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Sample records for hydrogen evolution reduction

  1. Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media.

    Science.gov (United States)

    Ooka, Hideshi; Figueiredo, Marta C; Koper, Marc T M

    2017-09-19

    Understanding the competition between hydrogen evolution and CO2 reduction is of fundamental importance to increase the faradaic efficiency for electrocatalytic CO2 reduction in aqueous electrolytes. Here, by using a copper rotating disc electrode, we find that the major hydrogen evolution pathway competing with CO2 reduction is water reduction, even in a relatively acidic electrolyte (pH 2.5). The mass-transport-limited reduction of protons takes place at potentials for which there is no significant competition with CO2 reduction. This selective inhibitory effect of CO2 on water reduction, as well as the difference in onset potential even after correction for local pH changes, highlights the importance of differentiating between water reduction and proton reduction pathways for hydrogen evolution. In-situ FTIR spectroscopy indicates that the adsorbed CO formed during CO2 reduction is the primary intermediate responsible for inhibiting the water reduction process, which may be one of the main mechanisms by which copper maintains a high faradaic efficiency for CO2 reduction in neutral media.

  2. Computational screening of core@shell nanoparticles for the hydrogen evolution and oxygen reduction reactions

    Science.gov (United States)

    Corona, Benjamin; Howard, Marco; Zhang, Liang; Henkelman, Graeme

    2016-12-01

    Using density functional theory calculations, a set of candidate nanoparticle catalysts are identified based on reactivity descriptors and segregation energies for the oxygen reduction and hydrogen evolution reactions. Trends in the data were identified by screening over 700 core@shell 2 nm transition metal nanoparticles for each reaction. High activity was found for nanoparticles with noble metal shells and a variety of core metals for both reactions. By screening for activity and stability, we obtain a set of interesting bimetallic catalysts, including cases that have reduced noble metal loadings and a higher predicted activity as compared to monometallic Pt nanoparticles.

  3. Study of gold-platinum and platinum-gold surface modification and its influence on hydrogen evolution and oxygen reduction

    Directory of Open Access Journals (Sweden)

    BRANIMIR N. GRGUR

    2005-02-01

    Full Text Available Surface modification of the electrodes was conducted from sulfuric acid solutions containing the corresponding metal–chloride complexes using cyclic voltammetry. Comparing the charges of the hydrogen underpotential deposition region, and the corresponding oxide reduction regions, it is concluded that a platinum overlayer on gold forms 3D islands, while gold on platinum forms 2D islands. Foreign metals present in an amount of up to one monolayer exert an influence on the change in reaction rate with respect to both hydrogen evolution (HER and oxygen reduction (ORR reactions. Aplatinum overlayer on a gold substrate increases the activity forHER and for ORR, compared with pure gold. These results can be understood in terms of a simple model, in which the change in the H and OH binding energies are directly proportional to the shift of the d-bond center of the overlayer. On the contrary, a gold layer on platinum slightly decreases the activity for both reactions compared with pure platinum.

  4. Hydrogenated uniform Pt clusters supported on porous CaMnO(3) as a bifunctional electrocatalyst for enhanced oxygen reduction and evolution.

    Science.gov (United States)

    Han, Xiaopeng; Cheng, Fangyi; Zhang, Tianran; Yang, Jingang; Hu, Yuxiang; Chen, Jun

    2014-04-01

    Hydrogenated uniform Pt clusters supported on porous CaMnO3 nanocomposites are synthesized and investigated as a new electrocatalytic material for oxygen reduction and evolution reactions. Due to the synergistic effect of Pt and CaMnO3, the nanocomposites exhibit superior activity and durability to the benchmark Pt/C catalyst.

  5. Electrochemical Hydrogen Evolution

    DEFF Research Database (Denmark)

    Laursen, A.B.; Varela Gasque, Ana Sofia; Dionigi, F.

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experimen...

  6. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems.

    Science.gov (United States)

    Zhang, Wei; Lai, Wenzhen; Cao, Rui

    2017-02-22

    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  7. Relation between Hydrogen Evolution and Hydrodesulfurization Catalysis

    DEFF Research Database (Denmark)

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

    2016-01-01

    A relation between hydrogen evolution and hydrodesulfurization catalysis was found by density functional theory calculations. The hydrogen evolution reaction and the hydrogenation reaction in hydrodesulfurization share hydrogen as a surface intermediate and, thus, have a common elementary step......, which indicates that the same catalyst should perform well for both hydrogen evolution and hydrogenation. If that catalyst also fulfills additional criteria for breaking carbon–sulfur bonds and releasing hydrogen sulfide, it will be a good hydrodesulfurization catalyst. The hydrogen evolution reaction...... is normally performed at room temperature and standard pressure, whereas the hydrodesulfurization reaction is driven by high temperature and pressure. Owing to the very different operating conditions, the adsorption free energy of hydrogen differs between hydrodesulfurization and the hydrogen evolution...

  8. Hydrogen evolution by a metal-free electrocatalyst

    KAUST Repository

    Zheng, Yao

    2014-04-28

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. © 2014 Macmillan Publishers Limited. All rights reserved.

  9. Hydrogen evolution by a metal-free electrocatalyst.

    Science.gov (United States)

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

    2014-04-28

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

  10. Screening of electrocatalytic materials for hydrogen evolution

    DEFF Research Database (Denmark)

    Björketun, Mårten; Bondarenko, Alexander S.; Abrams, Billie

    2010-01-01

    . As an example, the scheme is used to identify a binary “substrate-overlayer” electrocatalytic system for the hydrogen evolution reaction. The best catalysts found in this screening are based on Cu and W. The hydrogen evolution activity of W–Cu catalysts is evaluated by means of cyclic voltammetry. It turns out...

  11. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Y.; Xu, Q.; Cheah, S.

    2013-01-01

    Based on Density Functional Theory (DFT) simulations, we have studied the reduction of nickel oxide and biomass derived oxygenates (catechol, guaiacol, etc.) in hydrogen. Both the kinetic barrier and thermodynamic favorability are calculated with respect to the modeled reaction pathways. In early-stage reduction of the NiO(100) surface by hydrogen, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms coordinately dissociate the hydrogen molecules so that a water molecule can be formed, leaving an oxygen vacancy on the surface. In hydrogen reaction with oxygenates catalyzed by transition metals, hydrogenation of the aromatic carbon ring normally dominates. However, selective deoxygenation is of particular interest for practical application such as biofuel conversion. Our modeling shows that doping of the transition metal catalysts can change the orientation of oxygenates adsorbed on metal surfaces. The correlation between the selectivity of reaction and the orientation of adsorption are discussed.

  12. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    Energy Technology Data Exchange (ETDEWEB)

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  13. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    Energy Technology Data Exchange (ETDEWEB)

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  14. Exploring Hydrogen Evolution and the Overpotential

    Science.gov (United States)

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

    2015-01-01

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

  15. Exploring Hydrogen Evolution and the Overpotential

    Science.gov (United States)

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

    2015-01-01

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

  16. Dye sensitized hydrogen evolution from water

    Energy Technology Data Exchange (ETDEWEB)

    Dhanalakshmi, K.B.; Latha, S.; Anandan, S.; Maruthamuthu, P. [University of Madras (India). Dept. of Chemistry

    2001-07-01

    Photochemically stable catalysts for continuous production of dihydrogen from water in the presence of visible light are yet to be developed. Most of the proposed systems suffer from loss of activity with use, at varying extent. In the present investigation, the photoactivity of Pt/TiO{sub 2} system in the visible region is improved by the addition of the sensitizer ([Ru(dcbpy){sub 2}(dpq)]{sup 2+})[where dcbpy=4,4{sup '}-dicarboxy 2,2{sup '}-bipyridine and dpq=2,3-bis-(2{sup '}-pyridyl)-quinoxaline] leading to efficient water reduction. This system is relatively inexpensive, reproducible, extremely stable and efficient in conversion of light into dihydrogen in aqueous solution. In order to obtain maximum information about the performance of TiO{sub 2P}t catalysts, we varied the components and conditions of the system for water reduction. The dependence of the dihydrogen evolution rate on the amount of catalysts, concentration of the sensitizer and percentage of platinum on TiO{sub 2} has been studied. In addition to the above, a comparative study on the photocatalytic activities of Pt/TiO{sub 2} and Pt/ZnO in the presence of the above sensitizer for the production of hydrogen was also made. (author)

  17. Hydrogen storage and evolution catalysed by metal hydride complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  18. Kinetic reduction of mill scale via hydrogen

    Directory of Open Access Journals (Sweden)

    Gaballah N.M.

    2014-01-01

    Full Text Available Mill scale is very attractive industrial waste since it is rich in iron (about = 72 % Fe and it is suiTab. for direct recycling to the blast furnace via sintering plant. In this paper the characterizations of raw materials were studied by different methods of analyses. The produced briquettes were reduced with different amounts of hydrogen at varying temperatures, and the reduction kinetics was determined. Two models were applied and the energy of activation was calculated.

  19. Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Science.gov (United States)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

    2017-08-01

    Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

  20. Hydrogenations without Hydrogen: Titania Photocatalyzed Reductions of Maleimides and Aldehydes

    Directory of Open Access Journals (Sweden)

    David W. Manley

    2014-09-01

    Full Text Available A mild procedure for the reduction of electron-deficient alkenes and carbonyl compounds is described. UVA irradiations of substituted maleimides with dispersions of titania (Aeroxide P25 in methanol/acetonitrile (1:9 solvent under dry anoxic conditions led to hydrogenation and production of the corresponding succinimides. Aromatic and heteroaromatic aldehydes were reduced to primary alcohols in similar titania photocatalyzed reactions. A mechanism is proposed which involves two proton-coupled electron transfers to the substrates at the titania surface.

  1. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution.

    Science.gov (United States)

    Morales-Guio, Carlos G; Stern, Lucas-Alexandre; Hu, Xile

    2014-09-21

    Progress in catalysis is driven by society's needs. The development of new electrocatalysts to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks for today's scientists and engineers. The electrochemical splitting of water into hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged. Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches might pave the way for future development of highly efficient catalysts for energy conversion.

  2. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

  3. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    Science.gov (United States)

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  4. Hydrogen reduction of molybdenum oxide at room temperature

    Science.gov (United States)

    Borgschulte, Andreas; Sambalova, Olga; Delmelle, Renaud; Jenatsch, Sandra; Hany, Roland; Nüesch, Frank

    2017-01-01

    The color changes in chemo- and photochromic MoO3 used in sensors and in organic photovoltaic (OPV) cells can be traced back to intercalated hydrogen atoms stemming either from gaseous hydrogen dissociated at catalytic surfaces or from photocatalytically split water. In applications, the reversibility of the process is of utmost importance, and deterioration of the layer functionality due to side reactions is a critical challenge. Using the membrane approach for high-pressure XPS, we are able to follow the hydrogen reduction of MoO3 thin films using atomic hydrogen in a water free environment. Hydrogen intercalates into MoO3 forming HxMoO3, which slowly decomposes into MoO2 +1/2 H2O as evidenced by the fast reduction of Mo6+ into Mo5+ states and slow but simultaneous formation of Mo4+ states. We measure the decrease in oxygen/metal ratio in the thin film explaining the limited reversibility of hydrogen sensors based on transition metal oxides. The results also enlighten the recent debate on the mechanism of the high temperature hydrogen reduction of bulk molybdenum oxide. The specific mechanism is a result of the balance between the reduction by hydrogen and water formation, desorption of water as well as nucleation and growth of new phases.

  5. Two-dimensional metal dichalcogenides and oxides for hydrogen evolution

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Vojvodic, Aleksandra; Thygesen, Kristian Sommer

    2015-01-01

    We explore the possibilities of hydrogen evolution by basal planes of 2D metal dichalcogenides and oxides in the 2H and 1T class of structures using the hydrogen binding energy as a computational activity descriptor. For some groups of systems like the Ti, Zr, and Hf dichalcogenides the hydrogen...... of the two phases will be active for the hydrogen evolution reaction; however, in most cases the two phases are very close in formation energy, opening up the possibility for stabilizing the active phase. The study points to many new possible 2D HER materials beyond the few that are already known....

  6. Trends in the exchange current for hydrogen evolution

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Bligaard, Thomas; Logadottir, Ashildur;

    2005-01-01

    A density functional theory database of hydrogen chemisorption energies on close packed surfaces of a number of transition and noble metals is presented. The bond energies are used to understand the trends in the exchange current for hydrogen evolution. A volcano curve is obtained when measured...... exchange currents are plotted as a function of the calculated hydrogen adsorption energies and a simple kinetic model is developed to understand the origin of the volcano. The volcano curve is also consistent with Pt being the most efficient electrocatalyst for hydrogen evolution. (c) 2005...

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

    Science.gov (United States)

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

    2011-03-08

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

  8. Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

    Energy Technology Data Exchange (ETDEWEB)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2015-09-25

    Liquid natural rubber (LNR) with molecular weight of lower than 10{sup 5} and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA)

  9. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface

    Science.gov (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.

    2017-01-01

    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen. PMID:28233785

  10. Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface

    Science.gov (United States)

    Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.; Tilley, S. David; Francàs, Laia; Mesa, Camilo A.; Grätzel, Michael; Durrant, James R.

    2017-02-01

    Multi-electron heterogeneous catalysis is a pivotal element in the (photo)electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectroelectrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

  11. Hydrogen evolution on Au(111) covered with submonolayers of Pd

    DEFF Research Database (Denmark)

    Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan

    2011-01-01

    . The energetics of adsorption and desorption of hydrogen on/from different types of sites on the Pd-Au(111) surface are assessed by means of density functional theory calculations combined with thermodynamic modeling. Based on the density functional and Monte Carlo data, the hydrogen evolution activity......A theoretical investigation of electrochemical hydrogen evolution on Au(111) covered with submonolayers of Pd is presented. The size and shape of monoatomically high Pd islands formed on the Au(111) surface are determined using Monte Carlo simulations, for Pd coverages varying from 0.02 to 0.95 ML...... line defects for Pd island formation and hydrogen evolution are discussed. It is argued, with support from theoretical data, that this kind of defects is likely to be responsible for a dramatic increase in activity observed experimentally [ChemPhysChem 7, 985 (2006); Electrochim. Acta 52, 5548 (2007...

  12. Cathodic Hydrogen as Electron Donor in Enhanced Reductive Dechlorination

    Institute of Scientific and Technical Information of China (English)

    张瑞玲; 路晓霞; 焦刚珍; 秦松岩

    2013-01-01

    In situ capping is an attractive and cost-effective method for remediation of contaminated sediments, but few studies on enhancing contaminant degradation in sediment caps have been reported, especially for chlorin-ated benzenes. Electrically enhanced bioactive barrier is a new process for in situ remediation for reducible com-pounds in soil or sediments. The primary objective of this study is to determine if electrodes in sediment could cre-ate a redox gradient and provide electron acceptor/donor to stimulate degradation of chlorinated contaminant. The results demonstrate that graphite electrodes lead to sustainable evolution of hydrogen, displaying zero-order kinetics in the initial stages with different voltages. The constant rates of hydrogen evolution at 3, 4, and 5 V are 1.05, 2.54, and 4.3 nmol·L-1·d-1, respectively. Even higher voltage can produce more hydrogen, but it could not keep long time because the over potentials on electrode surfaces prevent its function. The study shows that 4 V is more appropriate for hydrogen evolution. The measured and evaluated concentration of 1,2,3,5-tetrachlorobenzene in pore water of sediment and concentration of sulfate show that dechlorination is inhibited at higher concentration of sulfate.

  13. Hydrogenation of iron in the early stage of Earth's evolution

    Science.gov (United States)

    Iizuka-Oku, Riko; Yagi, Takehiko; Gotou, Hirotada; Okuchi, Takuo; Hattori, Takanori; Sano-Furukawa, Asami

    2017-01-01

    Density of the Earth's core is lower than that of pure iron and the light element(s) in the core is a long-standing problem. Hydrogen is the most abundant element in the solar system and thus one of the important candidates. However, the dissolution process of hydrogen into iron remained unclear. Here we carry out high-pressure and high-temperature in situ neutron diffraction experiments and clarify that when the mixture of iron and hydrous minerals are heated, iron is hydrogenized soon after the hydrous mineral is dehydrated. This implies that early in the Earth's evolution, as the accumulated primordial material became hotter, the dissolution of hydrogen into iron occurred before any other materials melted. This suggests that hydrogen is likely the first light element dissolved into iron during the Earth's evolution and it may affect the behaviour of the other light elements in the later processes.

  14. Thermogravimetric Hydrogen Reduction Of LaCoO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Haas, O.; Schuler, A.; Struis, R.; Ludwig, Chr.

    2005-03-01

    The possibility to use thermogravimetric hydrogen reduction to determine the valence state of cobalt in perovskites was tested using the model compound LaCoO{sub 3}. The results reveal that small impurities of surface carbonates have a big influence to the apparent valence state evaluated from these experiments. (author)

  15. Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

    Science.gov (United States)

    Pan, Hui

    2016-02-01

    Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

  16. DIRECT REDUCTION OF HEMATITE POWDERS VIA COLD HYDROGEN PLASMA

    Directory of Open Access Journals (Sweden)

    Iraldo de Sá Silveira

    2014-12-01

    Full Text Available The goal of this work was to study the reduction kinetics of hematite powders (Fe2O3 using cold hydrogen plasma as reducing agent. Reduction experiments were carried out in a DC pulsed plasma reactor, under hydrogen flow-rates of 300 cm3/min, at pressure of 400 Pa, times from 30 to 120 minutes and temperatures of 320, 340, 360 and 380°C. Fe2O3 powders after reduction experiments were characterized by X-ray diffraction, weight loss of oxygen (gravimetric analyses and light microscopy. The results show that using a reduction temperature of 380°C after 120 min allows obtaining α-iron with a reduction fraction of about 0.93. The powder particles are transformed into two steps: Fe2O3→Fe3O4→Fe-α. The apparent activation energy experimentally established for the reduction of Fe2O3 is about 98.4 kJ/mol.

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

    Science.gov (United States)

    Zou, Xiaoxin; Zhang, Yu

    2015-08-07

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

  18. Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

    Science.gov (United States)

    Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G

    2016-11-23

    Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP(4+) ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P2 Mo18 O62(6-) and P2 W18 O62(6-) anions, and one Keplerate {Mo132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP(4+) sensitization in relation to the direct photoreduction of those compounds; (b) the P2 Mo18 O62(6-) anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P2 W18 O62(6-) anion; and (c) the high nuclearity Keplerate {Mo132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis

    Science.gov (United States)

    Gong, Ming; Zhou, Wu; Tsai, Mon-Che; Zhou, Jigang; Guan, Mingyun; Lin, Meng-Chang; Zhang, Bo; Hu, Yongfeng; Wang, Di-Yan; Yang, Jiang; Pennycook, Stephen J.; Hwang, Bing-Joe; Dai, Hongjie

    2014-08-01

    Active, stable and cost-effective electrocatalysts are a key to water splitting for hydrogen production through electrolysis or photoelectrochemistry. Here we report nanoscale nickel oxide/nickel heterostructures formed on carbon nanotube sidewalls as highly effective electrocatalysts for hydrogen evolution reaction with activity similar to platinum. Partially reduced nickel interfaced with nickel oxide results from thermal decomposition of nickel hydroxide precursors bonded to carbon nanotube sidewalls. The metal ion-carbon nanotube interactions impede complete reduction and Ostwald ripening of nickel species into the less hydrogen evolution reaction active pure nickel phase. A water electrolyzer that achieves ~20 mA cm-2 at a voltage of 1.5 V, and which may be operated by a single-cell alkaline battery, is fabricated using cheap, non-precious metal-based electrocatalysts.

  20. Non-isothermal reduction kinetics of titanomagnetite by hydrogen

    Science.gov (United States)

    Dang, Jie; Zhang, Guo-hua; Hu, Xiao-jun; Chou, Kuo-chih

    2013-12-01

    Reduction of titanomagnetite (TTM) powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to wüstite and ilmenite, whereas the second one was reduction of wüstite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated different variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90-98 and 115-132 kJ/mol for the first and second reactions, respectively.

  1. Non-isothermal reduction kinetics of titanomagnetite by hydrogen

    Institute of Scientific and Technical Information of China (English)

    Jie Dang; Guo-hua Zhang; Xiao-jun Hu; Kuo-chih Chou

    2013-01-01

    Reduction of titanomagnetite (TTM) powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to w¨ustite and ilmenite, whereas the second one was reduction of w¨ustite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated diff erent variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90-98 and 115-132 kJ/mol for the first and second reactions, respectively.

  2. Reduction of nickel oxide particles by hydrogen studied in an environmental TEM

    DEFF Research Database (Denmark)

    Jeangros, Q.; Hansen, Thomas Willum; Wagner, Jakob Birkedal;

    2013-01-01

    In situ reduction of nickel oxide (NiO) particles is performed under 1.3 mbar of hydrogen gas (H2) in an environmental transmission electron microscope (ETEM). Images, diffraction patterns and electron energy-loss spectra (EELS) are acquired to monitor the structural and chemical evolution...... of the system during reduction, whilst increasing the temperature. Ni nucleation on NiO is either observed to be epitaxial or to involve the formation of randomly oriented grains. The growth of Ni crystallites and the movement of interfaces result in the formation of pores within the NiO grains to accommodate...... the volume shrinkage associated with the reduction. Densification is then observed when the sample is nearly fully reduced. The reaction kinetics is obtained using EELS by monitoring changes in the shapes of the Ni L2,3 white lines. The activation energy for NiO reduction is calculated from the EELS data...

  3. Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

    Science.gov (United States)

    Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

  4. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Science.gov (United States)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  5. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

    2017-02-28

    A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

  6. Hydrogen peroxide evolution during V-UV photolysis of water.

    Science.gov (United States)

    Azrague, Kamal; Bonnefille, Eric; Pradines, Vincent; Pimienta, Véronique; Oliveros, Esther; Maurette, Marie-Thérèse; Benoit-Marquié, Florence

    2005-05-01

    Hydrogen peroxide evolution during the vacuum-ultraviolet (V-UV, 172 nm) photolysis of water is considerably affected by the presence of oxalic acid (employed as a model water pollutant) and striking differences are observed in the absence and in the presence of dioxygen.

  7. Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

    Science.gov (United States)

    Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

  8. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.;

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal sul...

