, are particularly interesting, but high efficiency is still hindered by the poor carrier transport properties (i.e., carrier mobility and lifetime). Here, a mild hydrogen treatment is introduced to bismuth vanadate (BiVO4), which is one

Shale gas opportunities. Dehydrogenation of light alkanes

Energy Technology Data Exchange (ETDEWEB)

Patcas, F.C.; Dieterle, M.; Rezai, A.; Asprion, N. [BASF SE, Ludwigshafen (Germany)

2013-11-01

The discovery and use of shale gas in North America has become a game changer for the chemical industry by access to a cheaper feedstock compared to conventional oil. Increased number of ethane crackers spurred increasing interest in light alkanes dehydrogenation. Several companies have announced their interest in new propane dehydrogenation units in North America. BASF is developing light alkanes dehydrogenation technologies for two decades now. BASF developed jointly with Linde the isothermal C3 dehydrogenation process. The latest dehydrogenation catalyst development at BASF focused on a supported and steam resistant Pt-Sn catalyst which yielded excellent selectivity and activity. Intense research work both internally as well as in cooperation with universities contributed to the understanding of the relationship between the surface structure and catalyst performances like activity, selectivity and coking resistance. Using such type of catalysts BASF developed an autothermal propane dehydrogenation as well as a butane dehydrogenation process. The most recent catalyst development was a dehydrogenation catalyst coated on a honeycomb monolith to improve catalyst usage and pressure drop. This will probably be the first industrial usage of catalytic monoliths in a chemical synthesis process. (orig.) (Published in summary form only)

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.

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.

Tin and tin-titanium as catalyst components for reversible hydrogen storage of sodium aluminium hydride

Energy Technology Data Exchange (ETDEWEB)

Qi Jia Fu; Shik Chi Tsang [University of Reading, Reading (United Kingdom). Surface and Catalysis Research Centre, School of Chemistry

2006-10-15

This paper is concerned with the effects of adding tin and/or titanium dopant to sodium aluminium hydride for both dehydrogenation and re-hydrogenation reactions during their reversible storage of molecular hydrogen. Temperature programmed decomposition (TPD) measurements show that the dehydrogenation kinetics of NaAlH{sub 4} are significantly enhanced upon doping the material with 2 mol% of tributyltin hydride, Sn(Bu)3H but the tin catalyst dopant is shown to be inferior than titanium. On the other hand, in this preliminary work, a significant synergetic catalytic effect is clearly revealed in material co-doped with both titanium and tin catalysts which shows the highest reversible rates of dehydrogenation and re-hydrogenation (after their hydrogen depletion). The re-hydrogenation rates of depleted Sn/Ti/NaAlH{sub 4} evaluated at both 9.5 and 140 bars hydrogen are also found to be favourable compared to the Ti/NaAlH{sub 4}, which clearly suggest the importance of the catalyst choice. Basing on these results some mechanistic insights for the catalytic reversible dehydrogenation and re-hydrogenation processes of Sn/Ti/NaAlH{sub 4} are therefore made. 31 refs., 8 figs., 2 tabs.

Renewable energy carriers: Hydrogen or liquid air/nitrogen?

International Nuclear Information System (INIS)

Li Yongliang; Chen Haisheng; Zhang Xinjing; Tan Chunqing; Ding Yulong

2010-01-01

The world's energy demand is met mainly by the fossil fuels today. The use of such fuels, however, causes serious environmental issues, including global warming, ozone layer depletion and acid rains. A sustainable solution to the issues is to replace the fossil fuels with renewable ones. Implementing such a solution, however, requires overcoming a number of technological barriers including low energy density, intermittent supply and mobility of the renewable energy sources. A potential approach to overcoming these barriers is to use an appropriate energy carrier, which can store, transport and distribute energy. The work to be reported in this paper aims to assess and compare a chemical energy carrier, hydrogen, with a physical energy carrier, liquid air/nitrogen, and discuss potential applications of the physical carrier. The ocean energy is used as an example of the renewable energy sources in the work. The assessment and comparison are carried out in terms of the overall efficiency, including production, storage/transportation and energy extraction. The environmental impact, waste heat recovery and safety issues are also considered. It is found that the physical energy carrier may be a better alternative to the chemical energy carrier under some circumstances, particularly when there are waste heat sources.

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

International Nuclear Information System (INIS)

Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al_2O_3 model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al_2O_3 catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al_2O_3 model catalyst and core–shell pellet were only

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

Energy Technology Data Exchange (ETDEWEB)

Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al{sub 2}O{sub 3} model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al{sub 2}O{sub 3} catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al{sub 2}O{sub 3} model catalyst and

Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

Energy Technology Data Exchange (ETDEWEB)

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

2015-12-15

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

In Pursuit of Sustainable Hydrogen Storage with Boron-Nitride Fullerene as the Storage Medium.

Science.gov (United States)

Ganguly, Gaurab; Malakar, Tanmay; Paul, Ankan

2016-06-22

Using well calibrated DFT studies we predict that experimentally synthesized B24 N24 fullerene can serve as a potential reversible chemical hydrogen storage material with hydrogen-gas storage capacity up to 5.13 wt %. Our theoretical studies show that hydrogenation and dehydrogenation of the fullerene framework can be achieved at reasonable rates using existing metal-free hydrogenating agents and base metal-containing dehydrogenation catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method and system for hydrogen evolution and storage

Science.gov (United States)

Thorn, David L.; Tumas, William; Hay, P. Jeffrey; Schwarz, Daniel E.; Cameron, Thomas M.

2012-12-11

A method and system for storing and evolving hydrogen (H.sub.2) employ chemical compounds that can be hydrogenated to store hydrogen and dehydrogenated to evolve hydrogen. A catalyst lowers the energy required for storing and evolving hydrogen. The method and system can provide hydrogen for devices that consume hydrogen as fuel.

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

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.

Renewable Hydrogen Carrier — Carbohydrate: Constructing the Carbon-Neutral Carbohydrate Economy

Directory of Open Access Journals (Sweden)

Y.-H. Percival Zhang

2011-01-01

Full Text Available The hydrogen economy presents an appealing energy future but its implementation must solve numerous problems ranging from low-cost sustainable production, high-density storage, costly infrastructure, to eliminating safety concern. The use of renewable carbohydrate as a high-density hydrogen carrier and energy source for hydrogen production is possible due to emerging cell-free synthetic biology technology—cell-free synthetic pathway biotransformation (SyPaB. Assembly of numerous enzymes and co-enzymes in vitro can create complicated set of biological reactions or pathways that microorganisms or catalysts cannot complete, for example, C6H10O5 (aq + 7 H2O (l à 12 H2 (g + 6 CO2 (g (PLoS One 2007, 2:e456. Thanks to 100% selectivity of enzymes, modest reaction conditions, and high-purity of generated hydrogen, carbohydrate is a promising hydrogen carrier for end users. Gravimetric density of carbohydrate is 14.8 H2 mass% if water can be recycled from proton exchange membrane fuel cells or 8.33% H2 mass% without water recycling. Renewable carbohydrate can be isolated from plant biomass or would be produced from a combination of solar electricity/hydrogen and carbon dioxide fixation mediated by high-efficiency artificial photosynthesis mediated by SyPaB. The construction of this carbon-neutral carbohydrate economy would address numerous sustainability challenges, such as electricity and hydrogen storage, CO2 fixation and long-term storage, water conservation, transportation fuel production, plus feed and food production.

Dehydrogenation of benzene on Pt(111) surface

Science.gov (United States)

Gao, W.; Zheng, W. T.; Jiang, Q.

2008-10-01

The dehydrogenation of benzene on Pt(111) surface is studied by ab initio density functional theory. The minimum energy pathways for benzene dehydrogenation are found with the nudge elastic band method including several factors of the associated barriers, reactive energies, intermediates, and transient states. The results show that there are two possible parallel minimum energy pathways on the Pt(111) surface. Moreover, the tilting angle of the H atom in benzene can be taken as an index for the actual barrier of dehydrogenation. In addition, the properties of dehydrogenation radicals on the Pt(111) surface are explored through their adsorption energy, adsorption geometry, and electronic structure on the surface. The vibrational frequencies of the dehydrogenation radicals derived from the calculations are in agreement with literature data.

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.

Dehydrogenative Diels-Alder reaction.

Science.gov (United States)

Ozawa, Takuya; Kurahashi, Takuya; Matsubara, Seijiro

2011-10-07

The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur. © 2011 American Chemical Society

Key study on the potential of hydrazine bisborane for solid- and liquid-state chemical hydrogen storage.

Science.gov (United States)

Pylypko, Sergii; Petit, Eddy; Yot, Pascal G; Salles, Fabrice; Cretin, Marc; Miele, Philippe; Demirci, Umit B

2015-05-04

Hydrazine bisborane N2H4(BH3)2 (HBB; 16.8 wt %) recently re-emerged as a potential hydrogen storage material. However, such potential is controversial: HBB was seen as a hazardous compound up to 2010, but now it would be suitable for hydrogen storage. In this context, we focused on fundamentals of HBB because they are missing in the literature and should help to shed light on its effective potential while taking into consideration any risk. Experimental/computational methods were used to get a complete characterization data sheet, including, e.g., XRD, NMR, FTIR, Raman, TGA, and DSC. From the reported results and discussion, it is concluded that HBB has potential in the field of chemical hydrogen storage given that both thermolytic and hydrolytic dehydrogenations were analyzed. In solid-state chemical hydrogen storage, it cannot be used in the pristine state (risk of explosion during dehydrogenation) but can be used for the synthesis of derivatives with improved dehydrogenation properties. In liquid-state chemical hydrogen storage, it can be studied for room-temperature dehydrogenation, but this requires the development of an active and selective metal-based catalyst. HBB is a thus a candidate for chemical hydrogen storage.

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.

Hydrogenation properties of pure magnesium and magnesium-aluminium thin films

Energy Technology Data Exchange (ETDEWEB)

Domenech-Ferrer, Roger; Gurusamy Sridharan, Madana; Garcia, Gemma; Pi, Francesc; Rodriguez-Viejo, Javier [Departament de Fisica, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain)

2007-06-10

We have studied the hydrogenation/dehydrogenation behaviour of multilayered stacks of Pd/Mg/Pd and Pd-Fe(Ti)-Mg-Al-Mg-Fe(Ti)-Pd grown by electron beam physical vapour deposition. The palladium coating was deposited at both sides of the structure to ensure a fast dissociation rate and good transport properties for hydrogen as well as to avoid oxidation of magnesium either from atmosphere as from the substrate surface. Fe and Ti layers were included in the stack composition in order to assess their possible catalyst effect as well as to prevent the formation of Mg{sub x}Pd{sub y} intermetallics during the thermal treatments. We have studied the structure evolution after thermal treatments as well as after the hydrogenation and dehydrogenation processes using XRD. We have also followed the reactions kinetics by resistometry and differential scanning calorimetry. The nanostructured Mg films have been hydrogenated at temperature as low as 50 C in few minutes. Adding aluminium to magnesium has improved its hydrogenation capacity. We have also observed that the formation of an Mg{sub x}Al{sub y} intermetallic before hydrogenation improves the storage capacity. We have confirmed that titanium is a better catalyst for the hydrogenation/dehydrogenation of the Mg films. (author)

Non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} on dehydrogenation high-energy ball milled MgH{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Hou, Xiaojiang; Hu, Rui; Kou, Hongchao; Li, Jinshan

2016-11-01

MgH{sub 2}-M (M = TiF{sub 3} or Nb{sub 2}O{sub 5} or both of them) composites prepared by high-energy ball milling are used in this work to illustrate the dehydrogenation behavior of MgH{sub 2} with the addition of catalysts. The phase compositions, microstructures, particle morphologies and distributions of MgH{sub 2} with catalysts have been evaluated. The non-isothermal synergetic catalytic-dehydrogenation effect of TiF{sub 3} and Nb{sub 2}O{sub 5} evaluated by differential scanning calorimetry gives the evidences that the addition of catalysts is an effective strategy to destabilize MgH{sub 2} and reduce hydrogen desorption temperatures and activation energies. Depending on additives, the desorption peak temperatures of catalyzed MgH{sub 2} reduce from 417 °C to 341 °C for TiF{sub 3} and from 417 °C to 336 °C for Nb{sub 2}O{sub 5}, respectively. The desorption peak temperature reaches as low as 310 °C for MgH{sub 2} catalyzed by TiF{sub 3} coupling with Nb{sub 2}O{sub 5}. The non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} is mainly attributed to electronic exchange reactions with hydrogen molecules, which improve the recombination of hydrogen atoms during dehydrogenation process of MgH{sub 2}. - Highlights: • Catalytic surface for MgH{sub 2} is achieved by high-energy ball milling. • Non-isothermal dehydrogenation behavior of MgH{sub 2} with TiF{sub 3} and/or Nb{sub 2}O{sub 5} is illustrated. • Dehydrogenation activation energies of synergetic catalyzed MgH{sub 2} are obtained. • Synergetic catalytic-dehydrogenation mechanism of TiF{sub 3} and Nb{sub 2}O{sub 5} is proposed.

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

Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.

Science.gov (United States)

Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-García, Alfredo; Martínez, Ana; Rayner, David M

2005-08-18

Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of

Nanodiamond for hydrogen storage: temperature-dependent hydrogenation and charge-induced dehydrogenation.

Science.gov (United States)

Lai, Lin; Barnard, Amanda S

2012-02-21

Carbon-based hydrogen storage materials are one of hottest research topics in materials science. Although the majority of studies focus on highly porous loosely bound systems, these systems have various limitations including use at elevated temperature. Here we propose, based on computer simulations, that diamond nanoparticles may provide a new promising high temperature candidate with a moderate storage capacity, but good potential for recyclability. The hydrogenation of nanodiamonds is found to be easily achieved, in agreement with experiments, though we find the stability of hydrogenation is dependent on the morphology of nanodiamonds and surrounding environment. Hydrogenation is thermodynamically favourable even at high temperature in pure hydrogen, ammonia, and methane gas reservoirs, whereas water vapour can help to reduce the energy barrier for desorption. The greatest challenge in using this material is the breaking of the strong covalent C-H bonds, and we have identified that the spontaneous release of atomic hydrogen may be achieved through charging of hydrogenated nanodiamonds. If the degree of induced charge is properly controlled, the integrity of the host nanodiamond is maintained, which indicates that an efficient and recyclable approach for hydrogen release may be possible. This journal is © The Royal Society of Chemistry 2012

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.

Promoting effect of active carbons on methanol dehydrogenation on sodium carbonate - hydrogen spillover

OpenAIRE

Su, S.; Prairie, M.; Renken, A.

1993-01-01

Methanol dehydrogenation to formaldehyde was conducted in a fixed-bed flow reactor with sodium carbonate catalyst mixed with active carbons or transition metals. The additives promoted the reaction rate at 880-970 K without modifying formaldehyde selectivity. This effect increases with increasing carbon content in the carbon-carbonate mixture. Activation energy of methanol conversion is the same for the mixture and the carbonate alone. Temperature-programmed desorption experiments showed that...

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

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

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

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

Ocean thermal plantships for production of ammonia as the hydrogen carrier.

Energy Technology Data Exchange (ETDEWEB)

Panchal, C.B.; Pandolfini, P. P.; Kumm, W. H.; Energy Systems; Johns Hopkins Univ.; Arctic Energies, Ltd.

2009-12-02

Conventional petroleum, natural gas, and coal are the primary sources of energy that have underpinned modern civilization. Their continued availability in the projected quantities required and the impacts of emission of greenhouse gases (GHGs) on the environment are issues at the forefront of world concerns. New primary sources of energy are being sought that would significantly reduce the emissions of GHGs. One such primary source that can help supply energy, water, and fertilizer without GHG emissions is available in the heretofore unexploited thermal gradients of the tropical oceans. The world's oceans are the largest natural collector and reservoir of solar energy. The potential of ocean energy is limitless for producing base-load electric power or ammonia as the hydrogen carrier and fresh water from seawater. However, until now, ocean energy has been virtually untapped. The general perception is that ocean thermal energy is limited to tropical countries. Therefore, the full potential of at-sea production of (1) ammonia as a hydrogen carrier and (2) desalinated water has not been adequately evaluated. Using ocean thermal plantships for the at-sea co-production of ammonia as a hydrogen carrier and desalinated water offer potential energy, environmental, and economic benefits that support the development of the technology. The introduction of a new widespread solution to our projected energy supply requires lead times of a decade or more. Although continuation of the ocean thermal program from the 1970s would likely have put us in a mitigating position in the early 2000s, we still have a window of opportunity to dedicate some of our conventional energy sources to the development of this renewable energy by the time new sources would be critically needed. The primary objective of this project is to evaluate the technical and economic viability of ocean thermal plantships for the production of ammonia as the hydrogen carrier. This objective is achieved by

Hydrogen peroxide as a sustainable energy carrier: Electrocatalytic production of hydrogen peroxide and the fuel cell

International Nuclear Information System (INIS)

Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.

2012-01-01

This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal–oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

Science.gov (United States)

Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

2012-11-01

This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

Hydrogen as an energy carrier and its production by nuclear power

International Nuclear Information System (INIS)

1999-05-01

The impact of power generation on environment is becoming an ever increasing concern in decision making when considering the energy options and power systems required by a country in order to sustain its economic growth and development. Hydrogen is a strong emerging candidate with a significant role as a clean, environmentally benign and safe to handle major energy carrier in the future. Its enhanced utilization in distributed power generation as well as in propulsion systems for mobile applications will help to significantly mitigate the strong negative effects on the environment. It ia also the nuclear power that will be of utmost importance in the energy supply of many countries over the next decades. The development of new, innovative reactor concepts utilizing passive safety features for process heat and electricity generation are considered by many to play a substantial role in the world's energy future in helping to reduce greenhouse gas emissions. This report produced by IAEA documents past and current activities in Member States in the development of hydrogen production as an energy carrier and its corresponding production through the use of nuclear power. It provides an introduction to nuclear technology as a means of producing hydrogen or other upgraded fuels and to the energy carries hydrogen and its main fields of application. Emphasis is placed on high-temperature reactor technology which can achieve the simultaneous generation of electricity and the production of high-temperature process heat

Hydrogen as an energy carrier and its production by nuclear power

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-05-01

The impact of power generation on environment is becoming an ever increasing concern in decision making when considering the energy options and power systems required by a country in order to sustain its economic growth and development. Hydrogen is a strong emerging candidate with a significant role as a clean, environmentally benign and safe to handle major energy carrier in the future. Its enhanced utilization in distributed power generation as well as in propulsion systems for mobile applications will help to significantly mitigate the strong negative effects on the environment. It ia also the nuclear power that will be of utmost importance in the energy supply of many countries over the next decades. The development of new, innovative reactor concepts utilizing passive safety features for process heat and electricity generation are considered by many to play a substantial role in the world`s energy future in helping to reduce greenhouse gas emissions. This report produced by IAEA documents past and current activities in Member States in the development of hydrogen production as an energy carrier and its corresponding production through the use of nuclear power. It provides an introduction to nuclear technology as a means of producing hydrogen or other upgraded fuels and to the energy carries hydrogen and its main fields of application. Emphasis is placed on high-temperature reactor technology which can achieve the simultaneous generation of electricity and the production of high-temperature process heat Refs, figs, tabs

Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N-C for Hydrogen Storage in NaAlH4.

Science.gov (United States)

Zhang, Xin; Ren, Zhuanghe; Lu, Yunhao; Yao, Jianhua; Gao, Mingxia; Liu, Yongfeng; Pan, Hongge

2018-05-09

Herein, we synthesize successfully ultrafine TiN nanoparticles (hydrogen storage in NaAlH 4 . Adding 7 wt % nano-TiN@N-C induces more than 100 °C reduction in the onset dehydrogenation temperature of NaAlH 4 . Approximately 4.9 wt % H 2 is rapidly released from the 7 wt % nano-TiN@N-C-containing NaAlH 4 at 140 °C within 60 min, and the dehydrogenation product is completely hydrogenated at 100 °C within 15 min under 100 bar of hydrogen, exhibiting significantly improved desorption/absorption kinetics. No capacity loss is observed for the nano-TiN@N-C-containing sample within 25 de-/hydrogenation cycles because nano-TiN functions as an active catalyst instead of a precursor. A severe structural distortion with extended bond lengths and reduced bond strengths for Al-H bonding when the [AlH 4 ] - group adsorbs on the TiN cluster is demonstrated for the first time by density functional theory calculations, which well-explains the reduced de-/hydrogenation temperatures of the nano-TiN@N-C-containing NaAlH 4 . These findings provide new insights into designing and synthesizing high-performance catalysts for hydrogen storage in complex hydrides.

Assessment of the potential future market in Sweden for hydrogen as an energy carrier

Science.gov (United States)

Carleson, G.

Future hydrogen markets for the period 1980-2025 are projected, the probable range of hydrogen production costs for various manufacturing methods is estimated, and expected market shares in competition with alternative energy carriers are evaluated. A general scenario for economic and industrial development in Sweden for the given period was evaluated, showing the average increase in gross national product to become 1.6% per year. Three different energy scenarios were then developed: alternatives were based on nuclear energy, renewable indigenous energy sources, and the present energy situation with free access to imported natural or synthetic fuels. An analysis was made within each scenario of the competitiveness of hydrogen on both the demand and the supply of the following sectors: chemical industry, steel industry, peak power production, residential and commercial heating, and transportation. Costs were calculated for the production, storage and transmission of hydrogen according to technically feasible methods and were compared to those of alternative energy carriers. Health, environmental and societal implications were also considered. The market penetration of hydrogen in each sector was estimated, and the required investment capital was shown to be less than 4% of the national gross investment sum.

Screening based approach and dehydrogenation kinetics for MgH2: Guide to find suitable dopant using first-principles approach.

Science.gov (United States)

Kumar, E Mathan; Rajkamal, A; Thapa, Ranjit

2017-11-14

First-principles based calculations are performed to investigate the dehydrogenation kinetics considering doping at various layers of MgH 2 (110) surface. Doping at first and second layer of MgH 2 (110) has a significant role in lowering the H 2 desorption (from surface) barrier energy, whereas the doping at third layer has no impact on the barrier energy. Molecular dynamics calculations are also performed to check the bonding strength, clusterization, and system stability. We study in details about the influence of doping on dehydrogenation, considering the screening factors such as formation enthalpy, bulk modulus, and gravimetric density. Screening based approach assist in finding Al and Sc as the best possible dopant in lowering of desorption temperature, while preserving similar gravimetric density and Bulk modulus as of pure MgH 2 system. The electron localization function plot and population analysis illustrate that the bond between Dopant-Hydrogen is mainly covalent, which weaken the Mg-Hydrogen bonds. Overall we observed that Al as dopant is suitable and surface doping can help in lowering the desorption temperature. So layer dependent doping studies can help to find the best possible reversible hydride based hydrogen storage materials.

Microstructural Evolution during Pressureless Sintering of Blended Elemental Ti-Al-V-Fe Titanium Alloys from Fine Hydrogenated-Dehydrogenated Titanium Powder

Directory of Open Access Journals (Sweden)

Changzhou Yu

2017-07-01

Full Text Available A comprehensive study was conducted on microstructural evolution of sintered Ti-Al-V-Fe titanium alloys utilizing very fine hydrogenation-dehydrogenation (HDH titanium powder with a median particle size of 8.84 μm. Both micropores (5–15 μm and macropores (50–200 μm were identified in sintered titanium alloys. Spherical micropores were observed in Ti-6Al-4V sintered with fine Ti at the lowest temperature of 1150 °C. The addition of iron can help reduce microporosity and improve microstructural and compositional homogenization. A theoretical calculation of evaporation based on the Miedema model and Langmuir equation indicates that the evaporation of aluminum could be responsible for the formation of the macropores. Although reasonable densification was achieved at low sintering temperatures (93–96% relative density the samples had poor mechanical properties due mainly to the presence of the macroporosity and the high inherent oxygen content in the as-received fine powders.

[Feasibility investigation of hydrogen instead of helium as carrier gas in the determination of five organophosphorus pesticides by gas chromatography-mass spectrometry].

Science.gov (United States)

Liu, Zhenxue; Zhou, Shixue

2015-01-01

Helium is almost the only choosable carrier gas used in gas chromatography-mass spectrometry (GC-MS). A mixed standard solution of five organophosphorus pesticides was analyzed by using GC-MS, and hydrogen or helium as carrier gas, so as to study the feasibility of hydrogen instead of helium as carrier gas for the determination of organophosphorus pesticides. Combining a mass spectrum database built by ourselves, the results were deconvolved and identified by Automated Mass Spectral Deconvolution & Identification System (AMDIS32), a software belonging to the workstation of the instrument. Then, the statistical software, IBM SPSS Statistics 19.0 was used for the clustering analysis of the data. The results indicated that when hydrogen was used as carrier gas, the peaks of the pesticides detected were slightly earlier than those when helium used as carrier gas, but the resolutions of the chromatographic peaks were lower, and the fraction good indices (Frac. Good) were lower, too. When hydrogen was used as carrier gas, the signals of the pesticides were unstable, the measuring accuracies of the pesticides were reduced too, and even more, some compounds were undetectable. Therefore, considering the measuring accuracy, the signal stability, and the safety, etc., hydrogen should be cautiously used as carrier gas in the determination of organophosphorus pesticides by GC-MS.

Destructive hydrogenation; dehydrogenation and dehydrogenation processes; purifying oils; polynuclear organic compounds

Energy Technology Data Exchange (ETDEWEB)

1934-02-08

Unitary organic compounds containing four or more nuclei are recovered from the high boiling fractions of destructive hydrogenation products of bituminous, resinous, or ligneous materials. Cooling, precipitation, crystallization, selective dissolution and distillation are some of the techniques discussed. These techniques may also be applied to the recovery of polynuclear compounds.

Effect of microwave irradiation on hydrogen sorption properties of hand mixed MgH{sub 2} – 10 wt.% carbon fibers

Energy Technology Data Exchange (ETDEWEB)

Awad, A.S. [Université de Bordeaux, ICMCB-CNRS, 87 Avenue du Dr Schweitzer, F-33600 Pessac (France); LCPM/PR2N, Université Libanaise, Faculté des Sciences 2, 90656 Jdeidet El Matn (Lebanon); Nakhl, M.; Zakhour, M. [LCPM/PR2N, Université Libanaise, Faculté des Sciences 2, 90656 Jdeidet El Matn (Lebanon); Santos, S.F.; Souza, F.L. [Universidade Federal do ABC, Avenida dos Estados 5001, 09210-580 Santo André – SP (Brazil); Bobet, J.-L., E-mail: jean-louis.bobet@u-bordeaux.fr [Université de Bordeaux, ICMCB-CNRS, 87 Avenue du Dr Schweitzer, F-33600 Pessac (France)

2016-08-15

The effect of microwave (MW) irradiation on the hydrogen sorption properties of magnesium powder is explored in the present work. MgH{sub 2} – 10 wt.% CFs (CFs = Carbons Fibers) was prepared by hand mixing, dehydrogenated under microwave irradiation for 20 s and then hydrogenated/dehydrogenated at about 300 °C – 1 MPa and 330 °C–0.03 MPa to investigate the effect of microwave irradiation on the solid/gas sorption properties. It has to be noted that the hydrogen absorption capacity and sorption kinetics of the MgH{sub 2} – 10 wt.% CFs mixture increased after dehydriding under MW irradiation. The MgH{sub 2} – 10 wt.% CFs mixture dehydrogenated by microwave irradiation can absorb about 5.8 wt.% and 5.3 wt.% H at 330 and 300 °C, respectively, within 2 h while the as-prepared MgH{sub 2} – 10 wt.% CFs mixture absorb only 4.6 wt.% H within the same duration. It is also demonstrated that MgH{sub 2} – 10 wt.% CFs mixture dehydrogenated by microwave irradiation exhibited good hydrogen desorption properties and, as an example, a microwave irradiated sample could release 5.8 wt.% H within 1 h at 330 °C in comparison to the as-prepared MgH{sub 2} – 10 wt.% CFs mixture which desorbed 4.4 wt.% H within 3 h. Scanning electron microscopy (SEM) images revealed that the particle sizes of the MW dehydrogenated mixture decreased after several solid/gas sorption cycles. This contribute to the improvement of hydrogen storage properties of the microwaves dehydrogenated MgH{sub 2} – 10 wt.% CFs mixture. In addition, the hydrogenated MgH{sub 2} – 10 wt.% CFs mixture show reproducible and better microwave-assisted dehydriding reaction during second microwaves cycle. - Highlights: • Dehydriding reaction of MgH{sub 2} by microwave method. • Effect of microwaves treatment on the hydrogen sorption properties of Mg. • Effect of discontinuous microwaves irradiation.

Comparative study of hydrogen and methanol as energy carriers

Energy Technology Data Exchange (ETDEWEB)

Johansson, Anna

1998-06-01

This report has been written with the purpose to compare hydrogen and methanol, with gasoline, as energy carriers for new energy systems in the future. This energy system must satisfy the demands for sustainable development. The report focuses on motor vehicle applications. A few different criteria has been developed to help form the characterisation method. The criteria proposed in this thesis are developed for an environmental comparison mainly based on emissions from combustion. The criteria concerns the following areas: Renewable resources, The ozone layer, The greenhouse effect, The acidification, and Toxic substances. In many ways, hydrogen may seem as a very good alternative compared with gasoline and diesel oil. Combustion of hydrogen in air results in water and small amounts of oxides of nitrogen. In this report, hydrogen produced from renewable resources is investigated. This is necessary to fulfill the demands for sustainable development. Today, however, steam reforming of fossil fuels represent 99% of the hydrogen production market. Problem areas connected with hydrogen use are for instance storage and distribution. Methanol has many advantages, while comparing methanol and gasoline, like lower emissions of nitrogen oxides and hydrocarbons, limited emissions of carbon dioxide and no sulphur content. Methanol can be produced from many different resources, for example natural gas, naphtha, oil, coal or peat, and biomass. To meet demands for sustainable production, methanol has to be produced from biomass Examination paper. 32 refs, 20 figs, 13 tabs

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

Science.gov (United States)

Sulaiman, N N; Ismail, M

2016-12-06

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

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).