  9. Wave packet evolution approach to ionization of hydrogen molecular ion by fast electrons

    CERN Document Server

    Serov, V V; Joulakian, B B; Vinitsky, S I; Serov, Vladislav V.; Derbov, Vladimir L.; Joulakian, Boghos B.; Vinitsky, Sergue I.

    2000-01-01

    The multiply differential cross section of the ionization of hydrogen molecular ion by fast electron impact is calculated by a direct approach, which involves the reduction of the initial 6D Schr\\"{o}dinger equation to a 3D evolution problem followed by the modeling of the wave packet dynamics. This approach avoids the use of stationary Coulomb two-centre functions of the continuous spectrum of the ejected electron which demands cumbersome calculations. The results obtained, after verification of the procedure in the case atomic hydrogen, reveal interesting mechanisms in the case of small scattering angles.

  10. Electrochemical reduction of hydrogen peroxide on stainless steel

    Indian Academy of Sciences (India)

    S Patra; N Munichandraiah

    2009-09-01

    Electrochemical reduction of hydrogen peroxide is studied on a sand-blasted stainless steel (SSS) electrode in an aqueous solution of NaClO4. The cyclic voltammetric reduction of H2O2 at low concentrations is characterized by a cathodic peak at -0.40 V versus standard calomel electrode (SCE). Cyclic voltammetry is studied by varying the concentration of H2O2 in the range from 0.2 mM to 20 mM and the sweep rate in the range from 2 to 100 mV s-1. Voltammograms at concentrations of H2O2 higher than 2 mM or at high sweep rates consist of an additional current peak, which may be due to the reduction of adsorbed species formed during the reduction of H2O2. Amperometric determination of H2O2 at -0.50 V vs SCE provides the detection limit of 5 M H2O2. A plot of current density versus concentration has two segments suggesting a change in the mechanism of H2O2 reduction at concentrations of H2O2 ≥ 2 mM. From the rotating disc electrode study, diffusion co-efficient of H2O2 and rate constant for reduction of H2O2 are evaluated.

  11. Effect of hydrogen on reduction of burden materials

    Energy Technology Data Exchange (ETDEWEB)

    Hooey, P.L. [Rautaruukki Oy, Raahe (Finland). Raahe Steel

    1996-12-31

    Efficient operation of iron blast furnaces requires that the iron bearing burden material have good reduction, softening and melting characteristics. These characteristics are determined by the physical operation of the blast furnace and the mineralogical composition of the agglomerate. Increasing oil injection rates will increase the hydrogen content of the reducing gas significantly. The aim of this work is to establish how different burden materials react to this change in gas environment, and develop sinters which have optimal properties. The testing of sinter and pellets is broken into two areas: development of the test methods; and determination of sinter and pellet characteristics. The test method requires development because recent testwork has shown that the reducibility of the sinter is now so high that the reduction under load test is no longer sensitive. A new control program and more realistic gas compositions are currently being tested. The softening and melting characteristics of sinters of varying composition, acid pellets and olivine pellets have been tested using the reduction under load test at Rautaruukki Oy Research Centre. The effect of hydrogen in the reducing gas on the different iron ore agglomerates has been evaluated SULA 2 Research Programme; 6 refs.

  12. The hydrogen evolution reaction on single crystal gold electrode

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yanhui [The Institute for Electrochemical Power Sources, Soochow University, No. 688, Moye Road, Suzhou 215006 (China); Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba-yama 04, Sendai 980-8579 (Japan)

    2009-01-15

    As one of the important candidate of power sources for the future, the research and production of hydrogen gas has a significant importance. In this article, the emphasis is on the influence of impurities on hydrogen evolution reaction, i.e., the influence of an addition of decacyclene, C{sub 12}H{sub 35}C{sub 6}H{sub 4}SO{sub 4}Na, CH{sub 3}CH{sub 2}OH, chromanone, H{sub 2}SO{sub 4}, HNO{sub 3}, 4,4'-biphenediol and 1,2,3,4-tetraphenyl-1,3-cyclopentadiene was studied by electrochemical impedance technique. The adsorption structure for some organics was measured by scanning tunneling spectroscopy techniques. Superstructure of adsorbed decacyclene on Au(111) surface was captured. The ordered adsorption structure of 4,4'-biphenyldiol on Au(111) and (100) was also observed. The addition of decacyclene has shown an opposite effects on hydrogen evolution for Au(111) and (100) surface, i.e., it inhibits the reaction at Au(100) but enhances the one at Au(111). The results show that the addition of C{sub 12}H{sub 35}C{sub 6}H{sub 4}SO{sub 4}Na and HNO{sub 3}, especially the latter, can improve the hydrogen evolution. In the article the adsorption structure and hydrogen evolution reaction have been studied in order to give some useful information about the relation between the adsorption structure and the properties. The purpose of this article is to attempt to find the relation between electrochemical performance and the adsorption structure, and to explore the effect of some additives. (author)

  13. Importance of the hydrogen route in up-scaling electrosynthesis for microbial CO2 reduction

    OpenAIRE

    Blanchet, Elise; Duquenne, François; Rafrafi, Yan; Etcheverry, Luc; Erable, Benjamin; Bergel, Alain

    2015-01-01

    International audience; Microbial electrochemical reduction of CO2 was carried out under two different applied potentials, −0.36 V and −0.66 V vs. SHE, using a biological sludge as the inoculum. Both potentials were thermodynamically appropriate for converting CO2 to acetate but only −0.66 V enabled hydrogen evolution. No acetate production was observed at −0.36 V, while up to 244 ± 20 mg L−1 acetate was produced at −0.66 V vs. SHE. The same microbial inoculum implemented in gas–liquid contac...

  14. Evolution of dust and molecular hydrogen in the Magellanic System

    CERN Document Server

    Yozin, Cameron

    2014-01-01

    We investigate the evolution of the interstellar medium (ISM) in self-consistent, chemodynamical simulations of the Magellanic Clouds (MCs) during their recent (z<0.3) past. An explicit modelling of dust and molecular hydrogen lifecycles enables the comparison of our models against the observed properties of the ISM, including elemental depletion from the gas-phase. Combining this model with a tidal-dominated paradigm for the formation for the Magellanic Stream and Bridge, we reproduce the age-metallicity relations, long gas depletion timescales, and presently observed dust and molecular hydrogen masses of the MCs to within their respective uncertainties. We find that these models' enrichment depends sensitively on the processing of dust within the ISM and the dynamical influence of external tides/stellar bars. The ratio of characteristic dust destruction timescales in our SMC and LMC models, a governing parameter of our models' evolution, is consistent with estimates based on observed supernova (SN) rates...

  15. Hydrogen evolution reaction measurements of dealloyed porous NiCu

    Science.gov (United States)

    Koboski, Kyla R.; Nelsen, Evan F.; Hampton, Jennifer R.

    2013-12-01

    Porous metals are of interest for their high surface area and potential for enhanced catalytic behavior. Electrodeposited NiCu thin films with a range of compositions were electrochemically dealloyed to selectively remove the Cu component. The film structure, composition, and reactivity of these samples were characterized both before and after the dealloying step using scanning electron microscopy, energy-dispersive spectroscopy, and electrochemical measurements. The catalytic behavior of the dealloyed porous Ni samples towards the hydrogen evolution reaction was measured and compared to that of the as-deposited samples. The dealloyed samples were generally more reactive than their as-deposited counterparts at low overpotentials, making the dealloying procedure a promising area of exploration for improved hydrogen evolution catalysts.

  16. Vapor hydrogen peroxide as alternative to dry heat microbial reduction

    Science.gov (United States)

    Chung, S.; Kern, R.; Koukol, R.; Barengoltz, J.; Cash, H.

    2008-09-01

    The Jet Propulsion Laboratory (JPL), in conjunction with the NASA Planetary Protection Officer, has selected vapor phase hydrogen peroxide (VHP) sterilization process for continued development as a NASA approved sterilization technique for spacecraft subsystems and systems. The goal was to include this technique, with an appropriate specification, in NASA Procedural Requirements 8020.12 as a low-temperature complementary technique to the dry heat sterilization process. The VHP process is widely used by the medical industry to sterilize surgical instruments and biomedical devices, but high doses of VHP may degrade the performance of flight hardware, or compromise material compatibility. The goal for this study was to determine the minimum VHP process conditions for planetary protection acceptable microbial reduction levels. Experiments were conducted by the STERIS Corporation, under contract to JPL, to evaluate the effectiveness of vapor hydrogen peroxide for the inactivation of the standard spore challenge, Geobacillus stearothermophilus. VHP process parameters were determined that provide significant reductions in spore viability while allowing survival of sufficient spores for statistically significant enumeration. In addition to the obvious process parameters of interest: hydrogen peroxide concentration, number of injection cycles, and exposure duration, the investigation also considered the possible effect on lethality of environmental parameters: temperature, absolute humidity, and material substrate. This study delineated a range of test sterilizer process conditions: VHP concentration, process duration, a process temperature range for which the worst case D-value may be imposed, a process humidity range for which the worst case D-value may be imposed, and the dependence on selected spacecraft material substrates. The derivation of D-values from the lethality data permitted conservative planetary protection recommendations.

  17. Evaluation of Heat Recuperation in a Concentric Hydrogen Reduction Reactor

    Science.gov (United States)

    Linne, Diane; Kleinhenz, Julie; Hegde, Uday

    2012-01-01

    Heat recuperation in an ISRU reactor system involves the recovery of heat from a reacted regolith batch by transferring this energy into a batch of fresh regolith. One concept for a hydrogen reduction reactor is a concentric chamber design where heat is transferred from the inner, reaction chamber into fresh regolith in the outer, recuperation chamber. This concept was tested and analyzed to define the overall benefit compared to a more traditional single chamber batch reactor. Data was gathered for heat-up and recuperation in the inner chamber alone, simulating a single chamber design, as well as recuperation into the outer chamber, simulating a dual chamber design. Experimental data was also used to improve two analytical models, with good agreement for temperature behavior during recuperation, calculated mass of the reactor concepts, and energy required during heat-up. The five tests, performed using JSC-1A regolith simulant, also explored the effectiveness of helium gas fluidization, hydrogen gas fluidization, and vibrational fluidization. Results indicate that higher hydrogen volumetric flow rates are required compared to helium for complete fluidization and mixing, and that vibrational fluidization may provide equivalent mixing while eliminating the need to flow large amounts of excess hydrogen. Analysis of the total energy required for heat-up and steady-state operations for a variety of conditions and assumptions shows that the dual-chamber concept requires the same or more energy than the single chamber concept. With no clear energy savings, the added mass and complexity of the dual-chamber makes it unlikely that this design concept will provide any added benefit to the overall ISRU oxygen production system.

  18. Effect of Doping on Hydrogen Evolution Reaction of Vanadium Disulfide Monolayer

    Science.gov (United States)

    Qu, Yuanju; Pan, Hui; Kwok, Chi Tat; Wang, Zisheng

    2015-12-01

    As cheap and abundant materials, transitional metal dichalcogenide monolayers have attracted increasing interests for their application as catalysts in hydrogen production. In this work, the hydrogen evolution reduction of doped vanadium disulfide monolayers is investigated based on first-principles calculations. We find that the doping elements and concentration affect strongly the catalytic ability of the monolayer. We show that Ti-doping can efficiently reduce the Gibbs free energy of hydrogen adsorption in a wide range of hydrogen coverage. The catalytic ability of the monolayer at high hydrogen coverage can be improved by low Ti-density doping, while that at low hydrogen coverage is enhanced by moderate Ti-density doping. We further show that it is much easier to substitute the Ti atom to the V atom in the vanadium disulfide (VS2) monolayer than other transitional metal atoms considered here due to its lowest and negative formation energy. It is expected that the Ti-doped VS2 monolayer may be applicable in water electrolysis with improved efficiency.

  19. Production of cobalt and nickel particles by hydrogen reduction

    Science.gov (United States)

    Forsman, J.; Tapper, U.; Auvinen, A.; Jokiniemi, J.

    2008-05-01

    Cobalt and nickel nanoparticles were produced by hydrogen reduction reaction from cobalt or nickel chloride precursor vapour in nitrogen carrier gas. This aerosol phase method to produce nanoparticles is a scalable one-step process. Two different setups were introduced in particle production: a batch type reactor and a continuously operated reactor. Common feature in these setups was hydrogen mixing in a vertical flow reactor. The process was monitored on-line for particle mass concentration and for gas phase chemical reactions. Tapered element oscillating microbalance measured the particle mass concentration and Fourier transform infrared spectroscopy was used to monitor relevant gas phase species. The produced cobalt and nickel particles were characterised using transmission electron microscopy and x-ray diffraction. The produced cobalt and nickel particles were crystalline with cubic fcc structure. Twinning was often observed in cobalt particles while nickel particles were mostly single crystals. The cobalt particles formed typically long agglomerates. No significant neck growth between the primary particles was observed. The primary particle size for cobalt and nickel was below 100 nm.

  20. Science Letters: Hydrogen transfer reduction of ketones using formic acid as a hydrogen donor under hydrothermal conditions

    Institute of Scientific and Technical Information of China (English)

    Zheng SHEN; Fang-ming JIN; Ya-lei ZHANG; Bing WU; Jiang-lin CAO

    2009-01-01

    The hydrothermal experiments with ketones and formic acid showed that the hydrogen transfer reduction of ketones can be conducted using formic acid as a hydride donor in the presence of NaOH at 300℃. The yield of alcohols was considerably higher at a much lower ratio of hydrogen source to ketones than the traditional Meerwein-Ponndorf-Verley (MPV) reduction,reaching 60% for isopropanol from acetone and 70% for lactic acid from pyruvic acid. Water molecules may act as a catalyst in the hydrogen transfer reduction of ketones under hydrothermal conditions.

  1. High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst

    KAUST Repository

    Zheng, Yao

    2016-11-28

    Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

  2. Catalytic hydrogen evolution by polyaminoacids using mercury electrode

    Directory of Open Access Journals (Sweden)

    Marko Živanovič

    2010-12-01

    Full Text Available It was shown that using constant current chronopotentiometricstripping (CPS peptides and proteins at nanomolar concentrations produce protein structure–sensitive peak H at mercury electrodes. This peak is due to the catalytic hydrogen evolution reaction (HER. Polyamino acids can be considered as an intermediate model system between peptides and macromolecular proteins. Here we used polyamino acids (poly(aa such as polylysine (polyLys and polyarginine (polyArg and cyclic voltammetry or CPS in combination with hanging mercury drop electrode to explore how different amino acid residues in proteins contribute to the catalyticHER.

  3. Facile Hydrogen Evolution Reaction on WO3Nanorods

    Directory of Open Access Journals (Sweden)

    Rajeswari Janarthanan

    2007-01-01

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

  4. Reductive genome evolution in Buchnera aphidicola

    Science.gov (United States)

    van Ham, Roeland C. H. J.; Kamerbeek, Judith; Palacios, Carmen; Rausell, Carolina; Abascal, Federico; Bastolla, Ugo; Fernández, Jose M.; Jiménez, Luis; Postigo, Marina; Silva, Francisco J.; Tamames, Javier; Viguera, Enrique; Latorre, Amparo; Valencia, Alfonso; Morán, Federico; Moya, Andrés

    2003-01-01

    We have sequenced the genome of the intracellular symbiont Buchnera aphidicola from the aphid Baizongia pistacea. This strain diverged 80–150 million years ago from the common ancestor of two previously sequenced Buchnera strains. Here, a field-collected, nonclonal sample of insects was used as source material for laboratory procedures. As a consequence, the genome assembly unveiled intrapopulational variation, consisting of ≈1,200 polymorphic sites. Comparison of the 618-kb (kbp) genome with the two other Buchnera genomes revealed a nearly perfect gene-order conservation, indicating that the onset of genomic stasis coincided closely with establishment of the symbiosis with aphids, ≈200 million years ago. Extensive genome reduction also predates the synchronous diversification of Buchnera and its host; but, at a slower rate, gene loss continues among the extant lineages. A computational study of protein folding predicts that proteins in Buchnera, as well as proteins of other intracellular bacteria, are generally characterized by smaller folding efficiency compared with proteins of free living bacteria. These and other degenerative genomic features are discussed in light of compensatory processes and theoretical predictions on the long-term evolutionary fate of symbionts like Buchnera. PMID:12522265

  5. The Origin and Evolution of Ribonucleotide Reduction

    Directory of Open Access Journals (Sweden)

    Daniel Lundin

    2015-02-01

    Full Text Available Ribonucleotide reduction is the only pathway for de novo synthesis of deoxyribonucleotides in extant organisms. This chemically demanding reaction, which proceeds via a carbon-centered free radical, is catalyzed by ribonucleotide reductase (RNR. The mechanism has been deemed unlikely to be catalyzed by a ribozyme, creating an enigma regarding how the building blocks for DNA were synthesized at the transition from RNA- to DNA-encoded genomes. While it is entirely possible that a different pathway was later replaced with the modern mechanism, here we explore the evolutionary and biochemical limits for an origin of the mechanism in the RNA + protein world and suggest a model for a prototypical ribonucleotide reductase (protoRNR. From the protoRNR evolved the ancestor to modern RNRs, the urRNR, which diversified into the modern three classes. Since the initial radical generation differs between the three modern classes, it is difficult to establish how it was generated in the urRNR. Here we suggest a model that is similar to the B12-dependent mechanism in modern class II RNRs.

  6. Hydrogen bubble formation and evolution in tungsten under different hydrogen irradiation conditions

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Wenhui; Luo, Fengfeng; Shen, Zhenyu [Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education, Hubei Nuclear Solid Physics Key Laboratory and School of Physics and Technology, Wuhan University, Wuhan 430072 (China); Guo, Liping, E-mail: guolp@whu.edu.cn [Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education, Hubei Nuclear Solid Physics Key Laboratory and School of Physics and Technology, Wuhan University, Wuhan 430072 (China); Zheng, Zhongcheng; Wen, Yongming [Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education, Hubei Nuclear Solid Physics Key Laboratory and School of Physics and Technology, Wuhan University, Wuhan 430072 (China); Ren, Yaoyao [Center for Electron Microscopy, Wuhan University, Wuhan 430072 (China)

    2015-01-15

    Highlights: • Direct and clear observation of hydrogen bubbles evolution by TEM is provided. • The role of temperature playing in bubble formation and evolution is fully explored. • Vacancy trapping mechanism is verified in this experiment. - Abstract: In order to see how hydrogen is behaving in tungsten and to understand the way bubbles form and grow up, specimens were irradiated by hydrogen ions from room temperature to 800 °C to fluence of 2.25 × 10{sup 21} m{sup −2}. Experimental results show that higher temperature helped bubble acquire higher internal pressure, causing interstitial loop punching to happen. In this process bubbles’ size grew and dislocation loops were formed but dislocation loops migrated away at and above 350 °C. And bubble number density reached peak value at 600 °C but then dropped dramatically at 800 °C. Because continuously increasing temperature would cause small bubbles dissolution or leaking out. Besides, high temperature also prevented tiny bubbles growing to be visible under TEM observation by their reaching equilibrium pressure before reaching threshold pressure for loop punching. In the other set of experiments, specimens were irradiated by low hydrogen fluence of 1 × 10{sup 20} m{sup −2} at 600 °C, in which case few hydrogen bubbles appeared. With further increasing irradiation fluence, bubble number density quickly increased. Small bubbles tended to coalesce to become larger visible bubbles. And they continued to grow through loop punching until their internal pressure cannot support their size expansion any more.

  7. Development of hydrogen peroxide technique for bioburden reduction

    Science.gov (United States)

    Rohatgi, N.; Schwartz, L.; Stabekis, P.; Barengoltz, J.

    In order to meet the National Aeronautics and Space Administration (NASA) Planetary Protection microbial reduction requirements for Mars in-situ life detection and sample return missions, entire planetary spacecraft (including planetary entry probes and planetary landing capsules) may have to be exposed to a qualified sterilization process. Presently, dry heat is the only NASA approved sterilization technique available for spacecraft application. However, with the increasing use of various man-made materials, highly sophisticated electronic circuit boards, and sensors in a modern spacecraft, compatibility issues may render this process unacceptable to design engineers and thus impractical to achieve terminal sterilization of the entire spacecraft. An alternative vapor phase hydrogen peroxide sterilization process, which is currently used in various industries, has been selected for further development. Strategic Technology Enterprises, Incorporated (STE), a subsidiary of STERIS Corporation, under a contract from the Jet Propulsion Laboratory (JPL) is developing systems and methodologies to decontaminate spacecraft using vaporized hydrogen peroxide (VHP) technology. The VHP technology provides an effective, rapid and low temperature means for inactivation of spores, mycobacteria, fungi, viruses and other microorganisms. The VHP application is a dry process affording excellent material compatibility with many of the components found in spacecraft such as polymers, paints and electronic systems. Furthermore, the VHP process has innocuous residuals as it decomposes to water vapor and oxygen. This paper will discuss the approach that is being used to develop this technique and will present lethality data that have been collected to establish deep vacuum VHP sterilization cycles. In addition, the application of this technique to meet planetary protection requirements will be addressed.

  8. Reduction of TiO2 with hydrogen cold plasma in DC pulsed glow discharge

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yu-wen; DING Wei-zhong; LU Xiong-gang; GUO Shu-qiang; XU Kuang-di

    2005-01-01

    The reduction of TiO2 to Ti2O3 with hydrogen cold plasma generated by a DC pulsed glow discharge was realized under 2 500 Pa at 1 233 K. Only a little of Ti10O19 and Ti9O17 was detected for using molecular hydrogen.Enhancement effects of hydrogen cold plasma on the reduction were discussed in terms of thermodynamic coupling,kinetics and plasma sheath. The exited hydrogen species are considered more effective reducing agents. It is instructive to reduce refractory oxides with plasma hydrogen at the reduced temperature.

  9. Modifications for the improvement of catalyst materials for hydrogen evolution

    Directory of Open Access Journals (Sweden)

    DRAGAN SLAVKOV

    2006-02-01

    Full Text Available The structural and electrocatalytic characteristics of composite materials based on non-precious metals were studied. Precursors of metallic phase (Ni, Co or CoNi and oxide phase (TiO2 were grafted on a carbon substrate (Vulcan XC-72 by the sol-gel procedure and thermally treated at 250 ºC. Ni and CoNi crystals of 10–20 nm were produced, in contrast the Co and TiO2 were amorphous. The dissimilar electronic character of the components gives rise to a significant electrocatalytic activity for the hydrogen evolution reaction (HER, even in the basic series of prepared materials. Further improvement of the catalysts was achieved by modification of all three components. Hence, Mo was added into the metallic phase, TiO2 was converted into the crystalline form and multiwall carbon nanotubes (MWCNTs were used instead of carbon particles. The improvement, expressed in terms of the lowering the hydrogen evolution overpotential at 60 mA cm–2, was the most pronounced in the Ni-based systems grafted on MWCNTs (120 mV lower HER overpotential compared to 60 mV in case of Ni-based systems grafted on crystalline TiO2 (TiO2 prepared at 450 ºC and of Ni-based systems containing 25 at.% Mo. Nevertheless, even with the realized enhancement, of all the fested materials, the Co-based systems remained superior HER catalysts.