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.

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.

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...

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 fro...

Improved hydrogen storage properties of LiAlH4 by mechanical milling with TiF3

International Nuclear Information System (INIS)

Zang, Lei; Cai, Jiaxing; Zhao, Lipeng; Gao, Wenhong; Liu, Jian; Wang, Yijing

2015-01-01

Dehydrogenation behavior of LiAlH 4 (lithium alanate) admixed with TiF 3 is investigated by pressure-composition-temperature (PCT), fourier transform infrared spectroscopy (FTIR), X-ray Diffraction (XRD), differential scanning calorimetry (DSC) and temperature programmed desorption (TPD). The TiF 3 addition enhances kinetics of LiAlH 4 and decreases the decomposition temperature. The LiAlH 4 -2 mol % TiF 3 sample starts to release hydrogen at about 35 °C and the dehydrogenation rate reaches a maximum value at 108.4 °C, compared with 145 °C and 179.9 °C for the as-received LiAlH 4 . As for the dehydrogenation kinetics, the LiAlH 4 -2 mol % TiF 3 sample releases about 7.0 wt % H 2 at 140 °C within 80 min. In comparison, the as-received LiAlH 4 sample releases only 0.8 wt % hydrogen under the same conditions. The existence of proposed catalyst, Al 3 Ti formed in-situ in the process of dehydrogenation, has been confirmed experimentally by XRD measurements. The activation energy of LiAlH 4 -2 mol % TiF 3 composite is deduced to be 66.76 kJ mol −1 and 88.21 kJ mol −1 for the first and second reaction stages of LiAlH 4 dehydrogenation. - Highlights: • TiF 3 considerably enhances the dehydrogenation kinetics of LiAlH 4 . • TiF 3 -doped LiAlH 4 dehydrogenates even at room temperature. • Low activation energy of the dehydrogenation reaction. • Al 3 Ti formed in-situ helps to explain the dehydrogenation mechanism

Scandium and vanadium borohydride ammoniates: Enhanced dehydrogenation behavior upon coordinative expansion and establishment of Hδ+⋯−δH interactions

International Nuclear Information System (INIS)

Tang, Ziwei; Yuan, Feng; Gu, Qinfen; Tan, Yingbin; Chen, Xiaowei; Jensen, Craig M.; Yu, Xuebin

2013-01-01

Graphical abstract: Two novel metal borohydride ammoniates—ScLi(BH 4 ) 4 ·4NH 3 and V(BH 4 ) 3 ·3NH 3 are shown to exhibit superior dehydrogenation performances established upon intensive interactions and balanced stoichiometry of dihydrogen. -- Abstract: LiSc(BH 4 ) 4 ·4NH 3 and V(BH 4 ) 3 ·3NH 3 , two novel metal borohydride ammoniates (MBAs), have been successfully synthesized via ball-milling the mixtures of MCl 3 ·xNH 3 (M = Sc, V and x = 3, 4) with LiBH 4 . Structure analysis reveals that LiSc(BH 4 ) 4 ·4NH 3 crystallizes in an orthorhombic structure with lattice parameters of a = 7.4376(3) Å, b = 11.1538(5) Å and c = 14.5132(7) Å and space group of Pc2 1 n, in which the base octahedral units are composed of central metal and an equivalent number of BH 4 and NH 3 units, distinct from other reported MBAs. Base units with the above constitution are also observed in the crystal structure of V(BH 4 ) 3 ·3NH 3 , which is identified as a cubic structure with lattice parameters of a = 10.78060(25) Å and space group of F23. These two compounds exhibit a favorable dehydrogenation capability, releasing 15.1 and 14.3 wt.% high-purity hydrogen, respectively, below 300 °C. Isothermal measurements reveal that, at a constant temperature of 110 °C, which meets the operation requirement of fuel cells, >8 and >10 wt.% pure hydrogen is released from the two compounds with favorable kinetics, respectively. Moreover, by reacting with N 2 H 4 in liquid ammonia, the decomposed LiSc(BH 4 ) 4 ·4NH 3 can be partly hydrogenated and can possibly establish a system that will undergo reversible dehydrogenation. These favorable properties point to potential on-board application. The dehydrogenation capacity, purity and temperature of the two systems can be adjusted, by tuning the ratios of the starting reagents LiBH 4 and MCl 3 ·xNH 3 , to achieve expected stoichiometric proportions of BH 4 and NH 3 units, which provides a facile and viable strategy for the synthesis of

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...

Nanoconfinement in activated mesoporous carbon of calcium borohydride for improved reversible hydrogen storage.

Science.gov (United States)

Comănescu, Cezar; Capurso, Giovanni; Maddalena, Amedeo

2012-09-28

Mesoporous carbon frameworks were synthesized using the soft-template method. Ca(BH(4))(2) was incorporated into activated mesoporous carbon by the incipient wetness method. The activation of mesoporous carbon was necessary to optimize the surface area and pore size. Thermal programmed absorption measurements showed that the confinement of this borohydride into carbon nanoscaffolds improved its reversible capacity (relative to the reactive portion) and performance of hydrogen storage compared to unsupported borohydride. Hydrogen release from the supported hydride started at a temperature as low as 100 °C and the dehydrogenation rate was fast compared to the bulk borohydride. In addition, the hydrogen pressure necessary to regenerate the borohydride from the dehydrogenation products was reduced.

Hydrogen as fuel carrier in PEM fuelcell for automobile applications

Science.gov (United States)

Sk, Mudassir Ali; Venkateswara Rao, K.; Ramana Rao, Jagirdar V.

2015-02-01

The present work focuses the application of nanostructured materials for storing of hydrogen in different carbon materials by physisorption method. To market a hydrogen-fuel cell vehicle as competitively as the present internal combustion engine vehicles, there is a need for materials that can store a minimum of 6.5wt% of hydrogen. Carbon materials are being heavily investigated because of their promise to offer an economical solution to the challenge of safe storage of large hydrogen quantities. Hydrogen is important as a new source of energy for automotive applications. It is clear that the key challenge in developing this technology is hydrogen storage. Combustion of fossil fuels and their overuse is at present a serious concern as it is creates severe air pollution and global environmental problems; like global warming, acid rains, ozone depletion in stratosphere etc. This necessitated the search for possible alternative sources of energy. Though there are a number of primary energy sources available, such as thermonuclear energy, solar energy, wind energy, hydropower, geothermal energy etc, in contrast to the fossil fuels in most cases, these new primary energy sources cannot be used directly and thus they must be converted into fuels, that is to say, a new energy carrier is needed. Hydrogen fuel cells are two to three times more efficient than combustion engines. As they become more widely available, they will reduce dependence on fossil fuels. In a fuel cell, hydrogen and oxygen are combined in an electrochemical reaction that produces electricity and, as a byproduct, water.

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℃.

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.

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

Science.gov (United States)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

Confined NaAlH4 nanoparticles inside CeO2 hollow nanotubes towards enhanced hydrogen storage.

Science.gov (United States)

Gao, Qili; Xia, Guanglin; Yu, Xuebin

2017-10-05

NaAlH 4 has been widely regarded as a potential hydrogen storage material due to its favorable thermodynamics and high energy density. The high activation energy barrier and high dehydrogenation temperature, however, significantly hinder its practical application. In this paper, CeO 2 hollow nanotubes (HNTs) prepared by a simple electrospinning technique are adopted as functional scaffolds to support NaAlH 4 nanoparticles (NPs) towards advanced hydrogen storage performance. The nanoconfined NaAlH 4 inside CeO 2 HNTs, synthesized via the infiltration of molten NaAlH 4 into the CeO 2 HNTs under high hydrogen pressure, exhibited significantly improved dehydrogenation properties compared with both bulk and ball-milled CeO 2 HNTs-catalyzed NaAlH 4 . The onset dehydrogenation temperature of the NaAlH 4 @CeO 2 composite was reduced to below 100 °C, with only one main dehydrogenation peak appearing at 130 °C, which is 120 °C and 50 °C lower than for its bulk counterpart and for the ball-milled CeO 2 HNTs-catalyzed NaAlH 4 , respectively. Moreover, ∼5.09 wt% hydrogen could be released within 30 min at 180 °C, while only 1.6 wt% hydrogen was desorbed from the ball-milled NaAlH 4 under the same conditions. This significant improvement is mainly attributed to the synergistic effects contributed by the CeO 2 HNTs, which could act as not only a structural scaffold to fabricate and confine the NaAlH 4 NPs, but also as an effective catalyst to enhance the hydrogen storage performance of NaAlH 4 .

Economic impacts of hydrogen as an energy carrier in European countries

International Nuclear Information System (INIS)

Wietschel, Martin; Seydel, Philipp

2007-01-01

The two objectives of this paper are to identify possible sectoral shifts and employment effects due to the application of hydrogen in the energy system for selected European countries till 2030. This is based on assumptions about the market penetration of hydrogen as an energy carrier, an analysis of the competitiveness of EU countries in this technology field and input-output model calculations. The analysis showed that the introduction of hydrogen leads to significant shifts between economic sectors and, as a policy recommendation, it is concluded that the required workforce skills in hydrogen technologies should be available in time in order to be properly prepared for this. Some employment gains are possible for the EU Member States analysed if the introduction of hydrogen does not result in significant changes in export/import flows. However, the lead market analysis also showed that the competitiveness of EU countries varies significantly and that, viewed as a whole, Europe is in danger of falling behind its main competitors. This may lead to job losses because the industry branches affected - automotive and plant manufacturers - represent key sectors for the EU. One policy goal, therefore, especially for countries with a large share of automobile and plant manufacturing, is to aim to be a lead market for hydrogen and fuel cells. (author)

Synthesis and electrochemical properties of binary MgTi and ternary MgTiX (X=Ni, Si) hydrogen storage alloys

NARCIS (Netherlands)

Gobichettipalayam Manivasagam, T.; Iliksu, M.; Danilov, D.L.; Notten, P.H.L.

2017-01-01

Mg-based hydrogen storage alloys are promising candidate for many hydrogen storage applications because of the high gravimetric hydrogen storage capacity and favourable (de)hydrogenation kinetics. In the present study we have investigated the synthesis and electrochemical hydrogen storage properties

Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

Directory of Open Access Journals (Sweden)

Aghamammadova S.

2016-01-01

Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

Sodium hydrazinidoborane: a chemical hydrogen-storage material.

Science.gov (United States)

Moury, Romain; Demirci, Umit B; Ichikawa, Takayuki; Filinchuk, Yaroslav; Chiriac, Rodica; van der Lee, Arie; Miele, Philippe

2013-04-01

Herein, we present the successful synthesis and full characterization (by (11) B magic-angle-spinning nuclear magnetic resonance spectroscopy, infrared spectroscopy, powder X-ray diffraction) of sodium hydrazinidoborane (NaN2 H3 BH3 , with a hydrogen content of 8.85 wt %), a new material for chemical hydrogen storage. Using lab-prepared pure hydrazine borane (N2 H4 BH3 ) and commercial sodium hydride as precursors, sodium hydrazinidoborane was synthesized by ball-milling at low temperature (-30 °C) under an argon atmosphere. Its thermal stability was assessed by thermogravimetric analysis and differential scanning calorimetry. It was found that under heating sodium hydrazinidoborane starts to liberate hydrogen below 60 °C. Within the range of 60-150 °C, the overall mass loss is as high as 7.6 wt %. Relative to the parent N2 H4 BH3 , sodium hydrazinidoborane shows improved dehydrogenation properties, further confirmed by dehydrogenation experiments under prolonged heating at constant temperatures of 80, 90, 95, 100, and 110 °C. Hence, sodium hydrazinidoborane appears to be more suitable for chemical hydrogen storage than N2 H4 BH3 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NARCIS (Netherlands)

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

2009-01-01

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

Activity and stability of a <> oxynitride in the dehydrogenation of isobutane

Energy Technology Data Exchange (ETDEWEB)

Delsarte, S.; Grange, P. [Univ. Catholique de Louvain (Belgium). Unite de Catalyse et Chimie des Materiaux Divises; Laurent, Y. [Lab. de Chimie des Materiaux, Univ. de Rennes 1, Rennes (France)

2000-07-01

Isobutane dehydrogenation was studied on platinum impregnated mixed aluminium gallium phosphorus oxide and oxynitride, in a continuous, flow micro-reactor at 500-550 C. Comparison of the <> and <> shows the importance of nitridation on the acido-basic properties of the catalyst. A deactivation of the catalyst, due to the deposition of carbonaceous species on the surface, was observed. As the properties of the oxynitride would be altered by a regeneration treatment at high temperature with flowing oxygen, the possibility of decreasing the deactivation rate by decreasing the reaction temperature and by adding hydrogen to the reactant mixture was explored. Catalytic tests, carried out at different hydrogen partial pressures, showed that the hydrogen inhibits the carbon deposition on the surface of the catalyst and thus increases the catalytic stability. (orig.)

Improved hydrogen storage properties of LiAlH{sub 4} by mechanical milling with TiF{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Zang, Lei; Cai, Jiaxing; Zhao, Lipeng; Gao, Wenhong; Liu, Jian, E-mail: liujian@nankai.eud.cn; Wang, Yijing

2015-10-25

Dehydrogenation behavior of LiAlH{sub 4} (lithium alanate) admixed with TiF{sub 3} is investigated by pressure-composition-temperature (PCT), fourier transform infrared spectroscopy (FTIR), X-ray Diffraction (XRD), differential scanning calorimetry (DSC) and temperature programmed desorption (TPD). The TiF{sub 3} addition enhances kinetics of LiAlH{sub 4} and decreases the decomposition temperature. The LiAlH{sub 4}-2 mol % TiF{sub 3} sample starts to release hydrogen at about 35 °C and the dehydrogenation rate reaches a maximum value at 108.4 °C, compared with 145 °C and 179.9 °C for the as-received LiAlH{sub 4}. As for the dehydrogenation kinetics, the LiAlH{sub 4}-2 mol % TiF{sub 3} sample releases about 7.0 wt % H{sub 2} at 140 °C within 80 min. In comparison, the as-received LiAlH{sub 4} sample releases only 0.8 wt % hydrogen under the same conditions. The existence of proposed catalyst, Al{sub 3}Ti formed in-situ in the process of dehydrogenation, has been confirmed experimentally by XRD measurements. The activation energy of LiAlH{sub 4}-2 mol % TiF{sub 3} composite is deduced to be 66.76 kJ mol{sup −1} and 88.21 kJ mol{sup −1} for the first and second reaction stages of LiAlH{sub 4} dehydrogenation. - Highlights: • TiF{sub 3} considerably enhances the dehydrogenation kinetics of LiAlH{sub 4}. • TiF{sub 3}-doped LiAlH{sub 4} dehydrogenates even at room temperature. • Low activation energy of the dehydrogenation reaction. • Al{sub 3}Ti formed in-situ helps to explain the dehydrogenation mechanism.

Influence of preparation conditions of hollow titania–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 Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Ohashi, Takato [Department of Materials and Applied Chemistry, College of Science and Technology, 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 Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

2014-04-01

Highlights: • We study influence of preparation conditions on activity of hollow titania–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Ti + Ni content. • The activity depends on the amount of PS residue in the hollow spheres. - Abstract: The present work reports influence of preparation conditions of hollow titania–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}). The as-prepared hollow titania–nickel composite spheres were characterized by transmission electron microscopy (TEM). Catalytic activities of the hollow spheres for hydrolytic dehydrogenation of aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution improve with the decrease of Ti + Ni content. From the results of FTIR spectra and elemental analysis, the amount of residual polystyrene (PS) templates is able to be reduced by increasing aging time for the preparation, and the catalytic activity of the hollow spheres increases when the amount of residual PS templates decreases. The carbon content in the hollow spheres prepared with aging time = 24 h is 17.3 wt.%, and the evolution of 62 mL hydrogen is finished in about 22 min in the presence of the hollow spheres from aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution. The molar ratio of the hydrolytically generated hydrogen to the initial NH{sub 3}BH{sub 3} in the presence of the hollow spheres is 2.7.

Measurements of hydrogen concentration in liquid sodium by using an inert gas carrier method

International Nuclear Information System (INIS)

Funada, T.; Nihei, I.; Yuhara, S.; Nakasuji, T.

1979-01-01

A technique was developed to measure the hydrogen level in liquid sodium using an inert gas carrier method. Hydrogen was extracted into an inert gas from sodium through a thin nickel membrane in the form of a helically wound tube. The amount of hydrogen in the inert gas was analyzed by gas chromatography. The present method is unique in that it can be used over the wide range of sodium temperatures (150 to 700 0 C) and has no problems associated with vacuum systems. The partial pressure of hydrogen in sodium was determined as a function of cold-trap temperature (T/sub c/). Sieverts' constant (K/sub s/) was determined as a function of sodium temperature (T). From Sieverts' constant, the solubility of hydrogen in sodium is calculated. It was found that other impurities in sodium, such as (O) and (OH), have little effect on the hydrogen pressure in the sodium loop

Thermal generation and mobility of charge carriers in collective proton transport in hydrogen-bonded chains

International Nuclear Information System (INIS)

Peyrard, M.; Boesch, R.; Kourakis, I.

1991-01-01

The transport of protons in hydrogen-bonded systems is a long standing problem which has not yet obtained a satisfactorily theoretical description. Although this problem was examined first for ice, it is relevant in many systems and in particular in biology for the transport along proteins or for proton conductance across membranes, an essential process in cell life. The broad relevance makes the study of proton conduction very appealing. Since the original work of Bernal and Fowler on ice, the idea that the transport occurs through chains of hydrogen bonds has been well accepted. Such ''proton wires'' were invoked by Nagle and Morowitz for proton transport across membranes proteins and more recently across lipid bilayers. In this report, we assume the existence of such an hydrogen-bonded chain and discuss its consequences on the dynamics of the charge carriers. We show that this assumption leads naturally to the idea of soliton transport and we put a special emphasis on the role of the coupling between the protons and heavy ions motions. The model is presented. We show how the coupling affects strongly the dynamics of the charge carriers and we discuss the role it plays in the thermal generation of carriers. The work presented has been performed in 1986 and 87 with St. Pnevmatikos and N. Flyzanis and was then completed in collaboration with D. Hochstrasser and H. Buettner. Therefore the results presented in this part are not new but we think that they are appropriate in the context of this multidisciplinary workshop because they provide a rather complete example of the soliton picture for proton conduction. This paper discusses the thermal generation of the charge carriers when the coupling between the protons and heavy ions dynamics is taken into account. The results presented in this part are very recent and will deserve further analysis but they already show that the coupling can assist for the formation of the charge carriers

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.

Chemical storage of hydrogen in few-layer graphene

Science.gov (United States)

Subrahmanyam, K. S.; Kumar, Prashant; Maitra, Urmimala; Govindaraj, A.; Hembram, K. P. S. S.; Waghmare, Umesh V.; Rao, C. N. R.

2011-01-01

Birch reduction of few-layer graphene samples gives rise to hydrogenated samples containing up to 5 wt % of hydrogen. Spectroscopic studies reveal the presence of sp3 C-H bonds in the hydrogenated graphenes. They, however, decompose readily on heating to 500 °C or on irradiation with UV or laser radiation releasing all the hydrogen, thereby demonstrating the possible use of few-layer graphene for chemical storage of hydrogen. First-principles calculations throw light on the mechanism of dehydrogenation that appears to involve a significant reconstruction and relaxation of the lattice. PMID:21282617

Effect of hydrogen on change carrier dissipation in 60Co irradiated by γ-quanta and non-alloyed n-type GaAs

International Nuclear Information System (INIS)

Korshunov, F.P.; Kurilovich, N.F.; Prokhorenko, T.A.; Shesholko, V.K.; Bumaj, Yu.A.

2001-01-01

The pretreatment in hydrogen plasma (the hydrogenation) influences on the charge carrier dissipation processes in the non-alloyed gallium arsenide of n-type with no = (5...7) centre dot 10 15 cm -3 and μo = (5...6) centre dot 10 13 cm 2 / (V centre dot c) irradiated by γ-quantum 60 Co was studied. The comparison of experimental dependence μ (T) with the designed one in the temperature range 77...291 K for non-hydrogenized and hydrogenized non irradiated and γ-quantum irradiated crystals was carried out. It is shown that the main dissipative mechanism that determine the charged carrier mobility in the non hydrogenized material is the dissipation on the charged centers - the radiation defects in the γ-quantum irradiated GaAs; the presence of double ionized defects is possible

THE INFRARED SPECTRA OF POLYCYCLIC AROMATIC HYDROCARBONS WITH SOME OR ALL HYDROGEN ATOMS REMOVED

International Nuclear Information System (INIS)

Bauschlicher, Charles W. Jr.; Ricca, Alessandra

2013-01-01

The loss of one hydrogen from C 96 H 24 does not significantly affect the infrared spectra of the neutral, cation, or anion. Excluding a very weak C-C stretching band at 5.1 μm, the loss of two adjacent duo hydrogens does not significantly affect the spectra compared with the parent. Removing all of the hydrogen atoms significantly increases the intensity of the new C-C stretching band, and, for the cation, shifts it to a longer (5.2 μm) wavelength. Observations show a feature near 5.25 μm, which has been attributed to overtone and combination bands from polycyclic aromatic hydrocarbons (PAHs). This current work suggests that dehydrogenated PAHs might also contribute to this band, but its weakness implies that fully dehydrogenated cationic or dicationic species are very rare

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)

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....

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

THE INFRARED SPECTRA OF POLYCYCLIC AROMATIC HYDROCARBONS WITH SOME OR ALL HYDROGEN ATOMS REMOVED

Energy Technology Data Exchange (ETDEWEB)

Bauschlicher, Charles W. Jr. [Entry Systems and Technology Division, Mail Stop 230-3, NASA Ames Research Center, Moffett Field, CA 94035 (United States); Ricca, Alessandra, E-mail: Charles.W.Bauschlicher@nasa.gov, E-mail: Alessandra.Ricca-1@nasa.gov [Carl Sagan Center, SETI Institute, 189 Bernardo Avenue, Mountain View, CA 94043 (United States)

2013-10-20

The loss of one hydrogen from C{sub 96}H{sub 24} does not significantly affect the infrared spectra of the neutral, cation, or anion. Excluding a very weak C-C stretching band at 5.1 μm, the loss of two adjacent duo hydrogens does not significantly affect the spectra compared with the parent. Removing all of the hydrogen atoms significantly increases the intensity of the new C-C stretching band, and, for the cation, shifts it to a longer (5.2 μm) wavelength. Observations show a feature near 5.25 μm, which has been attributed to overtone and combination bands from polycyclic aromatic hydrocarbons (PAHs). This current work suggests that dehydrogenated PAHs might also contribute to this band, but its weakness implies that fully dehydrogenated cationic or dicationic species are very rare.

Final Report: DE- FC36-05GO15063, Fundamental Studies of Advanced High-Capacity, Reversible Metal Hydrides

Energy Technology Data Exchange (ETDEWEB)

Jensen, Craig [Univ. of Hawaii, Honolulu, HI (United States); McGrady, Sean [Univ. of New Brunswick, Fredericton NB (Canada); Severa, Godwin [Univ. of Hawaii, Honolulu, HI (United States); Eliseo, Jennifer [Univ. of Hawaii, Honolulu, HI (United States); Chong, Marina [Univ. of Hawaii, Honolulu, HI (United States)

2013-05-31

The project was component of the US DOE, Metal Hydride Center of Excellence (MHCoE). The Sandia National Laboratory led center was established to conduct highly collaborative and multi-disciplinary applied R&D to develop new reversible hydrogen storage materials that meet or exceed DOE/FreedomCAR 2010 and 2015 system targets for hydrogen storage materials. Our approach entailed a wide variety of activities ranging from synthesis, characterization, and evaluation of new candidate hydrogen storage materials; screening of catalysts for high capacity materials requiring kinetics enhancement; development of low temperature methods for nano-confinement of hydrides and determining its effects on the kinetics and thermodynamics of hydrides; and development of novel processes for the direct re-hydrogenation of materials. These efforts have resulted in several advancements the development of hydrogen storage materials. We have greatly extended the fundamental knowledge about the highly promising hydrogen storage carrier, alane (AlH₃), by carrying out the first crystal structure determinations and the first determination of the heats of dehydrogenation of β–AlH₃ and γ-AlD₃. A low-temperature homogenous organometallic approach to incorporation of Al and Mg based hydrides into carbon aerogels has been developed that that allows high loadings without degradation of the nano-porous scaffold. Nano-confinement was found to significantly improve the dehydrogenation kinetics but not effect the enthalpy of dehydrogenation. We conceived, characterized, and synthesized a novel class of potential hydrogen storage materials, bimetallic borohydrides. These novel compounds were found to have many favorable properties including release of significant amounts of hydrogen at moderate temperatures (75-190 º C). However, in situ IR studies in tandem with thermal gravimetric analysis have shown that about 0.5 equivalents of diborane are released during the

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

Energy Technology Data Exchange (ETDEWEB)

Ma, F.F.; Ma, S.H., E-mail: mash.phy@htu.edu.cn; Jiao, Z.Y.; Dai, X.Q.

2017-05-31

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{sub 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.

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.

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...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

Influence of the formation- and passivation rate of boron-oxygen defects for mitigating carrier-induced degradation in silicon within a hydrogen-based model

International Nuclear Information System (INIS)

Hallam, Brett; Abbott, Malcolm; Nampalli, Nitin; Hamer, Phill; Wenham, Stuart

2016-01-01

A three-state model is used to explore the influence of defect formation- and passivation rates of carrier-induced degradation related to boron-oxygen complexes in boron-doped p-type silicon solar cells within a hydrogen-based model. The model highlights that the inability to effectively mitigate carrier-induced degradation at elevated temperatures in previous studies is due to the limited availability of defects for hydrogen passivation, rather than being limited by the defect passivation rate. An acceleration of the defect formation rate is also observed to increase both the effectiveness and speed of carrier-induced degradation mitigation, whereas increases in the passivation rate do not lead to a substantial acceleration of the hydrogen passivation process. For high-throughput mitigation of such carrier-induced degradation on finished solar cell devices, two key factors were found to be required, high-injection conditions (such as by using high intensity illumination) to enable an acceleration of defect formation whilst simultaneously enabling a rapid passivation of the formed defects, and a high temperature to accelerate both defect formation and defect passivation whilst still ensuring an effective mitigation of carrier-induced degradation

Adsorption and diffusion of H and NH{sub x} as key steps of the NH{sub x} dehydrogenation reaction at the V{sub 2}O{sub 5} (010) surface

Energy Technology Data Exchange (ETDEWEB)

Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, und Sfb 546, Berlin (Germany)

2009-07-01

Various selective oxidation reactions as the selective catalytic reduction (SCR) of NO{sub x} or the ammoxidation of propane/propene to acrylonitrile are processed on vanadium based metal-oxide catalysts in the presence of ammonia. In the reactions the intermediates NH{sub 2}, NH{sub 3}, and NH{sub 4} are involved indicating that the adsorption and dehydrogenation of NH{sub x}, x < 4, are important steps. We have performed theoretical studies of corresponding reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5} (010) surface. The calculations apply density-functional theory combined with clusters modeling the adsorbate system. The substrate lowers corresponding dehydrogenation energies considerably compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation of NH{sub 3} likely to happen. Our results on the role of oxygen vacancies for the dehydrogenation indicate that such surface defects become important for the reaction. Besides the energetics also the diffusion at the surface influences the reaction. A nudged elastic band (NEB) routine has been implemented to evaluate diffusion paths and barriers. Hydrogen diffusion on the surface will be discussed and additional examples for NH{sub x} diffusion will be shown. Based on these results possible reaction scenarios for the dehydrogenation reaction will be presented.

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.

Hydrogen Production by Homogeneous Catalysis: Alcohol Acceptorless Dehydrogenation

DEFF Research Database (Denmark)

Nielsen, Martin

2015-01-01

in hydrogen production from biomass using homogeneous catalysis. Homogeneous catalysis has the advance of generally performing transformations at much milder conditions than traditional heterogeneous catalysis, and hence it constitutes a promising tool for future applications for a sustainable energy sector...

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.

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.

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

Science.gov (United States)

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

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.

Conceptual study on HTGR-IS hydrogen supply system using organic hydrides

International Nuclear Information System (INIS)

Terada, Atsuhiko; Noguchi, Hiroki; Takegami, Hiroaki; Kamiji, Yu; Inagaki, Yoshiyuki

2012-02-01

We have proposed a hydrogen supply-chain system, which is a storage/supply system of large amount of hydrogen produced by HTGR-IS hydrogen production system. The organic chemical hydride method is one of the candidate techniques in the system for hydrogen storage and transportation. In this study, properties of organic hydrides and conventional hydrogen storage/supply system were surveyed to make use of the conceptual design of the hydrogen supply system using an organic hydrides method with VHTR-IS hydrogen production process (hydrogen production: 85,400 Nm 3 /h). Conceptual specifications of the main equipments were designed for the hydrogen supply system consisting of hydrogenation and dehydrogenation process. It was also clarified the problems of hydrogen supply system, such as energy efficiency and system optimization. (author)

Dehydrogenation of aromatic molecules under a scanning tunneling microscope: pathways and inelastic spectroscopy simulations.

Science.gov (United States)

Lesnard, Hervé; Bocquet, Marie-Laure; Lorente, Nicolas

2007-04-11

We have performed a theoretical study on the dehydrogenation of benzene and pyridine molecules on Cu(100) induced by a scanning tunneling microscope (STM). Density functional theory calculations have been used to characterize benzene, pyridine, and different dehydrogenation products. The adiabatic pathways for single and double dehydrogenation have been evaluated with the nudge elastic band method. After identification of the transition states, the analysis of the electronic structure along the reaction pathway yields interesting information on the electronic process that leads to H-scission. The adiabatic barriers show that the formation of double dehydrogenated fragments is difficult and probably beyond reach under the actual experimental conditions. However, nonadiabatic processes cannot be ruled out. Hence, in order to identify the final dehydrogenation products, the inelastic spectra are simulated and compared with the experimental ones. We can then assign phenyl (C6H5) and alpha-pyridil (alpha-C5H4N) as the STM-induced dehydrogenation products of benzene and pyridine, respectively. Our simulations permit us to understand why phenyl, pyridine, and alpha-pyridil present tunneling-active C-H stretch modes in opposition to benzene.