  10. Hydrogen evolution from water splitting on nanocomposite photocatalysts

    Directory of Open Access Journals (Sweden)

    Wenfeng Shangguan

    2007-01-01

    Full Text Available The photocatalytic production of H2 in one step is potentially one of the most promising ways for the conversion and storage of solar energy. The paper overviews our recent studies on the photocatalysts splitting water into hydrogen under irradiation. The attention was mainly focused on the promotion effects of nanosized modifications in the interlayer and surface of photocatalysts for hydrogen evolution with visible light. The photocatalytic activity depended significantly on modification techniques, such as loading, proton exchange, and intercalation. The formation of a "nest" on the particle surface promoted a uniform distribution and strong combination of the nanosized particles on the surface of catalysts. By the methods of intercalation and pillaring as well as by selecting both host and guest, a large variety of molecular designed host–guest systems were obtained. Cadmium sulfide (CdS-intercalated composites showed higher activity and stability. This activity of K4Ce2M10O30 (M=Ta, Nb evolving H2 under visible light irradiation was enhanced by the incorporation of Pt, RuO2 and NiO as co-catalysts. Especially, the nanosized NiOx (Ni–NiO double-layer structure greatly prompted the photocatalytic H2 evolution significantly.

  11. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

    DEFF Research Database (Denmark)

    Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

    2012-01-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction ...

  12. Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Salbo, Rune; Ploug, Michael

    2014-01-01

    Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically ...

  13. Solid State Materials for Hydrogen Production, Ionic Conduction and Oxygen Reduction

    OpenAIRE

    MAO, CHENGYU

    2016-01-01

    Fuel cells convert chemical energy directly into electricity with high efficiency and low pollutant emission via redox reactions at the anode and cathode. The implementation of hydrogen fuel cell depends on the large scale production of hydrogen. Though ‘’hydrogen economy” scenario looks attractive, a breakthrough in hydrogen production. An efficient fuel cell is also dependent on a good ionic conductor between the electrodes and good electrocatalysts for oxygen reduction reactions. Artificia...

  14. Searching for magnetism in hydrogenated graphene: using highly hydrogenated graphene prepared via Birch reduction of graphite oxides.

    Science.gov (United States)

    Eng, Alex Yong Sheng; Poh, Hwee Ling; Šaněk, Filip; Maryško, Miroslav; Matějková, Stanislava; Sofer, Zdeněk; Pumera, Martin

    2013-07-23

    Fully hydrogenated graphene (graphane) and partially hydrogenated graphene materials are expected to possess various fundamentally different properties from graphene. We have prepared highly hydrogenated graphene containing 5% wt of hydrogen via Birch reduction of graphite oxide using elemental sodium in liquid NH3 as electron donor and methanol as proton donor in the reduction. We also investigate the influence of preparation method of graphite oxide, such as the Staudenmaier, Hofmann or Hummers methods on the hydrogenation rate. A control experiment involving NaNH2 instead of elemental Na was also performed. The materials were characterized in detail by electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy both at room and low temperatures, X-ray fluorescence spectroscopy, inductively coupled plasma optical emission spectroscopy, combustible elemental analysis and electrical resistivity measurements. Magnetic measurements are provided of bulk quantities of highly hydrogenated graphene. In the whole temperature range up to room temperature, the hydrogenated graphene exhibits a weak ferromagnetism in addition to a contribution proportional to field that is caused not only by diamagnetism but also likely by an antiferromagnetic influence. The origin of the magnetism is also determined to arise from the hydrogenated graphene itself, and not as a result of any metallic impurities.

  15. Photoinduced hydrogen evolution in an artificial system containing photosystem I,hydrogenase,methyl viologen and mercaptoacetic acid

    Institute of Scientific and Technical Information of China (English)

    Dong Jin Qian; Ai Rong Liu; Chikashi Nakamura; Stephan Olav Wenk; Jun Miyake

    2008-01-01

    Hydrogen evolution was detected in an artificial system composed of light-harvesting unit of purified photosystem Ⅰ, catalyst ofhydrogenase, methyl viologen and electron donor under radiation. Absorption spectral features confirmed that electron transferfrom electron donors to proton was via a photoinduced reductive process of methyl viologen.2008 Dong Jin Qian. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  16. Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma

    Energy Technology Data Exchange (ETDEWEB)

    Vesel, Alenka, E-mail: alenka.vesel@guest.arnes.si [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Mozetic, Miran [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Balat-Pichelin, Marianne [PROMES-CNRS Laboratory, 7 Rue du four solaire, 66120 Font Romeu Odeillo (France)

    2016-11-30

    Highlights: • Oxidized Inconel alloy was exposed to hydrogen at temperatures up to 1500 K. • Oxide reduction in hydrogen plasma started at approximately 1300 K. • AES depth profiling revealed complete reduction of oxides in plasma. • Oxides were not reduced, if the sample was heated just in hydrogen atmosphere. • Surface of reduced Inconel preserved the same composition as the bulk material. - Abstract: Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.

  17. Development and Validation of a Model for Hydrogen Reduction of JSC-1A

    Science.gov (United States)

    Hegde, U.; Balasubramaniam, R.; Gokoglu, S.

    2009-01-01

    Hydrogen reduction of lunar regolith has been proposed as a viable technology for oxygen production on the moon. Hydrogen reduces FeO present in the lunar regolith to form metallic iron and water. The water may be electrolyzed to recycle the hydrogen and produce oxygen. Depending upon the regolith composition, FeO may be bound to TiO2 as ilmenite or it may be dispersed in glassy substrates. Some testing of hydrogen reduction has been conducted with Apollo-returned lunar regolith samples. However, due to the restricted amount of lunar material available for testing, detailed understanding and modeling of the reduction process in regolith have not yet been developed. As a step in this direction, hydrogen reduction studies have been carried out in more detail with lunar regolith simulants such as JSC-1A by NASA and other organizations. While JSC-1A has some similarities with lunar regolith, it does not duplicate the wide variety of regolith types on the moon, for example, it contains almost no ilmenite. Nonetheless, it is a good starting point for developing an understanding of the hydrogen reduction process with regolith-like material. In this paper, a model utilizing a shrinking core formulation coupled with the reactor flow is described and validated against experimental data on hydrogen reduction of JSC-1A.

  18. Enhancement of the efficiency of photocatalytic reduction of protons to hydrogen via molecular assembly.

    Science.gov (United States)

    Wu, Li-Zhu; Chen, Bin; Li, Zhi-Jun; Tung, Chen-Ho

    2014-07-15

    Conspectus One of the best solutions for meeting future energy demands is the conversion of water into hydrogen fuel using solar energy. The splitting of water into molecular hydrogen (H2) and oxygen (O2) using light involves two half-reactions: the oxidation of water to O2 and the reduction of protons to H2. To take advantage of the full range of the solar spectrum, researchers have extensively investigated artificial photosynthesis systems consisting of two photosensitizers and two catalysts with a Z-configuration: one photosensitizer-catalyst pair for H2 evolution and the other for O2 evolution. This type of complete artificial photosynthesis system is difficult to build and optimize; therefore, researchers typically study the reductive half-reaction and the oxidative half-reaction separately. To study the two half-reactions, researchers use a sacrificial electron donor to provide electrons for the reductive half-reaction, and a sacrificial electron acceptor to capture electrons for the oxidative half-reaction. After optimization, they can eliminate the added donors and acceptors as the two half reactions are coupled to a complete photocatalytic water spitting system. Most photocatalytic systems for the H2 evolution half-reaction consist of a photosensitizer, a catalyst, and a sacrificial electron donor. To promote photoinduced electron transfer and photocatalytic H2 production, these three components should be assembled together in a controlled manner. Researchers have struggled to design a photocatalytic system for H2 evolution that uses earth-abundant materials and is both efficient and durable. This Account reviews advances our laboratory has made in the development of new systems for photocatalytic H evolution that uses earth-abundant materials and is both efficient and durable. We used organometallic complexes and quantum-confined semiconductor nanocrystals (QDs) as photosensitizers, and [FeFe]-H2ase mimics and inorganic transition metal salts as catalysts

  19. Hg/HgO electrode and hydrogen evolution potentials in aqueous sodium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Nickell, Ryan A.; Zhu, Wenhua H.; Payne, Robert U.; Cahela, Donald R.; Tatarchuk, Bruce J. [Center for Microfibrous Materials Manufacturing, Department of Chemical Engineering, 230 Ross Hall, Auburn University, Auburn, AL 36849 (United States)

    2006-10-27

    The Hg/HgO electrode is usually utilized as a reference electrode in alkaline solution such as for development of an alkaline hydrogen electrode. The reference electrode provides a suitable reference point but is available from few commercial vendors and suffers from inadequate documentation on potential in varying electrolytes. A new numerical method uses activity, activity coefficients, and a few correlated empirical equations to determine the potential values in both dilute and concentrated sodium hydroxide solutions at temperatures of 0-90{sup o}C and at concentrations of 0.100-12.8mol kg{sub H{sub 2}O}{sup -1}. The computed potentials of the Hg/HgO electrodes versus a normal hydrogen electrode (NHE) at 25{sup o}C and 1atm are 0.1634V for 0.100m, 0.1077V for 1.00m, and 0.0976V for 1.45m NaOH solutions. The Hg/HgO reduction potential further changes to -0.0751V versus NHE and hydrogen evolution potential changes to -0.9916V versus NHE in a solution of 30.0wt.% NaOH at 80{sup o}C. The calculated values are compared with the measured data at 25 and 75{sup o}C. The experimental data agree well with the numerical values computed from the theoretical and empirical equations. (author)

  20. Hg/HgO electrode and hydrogen evolution potentials in aqueous sodium hydroxide

    Science.gov (United States)

    Nickell, Ryan A.; Zhu, Wenhua H.; Payne, Robert U.; Cahela, Donald R.; Tatarchuk, Bruce J.

    The Hg/HgO electrode is usually utilized as a reference electrode in alkaline solution such as for development of an alkaline hydrogen electrode. The reference electrode provides a suitable reference point but is available from few commercial vendors and suffers from inadequate documentation on potential in varying electrolytes. A new numerical method uses activity, activity coefficients, and a few correlated empirical equations to determine the potential values in both dilute and concentrated sodium hydroxide solutions at temperatures of 0-90 °C and at concentrations of 0.100-12.8 mol k gH2O-1 . The computed potentials of the Hg/HgO electrodes versus a normal hydrogen electrode (NHE) at 25 °C and 1 atm are 0.1634 V for 0.100m, 0.1077 V for 1.00m, and 0.0976 V for 1.45m NaOH solutions. The Hg/HgO reduction potential further changes to -0.0751 V versus NHE and hydrogen evolution potential changes to -0.9916 V versus NHE in a solution of 30.0 wt.% NaOH at 80 °C. The calculated values are compared with the measured data at 25 and 75 °C. The experimental data agree well with the numerical values computed from the theoretical and empirical equations.

  1. Mathematical Modelling of the Process of Tungsten Fluorides Reduction by Hydrogen

    OpenAIRE

    Brendakov Roman; Shvab Alexander; Brendakov Vladimir

    2016-01-01

    The process of tungsten fluorides reduction by hydrogen is a component part of Fluoride technology of tungsten conversion. Nowadays the researchers are definitely interested in studying this process. It is connected with common use of metal tungsten products in different sectors of the economy, which is the result of unique qualities of this metal. With the help of physical and mathematical modelling of the process of tungsten hexafluoride reduction by hydrogen, it becomes possible to create ...

  2. Bioinspired copper catalyst effective for both reduction and evolution of oxygen

    Science.gov (United States)

    Wang, Jiong; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-10-01

    In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water.

  3. Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

    DEFF Research Database (Denmark)

    Hou, Yidong; Abrams, Billie L.; Vesborg, Peter Christian Kjærgaard

    2011-01-01

    -abundant alternatives are needed for large-scale use. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum. The incomplete cubane-like clusters (Mo3S 4) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor......The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth...

  4. Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation

    DEFF Research Database (Denmark)

    Vesborg, Peter Christian Kjærgaard; Seger, Brian; Chorkendorff, Ib

    2015-01-01

    The past 10 years have seen great advances in the field of electrochemical hydrogen evolution. In particular, several new nonprecious metal electrocatalysts, for example, the MoS2 or the Ni2P family of materials, have emerged as contenders for electrochemical hydrogen evolution under harsh acidic...... conditions offering nearly platinum like catalytic performance. The developments have been particularly fast in the last 5 years, and the present Perspective highlights key developments and discusses them, along with hydrogen evolution in general, in the context of the global energy problem....

  5. Efficient electroreduction of CO2 on bulk silver electrode in aqueous solution via the inhibition of hydrogen evolution

    Science.gov (United States)

    Quan, Fengjiao; Xiong, Mubing; Jia, Falong; Zhang, Lizhi

    2017-03-01

    Electrochemical CO2 reduction provides a desirable pathway to convert greenhouse gas into useful chemicals. It is a great challenge to reduce CO2 efficiently in aqueous solution, especially on commercial bulk metal electrodes. Here, we report substantial improvement in CO2 reduction on bulk silver electrode through the introduction of ionic surfactant in aqueous electrolyte. The hydrogen evolution on the electrode surface is greatly suppressed by the surfactant, while the catalytic ability of silver towards CO2 reduction is maintained. The Faradaic efficiency for CO is greatly enhanced from 50% to 95% after the addition of this low-cost surfactant. This study may provide new pathways towards efficient CO2 reduction through the inhibition of proton reduction.

  6. Regulation of bacterial sulfate reduction and hydrogen sulfide fluxes in the central Namibian coastal upwelling zone

    DEFF Research Database (Denmark)

    Bruchert, V.; Jørgensen, BB; Neumann, K.;

    2003-01-01

    and the low capacity to oxidize and trap sulfide. The inner shelf break marks the seaward border of sulfidic bottom waters, and separates two different regimes of bacterial sulfate reduction. In the sulfidic bottom waters on the shelf, up to 55% of sulfide oxidation is mediated by the large nitrate...... to the sediment-water interface and reduce the hydrogen sulfide flux to the water column. Modeling of pore water sulfide concentration profiles indicates that sulfide produced by bacterial sulfate reduction in the uppermost 16 cm of sediment is sufficient to account for the total flux of hydrogen sulfide...... to the water column. However, the total pool of hydrogen sulfide in the water column is too large to be explained by steady state diffusion across the sediment-water interface. Episodic advection of hydrogen sulfide, possibly triggered by methane eruptions, may contribute to hydrogen sulfide in the water...

  7. Evolution of Hydrogen Storage Alloys Prepared by Special Methods

    Institute of Scientific and Technical Information of China (English)

    Guo Hong; Zhang Ximin; Jing Hai; Li Chengdong; Xu Jun

    2004-01-01

    Microstructure characteristics and electrochemical properties of hydrogen storage alloys prepared by gas atomization, melt spinning and strip casting respectively were outlined.The advantages, disadvantages and research development of the above methods for preparing hydrogen storage alloys were explained.The strip casting is a new special means for preparing AB5 rare earth hydrogen storage alloys of high performance and low cost, and the study of the strip casting for preparing hydrogen storage alloys is presented specially.

  8. A bifunctional perovskite catalyst for oxygen reduction and evolution.

    Science.gov (United States)

    Jung, Jae-Il; Jeong, Hu Young; Lee, Jang-Soo; Kim, Min Gyu; Cho, Jaephil

    2014-04-25

    La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3d is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm-scale rhombohedral LaCoO3 cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A-site cations with La3+ and local stress on Cosite sub-lattice with the cubic perovskite structure.

  9. Interface confined hydrogen evolution reaction in zero valent metal nanoparticles-intercalated molybdenum disulfide

    Science.gov (United States)

    Chen, Zhongxin; Leng, Kai; Zhao, Xiaoxu; Malkhandi, Souradip; Tang, Wei; Tian, Bingbing; Dong, Lei; Zheng, Lirong; Lin, Ming; Yeo, Boon Siang; Loh, Kian Ping

    2017-01-01

    Interface confined reactions, which can modulate the bonding of reactants with catalytic centres and influence the rate of the mass transport from bulk solution, have emerged as a viable strategy for achieving highly stable and selective catalysis. Here we demonstrate that 1T′-enriched lithiated molybdenum disulfide is a highly powerful reducing agent, which can be exploited for the in-situ reduction of metal ions within the inner planes of lithiated molybdenum disulfide to form a zero valent metal-intercalated molybdenum disulfide. The confinement of platinum nanoparticles within the molybdenum disulfide layered structure leads to enhanced hydrogen evolution reaction activity and stability compared to catalysts dispersed on carbon support. In particular, the inner platinum surface is accessible to charged species like proton and metal ions, while blocking poisoning by larger sized pollutants or neutral molecules. This points a way forward for using bulk intercalated compounds for energy related applications. PMID:28230105

  10. Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

    Science.gov (United States)

    Kye, Joohong; Shin, Muncheol; Lim, Bora; Jang, Jae-Won; Oh, Ilwhan; Hwang, Seongpil

    2013-07-23

    Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst.

  11. Bio-inspired co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

    DEFF Research Database (Denmark)

    Hou, Yidong; Abrams, Billie; Vesborg, Peter Christian Kjærgaard;

    2011-01-01

    part of the spectrum is utilized for hydrogen evolution while the blue part is reserved for the more difficult oxygen evolution. The samples have been illuminated with a simulated red part of the solar spectrum i.e. long wavelength (" > 620 nm) part of simulated AM 1.5G radiation. The current densities...... deposited on various supports. It will be demonstrated how this overpotential can be eliminated by depositing the same type of hydrogen evolution catalyst on p-type Si which can harvest the red part of the solar spectrum. Such a system could constitute the cathode part of a tandem dream device where the red...... at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by DFT calculations of the Mo3S4 cluster adsorbed on the hydrogen-terminated silicon surface providing insights...

  12. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis

    Science.gov (United States)

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-02-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel-carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm-2 and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis.

  13. Cobalt and Nickel Diimine-Dioxime Complexes as Molecular Electrocatalysts for Hydrogen Evolution with Low Overvoltages

    National Research Council Canada - National Science Library

    Pierre-André Jacques; Vincent Artero; Jacques Pécaut; Marc Fontecave; Jean-Marie P. Lehn

    2009-01-01

    ...) Proc Natl Acad Sei USA 103:1209-1214]. Here, we report on a new family of cobalt and nickel diimine-dioxime complexes as efficient and stable electrocatalysts for hydrogen evolution from acidic nonaqueous solutions with slightly lower...

  14. Hydrogen Evolution from Water under Aerobic Conditions Catalyzed by a Cobalt ATCUN Metallopeptide.

    Science.gov (United States)

    Kandemir, Banu; Kubie, Lenore; Guo, Yixing; Sheldon, Brian; Bren, Kara L

    2016-02-15

    The cobalt complex of an amino-terminal copper and nickel (ATCUN) motif model tripeptide (CoGGH) is shown to act as an electrocatalyst for hydrogen evolution from water near neutral pH with high Faradaic efficiency. The catalyst performance is not significantly impacted by exposure to oxygen. CoGGH represents a new class of hydrogen evolution catalyst that is straightforward to prepare and to modify.

  15. High-Sulfur-Vacancy Amorphous Molybdenum Sulfide as a High Current Electrocatalyst in Hydrogen Evolution

    KAUST Repository

    Lu, Ang-Yu

    2016-08-31

    The remote hydrogen plasma is able to create abundant S-vacancies on amorphous molybdenum sulfide (a-MoSx) as active sites for hydrogen evolution. The results demonstrate that the plasma-treated a-MoSx exhibits superior performance and higher stability than Pt in a proton exchange membrane based electrolyzers measurement as a proof-of-concept of industrial application.

  16. Photocatalytic hydrogen evolution over CuCrO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Saadi, S.; Bouguelia, A.; Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, U.S.T.H.B BP 32 Algiers (Algeria)

    2006-03-15

    We have been studying the technical feasibility of a photochemical H{sub 2} evolution based on a dispersion of CuCrO{sub 2} powder in aqueous electrolytes containing various reducing agents (S{sup 2-}, SO{sub 3}{sup 2-} and S{sub 2}O{sub 3}{sup 2-}). The title oxide combines a fair resistance to corrosion with an optimal band gap E{sub g} of 1.32eV. The intercalation of a small amount of oxygen should be accompanied by a partial oxidation of Cu{sup +} into Cu{sup 2+} implying a p-type semiconductivity. The S{sup 2-} oxidation inhibits the photocorrosion and the H{sub 2} evolution increases parallel to polysulfides S{sub n}{sup 2-} formation. Most of H{sub 2} is produced when p-CuCrO{sub 2} is connected to n-Cu{sub 2}O formed in situ. H{sub 2} liberation proceeds mostly on CuCrO{sub 2} while the oxidation of S{sup 2-} takes place over Cu{sub 2}O surface and the hetero system Cu{sub 2}O/CuCrO{sub 2} is optimized with respect to some physical parameters. The photoactivity is dependent on preparation conditions and lowering the synthesis temperature through nitrate route leads to an increase in specific surface area S{sub sp}. The photoelectrochemical H{sub 2} production is a multistep process where the rate determining step is the arrival of electrons at the interface because of their low mobility. Prolonged irradiation (>80min) leads to a pronounced decrease of the photoactivity; the tendency toward saturation is due to the undesired back reduction of polysulfides S{sub n}{sup 2-} in a closed system and to their strong absorption in the visible region (l{sub max}=520nm). (author)

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

    Science.gov (United States)

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

    2005-08-18

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

  18. Cost reductions in the nickel—hydrogen battery

    Science.gov (United States)

    Beauchamp, Richard L.; Sindorf, Jack F.