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

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...

Pressure-jump in heterogeneous catalysis--2. Dehydrogenation of propane over a Cr/sub 2/O/sub 3/-Al/sub 2/O/sub 3/-K/sub 2/O catalyst

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Y; Kaneko, I

1979-05-01

Dehydrogenation of propane over a Cr/sub 2/O/sub 3/-Al/sub 2/O/sub 3/-K/sub 2/O catalyst confirmed the previously derived Langmuir-Hinshelwood type equation with a rate constant for the rate-determining step of 1.81 x 10/sup 11/ molecules/sec/sq cm. The experiments were performed by monitoring the transient pressure change in a 3 l. vessel after hydrogen was admitted to an equilibrated mixture of propane/propylene/hydrogen at 443/sup 0/C.

Screening of NiFe₂O₄ Nanoparticles as Oxygen Carrier in Chemical Looping Hydrogen Production

DEFF Research Database (Denmark)

Liu, Shuai; He, Fang; Huang, Zhen

2016-01-01

) methods were used to prepare NiFe2O4 oxygen carriers. Samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurement, as well as Barrett-Joyner-Halenda (BJH......The objective of this paper is to systematically investigate the influences of different preparation methods on the properties of NiFe2O4 nanoparticles as oxygen carrier in chemical looping hydrogen production (CLH). The solid state (SS), coprecipitation (CP), hydrothermal (HT), and sol-gel (SG...... gas (24% H2 + 24% CO + 12% CO2 + N2 balance), then reacted with steam to produce H2, and finally fully oxidized by air. The NiFe2O4 oxygen carrier prepared by the sol gel method showed the best capacity for hydrogen production and the highest recovery degree of lattice oxygen, in agreement...

Effect of multi-wall carbon nanotubes supported nano-nickel and TiF{sub 3} addition on hydrogen storage properties of magnesium hydride

Energy Technology Data Exchange (ETDEWEB)

Su, Wei; Zhu, Yunfeng, E-mail: yfzhu@njtech.edu.cn; Zhang, Jiguang; Liu, Yana; Yang, Yang; Mao, Qifeng; Li, Liquan

2016-06-05

Multi-wall carbon nanotubes supported nano-nickel (Ni/MWCNTs) with superior catalytic effects was introduced to magnesium hydride by the process of hydriding combustion synthesis (HCS) and mechanical milling (MM). The effect of different Ni/MWCNTs contents (5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%) on the hydrogenation and dehydrogenation properties of the composite was investigated systematically. It is revealed that Mg{sub 85}-(Ni/MWCNTs){sub 15} composite shows the best comprehensive hydrogen storage properties, which absorbs 5.68 wt.% hydrogen within 100 s at 373 K and releases 4.31 wt.% hydrogen within 1800 s at 523 K under initial hydrogen pressures of 3.0 and 0.005 MPa, respectively. The in situ formed nano-Mg{sub 2}Ni and MWCNTs have excellent catalytic effect on the hydrogenation and dehydrogenation performances of MgH{sub 2}. To further improve the hydrogen absorption/desorption properties, TiF{sub 3} was added to the Mg–Ni/MWCNTs system. The result shows that TiF{sub 3} addition has little influence on the thermodynamic performance, but affects greatly the kinetic properties. The Mg{sub 85}-(Ni/MWCNTs){sub 15}-TiF{sub 3} composite exhibits an appreciably enhanced hydrogen desorption performance at low temperature, and the hydrogen desorption capacity within 1800 s at 473 K for the TiF{sub 3}-added composite is approximately four times the capacity of Mg{sub 85}-(Ni/MWCNTs){sub 15} under the same condition. The catalytic effects during hydrogenation and dehydrogenation have been discussed in the study. - Highlights: • The nanosized Ni/MWCNTs catalyst was successfully prepared. • Ni/MWCNTs shows superior catalytic effect on H absorption/desorption of Mg. • Mg{sub 85}-(Ni/MWCNTs){sub 15} composite shows the best hydrogen storage properties. • Ni/MWCNTs coupling with TiF{sub 3} improves the hydriding/dehydriding properties largely.

Determination of hydrogen in zirconium and its alloys by melt extraction under carrier gas flow using thermal conductivity cell as detector

International Nuclear Information System (INIS)

Akhtar, J.; Ahmed, M.; Mohammad, B.; Jan, S.; Waqar, F.

1987-06-01

In the production of zirconium metal and its alloys the presence of hydrogen impurity affects mechanical and corrosion resistance properties of the product. Therefore, determination of hydrogen contents of the product is necessary. Conditions for its analysis by melt extraction under carrier gas stream using thermal conductivity cell as detector were studied and optimised. The method is capable of measuring hydrogen impurity in parts per million range. (author)

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 _4.85Sn_0.15, 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.

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.

What is required to make hydrogen a real energy carrier option?

Energy Technology Data Exchange (ETDEWEB)

Braeuninger, S.; Schindler, G.; Schwab, E.; Weck, A. [BASF SE, Ludwigshafen (Germany)

2010-12-30

The driver for the introduction of hydrogen as mobile energy-carrier is regulatory measures to avoid the CO{sub 2} emissions which are related to the current fossil carbon based situation. H{sub 2} is a large volume chemical product with an annual production of about 45 million tons, most of which currently is also derived from fossil sources. The German transport sector consumes 2,6.10{sup 12} MJ/a which in terms of energy is equivalent to nearly 50% of the current world hydrogen production. There is the proposal to start the ''hydrogen economy'' with ''excess H{sub 2}'' which is believed to be available as inadvertently occurring byproduct of chemical processes. A potential {proportional_to}2 million tons is estimated for this ''excess H{sub 2}'' in Europe; the proposal however does not take into account, that current uses of this H{sub 2} would have to be substituted. Therefore, an overall gain for the environment cannot be expected. Therefore, a sustainable hydrogen based energy scenario has to rely on new sources. Besides Biomass gasification which in terms of technology would resemble the conventional fossil based hydrogen production, the only other viable carbon-free hydrogen source is water, which has to be split into its constituting elements. The current paper is restricted to the latter path, the feasibility of the biomass approach needs to be discussed elsewhere. If hypothetically the above mentioned energy for the German transport sector would be provided by H{sub 2} from water electrolysis an electricity input of 4.10{sup 12} MJ would be needed. This number exceeds the currently installed German wind turbine capacity by a factor of 6 and even by a factor of 36, if the weather-based {proportional_to}16% year-round on-stream factor for onshore plants is taken into account. (orig.)

The synthesis of benzimidazoles and quinoxalines from aromatic diamines and alcohols by iridium-catalyzed acceptorless dehydrogenative alkylation.

Science.gov (United States)

Hille, Toni; Irrgang, Torsten; Kempe, Rhett

2014-05-05

Benzimidazoles and quinoxalines are important N-heteroaromatics with many applications in pharmaceutical and chemical industry. Here, the synthesis of both classes of compounds starting from aromatic diamines and alcohols (benzimidazoles) or diols (quinoxalines) is reported. The reactions proceed through acceptorless dehydrogenative condensation steps. Water and two equivalents of hydrogen are liberated in the course of the reactions. An Ir complex stabilized by the tridentate P^N^P ligand N(2) ,N(6) -bis(di-isopropylphosphino)pyridine-2,6-diamine revealed the highest catalytic activity for both reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ hydrogen loading on zirconium powder

Energy Technology Data Exchange (ETDEWEB)

Maimaitiyili, Tuerdi, E-mail: tuerdi.maimaitiyili@mah.se; Blomqvist, Jakob [Malmö University, Östra Varvsgatan 11 A, Malmö, Skane 20506 (Sweden); Steuwer, Axel [Lund University, Ole Römers väg, Lund, Skane 22100 (Sweden); Nelson Mandela Metropolitan University, Gardham Avenue, Port Elizabeth 6031 (South Africa); Bjerkén, Christina [Malmö University, Östra Varvsgatan 11 A, Malmö, Skane 20506 (Sweden); Zanellato, Olivier [Ensam - Cnam - CNRS, 151 Boulevard de l’Hôpital, Paris 75013 (France); Blackmur, Matthew S. [Materials Performance Centre, School of Materials, The University of Manchester, Manchester M1 7HS (United Kingdom); Andrieux, Jérôme [European Synchrotron Radiation Facility, 6 rue J Horowitz, Grenoble 38043 (France); Université de Lyon, 43 Bd du 11 novembre 1918, Lyon 69100 (France); Ribeiro, Fabienne [Institut de Radioprotection et Sûreté Nucléaire, IRSN, BP 3, 13115 Saint-Paul Lez Durance (France)

2015-06-26

Commercial-grade Zr powder loaded with hydrogen in situ and phase transformations between various Zr and ZrH{sub x} phases have been monitored in real time. For the first time, various hydride phases in a zirconium–hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr–H phase diagram are obtained from a single experimental arrangement.

In situ hydrogen loading on zirconium powder

International Nuclear Information System (INIS)

Maimaitiyili, Tuerdi; Blomqvist, Jakob; Steuwer, Axel; Bjerkén, Christina; Zanellato, Olivier; Blackmur, Matthew S.; Andrieux, Jérôme; Ribeiro, Fabienne

2015-01-01

Commercial-grade Zr powder loaded with hydrogen in situ and phase transformations between various Zr and ZrH x phases have been monitored in real time. For the first time, various hydride phases in a zirconium–hydrogen system have been prepared in a high-energy synchrotron X-ray radiation beamline and their transformation behaviour has been studied in situ. First, the formation and dissolution of hydrides in commercially pure zirconium powder were monitored in real time during hydrogenation and dehydrogenation, then whole pattern crystal structure analysis such as Rietveld and Pawley refinements were performed. All commonly reported low-pressure phases presented in the Zr–H phase diagram are obtained from a single experimental arrangement

Regeneration of ammonia borane from spent fuel materials.

Science.gov (United States)

Summerscales, Owen T; Gordon, John C

2013-07-28

A shift to the hydrogen economy requires the development of an effective hydrogen fuel carrier with high volumetric and gravimetric storage capacity. Ammonia borane (AB) has emerged as a leading candidate due to its light weight and multiple protic (N-H) and hydridic (B-H) hydrogens. As a consequence, much work has been directed towards fine tuning the release of H2 from AB, in addition to its regeneration from the dehydrogenated "spent fuel" materials. This review summarizes the development of these regeneration methodologies.

New Transition metal assisted complex borohydrides for hydrogen storage

International Nuclear Information System (INIS)

Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

2006-01-01

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

Properties of Mg-Al alloys in relation to hydrogen storage

DEFF Research Database (Denmark)

Andreasen, A.

2005-01-01

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 doesnot form a hydride under conventional hydriding conditions, however both the thermodynamical......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...... 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....

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.

Experimental study of temperature sensor for an ocean-going liquid hydrogen (LH2) carrier

Science.gov (United States)

Nakano, A.; Shimazaki, T.; Sekiya, M.; Shiozawa, H.; Aoyagi, A.; Ohtsuka, K.; Iwakiri, T.; Mikami, Z.; Sato, M.; Kinoshita, K.; Matsuoka, T.; Takayama, Y.; Yamamoto, K.

2018-04-01

The prototype temperature sensors for an ocean-going liquid hydrogen (LH2) carrier were manufactured by way of trial. All of the sensors adopted Platinum 1000 (PT-1000) resistance thermometer elements. Various configurations of preproduction temperature sensors were tested in AIST's LH2 test facility. In the experiments, a PT-1000 resistance thermometer, calibrated at the National Metrology Institute of Japan at AIST, was used as the standard thermometer. The temperatures measured by the preproduction sensors were compared with the temperatures measured by the standard thermometer, and the measurement accuracy of the temperature sensors in LH2 was investigated and discussed. It was confirmed that the measurement accuracies of the preproduction temperature sensors were within ±50 mK, which is the required measurement accuracy for a technical demonstration ocean-going LH2 carrier.

Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen 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.

Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

Science.gov (United States)

Kondoh, Azusa; Jamison, Timothy F.

2010-01-01

A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

Synthesis and hydrogen storage of La23Nd7.8Ti1.1Ni33.9Co32.9Al0.65 alloys

Directory of Open Access Journals (Sweden)

Priyanka Meena

2018-04-01

Full Text Available The present work investigates structural and hydrogen storage properties of first time synthesized La23Nd7.8Ti1.1Ni33.9Co32.9Al0.65 alloy by arc melting process and ball milled to get it in nano structure form. XRD analysis of as-prepared alloy showed single phased hexagonal LaNi5-type structure with 52 nm average particle size, which reduces to about 31 nm after hydrogenations. Morphological studies by SEM were undertaken to investigate the effect of hydrogenation of nanostructured alloy. EDX analysis confirmed elemental composition of the as-prepared alloy. Activation energy for hydrogen desorption was studied using TGA analysis and found to be −76.86 kJ/mol. Hydrogenation/dehydrogenation reactions and absorption kinetics were measured at temperature 100 °C. The equilibrium plateau pressure was determined to be 2 bar at 100 °C giving hydrogen storage capacity of about 2.1 wt%. Keywords: Hydrogen storage, La23Nd7.8Ti1.1Ni33.9Co32.9Al0.65 alloy, SEM, EDS, TGA, Hydrogenation/dehydrogenation

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, LaNi_4.85Sn_0.15, 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.

Hydrogen as an energy carrier. Final report; Wasserstoff als Energietraeger. Abschlussbericht

Energy Technology Data Exchange (ETDEWEB)

Rebholz, H. [ed.

1998-12-01

This final report of the Special Field of Research 270 (SFB 270) documents the work and results of the four promotion phases from 1989 to 1998, presented in reports on 15 part-projects. From its inception, SFB 270, which bears the title ''Hydrogen as an Energy Carrier'', has been dedicated to two fields of work: in Project Area A to the production of hydrogen (7 part-projects) and in Project Area B to the transport and storage of hydrogen (8 part-projects). The scientific results of the part-projects have also been presented in detail in the progress reports and interim reports of 1991, 1994 and 1997. Some of them have also been presented at the colloquiums of SFB 270. Twelve part-projects have been abstracted individually for the ENERGY database. [German] Der vorliegende Abschlussbericht des Sonderforschungsbereichs 270 dokumentiert die Arbeiten und Ergebnisse der vier Foerderungsphasen von 1989 bis 1998. Sie sind in den Berichten von 15 Teilprojekten wiedergegeben. Der Sonderforschungsbereich 270 'Wasserstoff als Energietraeger' hat sich von Anfang an zwei Aufgabengebieten gewidmet: Im Projektbereich A der Herstellung von Wasserstoff (7 Teilprojekte) und im Projektbereich B dem Transport und der Speicherung von Wasserstoff (8 Teilprojekte). Wissenschaftliche Ergebnisse der Teilprojekte sind ausfuehrlich auch in den Arbeits- und Ergebnisberichten 1991, 1994 und 1997 wiedergegeben. Sie wurden auch, in Teilen, in entsprechenden Kolloquien des SFB 270 praesentiert. Fuer die Datenbank ENERGY wurden 12 Teilprojekte separat aufgenommen. (orig.)

Enhancing hydrogen storage performances of MgH2 by Ni nano-particles over mesoporous carbon CMK-3

Science.gov (United States)

Chen, Gang; Zhang, Yao; Chen, Jian; Guo, Xinli; Zhu, Yunfeng; Li, Liquan

2018-06-01

Nano-dispersed Ni particles over mesoporous carbon material CMK-3 (Ni/CMK-3) was fabricated by means of impregnation-reduction strategy using precursor NiCl2 · 6H2O, which is beneficial to improving the de/rehydrogenation performances of MgH2. The dehydrogenation onset temperature of MgH2–Ni/CMK-3 is significantly lowered by 170 K from that of pristine MgH2 (around 603 K). Totally 5.9 wt% of hydrogen absorption capacity is liberated within 1 h at a temperature of 423 K under a pressure of 3 MPa. This composite can absorb 3.9 wt% hydrogen even at a temperature of 328 K under 3 MPa H2. Activation energy values of both dehydrogenation (43.4 kJ mol‑1) and rehydrogenation (37.4 kJ mol‑1) for MgH2–Ni/CMK-3 are greatly enhanced from those of as-milled MgH2. Ni/CMK-3 also slightly destabilizes the dehydrogenation of MgH2 by 1.5 kJ mol {{{{H}}}2}-1. The enhanced performances can be attributed to the synergistic effects of both destabilization and activation from nano-dispersed Ni particles.

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)

Thermodynamic evaluation of hydrogen production for fuel cells by using bio-ethanol steam reforming: Effect of carrier gas addition

Science.gov (United States)

Hernández, Liliana; Kafarov, Viatcheslav

Omitting the influence of the addition of carrier gas to the reaction system for hydrogen production by bio-ethanol steam reforming can lead to wrong conclusions, especially when it is going to be made to scale. The effect of carrier gas addition to produce hydrogen using bio-ethanol steam reforming to feed fuel cells was evaluated. Thermodynamic calculations in equilibrium conditions were made, however the analysis derived from them can also be applied to kinetic conditions. These calculations were made by using the Aspen-HYSYS software at atmospheric pressure and different values of temperature, water/ethanol molar ratios, and inert (argon)/(water/ethanol) molar ratios. The addition of inert carrier gas modifies the concentrations of the reaction products in comparison to those obtained without its presence. This behavior occurs because most of the reactions which take place in bio-ethanol steam reforming have a positive difference of moles. This fact enhances the system sensitivity to inert concentration at low and moderated temperatures (<700 °C). At high values of temperature, the inert addition does not influence the composition of the reaction products because of the predominant effect of inverse WGS reaction.

Thermodynamic evaluation of hydrogen production for fuel cells by using bio-ethanol steam reforming: Effect of carrier gas addition

Energy Technology Data Exchange (ETDEWEB)

Hernandez, Liliana; Kafarov, Viatcheslav [Universidad Industrial de Santander, Escuela de Ingenieria Quimica, Bucaramanga 678 (Colombia)

2009-07-01

Omitting the influence of the addition of carrier gas to the reaction system for hydrogen production by bio-ethanol steam reforming can lead to wrong conclusions, especially when it is going to be made to scale. The effect of carrier gas addition to produce hydrogen using bio-ethanol steam reforming to feed fuel cells was evaluated. Thermodynamic calculations in equilibrium conditions were made, however the analysis derived from them can also be applied to kinetic conditions. These calculations were made by using the Aspen-HYSYS software at atmospheric pressure and different values of temperature, water/ethanol molar ratios, and inert (argon)/(water/ethanol) molar ratios. The addition of inert carrier gas modifies the concentrations of the reaction products in comparison to those obtained without its presence. This behavior occurs because most of the reactions which take place in bio-ethanol steam reforming have a positive difference of moles. This fact enhances the system sensitivity to inert concentration at low and moderated temperatures (<700 C). At high values of temperature, the inert addition does not influence the composition of the reaction products because of the predominant effect of inverse WGS reaction. (author)

Probing the structure, stability and hydrogen storage properties of calcium dodecahydro-closo-dodecaborate

International Nuclear Information System (INIS)

Stavila, Vitalie; Her, Jae-Hyuk; Zhou Wei; Hwang, Son-Jong; Kim, Chul; Ottley, Leigh Anna M.; Udovic, Terrence J.

2010-01-01

Calcium borohydride can reversibly store up to 9.6 wt% hydrogen; however, the material displays poor cyclability, generally associated with the formation of stable intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of Ca(BH 4 ) 2 , calcium dodecahydro-closo-dodecaborate was isolated and characterized by diffraction and spectroscopic techniques. The crystal structure of CaB 12 H 12 was determined from powder XRD data and confirmed by DFT and neutron vibrational spectroscopy studies. Attempts to dehydrogenate/hydrogenate mixtures of CaB 12 H 12 and CaH 2 were made under conditions known to favor partial reversibility in calcium borohydride. However, up to 670 K no notable formation of Ca(BH 4 ) 2 (during hydrogenation) or CaB 6 (during dehydrogenation) occurred. It was demonstrated that the stability of CaB 12 H 12 can be significantly altered using CaH 2 as a destabilizing agent to favor the hydrogen release. - Graphical abstract: Calcium dodecahydro-closo-dodecaborate, CaB 12 H 12 (1), was isolated by dehydration/desolvation of [Ca(H 2 O) 7 ][B 12 H 12 ].H 2 O (2) or [Ca(H 2 O) 5 (MeCN) 2 ][B 12 H 12 ] (3). The crystal structure of 1 was determined by powder X-ray diffraction and confirmed by neutron vibrational spectroscopy and first-principles calculations. Hydrogen storage properties of 1 in the presence of calcium hydride were elucidated.

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.

Hydrogen production by nuclear heat

International Nuclear Information System (INIS)

Crosbie, Leanne M.; Chapin, Douglas

2003-01-01

A major shift in the way the world obtains energy is on the horizon. For a new energy carrier to enter the market, several objectives must be met. New energy carriers must meet increasing production needs, reduce global pollution emissions, be distributed for availability worldwide, be produced and used safely, and be economically sustainable during all phases of the carrier lifecycle. Many believe that hydrogen will overtake electricity as the preferred energy carrier. Hydrogen can be burned cleanly and may be used to produce electricity via fuel cells. Its use could drastically reduce global CO 2 emissions. However, as an energy carrier, hydrogen is produced with input energy from other sources. Conventional hydrogen production methods are costly and most produce carbon dioxide, therefore, negating many of the benefits of using hydrogen. With growing concerns about global pollution, alternatives to fossil-based hydrogen production are being developed around the world. Nuclear energy offers unique benefits for near-term and economically viable production of hydrogen. Three candidate technologies, all nuclear-based, are examined. These include: advanced electrolysis of water, steam reforming of methane, and the sulfur-iodine thermochemical water-splitting cycle. The underlying technology of each process, advantages and disadvantages, current status, and production cost estimates are given. (author)

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......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 conversion of ethane. A tendency is clear for all catalysts: In the first period of time 100% ethane is converted and roughly half of the carbon is converted into coke and deposited on the catalyst. The other half of the carbon is converted into methane. The active sites in the hydrogenolysis are blocked...... by coke during the initial period where after dehydrogenation of ethane is observed. It has previously been predicted in surface science studies that Ag covers the steps of certain transition metals. Here it is documented that the hydrogenolysis and coking reactions are significantly suppressed by co...

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.)

Light alkane (mixed feed) selective dehydrogenation using bi ...

African Journals Online (AJOL)

... refinery processes and their catalytic dehydrogenation gives corresponding alkenes. ... was prepared by sequentional impregnation method and characterized by BET, ... Optimum propene selectivity is about 48 %, obtained at 600 oC and ...

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

Science.gov (United States)

Marashdeh, Ali; Frankcombe, Terry J

2008-06-21

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) 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 dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.

Compaction of LiBH4-LiAlH4 nanoconfined in activated carbon nanofibers: Dehydrogenation kinetics, reversibility, and mechanical stability during cycling

DEFF Research Database (Denmark)

Plerdsranoy, Praohatsorn; Javadian-Deylami, Seyd Payam; Jensen, Nicholai Daugaard

2017-01-01

To enhance volumetric hydrogen capacity for on-board fuel cells, compaction of LiAlH4-LiBH4 nanoconfined in activated carbon nanofibers (ACNF) is for the first time proposed. Loose powders of milled and nanoconfined LiAlH4-LiBH4 samples are compacted under 976 MPa to obtain the pellet samples...... with thickness and diameter of ∼1.20–1.30 and 8.0 mm, respectively. Dehydrogenation temperature of milled LiAlH4-LiBH4 increases from 415 to 434 °C due to compaction, while those of both compacted and loose powder samples of nanoconfined LiAlH4-LiBH4 are lower at comparable temperature of 330–335 °C. Hydrogen...

High-frequency conductivity of optically excited charge carriers in hydrogenated nanocrystalline silicon investigated by spectroscopic femtosecond pump–probe reflectivity measurements

Energy Technology Data Exchange (ETDEWEB)

He, Wei [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom); Yurkevich, Igor V. [Aston University, Nonlinearity and Complexity Research Group, Birmingham B4 7ET (United Kingdom); Zakar, Ammar [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom); Kaplan, Andrey, E-mail: a.kaplan.1@bham.ac.uk [University of Birmingham, School of Physics and Astronomy, Birmingham B15 2TT (United Kingdom)

2015-10-01

We report an investigation into the high-frequency conductivity of optically excited charge carriers far from equilibrium with the lattice. The investigated samples consist of hydrogenated nanocrystalline silicon films grown on a thin film of silicon oxide on top of a silicon substrate. For the investigation, we used an optical femtosecond pump–probe setup to measure the reflectance change of a probe beam. The pump beam ranged between 580 and 820 nm, whereas the probe wavelength spanned 770 to 810 nm. The pump fluence was fixed at 0.6 mJ/cm{sup 2}. We show that at a fixed delay time of 300 fs, the conductivity of the excited electron–hole plasma is described well by a classical conductivity model of a hot charge carrier gas found at Maxwell–Boltzmann distribution, while Fermi–Dirac statics is not suitable. This is corroborated by values retrieved from pump–probe reflectance measurements of the conductivity and its dependence on the excitation wavelength and carrier temperature. The conductivity decreases monotonically as a function of the excitation wavelength, as expected for a nondegenerate charge carrier gas. - Highlights: • We study high‐frequency conductivity of excited hydrogenated nanocrystalline silicon. • Reflectance change was measured as a function of pump and probe wavelength. • Maxwell–Boltzmann transport theory was used to retrieve the conductivity. • The conductivity decreases monotonically as a function of the pump wavelength.

Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts.

Science.gov (United States)

Witzke, M E; Dietrich, P J; Ibrahim, M Y S; Al-Bardan, K; Triezenberg, M D; Flaherty, D W

2017-01-03

Selective dehydrogenation catalysts that produce acetaldehyde from bio-derived ethanol can increase the efficiency of subsequent processes such as C-C coupling over metal oxides to produce 1-butanol or 1,3-butadiene or oxidation to acetic acid. Here, we use in situ X-ray absorption spectroscopy and steady state kinetics experiments to identify Cu δ+ at the perimeter of supported Cu clusters as the active site for esterification and Cu 0 surface sites as sites for dehydrogenation. Correlation of dehydrogenation and esterification selectivities to in situ measures of Cu oxidation states show that this relationship holds for Cu clusters over a wide-range of diameters (2-35 nm) and catalyst supports and reveals that dehydrogenation selectivities may be controlled by manipulating either.

The hydrogen coverage of interstellar PAHs [Polycyclic Aromatic Hydrocarbons

International Nuclear Information System (INIS)

Tielens, A.G.G.M.; Allamandola, L.J.; Barker, J.R.; Cohen, M.

1986-02-01

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a uv photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense uv fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments

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.

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, LaNi_4.85Sn_0.15, Al₃Ti, and PdCl₂ were combined , LaNi_4.85Sn_0.15, 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.

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.

Improved dehydrogenation of TiF{sub 3}-doped NaAIH{sub 4} using mesoporous SiO{sub 2} as a co-dopant

Energy Technology Data Exchange (ETDEWEB)

Li, Y.; Zheng, S.; Fang, F.; Song, Y.; Sun, D. [Fudan Univ., Shanghai (China). Dept. of Materials Science

2010-07-01

This paper examined the improved dehydrogenation of titanium fluoride (TiF{sub 3})-doped sodium aluminum hydride (NaAIH{sub 4}) using mesoporous silicon dioxide (SiO{sub 2}) as a Co-dopant. The study revealed that the amount of hydrogen evolved was 3.8 wt. per cent for the pristine NaAlH{sub 4} and approximately 4.2 wt. per cent for the TiF{sub 3}-doped NaAlH{sub 4}. It increased to 4.9-5.0 wt. per cent once the samples were doped with mesoporous SiO{sub 2}. A favorable synergistic effect on the NaAlH{sub 4} dehydrogenation was achieved as mesoporous SiO{sub 2} was added as a co-dopant along with TiF{sub 3} which was associated with the nanosized pores and high specific surface area of mesoporous SiO{sub 2}. The catalytic mechanism of mesoporous SiO{sub 2} was more physical than chemical relative to the catalytic mechanism of TiF{sub 3}. 1 fig.

Ultrafine Nanocrystalline CeO2@C-Containing NaAlH4 with Fast Kinetics and Good Reversibility for Hydrogen Storage.

Science.gov (United States)

Zhang, Xin; Liu, Yongfeng; Wang, Ke; Li, You; Gao, Mingxia; Pan, Hongge

2015-12-21

A nanocrystalline CeO2@C-containing NaAlH4 composite is successfully synthesized in situ by hydrogenating a NaH-Al mixture doped with CeO2@C. Compared with NaAlH4 , the as-prepared CeO2@C-containing NaAlH4 composite, with a minor amount of excess Al, exhibits significantly improved hydrogen storage properties. The dehydrogenation onset temperature of the hydrogenated [NaH-Al-7 wt % CeO2@C]-0.04Al sample is 77 °C lower than that of the pristine sample because of a reduced kinetic barrier. More importantly, the dehydrogenated sample absorbs ∼4.7 wt % hydrogen within 35 min at 100°C and 10 MPa of hydrogen. Compositional and structural analyses reveal that CeO2 is converted to CeH2 during ball milling and that the newly formed CeH2 works with the excess of Al to synergistically improve the hydrogen storage properties of NaAlH4. Our findings will aid in the rational design of novel catalyst-doped complex hydride systems with low operating temperatures, fast kinetics, and long-term cyclability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol

DEFF Research Database (Denmark)

Christensen, Stig Holden; Olsen, Esben Paul Krogh; Rosenbaum, Jascha

2014-01-01

A variety of primary alcohols have been investigated as convenient substrates for the ex situ delivery of carbon monoxide and molecular hydrogen in a two-chamber reactor. The gaseous mixture is liberated in one chamber by an iridium-catalysed dehydrogenative decarbonylation of the alcohol...... and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes...

Formation of Multiple-Phase Catalysts for the Hydrogen Storage of Mg Nanoparticles by Adding Flowerlike NiS.

Science.gov (United States)

Xie, Xiubo; Ma, Xiujuan; Liu, Peng; Shang, Jiaxiang; Li, Xingguo; Liu, Tong

2017-02-22

In order to enhance the hydrogen storage properties of Mg, flowerlike NiS particles have been successfully prepared by solvothermal reaction method, and are subsequently ball milled with Mg nanoparticles (NPs) to fabricate Mg-5 wt % NiS nanocomposite. The nanocomposite displays Mg/NiS core/shell structure. The NiS shell decomposes into Ni, MgS and Mg 2 Ni multiple-phases, decorating on the surface of the Mg NPs after the first hydrogen absorption and desorption cycle at 673 K. The Mg-MgS-Mg 2 Ni-Ni nanocomposite shows enhanced hydrogenation and dehydrogenation rates: it can quickly uptake 3.5 wt % H 2 within 10 min at 423 K and release 3.1 wt % H 2 within 10 min at 573 K. The apparent hydrogen absorption and desorption activation energies are decreased to 45.45 and 64.71 kJ mol -1 . The enhanced sorption kinetics of the nanocomposite is attributed to the synergistic catalytic effects of the in situ formed MgS, Ni and Mg 2 Ni multiple-phase catalysts during the hydrogenation/dehydrogenation process, the porthole effects for the volume expansion and microstrain of the phase transformation of Mg 2 Ni and Mg 2 NiH 4 and the reduced hydrogen diffusion distance caused by nanosized Mg. This novel method of in situ producing multiple-phase catalysts gives a new horizon for designing high performance hydrogen storage material.

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.

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.

Synthetic nanocomposite MgH2/5 wt. % TiMn2 powders 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.

Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

Science.gov (United States)

Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

2015-03-01

A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts

Energy Technology Data Exchange (ETDEWEB)

Irvine, E.A.; Taylor, D.

1978-01-01

The dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts which had been outgassed at 698/sup 0/K were carried out in the presence of oxygen at 474/sup 0/K, and the initial approximately zero-order rates of 1,3-butadiene formation and rates of isomerization were used as a measure of catalytic activity to construct activity patterns as a function of catalyst composition. A comparison of the patterns with those for the isomerization of 3,3-dimethyl-1-butene and for the selective oxidation of propane on the same catalysts indicated that the dehydrogenation of 1-butene involves a m-allyl intermediate, but isomerization occurs through carbonium ion formation. For the cis- and trans-isomers, both reactions apparently occurred via a common allyl (but not m-allyl) intermediate. Dehydrogenation to butadiene decreased in the order 1-butene > cis-2-butene trans-2-butene and was maximum at 10% antimony for 1-butene and 21% antimony for 2-butene. Isomerization was always slower than dehydrogenation and showed two maEima, at 21 (or 27%) and at 75% antimony.

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)).

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.

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.

Tritium removal by hydrogen isotopic exchange between hydrogen gas and water on hydrophobic catalyst

International Nuclear Information System (INIS)

Morishita, T.; Isomura, S.; Izawa, H.; Nakane, R.

1980-01-01

Many kinds of the hydrophobic catalysts for hydrogen isotopic exchange between hydrogen gas and water have been prepared. The carriers are the hydrophobic organic materials such as polytetrafluoroethylene(PTFE), monofluorocarbon-PTFE mixture(PTFE-FC), and styrene-divinylbenzene copolymer(SDB). 0.1 to 2 wt % Pt is deposited on the carriers. The Pt/SDB catalyst has much higher activity than the Pt/PTFE catalyst and the Pt/PTFE-FC catalyst shows the intermediate value of catalytic activity. The observation of electron microscope shows that the degrees of dispersion of Pt particles on the hydrophobic carriers result in the difference of catalytic activities. A gas-liquid separated type column containing ten stages is constructed. Each stage is composed of both the hydrophobic catalyst bed for the hydrogen gas/water vapor isotopic exchange and the packed column type bed for the water vapor/liquid water isotopic exchange. In the column hydrogen gas and water flow countercurrently and hydrogen isotopes are separated

Pressure Drop and Catalytic Dehydrogenation of NaBH{sub 4} Solution Across Pin Fin Structures in a Microchannel Reactor

Energy Technology Data Exchange (ETDEWEB)

Jung, Ki Moon [Korea Institute of Industrial Technology, Cheonan (Korea, Republic of); Choi, Seok Hyun [Key Valve Technologies Ltd., Siheung (Korea, Republic of); Lee, Hee Joon [Kookmin Univ., Seoul (Korea, Republic of)

2017-06-15

Dehydrogenation from the hydrolysis of a sodium borohydride (NaBH{sub 4}) solution has been of interest owing to its high theoretical hydrogen storage capacity (10.8 wt.%) and potentially safe operation. An experimental study has been performed on the catalytic reaction rate and pressure drop of a NaBH4 solution over both a single microchannel with a hydraulic diameter of 300 μm and a staggered array of micro pin fins in the microchannel with hydraulic diameter of 50 μm. The catalytic reaction rates and pressure drops were obtained under Reynolds numbers from 1 to 60 and solution concentrations from 5 to 20 wt.%. Moreover, reacting flows were visualized using a high-speed camera with a macro zoom lens. As a result, both the amount of hydrogenation and pressure drop are 2.45 times and 1.5 times larger in a pin fin microchannel array than in a single microchannel, respectively.

Rational construction of multiple interfaces in ternary heterostructure for efficient spatial separation and transfer of photogenerated carriers in the application of photocatalytic hydrogen evolution

Science.gov (United States)

Shi, Jian-Wen; Ma, Dandan; Zou, Yajun; Fan, Zhaoyang; Shi, Jinwen; Cheng, Linhao; Ji, Xin; Niu, Chunming

2018-03-01

The design of efficient and stable photocatalyst plays a critical role in the photocatalytic hydrogen evolution from water splitting. Herein, we develop a novel ZnS/CdS/ZnO ternary heterostructure by the in-situ sulfuration of CdS/ZnO, which includes four contact interfaces: CdS-ZnS interface, ZnS-ZnO interface, CdS-ZnO interface and ZnS-CdS-ZnO ternary interface, forming three charge carrier-transfer modes (type-I, type-II and direct Z-scheme) through five carrier-transfer pathways. As a result, the separation and transfer of photoexcited electron-hole pairs are promoted significantly, resulting in a high hydrogen evolution rate of 44.70 mmol h-1 g-1, which is 2, 3.7 and 8 times higher than those of binary heterostructures, CdS/ZnO, CdS/ZnS and ZnS/ZnO, respectively, and 26.5, 280 and 298 times higher than those of single CdS, ZnO and ZnS, respectively. As a counterpart ternary heterostructure, CdS/ZnS/ZnO contains only two interfaces: CdS-ZnS interface and ZnS-ZnO interface, which form two charge carrier-transfer modes (type-I and type-II) through two carrier-transfer pathways, leading to its much lower hydrogen evolution rate (27.25 mmol h-1 g-1) than ZnS/CdS/ZnO ternary heterostructure. This work is relevant for understanding the charge-transfer pathways between multi-interfaces in multicomponent heterojunctions.

Tailored ceria nanoparticles for CO2 mediated ethylbenzene dehydrogenation

NARCIS (Netherlands)

Kovacevic, M.

2016-01-01

Styrene production via ethylbenzene dehydrogenation (EBDH) is one of the ten most important petrochemical processes. Possessing highly reactive double bond which facilitates self-polymerization and polymerization with other monomers, styrene is the fourth utmost essential bulk monomer at present.

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.

Substitution of Tyr254 with Phe at the active site of flavocytochrome b2: consequences on catalysis of lactate dehydrogenation

International Nuclear Information System (INIS)

Dubois, J.; Chapman, S.K.; Mathews, F.S.; Reid, G.A.; Lederer, F.

1990-01-01

A role for Tyr254 in L-lactate dehydrogenation catalyzed by flavocytochrome b2 has recently been proposed on the basis of the known active-site structure and of studies that had suggested a mechanism involving the initial formation of a lactate carbanion. This role is now examined after replacement of Tyr254 with phenylalanine. The kcat is decreased about 40-fold, Km for lactate appears unchanged, and the mainly rate-limiting step is still alpha-hydrogen abstraction, as judged from the steady-state deuterium isotope effect. Modeling studies with lactate introduced into the active site indicate two possible substrate conformations with different hydrogen-bonding partners for the substrate hydroxyl. If the hydrogen bond is formed with Tyr254, as was initially postulated, the mechanism must involve removal by His373 of the C2 hydrogen, with carbanion formation. If, in the absence of the Tyr254 phenol group, the hydrogen bond is formed with His373 N3, the substrate is positioned in such a way that the reaction must proceed by hydride transfer. Therefore the mechanism of the Y254F enzyme was investigated so as to distinguish between the two mechanistic possibilities. 2-Hydroxy-3-butynoate behaves with the mutant as a suicide reagent, as with the wild-type enzyme. Similarly, the mutant protein also catalyzes the reduction and the dehydrohalogenation of bromopyruvate under transhydrogenation conditions

Design and Development of New Carbon-Based Sorbent Systems for an Effective Containment of Hydrogen

Energy Technology Data Exchange (ETDEWEB)

Alan C. Cooper

2012-05-03

This is a summary for work performed under cooperative agreement DE FC36 04GO14006 (Design and Development of New Carbon-based Sorbent Systems for an Effective Containment of Hydrogen). The project was directed to discover new solid and liquid materials that use reversible catalytic hydrogenation as the mechanism for hydrogen capture and storage. After a short period of investigation of solid materials, the inherent advantages of storing and transporting hydrogen using liquid-phase materials focused our attention exclusively on organic liquid hydrogen carriers (liquid carriers). While liquid carriers such as decalin and methylcyclohexane were known in the literature, these carriers suffer from practical disadvantages such as the need for very high temperatures to release hydrogen from the carriers and difficult separation of the carriers from the hydrogen. In this project, we were successful in using the prediction of reaction thermodynamics to discover liquid carriers that operate at temperatures up to 150 C lower than the previously known carriers. The means for modifying the thermodynamics of liquid carriers involved the use of certain molecular structures and incorporation of elements other than carbon into the carrier structure. The temperature decrease due to the more favorable reaction thermodynamics results in less energy input to release hydrogen from the carriers. For the first time, the catalytic reaction required to release hydrogen from the carriers could be conducted with the carrier remaining in the liquid phase. This has the beneficial effect of providing a simple means to separate the hydrogen from the carrier.

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.

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.

Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

Science.gov (United States)

Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

2015-07-21

Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

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.

A combinatorial characterization scheme for high-throughput investigations of hydrogen storage materials

International Nuclear Information System (INIS)

Hattrick-Simpers, Jason R; Chiu, Chun; Bendersky, Leonid A; Tan Zhuopeng; Oguchi, Hiroyuki; Heilweil, Edwin J; Maslar, James E

2011-01-01

In order to increase measurement throughput, a characterization scheme has been developed that accurately measures the hydrogen storage properties of materials in quantities ranging from 10 ng to 1 g. Initial identification of promising materials is realized by rapidly screening thin-film composition spread and thickness wedge samples using normalized IR emissivity imaging. The hydrogen storage properties of promising samples are confirmed through measurements on single-composition films with high-sensitivity (resolution <0.3 μg) Sievert's-type apparatus. For selected samples, larger quantities of up to ∼100 mg may be prepared and their (de)hydrogenation and micro-structural properties probed via parallel in situ Raman spectroscopy. Final confirmation of the hydrogen storage properties is obtained on ∼1 g powder samples using a combined Raman spectroscopy/Sievert's apparatus.

Aerobic, Metal-Free, and Catalytic Dehydrogenative Coupling of Heterocycles: En Route to Hedgehog Signaling Pathway Inhibitors.

Science.gov (United States)

Bering, Luis; Paulussen, Felix M; Antonchick, Andrey P

2018-04-06

The nitrosonium ion-catalyzed dehydrogenative coupling of heteroarenes under mild reaction conditions is reported. The developed method utilizes ambient molecular oxygen as a terminal oxidant, and only water is produced as byproduct. Dehydrogenative coupling of heteroarenes translated into the rapid discovery of novel hedgehog signaling pathway inhibitors, emphasizing the importance of the developed methodology.

Prospects for hydrogen in the German energy system

International Nuclear Information System (INIS)

Hake, J.-F.; Linssen, J.; Walbeck, M.

2006-01-01

The focus of the paper concerns the current discussion on the contribution of the hydrogen economy to a 'sustainable energy system'. It considers whether advantages for the environmental situation and energy carrier supply can be expected from the already visible future characteristics of hydrogen as a new secondary energy carrier. Possible production paths for hydrogen from hydrocarbon-based, renewable or carbon-reduced/-free primary energy carriers are evaluated with respect to primary energy use and CO 2 emissions from the fuel cycle. Hydrogen has to be packaged by compression or liquefaction, transported by surface vehicles or pipelines, stored and transferred to the end user. Whether generated by electrolysis or by reforming, and even if produced locally at filling stations, the gaseous or liquid hydrogen has to undergo these market processes before it can be used by the customer. In order to provide an idea of possible markets with special emphasis on the German energy sector, a technical systems analysis of possible hydrogen applications is performed for the stationary, mobile and portable sector. Furthermore, different 'business as usual' scenarios are analysed for Germany, Europe and the World concerning end energy use in different sectors. The very small assumed penetration of hydrogen in the analysed scenarios up to the year 2050 indicates that the hydrogen economy is a long-term option. With reference to the assumed supply paths and analysed application possibilities, hydrogen can be an option for clean energy use if hydrogen can be produced with carbon-reduced or -free primary energy carriers like renewable energy or biomass. However, the energetic use of hydrogen competes with the direct use of clean primary energy and/or with the use of electric energy based on renewable primary energy. As a substitution product for other secondary energy carriers hydrogen is therefore under pressure of costs and/or must have advantages in comparison to the use of

Fabrication of hollow silica–zirconia composite spheres and their 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); Hosoya, Tatsuya; Toyama, Naoki [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)

2014-09-01

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{sub 3}BH{sub 3}) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0 mL hydrogen from aqueous NH{sub 3}BH{sub 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

Hydrogen storage by organic chemical hydrides and hydrogen supply to fuel cells with superheated liquid-film-type catalysis

International Nuclear Information System (INIS)

Hodoshima, S.; Shono, A.; Sato, K.; Saito, Y.

2004-01-01

Organic chemical hydrides, consisting of decalin / naphthalene and tetralin / naphthalene pairs, have been proposed as the storage medium of hydrogen for operating fuel cells in mobile and static modes. The target values in the DOE Hydrogen Plan, U.S., on storage ( 6.5 wt%, 62.0 kg-H 2 / m 3 ) are met with decalin ( 7.3 wt%, 64.8 kg-H 2 / m 3 ). In addition, existing gas stations and tank lorries are available for storage and supply of hydrogen by utilizing the decalin / naphthalene pair, suggesting that decalin is suitable for operating fuel-cell vehicles. Tetralin dehydrogenation proceeds quite rapidly, assuring a predominant power density, though its storage densities ( 3.0 wt%, 28.2 kg-H 2 / m 3 ) are relatively low. Efficient hydrogen supply from decalin or tetralin by heating at 210-280 o C was attained only with the carbon-supported nano-size metal catalysts in the 'superheated liquid-film states' under reactive distillation conditions, where coke formation over the catalyst surface was prevented. The catalyst layer superheated in the liquid-film states gave high reaction rates and conversions, minimizing the evaporation loss under boiling conditions and exergy loss in hydrogen energy systems. (author)

Combustion kinetics of the coke on deactivated dehydrogenation catalysts

NARCIS (Netherlands)

Luo, Sha; He, Songbo; Li, XianRu; Li, Jingqiu; Bi, Wenjun; Sun, Chenglin

2015-01-01

The coke combustion kinetics on the deactivated catalysts for long chain paraffin dehydrogenation was studied by the thermogravimetry and differential thermogravimetry (TG–DTG) technique. The amount and H/C mole ratio of the coke were determined by the TG and elemental analysis. And the

THE LATEST ADVANCEMENTS IN THE ACYLATION REACTIONS VIA CROSS-DEHYDROGENATIVE COUPLING AND/OR METAL CATALYSTS

Directory of Open Access Journals (Sweden)

Soykan Ağar

2017-12-01

Full Text Available There are quite many examples in the scientific literature regarding the acylation reactions, especially the metal-catalyzed acylation reactions, metal-free acylation reactions, metal-catalyzed acylation via cross-dehydrogenative coupling (CDC reactions and metal-free acylation via cross-dehydrogenative coupling (CDC reactions. In this review paper, the most important examples of these domains were brought together and their mechanisms were exhibited in a clear, chronological format. Following these, the best example study towards green chemistry with a metal-free and high-yielding route was mentioned and discussed to demonstrate what has achieved in this field regarding the new acylation reaction mechanisms using the advantages of cross-dehydrogenative coupling (CDC reactions. The most prominent studies regarding these domains have been examined thoroughly and the latest progress in this field was explained in detail.

Evaluation of the Parameters and Conditions of Process in the Ethylbenzene Dehydrogenation with Application of Permselective Membranes to Enhance Styrene Yield.

Science.gov (United States)

Araújo, Paulo Jardel P; Leite, Manuela Souza; Ravagnani, Teresa M Kakuta

2016-01-01

Styrene is an important monomer in the manufacture of thermoplastic. Most of it is produced by the catalytic dehydrogenation of ethylbenzene. In this process that depends on reversible reactions, the yield is usually limited by the establishment of thermodynamic equilibrium in the reactor. The styrene yield can be increased by using a hybrid process, with reaction and separation simultaneously. It is proposed using permselective composite membrane to remove hydrogen and thus suppress the reverse and secondary reactions. This paper describes the simulation of a dehydrogenation process carried out in a tubular fixed-bed reactor wrapped in a permselective composite membrane. A mathematical model was developed, incorporating the various mass transport mechanisms found in each of the membrane layers and in the catalytic fixed bed. The effects of the reactor feed conditions (temperature, steam-to-oil ratio, and the weight hourly space velocity), the fixed-bed geometry (length, diameter, and volume), and the membrane geometry (thickness of the layers) on the styrene yield were analyzed. These variables were used to determine experimental conditions that favour the production of styrene. The simulation showed that an increase of 40.98% in the styrene yield, compared to a conventional fixed-bed process, could be obtained by wrapping the reactor in a permselective composite membrane.

Evaluation of the Parameters and Conditions of Process in the Ethylbenzene Dehydrogenation with Application of Permselective Membranes to Enhance Styrene Yield

Directory of Open Access Journals (Sweden)

Paulo Jardel P. Araújo

2016-01-01

Full Text Available Styrene is an important monomer in the manufacture of thermoplastic. Most of it is produced by the catalytic dehydrogenation of ethylbenzene. In this process that depends on reversible reactions, the yield is usually limited by the establishment of thermodynamic equilibrium in the reactor. The styrene yield can be increased by using a hybrid process, with reaction and separation simultaneously. It is proposed using permselective composite membrane to remove hydrogen and thus suppress the reverse and secondary reactions. This paper describes the simulation of a dehydrogenation process carried out in a tubular fixed-bed reactor wrapped in a permselective composite membrane. A mathematical model was developed, incorporating the various mass transport mechanisms found in each of the membrane layers and in the catalytic fixed bed. The effects of the reactor feed conditions (temperature, steam-to-oil ratio, and the weight hourly space velocity, the fixed-bed geometry (length, diameter, and volume, and the membrane geometry (thickness of the layers on the styrene yield were analyzed. These variables were used to determine experimental conditions that favour the production of styrene. The simulation showed that an increase of 40.98% in the styrene yield, compared to a conventional fixed-bed process, could be obtained by wrapping the reactor in a permselective composite membrane.

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.

Thermodynamic Tuning of Mg-Based Hydrogen Storage Alloys: A Review

Science.gov (United States)

Zhu, Min; Lu, Yanshan; Ouyang, Liuzhang; Wang, Hui

2013-01-01

Mg-based hydrides are one of the most promising hydrogen storage materials because of their relatively high storage capacity, abundance, and low cost. However, slow kinetics and stable thermodynamics hinder their practical application. In contrast to the substantial progress in the enhancement of the hydrogenation/dehydrogenation kinetics, thermodynamic tuning is still a great challenge for Mg-based alloys. At present, the main strategies to alter the thermodynamics of Mg/MgH2 are alloying, nanostructuring, and changing the reaction pathway. Using these approaches, thermodynamic tuning has been achieved to some extent, but it is still far from that required for practical application. In this article, we summarize the advantages and disadvantages of these strategies. Based on the current progress, finding reversible systems with high hydrogen capacity and effectively tailored reaction enthalpy offers a promising route for tuning the thermodynamics of Mg-based hydrogen storage alloys. PMID:28788353

A Rechargeable Hydrogen Battery.

Science.gov (United States)

Christudas Dargily, Neethu; Thimmappa, Ravikumar; Manzoor Bhat, Zahid; Devendrachari, Mruthunjayachari Chattanahalli; Kottaichamy, Alagar Raja; Gautam, Manu; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2018-04-27

We utilize proton-coupled electron transfer in hydrogen storage molecules to unlock a rechargeable battery chemistry based on the cleanest chemical energy carrier molecule, hydrogen. Electrochemical, spectroscopic, and spectroelectrochemical analyses evidence the participation of protons during charge-discharge chemistry and extended cycling. In an era of anthropogenic global climate change and paramount pollution, a battery concept based on a virtually nonpolluting energy carrier molecule demonstrates distinct progress in the sustainable energy landscape.

Tritium labelling of testosteron by selective hydrogenation of dihydrotestosteron

International Nuclear Information System (INIS)

Postolache, Cristian; Matei, Lidia; Simion, Elena; Barna, Catalina; Condac, Eduard

2002-01-01

Elemental tritium is obtained during the decontamination process of the moderator from Cernavoda Nuclear Power Plant. It might be stocked for use in controlled fusion, in a relatively far future, or, it might be immediately used as raw material in the synthesis of labelled compounds with important economic value. Labelling of testosteron with tritium was necessary for the carrying out of radiometric and molecular biology studies concerning androgen dependent diseases. Testosteron was labelled by selective hydrogenation of 1,2 dihydrotestosteron acetate. The forerunner was synthesized in two steps: 1) esterification of testosteron using acetic anhydride, and 2) selective dehydrogenation with 2,6-dichloro-3,5-dicyan-1,4 quinone (DDQ) of the ester formed in the first step. Testosteron acetate was synthesized and purified with yields of 73%, and 80%, respectively. The dehydrogenation process was characterized by yields of 82% for synthesis and 33% for purification. The tritium labelled hormone was obtained in two steps: 1) selective hydrogenation of Δ 1 - testosteron acetate in the presence of T 2 gas, at low pressure, and 2) hydrolysis of the ester at basic pH. The raw product obtained was purified by preparative thin layer chromatography. The physical and chemical characterization of labelled testosteron reveals a radiochemical purity higher than 98% and a specific activity of 53.4 Ci/mmol. (authors)

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

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.

Experimental study on steam gasification of coal using molten blast furnace slag as heat carrier for producing hydrogen-enriched syngas

International Nuclear Information System (INIS)

Duan, Wenjun; Yu, Qingbo; Wu, Tianwei; Yang, Fan; Qin, Qin

2016-01-01

Highlights: • New method for producing HRG by gasification using BFS as heat carrier was proposed. • The continuous experiment of steam gasification in molten BFS was conducted. • The hydrogen-enriched syngas was produced by this method. • The molten BFS waste heat was utilized effectively by steam gasification. • This method could be widely used in steam gasification of different types of coal. - Abstract: The new method for producing hydrogen-enriched syngas (HRG) by steam gasification of coal using molten blast furnace slag (BFS) as heat carrier was established. In order to achieve the HRG production, a gasification system using this method was proposed and constructed. The carbon gasification efficiency (CE), hydrogen yield (YH_2) and cold gasification efficiency (CGE) in the molten slag reactor were measured, and the effects of temperature, S/C (steam to coal) ratio and coal type on the reaction performance were accessed. The results indicated that the preferred temperature was 1350 °C, which ensured the miscibility of coal–steam–slag, the diffusion of reactant in molten BFS as well as recovering waste heat. The optimal S/C ratio was 1.5–2.0 for producing HRG. Under these conditions, the hydrogen fraction was higher than 63% and the gas yield reached to 1.89 Nm"3/kg. The CE and CGE were higher than 96% and 102%, respectively. The YH_2 also reached to 1.20 Nm"3/kg. Meanwhile, different types of coal were successfully gasified in molten BFS reactor for producing HRG. The proposed method enhanced the gasification efficiency of different types of coal, recovered the BFS waste heat effectively, and had important guidance for industrial manufacture.

Upgrading Lignocellulosic Products to Drop-In Biofuels via Dehydrogenative Cross-Coupling and Hydrodeoxygenation Sequence.

Science.gov (United States)

Sreekumar, Sanil; Balakrishnan, Madhesan; Goulas, Konstantinos; Gunbas, Gorkem; Gokhale, Amit A; Louie, Lin; Grippo, Adam; Scown, Corinne D; Bell, Alexis T; Toste, F Dean

2015-08-24

Life-cycle analysis (LCA) allows the scientific community to identify the sources of greenhouse gas (GHG) emissions of novel routes to produce renewable fuels. Herein, we integrate LCA into our investigations of a new route to produce drop-in diesel/jet fuel by combining furfural, obtained from the catalytic dehydration of lignocellulosic pentose sugars, with alcohols that can be derived from a variety of bio- or petroleum-based feedstocks. As a key innovation, we developed recyclable transition-metal-free hydrotalcite catalysts to promote the dehydrogenative cross-coupling reaction of furfural and alcohols to give high molecular weight adducts via a transfer hydrogenation-aldol condensation pathway. Subsequent hydrodeoxygenation of adducts over Pt/NbOPO4 yields alkanes. Implemented in a Brazilian sugarcane biorefinery such a process could result in a 53-79% reduction in life-cycle GHG emissions relative to conventional petroleum fuels and provide a sustainable source of low carbon diesel/jet fuel. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Frontiers, Opportunities and Challenges for a Hydrogen Economy

Science.gov (United States)

Turner, John

2015-03-01

Energy carriers are the staple for powering the society we live in. Coal, oil, natural gas, gasoline and diesel all carry energy in chemical bonds, used in almost all areas of our civilization. But these carriers have a limited-use lifetime on this planet. They are finite, contribute to climate change and carry significant geopolitical issues. If mankind is to maintain and grow our societies, new energy carriers must be developed and deployed into our energy infrastructure. Hydrogen is the simplest of all the energy carriers and when refined from water using renewable energies like solar and wind, represents a sustainable energy carrier, viable for millennia to come. This talk with discuss the challenges for sustainable production of hydrogen, along with the promise and possible pathways for implementing hydrogen into our energy infrastructure.

Chemical-clathrate hybrid hydrogen storage: storage in both guest and host.

Science.gov (United States)

Strobel, Timothy A; Kim, Yongkwan; Andrews, Gary S; Ferrell, Jack R; Koh, Carolyn A; Herring, Andrew M; Sloan, E Dendy

2008-11-12

Hydrogen storage from two independent sources of the same material represents a novel approach to the hydrogen storage problem, yielding storage capacities greater than either of the individual constituents. Here we report a novel hydrogen storage scheme in which recoverable hydrogen is stored molecularly within clathrate cavities as well as chemically in the clathrate host material. X-ray diffraction and Raman spectroscopic measurements confirm the formation of beta-hydroquinone (beta-HQ) clathrate with molecular hydrogen. Hydrogen within the beta-HQ clathrate vibrates at considerably lower frequency than hydrogen in the free gaseous phase and rotates nondegenerately with splitting comparable to the rotational constant. Compared with water-based clathrate hydrate phases, the beta-HQ+H2 clathrate shows remarkable stability over a range of p-T conditions. Subsequent to clathrate decomposition, the host HQ was used to directly power a PEM fuel cell. With one H2 molecule per cavity, 0.61 wt % hydrogen may be stored in the beta-HQ clathrate cavities. When this amount is combined with complete dehydrogenation of the host hydroxyl hydrogens, the maximum hydrogen storage capacity increases nearly 300% to 2.43 wt %.

The effect of substitutional elements (Al, Co) in LaNi4.5M0.5 on the lattice defect formation in the initial hydrogenation and dehydrogenation

International Nuclear Information System (INIS)

Sakaki, Kouji; Akiba, Etsuo; Mizuno, Masataka; Araki, Hideki; Shirai, Yasuharu

2009-01-01

The formation of the vacancy and dislocation by the initial hydrogenation and dehydrogenation in LaNi 4.5 M 0.5 (M = Al, Co, and Ni) was observed by means of the positron lifetime technique. The concentrations of vacancy introduced by these processes were 0.25, 0.13 and 0.01 at.% for LaNi 5 , LaNi 4.5 Co 0.5 and LaNi 4.5 Al 0.5 , respectively. Al substitution into LaNi 5 significantly prevented from vacancy formation, compared with LaNi 5 and LaNi 4.5 Co 0.5 . In LaNi 4.5 Al 0.5 , the increase of the hardness and the enhancement of the pulverization, i.e. enhancement of the formation of micro cracks compared with LaNi 5 were observed while the Co substitution had little effect on pulverization and hardness as well as vacancy formation. These results show that the formation of micro cracks became more active process by Al substitution than the formation of the lattice defects to release the strain energy generated by the hydride formation because of the higher formation energy of the lattice defects in LaNi 4.5 Al 0.5 , although both the formation of micro cracks and lattice defects were still observed in all alloys we studied

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.

Interaction of hydrogen with an Mg-Al alloy

International Nuclear Information System (INIS)

Andreasen, A.; Sorensen, M.B.; Burkarl, R.; Moller, B.; Molenbroek, A.M.; Pedersen, A.S.; Andreasen, J.W.; Nielsen, M.M.; Jensen, T.R.

2005-01-01

The interaction of hydrogen with an Mg-Al alloy pre-exposed to air have been studied with in situ time resolved X-ray powder diffraction. Phase fractions as a function of time are derived from series of consecutive diffraction patterns allowing kinetic analysis. The apparent activation energy for dehydrogenation of the Mg-Al alloy is found to be 160 kJ/mol. This is not significantly higher than for pure and fully activated Mg. It is suggested that the addition of Al improves the resistance towards oxygen contamination

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 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...... 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....