    1988-04-01

    For the past several years, Johnson Controls, Inc. has been working with COMSAT Laboratories and Sandia National Laboratories on the development of the The major emphasis of the program was on reduction of the manufacturing cost of the aerospace cell. The intent of the developmental effort was to redes The approach was to adapt JCI's experience in the high-volume production of lead—acid automotive batteries to the manufacture of the nickel—hydroge A significant reduction in cost was achieved through several technical developments, component changes, and process improvements. Two technical develop As an integral part of the program, the details of the manufacturing costs were carefully studied. One purpose was to highlight those raw material and

  19. Oxygen reduction and evolution at single-metal active sites

    DEFF Research Database (Denmark)

    Calle-Vallejo, F.; Martínez, J.I.; García Lastra, Juan Maria

    2013-01-01

    of functionalized graphitic materials and gas-phase porphyrins with late transition metals. We find that both kinds of materials follow approximately the same activity trends, and active sites with transition metals from groups 7 to 9 may be good ORR and OER electrocatalysts. However, spin analyses show more...... overpotentials and is made of precious materials. A possible solution is the use of non-noble electrocatalysts with single-metal active sites. Here, on the basis of DFT calculations of adsorbed intermediates and a thermodynamic analysis, we compare the oxygen reduction (ORR) and evolution (OER) activities...... flexibility in the possible oxidation states of the metal atoms in solid electrocatalysts, while in porphyrins they must be +2. These observations reveal that the catalytic activity of these materials is mainly due to nearest-neighbor interactions. Based on this, we propose that this class of electrocatalysts...

  20. Efficient and durable hydrogen evolution electrocatalyst based on nonmetallic nitrogen doped hexagonal carbon

    Science.gov (United States)

    Liu, Yanming; Yu, Hongtao; Quan, Xie; Chen, Shuo; Zhao, Huimin; Zhang, Yaobin

    2014-10-01

    The feasibility of renewable energy technology, hydrogen production by water electrolysis, depends on the design of efficient and durable electrocatalyst composed of earth-abundant elements. Herein, a highly active and stable nonmetallic electrocatalyst, nitrogen doped hexagonal carbon (NHC), was developed for hydrogen production. It exhibited high activity for hydrogen evolution with a low overpotential of only 65 mV, an apparent exchange current density of 5.7 × 10-2 mA cm-2 and a high hydrogen production rate of 20.8 mL cm-2 h-1 at -0.35 V. The superior hydrogen evolution activity of NHC stemmed from the intrinsic electrocatalytic property of hexagonal nanodiamond, the rapid charge transfer and abundance of electrocatalytic sites after nitrogen doping. Moreover, NHC was stable in a corrosive acidic solution during electrolysis under high current density.

  1. The Evolution of Stellar Rotation and the hydrogen atmospheres of habitable-zone Terrestrial Planets

    CERN Document Server

    Johnstone, C P; Stökl, A; Lammer, H; Tu, L; Kislyakova, K G; Lüftinger, T; Odert, P; Erkaev, N V; Dorfi, E A

    2015-01-01

    Terrestrial planets formed within gaseous protoplanetary disks can accumulate significant hydrogen envelopes. The evolution of such an atmosphere due to XUV driven evaporation depends on the activity evolution of the host star, which itself depends sensitively on its rotational evolution, and therefore on its initial rotation rate. In this letter, we derive an easily applicable method for calculating planetary atmosphere evaporation that combines models for a hydrostatic lower atmosphere and a hydrodynamic upper atmosphere. We show that the initial rotation rate of the central star is of critical importance for the evolution of planetary atmospheres and can determine if a planet keeps or loses its primordial hydrogen envelope. Our results highlight the need for a detailed treatment of stellar activity evolution when studying the evolution of planetary atmospheres.

  2. Composite Ni/NiO-Cr2O3 Catalyst for Alkaline Hydrogen Evolution Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bates, MK; Jia, QY; Ramaswamy, N; Allen, RJ; Mukerjee, S

    2015-03-12

    We report a Ni-Cr/C electrocatalyst with unpreeedented massactivity for the hydrogen evolution reaction (HER). in alkaline electrolyte. The HER Oietics of numerous binary and ternary Ni-alloys and composite Ni/metal-euride/C samples were evaluated in aquebus 0.1 M KOH electrolyte. The highest HER mass-activity was observed for Ni-Cr materials which exhibit metallic Ni as well as NiOx and Cr2O3 phases as determined by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. The onset of the HER is significantly improved compared to munerous binary dor ternary Ni-alloys, inCluding Ni Mg materials. It is likely that at adjacent Ni/NiOx sites, the oxide acts as a sink for OHads, while the metallic Ni acts as a, sink for the H-ads, intermediate of the HER, thus minimizing the high activation energy of hydrogen evolution via water reduction. This is confirmed by in situ XAS studies that show that the synergistic HER enhancement is due to NiO content and that the Cr2O3 appears to stabilize the composite NiO component-under HER conditions (where NiOx would typically be reduced to metallic Ni-0). Furthermore, in contrast to Pt, the Ni(O-x)/Cr2O3 catalyst appears resistant to poisoning by the anion.exchange ionomer (AEI), a serloua consideration when applied to an anionic polymer electrolyte interface. Furthermore, we report a: detailed model of the double layer interface which helps explain the observed ensemble effect in the presence of AEI.

  3. Reduction of uranium hexafluoride to tetrafluoride by using the hydrogen atoms

    Science.gov (United States)

    Aleksandrov, B. P.; Gordon, E. B.; Ivanov, A. V.; Kotov, A. A.; Smirnov, V. E.

    2016-09-01

    We consider the reduction of UF6 to UF4 by chemical reaction with hydrogen atoms originated in the powerful chemical generator. The principal design of such a chemical convertor is described. The results of the mathematical modeling of the thermodynamics and kinetics of the UF6 to UF4 reduction process are analyzed. The few options for the hydrogen atom generator design are proposed. A layout of the experimental setup with the chemical reactor is presented. The high efficiency together with the ability of the process scaling without loss of its efficiency makes this approach to the uranium hexafluoride depletion into tetrafluoride promising for its application in the industry.

  4. Tunable organic photocatalysts for visible-light-driven hydrogen evolution

    OpenAIRE

    Sprick, Reiner Sebastian; Jiang, Jia-Xing; Bonillo, Baltasar; Ren, Shijie; Ratvijitvech, Thanchano; Guiglion, Pierre; Zwijnenburg, Martijn A.; Adams, Dave J; Cooper, Andrew I.

    2015-01-01

    Photocatalytic hydrogen production from water offers an abundant, clean fuel source, but it is challenging to produce photocatalysts that use the solar spectrum effectively. Many hydrogen-evolving photocatalysts are active in the ultraviolet range, but ultraviolet light accounts for only 3% of the energy available in the solar spectrum at ground level. Solid-state crystalline photocatalysts have light absorption profiles that are a discrete function of their crystalline phase and that are not...

  5. Hydrogen partitioning in pure cast aluminum as determined by dynamic evolution rate measurements

    Science.gov (United States)

    Outlaw, R. A.; Peterson, D. T.; Schmidt, F. A.

    1981-01-01

    Hydrogen in pure aluminum can be found in two different states. One is related to a presence in gas-filled pores, while the other state involves the formation of a solid solution between hydrogen and aluminum. The considered investigation is concerned with the distribution of the hydrogen between various states. A dynamic technique is employed to measure the evolution of hydrogen from commercially available samples of polycrystalline pure aluminum under ultrahigh vacuum conditions. The obtained data are compared with the results of a statistical analysis concerning the porosity in the cast aluminum. It was found that more than 99 pct of the hydrogen in the aluminum is located in large pores. Less than 1 pct of the hydrogen is partitioned between the solid solution and the small pores.

  6. Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles.

    Science.gov (United States)

    Jia, Zhiqian; Sun, Huijie; Du, Zhenxia; Lei, Zhigang

    2014-02-01

    Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium (Pd) nanoparticles was studied for the first time. The effects of Pd loading, dye concentration and reuse repetitions of membranes were investigated. In reduction, the dye concentration decreased whereas the pH rose gradually. An optimal Pd loading was found. The catalytic membranes were able to be reused more than 3 times.

  7. Hydrogen Evolution by Plasma Electrolysis in Aqueous Solution

    Science.gov (United States)

    Mizuno, Tadahiko; Akimoto, Tadashi; Azumi, Kazuhisa; Ohmori, Tadayoshi; Aoki, Yoshiaki; Takahashi, Akito

    2005-01-01

    Hydrogen has recently attracted attention as a possible solution to environmental and energy problems. If hydrogen should be considered an energy storage medium rather than a natural resource. However, free hydrogen does not exist on earth. Many techniques for obtaining hydrogen have been proposed. It can be reformulated from conventional hydrocarbon fuels, or obtained directly from water by electrolysis or high-temperature pyrolysis with a heat source such as a nuclear reactor. However, the efficiencies of these methods are low. The direct heating of water to sufficiently high temperatures for sustaining pyrolysis is very difficult. Pyrolysis occurs when the temperature exceeds 4000°C. Thus plasma electrolysis may be a better alternative, it is not only easier to achieve than direct heating, but also appears to produce more hydrogen than ordinary electrolysis, as predicted by Faraday’s laws, which is indirect evidence that it produces very high temperatures. We also observed large amounts of free oxygen generated at the cathode, which is further evidence of direct decomposition, rather than electrolytic decomposition. To achieve the continuous generation of hydrogen with efficiencies exceeding Faraday efficiency, it is necessary to control the surface conditions of the electrode, plasma electrolysis temperature, current density and input voltage. The minimum input voltage required induce the plasma state depends on the density and temperature of the solution, it was estimated as 120 V in this study. The lowest electrolyte temperature at which plasma forms is ˜75°C. We have observed as much as 80 times more hydrogen generated by plasma electrolysis than by conventional electrolysis at 300 V.

  8. Surface modification-a novel way of attaching cocatalysts on CdS semiconductors for photocatalytic hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-22

    Noble metals as cocatalysts for hydrogen evolution are widely investigated for semiconductor photocatalytic water splitting. In this paper, we present a novel way to attach not only noble metals, but also transitional metals onto CdS nanocrystals as cocatalysts for hydrogen evolution. The hydrogen evolution performances for each metal were compared and result shows that Pd attached CdS gives the highest hydrogen evolution rate of 250 μmol/h. The amounts of metal ions attached on the surface were measured by inductively coupled plasma optical emission spectrometry (ICP-OES). This work confirms that surface modification is a promising way of attaching cocatalysts onto semiconductor photocatalysts.

  9. Initial reduction of the NiO(100) surface in hydrogen.

    Science.gov (United States)

    Xu, Qiang; Cheah, Singfoong; Zhao, Yufeng

    2013-07-14

    The reduction of NiO in hydrogen, a reaction with many industrial applications, has not received sufficient attention from theoretical standpoint because the complexity of the material properties and the process present considerable computational challenges. We report here the results of a systematic study on the hydrogen reduction of an ideal NiO(100) surface that produces a water molecule and an NiO(100) surface with an oxygen vacancy, using the Hubbard U corrected density functional theory method, with some of the key results verified by the hybrid density functional method. The major findings are: (1) the O vacancy in the NiO(100) surface slab is stabilized in the subsurface layer, although the vacancy is likely to remain on the outermost surface layer because the barrier for O vacancy migration from the surface to the second layer is as high as 3.02 eV; (2) regarding the energetics of hydrogen interaction with the ideal NiO(100) surface, water formation, and concomitant reduction of NiO is favored at higher H coverage even though surface hydrogenation is energetically more favorable than water formation at lower H coverage; (3) kinetically, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms play key roles in hydrogen reduction of NiO(100); and (4) a dual role of hydrogen is revealed as both a reactant and a mediator, which reduces the maximum kinetic barrier from 2.41 eV to 1.86 eV.

  10. On the Evolution of Hydrogen-Deficient White Dwarfs

    Science.gov (United States)

    Camisassa, M. E.; Althaus, L. G.; Rohrmann, R. D.; García–Berro, E.; Córsico, A. H.

    2017-03-01

    We present full evolutionary calculations for hydrogen-deficient white dwarfs. We take into account the evolutionary history of the progenitor stars, all relevant energy sources, element diffusion, and outer boundary conditions provided by new and detailed non-gray white dwarf model atmospheres for pure helium composition. Model atmospheres are based on the most up-to-date physical inputs. The calculations are extended down to an effective temperature of 2500 K. Our calculations provide a homogeneous set of evolutionary cooling tracks appropriate for mass and age determinations of old hydrogen-deficient white dwarfs.

  11. Study on hydrogen evolution performance of the carbon supported PtRu alloy film electrodes

    Institute of Scientific and Technical Information of China (English)

    YANG; Bin; LI; Yang; ZAN; Lin-han

    2005-01-01

    The carbon supported PtRu alloy film electrodes having Pt about 0.10 mg/cm2 or even less were prepared by ion beam sputtering method (IBSM). It was valued on the hydrogen analyse performance, the temperature influence factor and the stability by electroanalysis hydrogen analyse method. It was found that the carbon supported PtRu alloy film electrodes had higher hydrogen evolution performance and stability, such as the hydrogen evolution exchange current density (j0) was increase as the temperature (T) rised, and it overrun 150 mA/cm2 as the trough voltage in about 0.68V, and it only had about 2.8% decline in 500 h electrolytic process. The results demonstrated that the carbon supported PtRu alloy film electrodes kept highly catalytic activity and stability, and it were successfully used in pilot plant for producing H2 on electrolysis of H2S.

  12. The mathematical model of the stripping voltammetry hydrogen evolution/dissolution process on Pd layer

    Energy Technology Data Exchange (ETDEWEB)

    Skital, Piotr M. [Faculty of Chemistry, Rzeszow University of Technology, Wincentego Pola Str. 2, 35-959 Rzeszow (Poland); Sanecki, Przemyslaw T., E-mail: psanecki@prz.rzeszow.p [Faculty of Chemistry, Rzeszow University of Technology, Wincentego Pola Str. 2, 35-959 Rzeszow (Poland); Kaczmarski, Krzysztof [Faculty of Chemistry, Rzeszow University of Technology, Wincentego Pola Str. 2, 35-959 Rzeszow (Poland)

    2010-08-01

    The advanced two-plate mathematical model of electrochemical hydrogen evolution/dissolution process has been presented and discussed. The model, with Langmuir adsorption equation, has been experimentally verified by the use of the glassy carbon/Pd layer electrode system at different scan rates. The two cathodic-anodic stages of hydrogen evolution/dissolution process in 0.1 M and 0.001 M HCl solutions have been interpreted and discussed. The thickness of the layer and the way of deposition were also investigated. The fundamental kinetic problem of a change of electrode properties during electrode process as an effect of the elementary hydrogen presence in the solid electrode is presented and interpreted. The isopotential point phenomenon, an electrochemical analog of isosbestic point in absorption spectroscopy, was unexpectedly discovered as experimental effect of hydrogen adsorption and {alpha} variability.

  13. Facile charge transport in FeNx/Mo₂N/CNT nanocomposites for efficient hydrogen evolution reactions

    Indian Academy of Sciences (India)

    KASINATH OJHA; SHIVALI BANERJEE; ASHOK K GANGULI

    2017-07-01

    Molybdenum based materials are gaining importance as electrocatalysts for hydrogen evolution reaction because of their lowcost and good electrocatalytic efficiency. Introducing iron nitride with molybdenum nitride as a composite results in efficient hydrogen evolution activity with current density of ∼120mA/cm2 at −400 mVvs. RHE. The nanocomposites were characterized using powder XRD, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), ElectronDiffraction, ThermogravimetricAnalysis and FTIRSpectroscopy. The electrochemical investigations suggest that the electrocatalytic activity of the composite increases with iron nitride content. The composite exhibits good electrochemical stability upto 42 hours in acidic medium. The hydrogen evolution reaction (HER) follows Volmer-Heyrovsky mechanism where Volmer reaction is the rate determing step.

  14. A highly efficient noble metal free photocatalytic hydrogen evolution system containing MoP and CdS quantum dots

    Science.gov (United States)

    Yin, Shengming; Han, Jianyu; Zou, Yinjun; Zhou, Tianhua; Xu, Rong

    2016-07-01

    We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation.We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation. Electronic supplementary information (ESI) available: SEM image with EDS, XPS survey spectrum, XRD and TEM images of MoP samples prepared under different conditions; XRD, TEM, UV-vis and photoluminescence spectra of CdS QDs; H2 evolution activity comparison for different MoP/CdS samples; the effect of pH value on H2 evolution activity of a MoP/CdS system; the XPS spectrum of MoP/CdS after photoreaction; table of literature studies on H2 evolution activity by different noble metal free photocatalytic systems

  15. Synthesis of hierarchical MoO2/MoS2 nanofibers for electrocatalytic hydrogen evolution

    Science.gov (United States)

    Rheem, Youngwoo; Han, Yosep; Lee, Kyu Hwan; Choi, Sung-Mook; Myung, Nosang V.

    2017-03-01

    Perpendicularly attached MoS2 nanosheets on MoO2 conductive nanofibers were synthesized by combining electrospinning, calcination, and sulfurization processes. Compared to randomly stacked MoS2 nanosheets on MoO2 nanofiber, they show greater hydrogen evolution reaction (HER) performance (i.e., onset potential of ‑180 mV versus normal hydrogen electrode with the Tafel slope of 59 mV dec‑1). HER performance decreases with increasing MoS2 nanocrystal size.

  16. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water

    OpenAIRE

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M.; Warnan, Julien; Kuehnel, Moritz F; Friend, Richard H.; Reisner, Erwin

    2016-01-01

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqu...

  17. Uranium- and thorium-doped graphene for efficient oxygen and hydrogen peroxide reduction.

    Science.gov (United States)

    Sofer, Zdeněk; Jankovský, Ondřej; Šimek, Petr; Klímová, Kateřina; Macková, Anna; Pumera, Martin

    2014-07-22

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in the fields of energy generation and sensing. Metal-doped graphenes, where metal serves as the catalytic center and graphene as the high area conductor, have been used as electrocatalysts for such applications. In this paper, we investigated the use of uranium-graphene and thorium-graphene hybrids prepared by a simple and scalable method. The hybrids were synthesized by the thermal exfoliation of either uranium- or thorium-doped graphene oxide in various atmospheres. The synthesized graphene hybrids were characterized by high-resolution XPS, SEM, SEM-EDS, combustible elemental analysis, and Raman spectroscopy. The influence of dopant and exfoliation atmosphere on electrocatalytic activity was determined by electrochemical measurements. Both hybrids exhibited excellent electrocatalytic properties toward oxygen and hydrogen peroxide reduction, suggesting that actinide-based graphene hybrids have enormous potential for use in energy conversion and sensing devices.

  18. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution

    Science.gov (United States)

    Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

    2016-01-01

    Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites. PMID:27032372

  19. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution.

    Science.gov (United States)

    Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

    2016-04-01

    Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Denise [University of Wisconsin, Madison; Nilekar, Anand Udaykumar [University of Wisconsin, Madison; Xu, Ye [ORNL; Mavrikakis, Manos [University of Wisconsin, Madison

    2010-01-01

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

  1. Visible-light-induced hydrogen evolution reaction with WS$_x$Se$_{2−x}$

    Indian Academy of Sciences (India)

    UTTAM GUPTA; DEEPA S NARANG

    2017-04-01

    WS$_2$ is a promising catalyst for the hydrogen evolution reaction.We have explored photocatalytic properties of ternary sulphoselenides of tungsten (WS$_x$Se$_{2−x}$) by the dye-sensitized hydrogen evolution.WSxSe2−x solidsolutions are found to exhibit high activity reaching 2339 $\\mu$mol h$^{−1}$ g$^{−1}$ for WSSe, which is three times higher than that of WS2 alone (866 $\\mu$mol h$^{−1}$ g$^{−1}$). The turnover frequency is also high (0.7 h$^{−1}$). Such synergistic effect of selenium substitution in WS2 is noteworthy.

  2. A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability

    DEFF Research Database (Denmark)

    Laursen, Anders B.; Vesborg, Peter C. K.; Chorkendorff, Ib

    2013-01-01

    This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show an impro......This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show...

  3. Modeling of nucleation and evolution of hydrogen-induced platelets in silicon crystals

    Energy Technology Data Exchange (ETDEWEB)

    Velichko, Oleg; Shaman, Yury [Belarusian State University of Informatics and Radioelectronics, Minsk (Belarus); Fedotov, Alexander [Belarusian State University, Minsk (Belarus)

    2009-08-15

    A model for nucleation and evolution of hydrogen induced platelets (HIPs) in silicon crystals during plasma treatment is proposed and analyzed. The derived equations allow one to trace the evolution of the concentration distribution for platelets depending on their size and to calculate the total concentration of hydrogen trapped by HIPs. The results of numerical simulation agree well with the available experimental data confirming the validity of the assumptions made to develop the model. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Carbothermal Reduction of Quartz in Methane-Hydrogen-Argon Gas Mixture

    Science.gov (United States)

    Li, Xiang; Zhang, Guangqing; Tang, Kai; Ostrovski, Oleg; Tronstad, Ragnar

    2015-10-01

    Synthesis of silicon carbide (SiC) by carbothermal reduction of quartz in a CH4-H2-Ar gas mixture was investigated in a laboratory fixed-bed reactor in the temperature range of 1573 K to 1823 K (1300 °C to 1550 °C). The reduction process was monitored by an infrared gas analyser, and the reduction products were characterized by LECO, XRD, and SEM. A mixture of quartz-graphite powders with C/SiO2 molar ratio of 2 was pressed into pellets and used for reduction experiments. The reduction was completed within 2 hours under the conditions of temperature at or above 1773 K (1500 °C), methane content of 0.5 to 2 vol pct, and hydrogen content ≥70 vol pct. Methane partially substituted carbon as a reductant in the SiC synthesis and enhanced the reduction kinetics significantly. An increase in the methane content above 2 vol pct caused excessive carbon deposition which had a detrimental effect on the reaction rate. Hydrogen content in the gas mixture above 70 vol pct effectively suppressed the cracking of methane.

  5. Hydrogenated anatase: Strong photocatalytic H2 evolution without the use of a co-catalyst

    CERN Document Server

    Liu, Ning; Freitag, Detlef; Venkatesan, Umamaheswari; Marthala, V R Reddy; Hartmann, Martin; Winter, Benjamin; Spiecker, Erdmann; Zolnhofer, Eva; Meyer, Karsten; Schmuki, Patrik

    2016-01-01

    In the present work we show, how a high pressure hydrogenation of commercial anatase or anatase/rutile powder can create a photocatalyst for hydrogen evolution that is highly effective and stable without the need of any additional co-catalyst. This activation effect can not be observed for rutile. For anatase/rutile mixtures, however, a strong synergistic effect is found (similar to findings commonly observed for noble metal decorated TiO2). ESR measurements indicate the intrinsic co-catalytic activation of anatase TiO2 to be due to specific defect centers formed during hydrogenation.