Hydrogen: an energy carrier of the future

Energy Technology Data Exchange (ETDEWEB)

Hamerak, K

1977-02-01

Some advantages and fields of application of hydrogen are outlined in the introduction. Hydrogen production by conventional water electrolysis, by the thermochemical iron-chlorine cycle process, and by a new water electrolysis method still in the laboratory stage are dealt with in which the electrolysis voltage is considerably reduced by the action of solar UV light on an anode consisting of p-conducting material.

Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow

DEFF Research Database (Denmark)

Corker, Emily C.; Ruiz-Martínez, Javier; Riisager, Anders

2015-01-01

The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions...... and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over RuO2/Al2O3...

Hydrogenation study of suction-cast Ti{sub 40}Zr{sub 40}Ni{sub 20} quasicrystal

Energy Technology Data Exchange (ETDEWEB)

Huang, Huogen; Li, Rong; Yin, Chen; Zheng, Shaotao; Zhang, Pengcheng [National Key Laboratory for Surface Physics and Chemistry, P.O. Box 718-35, Mian Yang 621907, Sichuan (China)

2008-09-15

Suction casting was predicted to be an usable method for improving the hydriding kinetics of Ti/Zr-based icosahedral quasicrystals (IQCs) in our previous work. To further determine it, a suction-cast Ti{sub 40}Zr{sub 40}Ni{sub 20} IQC alloy was used for hydrogenation studies by Pressure Composition Isotherm (PCI) and Temperature Programmed Desorption (TPD) techniques. The results showed that, this alloy absorbed hydrogen rapidly with obvious hydrogen pressure plateau and some reversibility, however, displayed very limited hydrogen capacity (about 0.7 wt.%) and low equilibrium pressure. After several hydrogenation/dehydrogenation cycles, the IQC structure transformed into two hydride phases, ZrH{sub 2-x} and one unknown, both of which decomposed at above 600 C, suggesting high thermo-stability for them. On the whole, indeed the suction-casting method can increase the hydrogen absorption rate of Ti/Zr-based IQCs, however, the hydrogenation properties of the Ti{sub 40}Zr{sub 40}Ni{sub 20} IQC alloy still need a mighty advancement. (author)

Hydrogen from biomass

NARCIS (Netherlands)

Claassen, P.A.M.; Vrije, de G.J.

2006-01-01

Hydrogen is generally regarded as the energy carrier of the future. The development of a process for hydrogen production from biomass complies with the policy of the Dutch government to obtain more renewable energy from biomass. This report describes the progress of the BWP II project, phase 2 of

Ammonia for hydrogen storage: challenges and opportunities

DEFF Research Database (Denmark)

Klerke, Asbjørn; Christensen, Claus H.; Nørskov, Jens Kehlet

2008-01-01

The possibility of using ammonia as a hydrogen carrier is discussed. Compared to other hydrogen storage materials, ammonia has the advantages of a high hydrogen density, a well-developed technology for synthesis and distribution, and easy catalytic decomposition. Compared to hydrocarbons...... and alcohols, it has the advantage that there is no CO2 emission at the end user. The drawbacks are mainly the toxicity of liquid ammonia and the problems related to trace amounts of ammonia in the hydrogen after decomposition. Storage of ammonia in metal ammine salts is discussed, and it is shown...... that this maintains the high volumetric hydrogen density while alleviating the problems of handling the ammonia. Some of the remaining challenges for research in ammonia as a hydrogen carrier are outlined....

Hydrogen storage properties of Mg-23.3wt.%Ni eutectic alloy prepared via hydriding combustion synthesis followed by mechanical milling

International Nuclear Information System (INIS)

Liquan Li; Yunfeng Zhu; Xiaofeng Liu

2006-01-01

A Mg-23.3wt.%Ni eutectic alloy was prepared by the process of hydriding combustion synthesis followed by mechanical milling (HCS+MM). The product showed a high hydriding rate at 373 K and the dehydrogenation started at temperature as low as 423 K. Several reasons contributing to the improvement in hydrogen storage properties were presented. The result of this study will provide attractive information for mobile applications of magnesium hydrogen storage materials, and the process of HCS+MM developed in this study showed its potential for synthesizing magnesium based hydrogen storage materials with novel hydriding/de-hydriding properties. (authors)

Preparation and Hydrogen Storage Properties of Mg-Rich Mg-Ni Ultrafine Particles

Directory of Open Access Journals (Sweden)

Jianxin Zou

2012-01-01

Full Text Available In the present work, Mg-rich Mg-Ni ultrafine powders were prepared through an arc plasma method. The phase components, microstructure, and hydrogen storage properties of the powders were carefully investigated. It is found that Mg2Ni and MgNi2 could be obtained directly from the vapor state reactions between Mg and Ni, depending on the local vapor content in the reaction chamber. A nanostructured MgH2 + Mg2NiH4 hydrogen storage composite could be generated after hydrogenation of the Mg-Ni ultrafine powders. After dehydrogenation, MgH2 and Mg2NiH4 decomposed into nanograined Mg and Mg2Ni, respectively. Thermogravimetry/differential scanning calorimetry (TG/DSC analyses showed that Mg2NiH4 phase may play a catalytic role in the dehydriding process of the hydrogenated Mg ultrafine particles.

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.

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�

Demonstrative study on the production of hydrogen and aromatic compounds originated from biogas in the Dairy area

International Nuclear Information System (INIS)

Yukoh Shudo; Takashi Ohkubo; Yoshiaki Hideshima

2006-01-01

The biogas yielded by methane fermentation of cow slurry was provided for the experimental facilities and the refined methane was introduced to the methane direct reformer. Dehydrogenation and aromatization of methane generated hydrogen and aromatic compounds, such as benzene. In order to keep the conversion rate, pre-treatment and regeneration of the catalysts were carried out and in order to control coking at the catalysts, hydrogen was added to the material methane. Moreover a part of the un-reacted methane was introduced to the steam reformer and 99.99% pure hydrogen was produced by the pressure swing adsorption (PSA). With the result that, it was supposed that pre-treating by methane and hydrogen, repeating regeneration by hydrogen, and more than 9% hydrogen addition were needed to stabilize the formation of hydrogen and benzene. And furthermore, material balance of the experimental facilities was clarified. (authors)

Realizing nanographene activated by a vacancy to solve hydrogen storage problem

Science.gov (United States)

Sunnardianto, Gagus Ketut; Maruyama, Isao; Kusakabe, Koichi

We found a triply hydrogenated vacancy (V111) in nanographene reduces an activation barrier of adsorption-desorption process in both ways in an equal manner from the known values for pristine graphene as well as those of other hydrogenated vacancies of graphene. This finding may give a key to overcome existing problems in the hydrogen uptake and release processes in known hydrogen storage materials, e.g. graphene and organic hydrides (OHs) in near ambient operation temperature. In this study, we used DFT-NEB simulation to estimate the barrier height, which is supported by realized real experiments. We consider a nanographene molecule (VANG) which contains V111 with armchair structure at the periphery. We found interesting feature in comparable values of energy barriers for both hydrogen uptake and release, where hydrogenation process is even a little bit endothermic and dehydrogenation is a little but exothermic nature. Thus, this material structure acts as ``self-catalytic properties'', which has an important role in reducing an energy barrier and as a trapping site for hydrogen serving a new material prevailing other hopeful candidates. The work is supported by JSPS KAKENHI in Science of Atomic Layers\\x9D.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-12-12

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

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...

Storage, generation, and use of hydrogen

Science.gov (United States)

McClaine, Andrew W.; Rolfe, Jonathan L.; Larsen, Christopher A.; Konduri, Ravi K.

2006-05-30

A composition comprising a carrier liquid; a dispersant; and a chemical hydride. The composition can be used in a hydrogen generator to generate hydrogen for use, e.g., as a fuel. A regenerator recovers elemental metal from byproducts of the hydrogen generation process.

Simple and Efficient System for Combined Solar Energy Harvesting and Reversible Hydrogen Storage.

Science.gov (United States)

Li, Lu; Mu, Xiaoyue; Liu, Wenbo; Mi, Zetian; Li, Chao-Jun

2015-06-24

Solar energy harvesting and hydrogen economy are the two most important green energy endeavors for the future. However, a critical hurdle to the latter is how to safely and densely store and transfer hydrogen. Herein, we developed a reversible hydrogen storage system based on low-cost liquid organic cyclic hydrocarbons at room temperature and atmospheric pressure. A facile switch of hydrogen addition (>97% conversion) and release (>99% conversion) with superior capacity of 7.1 H2 wt % can be quickly achieved over a rationally optimized platinum catalyst with high electron density, simply regulated by dark/light conditions. Furthermore, the photodriven dehydrogenation of cyclic alkanes gave an excellent apparent quantum efficiency of 6.0% under visible light illumination (420-600 nm) without any other energy input, which provides an alternative route to artificial photosynthesis for directly harvesting and storing solar energy in the form of chemical fuel.

High and rapid hydrogen release from thermolysis of ammonia borane near PEM fuel cell operating temperature

Science.gov (United States)

Varma, Arvind; Hwang, Hyun Tae; Al-Kukhun, Ahmad

2016-11-15

A system for generating and purifying hydrogen. To generate hydrogen, the system includes inlets configured to receive a hydrogen carrier and an inert insulator, a mixing chamber configured to combine the hydrogen carrier and the inert insulator, a heat exchanger configured to apply heat to the mixture of hydrogen carrier and the inert insulator, wherein the applied heat results in the generation of hydrogen from the hydrogen carrier, and an outlet configured to release the generated hydrogen. To purify hydrogen, the system includes a primary inlet to receive a starting material and an ammonia filtration subassembly, which may include an absorption column configured to absorb the ammonia into water for providing purified hydrogen at a first purity level. The ammonia filtration subassembly may also include an adsorbent member configured to adsorb ammonia from the starting material into an adsorbent for providing purified hydrogen at a second purity level.

Dehydrogenation of Light Alkanes over Supported Pt Catalysts

OpenAIRE

Wu, Jason

2015-01-01

The production of light alkenes comprises a 250 million ton per year industry due to their extensive use in the production of plastics, rubbers, fuel blending agents, and chemical intermediates. While steam cracking and fluid catalytic cracking of petroleum crude oils are the most common methods for obtaining light alkenes, rising oil prices and low selectivities toward specific alkenes have driven the search for a more economical and efficient process. Catalytic dehydrogenation of light alka...

Hydrogen Production from Cyclic Chemical Looping Steam Methane Reforming over Yttrium Promoted Ni/SBA-16 Oxygen Carrier

Directory of Open Access Journals (Sweden)

Sanaz Daneshmand-Jahromi

2017-09-01

Full Text Available In this work, the modification of Ni/SBA-16 oxygen carrier (OC with yttrium promoter is investigated. The yttrium promoted Ni-based oxygen carrier was synthesized via co-impregnation method and applied in chemical looping steam methane reforming (CL-SMR process, which is used for the production of clean energy carrier. The reaction temperature (500–750 °C, Y loading (2.5–7.4 wt. %, steam/carbon molar ratio (1–5, Ni loading (10–30 wt. % and life time of OCs over 16 cycles at 650 °C were studied to investigate and optimize the structure of OC and process temperature with maximizing average methane conversion and hydrogen production yield. The synthesized OCs were characterized by multiples techniques. The results of X-ray powder diffraction (XRD and energy dispersive X-ray spectroscopy (EDX of reacted OCs showed that the presence of Y particles on the surface of OCs reduces the coke formation. The smaller NiO species were found for the yttrium promoted OC and therefore the distribution of Ni particles was improved. The reduction-oxidation (redox results revealed that 25Ni-2.5Y/SBA-16 OC has the highest catalytic activity of about 99.83% average CH4 conversion and 85.34% H2 production yield at reduction temperature of 650 °C with the steam to carbon molar ratio of 2.

Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

Science.gov (United States)

Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

2016-10-20

Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

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.

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).

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 =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.

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.

Center for Electrocatalysis, Transport Phenomena, and Materials (CETM) for Innovative Energy Storage - Final Report

Energy Technology Data Exchange (ETDEWEB)

Soloveichik, Grigorii [GE Global Research, Niskayuna, New York (United States)

2015-11-30

EFRC vision. The direct use of organic hydrides in fuel cells as virtual hydrogen carriers that generate stable organic molecules, protons, and electrons upon electro-oxidation and can be electrochemically charged by re-hydrogenating the oxidized carrier was the major focus of the Center for Electrocatalysis, Transport Phenomena and Materials for Innovative Energy Storage (EFRC-ETM). Compared to a hydrogen-on-demand design that includes thermal decomposition of organic hydrides in a catalytic reactor, the proposed approach is much simpler and does not require additional dehydrogenation catalysts or heat exchangers. Further, this approach utilizes the advantages of a flow battery (i.e., separation of power and energy, ease of transport and storage of liquid fuels) with fuels that have system energy densities similar to current hydrogen PEM fuel cells. EFRC challenges. Two major EFRC challenges were electrocatalysis and transport phenomena. The electrocatalysis challenge addresses fundamental processes which occur at a single molecular catalyst (microscopic level) and involve electron and proton transfer between the hydrogen rich and hydrogen depleted forms of organic liquid fuel and the catalyst. To form stable, non-radical dehydrogenation products from the organic liquid fuel, it is necessary to ensure fast transport of at least two electrons and two protons (per double bond formation). The same is true for the reverse hydrogenation reaction. The transport phenomena challenge addresses transport of electrons to/from the electrocatalyst and the current collector as well as protons across the polymer membrane. Additionally it addresses prevention of organic liquid fuel, water and oxygen transport through the PEM. In this challenge, the transport of protons or molecules involves multiple sites or a continuum (macroscopic level) and water serves as a proton conducting medium for the majority of known sulfonic acid based PEMs. Proton transfer in the presence of

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.)

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.

Adsorption and dehydrogenation of ammonia at the V{sub 2}O{sub 5}(010) surface: DFT cluster studies

Energy Technology Data Exchange (ETDEWEB)

Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, Berlin (Germany)

2008-07-01

Transition metal oxide catalysts are widely used for selective oxidation reactions. However, in many cases details of the catalytic reaction mechanisms are still under discussion. One prominent example is the ammoxidation of propylene to acrylonitrile at transition metal oxide surfaces (SOHIO process). This catalytic reaction includes, amongst other steps, the adsorption and dehydrogenation of NH{sub x}, x<4, at the catalyst surface. We have performed theoretical studies on these reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5}(010) surface. The calculations use density-functional theory combined with clusters modeling the surface and adsorbate system. Calculations for the clean V{sub 2}O{sub 5}(010) surface show that binding energies of the H atom are always significantly larger than of the NH{sub x} species. Further, the substrate is found to lower corresponding dehydrogenation energies compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation likely to happen under ammoxidation reaction conditions. This suggests that surface defects such as oxygen vacancies become important for the reaction. Therefore, the role of oxygen vacancies for the dehydrogenation of NH{sub x} is discussed in detail.

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.

Alkane Metathesis

KAUST Repository

Basset, Jean-Marie; Callens, Emmanuel; Riache, Nassima

2015-01-01

metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two

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.)

An aqueous rechargeable formate-based hydrogen battery driven by heterogeneous Pd catalysis.

Science.gov (United States)

Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; Du, Xian-Long; Wang, Jian-Qiang; He, He-Yong; Cao, Yong

2014-12-01

The formate-based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H2 storage used in fuel cell applications. Described herein is an additive-free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H2 handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner. Up to six repeated discharging/charging cycles can be performed without noticeable degradation in the storage capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope.

Science.gov (United States)

Kitaguchi, Y; Shiotari, A; Okuyama, H; Hatta, S; Aruga, T

2011-05-07

Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.

Scenarios for total utilisation of hydrogen as an energy carrier in the future Danish energy system. Final report; Scenarier for samlet udnyttelse af brint som energibaerer i Danmarks fremtidige energisystem. Slutrapport

Energy Technology Data Exchange (ETDEWEB)

Hauge Petersen, A; Engberg Pedersen, T; Joergensen, K [and others

2001-04-01

This is the final report from a project performed for the Danish Energy Agency under its Hydrogen Programme. The project, which within the project group goes by the abbreviated title 'Hydrogen as an energy carrier', constructs and analyses different total energy scenarios for introducing hydrogen as an energy carrier, as energy storage medium and as a fuel in the future Danish energy system. The primary aim of the project is to study ways of handling the large deficits and surpluses of electricity from wind energy expected in the future Danish energy system. System-wide aspects of the choice of hydrogen production technologies, distribution methods, infrastructure requirements and conversion technologies are studied. Particularly, the possibility of using in the future the existing Danish natural gas distribution grid for carrying hydrogen will be assessed. For the year 2030, two scenarios are constructed: One using hydrogen primarily in the transportation sector, the other using it as a storage option for the centralised power plants still in operation by this year. For the year 2050, where the existing fossil power plants are expected to have been phased out completely, the scenarios for two possible developments are investigated: Either, there is a complete decentralisation of the use of hydrogen, converting and storing electricity surpluses into hydrogen in individual buildings, for later use in vehicles or regeneration of power and heat. Or, some centralised infrastructure is retained, such as hydrogen cavern stores and a network of vehicle hydrogen filling stations. The analysis is used to identify the components in an implementation strategy, for the most interesting scenarios, including a time sequence of necessary decisions and technology readiness. The report is in Danish, because it is part of the dissemination effort of the Hydrogen Committee, directed at the Danish population in general and the Danish professional community in particular. (au)

Scenarios for total utilisation of hydrogen as an energy carrier in the future Danish energy system. Final report; Scenarier for samlet udnyttelse af brint som energibaerer i Danmarks fremtidige energisystem. Slutrapport

Energy Technology Data Exchange (ETDEWEB)

Hauge Petersen, A.; Engberg Pedersen, T.; Joergensen, K. (and others)

2001-04-01

This is the final report from a project performed for the Danish Energy Agency under its Hydrogen Programme. The project, which within the project group goes by the abbreviated title 'Hydrogen as an energy carrier', constructs and analyses different total energy scenarios for introducing hydrogen as an energy carrier, as energy storage medium and as a fuel in the future Danish energy system. The primary aim of the project is to study ways of handling the large deficits and surpluses of electricity from wind energy expected in the future Danish energy system. System-wide aspects of the choice of hydrogen production technologies, distribution methods, infrastructure requirements and conversion technologies are studied. Particularly, the possibility of using in the future the existing Danish natural gas distribution grid for carrying hydrogen will be assessed. For the year 2030, two scenarios are constructed: One using hydrogen primarily in the transportation sector, the other using it as a storage option for the centralised power plants still in operation by this year. For the year 2050, where the existing fossil power plants are expected to have been phased out completely, the scenarios for two possible developments are investigated: Either, there is a complete decentralisation of the use of hydrogen, converting and storing electricity surpluses into hydrogen in individual buildings, for later use in vehicles or regeneration of power and heat. Or, some centralised infrastructure is retained, such as hydrogen cavern stores and a network of vehicle hydrogen filling stations. The analysis is used to identify the components in an implementation strategy, for the most interesting scenarios, including a time sequence of necessary decisions and technology readiness. The report is in Danish, because it is part of the dissemination effort of the Hydrogen Committee, directed at the Danish population in general and the Danish professional community in particular. (au)

Methanol as an energy source and/or energy carrier in membrane processes

NARCIS (Netherlands)

Gallucci, F.; Basile, A.; Drioli, E.

2007-01-01

Methanol is commonly considered a hydrogen source and/or hydrogen carrier. In fact, methanol can be produced by partial oxidation of biomass and in this case it is considered a source for hydrogen and therefore for energy. It can also be produced from carbon dioxide and hydrogen; in this case, it

Oxidative dehydrogenation of aqueous ethanol on a carbon supported platinum catalyst

NARCIS (Netherlands)

Tillaart, van den J.A.A.; Kuster, B.F.M.; Marin, G.B.M.M.

1994-01-01

The kinetics of the selective oxidative dehydrogenation of ethanol to ethanal over a platinum on graphite catalyst with oxygen in water was investigated in a three-phase continuous stirred tank reactor by variation of temp., pH and reactant concns. No effect of the pH on the disappearance rate of

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

Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

Energy Technology Data Exchange (ETDEWEB)

Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

2005-11-15

This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

Carbon Dioxide-Free Hydrogen Production with Integrated Hydrogen Separation and Storage.

Science.gov (United States)

Dürr, Stefan; Müller, Michael; Jorschick, Holger; Helmin, Marta; Bösmann, Andreas; Palkovits, Regina; Wasserscheid, Peter

2017-01-10

An integration of CO 2 -free hydrogen generation through methane decomposition coupled with hydrogen/methane separation and chemical hydrogen storage through liquid organic hydrogen carrier (LOHC) systems is demonstrated. A potential, very interesting application is the upgrading of stranded gas, for example, gas from a remote gas field or associated gas from off-shore oil drilling. Stranded gas can be effectively converted in a catalytic process by methane decomposition into solid carbon and a hydrogen/methane mixture that can be directly fed to a hydrogenation unit to load a LOHC with hydrogen. This allows for a straight-forward separation of hydrogen from CH 4 and conversion of hydrogen to a hydrogen-rich LOHC material. Both, the hydrogen-rich LOHC material and the generated carbon on metal can easily be transported to destinations of further industrial use by established transport systems, like ships or trucks. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Diversity of hydrogen configuration and its roles in SrTiO3−δ

Directory of Open Access Journals (Sweden)

Yoshiki Iwazaki

2014-01-01

Full Text Available As a source of carrier electron, various configurations of hydrogen in SrTiO3 are searched by using first-principles calculations. The most stable form of hydrogen is found to be H−, where doubly charged oxygen vacancy VO2+ changes into singly charged HO+. Most importantly, an additional H− is found to be weakly trapped by HO+, which completely neutralizes carrier electrons by forming (2HO0. These unexpected behaviors of hydrogen, which can explain reported experimental results, expand the role of the hydrogen in carrier-control technology in transition-metal oxides.

Development of packed bed membrane reactor for the oxidative dehydrogenation of propane

NARCIS (Netherlands)

Kotanjac, Zeljko

2009-01-01

In this research, a reactor concept for the oxidative dehydrogenation of propane was studied. First a literature survey was performed, to investigate which are the best catalyst systems and best operating conditions that result in the largest propylene yield. In the kinetic study of ODHP over a

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

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

Science.gov (United States)

Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi

2015-04-28

The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

The hydrogen economy for a sustainable future and the potential contribution of nuclear power

International Nuclear Information System (INIS)

Hardy, C.

2003-01-01

The Hydrogen Economy encompasses the production of hydrogen using a wide range of energy sources, its storage and distribution as an economic and universal energy carrier, and its end use by industry and individuals with negligible emission of pollutants and greenhouse gases. Hydrogen is an energy carrier not a primary energy source, just like electricity is an energy carrier. The advantages of hydrogen as a means of storage and distribution of energy, and the methods of production of hydrogen, are reviewed. Energy sources for hydrogen production include fossil fuels, renewables, hydropower and nuclear power. Hydrogen has many applications in industry, for residential use and for transport by air, land and sea. Fuel cells are showing great promise for conversion of hydrogen into electricity and their development and current status are discussed. Non-energy uses of hydrogen and the safety aspects of hydrogen are also considered. It is concluded that the Hydrogen Economy, especially if coupled to renewable and nuclear energy sources, is a technically viable and economic way of achieving greater energy diversity and security and a sustainable future in this century

Efficiency analysis of hydrogen production methods from biomass

NARCIS (Netherlands)

Ptasinski, K.J.

2008-01-01

Abstract: Hydrogen is considered as a universal energy carrier for the future, and biomass has the potential to become a sustainable source of hydrogen. This article presents an efficiency analysis of hydrogen production processes from a variety of biomass feedstocks by a thermochemical method –

Biomass-based energy carriers in the transportation sector

International Nuclear Information System (INIS)

Johansson, Bengt.

1995-03-01

The purpose of this report is to study the technical and economic prerequisites to attain reduced carbon dioxide emissions through the use of biomass-based energy carriers in the transportation sector, and to study other environmental impacts resulting from an increased use of biomass-based energy carriers. CO 2 emission reduction per unit arable and forest land used for biomass production (kg CO 2 /ha,year) and costs for CO 2 emission reduction (SEK/kg CO 2 ) are estimated for the substitution of gasoline and diesel with rape methyl ester, biogas from lucerne, ethanol from wheat and ethanol, methanol, hydrogen and electricity from Salix and logging residues. Of the studied energy carriers, those based on Salix provide the largest CO 2 emission reduction. In a medium long perspective, the costs for CO 2 emission reduction seem to be lowest for methanol from Salix and logging residues. The use of fuel cell vehicles, using methanol or hydrogen as energy carriers, can in a longer perspective provide more energy efficient utilization of biomass for transportation than the use of internal combustion engine vehicles. 136 refs, 12 figs, 25 tabs

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.

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

International Nuclear Information System (INIS)

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

1977-01-01

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

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

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.

A first-principles study of lithium-decorated hybrid boron nitride and graphene domains for hydrogen storage

International Nuclear Information System (INIS)

Hu, Zi-Yu; Shao, Xiaohong; Wang, Da; Liu, Li-Min; Johnson, J. Karl

2014-01-01

First-principles calculations are performed to investigate the adsorption of hydrogen onto Li-decorated hybrid boron nitride and graphene domains of (BN) x C 1−x complexes with x = 1, 0.25, 0.5, 0.75, 0, and B 0.125 C 0.875 . The most stable adsorption sites for the nth hydrogen molecule in the lithium-decorated (BN) x C 1−x complexes are systematically discussed. The most stable adsorption sites were affected by the charge localization, and the hydrogen molecules were favorably located above the C-C bonds beside the Li atom. The results show that the nitrogen atoms in the substrate planes could increase the hybridization between the 2p orbitals of Li and the orbitals of H 2 . The results revealed that the (BN) x C 1−x complexes not only have good thermal stability but they also exhibit a high hydrogen storage of 8.7% because of their dehydrogenation ability

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.

Metal ammine complexes for hydrogen storage

DEFF Research Database (Denmark)

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

2005-01-01

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

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.

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

KAUST Repository

Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

2015-01-01

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

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

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...

Controlling reaction pathways for alcohol dehydration and dehydrogenation over FeSBA-15 catalysts

NARCIS (Netherlands)

Guan, Y.; Li, Y.; Santen, van R.A.; Hensen, E.J.M.; Li, Can

2007-01-01

The iron location in FeSBA-15 strongly influences the selectivity to dehydrogenation and dehydration in ethanol conversion. At low iron loading, Fe is present as isolated species in the amorphous silica phase. At higher loading additional aggregated forms of iron oxide exist. Isolated species in the

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.

Ultrafast carrier dynamics unravel role of surface ligands and metal domain size on the photocatalytic hydrogen evolution efficiency of Au-tipped CdS nanorods: an ultrafast transient absorption spectroscopy study

Science.gov (United States)

Ben-Shahar, Yuval; Kriegel, Ilka; Scotognella, Francesco; Waiskopf, Nir; Dal Conte, Stefano; Moretti, Luca; Cerullo, Giulio; Rabani, Eran; Banin, Uri

2017-02-01

Semiconductor-metal hybrid nanostructures are interesting materials for photocatalysis. Their tunable properties offer a highly controllable platform to design light-induced charge separation, a key to their function in photocatalytic water splitting. Hydrogen evolution quantum yields are influenced by factors as size, shape, material and morphology of the system, additionally the surface coating or the metal domain size play a dominant role. In this paper we present a study on a well-defined model system of Au-tipped CdS nanorods. We use transient absorption spectroscopy to get insights into the charge carrier dynamics after photoexcitation of the bandgap of CdS nanorods. The study of charge transfer processes combined with the hydrogen evolution efficiency unravels the effects of surface coating and the gold tip size on the photocatalytic efficiency. Differences in efficiency with various surface ligands are primarily ascribed to the effects of surface passivation. Surface trapping of charge carriers is competing with effective charge separation, a prerequisite for photocatalysis, leading to the observed lower hydrogen production quantum yields. Interestingly, non-monotonic hydrogen evolution efficiency with size of the gold tip is observed, resulting in an optimal metal domain size for the most efficient photocatalysis. These results are explained by the sizedependent interplay of the metal domain charging and the relative band-alignments. Taken together our findings are of major importance for the potential application of hybrid nanoparticles as photocatalysts.

Feasibility study of hydrogen determination in blended gas mixture by an indigenously developed hydrogen determinator

International Nuclear Information System (INIS)

Gaikwad, Revati; Sonar, V.R.; Pandey, R.K.; Karekar, C.D.; Raul, Seema; Mahanty, B.; Kelkar, A.; Bhatt, R.B.; Behere, P.G.

2017-01-01

It is required to determine accurately the percentage composition of hydrogen in the blended gas of N 2 and H 2 prior to deliver to the sintering furnace. A feasibility study has been carried out to determine the percentage composition of hydrogen in the blended gas by using an indigenously developed hydrogen determinator. The instrument uses gas chromatograph-thermal conductivity (GC-TCD) technique to determine hydrogen. The flow of carrier gas was kept at 100 mL min -1 during the analysis. A very close agreement between the determined value and the reported value of hydrogen content in the commercially available N 2 -H 2 mixed cylinder was found by using the indigenous hydrogen determinator. (author)

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

Developments and constraints in fermentative hydrogen production

NARCIS (Netherlands)

Bartacek, J.; Zabranska, J.; Lens, P.N.L.

2007-01-01

Fermentative hydrogen production is a novel aspect of anaerobic digestion. The main advantage of hydrogen is that it is a clean and renewable energy source/carrier with high specific heat of combustion and no contribution to the Greenhouse effect, and can be used in many industrial applications.

Gas-chromatographic separation of hydrogen isotopic mixtures

International Nuclear Information System (INIS)

Preda, Anisoara; Bidica, Nicolae

2005-01-01

Full text: Gas chromatographic separation of hydrogen isotopes have been reported in the literature since late of 1950's. Gas chromatography is primarily an analytical method, but because of its properties it may be used in many other fields with excellent results. A simple method is proposed for the gas-chromatographic analysis of complex gas mixtures containing hydrogen isotopes; the method is based on the substantial difference in the thermal conductivity of these isotopes. One of the main disadvantages of the conventional gas chromatography is the long retention times required for the analysis of hydrogen gas mixtures while the column is operated at very low temperature. The method described in this paper was based on using a capillary molecular sieve 5A column operated for this kind of separation at 173 K. The carrier gas was Ne and the detector was TCD. In the paper chromatograms for various carrier flow rates and various hydrogen isotope mixtures are presented. (authors)

Carrier-selective p- and n-contacts for efficient and stable photocatalytic water reduction

DEFF Research Database (Denmark)

Bae, Dowon; Pedersen, Thomas; Seger, Brian

2017-01-01

The successful realization of carrier-selective contacts for crystalline silicon (c-Si) based device for pho-tocatalytic hydrogen production has been demonstrated. The proposed TiO2protected carrier-selectivecontacts resemble a metal-oxide-semiconductor configuration, including a highly-doped nan...

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.)

Hydriding and dehydriding rates and hydrogen-storage capacity of ...

Indian Academy of Sciences (India)

means of nuclear, wind, solar, tidal or geothermal energy. When hydrogen is converted into energy, water is the only exhaust product. It is thus extremely environmental friendly as an energy carrier. Although hydrogen has obvious benefits, an immediate incorporation of hydrogen into the world economy has a number of ...

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.)

Oxidative dehydrogenation of the 2-aminomethylpyridine (EDTA) ruthenium (III) complex

International Nuclear Information System (INIS)

Toma, H.E.; Tsurumaki, M.

1990-01-01

The oxidative dehydrogenation of the 2-aminomethylpyridine (ampy) ligand coordinated to the (EDTA)RU(III) complex was investigated based on cyclic voltammetry, spectoelectrochemistry and stopped-flow kinetic measurements in aqueous solution. The reaction mechanism is consistent with the deprotonation of the ampy ligand (pk a =7.48), followed by a reversible one-electron transfer step. The intermediate species generated at this step undergoes a metal-induced electron transfer process, with k=227 s -1 , converting into the corresponding 2-iminomethylpyridine complex. (author) [pt

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.; Holt, Christopher; Abou-Hamad, Edy; Al-Talla, Zeyad; Saih, Youssef; Chaieb, Saharoui

2015-01-01

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.

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.

Hydrogen energy for the transportation sector in China

International Nuclear Information System (INIS)

Zong Qiangmao

2006-01-01

Hydrogen is a promising energy carrier for providing a clean, reliable and affordable energy supply. This paper provides a blueprint for the hydrogen energy in the transportation sector in the future of China. This paper is divided into three parts. The first part answers this question: why is China interested in hydrogen energy? The second part describes the possibility of a hydrogen fuel cell engine and a hydrogen internal-combustion engine in the transportation in China in the near future. The final part describes the production of hydrogen in China. (author)

Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline-Based, Proton-Responsive Ligand.

Science.gov (United States)

Wang, Lin; Onishi, Naoya; Murata, Kazuhisa; Hirose, Takuji; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

2017-03-22

A series of new imidazoline-based iridium complexes has been developed for hydrogenation of CO 2 and dehydrogenation of formic acid. One of the proton-responsive complexes bearing two -OH groups at ortho and para positions on a coordinating pyridine ring (3 b) can catalyze efficiently the chemical fixation of CO 2 and release H 2 under mild conditions in aqueous media without using organic additives/solvents. Notably, hydrogenation of CO 2 can be efficiently carried out under CO 2 and H 2 at atmospheric pressure in basic water by 3 b, achieving a turnover frequency of 106 h -1 and a turnover number of 7280 at 25 °C, which are higher than ever reported. Moreover, highly efficient CO-free hydrogen production from formic acid in aqueous solution employing the same catalyst under mild conditions has been achieved, thus providing a promising potential H 2 -storage system in water. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrolysis of ammonia borane as a hydrogen source: fundamental issues and potential solutions towards implementation.

Science.gov (United States)

Sanyal, Udishnu; Demirci, Umit B; Jagirdar, Balaji R; Miele, Philippe

2011-12-16

In today's era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO(2)-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B-N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt % H(2) and 0.145 kg(H2)L(-1), have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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…

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.

The hydrogen-storing microporous silica 'Microcluster' reduces acetaldehyde contained in a distilled spirit.

Science.gov (United States)

Kato, Shinya; Miwa, Nobuhiko

2016-12-01

Acetaldehyde is a detrimental substance produced in alcoholic liquor aging. We assessed an ability of hydrogen-storing microporous silica 'Microcluster' (MC+) to reduce acetaldehyde, as compared with autoclave-dehydrogenated MC+ (MC-). Acetaldehyde was quantified spectrophotometrically by an enzymatic method. Authentic acetaldehyde was treated by MC+ for 20min, and decreased from 43.4ppm to 10.9ppm, but maintained at 49.3ppm by MC-. On the other hand, acetaldehyde contained in a distilled spirit was decreased from 29.5ppm to 3.1ppm at 20min by MC+, but not decreased by MC-. Addition of MC+ or MC- to distilled water without acetaldehyde showed no seeming effect on the quantification used. Accordingly acetaldehyde in a distilled spirit is reduced to ethanol by hydrogen contained in MC+, but not by the silica moiety of MC+. Hydrogen gas of 1.2mL was released for 20min from MC+ of 0.59g in water, resulting in dissolved hydrogen of 1.09ppm and an oxidation- reduction potential of -687.0mV indicative of a marked reducing ability. Thus, MC+ has an ability to reduce acetaldehyde in a distilled spirit due to dissolved hydrogen released from MC+. Copyright © 2016 Elsevier B.V. All rights reserved.

Study of vanadium based mesoporous silicas for oxidative dehydrogenation of propane and n-butane

Czech Academy of Sciences Publication Activity Database

Bulánek, R.; Kalužová, A.; Setnička, M.; Zukal, Arnošt; Čičmanec, P.; Mayerová, Jana

2012-01-01

Roč. 179, č. 1 (2012), s. 149-158 ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/0196 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium * oxidative dehydrogenation * mesoporous silicas Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.980, year: 2012

The hydrogen issue.

Science.gov (United States)

Armaroli, Nicola; Balzani, Vincenzo

2011-01-17

Hydrogen is often proposed as the fuel of the future, but the transformation from the present fossil fuel economy to a hydrogen economy will need the solution of numerous complex scientific and technological issues, which will require several decades to be accomplished. Hydrogen is not an alternative fuel, but an energy carrier that has to be produced by using energy, starting from hydrogen-rich compounds. Production from gasoline or natural gas does not offer any advantage over the direct use of such fuels. Production from coal by gasification techniques with capture and sequestration of CO₂ could be an interim solution. Water splitting by artificial photosynthesis, photobiological methods based on algae, and high temperatures obtained by nuclear or concentrated solar power plants are promising approaches, but still far from practical applications. In the next decades, the development of the hydrogen economy will most likely rely on water electrolysis by using enormous amounts of electric power, which in its turn has to be generated. Producing electricity by burning fossil fuels, of course, cannot be a rational solution. Hydroelectric power can give but a very modest contribution. Therefore, it will be necessary to generate large amounts of electric power by nuclear energy of by renewable energies. A hydrogen economy based on nuclear electricity would imply the construction of thousands of fission reactors, thereby magnifying all the problems related to the use of nuclear energy (e.g., safe disposal of radioactive waste, nuclear proliferation, plant decommissioning, uranium shortage). In principle, wind, photovoltaic, and concentrated solar power have the potential to produce enormous amounts of electric power, but, except for wind, such technologies are too underdeveloped and expensive to tackle such a big task in a short period of time. A full development of a hydrogen economy needs also improvement in hydrogen storage, transportation and distribution

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%.

Hydrogen can be used as a perfect fuel

International Nuclear Information System (INIS)

Aydin, E.

2005-01-01

At present, hydrogen is one of the new and clean energy production sources. Hydrogen is the perfect partner for electricity, and together they create an integrated energy system based on distributed power generation and use. Hydrogen and electricity are interchangeable using a fuel cell (to convert hydrogen to electricity) or an electrolyzer (for converting electricity to hydrogen). A regenerative fuel cell works either way, converting hydrogen to electricity and vice versa. Hydrogen and electricity are both energy carriers because, unlike naturally occurring hydrocarbon fuels, they must both be produced using a primary energy source. In this study, it will be discussed whether hydrogen is perfect fuel or not

Hydrogen perspectives in Japan

International Nuclear Information System (INIS)

Furutani, H.

2000-01-01

Hydrogen energy is considered to present a potential effective options for achieving the greenhouse gas minimization. The MITI (Ministry of International Trade and Industry) of Japanese Government is promoting the WE-NET (World Energy Network System) Project which envisions (1) construction of a global energy network for effective supply, transportation, storage and utilization of renewable energy using hydrogen as an energy carrier as a long-term options of sustainable energy economy, and (2) promotion of market entry of hydrogen energy in near and/or mid future even before construction of a WE-NET system. In this paper, I would like to report how far the hydrogen energy technology development addressed under Phase I has progressed, and describe the outline of the Phase II Plan. (author)

Development of Efficient Flowsheet and Transient Modeling for Nuclear Heat Coupled Sulfur Iodine Cyclefor Hydrogen Production

Energy Technology Data Exchange (ETDEWEB)

Shripad T. Revankar; Nicholas R. Brown; Cheikhou Kane; Seungmin Oh

2010-05-01

The realization of the hydrogen as an energy carrier for future power sources relies on a practical method of producing hydrogen in large scale with no emission of green house gases. Hydrogen is an energy carrier which can be produced by a thermochemical water splitting process. The Sulfur-Iodine (SI) process is an example of a water splitting method using iodine and sulfur as recycling agents.

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.

Hydrogen transmission/storage with a metal hydride/organic slurry

Energy Technology Data Exchange (ETDEWEB)

Breault, R.W.; Rolfe, J.; McClaine, A. [Thermo Power Corp., Waltham, MA (United States)

1998-08-01

Thermo Power Corporation has developed a new approach for the production, transmission, and storage of hydrogen. In this approach, a chemical hydride slurry is used as the hydrogen carrier and storage media. The slurry protects the hydride from unanticipated contact with moisture in the air and makes the hydride pumpable. At the point of storage and use, a chemical hydride/water reaction is used to produce high-purity hydrogen. An essential feature of this approach is the recovery and recycle of the spent hydride at centralized processing plants, resulting in an overall low cost for hydrogen. This approach has two clear benefits: it greatly improves energy transmission and storage characteristics of hydrogen as a fuel, and it produces the hydrogen carrier efficiently and economically from a low cost carbon source. The preliminary economic analysis of the process indicates that hydrogen can be produced for $3.85 per million Btu based on a carbon cost of $1.42 per million Btu and a plant sized to serve a million cars per day. This compares to current costs of approximately $9.00 per million Btu to produce hydrogen from $3.00 per million Btu natural gas, and $25 per million Btu to produce hydrogen by electrolysis from $0.05 per Kwh electricity. The present standard for production of hydrogen from renewable energy is photovoltaic-electrolysis at $100 to $150 per million Btu.

An intronic variation in SLC52A1 causes exon skipping and transient riboflavin-responsive multiple acyl-CoA dehydrogenation deficiency

DEFF Research Database (Denmark)

Mosegaard, Signe; Bruun, Gitte Hoffmann; Flyvbjerg, Karen Freund

2017-01-01

Vitamin B2, riboflavin is essential for cellular function, as it participates in a diversity of redox reactions central to human metabolism, through its role as precursor for the cofactors flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD), which are electron carriers. The electron...... site for the splice inhibitory hnRNP A1 protein and causes exon 4 skipping. Riboflavin deficiency and maternal malnutrition during pregnancy might have been the determining factor in the outcome of this case....... transfer flavoprotein (ETF) and its dehydrogenase (ETFDH), uses FAD as cofactor. The ETF and ETFDH are forming the electron transport pathway for many mitochondrial flavoprotein dehydrogenases involved in fatty acid, amino acid and choline metabolism. A variation in either ETF or ETFDH causes multiple acyl......-CoA dehydrogenation deficiency (MADD), but genetic variations in the riboflavin metabolism or transportation of riboflavin can also cause MADD. The most common variations are located in the riboflavin transporter 2 (RFVT2) and 3 (RFVT3), that are highly expressed in brain and intestinal tissues, respectively...

Hydrogen extraction from liquid lithium-lead alloy by gas-liquid contact method

International Nuclear Information System (INIS)

Xie Bo; Weng Kuiping; Hou Jianping; Yang Guangling; Zeng Jun

2013-01-01

Hydrogen extraction experiment from liquid lithium-lead alloy by gas-liquid contact method has been carried out in own liquid lithium-lead bubbler (LLLB). Experimental results show that, He is more suitable than Ar as carrier gas in the filler tower. The higher temperature the tower is, the greater hydrogen content the tower exports. Influence of carrier gas flow rate on the hydrogen content in the export is jagged, no obvious rule. Although the difference between experimental results and literature data, but it is feasible that hydrogen isotopes extraction experiment from liquid lithium-lead by gas-liquid contact method, and the higher extraction efficiency increases with the growth of the residence time of the alloy in tower. (authors)

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.

Nanoconfined Alkali-metal borohydrides for Reversible Hydrogen Storage

NARCIS (Netherlands)

Ngene, P.

2012-01-01

Hydrogen has been identified as a promising energy carrier. Its combustion is not associated with pollution when generated from renewable energy sources like solar and wind. The large-scale use of hydrogen for intermittent energy storage and as a fuel for cars can contribute to the realization of a

An Organometallic Future in Green and Energy Chemistry?

Energy Technology Data Exchange (ETDEWEB)

Crabtree, Robert H

2011-01-10

The title topic is reviewed with selected examples taken from recent work, such as: the 'hydrogen borrowing' amine alkylation by alcohols; the dehydrogenative coupling of amine and alcohol to give amide; Ru complexes as solar cell photosensitizers; Ir organometallics as water oxidation catalyst precursors and as OLED emitters; as well as recent hydrogen storage strategies involving catalytic dehydrogenation of ammonia-borane and of organic heterocycles.

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

Energy Technology Data Exchange (ETDEWEB)

Liu, Hua Kun, E-mail: hua@uow.edu.au

2013-12-15

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.

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

Unravelling The Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed By Ru-PNP Pincer Complexes

DEFF Research Database (Denmark)

Alberico, Elisabetta; Lennox, Alastair J. J.; Vogt, Lydia K.

2016-01-01

Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (methanol dehydrogenation to H2 and CO2. Herein, we describe an investigation that combines experiment, spectroscopy, and theory to provide a mechanistic rationale...

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump

Energy Technology Data Exchange (ETDEWEB)

Dong, Liang; Xie, Yun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Du, Liang [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); School of Radiation Medicine and Protection (SRMP), School for Radiological and Interdisciplinary Sciences (RAD-X), Suzhou 215000 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Tan, Zhaoyi, E-mail: zhyitan@126.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

2015-04-28

Highlights: • This is the first theoretical investigation about T–H exchange in vacuum oil. • T–H isotope exchange is accomplished through two different change mechanisms. • Isotope exchange is selective, molecules with −OH and −COOH exchange more easily. • The methyl and methylene radicals in waste oil were observed by {sup 1}HNMR. - Abstract: The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium–hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T–H exchange mechanism and the hyrogenation–dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation–dehydrogenation exchange mechanism, the T–H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with −OH and −COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T–H isotope exchange can be determined by the hydrogenation of T{sub 2} or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

Correlation between minority carrier diffusion length and microstructure in a-Si:H thin films

International Nuclear Information System (INIS)

Conte, G.; Fameli, G.; Nobile, G.; Rubino, A.; Terzini, E.; Villani, F.

1993-01-01

The aim of this work is to investigate the opto-electronic properties of amorphous hydrogenated silicon (a-Si:H). The deposition temperature was used as a driving force to modify the morphology and bonded hydrogen distribution. The influence of the hydrogen microstructure on the carrier m-t products was examined. The m-t products, for both carriers, were evaluated from the diffusion length measurement, by using the Steady State Photocarrier Grating (SSPG) technique, and from the photoconductivity in the steady state condition (SSPC). The m-t products were correlated with the defect density and Fermi level position. The effects of the defect density on the Fermi level position were examined within the framework of a defect pool model in order to justify the consistency of the results

Process and device for stage by stage enrichment of deuterium and/or tritium in a material suitable for isotope exchange of deuterium and tritium with hydrogen

International Nuclear Information System (INIS)

Iniotakis, N.; Decken, C.B. von der.

1983-01-01

Water containing deuterium and/or tritium is first introduced into a carrier gas flow and reduced for the stage by stage enrichment of deuterium and/or tritium. A hydrogen partial pressure of a maximum of 100 millibar is set in the carrier gas flow. The carrier gas flow is taken along the primary side of an exchange wall suitable for the permeation of hydrogen, and a further carrier gas flow flows on its secondary side, which contains water or hydrogen. Reaction products formed after isotope exchange of deuterium and/or tritium with hydrogen are removed by the secondary carrier gas flow. (orig./HP) [de

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

KAUST Repository

Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Sangaru, Shiv; Saih, Youssef; Ould-Chikh, Samy; Basset, Jean-Marie

2015-01-01

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

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...

The impact of large-scale energy storage requirements on the choice between electricity and hydrogen as the major energy carrier in a non-fossil renewables-only scenario

International Nuclear Information System (INIS)

Converse, Alvin O.

2006-01-01

The need for large-scale storage, when the energy source is subject to periods of low-energy generation, as it would be in a direct solar or wind energy system, could be the factor which justifies the choice of hydrogen, rather than electricity, as the principal energy carrier. It could also be the 'Achilles heel' of a solar-based sustainable energy system, tipping the choice to a nuclear breeder system

Renewable Hydrogen Carrier - Carbohydrate: Constructing the Carbon-Neutral Carbohydrate Economy

Science.gov (United States)

2011-01-31

combinations have been investigated for the production of hydrogen from biomass carbohydrate. Chemical catalysis approaches include pyrolysis [19...temperature. High fructose corn syrup, low-cost sucrose replacement, is made by stabilized glucose isomerase, which can work at ~60 °C for even about two...gasoline, vegetable oil vs. biodiesel, corn kernels vs. ethanol [31,109]. Given a price of $0.18/kg carbohydrate (i.e., $10.6/GJ) [2,44], the hydrogen

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%.

Chromium oxide over activated carbons as catalyst for oxidative dehydrogenation of isobutane

International Nuclear Information System (INIS)

Cardenas, Agobardo; Acero Fabio N; Diaz, Jose de J

2007-01-01

The functional groups at the surface of an activated carbon Norit ROX 08 were modified through reaction with nitric acid, 8.8% 0 2 in N 2 and H 2 . the modified carbons were impregnated with a CrO 3 aqueous solution and used in the oxidative dehydrogenation of isobutane to isobutene (ODH). The formation of isobutene was observed at 443 k, with a maximum selectivity of 85% and a yield of 9%

Emission scenarios for a global hydrogen economy and the consequences for global air pollution

NARCIS (Netherlands)

van Ruijven, B.J.; Lamarque, J.F.; van Vuuren, D.P.; Kram, T.; Eerens, H.

2011-01-01

Hydrogen is named as possible energy carrier for future energy systems. However, the impact of large-scale hydrogen use on the atmosphere is uncertain. Application of hydrogen in clean fuel cells reduces emissions of air pollutants, but emissions from hydrogen production and leakages of molecular

A high resolution EELS study of free-carrier variations in H2+/H+ bombarded (100)GaAs

International Nuclear Information System (INIS)

Dubois, L.H.; Schwartz, G.P.

1984-01-01

High resolution electron energy loss spectroscopy (EELS) has been used to examine whether thermal recovery of the near-surface free-carrier concentration in Te-doped (100) GaAs is accomplished following low energy (250--1500 eV) hydrogen ion bombardment. For hydrogen ion impact energies below 500 eV, the nominal bulk free-carrier density is recovered by annealing at 725 K for 2 h. For comparable ion doses, the net free-carrier concentration decreases monotonically at higher impact energies under similar annealing conditions. The threshold for damage retention occurs close to the value of transmitted energy which is necessary to create either a Ga or an As interstitial point defect

Microbiological Hydrogen Production by Anaerobic Fermentation and Photosynthetic Process

International Nuclear Information System (INIS)

Asada, Y.; Ohsawa, M.; Nagai, Y.; Fukatsu, M.; Ishimi, K.; Ichi-ishi, S.

2009-01-01

Hydrogen gas is a clean and renewable energy carrier. Microbiological hydrogen production from glucose or starch by combination used of an anaerobic fermenter and a photosynthetic bacterium, Rhodobacter spheroides RV was studied. In 1984, the co-culture of Clostridium butyricum and RV strain to convert glucose to hydrogen was demonstrated by Miyake et al. Recently, we studied anaerobic fermentation of starch by a thermophilic archaea. (Author)

Influence of post-hydrogenation upon electrical, optical and structural properties of hydrogen-less sputter-deposited amorphous silicon

Energy Technology Data Exchange (ETDEWEB)

Gerke, S., E-mail: sebastian.gerke@uni-konstanz.de [Department of Physics, University of Konstanz, Konstanz, 78457 (Germany); Becker, H.-W.; Rogalla, D. [RUBION — Central Unit for Ion Beams and Radioisotopes, University of Bochum, Bochum, 44780 (Germany); Singer, F.; Brinkmann, N.; Fritz, S.; Hammud, A.; Keller, P.; Skorka, D.; Sommer, D. [Department of Physics, University of Konstanz, Konstanz, 78457 (Germany); Weiß, C. [Fraunhofer Institute for Solar Energy Systems ISE, Heidenhofstraße 2, 79110 Freiburg (Germany); Flege, S. [Department of Materials Science, TU Darmstadt, Darmstadt 64287 (Germany); Hahn, G. [Department of Physics, University of Konstanz, Konstanz, 78457 (Germany); Job, R. [Department of Electrical Engineering and Computer Science, Münster University of Applied Sciences, Steinfurt 48565 (Germany); Terheiden, B. [Department of Physics, University of Konstanz, Konstanz, 78457 (Germany)

2016-01-01

Amorphous silicon (a-Si) is common in the production of technical devices and can be deposited by several techniques. In this study intrinsic and doped, hydrogen-less amorphous silicon films are RF magnetron sputter deposited and post-hydrogenated in a remote hydrogen plasma reactor at a temperature of 370 °C. Secondary ion mass spectrometry of a boron doped (p) a-Si layer shows that the concentration of dopants in the sputtered layer becomes the same as present in the sputter-target. Improved surface passivation of phosphorous doped 5 Ω cm, FZ, (n) c-Si can be achieved by post-hydrogenation yielding a minority carrier lifetime of ~ 360 μs finding an optimum for ~ 40 nm thin films, deposited at 325 °C. This relatively low minority carrier lifetime indicates high disorder of the hydrogen-less sputter deposited amorphous network. Post-hydrogenation leads to a decrease of the number of localized states within the band gap. Optical band gaps (Taucs gab as well as E{sub 04}) can be determined to ~ 1.88 eV after post-hydrogenation. High resolution transmission electron microscopy and optical Raman investigations show that the sputtered layers are amorphous and stay like this during post-hydrogenation. As a consequence of the missing hydrogen during deposition, sputtered a-Si forms a rough surface compared to CVD a-Si. Atomic force microscopy points out that the roughness decreases by up to 25% during post-hydrogenation. Nuclear resonant reaction analysis permits the investigation of hydrogen depth profiles and allows determining the diffusion coefficients of several post-hydrogenated samples from of a model developed within this work. A dependency of diffusion coefficients on the duration of post-hydrogenation indicates trapping diffusion as the main diffusion mechanism. Additional Fourier transform infrared spectroscopy measurements show that hardly any interstitial hydrogen exists in the post-hydrogenated a-Si layers. The results of this study open the way for

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

Science.gov (United States)

Patki, Gauri Dilip

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

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.

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

Processing method of radioactive metal wastes

International Nuclear Information System (INIS)

Uetake, Naoto; Urata, Megumu; Sato, Masao.

1985-01-01

Purpose: To reduce the volume and increase the density of radioactive metal wastes easily while preventing scattering of radioactivity and process them into suitable form to storage and treatment. Method: Metal wastes mainly composed of zirconium are discharged from nuclear power plants or fuel re-processing plants, and these metals such as zirconium and titanium vigorously react with hydrogen and rapidly diffuse as hydrides. Since the hydrides are extremely brittle and can be pulverized easily, they can be volume-reduced. However, since metal hydrides have no ductility, dehydrogenation is applied for the molding fabrication in view of the subsequent storage and processing. The dehydrogenation is easy like the hydrogenation and fine metal pieces can be molded in a small compression device. For the dehydrogenation, a temperature is slightly increased as compared with that in the hydrogenation, pressure is reduced through the vacuum evacuation system and the removed hydrogen is purified for reuse. The upper limit for the temperature of the hydrogenation is 680 0 C in order to prevent the scttering of radioactivity. (Kamimura, M.)

Micro-reactor for heterogeneous catalysis. Application: hydrogen production from methyl-cyclohexane; Microreacteur pour la catalyse heterogene. Application: production d'hydrogene a partir du methylcyclohexane

Energy Technology Data Exchange (ETDEWEB)

Roumanie, M.; Pijolat, C. [Ecole des Mines de Saint Etienne, Centre SPIN (DMICC/LPMG/URA/CNRS-D2021), 42 - Saint Etienne (France); Meille, V.; Bellefon, C. de [Centre National de la Recherche Scientifique (CNRS/CPE), Lab. de Genie des Procedes Catalytiques, 69 - Villeurbanne (France); Pouteau, P.; Delattre, C. [CEA Grenoble, Lab. d' Electronique et de Technologie de l' Informatique (LETI), 38 (France)

2004-07-01

First developed by the pharmaceutical industry to find new drugs (combinatorial analysis), the lab on chip is also extremely interesting for the catalysis field. This major interest comes from the miniaturize size and the high surface on volume ratio which lead to improve mass and heat transfer but also the safety in regards of industrial application. The use of micro-technology and the miniaturization of various systems such as micro-fuel cell is also a current field of activity. So for the future research the production of hydrogen is a point to develop in order to supply a micro-fuel cell. The aim of this work is to study and to realize an autonomous catalytic micro-reactor for hydrogen production from methyl-cyclohexane. For this reaction of dehydrogenation, the common catalyst is platinum supported on alumina. Consequently, the general objectives of this work are: 1)to develop a micro-reactor with its heaters, sensors...2)to deposit catalysts in the micro-reactor 3)to study the catalytic conversion of this system.

Direct-hydrogen-fueled proton-exchange-membrane fuel cell system for transportation applications. Hydrogen vehicle safety report

Energy Technology Data Exchange (ETDEWEB)

Thomas, C.E. [Directed Technologies, Inc., Arlington, VA (United States)

1997-05-01

This report reviews the safety characteristics of hydrogen as an energy carrier for a fuel cell vehicle (FCV), with emphasis on high pressure gaseous hydrogen onboard storage. The authors consider normal operation of the vehicle in addition to refueling, collisions, operation in tunnels, and storage in garages. They identify the most likely risks and failure modes leading to hazardous conditions, and provide potential countermeasures in the vehicle design to prevent or substantially reduce the consequences of each plausible failure mode. They then compare the risks of hydrogen with those of more common motor vehicle fuels including gasoline, propane, and natural gas.

Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

Science.gov (United States)

Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

2014-07-14

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

The influence of water on the oxygen-silver interaction and on the oxidative dehydrogenation of methanol

NARCIS (Netherlands)

Lefferts, Leon; Van Ommen, Jan G.; Ross, Julian R H

1988-01-01

Experiments carried out using temperature-programmed desorption and reduction could detect no interaction between water and silver at 200 °C. However, separate experiments on the effect of water on the oxidative dehydrogenation of methanol over a silver catalyst showed that water affected the

Process for the exchange of hydrogen isotopes using a catalyst packed bed assembly

International Nuclear Information System (INIS)

Butler, J.P.; den Hartog, J.; Molson, F.W.R.

1978-01-01

A process for the exchange of hydrogen isotopes between streams of gaseous hydrogen and liquid water is described, wherein the streams of liquid water and gaseous hydrogen are simultaneously brought into contact with one another and a catalyst packed bed assembly while at a temperature in the range 273 0 to 573 0 K. The catalyst packed bed assembly may be composed of discrete carrier bodies of e.g. ceramics, metals, fibrous materials or synthetic plastics with catalytically active metal crystallites selected from Group VIII of the Periodic Table, partially enclosed in and bonded to the carrier bodies by a water repellent, water vapor and hydrogen gas permeable, porous, polymeric material, and discrete packing bodies having an exterior surface which is substantially hydrophilic and relatively noncatalytically active with regard to hydrogen isotope exchange between hydrogen gas and water vapor to that of the catalyst bodies

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.

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

KAUST Repository

Hong, Eunpyo; Park, Jung-Hyun; Shin, Chae-Ho

2015-01-01

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

Biomass-based energy carriers in the transportation sector; Biomassebaserade energibaerare foer transportsektorn

Energy Technology Data Exchange (ETDEWEB)

Johansson, Bengt

1995-03-01

The purpose of this report is to study the technical and economic prerequisites to attain reduced carbon dioxide emissions through the use of biomass-based energy carriers in the transportation sector, and to study other environmental impacts resulting from an increased use of biomass-based energy carriers. CO{sub 2} emission reduction per unit arable and forest land used for biomass production (kg CO{sub 2}/ha,year) and costs for CO{sub 2} emission reduction (SEK/kg CO{sub 2}) are estimated for the substitution of gasoline and diesel with rape methyl ester, biogas from lucerne, ethanol from wheat and ethanol, methanol, hydrogen and electricity from Salix and logging residues. Of the studied energy carriers, those based on Salix provide the largest CO{sub 2} emission reduction. In a medium long perspective, the costs for CO{sub 2} emission reduction seem to be lowest for methanol from Salix and logging residues. The use of fuel cell vehicles, using methanol or hydrogen as energy carriers, can in a longer perspective provide more energy efficient utilization of biomass for transportation than the use of internal combustion engine vehicles. 136 refs, 12 figs, 25 tabs

Utilizing hydrogen in aqueous phase conversion of biomass

Energy Technology Data Exchange (ETDEWEB)

Peng, Baoxiang; Zhao, Chen; Li, Xuebing; Lercher, Johannes A. [Technische Univ. Muenchen, Garching (Germany). Technische Chemie II

2010-12-30

Hydrogen generation and selective hydrodeoxygenation of biomass are the key for the successful integration of biogenic carbon resources for energy carriers and intermediates. This includes the generation of hydrogen from biomass in the liquid phase and more importantly, for the direct utilization of the hydrogen generated into the molecules. We will outline this strategy with two groups of oxofunctionalized molecules, i.e., glycerol as example for the aliphatic group and substituted phenols as the aromatic group. (orig.)