  6. Heteroatom-modulated switching of photocatalytic hydrogen and oxygen evolution preferences of anatase TiO{sub 2} microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Gang; Pan, Jian; Yin, Lichang; Li, Feng; Tan, Jun; Cheng, Hui-Ming [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang (China); Irvine, John T.S.; Wormald, Philip [School of Chemistry, University of St. Andrews, Fife (United Kingdom)

    2012-08-07

    Understanding and manipulating the two half-reactions of photoinduced electron reduction and hole oxidation are key to designing and constructing efficient photocatalysts. Here, how the spatial distribution of the heteroatom modulates photocatalytic reduction (hydrogen evolution) and oxidation (oxygen evolution) reaction preferences is investigated by moving boron from the core to the shell of an anatase TiO{sub 2} microsphere along [001] via thermal diffusion control. The preference towards photocatalytic hydrogen and oxygen producing reactions from splitting water can be switched by creating a shell with an interstitial B{sup {sigma}}{sup +}({sigma}{<=}3) gradient in the TiO{sub 2} microsphere. This switching stems from the downward shift of electronic band edges of the shell by a band bending effect that originates from the extra electrons coming from the interstitial B{sup {sigma}}{sup +}. These results create new opportunities for designing and constructing efficient photocatalysts by spatial heteroatom engineering. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Examination of prokaryotic multipartite genome evolution through experimental genome reduction.

    Directory of Open Access Journals (Sweden)

    George C diCenzo

    2014-10-01

    Full Text Available Many bacteria carry two or more chromosome-like replicons. This occurs in pathogens such as Vibrio cholerea and Brucella abortis as well as in many N2-fixing plant symbionts including all isolates of the alfalfa root-nodule bacteria Sinorhizobium meliloti. Understanding the evolution and role of this multipartite genome organization will provide significant insight into these important organisms; yet this knowledge remains incomplete, in part, because technical challenges of large-scale genome manipulations have limited experimental analyses. The distinct evolutionary histories and characteristics of the three replicons that constitute the S. meliloti genome (the chromosome (3.65 Mb, pSymA megaplasmid (1.35 Mb, and pSymB chromid (1.68 Mb makes this a good model to examine this topic. We transferred essential genes from pSymB into the chromosome, and constructed strains that lack pSymB as well as both pSymA and pSymB. This is the largest reduction (45.4%, 3.04 megabases, 2866 genes of a prokaryotic genome to date and the first removal of an essential chromid. Strikingly, strains lacking pSymA and pSymB (ΔpSymAB lost the ability to utilize 55 of 74 carbon sources and various sources of nitrogen, phosphorous and sulfur, yet the ΔpSymAB strain grew well in minimal salts media and in sterile soil. This suggests that the core chromosome is sufficient for growth in a bulk soil environment and that the pSymA and pSymB replicons carry genes with more specialized functions such as growth in the rhizosphere and interaction with the plant. These experimental data support a generalized evolutionary model, in which non-chromosomal replicons primarily carry genes with more specialized functions. These large secondary replicons increase the organism's niche range, which offsets their metabolic burden on the cell (e.g. pSymA. Subsequent co-evolution with the chromosome then leads to the formation of a chromid through the acquisition of functions core to all

  8. Thermodynamic Analysis of the Selective Reduction of a Nickeliferous Limonitic Laterite Ore by Hydrogen

    Science.gov (United States)

    Elliott, R.; Pickles, C. A.

    2017-09-01

    Nickeliferous limonitic laterite ores are becoming increasingly attractive as a source of metallic nickel as the costs associated with recovering nickel from the sulphide ores increase. Unlike the sulphide ores, however, the laterite ores are not amenable to concentration by conventional mineral processing techniques such as froth flotation. One potential concentrating method would be the pyrometallurgical solid state reduction of the nickeliferous limonitic ores at relatively low temperatures, followed by beneficiation via magnetic separation. A number of reductants can be utilized in the reduction step, and in this research, a thermodynamic model has been developed to investigate the reduction of a nickeliferous limonitic laterite by hydrogen. The nickel recovery to the ferronickel phase was predicted to be greater than 95 % at temperatures of 673-873 K. Reductant additions above the stoichiometric requirement resulted in high recoveries over a wider temperature range, but the nickel grade of the ferronickel decreased.

  9. Evolution of hyperphalangy and digit reduction in the cetacean manus.

    Science.gov (United States)

    Cooper, Lisa Noelle; Berta, Annalisa; Dawson, Susan D; Reidenberg, Joy S

    2007-06-01

    Cetaceans (whales, dolphins, and porpoises) have a soft tissue flipper that encases most of the forelimb, and elongated digits with an increased number of phalanges (hyperphalangy). In addition, some cetaceans exhibit a reduction in digit number. Although toothed cetaceans (odontocetes) are pentadactylous, most baleen whales (mysticetes) are tetradactylous and also lack a metacarpal. This study conducts a survey of cetacean metacarpal and phalangeal morphologies, traces the evolution of hyperphalangy in a phylogenetic context, optimizes characters onto previously published cetacean phylogenies, and tests various digit loss hypotheses. Dissections were performed on 16 cetacean flippers representing 10 species (8 mysticetes, 2 odontocetes). Phalangeal count data were derived from forelimb radiographs (36 odontocetes, 5 mysticetes), osteological specimens of articulated forelimbs (8 mysticetes), and were supplemented with published counts. Modal phalangeal counts were coded as ordered and unpolarized characters and optimized onto two known cetacean phylogenies. Results indicate that digital ray I is reduced in many cetaceans (except Globicephala) and all elements of digital ray I were lost in tetradactylous mysticetes. Fossil evidence indicates this ray may have been lost approximately 14 Ma. Most odontocetes also reduce the number of phalangeal elements in digit V, while mysticetes typically retain the plesiomorphic condition of three phalanges. Results from modal phalangeal counts show the greatest degree of hyperphalangy in digits II and III in odontocetes and digits III and IV in mysticetes. Fossil evidence indicates cetacean hyperphalangy evolved by at least 7-8 Ma. Digit loss and digit positioning may underlie disparate flipper shapes, with narrow, elongate flippers facilitating fast swimming and broad flippers aiding slow turns. Hyperphalangy may help distribute leading edge forces, and multiple interphalangeal joints may smooth leading edge flipper contour.

  10. Hydrogen Production with High Evolution Rate and High Yield by Immobilized Cells of Hydrogen-producing Bacteria Strain B49 in a Column Reactor

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    To improve the hydrogen evolution rate in continuous hydrogen production of a novel fermentative hydrogen-producing bacteria strain B49 (AF481148 in EMBL), 4 % immobilized cells by polyvinyl alcohol-boric acid method, with the addition of a small amount of calcium alginate in a column reactor obtain hydrogen yield of 2.31 mol H2/mol glucose and hydrogen evolution rate of 1435.4 ml/L culture*h respectively at medium retention time of 2.0 h with a medium containing 10g glucose/L. Moreover, as the cell density in gel beads is increased to 8%, hydrogen yield and hydrogen evolution rate for 10g glucose/L are 2.34 mol H2/mol glucose and 2912.4 ml/L culture*h respectively at medium retention time of 1.0 h, and for molasses wastewater COD of 7505.9 mg/L hydrogen production potential of 205.6 ml/g COD and hydrogen evolution rate of 2057.7 ml/L culture*h at hydraulic retention time of 0.75 h are observed. In the continuous culture pH value keeps around 3.9 by self-regulating.

  11. Electrolyte effects on hydrogen evolution and solution resistance in microbial electrolysis cells

    Science.gov (United States)

    Merrill, Matthew D.; Logan, Bruce E.

    Protonated weak acids commonly used in microbial electrolysis cell (MEC) solutions can affect the hydrogen evolution reaction (HER) through weak acid catalysis, and by lowering solution resistance between the anode and the cathode. Weak acid catalysis of the HER with protonated phosphate, acetate, and carbonate electrolyte species improved MEC performance by lowering the cathode's overpotential by up to 0.30 V at pH 5, compared to sodium chloride electrolytes. Deprotonation of weak acids into charged species at higher pHs improved MEC performance primarily by increasing the electrolyte's conductivity and therefore decreasing the solution resistance between electrodes. The potential contributions from weak acid catalysis and solution resistance were compared to determine whether a reactor would operate more efficiently at lower pH because of the HER, or at higher pH because of solution resistance. Phosphate and acetate electrolytes allowed the MEC to operate more efficiently under more acidic conditions (pH 5). Carbonate electrolytes increased performance from pH 5 to 9 due to a relatively large increases in conductivity. These results demonstrate that specific buffers can substantially contribute to MEC performance through both reduction in cathode overpotential and solution resistance.

  12. Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold

    Science.gov (United States)

    Muglali, Mutlu I.; Erbe, Andreas; Chen, Ying; Barth, Christoph; Koelsch, Patrick; Rohwerder, Michael

    2013-01-01

    Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum–frequency–generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two–dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre–orientation of water present in the nanometer–sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER. PMID:24235778

  13. Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold.

    Science.gov (United States)

    Muglali, Mutlu I; Erbe, Andreas; Chen, Ying; Barth, Christoph; Koelsch, Patrick; Rohwerder, Michael

    2013-02-15

    Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum-frequency-generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which di er between Au(111) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two-dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre-orientation of water present in the nanometer-sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER.

  14. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

    Science.gov (United States)

    Kügler, Merle; Scholz, Julius; Kronz, Andreas; Siewert, Inke

    2016-04-28

    Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER.

  15. Mechanistic analysis of the hydrogen evolution and absorption reactions on iron

    Science.gov (United States)

    Abd Elhamid, Mahmoud Hassan

    2000-10-01

    The work in this thesis investigates the effect of additives on the kinetics of the hydrogen evolution reaction (HER) and hydrogen absorption reaction (HAR) on iron. The electrochemical hydrogen permeation cell has been used to collect data on both reactions in the absence and presence of the additives. The effect of two additives on the kinetics of both the HER and HAR on iron in acidic solutions was quantified. These two compounds have different behaviors towards both reactions. While benzotriazole (BTA) inhibits both reactions, iodide enhances hydrogen absorption while inhibiting the HER. Analysis of the results using the IPZ (Iyer, Pickering, Zamanzadeh) model shows that both compounds inhibit the HER by decreasing its discharge rate constant and hence the exchange current density. On the other hand, while BTA decreases the rate of hydrogen absorption by decreasing both the hydrogen surface coverage and the kinetic-diffusion constant, k (see chapter 5), iodide ions decrease the rate of hydrogen absorption by increasing the kinetic-diffusion constant, k, while decreasing the hydrogen surface coverage (see chapter 6). A separate study was devoted to investigate the effect of thiosulfate on the kinetics of the HER and HAR on iron (chapter 7). It was shown that thiosulfate enhances both reactions in acidic solutions. The promoting effect was mainly due to its decomposition product H2SO3 with a small contribution from the colloidal sulfur and/or the undecomposed thiosulfate. In chapter 8 it was shown that the polarization data of the hydrogen evolution reaction (HER) can be analyzed to calculate the hydrogen surface coverage and the rate constants of the hydrogen discharge and recombination reactions for metals which have very low permeabilities of hydrogen, and on which the HER proceeds through a coupled Volmer discharge-Tafel recombination mechanism. The analysis is applied to the results of the HER on copper and iron and the rate constants obtained using the

  16. Mechanism of electrochemical reduction of hydrogen peroxide on copper in acidic sulfate solutions.

    Science.gov (United States)

    Stewart, Karen L; Gewirth, Andrew A

    2007-09-11

    Hydrogen peroxide is a commonly used oxidizer component in chemical mechanical planarization slurries, used in the processing of Cu metallization in microelectronics applications. We studied the electrochemical reduction of hydrogen peroxide on Cu in 0.1 M H2SO4 solutions using methods including cyclic voltammetry, rotating disk electrode experiments, surface-enhanced Raman spectroscopy, and density functional theory (DFT) calculations. The spectroscopy reveals that the hydrogen peroxide molecule is reduced at negative potentials to form a Cu-OH surface species in acidic solutions, a result consistent with the insight from Tafel slope measurements. DFT calculations support the instability of peroxide relative to the surface-coordinated hydroxide on both Cu(111) and Cu(100) surfaces.

  17. Widely available active sites on Ni2P for electrochemical hydrogen evolution - insights from first principles calculations

    DEFF Research Database (Denmark)

    Hansen, Martin Hangaard; Stern, Lucas-Alexandre; Feng, Ligang;

    2015-01-01

    We present insights into the mechanism and the active site for hydrogen evolution on nickel phosphide (Ni2P). Ni2P was recently discovered to be a very active non-precious hydrogen evolution catalyst. Current literature attributes the activity of Ni2P to a particular site on the (0001) facet. In ...

  18. Tethered Transition Metals Promoted Photocatalytic System for Efficient Hydrogen Evolutions

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

    The present invention is directed, at least in part, to a process for improving the efficiency of a photocatalyst (a semiconductor photocatalyst) by tethering (depositing) a metal (e.g., metal ions of a late transition metal, such as nickel) to the semiconductor (photocatalyst) surface through the use of an organic ligand. More specifically, 1,2-ethanedithiol (EDT) functions as an excellent molecular linker (organic ligand) to attach a transition metal complex (e.g., nickel (Ni.sup.2+ ions)) to the semiconductor surface, which can be in the form of a cadmium sulfide surface. The photocatalyst has particular utility in generating hydrogen from H.sub.2S.

  19. Analysis of Thermal and Reaction Times for Hydrogen Reduction of Lunar Regolith

    Science.gov (United States)

    Hegde, U.; Balasubramaniam, R.; Gokoglu, S.

    2009-01-01

    System analysis of oxygen production by hydrogen reduction of lunar regolith has shown the importance of the relative time scales for regolith heating and chemical reaction to overall performance. These values determine the sizing and power requirements of the system and also impact the number and operational phasing of reaction chambers. In this paper, a Nusselt number correlation analysis is performed to determine the heat transfer rates and regolith heat up times in a fluidized bed reactor heated by a central heating element (e.g., a resistively heated rod, or a solar concentrator heat pipe). A coupled chemical and transport model has also been developed for the chemical reduction of regolith by a continuous flow of hydrogen. The regolith conversion occurs on the surfaces of and within the regolith particles. Several important quantities are identified as a result of the above analyses. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the particle Reynolds number, the Archimedes number, and the time needed for hydrogen to diffuse into the pores of the regolith particles. The analysis is used to determine the heat up and reaction times and its application to NASA s oxygen production system modeling tool is noted.

  20. Hydrogen Evolution on Supported Incomplete Cubane-type [Mo3S4](4+) Electrocatalysts

    DEFF Research Database (Denmark)

    Jaramillo, Thomas; Bonde, Jacob Lindner; Zhang, Jingdong

    2008-01-01

    Electrocatalytic properties of biomimetic supported incomplete cubane-type [Mo3S4](4+) clusters are investigated. The activity toward the hydrogen evolution reaction (HER) is evaluated on both a high surface area gas diffusion electrode in a membrane electrode assembly and on highly orientated...

  1. Hydrogen Evolution from Water Coupled with the Oxidation of As(III) in a Photocatalytic System.

    Science.gov (United States)

    Zou, Jian-Ping; Wu, Dan-Dan; Bao, Shao-Kui; Luo, Jinming; Luo, Xu-Biao; Lei, Si-Liang; Liu, Hui-Long; Du, Hong-Mei; Luo, Sheng-Lian; Au, Chak-Tong; Suib, Steven L

    2015-12-30

    A series of heterostructured CdS/Sr2(Nb17/18Zn1/18)2O7-δ composites with excellent photocatalytic ability for simultaneous hydrogen evolution and As(III) oxidation under simulated sunlight were synthesized and characterized. Among them, 30% CdS/Sr2(Nb17/18Zn1/18)2O7-δ (30CSNZO) has the highest in activity, exhibiting a H2 production rate of 1669.1 μmol·h(-1)·g(-1) that is higher than that of many photocatalysts recently reported in the literature. At pH 9, As(III) is completely oxidized to As(V) over 30CSNZO in 30 min of irradiation of simulated sunlight. In the photocatalytic system, H2 production rate decreases with the increase of As(III) concentration, and the recycle experiments show that 30CSNZO exhibits excellent stability, durability, and recyclability for photocatalytic hydrogen evolution and As(III) oxidation. We propose a mechanism in which superoxide radical (·O2(-)) is the active species for As(III) oxidation and the oxidation of As(III) has an effect on hydrogen evolution. For the first time, it is demonstrated that simultaneous hydrogen evolution and arsenite oxidation is possible in a photocatalytic system.

  2. Use of Biocompatible Buffers to Reduce the Concentration Overpotential for Hydrogen Evolution

    NARCIS (Netherlands)

    Jeremiasse, A.W.; Hamelers, H.V.M.; Kleijn, J.M.; Buisman, C.J.N.

    2009-01-01

    The hydrogen evolution reaction (HER) at Pt-cathodes of microbial electrolysis cells (MEC) has been associated with overpotentials of several hundred millivolts. The high overpotentials challenge the sustainability of an MEC. This paper shows that the HER overpotential at MEC relevant pH values is r

  3. Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

    Science.gov (United States)

    Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

    2016-09-01

    With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

  4. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide.

    Science.gov (United States)

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-05-20

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH(-) oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion.

  5. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

    Science.gov (United States)

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-05-01

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH-->Ni(OH)2) and an anodic OH- oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion.

  6. High-performance a -Si/c-Si heterojunction photoelectrodes for photoelectrochemical oxygen and hydrogen evolution

    KAUST Repository

    Wang, Hsin Ping

    2015-05-13

    Amorphous Si (a-Si)/crystalline Si (c-Si) heterojunction (SiHJ) can serve as highly efficient and robust photoelectrodes for solar fuel generation. Low carrier recombination in the photoelectrodes leads to high photocurrents and photovoltages. The SiHJ was designed and fabricated into both photoanode and photocathode with high oxygen and hydrogen evolution efficiency, respectively, by simply coating of a thin layer of catalytic materials. The SiHJ photoanode with sol-gel NiOx as the catalyst shows a current density of 21.48 mA/cm2 at the equilibrium water oxidation potential. The SiHJ photocathode with 2 nm sputter-coated Pt catalyst displays excellent hydrogen evolution performance with an onset potential of 0.640 V and a solar to hydrogen conversion efficiency of 13.26%, which is the highest ever reported for Si-based photocathodes. © 2015 American Chemical Society.

  7. Enhanced photocatalytic hydrogen evolution by combining water soluble graphene with cobalt salts

    Directory of Open Access Journals (Sweden)

    Jing Wang

    2014-07-01

    Full Text Available There is tremendous effort put in the pursuit for cheap and efficient catalysts for photocatalytic hydrogen evolution systems. Herein, we report an active catalyst that uses the earth-abundant element cobalt and water-dispersible sulfonated graphene. The photocatalytic hydrogen evolution activity of the catalyst was tested by using triethanolamine (TEOA as electron donor and eosin Y (EY as the photosensitizer under LED irradiation at 525 nm. Hydrogen was produced constantly even after 20 h, and the turnover number (TON reached 148 (H2/Co in 4 h with respect to the initial concentration of the added cobalt salts was shown to be 5.6 times larger than that without graphene.

  8. Confinement dependence of electro-catalysts for hydrogen evolution from water splitting

    Directory of Open Access Journals (Sweden)

    Mikaela Lindgren

    2014-02-01

    Full Text Available Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE, where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.

  9. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water

    Science.gov (United States)

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M.; Warnan, Julien; Kuehnel, Moritz F.; Friend, Richard H.; Reisner, Erwin

    2016-09-01

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of -9.8 mA cm-2 at 0 V versus RHE with an onset potential as positive as 0.95+/-0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ~1 h under continuous illumination.

  10. Silicon Nanowires with MoSx and Pt as Electrocatalysts for Hydrogen Evolution Reaction

    Directory of Open Access Journals (Sweden)

    S. H. Hsieh

    2016-01-01

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

  11. Perchlorate reduction by hydrogen autotrophic bacteria and microbial community analysis using high-throughput sequencing.

    Science.gov (United States)

    Wan, Dongjin; Liu, Yongde; Niu, Zhenhua; Xiao, Shuhu; Li, Daorong

    2016-02-01

    Hydrogen autotrophic reduction of perchlorate have advantages of high removal efficiency and harmless to drinking water. But so far the reported information about the microbial community structure was comparatively limited, changes in the biodiversity and the dominant bacteria during acclimation process required detailed study. In this study, perchlorate-reducing hydrogen autotrophic bacteria were acclimated by hydrogen aeration from activated sludge. For the first time, high-throughput sequencing was applied to analyze changes in biodiversity and the dominant bacteria during acclimation process. The Michaelis-Menten model described the perchlorate reduction kinetics well. Model parameters q(max) and K(s) were 2.521-3.245 (mg ClO4(-)/gVSS h) and 5.44-8.23 (mg/l), respectively. Microbial perchlorate reduction occurred across at pH range 5.0-11.0; removal was highest at pH 9.0. The enriched mixed bacteria could use perchlorate, nitrate and sulfate as electron accepter, and the sequence of preference was: NO3(-) > ClO4(-) > SO4(2-). Compared to the feed culture, biodiversity decreased greatly during acclimation process, the microbial community structure gradually stabilized after 9 acclimation cycles. The Thauera genus related to Rhodocyclales was the dominated perchlorate reducing bacteria (PRB) in the mixed culture.

  12. Mathematical Modelling of the Process of Tungsten Fluorides Reduction by Hydrogen

    Directory of Open Access Journals (Sweden)

    Brendakov Roman

    2016-01-01

    Full Text Available The process of tungsten fluorides reduction by hydrogen is a component part of Fluoride technology of tungsten conversion. Nowadays the researchers are definitely interested in studying this process. It is connected with common use of metal tungsten products in different sectors of the economy, which is the result of unique qualities of this metal. With the help of physical and mathematical modelling of the process of tungsten hexafluoride reduction by hydrogen, it becomes possible to create an import substitution technology of metal tungsten conversion. Fluoride technology of tungsten conversion allows putting different coverings and make tungsten products of different shapes, which is impossible to get traditionally. The process of tungsten fluorides reduction by hydrogen can be referred to CVD processes (Chemical Vapor Deposition. Common use of CVD technologies for getting metal products and coverings is limited by definite problems, connected with access difficulties to initial components of research and the lack of information about their basic thermal characteristics. Therefore, mathematical description of the initial components mass-moving process, which provides with optimal value of their concentration in gas flow and in precipitation zone, is a question of current importance.