Oxidative dehydrogenation of ethane over vanadium supported on mesoporous materials of M41S family

Czech Academy of Sciences Publication Activity Database

Čapek, J.; Adam, J.; Grygar, Tomáš; Bulánek, R.; Vradman, L.; Košová-Kučerová, G.; Čičmanec, P.; Knotek, P.

2008-01-01

Roč. 342, 1-2 (2008), s. 99-106 ISSN 0926-860X Grant - others:GA ČR(CZ) GP104/07/P038 Program:GP Institutional research plan: CEZ:AV0Z40320502 Keywords : oxidative dehydrogenation * ethane * vanadium * mesoporous materials Subject RIV: CA - Inorganic Chemistry Impact factor: 3.190, year: 2008

The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers.

Science.gov (United States)

Harman-Ware, Anne E; Happs, Renee M; Davison, Brian H; Davis, Mark F

2017-01-01

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.

Biomimetic hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Krassen, Henning

2009-05-15

Hydrogenases catalyze the reduction of protons to molecular hydrogen with outstanding efficiency. An electrode surface which is covered with active hydrogenase molecules becomes a promising alternative to platinum for electrochemical hydrogen production. To immobilize the hydrogenase on the electrode, the gold surface was modified by heterobifunctional molecules. A thiol headgroup on one side allowed the binding to the gold surface and the formation of a self-assembled monolayer. The other side of the molecules provided a surface with a high affinity for the hydrogenase CrHydA1 from Chlamydomonas reinhardtii. With methylviologen as a soluble energy carrier, electrons were transferred from carboxy-terminated electrodes to CrHydA1 and conducted to the active site (H-cluster), where they reduce protons to molecular hydrogen. A combined approach of surface-enhanced infrared absorption spectroscopy, gas chromatography, and surface plasmon resonance allowed quantifying the hydrogen production on a molecular level. Hydrogen was produced with a rate of 85 mol H{sub 2} min{sup -1} mol{sup -1}. On a 1'- benzyl-4,4'-bipyridinum (BBP)-terminated surface, the electrons were mediated by the monolayer and no soluble electron carrier was necessary to achieve a comparable hydrogen production rate (approximately 50% of the former system). The hydrogen evolution potential was determined to be -335 mV for the BBP-bound hydrogenase and -290 mV for the hydrogenase which was immobilized on a carboxy-terminated mercaptopropionic acid SAM. Therefore, both systems significantly reduce the hydrogen production overpotential and allow electrochemical hydrogen production at an energy level which is close to the commercially applied platinum electrodes (hydrogen evolution potential of -270 mV). In order to couple hydrogen production and photosynthesis, photosystem I (PS1) from Synechocystis PCC 6803 and membrane-bound hydrogenase (MBH) from Ralstonia eutropha were bound to each other

Dendrimer-Stabilized Ru Nanoparticles Immobilized in Organo-Silica Materials for Hydrogenation of Phenols

Directory of Open Access Journals (Sweden)

Eduard Karakhanov

2017-03-01

Full Text Available New hybrid catalysts based on Ru nanoparticles, encapsulated into poly(propylene imine dendrimers, immobilized into silica pores, were synthesized and examined for the hydrogenation of alkyl-substituted phenols. The corresponding alkyl-substituted cyclohexanols were presented as the major reaction products, while incomplete hydrogenation products appeared to be minor. A competition between the sterical factors of dendrimer-containing carriers and the electronic factors of substrate substituents influenced the hydrogenation rate of the alkyl-substituted phenols. The carrier structure was found to have a significant influence on both the physical and chemical properties of the catalysts and their hydrogenation activity. The synthesized hybrid catalysts appeared to be stable after recycling and could be re-used several times without significant loss of activity.

Proceedings of a Canadian Hydrogen Association workshop in support of the transition to the hydrogen age : Greening the fleet : the status of hydrogen-powered vehicles for fleet applications

Energy Technology Data Exchange (ETDEWEB)

NONE

2007-07-01

The Canadian Hydrogen Association (CHA) endorses hydrogen as an energy carrier and promotes the development of a supporting hydrogen infrastructure. It promotes the research, development and commercialization of innovative ways to accelerate the application of hydrogen technologies to reduce greenhouse gas emissions. The presentations at this conference described new technologies and the companies that are developing hydrogen-powered vehicles, including hybrid-electric powered vehicles for fleet application. Some international activities were also covered, including lessons learned from the California experience and European fuel cell fleets. The benefits of fuel cell hybrids were highlighted along with methods to overcome the barriers to the introduction of new vehicle fuels. A review of current and future hydrogen supply infrastructure systems was also provided. The conference featured 14 presentations, of which 2 have been catalogued separately for inclusion in this database. refs., tabs., figs.

Core--strategy leading to high reversible hydrogen storage capacity for NaBH4.

Science.gov (United States)

Christian, Meganne L; Aguey-Zinsou, Kondo-François

2012-09-25

Owing to its high storage capacity (10.8 mass %), sodium borohydride (NaBH(4)) is a promising hydrogen storage material. However, the temperature for hydrogen release is high (>500 °C), and reversibility of the release is unachievable under reasonable conditions. Herein, we demonstrate the potential of a novel strategy leading to high and stable hydrogen absorption/desorption cycling for NaBH(4) under mild pressure conditions (4 MPa). By an antisolvent precipitation method, the size of NaBH(4) particles was restricted to a few nanometers (hydrogen at 400 °C. Further encapsulation of these nanoparticles upon reaction of nickel chloride at their surface allowed the synthesis of a core--shell nanostructure, NaBH(4)@Ni, and this provided a route for (a) the effective nanoconfinement of the melted NaBH(4) core and its dehydrogenation products, and (b) reversibility and fast kinetics owing to short diffusion lengths, the unstable nature of nickel borohydride, and possible modification of reaction paths. Hence at 350 °C, a reversible and steady hydrogen capacity of 5 mass % was achieved for NaBH(4)@Ni; 80% of the hydrogen could be desorbed or absorbed in less than 60 min, and full capacity was reached within 5 h. To the best of our knowledge, this is the first time that such performances have been achieved with NaBH(4). This demonstrates the potential of the strategy in leading to major advancements in the design of effective hydrogen storage materials from pristine borohydrides.

New hydrogen technologies

International Nuclear Information System (INIS)

1992-01-01

This report presents an overview of the overall hydrogen system. There are separate sections for production, distribution, transport, storage; and applications of hydrogen. The most important methods for hydrogen production are steam reformation of natural gas and electrolysis of water. Of the renewable energy options, production of hydrogen by electrolysis using electricity from wind turbines or by gasification of biomass were found to be the most economic for Finland. Direct use of this electricity or the production of liquid fuels from biomass will be competing alternatives. When hydrogen is produced in the solar belt or where there is cheap hydropower it must be transported over long distances. The overall energy consumed for the transport is from 25 to 40 % of the initial available energy. Hydrogen storage can be divided into stationary and mobile types. The most economic, stationary, large scale hydrogen storage for both long and short periods is underground storage. When suitable sites are not available, then pressure vessels are the best for short period and liquid H 2 for long period. Vehicle storage of hydrogen is by either metal hydrides or liquid H 2 . Hydrogen is a very versatile energy carrier. It can be used to produce heat directly in catalytic burners without flame, to produce electricity in fuel cells with high efficiency for use in vehicles or for peak power shaving, as a fuel component with conventional fuels to reduce emissions, as a way to store energy and as a chemical reagent in reactions

Deep levels due to hydrogen in ZnO single crystals

Science.gov (United States)

Parmar, Narendra; Weber, Marc; Lynn, Kelvin

2009-05-01

Hydrogen impurities and oxygen vacancies are involved in the ˜0.7 eV shift of the optical absorption edge of ZnO. Deuterium causes a smaller shift. Titanium metal is used to bind hydrogen as it diffuses out of ZnO. Positron annihilation spectroscopy coupled with other techniques point to the presence of oxygen vacancies. Removing hydrogen followed by annealing in oxygen reduces the carrier concentration.

A comparison of hydrogen with alternate energy forms from coal and nuclear energy

International Nuclear Information System (INIS)

Cox, K.E.

1976-01-01

Alternate energy forms that can be produced from coal and nuclear energy have been analyzed on efficiency, economic and end-use grounds. These forms include hydrogen, methane, electricity, and EVA-ADAM, a 'chemical heat pipe' approach to energy transmission. The EVA-ADAM system for nuclear heat appears to be economically competitive with the other energy carriers except over very large distances. The cost of hydrogen derived from coal is approximately equal to that of methane derived from the same source when compared on an equal BTU basis. Thermochemically derived hydrogen from nuclear energy shows a break-even range with hydrogen derived from coal at coal costs of from Pound33 to 80/ton depending on the cost of nuclear heat. Electricity and electrolytically derived hydrogen are the most expensive energy carriers and electricity's use should be limited to applications involving work rather than heat. Continued work in thermochemical hydrogen production schemes should be supported as an energy option for the future. (author)

Thermo-hydrogenating treatments in Ti-6Al-4V

International Nuclear Information System (INIS)

Guitar, A; Domizzi, G; Luppo, M.I; Vigna, G

2006-01-01

The production of components of Ti alloys, specifically Ti-6Al-4V, involves some difficulties in obtaining the final desired microstructure, producing decrease in the material's mechanical properties. In the specific case of materials to be used for surgical implants an equiaxial fine grain microstructure of α phase a with an homogenously precipitated β phase is needed. The modification of certain microstructural features is not possible based on simple thermal treatments. Thermomechanical treatments are effective for transforming the lamellar α phase into equiaxial α, but these methods include major deformations in the (α + β) two-phase field. In order to avoid this stage, thermo-hydrogenating processes were used (THP). The THP involve a treatment of β solubilization before, during or after the hydrogenation, a possible isothermal treatment below the β hydrogenated transus temperature and the final vacuum dehydrogenation. The development of treatments using hydrogen as a temporary alloying element creates a new class of microstructures, which are finer than equiaxial structures and respond well to resistance to traction and fatigue. Since the THP do not include the working of the material to control the microstructure, they are more appropriate for use with shaped components close to the end, like those obtained by powder metallurgy or smelting. Different thermo-hydrogenating treatments in Ti-6Al-4V to modify the microstructure were studied. Final microstructures of α fine phase and β disperse phase were obtained using THP in samples with initial lamellar α phase separated by thin sheets of β phase. The characterization of the initial material and of the transformed material was carried out using optic and scanning electron microscopy (CW)

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.

CO2-based hydrogen storage - Hydrogen generation from formaldehyde/water

Science.gov (United States)

Trincado, Monica; Grützmacher, Hansjörg; Prechtl, Martin H. G.

2018-04-01

Formaldehyde (CH2O) is the simplest and most significant industrially produced aldehyde. The global demand is about 30 megatons annually. Industrially it is produced by oxidation of methanol under energy intensive conditions. More recently, new fields of application for the use of formaldehyde and its derivatives as, i.e. cross-linker for resins or disinfectant, have been suggested. Dialkoxymethane has been envisioned as a combustion fuel for conventional engines or aqueous formaldehyde and paraformaldehyde may act as a liquid organic hydrogen carrier molecule (LOHC) for hydrogen generation to be used for hydrogen fuel cells. For the realization of these processes, it requires less energy-intensive technologies for the synthesis of formaldehyde. This overview summarizes the recent developments in low-temperature reductive synthesis of formaldehyde and its derivatives and low-temperature formaldehyde reforming. These aspects are important for the future demands on modern societies' energy management, in the form of a methanol and hydrogen economy, and the required formaldehyde feedstock for the manufacture of many formaldehyde-based daily products.

Hydrogen-bearing iron peroxide and its implications to the deep Earth

Science.gov (United States)

Liu, J.; Hu, Q.; Kim, D. Y.; Wu, Z.; Wang, W.; Alp, E. E.; Yang, L.; Xiao, Y.; Meng, Y.; Chow, P.; Greenberg, E.; Prakapenka, V. B.; Mao, H. K.; Mao, W. L.

2017-12-01

Hydrous materials subducted into the deep mantle may play a significant role in the geophysical and geochemical processes of the lower mantle through geological time, but their roles have not become clear yet in the region. Hydrogen-bearing iron peroxide (FeO2Hx) was recently discovered to form through dehydrogenation of goethite (e.g., FeOOH) and the reaction between hematite (Fe2O3) and water under deep lower mantle conditions. We conducted synchrotron Mössbauer, X-ray absorption, and X-ray emission spectroscopy measurements to investigate the electronic spin and valence states of iron in hydrogen-bearing iron peroxide (FeO2Hx) in-situ at high pressures. Combined with theoretical calculations and other high-pressure experiments (i.e., nuclear resonant inelastic x-ray scattering spectroscopy and X-ray diffraction coupled with laser-heated diamond-anvil cell techniques), we find that the intriguing properties of FeO2Hx could shed light on the origin of a number of the observed geochemical and geophysical anomalies in the deep Earth.

High-rate continuous hydrogen production by Thermoanaerobacterium thermosaccharolyticum PSU-2 immobilized on heat-pretreated methanogenic granules

DEFF Research Database (Denmark)

O-Thong, Sompong; Prasertsan, P.; Karakashev, Dimitar Borisov

2008-01-01

as carrier to immobilize T. thermosaccharolyticum strain PSU-2 in UASB reactor operated at a hydraulic retention time (HRT) ranging from 0.75 to 24h and corresponding sucrose loading rate from 58.5 to 2.4 mmol sucrose l(-1)h(-1). In comparison with hydrogen production rate of 12.1 mmol H(2)l(-1)h(-1......) obtained by carrier-free reactor upflow anaerobic (UA) system, a greatly improved hydrogen production rate up to 152 mmol H(2)l(-1)h(-1) was demonstrated by the granular cells in UASB system. The biofilm of T. thermosaccharolyticum strain PSU-2 developed on treated methanogenic granules in UASB reactor...... substantially enhanced biomass retention (3 times), and production of hydrogen (12 times) compared to carrier-free reactor. It appears to be the most preferred process for highly efficient dark fermentative hydrogen production from sugar containing wastewater under thermophilic conditions. (C) 2008...

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.

Aqueous-Phase Reforming of Renewable Polyols for Production of Hydrogen using Platinum Catalysts

NARCIS (Netherlands)

Boga, D.A.

2013-01-01

Hydrogen has the potential to fuel the energy needs of a more sustainable society. As hydrogen is not found in nature in any appreciable quantities, this energy carrier needs to be produced from a primary energy source. Biomass can serve as a source for sustainable hydrogen production. In principle,

Hydrogen production from hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Docekal, J

1986-01-01

Hydrogen is an important feed stock for chemical and petroleum industries, in addition to being considered as the energy carrier of the future. At the present time the feed stock hydrogen is mainly manufactured from hydrocarbons using steam reforming. In steam reforming two processes are employed, the conventional process and PSA (pressure swing adsorption) process. These two processes are described and compared. The results show that the total costs and the maintenance costs are lower for the PSA process, the capital outlay is lower for the conventional process, and the operating costs are similar for the two processes.

Novel hydrogen storage materials: A review of lightweight complex hydrides

International Nuclear Information System (INIS)

Jain, I.P.; Jain, Pragya; Jain, Ankur

2010-01-01

review article the fundamental understanding of the physical, chemical and structural properties of light weight hydride materials, e.g. Alanates, Borohydrides, Amide Borohydrides, Amide-Imide system, Amineborane and Alane for hydrogen storage has been presented. Lot of details of these materials has been incorporated such as synthesis, crystal structure, thermodynamics and kinetics of hydrogenation-dehydrogenation processes, reversibility and hydrogen storage capacity has been presented.

Oxidative Dehydrogenation of n-​Butane: Activity and Kinetics Over VOx​/Al2O3 Catalysts

NARCIS (Netherlands)

Madaan, N.; Haufe, R.; Shiju, N.R.; Rothenberg, G.

2014-01-01

The catalytic activity of a VOx/Al2O3 catalyst for the oxidative dehydrogenation of n-​butane is investigated. The effects of reaction temp., oxygen to n-​butane ratio and GHSV on the catalytic performance are examd. and optimized. Interestingly, this simple catalyst gives good conversion and

Studies on the separation of hydrogen isotopes and spin isomers by gas chromatography

International Nuclear Information System (INIS)

Pushpa, K.K.; Annaji Rao, K.

2000-08-01

Separation and analysis of mixture of hydrogen isotopes has gained considerable importance because of various applications needing different isotopes in lasers, nuclear reactions and tracer or labelled compounds. In the literature gas chromatographic methods are reported using columns packed with partly dehydrated or thoroughly dehydrated alumina/molecular sieve stationary phase at 77 deg K with helium, neon and even hydrogen or deuterium as carrier gas. In the present study an attempt is made to compare the chromatographic behaviour of these two stationary phases using virgin and Fe doped form in partly dehydrated and thoroughly dehydrated state, using helium, neon, hydrogen and deuterium as carrier gas. The results of this study show that helium or neon carrier gas behave similarly broad peaks with some tailing. Sharp symmetric peaks are obtained with hydrogen or deuterium carrier gas. This is attributed to large hold up capacity for H 2 or D 2 at 77 deg K in these materials as compared to helium or neon. Spin isomers of H 2 or D 2 are separated on Fe free stationary phases, though ortho H 2 and HD are not resolved. Using a combination of Fe doped short column and plain alumina column, both maintained in dehydrated form, the effect of Fe doping on thermal equilibrium of ortho/para forms at 77 deg K is clearly demonstrated. (author)

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

Reactivity of organic compounds in catalytic synthesis

Energy Technology Data Exchange (ETDEWEB)

Minachev, Kh M; Bragin, O V

1978-01-01

A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

High-rate continuous hydrogen production by Thermoanaerobacterium thermosaccharolyticum PSU-2 immobilized on heat-pretreated methanogenic granules

Energy Technology Data Exchange (ETDEWEB)

O-Thong, Sompong [Department of Environmental Engineering, Technical University of Denmark, Bygningstorvet 115, DK-2800, Kgs Lyngby (Denmark); Department of Biology, Faculty of Science, Thaksin University, Patthalung 93110 (Thailand); Prasertsan, Poonsuk [Department of Industrial Biotechnology, Faculty of Agro-Industry, Prince of Songkla University, Hat-Yai, Songkhla 90120 (Thailand); Karakashev, Dimitar; Angelidaki, Irini [Department of Environmental Engineering, Technical University of Denmark, Bygningstorvet 115, DK-2800, Kgs Lyngby (Denmark)

2008-11-15

Biohydrogen production from Thermoanaerobacterium thermosaccharolyticum strain PSU-2 was examined in upflow anaerobic sludge blanket (UASB) reactor and carrier-free upflow anaerobic reactor (UA), both fed with sucrose and operating at 60 C. Heat-pretreated methanogenic granules were used as carrier to immobilize T. thermosaccharolyticum strain PSU-2 in UASB reactor operated at a hydraulic retention time (HRT) ranging from 0.75 to 24 h and corresponding sucrose loading rate from 58.5 to 2.4 mmol sucrose l{sup -1} h{sup -1}. In comparison with hydrogen production rate of 12.1 mmol H{sub 2} l{sup -1} h{sup -1} obtained by carrier-free reactor upflow anaerobic (UA) system, a greatly improved hydrogen production rate up to 152 mmol H{sub 2} l{sup -1} h{sup -1} was demonstrated by the granular cells in UASB system. The biofilm of T. thermosaccharolyticum strain PSU-2 developed on treated methanogenic granules in UASB reactor substantially enhanced biomass retention (3 times), and production of hydrogen (12 times) compared to carrier-free reactor. It appears to be the most preferred process for highly efficient dark fermentative hydrogen production from sugar containing wastewater under thermophilic conditions. (author)

Synthesis and thermal decomposition behaviors of magnesium borohydride ammoniates with controllable composition as hydrogen storage materials.

Science.gov (United States)

Yang, Yanjing; Liu, Yongfeng; Li, You; Gao, Mingxia; Pan, Hongge

2013-02-01

An ammonia-redistribution strategy for synthesizing metal borohydride ammoniates with controllable coordination number of NH(3) was proposed, and a series of magnesium borohydride ammoniates were easily synthesized by a mechanochemical reaction between Mg(BH(4))(2) and its hexaammoniate. A strong dependence of the dehydrogenation temperature and purity of the released hydrogen upon heating on the coordination number of NH(3) was elaborated for Mg(BH(4))(2)·xNH(3) owing to the change in the molar ratio of H(δ+) and H(δ-), the charge distribution on H(δ+) and H(δ-), and the strength of the coordinate bond N:→Mg(2+). The monoammoniate of magnesium borohydride (Mg(BH(4))(2)·NH(3)) was obtained for the first time. It can release 6.5% pure hydrogen within 50 minutes at 180 °C. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Hydrogen production from biomass by biological systems

International Nuclear Information System (INIS)

Sharifan, H.R.; Qader, S.

2009-01-01

Hydrogen gas is seen as a future energy carrier, not involved in 'greenhouse' gas and its released energy in combustion can be converted to electric power. Biological system with low energy can produce hydrogen compared to electrochemical hydrogen production via solar battery-based water splitting which requires the use of solar batteries with high energy requirements. The biological hydrogen production occurs in microalgae and cyanobacteria by photosynthesis. They consume biochemical energy to produce molecular hydrogen. Hydrogen in some algae is an anaerobic production in the absence of light. In cyanobacteria the hydrogen production simultaneously happens with nitrogen fixation, and also catalyzed by nitrogenase as a side reaction. Hydrogen production by photosynthetic bacteria is mediated by nitrogenase activity, although hydrogenases may be active for both hydrogen production and hydrogen uptake under some conditions. Genetic studies on photosynthetic microorganisms have markedly increased in recent times, relatively few genetic engineering studies have focused on altering the characteristics of these microorganisms, particularly with respect to enhancing the hydrogen-producing capabilities of photosynthetic bacteria and cyanobacteria. (author)

Improvements in Fermentative Biological Hydrogen Production Through Metabolic Engineering

Energy Technology Data Exchange (ETDEWEB)

Hallenbeck, P. C.; Ghosh, D.; Sabourin-Provost, G.

2009-07-01

Dramatically rising oil prices and increasing awareness of the dire environmental consequences of fossil fuel use, including startling effects of climate change, are refocusing attention world-wide on the search for alternative fuels. Hydrogen is poised to become an important future energy carrier. Renewable hydrogen production is pivotal in making it a truly sustainable replacement for fossil fuels. (Author)

Improvements in Fermentative Biological Hydrogen Production Through Metabolic Engineering

International Nuclear Information System (INIS)

Hallenbeck, P. C.; Ghosh, D.; Sabourin-Provost, G.

2009-01-01

Dramatically rising oil prices and increasing awareness of the dire environmental consequences of fossil fuel use, including startling effects of climate change, are refocusing attention world-wide on the search for alternative fuels. Hydrogen is poised to become an important future energy carrier. Renewable hydrogen production is pivotal in making it a truly sustainable replacement for fossil fuels. (Author)

CH{sub 4} dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

Energy Technology Data Exchange (ETDEWEB)

Zhang, Riguang; Duan, Tian [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ling, Lixia [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

2015-06-30

Highlights: • Adsorbed Rh atom on Cu catalyst exhibits better catalytic activity for CH{sub 4} dehydrogenation. • The adsorbed Rh atom is the reaction active center for CH{sub 4} dehydrogenation. • The morphology of Cu substrate has negligible effect on CH{sub 4} dehydrogenation. - Abstract: In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH{sub 4} dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH{sub 4} dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol{sup −1} on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol{sup −1} on RhCu(1 1 1) surface, and to 180.0 kJ mol{sup −1} on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH{sub 4} complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH{sub 4}, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH{sub 4} dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the

Carrier gas effects on aluminum-catalyzed nanowire growth

International Nuclear Information System (INIS)

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

2016-01-01

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

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

Science.gov (United States)

Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

2017-06-01

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg 2 NiH 4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg 2 NiH 4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol -1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Bio-immobilization of dark fermentative bacteria for enhancing continuous hydrogen production from cornstalk hydrolysate.

Science.gov (United States)

Zhao, Lei; Cao, Guang-Li; Sheng, Tao; Ren, Hong-Yu; Wang, Ai-Jie; Zhang, Jian; Zhong, Ying-Juan; Ren, Nan-Qi

2017-11-01

Mycelia pellets were employed as biological carrier in a continuous stirred tank reactor to reduce biomass washout and enhance hydrogen production from cornstalk hydrolysate. Hydraulic retention time (HRT) and influent substrate concentration played critical roles on hydrogen production of the bioreactor. The maximum hydrogen production rate of 14.2mmol H 2 L -1 h -1 was obtained at optimized HRT of 6h and influent concentration of 20g/L, 2.6 times higher than the counterpart without mycelia pellets. With excellent immobilization ability, biomass accumulated in the reactor and reached 1.6g/L under the optimum conditions. Upon further energy conversion analysis, continuous hydrogen production with mycelia pellets gave the maximum energy conversion efficiency of 17.8%. These results indicate mycelia pellet is an ideal biological carrier to improve biomass retention capacity of the reactor and enhance hydrogen recovery efficiency from lignocellulosic biomass, and meanwhile provides a new direction for economic and efficient hydrogen production process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lifetime degradation of n-type Czochralski silicon after hydrogenation

Science.gov (United States)

Vaqueiro-Contreras, M.; Markevich, V. P.; Mullins, J.; Halsall, M. P.; Murin, L. I.; Falster, R.; Binns, J.; Coutinho, J.; Peaker, A. R.

2018-04-01

Hydrogen plays an important role in the passivation of interface states in silicon-based metal-oxide semiconductor technologies and passivation of surface and interface states in solar silicon. We have shown recently [Vaqueiro-Contreras et al., Phys. Status Solidi RRL 11, 1700133 (2017)] that hydrogenation of n-type silicon slices containing relatively large concentrations of carbon and oxygen impurity atoms {[Cs] ≥ 1 × 1016 cm-3 and [Oi] ≥ 1017 cm-3} can produce a family of C-O-H defects, which act as powerful recombination centres reducing the minority carrier lifetime. In this work, evidence of the silicon's lifetime deterioration after hydrogen injection from SiNx coating, which is widely used in solar cell manufacturing, has been obtained from microwave photoconductance decay measurements. We have characterised the hydrogenation induced deep level defects in n-type Czochralski-grown Si samples through a series of deep level transient spectroscopy (DLTS), minority carrier transient spectroscopy (MCTS), and high-resolution Laplace DLTS/MCTS measurements. It has been found that along with the hydrogen-related hole traps, H1 and H2, in the lower half of the gap reported by us previously, hydrogenation gives rise to two electron traps, E1 and E2, in the upper half of the gap. The activation energies for electron emission from the E1 and E2 trap levels have been determined as 0.12, and 0.14 eV, respectively. We argue that the E1/H1 and E2/H2 pairs of electron/hole traps are related to two energy levels of two complexes, each incorporating carbon, oxygen, and hydrogen atoms. Our results show that the detrimental effect of the C-O-H defects on the minority carrier lifetime in n-type Si:O + C materials can be very significant, and the carbon concentration in Czochralski-grown silicon is a key parameter in the formation of the recombination centers.

Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

KAUST Repository

Takanabe, Kazuhiro; Shahid, Salman

2016-01-01

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

Hydrogen energy systems studies

Energy Technology Data Exchange (ETDEWEB)

Ogden, J.M.; Kreutz, T.G.; Steinbugler, M. [Princeton Univ., NJ (United States)] [and others

1996-10-01

In this report the authors describe results from technical and economic assessments carried out during the past year with support from the USDOE Hydrogen R&D Program. (1) Assessment of technologies for small scale production of hydrogen from natural gas. Because of the cost and logistics of transporting and storing hydrogen, it may be preferable to produce hydrogen at the point of use from more readily available energy carriers such as natural gas or electricity. In this task the authors assess near term technologies for producing hydrogen from natural gas at small scale including steam reforming, partial oxidation and autothermal reforming. (2) Case study of developing a hydrogen vehicle refueling infrastructure in Southern California. Many analysts suggest that the first widespread use of hydrogen energy is likely to be in zero emission vehicles in Southern California. Several hundred thousand zero emission automobiles are projected for the Los Angeles Basin alone by 2010, if mandated levels are implemented. Assuming that hydrogen vehicles capture a significant fraction of this market, a large demand for hydrogen fuel could evolve over the next few decades. Refueling a large number of hydrogen vehicles poses significant challenges. In this task the authors assess near term options for producing and delivering gaseous hydrogen transportation fuel to users in Southern California including: (1) hydrogen produced from natural gas in a large, centralized steam reforming plant, and delivered to refueling stations via liquid hydrogen truck or small scale hydrogen gas pipeline, (2) hydrogen produced at the refueling station via small scale steam reforming of natural gas, (3) hydrogen produced via small scale electrolysis at the refueling station, and (4) hydrogen from low cost chemical industry sources (e.g. excess capacity in refineries which have recently upgraded their hydrogen production capacity, etc.).

An examination of the criteria necessary for successful worldwide deployment of isolated, renewable hydrogen stationary power systems

International Nuclear Information System (INIS)

Rambach, G. D.; Snyder, J. D.