  13. Reduction of Quartz to Silicon Monoxide by Methane-Hydrogen Mixtures

    Science.gov (United States)

    Li, Xiang; Zhang, Guangqing; Tronstad, Ragnar; Ostrovski, Oleg

    2016-08-01

    The reduction of quartz was studied isothermally in a fluidized bed reactor using continuously flowing methane-hydrogen gas mixture in the temperature range from 1623 K to 1773 K (1350 °C to 1500 °C). The CO content in the off-gas was measured online using an infrared gas analyzer. The main phases of the reduced samples identified by XRD analysis were quartz and cristobalite. Significant weight loss in the reduction process indicated that the reduction products were SiO and CO. Reduction of SiO2 to SiO by methane starts with adsorption and dissociation of CH4 on the silica surface. The high carbon activity in the CH4-H2 gas mixture provided a strongly reducing condition. At 1623 K (1350 °C), the reduction was very slow. The rate and extent of reduction increased with the increasing temperature to 1723 K (1450 °C). A further increase in temperature to 1773 K (1500 °C) resulted in a decrease in the rate and extent of reduction. An increase in the gas flow rate from 0.4 to 0.8 NL/min and an increase in the methane content in the CH4-H2 gas mixture from 0 to 5 vol pct facilitated the reduction. Methane content in the gas mixture should be maintained at less than 5 vol pct in order to suppress methane cracking.

  14. Evolution of Sm2Fe17 Alloys during Hydrogenation-Disproportion Process

    Institute of Scientific and Technical Information of China (English)

    Ye Jinwen; Liu Ying; Li Meng; Gao Shengji; Tu Mingjing

    2005-01-01

    The evolution of phase compositions, phase change and microstructure in Sm2Fe17 alloys during hydrogenation-disproportion process were systematically studied with XRD, SEM, EDX methods. Research indicates that HD process of Sm2Fe17 alloys is as follows: Sm2Fe17 alloy absorbs hydrogen first in the atmosphere of hydrogenation with a pressure of 0.1 MPa. Disproportionation begins at T≥500 ℃, then the alloys turn into lots of SmHx and α-Fe phases which are partly in microcrystal or amorphous structures. Along with the increase of temperature, the microcrystal and amorphous structures transformed into crystal structure and this transformation thoroughly completed at 750 ℃. The size of obtained crystal grain is about 20~100 nm. Based on the experimental data, a microstructural transformation model of Sm2Fe17 alloys during hydrogenation-disproportion process was made.

  15. Experimental study and modelling of iron ore reduction by hydrogen; Etude experimentale et modelisation de la reduction du minerai de fer par l'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, D

    2008-01-15

    In an effort to find new ways to drastically reduce the CO{sub 2} emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterizations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen process. (author)

  16. Symmetry Reduction and Cauchy Problems for a Class of Fourth-Order Evolution Equations

    Institute of Scientific and Technical Information of China (English)

    LI Ji-Na; ZHANG Shun-Li

    2008-01-01

    We exploit higher-order conditional symmetry to reduce initial-value problems for evolution equations to Cauehy problems for systems of ordinary differential equations (ODEs).We classify a class of fourth-order evolution equations which admit certain higher-order generalized conditional symmetries (GCSs) and give some examples to show the main reduction procedure.These reductions cannot be derived within the framework of the standard Lie approach,which hints that the technique presented here is something essential for the dimensional reduction of evolution equations.

  17. Influence of plastic strain on the hydrogen evolution reaction on nickel (100) single crystal surfaces to improve hydrogen embrittlement

    Energy Technology Data Exchange (ETDEWEB)

    Lekbir, C., E-mail: choukri.lekbir@univ-lr.fr; Creus, J.; Sabot, R.; Feaugas, X.

    2013-08-20

    Hydrogen-induced embrittlement can be accountable for premature failure of structure in relation with physical and/or chemical processes occurring on material's surface or in the bulk of the material. Hydrogen Evolution Reaction (HER) corresponding to the early step of hydrogen ingress in the material is explored in present study in relation with plastic strain. HER on nickel (100) single crystal in sulphuric acid medium can be related by a Volmer–Heyrovsky mechanism. The corresponding elementary kinetic parameters as symmetry coefficients, activation enthalpies, and number of active sites have been identified via a thermokinetic model using experimental data. These parameters can be affected by defects associated with plastic strain. Irreversible plastic strain modifies the density and the distribution of storage dislocations affecting the surface roughness at atomic scale and generating additional active adsorption sites. Furthermore, surface emergence of mobile dislocations induces the formation of slip bands, which modify the surface roughness and the electronic state of the surface and increases the (111) surface density. The consequence of plastic strain on HER is explored and discussed in relation with both processes.

  18. The Evolution of University Responses to Financial Reduction.

    Science.gov (United States)

    Davies, John L.

    1997-01-01

    Examines the nature and characteristics of the phenomenon of retrenchment in universities and systems since the late 1970s. Five categories of financial reduction are identified, giving special attention to the situation of financial reduction coupled with increased demand and to approaches characterized by restructuring. Discusses consequences…

  19. Binary platinum alloy electrodes for hydrogen and oxygen evolutions by seawater splitting

    Science.gov (United States)

    Zheng, Jingjing

    2017-08-01

    Hydrogen and oxygen evolutions by seawater splitting are persistent objectives for green energy production. We present here the experimental realization of Ti foil supported PtM (M = Fe, Co, Ni, Pd) alloy electrodes by a cycle voltammetry method for seawater splitting. The preliminary results demonstrate that the resultant Ti supported PtM alloy electrodes are robust in realizing high-efficiency hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), arising from enhanced current density, reduced potential, and good durability. By tuning M species, the Ti supported PtPd alloy electrode displays a maximal efficiency, yielding an onset potential of -52 mV and 690 mV (vs RHE) in HER and OER, respectively. The current densities of Ti supported PtPd electrode are as high as 270 mA cm-2 at 1.32 V (vs RHE) and 590 mA cm-2 at 3.99 V (vs RHE). Moreover, the long-term stability has also been increased by alloying Pt with M. Although the work presented here is far from optimized, the concept of alloying transition metals with Pt can guide us to design highly efficient alloy electrodes for hydrogen and oxygen evolutions from seawater splitting.

  20. Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction

    Science.gov (United States)

    Zhang, Tingting; He, Chuansheng; Sun, Fengzhan; Ding, Yongqi; Wang, Manchao; Peng, Lin; Wang, Jiahui; Lin, Yuqing

    2017-03-01

    This study describes a facile and effective route to synthesize hybrid material consisting of Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide (Co3O4/N-rGO) as a high-performance tri-functional catalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and H2O2 sensing. Electrocatalytic activity of Co3O4/N-rGO to hydrogen peroxide reduction was tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry. Under a reduction potential at ‑0.6 V to H2O2, this constructing H2O2 sensor exhibits a linear response ranging from 0.2 to 17.5 mM with a detection limit to be 0.1 mM. Although Co3O4/rGO or nitrogen-doped reduced graphene oxide (N-rGO) alone has little catalytic activity, the Co3O4/N-rGO exhibits high ORR activity. The Co3O4/N-rGO hybrid demonstrates satisfied catalytic activity with ORR peak potential to be ‑0.26 V (vs. Ag/AgCl) and the number of electron transfer number is 3.4, but superior stability to Pt/C in alkaline solutions. The same hybrid is also highly active for OER with the onset potential, current density and Tafel slope to be better than Pt/C. The unusual catalytic activity of Co3O4/N-rGO for hydrogen peroxide reduction, ORR and OER may be ascribed to synergetic chemical coupling effects between Co3O4, nitrogen and graphene.

  1. Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction

    Science.gov (United States)

    Zhang, Tingting; He, Chuansheng; Sun, Fengzhan; Ding, Yongqi; Wang, Manchao; Peng, Lin; Wang, Jiahui; Lin, Yuqing

    2017-01-01

    This study describes a facile and effective route to synthesize hybrid material consisting of Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide (Co3O4/N-rGO) as a high-performance tri-functional catalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and H2O2 sensing. Electrocatalytic activity of Co3O4/N-rGO to hydrogen peroxide reduction was tested by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry. Under a reduction potential at −0.6 V to H2O2, this constructing H2O2 sensor exhibits a linear response ranging from 0.2 to 17.5 mM with a detection limit to be 0.1 mM. Although Co3O4/rGO or nitrogen-doped reduced graphene oxide (N-rGO) alone has little catalytic activity, the Co3O4/N-rGO exhibits high ORR activity. The Co3O4/N-rGO hybrid demonstrates satisfied catalytic activity with ORR peak potential to be −0.26 V (vs. Ag/AgCl) and the number of electron transfer number is 3.4, but superior stability to Pt/C in alkaline solutions. The same hybrid is also highly active for OER with the onset potential, current density and Tafel slope to be better than Pt/C. The unusual catalytic activity of Co3O4/N-rGO for hydrogen peroxide reduction, ORR and OER may be ascribed to synergetic chemical coupling effects between Co3O4, nitrogen and graphene. PMID:28272415

  2. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

    2010-01-01

    Density functional theory calculations have been performed for the three elementary steps―Tafel, Heyrovsky, and Volmer―involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively...... charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...

  3. A Novel Eco-Friendly Vanadium Precipitation Method by Hydrothermal Hydrogen Reduction Technology

    Directory of Open Access Journals (Sweden)

    Guobin Zhang

    2017-09-01

    Full Text Available In view of the serious pollution problems caused by the traditional vanadium precipitation process, the eco-friendly technology of hydrothermal hydrogen reduction was first applied to precipitate phase pure vanadium sesquioxide (V2O3 products from stripped pentavalent vanadium (V (V solution extracted from vanadium-bearing shale. Thermodynamic analysis demonstrate the method of hydrothermal hydrogen reduction is feasible for precipitating V2O3 from V (V solution at a suitable pH range, and the reduction should better be carried out at a lower pH under the pH range in which V2O3 can exist stably. The V2O3 products of 99.92% in purity and a high vanadium precipitation percentage of 99.25% were achieved under a facile reaction condition of initial solution pH of 6, reaction temperature of 523 K, H2 partial pressure of 4 MPa and reaction time of 2 h. Based on the analysis of XRD and FE-SEM with EDS for the precipitation products obtained at serial reaction times, the phase transformation mechanism was summarized to serial reductions with the phase transformation of HxVyOz(2z−x−5y− → NaV2O5 → VO2(H2O0.5 → VOOH → V2O3. Compared with the two-step traditional method of precipitating vanadium with ammonium salt and roast-reduction (react at above 773 K for more than 3 h for preparing V2O3, this method only experiences one-step reduction under a green atmosphere of H2 gas with a lower reaction temperature of 523 K and a shorter reaction time of 2h. Therefore, this method for vanadium precipitation is characterized by being eco-friendly, having a short process and being low-energy consumption, which has great significance for the sustainable development of vanadium industry.

  4. Enhanced hydrogen evolution rates at high pH with a colloidal cadmium sulphide–platinum hybrid system

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, Julian; Vaneski, Aleksandar; Susha, Andrei S.; Rogach, Andrey L., E-mail: andrey.rogach@cityu.edu.hk [Department of Physics and Materials Science and Centre for Functional Photonics (CFP), City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong); Pesch, Georg R.; Yang Teoh, Wey [Clean Energy and Nanotechnology (CLEAN) Laboratory, School of Energy and Environment, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong)

    2014-12-01

    We demonstrate enhanced hydrogen generation rates at high pH using colloidal cadmium sulphide nanorods decorated with Pt nanoparticles. We introduce a simplified procedure for the decoration and subsequent hydrogen generation, reducing both the number of working steps and the materials costs. Different Pt precursor concentrations were tested to reveal the optimal conditions for the efficient hydrogen evolution. A sharp increase in hydrogen evolution rates was measured at pH 13 and above, a condition at which the surface charge transfer was efficiently mediated by the formation of hydroxyl radicals and further consumption by the sacrificial triethanolamine hole scavenger.

  5. Enhanced hydrogen evolution rates at high pH with a colloidal cadmium sulphide–platinum hybrid system

    Directory of Open Access Journals (Sweden)

    Julian Schneider

    2014-12-01

    Full Text Available We demonstrate enhanced hydrogen generation rates at high pH using colloidal cadmium sulphide nanorods decorated with Pt nanoparticles. We introduce a simplified procedure for the decoration and subsequent hydrogen generation, reducing both the number of working steps and the materials costs. Different Pt precursor concentrations were tested to reveal the optimal conditions for the efficient hydrogen evolution. A sharp increase in hydrogen evolution rates was measured at pH 13 and above, a condition at which the surface charge transfer was efficiently mediated by the formation of hydroxyl radicals and further consumption by the sacrificial triethanolamine hole scavenger.

  6. SIMILARITY REDUCTIONS FOR THE NONLINEAR EVOLUTION EQUATION ARISING IN THE FERMI-PASTA-ULAM PROBLEM

    Institute of Scientific and Technical Information of China (English)

    谢福鼎; 闫振亚; 张鸿庆

    2002-01-01

    Four families of similarity reductions are obtained for the nonlinear evolution equation arising in the Fermi-Pasta-Ulam problem via using both the direct method due to Clarkson and Kruskal and the improved direct method due to Lou.

  7. Hydrogenation of Styrene Oxide to 2-Phenylethanol over Nanocrystalline Ni Prepared by Ethylene Glycol Reduction Method

    Directory of Open Access Journals (Sweden)

    Sunil K. Kanojiya

    2014-01-01

    Full Text Available Nanocrystalline nickel prepared by glycol reduction method and characterized by XRD and magnetic measurements has been used as a catalyst for hydrogenation of styrene oxide to 2-phenylethanol. Effect of process variables such as particle size of the catalyst, temperature, and pressure have been optimized to achieve a maximum conversion of 98% of styrene oxide with 99% selectivity towards 2-phenylethanol. The structure of the transition state has been computed employing density functional theory and using Gaussian 09 suite. The enthalpy of reaction (ΔH and activation energy (Ea are calculated to be 85.3 kcal·mol−1 and 123.03 kcal·mol−1, respectively. A tentative mechanism for the reaction is proposed according to which atomized hydrogen and styrene oxide react together over the catalyst surface to produce 2-phenylethanol.

  8. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

    KAUST Repository

    Cabán-Acevedo, Miguel

    2015-09-14

    The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS 2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm at overpotentials as low as 48mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n -p-p silicon micropyramids achieved photocurrents up to 35 mA cm at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

  9. Using directed evolution to improve hydrogen production in chimeric hydrogenases from Clostridia species.

    Science.gov (United States)

    Plummer, Scott M; Plummer, Mark A; Merkel, Patricia A; Hagen, Moira; Biddle, Jennifer F; Waidner, Lisa A

    2016-11-01

    Hydrogenases are enzymes that play a key role in controlling excess reducing equivalents in both photosynthetic and anaerobic organisms. This enzyme is viewed as potentially important for the industrial generation of hydrogen gas; however, insufficient hydrogen production has impeded its use in a commercial process. Here, we explore the potential to circumvent this problem by directly evolving the Fe-Fe hydrogenase genes from two species of Clostridia bacteria. In addition, a computational model based on these mutant sequences was developed and used as a predictive aid for the isolation of enzymes with even greater efficiency in hydrogen production. Two of the improved mutants have a logarithmic increase in hydrogen production in our in vitro assay. Furthermore, the model predicts hydrogenase sequences with hydrogen productions as high as 540-fold over the positive control. Taken together, these results demonstrate the potential of directed evolution to improve the native bacterial hydrogenases as a first step for improvement of hydrogenase activity, further in silico prediction, and finally, construction and demonstration of an improved algal hydrogenase in an in vivo assay of C. reinhardtii hydrogen production. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Role of the Edge Properties in the Hydrogen Evolution Reaction on MoS2.

    Science.gov (United States)

    Lazar, Petr; Otyepka, Michal

    2017-04-06

    Molybdenum disulfide, in particular its edges, has attracted considerable attention as possible substitute for platinum catalysts in the hydrogen evolution reaction (HER). The complex nature of the reaction complicates its detailed experimental investigations, which are mostly indirect and sample dependent. Therefore, density functional theory calculations were employed to study how the properties of the MoS2 Mo-edge influence the thermodynamics of hydrogen adsorption onto the edge. The effect of the computational model (one-dimensional nanostripe), border symmetry imposed by its length, sulfur saturation of the edge, and dimensionality of the material are discussed. Hydrogen adsorption was found to depend critically on the coverage of extra sulfur at the Mo edge. The bare Mo-edge and fully sulfur-covered Mo-edge are catalytically inactive. The most favorable hydrogen binding towards HER was found for the Mo-edge covered by sulfur monomers. This edge provides hydrogen adsorption free energies positioned around -0.25 eV at up to 50 % hydrogen coverage, close to the experimental values of overpotential needed for the HER reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The effect of urea on microstructures of Ni3S2 on nickel foam and its hydrogen evolution reaction

    Science.gov (United States)

    Jinlong, Lv; Tongxiang, Liang

    2016-11-01

    The effects of urea concentration on microstructures of Ni3S2formed on nickel foam and its hydrogen evolution reaction were investigated. The Ni3S2 nanosheets with porous structure were formed on nickel foam during hydrothermal process due to low urea concentration. While high urea concentration facilitated the forming of Ni3S2 nanotube arrays. The resulting Ni3S2 nanotube arrays exhibited higher catalytic activity than Ni3S2nanosheets for hydrogen evolution reaction. This was mainly attributed to a fact that Ni3S2 nanotube arrays facilitated diffusion of electrolyte for hydrogen evolution reaction.

  12. MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution.

    Science.gov (United States)

    Zhao, Yufei; Xie, Xiuqiang; Zhang, Jinqiang; Liu, Hao; Ahn, Hyo-Jun; Sun, Kening; Wang, Guoxiu

    2015-11-01

    The development of efficient catalysts for electrochemical hydrogen evolution is essential for energy conversion technologies. Molybdenum disulfide (MoS2 ) has emerged as a promising electrocatalyst for hydrogen evolution reaction, and its performance greatly depends on its exposed edge sites and conductivity. Layered MoS2 nanosheets supported on a 3D graphene aerogel network (GA-MoS2 ) exhibit significant catalytic activity in hydrogen evolution. The GA-MoS2 composite displays a unique 3D architecture with large active surface areas, leading to high catalytic performance with low overpotential, high current density, and good stability.

  13. Reduction of neoclassical polarization current contribution to NTM evolution

    Science.gov (United States)

    Qu, Hongpeng; Peng, Xiaodong; Wang, Feng; Wang, Aike; Shen, Yong

    2016-09-01

    The neoclassical polarization current, which can be generated by a time-dependent electric field resulting from magnetic island rotation, is believed to play an important role in the initial stage of the neoclassical tearing mode (NTM) evolution in tokamak plasmas. In the previous analytical description of the neoclassical polarization current contribution to the evolution of NTMs in the limit of low collision frequency ( νii≪ɛω , νii is ion collision frequency, ɛ is the inverse aspect ratio, and ω is the island propagation frequency in the plasma rest frame), the width of magnetic islands has been assumed to be much larger than the finite-banana-width (FBW) of the trapped ions in order to solve the drift-kinetic equation of ions by using the perturbation method. In this paper, we introduce a new analytical approach to investigate the neoclassical polarization current contribution to the NTM evolution without the assumption of the large island width by solving the drift-kinetic equation in a so-called ion-banana-center coordinate system. The results show that, when the island width is comparable to the FBW of the thermal ion, the neoclassical polarization current term in the equation of the NTM evolution is much smaller than the previous analytical expression but matches well with the empirical anticipation commonly adopted in experiments.

  14. Hydrogen Reduction of Hematite Ore Fines to Magnetite Ore Fines at Low Temperatures

    Directory of Open Access Journals (Sweden)

    Wenguang Du

    2017-01-01

    Full Text Available Surplus coke oven gases (COGs and low grade hematite ores are abundant in Shanxi, China. Our group proposes a new process that could simultaneously enrich CH4 from COG and produce separated magnetite from low grade hematite. In this work, low-temperature hydrogen reduction of hematite ore fines was performed in a fixed-bed reactor with a stirring apparatus, and a laboratory Davis magnetic tube was used for the magnetic separation of the resulting magnetite ore fines. The properties of the raw hematite ore, reduced products, and magnetic concentrate were analyzed and characterized by a chemical analysis method, X-ray diffraction, optical microscopy, and scanning electron microscopy. The experimental results indicated that, at temperatures lower than 400°C, the rate of reduction of the hematite ore fines was controlled by the interfacial reaction on the core surface. However, at temperatures higher than 450°C, the reaction was controlled by product layer diffusion. With increasing reduction temperature, the average utilization of hydrogen initially increased and tended to a constant value thereafter. The conversion of Fe2O3 in the hematite ore played an important role in the total iron recovery and grade of the concentrate. The grade of the concentrate decreased, whereas the total iron recovery increased with the increasing Fe2O3 conversion.

  15. Storage of Renewable Energy by Reduction of CO2 with Hydrogen.

    Science.gov (United States)

    Züttel, Andreas; Mauron, Philippe; Kato, Shunsuke; Callini, Elsa; Holzer, Marco; Huang, Jianmei

    2015-01-01

    The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. 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. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO(2) into the cycle and storing hydrogen by the reduction of CO(2) to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO(2) neutral) if CO(2) is extracted from the atmosphere. Today's technology allows CO(2) to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer-Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO(2) from the atmosphere close to the thermodynamic limit and to reduce CO(2) with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with

  16. Ultrahigh hydrogen evolution performance of under-water "superaerophobic" MoS₂ nanostructured electrodes.

    Science.gov (United States)

    Lu, Zhiyi; Zhu, Wei; Yu, Xiaoyou; Zhang, Haichuan; Li, Yingjie; Sun, Xiaoming; Wang, Xinwei; Wang, Hao; Wang, Jingming; Luo, Jun; Lei, Xiaodong; Jiang, Lei

    2014-05-01

    The adhesion of as-formed gas bubbles on the electrode surface usually impedes mass-transfer kinetics and subsequently decreases electrolysis efficiency. Here it is demonstrated that nanostructured MoS₂ films on conductive substrates show a faster hydrogen evolution reaction (HER), current increase, and a more-stable working state than their flat counterpart by significantly alleviating the adhesion of as-formed gas bubbles on the electrode. This study clearly reveals the importance of a nano-porous structure for HER, which should be general and beneficial for constructing other gas-evolution electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Precise tuning in platinum-nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis

    Science.gov (United States)

    Wang, Pengtang; Zhang, Xu; Zhang, Jin; Wan, Sheng; Guo, Shaojun; Lu, Gang; Yao, Jianlin; Huang, Xiaoqing

    2017-01-01

    Comprising abundant interfaces, multicomponent heterostructures can integrate distinct building blocks into single entities and yield exceptional functionalities enabled by the synergistic components. Here we report an efficient approach to construct one-dimensional metal/sulfide heterostructures by directly sulfuring highly composition-segregated platinum-nickel nanowires. The heterostructures possess a high density of interfaces between platinum-nickel and nickel sulfide components, which cooperate synergistically towards alkaline hydrogen evolution reaction. The platinum-nickel/nickel sulfide heterostructures can deliver a current density of 37.2 mA cm−2 at an overpotential of 70 mV, which is 9.7 times higher than that of commercial Pt/C. The heterostructures also offer enhanced stability revealed by long-term chronopotentiometry measurements. The present work highlights a potentially powerful interface-engineering strategy for designing multicomponent heterostructures with advanced performance in hydrogen evolution reaction and beyond. PMID:28239145

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

    Science.gov (United States)

    Mir, Showkat H.; Chakraborty, Sudip; Jha, Prakash C.; Wärnâ, John; Soni, Himadri; Jha, Prafulla K.; Ahuja, Rajeev

    2016-08-01

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

  19. Electrocatalytic properties of Ni-S-Co coating electrode for hydrogen evolution in alkaline medium

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Amorphous Ni-S-Co alloy was prepared by means of chemical electro-deposition method on the foam nickel matrix. The surface morphology and microstructure of Ni-S-Co coatings were studied using SEM and XRD, and the electrochemical properties were tested by electrochemical methods. The results show that the coating has amorphous structure and the particles of the surface are fine with large specific surface area. The Ni-S-Co alloy is more active with lower potential for hydrogen evolution, higher exchange current density and lower activation energy compared with Ni and Ni-S electrode. Its hydrogen evolution reaction(HER) is enhanced, the size of particles of surface decreases and the surface area increases after being activated by KOH alkaline solution.

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

    Science.gov (United States)

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-08-19

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry.

  1. Lunar Regolith Simulant Feed System for a Hydrogen Reduction Reactor System

    Science.gov (United States)

    Mueller, R. P.; Townsend, Ivan I., III

    2009-01-01

    One of the goals of In-Situ Resource Utilization (ISRU) on the moon is to produce oxygen from the lunar regolith which is present in the form of Ilmenite (FeTi03) and other compounds. A reliable and attainable method of extracting some of the oxygen from the lunar regolith is to use the hydrogen reduction process in a hot reactor to create water vapor which is then condensed and electrolyzed to obtain oxygen for use as a consumable. One challenge for a production system is to reliably acquire the regolith with an excavator hauler mobility platform and then introduce it into the reactor inlet tube which is raised from the surface and above the reactor itself. After the reaction, the hot regolith (-1000 C) must be expelled from the reactor for disposal by the excavator hauler mobility system. In addition, the reactor regolith inlet and outlet tubes must be sealed by valves during the reaction in order to allow collection of the water vapor by the chemical processing sub-system. These valves must be able to handle abrasive regolith passing through them as well as the heat conduction from the hot reactor. In 2008, NASA has designed and field tested a hydrogen reduction system called ROxygen in order to demonstrate the feasibility of extracting oxygen from lunar regolith. The field test was performed with volcanic ash known as Tephra on Mauna Kea volcano on the Big Island of Hawai'i. The tephra has similar properties to lunar regolith, so that it is regarded as a good simulant for the hydrogen reduction process. This paper will discuss the design, fabrication, operation, test results and lessons learned with the ROxygen regolith feed system as tested on Mauna Kea in November 2008.

  2. Modeling of hydrogen evolution reaction on the surface of GaInP2

    Science.gov (United States)

    Choi, Woon Ih; Wood, Brandon; Schwegler, Eric; Ogitsu, Tadashi

    2012-02-01

    GaInP2 is promising candidate material for hydrogen production using sunlight. It reduces solvated proton into hydrogen molecule using light-induced excited electrons in the photoelectrochemical cell. However, it is challenging to model hydrogen evolution reaction (HER) using first-principles molecular dynamics. Instead, we use Anderson-Newns model and generalized solvent coordinate in Marcus-Hush theory to describe adiabatic free energy surface of HER. Model parameters are fitted from the DFT calculations. We model Volmer-Heyrovsky reaction path on the surfaces of CuPt phase of GaInP2. We also discuss effects of surface oxide and catalyst atoms that exist on top of bare surfaces in experimental circumstances.

  3. Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries

    Science.gov (United States)

    Sun, Che-Nan; Delnick, Frank M.; Baggetto, Loïc; Veith, Gabriel M.; Zawodzinski, Thomas A.

    2014-02-01

    This work demonstrates a quantitative method to determine the hydrogen evolution rate occurring at the negative carbon electrode of the all vanadium redox flow battery (VRFB). Two carbon papers examined by buoyancy measurements yield distinct hydrogen formation rates (0.170 and 0.005 μmol min-1 g-1). The carbon papers have been characterized using electron microscopy, nitrogen gas adsorption, capacitance measurement by electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). We find that the specific electrochemical surface area (ECSA) of the carbon material has a strong influence on the hydrogen generation rate. This is discussed in light of the use of high surface area material to obtain high reaction rates in the VRFB.

  4. Influence of hydrogen concentration on Fe2O3 particle reduction in fluidized beds under constant drag force

    Institute of Scientific and Technical Information of China (English)

    Lei Guo; Han Gao; Jin-tao Yu; Zong-liang Zhang; Zhan-cheng Guo

    2015-01-01

    The fixed-gas drag force from a model calculation method that stabilizes the agitation capabilities of different gas ratios was used to explore the influence of temperature and hydrogen concentration on fluidizing duration, metallization ratio, utilization rate of reduction gas, and sticking behavior. Different hydrogen concentrations from 5vol%to 100vol%at 1073 and 1273 K were used while the drag force with the flow of N2 and H2 (N2:2 L·min−1;H2:2 L·min−1) at 1073 K was chosen as the standard drag force. The metallization ratio, mean reduc-tion rate, and utilization rate of reduction gas were observed to generally increase with increasing hydrogen concentration. Faster reduction rates and higher metallization ratios were obtained when the reduction temperature decreased from 1273 to 1073 K. A numerical relation among particle diameter, particle drag force, and fluidization state was plotted in a diagram by this model.

  5. Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Jensen, Jens Oluf; Bjerrum, Niels J.

    2014-01-01

    Alternative catalysts based on carbides of Group 5 (niobium and tantalum) and 6 (chromium, molybdenum and tungsten) metals were prepared as films on the metallic substrates. The electrochemical activities of these carbide electrodes towards the hydrogen evolution reaction (HER) in concentrated......, attributable to the different electronic structures. Tungsten carbide among the studied electrode samples exhibited the highest HER activity. Upon anodic potential scans in the presence of oxygen, chromium, tantalum and tungsten carbides displayed passivation due to the formation of stable surface layers...

  6. Photocatalytic Hydrogen or Oxygen Evolution from Water over S- or N-Doped TiO2 under Visible Light

    Directory of Open Access Journals (Sweden)

    Kazumoto Nishijima

    2008-01-01

    Full Text Available S- or N-doping of TiO2 powder having an anatase or rutile phase extended the photocatalytic activity for water oxidation and reduction under UV light and visible light irradiation. For the reduction of water, anatase-doped TiO2 showed higher level of activity than that of doped TiO2 having a rutile phase using ethanol as an electron donor. Furthermore, the activity level of S-doped TiO2 for hydrogen evolution was higher than that of N-doped TiO2 photocatalysts under visible light. Photocatalytic oxidation of water on doped TiO2 having a rutile phase proceeded with fairly high efficiency when Fe3+ ions were used as electron acceptors compared to that on doped TiO2 having an anatase phase. In addition, water splitting under visible light irradiation was achieved by construction of a Z-scheme photocatalysis system employing the doped TiO2 having anatase and rutile phases for H2 and O2 evolution and the I−/IO3− redox couple as an electron relay.

  7. A CNT@MoSe2 hybrid catalyst for efficient and stable hydrogen evolution

    Science.gov (United States)

    Huang, Yunpeng; Lu, Hengyi; Gu, Huahao; Fu, Jun; Mo, Shuyi; Wei, Chun; Miao, Yue-E.; Liu, Tianxi

    2015-11-01

    Exploration of high-efficiency Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is considered as a great challenge for the development of sustainable and carbon dioxide free energy conversion systems. In this work, a unique hierarchical nanostructure of few-layered MoSe2 nanosheets perpendicularly grown on carbon nanotubes (CNTs) is synthesized through a one-step solvothermal reaction. This rationally designed architecture based on a highly conductive CNT substrate possesses fully exposed active edges and open structures for fast ion/electron transfer, thus leading to remarkable HER activity with a low onset potential of -0.07 V vs. RHE (reversible hydrogen electrode), a small Tafel slope of 58 mV per decade and excellent long-cycle stability. Therefore, this noble-metal-free and highly efficient catalyst enables prospective applications for industrial, renewable hydrogen production.Exploration of high-efficiency Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is considered as a great challenge for the development of sustainable and carbon dioxide free energy conversion systems. In this work, a unique hierarchical nanostructure of few-layered MoSe2 nanosheets perpendicularly grown on carbon nanotubes (CNTs) is synthesized through a one-step solvothermal reaction. This rationally designed architecture based on a highly conductive CNT substrate possesses fully exposed active edges and open structures for fast ion/electron transfer, thus leading to remarkable HER activity with a low onset potential of -0.07 V vs. RHE (reversible hydrogen electrode), a small Tafel slope of 58 mV per decade and excellent long-cycle stability. Therefore, this noble-metal-free and highly efficient catalyst enables prospective applications for industrial, renewable hydrogen production. Electronic supplementary information (ESI) available: the FESEM image of CNT@MoSe2-6 hybrid at low magnification; EDS mapping of CNT@MoSe2-6 hybrid. See DOI: 10

  8. Achieving cost reductions in EOSDIS operations through technology evolution

    Science.gov (United States)

    Newsome, Penny; Moe, Karen; Harberts, Robert

    1996-01-01

    The earth observing system (EOS) data information system (EOSDIS) mission includes the cost-effective management and distribution of large amounts of data to the earth science community. The effect of the introduction of new information system technologies on the evolution of EOSDIS is considered. One of the steps taken by NASA to enable the introduction of new information system technologies into the EOSDIS is the funding of technology development through prototyping. Recent and ongoing prototyping efforts and their potential impact on the performance and cost-effectiveness of the EOSDIS are discussed. The technology evolution process as it related to the effective operation of EOSDIS is described, and methods are identified for the support of the transfer of relevant technology to EOSDIS components.

  9. Order reduction for a model of marine bacteriophage evolution

    Science.gov (United States)

    Pagliarini, Silvia; Korobeinikov, Andrei

    2017-02-01

    A typical mechanistic model of viral evolution necessary includes several time scales which can differ by orders of magnitude. Such a diversity of time scales makes analysis of these models difficult. Reducing the order of a model is highly desirable when handling such a model. A typical approach applied to such slow-fast (or singularly perturbed) systems is the time scales separation technique. Constructing the so-called quasi-steady-state approximation is the usual first step in applying the technique. While this technique is commonly applied, in some cases its straightforward application can lead to unsatisfactory results. In this paper we construct the quasi-steady-state approximation for a model of evolution of marine bacteriophages based on the Beretta-Kuang model. We show that for this particular model the quasi-steady-state approximation is able to produce only qualitative but not quantitative fit.

  10. Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

    KAUST Repository

    Xia, Chuan

    2017-01-06

    An effective multifaceted strategy is demonstrated to increase active edge site concentration in NiCoSe solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as-prepared ternary solid solution with extremely high electrochemically active surface area (C = 197 mF cm), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic-like electrical conductivity and lower free energy for atomic hydrogen adsorption in NiCoSe, identified by temperature-dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the NiCoSe solid solutions show a low overpotential of 65 mV at -10 mV cm, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec, and a large exchange current density of 184 μA cm in acidic electrolyte. Further, it is shown that the as-prepared NiCoSe solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.

  11. The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media.

    Science.gov (United States)

    Rahul, R; Singh, R K; Bera, B; Devivaraprasad, R; Neergat, M

    2015-06-21

    Oxygen reduction reaction (ORR) is investigated on bulk PdO-based catalysts (oxides of Pd and Pd3Co) in oxygen-saturated 0.1 M HClO4 to establish the role of surface oxides and adsorbed hydrogen in the activity and product selectivity (H2O/H2O2). The initial voltammetric features suggest that the oxides are inactive toward ORR. The evolution of the ORR voltammograms and potential-dependent H2O2 generation features on the PdO catalyst suggest gradual and parallel in situ reduction of the bulk PdO phase below ∼0.4 V in the hydrogen underpotential deposition (Hupd) region; the reduction of the bulk PdO catalyst is confirmed from the X-ray photoelectron spectra (XPS) and X-ray diffraction (XRD) patterns. The potential-dependent H2O2 generation features originate due to the presence of surface oxides and adsorbed hydrogen; this is further confirmed using halide ions (Cl(-) and Br(-)) and peroxide as the external impurities.

  12. Experimental and Modeling Study on Reduction of Hematite Pellets by Hydrogen Gas

    Science.gov (United States)

    Kazemi, Mania; Pour, Mohsen Saffari; Sichen, Du

    2017-01-01

    Gaseous reduction by hydrogen was performed for three types of hematite pellets, two from industry and one prepared in the laboratory. The reduction mechanisms of the pellets were studied based on the morphologies of the partially reduced samples. Two mechanisms were found, the mechanisms of the two types of industrial pellets being very similar. The degree of reduction was followed as a function of time for each type of pellets. On the basis of the reaction mechanism of the industrial pellets, a mathematical model was developed. As a pioneer effort, the model combined the computational fluid dynamics approach for the flow and mass transfer in the gas phase with model of gas diffusion in the solid phase as well as the description of the chemical reaction at the reaction sites. The calculation results agreed well with the experimentally obtained reduction curves. The present work also emphasized the importance of evaluation of the reduction mechanisms and the properties of different types of iron ore pellets prior to developing a process model. While the present approach has established a good foundation for the dynamic modeling of the shaft reactor, more efforts are required to accomplish a realistic process model.

  13. Experimental and Modeling Study on Reduction of Hematite Pellets by Hydrogen Gas

    Science.gov (United States)

    Kazemi, Mania; Pour, Mohsen Saffari; Sichen, Du

    2017-04-01

    Gaseous reduction by hydrogen was performed for three types of hematite pellets, two from industry and one prepared in the laboratory. The reduction mechanisms of the pellets were studied based on the morphologies of the partially reduced samples. Two mechanisms were found, the mechanisms of the two types of industrial pellets being very similar. The degree of reduction was followed as a function of time for each type of pellets. On the basis of the reaction mechanism of the industrial pellets, a mathematical model was developed. As a pioneer effort, the model combined the computational fluid dynamics approach for the flow and mass transfer in the gas phase with model of gas diffusion in the solid phase as well as the description of the chemical reaction at the reaction sites. The calculation results agreed well with the experimentally obtained reduction curves. The present work also emphasized the importance of evaluation of the reduction mechanisms and the properties of different types of iron ore pellets prior to developing a process model. While the present approach has established a good foundation for the dynamic modeling of the shaft reactor, more efforts are required to accomplish a realistic process model.

  14. Dimeric [Mo2 S12 ](2-) Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen-Evolution Electrocatalysis.

    Science.gov (United States)

    Huang, Zhongjie; Luo, Wenjia; Ma, Lu; Yu, Mingzhe; Ren, Xiaodi; He, Mingfu; Polen, Shane; Click, Kevin; Garrett, Benjamin; Lu, Jun; Amine, Khalil; Hadad, Christopher; Chen, Weilin; Asthagiri, Aravind; Wu, Yiying

    2015-12-07

    Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo2 S12 ](2-) , as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo2 S12 ](2-) is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo2 S12 ](2-) exhibits a hydrogen adsorption free energy near zero (-0.05 eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

  15. Dimeric [Mo₂S₁₂]²⁻ Cluster: A Molecular Analogue of MoS₂ Edges for Superior Hydrogen-Evolution Electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhongjie; Luo, Wenjia; Ma, Lu; Yu, Mingzhe; Ren, Xiaodi; He, Mingfu; Polen, Shan; Click, Kevin; Garrett, Benjamin R.; Lu, Jun; Amine, Khalil

    2015-12-07

    Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo₂S₁₂]²⁻, as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo₂S₁₂]²⁻ is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo₂S₁₂]²⁻ exhibits a hydrogen adsorption free energy near zero (-0.05eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

  16. [Evolution of disposable diapers and reduction of diaper dermatitis].

    Science.gov (United States)

    Erasala, G-N; Merlay, I; Romain, C

    2007-05-01

    Keeping babies skin dry in the diaper environment, reducing leaking while increasing absorbency and preventing skin pH increase lead to provide better skin tolerance disposable diapers. During 80's, basic cellulose diapers were replaced by the introduction of absorbent gelling materials (AGM) and since 90's by microbreatheable diapers. These advances in diaper technology have contributed to the reduction of diaper dermatitis.

  17. Electrochemical promotion of NO reduction by hydrogen on a platinum/polybenzimidazole catalyst

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm;

    2003-01-01

    The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference...... and 140 mL/min, respectively), NO reduction increased 20 times even without polarization compared to the high gas flow rate. The electrochemical promotion effect occurs at positive polarization with a maximum increase at approximately 0.08 V and with 1.5 times the zero polarization value. The promotion...... at the negative polarization can be attributed to the electrochemical production of the promoters. At low gas flow rates, a charge-induced change of the strength of chemisorptive bonds can take place....

  18. Visible light active zeolite-based photocatalysts for hydrogen evolution from water

    Energy Technology Data Exchange (ETDEWEB)

    Dubey, Nidhi; Rayalu, Sadhana S.; Labhsetwar, Nitin K.; Devotta, Sukumar [Environmental Materials Unit, National Environmental Engineering Research Institute (NEERI), Nehru Marg, Nagpur, Maharashtra 440020 (India)

    2008-11-15

    Hydrogen, considered as the fuel for future can be produced from non-conventional, renewable and plentiful source like water. Novel zeolite-based materials that show photocatalytic properties in the visible light have been synthesized by incorporating titanium dioxide (TiO{sub 2}), heteropolyacid (HPA) and transition metals like cobalt (Co). These materials show high efficiency for water splitting under visible light irradiation. Hydrogen (H{sub 2}) generation to the tune of 2730 {mu}mol/h/g TiO{sub 2} has been obtained for the composite photocatalyst synthesized. Platinum (Pt) doping has also been attempted in this composite photocatalyst, however, no substantial enhancement in hydrogen generation was observed. The high efficiency of the composite photocatalyst suggests that the TiO{sub 2} which gets effectively dispersed and stabilized on the surface of zeolite works synergistically with transition metal like cobalt and heteropolyacid to make the material active in visible light for photoreduction of water to hydrogen. The aluminosilicate framework of zeolite also contributes towards delayed charge separation. This composite photocatalyst shows improvement in hydrogen evolution rate over other TiO{sub 2} based visibly active photocatalyst reported. (author)

  19. Influences of hydrogen-enriched atmosphere under coke oven gas injection on reduction swelling behaviors of oxidized pellet

    Institute of Scientific and Technical Information of China (English)

    龙红明; 王宏涛; 狄瞻霞; 春铁军; 柳政根

    2016-01-01

    It is of great importance to elucidate reduction swelling behaviors and reaction mechanism of oxidized pellet in hydrogen-enriched atmosphere under coke oven gas injection. In this work, the effects of hydrogen concentration in N2−CO−H2 atmosphere with unchanged CO content on reduction swelling behaviors of oxidized pellet at 1173 K were studied, to clarify the mechanism of hydrogen-enriched reduction and exclude the influences of CO. Then, the reduction swelling behaviors of oxidized pellet at 1173 K in actual atmosphere under coke oven gas (COG) injection, got from the simulation results of multi-fluid blast furnace model, were investigated. The results show that with the concentration of hydrogen increasing in N2−CO−H2 gas from 2% to 18%, the reduction swelling index of pellet decreases from 10.12% to 5.57% while the reduction ratio of pellet increases obviously from 39.85% to 69.58%. In addition, with COG injection rate increasing from 0 to 152.34 m3/t, the reduction swelling index of pellet decreases slightly from 10.71% to 9.54% while the reduction ratio of pellet is increased from 31.57% to 36.39%. The microstructures of pellet are transformed from the platy structure to the flocculent structure.

  20. Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study.

    Science.gov (United States)

    Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc

    2015-10-29

    Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

  1. Harvesting solar light with crystalline carbon nitrides for efficient photocatalytic hydrogen evolution

    KAUST Repository

    Bhunia, Manas Kumar

    2014-08-14

    Described herein is the photocatalytic hydrogen evolution using crystalline carbon nitrides (CNs) obtained by supramolecular aggregation followed by ionic melt polycondensation (IMP) using melamine and 2,4,6-triaminopyrimidine as a dopant. The solid state NMR spectrum of 15N-enriched CN confirms the triazine as a building unit. Controlling the amount and arrangements of dopants in the CN structure can dramatically enhance the photocatalytic performance for H2 evolution. The polytriazine imide (PTI) exhibits the apparent quantum efficiency (AQE) of 15% at 400 nm. This method successfully enables a substantial amount of visible light to be harvested for H2 evolution, and provides a promising route for the rational design of a variety of highly active crystalline CN photocatalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-01

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

  3. Hydrogen and oxygen plasma enhancement in the Cu electrodeposition and consolidation processes on BDD electrode applied to nitrate reduction

    Science.gov (United States)

    Couto, A. B.; Santos, L. C. D.; Matsushima, J. T.; Baldan, M. R.; Ferreira, N. G.