1998-01-01

This paper examines the top-down rationale and methods for using hydrogen as an energy carrier in isolated, stationary power systems. Such an examination can be useful because it provides a framework for detailed research on subsystems and helps clarify why, when and where large-scale hydrogen use would be beneficial. It also helps define the pathway for an evolving hydrogen stationary power market worldwide. Remote, stationary power systems are an ideal market entry opportunity for hydrogen. For example, if it is sufficiently difficult for conventional fuels to reach a community, and indigenous renewable sources are present, then on-site clean energy production becomes economically competitive. Relying heavily on intermittent sources of energy requires an energy carrier system that is efficient over long periods of time. In addition, the energy carrier must not defeat the reasons for initially switching to the clean sources of energy, and must be economically feasible. Hydrogen is an elegant solution to all of these needs. Choices exist for the methods of producing hydrogen, storing and transporting it, and converting it back to useful energy. There is considerable debate about how best to increase the use of renewable hydrogen because it is not yet economically competitive with conventional energy carriers in most applications. The deployment of isolated power systems relying on hydrogen as the energy storage medium requires complex and comprehensive planning and design considerations to provide successful market entry strategies as well as appropriate system engineering. This paper will discuss the criteria and framework necessary to determine how to successfully deploy any specific system or to plan a global marketing strategy. (author)

Hydrogen storage properties for Mg–Zn–Y quasicrystal and ternary alloys

Energy Technology Data Exchange (ETDEWEB)

Luo, Xuanli, E-mail: Xuanli.Luo@nottingham.ac.uk; Grant, David M., E-mail: David.Grant@nottingham.ac.uk; Walker, Gavin S., E-mail: Gavin.Walker@nottingham.ac.uk

2015-10-05

Highlights: • Quasicrystal (QC) and H-phase alloys were detected in the Zn–Mg–Y samples. • Hydrogen storage properties of Zn–Mg–Y samples were investigated. • Zn{sub 50}Mg{sub 42}Y{sub 8} showed a capacity of 0.9 wt.% and decomposition temperature of 445 °C. - Abstract: Three Zn–Mg–Y alloys with nominal compositions of Zn{sub 50}Mg{sub 42}Y{sub 8} and Zn{sub 60}Mg{sub 30}Y{sub 10} were prepared by induction melting or gas atomisation. XRD and SEM analysis shows samples ZMY-1 and ZMY-2 consisted of multiple phases including icosahedral quasicrystal (QC) i-phase, hexagonal H-phase and Mg{sub 7}Zn{sub 3}, whilst ZMY-3 contained QC only. The hydrogen storage properties of the Zn–Mg–Y quasicrystal and ternary alloys were investigated for the first time. The quasicrystal sample ZMY-3 hydrogenated at 300 °C had 0.3 wt.% capacity and the DSC decomposition peak temperature was 503 °C. Amongst the three samples, the highest hydrogen storage capacity (0.9 wt.%) and the lowest decomposition peak temperature (445 °C) was achieved by sample ZMY-1. The pressure–composition–isotherm (PCI) curve of ZMY-1 sample showed a flat plateau gave a plateau pressure of 3.5 bar at 300 °C, which indicates a lower dehydrogenation enthalpy than MgH{sub 2}.

Enhanced Hydrogen Storage Properties and Reversibility of LiBH4 Confined in Two-Dimensional Ti3C2.

Science.gov (United States)

Zang, Lei; Sun, Weiyi; Liu, Song; Huang, Yike; Yuan, Huatang; Tao, Zhanliang; Wang, Yijing

2018-05-30

LiBH 4 is of particular interest as one of the most promising materials for solid-state hydrogen storage. Herein, LiBH 4 is confined into a novel two-dimensional layered Ti 3 C 2 MXene through a facile impregnation method for the first time to improve its hydrogen storage performance. The initial desorption temperature of LiBH 4 is significantly reduced, and the de-/rehydrogenation kinetics are remarkably enhanced. It is found that the initial desorption temperature of LiBH 4 @2Ti 3 C 2 hybrid decreases to 172.6 °C and releases 9.6 wt % hydrogen at 380 °C within 1 h, whereas pristine LiBH 4 only releases 3.2 wt % hydrogen under identical conditions. More importantly, the dehydrogenated products can partially rehydrogenate at 300 °C and under 95 bar H 2 . The nanoconfined effect caused by unique layered structure of Ti 3 C 2 can hinder the particles growth and agglomeration of LiBH 4 . Meanwhile, Ti 3 C 2 could possess superior effect to destabilize LiBH 4 . The synergetic effect of destabilization and nanoconfinement contributes to the remarkably lowered desorption temperature and improved de-/rehydrogenation kinetics.

Multislice simulations for in-situ HRTEM studies of nanostructured magnesium hydride at ambient hydrogen pressure

International Nuclear Information System (INIS)

Surrey, Alexander; Schultz, Ludwig; Rellinghaus, Bernd

2017-01-01

Highlights: • Multislice HRTEM contrast simulations of a windowed environmental cell. • Study of Mg and MgH2 nanocrystals as model system in hydrogen at ambient pressure. • Investigation of spatial resolution and contrast depending on specimen thickness, defocus, and hydrogen pressure. • Atomic resolution is expected for specimens as thin as 5  nm. - Abstract: The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a “nanoreactor” is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH_2, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

Multislice simulations for in-situ HRTEM studies of nanostructured magnesium hydride at ambient hydrogen pressure

Energy Technology Data Exchange (ETDEWEB)

Surrey, Alexander, E-mail: a.surrey@ifw-dresden.de [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Schultz, Ludwig [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Rellinghaus, Bernd, E-mail: b.rellinghaus@ifw-dresden.de [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany)

2017-04-15

Highlights: • Multislice HRTEM contrast simulations of a windowed environmental cell. • Study of Mg and MgH2 nanocrystals as model system in hydrogen at ambient pressure. • Investigation of spatial resolution and contrast depending on specimen thickness, defocus, and hydrogen pressure. • Atomic resolution is expected for specimens as thin as 5  nm. - Abstract: The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a “nanoreactor” is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH{sub 2}, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

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.

Characteristics of hydrogen co-doped ZnO : Al thin films

International Nuclear Information System (INIS)

Lee, S H; Lee, T S; Lee, K S; Cheong, B; Kim, W M; Kim, Y D

2008-01-01

ZnO films co-doped with H and Al (HAZO) were prepared by sputtering ZnO targets containing 1 wt% Al 2 O 3 on Corning glass at a substrate temperature of 150 deg. C with Ar and H 2 /Ar gas mixtures. The effects of hydrogen addition to Al-doped ZnO (AZO) films with low Al content on the electrical, the optical and the structural properties of the as-grown films as well as the vacuum- and air-annealed films were examined. Secondary ion mass spectroscopy analysis showed that the hydrogen concentration increased with increasing H 2 in sputter gas. For the as-deposited films, the free carrier number increased with increasing H 2 . The Hall mobility increased at low hydrogen content, reaching a maximum before decreasing with a further increase of H 2 content in sputter gas. Annealing at 300 deg. C resulted in the removal of hydrogen, causing a decrease in the carrier concentration. It was shown that hydrogen might exist as single isolated interstitial hydrogen bound with oxygen, thereby acting like an anionic dopant. Also, it was shown that the addition of hydrogen to ZnO films doped with low metallic dopant concentration could yield transparent conducting films with very low absorption loss as well as with proper electrical properties, which is suitable for thin film solar cell applications

Development of nickel membranes deposited on ceramic materials by electroless plating: studies of the hydrogen perm-selectivity properties at elevated temperatures

International Nuclear Information System (INIS)

Amer, J.

2008-09-01

The main objective of this work was to synthesize nickel based membranes by electroless plating on materials such as alumina-α, alumina-γ and zirconia with various textures and to determine their hydrogen perm-selectivity at high temperatures. The synthesis of metal films of high purity (≥ 99% mass Ni) resulting from the choice of hydrazine with its dual role of reducing and complexing agent has revealed that the diameter of pores on the surface support has an impact on the quality of metal adherence. The various contributions of hydrogen transport through these composite membranes at low temperatures (Knudsen and surface diffusion) and at high temperatures (Knudsen and activated diffusion) was established. At its implementation in a membrane reactor (reaction of propane dehydrogenation), the layer of nickel showed a very good resistance to coking. (author)

Prospects for hydrogen storage in graphene.

Science.gov (United States)

Tozzini, Valentina; Pellegrini, Vittorio

2013-01-07

Hydrogen-based fuel cells are promising solutions for the efficient and clean delivery of electricity. Since hydrogen is an energy carrier, a key step for the development of a reliable hydrogen-based technology requires solving the issue of storage and transport of hydrogen. Several proposals based on the design of advanced materials such as metal hydrides and carbon structures have been made to overcome the limitations of the conventional solution of compressing or liquefying hydrogen in tanks. Nevertheless none of these systems are currently offering the required performances in terms of hydrogen storage capacity and control of adsorption/desorption processes. Therefore the problem of hydrogen storage remains so far unsolved and it continues to represent a significant bottleneck to the advancement and proliferation of fuel cell and hydrogen technologies. Recently, however, several studies on graphene, the one-atom-thick membrane of carbon atoms packed in a honeycomb lattice, have highlighted the potentialities of this material for hydrogen storage and raise new hopes for the development of an efficient solid-state hydrogen storage device. Here we review on-going efforts and studies on functionalized and nanostructured graphene for hydrogen storage and suggest possible developments for efficient storage/release of hydrogen under ambient conditions.

Hydrogen production by using Rhodobacter capsulatus mutants with genetically modified electron transfer chains

Energy Technology Data Exchange (ETDEWEB)

OEztuerk, Yavuz; Yuecel, Meral; Guenduez, Ufuk [Department of Biology, Middle East Technical University, Ankara (Turkey); Daldal, Fevzi [Department of Biology, Plant Science Institute, University of Pennsylvania, Philadelphia, PA 19104-6018 (United States); Mandaci, Sevnur [TUEBITAK Research Institute for Genetic Engineering and Biotechnology, Gebze Kocaeli 41470 (Turkey); Tuerker, Lemi [Department of Chemistry, Middle East Technical University, Ankara (Turkey); Eroglu, Inci [Department of Chemical Engineering, Middle East Technical University, Ankara (Turkey)

2006-09-15

In Rhodobacter capsulatus excess reducing equivalents generated by organic acid oxidation is consumed to reduce protons into hydrogen by the activity of nitrogenase. Nitrogenase serves as a redox-balancing tool and is activated by the RegB/RegA global regulatory system during photosynthetic growth. The terminal cytochrome cbb{sub 3} oxidase and the redox state of the cyclic photosynthetic electron transfer chain serve redox signaling to the RegB/RegA regulatory systems in Rhodobacter. In this study, hydrogen production of various R. capsulatus strains harboring the genetically modified electron carrier cytochromes or lacking the cyt cbb{sub 3} oxidase or the quinol oxidase were compared with the wild type. The results indicated that hydrogen production of mutant strains with modified electron carrier cytochromes decreased 3- to 4-fold, but the rate of hydrogen production increased significantly in a cbb{sub 3}{sup -} mutant. Moreover, hydrogen production efficiency of various R. capsulatus strains further increased by inactivation of uptake hydrogenase genes. (author)

Tuning carrier mobility of phosphorene nanoribbons by edge passivation and strain

International Nuclear Information System (INIS)

Zhang, Xiaoou; Li, Qingfang; Xu, Bo; Wan, Bo; Yin, Jiang; Wan, X.G.

2016-01-01

Using first-principles calculations, we have studied the effects of different edge passivation groups on the carrier mobility of the phosphorene nanoribbons (PNRs) and strain effect on the transport property in passivated PNRs. The numerical results show that the size-dependent carrier mobility of passivated PNRs is not very sensitive to the different passivation groups, such as hydrogen (H), fluorine (F) and chlorine (Cl), but strongly associated with the orientation of nanoribbons. Passivated armchair-PNR has much larger carrier mobility than passivated zigzag-PNR at the similar ribbon width. With increasing ribbon width, the electron mobility of passivated PNRs can be further enhanced. We also find that the anisotropy of carrier mobility in passivated PNRs can be reversed by applying tensile strain resulting from order switching of the conduction bands around Fermi level.

Tuning carrier mobility of phosphorene nanoribbons by edge passivation and strain

Energy Technology Data Exchange (ETDEWEB)

Zhang, Xiaoou [National Laboratory of Solid State Microstructures, College of Physics, Nanjing University, Nanjing 210093 (China); Li, Qingfang, E-mail: qingfangli@nuist.edu.cn [National Laboratory of Solid State Microstructures, College of Physics, Nanjing University, Nanjing 210093 (China); Department of Physics, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Xu, Bo, E-mail: xubonju@gmail.com [National Laboratory of Solid State Microstructures and Department of Materials Science and Engineering, Nanjing University, Nanjing 210093 (China); Wan, Bo [National Laboratory of Solid State Microstructures, College of Physics, Nanjing University, Nanjing 210093 (China); Yin, Jiang [National Laboratory of Solid State Microstructures and Department of Materials Science and Engineering, Nanjing University, Nanjing 210093 (China); Wan, X.G. [National Laboratory of Solid State Microstructures, College of Physics, Nanjing University, Nanjing 210093 (China)

2016-02-05

Using first-principles calculations, we have studied the effects of different edge passivation groups on the carrier mobility of the phosphorene nanoribbons (PNRs) and strain effect on the transport property in passivated PNRs. The numerical results show that the size-dependent carrier mobility of passivated PNRs is not very sensitive to the different passivation groups, such as hydrogen (H), fluorine (F) and chlorine (Cl), but strongly associated with the orientation of nanoribbons. Passivated armchair-PNR has much larger carrier mobility than passivated zigzag-PNR at the similar ribbon width. With increasing ribbon width, the electron mobility of passivated PNRs can be further enhanced. We also find that the anisotropy of carrier mobility in passivated PNRs can be reversed by applying tensile strain resulting from order switching of the conduction bands around Fermi level.

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.

Production of chemical energy carriers by non-expendable energy sources

Energy Technology Data Exchange (ETDEWEB)

Nitsch, J

1976-01-01

The different forms of energy (radiation, high-temperature heat and electricity) arising from non-expendable energy sources like solar energy can be used for the production of chemical energy-carriers. Possible methods are the splitting of water by means of photolysis, thermochemical cycles and electrolysis, as well as the storage of energy in closed loop chemical systems. These methods are described and efficiencies and costs of the production of these energy carriers are specified. Special problems of the long-distance transportation of hydrogen produced by solar energy are described and the resulting costs are estimated.

Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

1980-02-21

Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

Synthesis and characterization of conventional and mesoporous Ga-MFI for ethane dehydrogenation

DEFF Research Database (Denmark)

Leth, Karen Thrane; Rovik, Anne Krogh; Holm, Martin Spangsberg

2008-01-01

difference being the morphology of the crystals. The catalytic properties of the samples were tested in ethane dehydrogenation at 823 K and at atmospheric pressure. The two Ga-MFI samples differ greatly in conversion of ethane, as a result of their difference in porosity, and it is found that the conversion...... is reported for tetrahedral Ga incorporated in the MFI structure and it is shown that absorbed water molecules have an important impact on the Ga-71 electric field gradients and thereby on the quantitative evaluation of the Ga-71 MAS NMR intensities....

Strategy for research development and demonstration regarding hydrogen technology in Denmark. Hydrogen production. An account of production technologies against planning of a optimal danish effort within hydrogen; Strategi for forskning, udvikling og demonstration vedroerende brintteknologi i Danmark. Brintproduktion - Gennemgang af produktionsteknologier med henblik pae planlaegning af en optimal dansk indsats pae brintomraedet

Energy Technology Data Exchange (ETDEWEB)

NONE

2004-12-01

This report has been prepared as part of the Danish Energy Authorities' formulation of a Danish strategy for hydrogen as an energy carrier, especially within production of hydrogen and hydrogen-containing fuels. The working-group has defined hydrogen production as the chain of processes necessary to convert a specific energy into enough clean hydrogen or hydrogen-containing fuels. The work has focused on energy sources that can be converted to hydrogen directly, i.e. biomass, solar energy, electricity, and fossil sources. (BA)

Proceedings of the 1999 U.S. DOE Hydrogen Program Review

Energy Technology Data Exchange (ETDEWEB)

NREL

2000-08-28

The Proceedings of the 1999 US Department of Energy (DOE) Hydrogen Program Review serve as an important technology reference for the DOE Hydrogen Program. This document contains technical progress reports on 60 research and technology validation projects funded by the DOE Hydrogen Program in Fiscal Year 1999, in support of its mission to make hydrogen a cost-effective energy carrier for utility, building, and transportation applications. Each year, the Program conducts a rigorous review of its portfolio of projects, utilizing teams of experts to provide vital feedback on the progress of research.

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).

Hydrogen energy based on nuclear energy

International Nuclear Information System (INIS)

2002-06-01

A concept to produce hydrogen of an energy carrier using nuclear energy was proposed since 1970s, and a number of process based on thermochemical method has been investigated after petroleum shock. As this method is used high temperature based on nuclear reactors, these researches are mainly carried out as a part of application of high temperature reactors, which has been carried out at an aim of the high temperature reactor application in the Japan Atomic Energy Research Institute. On October, 2000, the 'First International Conference for Information Exchange on Hydrogen Production based on Nuclear Energy' was held by auspice of OECD/NEA, where hydrogen energy at energy view in the 21st Century, technology on hydrogen production using nuclear energy, and so on, were published. This commentary was summarized surveys and researches on hydrogen production using nuclear energy carried out by the Nuclear Hydrogen Research Group established on January, 2001 for one year. They contains, views on energy and hydrogen/nuclear energy, hydrogen production using nuclear energy and already finished researches, methods of hydrogen production using nuclear energy and their present conditions, concepts on production plants of nuclear hydrogen, resources on nuclear hydrogen production and effect on global environment, requests from market and acceptability of society, and its future process. (G.K.)

CU-ICAR Hydrogen Infrastructure Final Report

Energy Technology Data Exchange (ETDEWEB)

Robert Leitner; David Bodde; Dennis Wiese; John Skardon; Bethany Carter

2011-09-28

The goal of this project was to establish an innovation center to accelerate the transition to a 'hydrogen economy' an infrastructure of vehicles, fuel resources, and maintenance capabilities based on hydrogen as the primary energy carrier. The specific objectives of the proposed project were to: (a) define the essential attributes of the innovation center; (b) validate the concept with potential partners; (c) create an implementation plan; and (d) establish a pilot center and demonstrate its benefits via a series of small scale projects.

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

Science.gov (United States)

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

2018-06-01

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

Hydrogen storage in complex hydrides

International Nuclear Information System (INIS)

Lupu, D.; Biris, A. R.; Misan, I.

2005-01-01

Full text: Hydrogen storage is a key enabling technology for the advancement of hydrogen and fuel cell power technologies in mobile and stationary applications. A relevant role of the fuel cell powered vehicles on the market of the transportation systems will be achieved only if the research and development of on-board vehicular hydrogen storage are able to allow a driving range of at least 500 km. The on-board hydrogen storage systems are more challenging due to the space, weight and cost limitations. This range of autonomy between refueling requires materials able to store at least 6.5% weight hydrogen, available at moderate pressures, at the working temperature of the fuel cells and with acceptable cycling stability. The intensive research on the hydrogen storage in alloys and intermetallic of the LaNi 5 , FeTi or Laves phase type compounds, which started more than three decades ago did not resulted in materials of more than about 3% H storage capacities. The 7.5% H content of the Mg hydride is still of attracting interest but though the absorption has been achieved at lower temperatures by ball milling magnesium with various amounts of nickel, the desorption can not be attained at 1 bar H 2 below 280 deg. C and the kinetics of the process is too slow. In the last decade, the attention is focused on another class of compounds, the complex hydrides of aluminum with alkali metals (alanates), due to their high hydrogen content. It was found that doping with Ti-based catalysts improve the hydrogenation/dehydrogenation conditions of NaAlH 4 . Later on, it was shown that ball milling with solid state catalysts greatly improve the hydrogen desorption kinetics of NaAlH 4 , and this also helps to the rehydriding process. The hydrogen desorption from NaAlH 4 occurs in three steps, it shows a reversible storage capacity of 5.5% H and this led to further research work for a better knowledge of its application relating properties. In this work, ball milling experiments on Na

Production of bioplastics and hydrogen gas by photosynthetic microorganisms

Science.gov (United States)

Yasuo, Asada; Masato, Miyake; Jun, Miyake

1998-03-01

Our efforts have been aimed at the technological basis of photosynthetic-microbial production of materials and an energy carrier. We report here accumulation of poly-(3-hydroxybutyrate) (PHB), a raw material of biodegradable plastics and for production of hydrogen gas, and a renewable energy carrier by photosynthetic microorganisms (tentatively defined as cyanobacteria plus photosynthetic bateria, in this report). A thermophilic cyanobacterium, Synechococcus sp. MA19 that accumulates PHB at more than 20% of cell dry wt under nitrogen-starved conditions was isolated and microbiologically identified. The mechanism of PHB accumulation was studied. A mesophilic Synechococcus PCC7942 was transformed with the genes encoding PHB-synthesizing enzymes from Alcaligenes eutrophus. The transformant accumulated PHB under nitrogen-starved conditions. The optimal conditions for PHB accumulation by a photosynthetic bacterium grown on acetate were studied. Hydrogen production by photosynthetic microorganisms was studied. Cyanobacteria can produce hydrogen gas by nitrogenase or hydrogenase. Hydrogen production mediated by native hydrogenase in cyanobacteria was revealed to be in the dark anaerobic degradation of intracellular glycogen. A new system for light-dependent hydrogen production was targeted. In vitro and in vivo coupling of cyanobacterial ferredoxin with a heterologous hydrogenase was shown to produce hydrogen under light conditions. A trial for genetic trasformation of Synechococcus PCC7942 with the hydrogenase gene from Clostridium pasteurianum is going on. The strong hydrogen producers among photosynthetic bacteria were isolated and characterized. Co-culture of Rhodobacter and Clostriumdium was applied to produce hydrogen from glucose. Conversely in the case of cyanobacteria, genetic regulation of photosynthetic proteins was intended to improve conversion efficiency in hydrogen production by the photosynthetic bacterium, Rhodobacter sphaeroides RV. A mutant acquired by

A Thermal Dehydrogenative Diels–Alder Reaction of Styrenes for the Concise Synthesis of Functionalized Naphthalenes

Science.gov (United States)

Kocsis, Laura S.; Benedetti, Erica

2012-01-01

Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan. PMID:22913473

A thermal dehydrogenative Diels-Alder reaction of styrenes for the concise synthesis of functionalized naphthalenes.

Science.gov (United States)

Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

2012-09-07

Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan.

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.

The U.S. National Hydrogen Storage Project

International Nuclear Information System (INIS)

Sunita Satyapal; Carole Read; Grace Ordaz; John Petrovic; George Thomas

2006-01-01

Hydrogen is being considered by many countries as a potential energy carrier for vehicular applications. In the United States, hydrogen-powered vehicles must possess a driving range of greater than 300 miles in order to meet customer requirements and compete effectively with other technologies. For the overall vehicular fleet, this requires that a range of 5-13 kg of hydrogen be stored on-board. The storage of such quantities of hydrogen within vehicular weight, volume, and system cost constraints is a major scientific and technological challenge. The targets for on-board hydrogen storage were established in the U.S. through the FreedomCAR and Fuel partnership, a partnership among the U.S. Department of Energy, the U.S. Council for Automotive Research (USCAR) and major energy companies. In order to achieve these long-term targets, the Department of Energy established a National Hydrogen Storage Project to develop the areas of metal hydrides, chemical hydrogen storage, carbon-based and high-surface-area sorbent materials, and new hydrogen storage materials and concepts. The current status of vehicular hydrogen storage is reviewed and hydrogen storage research associated with the National Hydrogen Storage Project is discussed. (authors)

Hydrogen energy systems studies

Energy Technology Data Exchange (ETDEWEB)

Ogden, J.M.; Steinbugler, M.; Dennis, E. [Princeton Univ., NJ (United States)] [and others

1995-09-01

For several years, researchers at Princeton University`s Center for Energy and Environmental Studies have carried out technical and economic assessments of hydrogen energy systems. Initially, we focussed on the long term potential of renewable hydrogen. More recently we have explored how a transition to renewable hydrogen might begin. The goal of our current work is to identify promising strategies leading from near term hydrogen markets and technologies toward eventual large scale use of renewable hydrogen as an energy carrier. Our approach has been to assess the entire hydrogen energy system from production through end-use considering technical performance, economics, infrastructure and environmental issues. This work is part of the systems analysis activity of the DOE Hydrogen Program. In this paper we first summarize the results of three tasks which were completed during the past year under NREL Contract No. XR-11265-2: in Task 1, we carried out assessments of near term options for supplying hydrogen transportation fuel from natural gas; in Task 2, we assessed the feasibility of using the existing natural gas system with hydrogen and hydrogen blends; and in Task 3, we carried out a study of PEM fuel cells for residential cogeneration applications, a market which might have less stringent cost requirements than transportation. We then give preliminary results for two other tasks which are ongoing under DOE Contract No. DE-FG04-94AL85803: In Task 1 we are assessing the technical options for low cost small scale production of hydrogen from natural gas, considering (a) steam reforming, (b) partial oxidation and (c) autothermal reforming, and in Task 2 we are assessing potential markets for hydrogen in Southern California.

Improved hydrogen storage properties of MgH2 catalyzed with TiO2

Science.gov (United States)

Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

2018-05-01

In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

Photocatalytic hydrogen generation enhanced by band gap narrowing and improved charge carrier mobility in AgTaO3 by compensated co-doping.

Science.gov (United States)

Li, Min; Zhang, Junying; Dang, Wenqiang; Cushing, Scott K; Guo, Dong; Wu, Nianqiang; Yin, Penggang

2013-10-14

The correlation of the electronic band structure with the photocatalytic activity of AgTaO3 has been studied by simulation and experiments. Doping wide band gap oxide semiconductors usually introduces discrete mid-gap states, which extends the light absorption but has limited benefit for photocatalytic activity. Density functional theory (DFT) calculations show that compensated co-doping in AgTaO3 can overcome this problem by increasing the light absorption and simultaneously improving the charge carrier mobility. N/H and N/F co-doping can delocalize the discrete mid-gap states created by sole N doping in AgTaO3, which increases the band curvature and the electron-to-hole effective mass ratio. In particular, N/F co-doping creates a continuum of states that extend the valence band of AgTaO3. N/F co-doping thus improves the light absorption without creating the mid-gap states, maintaining the necessary redox potentials for water splitting and preventing from charge carrier trapping. The experimental results have confirmed that the N/F-codoped AgTaO3 exhibits a red-shift of the absorption edge in comparison with the undoped AgTaO3, leading to remarkable enhancement of photocatalytic activity toward hydrogen generation from water.

Ultraviolet-Visible (UV-Vis) Microspectroscopic System Designed for the In Situ Characterization of the Dehydrogenation Reaction Over Platinum Supported Catalytic Microchannel Reactor.

Science.gov (United States)

Suarnaba, Emee Grace Tabares; Lee, Yi Fuan; Yamada, Hiroshi; Tagawa, Tomohiko

2016-11-01

An ultraviolet visible (UV-Vis) microspectroscopic system was designed for the in situ characterization of the activity of the silica supported platinum (Pt) catalyst toward the dehydrogenation of 1-methyl-1,4-cyclohexadiene carried out in a custom-designed catalytic microreactor cell. The in situ catalytic microreactor cell (ICMC) with inlet/outlet ports was prepared using quartz cover as the optical window to facilitate UV-Vis observation. A fabricated thermometric stage was adapted to the UV-Vis microspectrophotometer to control the reaction temperature inside the ICMC. The spectra were collected by focusing the UV-Vis beam on a 30 × 30 µm area at the center of ICMC. At 393 K, the sequential measurement of the spectra recorded during the reaction exhibited a broad absorption peak with maximum absorbance at 260 nm that is characteristic for gaseous toluene. This result indicates that the silica supported Pt catalyst is active towards the dehydrogenation of 1-methyl-1,4-cyclohexadiene at the given experimental conditions. The onset of coke formation was also detected based on the appearance of absorption bands at 300 nm. The UV-Vis microspectroscopic system developed can be used further in studying the mechanism of the dehydrogenation reaction. © The Author(s) 2016.

Highly enantioselective catalytic cross-dehydrogenative coupling of N-carbamoyl tetrahydroisoquinolines and terminal alkynes.

Science.gov (United States)

Sun, Shutao; Li, Chengkun; Floreancig, Paul E; Lou, Hongxiang; Liu, Lei

2015-04-03

The first catalytic asymmetric cross-dehydrogenative coupling of cyclic carbamates and terminal alkynes has been established. The reaction features high enantiocontrol and excellent functional group tolerance and displays a wide range of structurally and electronically diverse carbamates as well as terminal alkynes. N-Acyl hemiaminals were identified as the reactive intermediates through preliminary control experiments. Employing readily removable carbamates as substrates rather than traditionally adopted N-aryl amines allows applications in complex molecule synthesis and therefore advances the C-H functionalization strategy to a synthetically useful level.

Storing Renewable Energy in the Hydrogen Cycle.

Science.gov (United States)

Züttel, Andreas; Callini, Elsa; Kato, Shunsuke; Atakli, Züleyha Özlem Kocabas

2015-01-01

An energy economy based on renewable energy requires massive energy storage, approx. half of the annual energy consumption. Therefore, the production of a synthetic energy carrier, e.g. hydrogen, is necessary. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines is a closed cycle. Electrolysis splits water into hydrogen and oxygen and represents a mature technology in the power range up to 100 kW. However, the major technological challenge is to build electrolyzers in the power range of several MW producing high purity hydrogen with a high efficiency. After the production of hydrogen, large scale and safe hydrogen storage is required. Hydrogen is stored either as a molecule or as an atom in the case of hydrides. The maximum volumetric hydrogen density of a molecular hydrogen storage is limited to the density of liquid hydrogen. In a complex hydride the hydrogen density is limited to 20 mass% and 150 kg/m(3) which corresponds to twice the density of liquid hydrogen. Current research focuses on the investigation of new storage materials based on combinations of complex hydrides with amides and the understanding of the hydrogen sorption mechanism in order to better control the reaction for the hydrogen storage applications.

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

Dehydrogenation kinetics of pure and nickel-doped magnesium hydride investigated by in situ time-resolved powder X-ray diffraction

DEFF Research Database (Denmark)

Jensen, T.R.; Andreasen, A.; Vegge, Tejs

2006-01-01