    2011-09-01

    Copper nanoparticle electrodeposition and consolidation processes were studied on boron doped diamond (BDD) electrode submitted to hydrogen and oxygen plasma treatments. The modified BDD films were applied as electrodes for nitrate electroreduction. The results showed that both treatments have a strong influence on the copper deposition and dissolution processes. For BDD treated with hydrogen plasma the copper electrodeposit was homogeneous with high particle density. This behavior was attributed to the BDD surface hydrogenation that improved its conductivity. On the other hand, the treatment with oxygen plasma was important for the copper nanoparticle consolidation on BDD surface, confirmed by the result's reproducibility for nitrate reduction. This performance may be associated with the formation of oxygen groups that can act as anchor points for Cu-clusters, enhancing the interfacial adhesion between diamond and the metal coating. The best electrochemical nitrate reduction response was obtained in acid media, where occurred the separation of the nitrate reduction process and the water reduction reaction.

  4. Low temperature selective catalytic reduction of NO over Pt-Zeolite using hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Ramachandran, B.; Choi, S.; Herman, R.G.; Stenger, H.G.; Sale, J.W.; Lyman, C.E.

    1999-07-01

    It has been found that platinum based zeolite catalysts are very active for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) with hydrogen at low reaction temperatures, i.e. 200 C. The catalysts are active for NOx reduction in the presence of oxygen, water vapor (steam), and sulfur dioxide. It is notable that the use of hydrogen instead of ammonia as the reducing agent greatly reduces the formation of N{sub 2}O from NO over these low temperature catalysts. A testing protocol was established for testing NO reduction catalysts, and the reaction conditions utilized in this study, carried out at approximately ambient pressure, were the following (on a dry basis): NO = 400 ppm, H{sub 2} = 40000-20,000 ppm (0.4--2 vol%), O{sub 2} = 5 vol%, CO{sub 2} = 13 vol%, and N{sub 2} = balance. When water was added to the reactant mixture, it was added so that H{sub 2}O = 8 vol%. The total gas flow, expressed as gas hourly space velocity (GHSV), was 10,000 hr{sup {minus}1}, unless specified otherwise. Comparison tests were carried out using NH{sub 3} = 400 ppm in place of the H{sub 2}. Each of the gases was fed into the reactor gas manifold and controlled by a separate flow meter. The NO, H{sub 2} and NH{sub 3} components were utilized as mixtures in N{sub 2}, while CO{sub 2}, and O{sub 2} were added as pure gases. When experiments were carried out in the presence of sulfur dioxide, the SO{sub 2} was added via a SO{sub 2}/N{sub 2} gas mixture to achieve the desired SO{sub 2} concentration in the reactant gas mixture. In the exit stream, NO and N{sub 2}O were determined by an infrared analyzer.

  5. Cooperative cathode electrode and in situ deposited copper for subsequent enhanced Cd(II) removal and hydrogen evolution in bioelectrochemical systems.

    Science.gov (United States)

    Wang, Qiang; Huang, Liping; Pan, Yuzhen; Zhou, Peng; Quan, Xie; Logan, Bruce E; Chen, Hongbo

    2016-01-01

    Bioelectrochemical systems (BESs) were first operated in microbial fuel cell mode for recovering Cu(II), and then shifted to microbial electrolysis cells for Cd(II) reduction on the same cathodes of titanium sheet (TS), nickel foam (NF) or carbon cloth (CC). Cu(II) reduction was similar to all materials (4.79-4.88mg/Lh) whereas CC exhibited the best Cd(II) reduction (5.86±0.25mg/Lh) and hydrogen evolution (0.35±0.07m(3)/m(3)d), followed by TS (5.27±0.43mg/Lh and 0.15±0.02m(3)/m(3)d) and NF (4.96±0.48mg/Lh and 0.80±0.07m(3)/m(3)d). These values were higher than no copper controls by factors of 2.0 and 5.0 (TS), 4.2 and 2.0 (NF), and 1.8 and 7.0 (CC). These results demonstrated cooperative cathode electrode and in situ deposited copper for subsequent enhanced Cd(II) reduction and hydrogen production in BESs, providing an alternative approach for efficiently remediating Cu(II) and Cd(II) co-contamination with simultaneous hydrogen production.

  6. Mechanism of reduction in hydrogen atmosphere and thermal transformation of synthetic ferrihydrite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Masina, C.J., E-mail: colani.masina@nmmu.ac.za [Centre for HRTEM, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth (South Africa); Neethling, J.H.; Olivier, E.J. [Centre for HRTEM, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth (South Africa); Ferg, E. [Department of Chemistry, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Manzini, S.; Lodya, L.; Mohlala, P.; Ngobeni, M.W. [Sasol Technology R and D, 1 Klasie Havenga Road, Sasolburg (South Africa)

    2015-01-10

    Highlights: • Magnetic measurements used to study thermal transformation of ferrihydrite. • Reduction mechanisms of ferrihydrite were monitored by TPR, MS, and in-situ XRD. • Nanocrystalline Fe was produced by the reducing ferrihydrite in H{sub 2}. • The presence of SiO{sub 2} in ferrihydrite alters the reduction pathway of ferrihydrite. - Abstract: The thermal transformation under vacuum and the reduction behavior in hydrogen atmosphere of 2- and 6-line ferrihydrite (FeOOH·nH{sub 2}O) as well as 2-line FeOOH·nH{sub 2}O deposited onto silica are reported. The investigation methods include magnetization measurements, temperature programmed reduction, in-situ X-ray diffraction and Mössbauer spectroscopy. The thermal transformation of FeOOH·nH{sub 2}O to hematite (α-Fe{sub 2}O{sub 3}) was monitored through changes in the magnetization as a function of temperature; it appears to proceed through the loss of the lattice water and sintering accompanied by improved crystallinity and structural changes. Such a transformation is initiated at T ∼ 580 K for 2-line and 6-line FeOOH·nH{sub 2}O and at T ∼ 660 K for 2-line FeOOH·nH{sub 2}O/SiO{sub 2}, i.e., the presence of SiO{sub 2} appears to inhibit the transformation. SiO{sub 2} also tends to prevent the increase of the crystallite size above a certain threshold value. Reduction reactions are initiated at relatively lower temperatures (∼480 K) implying that a gaseous environment facilitates the thermal dehydration/dehydroxylation process. Three different reduction mechanisms of FeOOH·nH{sub 2}O to metallic iron (α-Fe) are observed: a two-stage process via magnetite (Fe{sub 3}O{sub 4}) as an intermediate phase for 2-line FeOOH·nH{sub 2}O, a three-step reduction involving Fe{sub 3}O{sub 4} and wüstite (FeO) as intermediate phases for 2-line FeOOH·nH{sub 2}O/SiO{sub 2} and a thermal transformation to α-Fe{sub 2}O{sub 3} followed by a two-step reduction via Fe{sub 3}O{sub 4} intermediate for 6-line Fe

  7. High specific surface area Mo2C nanoparticles as an efficient electrocatalyst for hydrogen evolution

    Science.gov (United States)

    Tang, Chaoyun; Sun, Aokui; Xu, Yushuai; Wu, Zhuangzhi; Wang, Dezhi

    2015-11-01

    Mo2C nanoparticles with high specific surface area (120 m2 g-1) are successfully synthesized using a typical and low-cost monosaccharide of glucose via a facile calcination and subsequent reduction process. The HER functions of the obtained Mo2C nanoparticles are investigated and the effect of reduction time in hydrogen is also discussed. It is found that η-MoC can be obtained at 800 °C with a reduction time of 10 min, but the formation of β-Mo2C phase requires more than 20 min. Moreover, the β-Mo2C obtained with a reduction time of 20 min exhibits the best HER activity with a small Tafel slope of 55 mV dec-1 and a large current density of 60 mA cm-2 at -200 mV, which is among the best records over Mo2C-based HER catalysts.

  8. Growth and Tunable Surface Wettability of Vertical MoS2 Layers for Improved Hydrogen Evolution Reactions.

    Science.gov (United States)

    Bhimanapati, Ganesh R; Hankins, Trevor; Lei, Yu; Vilá, Rafael A; Fuller, Ian; Terrones, Mauricio; Robinson, Joshua A

    2016-08-31

    Layered materials, especially the transition metal dichalcogenides (TMDs), are of interest for a broad range of applications. Among the class of TMDs, molybdenum disulfide (MoS2) is perhaps the most studied because of its natural abundance and use in optoelectronics, energy storage and energy conversion applications. Understanding the fundamental structure-property relations is key for tailoring the enhancement in the above-mentioned applications. Here, we report a controlled powder vaporization synthesis of MoS2 flower-like structures consisting of vertically grown layers of MoS2 exhibiting exposed edges. This growth is readily achievable on multiple substrates, such as graphite, silicon, and silicon dioxide. The resulting MoS2 flowers are highly crystalline and stoichiometric. Further observations using contact angle indicate that MoS2 flowers exhibit the highest reported contact angle of ∼160 ± 10°, making the material super hydrophobic. This surface wettability was further tuned by changing the edge chemistry of the MoS2 flowers using an ozone etching treatment. Hydrogen evolution reaction (HER) measurements indicate that the surface treated with UV-ozone showed a reduction in the Tafel slope from 185 to 54 mV/dec, suggesting an increase in the amount of reactive surface to generate hydrogen.

  9. The microstructure evolution of hydrogenated microcrystalline germanium promoted by power gradient method

    Science.gov (United States)

    Wang, Xinyu; Ni, Jian; Li, Chang; Sun, Xiaoxiang; Li, Zhenglong; Cai, Hongkun; Li, Juan; Zhang, Jianjun

    2016-12-01

    This paper studies the microstructure evolution of hydrogenated microcrystalline germanium (μc-Ge:H) thin films deposited by plasma enhanced chemical vapor deposition (PECVD). There is an amorphous incubation layer formed in the initial deposition stage of μc-Ge:H thin film. It is demonstrated that the thickness of incubation layer can be reduced by high hydrogen dilution and high discharge power method. However, at high hydrogen dilution, the deposition rate of μc-Ge:H appears a sharply decrease. Using a high discharge power can compensate the deposition rate decrease but lead to decrease of average grain size and appearance of micro-void in the μc-Ge:H thin film. In addition, by comparing two thickness groups of μc-Ge:H thin films deposited at different discharge powers, it is noticed that the evolution process relates to the formation of crystal nucleuses. Thus, a power gradient method is proposed to understand the mechanism of nucleation and crystal growth in the initial deposition process of μc-Ge:H films. Finally, by power gradient method, the incubation layer thickness of μc-Ge:H thin films has been decreased to less than 6 nm. Moreover, Raman scattering spectra shows a 38 nm μc-Ge:H film has a crystal fraction (XC) of 62.4%. Meanwhile, the mobility of TFT devices shows the improved electrical property of μc-Ge:H film deposited by power gradient method.

  10. Autotrophic antimonate bio-reduction using hydrogen as the electron donor.

    Science.gov (United States)

    Lai, Chun-Yu; Wen, Li-Lian; Zhang, Yin; Luo, Shan-Shan; Wang, Qing-Ying; Luo, Yi-Hao; Chen, Ran; Yang, Xiaoe; Rittmann, Bruce E; Zhao, He-Ping

    2016-01-01

    Antimony (Sb), a toxic metalloid, is soluble as antimonate (Sb(V)). While bio-reduction of Sb(V) is an effective Sb-removal approach, its bio-reduction has been coupled to oxidation of only organic electron donors. In this study, we demonstrate, for the first time, the feasibility of autotrophic microbial Sb(V) reduction using hydrogen gas (H2) as the electron donor without extra organic carbon source. SEM and EDS analysis confirmed the production of the mineral precipitate Sb2O3. When H2 was utilized as the electron donor, the consortium was able to fully reduce 650 μM of Sb(V) to Sb(III) in 10 days, a rate comparable to the culture using lactate as the electron donor. The H2-fed culture directed a much larger fraction of it donor electrons to Sb(V) reduction than did the lactate-fed culture. While 98% of the electrons from H2 were used to reduce Sb(V) by the H2-fed culture, only 12% of the electrons from lactate was used to reduce Sb(V) by the lactate-fed culture. The rest of the electrons from lactate went to acetate and propionate through fermentation, to methane through methanogenesis, and to biomass synthesis. High-throughput sequencing confirmed that the microbial community for the lactate-fed culture was much more diverse than that for the H2-fed culture, which was dominated by a short rod-shaped phylotype of Rhizobium (α-Protobacteria) that may have been active in Sb(V) reduction.

  11. A kinetic study of copper(II) oxide powder reduction with hydrogen, based on thermogravimetry

    Energy Technology Data Exchange (ETDEWEB)

    Jelic, Dijana [Faculty of Medicine, Departmet of Pharmacy - Chair of Physical Chemistry, University of Banja Luka, Banja Luka, Bosnia and Herzegovina (Bosnia and Herzegowina); Tomic-Tucakovic, Biljana [Institute of General and Physical Chemistry, Studentski trg 12, 11158 Belgrade (Serbia); Mentus, Slavko, E-mail: slavko@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12, 11185 Belgrade (Serbia)

    2011-07-10

    Highlights: {yields} The reduction of CuO by hydrogen was studied by thermogravimetry. {yields} The particle size of the samples varied inside the submicron range. {yields} The experimental data were fitted by means of a nucleation-growth model. {yields} The particle size influenced the kinetic parameters but not the reaction model. - Abstract: The reduction of powdery copper(II) oxide was carried out in a stream of gaseous mixture 25% H{sub 2} + Ar, and followed by thermogravimetry. The two samples of different history were studied: the commercial one, and that synthesized by citrate gel combustion method. The characterization of the starting materials, based on X-ray diffractometry and scanning electron microscopy, indicated equal crystal structure, but different particle size and morphology. The particle size and shape of the metallic particles obtained upon the reduction were observed by means of electron microscope. By a nonlinear regression analysis by means of a software Kinetics05, the experimental data were fitted with the nucleation-growth kinetic model, and the corresponding kinetic parameters were determined.

  12. Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

    Science.gov (United States)

    Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan

    2017-04-01

    Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H2-production rate of 920 μmol h-1, exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H2-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst.

  13. Highly efficient photocatalytic hydrogen evolution from nickel quinolinethiolate complexes under visible light irradiation

    Science.gov (United States)

    Rao, Heng; Yu, Wen-Qian; Zheng, Hui-Qin; Bonin, Julien; Fan, Yao-Ting; Hou, Hong-Wei

    2016-08-01

    Earth-abundant metal complexes have emerged as promising surrogates of platinum for catalyzing the hydrogen evolution reaction (HER). In this study, we report the design and synthesis of two novel nickel quinolinethiolate complexes, namely [Ni(Hqt)2(4, 4‧-Z-2, 2‧-bpy)] (Hqt = 8-quinolinethiol, Z = sbnd H [1] or sbnd CH3 [2], bpy = bipyridine). An efficient three-component photocatalytic homogeneous system for hydrogen generation working under visible light irradiation was constructed by using the target complexes as catalysts, triethylamine (TEA) as sacrificial electron donor and xanthene dyes as photosensitizer. We obtain turnover numbers (TON, vs. catalyst) for H2 evolution of 5923/7634 under the optimal conditions with 5.0 × 10-6 M complex 1/2 respectively, 1.0 × 10-3 M fluorescein and 5% (v/v) TEA at pH 12.3 in EtOH/H2O (1:1, v/v) mixture after 8 h irradiation (λ > 420 nm). We discuss the mechanism of H2 evolution in the homogeneous photocatalytic system based on fluorescence spectrum and cyclic voltammetry data.

  14. Graphene/TiO$_2$ hydrogel: a potential catalyst to hydrogen evolution reaction

    Indian Academy of Sciences (India)

    VIRGIL CHRISTIAN CASTILLO; JULIET Q DALAGAN

    2016-10-01

    In this study, graphene was synthesized from graphite. Graphite was oxidized via modified Hummer’s method and sonicated to form graphene oxide (GO). Infrared spectroscopy revealed the successful oxidation of graphite by the emergence of oxygen functionalities. The spectrum of GO showed peaks at 3270, 1629, 1227 and 1096 cm$^{−1}$, indicating O–H, C=O, C–OH and C–O–C functional groups, respectively. Graphene hydrogels were prepared by the addition of L-ascorbic acid to GO suspensions and subsequent heating at 90$^{\\circ}$C. Composite hydrogels of graphene and titanium (IV) oxide (TiO$_2$) were synthesized with various TiO$_2$ to GO mass ratios. Composites were applied to photocatalytic hydrogen evolution reaction (HER) and the hydrogen gas produced was analysed by gas chromatography with thermal conductivity detector. Highest HER yield was 66.00% H$_2$.

  15. Introductory lecture on corrosion chemistry: a focus on anodic hydrogen evolution on Al and Mg.

    Science.gov (United States)

    Frankel, G S; Fajardo, S; Lynch, B M

    2015-01-01

    The increase in the rate of hydrogen evolution (HE) on dissolving Mg surfaces with increasing anodic current density or potential, which is sometimes called the negative difference effect, has been the topic of much discussion in recent years. A review of the very recent contributions to this subject is given in this paper. Increased catalytic activity of the corrosion product layer, either from the accumulated impurities or from the Mg oxy-hydroxide itself, is shown to have a minor influence on the anodic HE observed on dissolving Mg at high anodic current densities and potentials. Al exhibits similar characteristics during anodic polarization in concentrated HCl, although the anodic HE rate on Al is less than on Mg. Possible mechanisms for the anodic hydrogen are provided and implications in the area of intergranular corrosion and environmental cracking are discussed.

  16. Hydrogen evolution at catalytically-modified nickel foam in alkaline solution

    Science.gov (United States)

    Pierozynski, Boguslaw; Mikolajczyk, Tomasz; Kowalski, Ireneusz M.

    2014-12-01

    This work reports on hydrogen evolution reaction (HER) studied at catalytically modified nickel foam material. The HER was examined in 0.1 M NaOH solution on as received, as well as for Pd and Ru-activated nickel foam catalyst materials, produced via spontaneous deposition of trace amounts of these elements. Catalytic modification of nickel foam results in significant facilitation of the HER kinetics, as manifested through considerably reduced, a.c. impedance-derived values of charge-transfer resistance parameter and substantially altered Tafel polarization slopes. The presence of catalytic additives is clearly revealed through hydrogen underpotential deposition (H UPD) phenomenon, as well as spectroscopically from SEM (Scanning Electron Microscopy) analysis.

  17. High Intrinsic Catalytic Activity of Two-Dimensional Boron Monolayers for Hydrogen Evolution Reaction

    CERN Document Server

    Shi, Li; Ouyang, Yixin; Wang, Jinlan

    2016-01-01

    Two-dimensional (2D) boron monolayers have been successfully synthesized on silver substrate very recently. Their potential application is thus of great significance. In this work, we explore the possibility of boron monolayers (BMs) as electrocatalysts for hydrogen evolution reaction (HER) by first-principle method. Our calculations show that the BMs are active catalysts for HER with nearly zero free energy of hydrogen adsorption, metallic conductivity and plenty of active sites in the basal plane. The effect of the substrate on the HER activity is further assessed. It is found that the substrate has a positive effect on the HER performance caused by the competitive effect of mismatch strain and charge transfer. The indepth understanding of the structure dependent HER activity is also provided.

  18. Factors regulating nitrogenase activity and hydrogen evolution in Azolla-Anabaena symbiosis

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, M.; Kumar, A.; Kumar, H.D. (Banaras Hindu Univ., Varanasi (India). Dept. of Botany)

    1989-01-01

    Nitrogenase activity and H{sub 2} production capacity have been studied in intact Azolla plants. Under aerobic conditions the plants showed a C{sub 2}H{sub 2} reduction rate of 6.65 nmoles C{sub 2}H{sub 4} mg {sup -1} fresh weight in light at 48 h. Considerable activity was also present in the dark. Though H{sub 2} evolution was detected under aerobic conditions there was multifold stimulation under anaerobic conditions. There was no significant change in nitrogenase activity under anaerobic conditions. Increasing concentrations of O{sub 2} inhibited nitrogenase activity but 5% O{sub 2} proved stimulatory for H{sub 2} evolution in light. In the dark, there was a gradual stimulation in H{sub 2} evolution even up to 20% O{sub 2}. The addition of combined nitrogen sources, namely NH{sub 4}Cl or KNO{sub 3} (10 mM), resulted in complete inhibition of the C{sub 2}H{sub 2}-reduction activity within 48 h, but H{sub 2} evolution was not inhibited. Indeed, these combined nitrogen sources stimulated H{sub 2} evolution. Though nitrogenase activity was affected, the heterocyst frequency remained unaltered. Phosphate addition resulted in significant stimulation of nitrogenase and H{sub 2} evolution activity. These results suggest that nitrogenase and H{sub 2} evolution activity in Azolla are affected by a number of factors which show a differential effect on nitrogenase and H{sub 2} evolution. Furthermore, our results indicate the presence of a soluble reversible hydrogenase in Azolla. (author).

  19. Effects of pretreatment and reduction on the Co/Al2O3 catalyst for CO hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Xiaoping Dai; Changchun Yu

    2008-01-01

    The purpose of this study was to investigate the effect of preadsorbed CO at different temperatures,calcination temperatures,the combined influence of reduction temperature and time,and pretreatment using hydrogen or syngas as reduction agents on the F-T synthesis(FTS)activity and selectivity of Co/Al2O3 catalyst.The reactivity of the carbon species at higher preadsorption temperature with H2 in TPSR decreased,whereas the carbon-containing species showed higher reactivity over Co/Al2O3 catalyst with 10W calcination temperature.This agreed well with the order of catalytic activity for F-T synthesis on this catalyst.The catalytic activity of the catalyst varied with reduction temperature and time remarkably.CODEX optimization gave an optimum reduction temperature of 756 K and reduction time of 6.2 h and estimated C5+ yield perfectly.The pretreatment of Co/Al2O3 catalyst with different reduction agents (hydrogen or syngas)showed important influences on the catalytic performance.A high CO conversion and C5+yield were obtained on the catalyst reduced by hydrogen,wherea smethane selectivity on the catalyst reduced by syngas was much higher than that on the catalyst reduced by hydrogen.

  20. Hydrogen reduction in heat transfer fluid in parabolic trough CSP plants

    Science.gov (United States)

    Lang, Christoph; Belkheir, Mohamed; Kim, Eungkyu; Davidson, Chet; Holden, Bruce; Hook, Bruce

    2017-06-01

    Hydrogen (H2) has been found to be generated in very small proportions when diphenyl oxide/ biphenyl heat transfer fluid (HTF) is operated at temperatures close to 400°C. At such temperatures, H2 can permeate through steel walls to the vacuum space of parabolic trough (PT) solar receivers, where it increases heat losses that can significantly impact the economics of PT concentrated solar power plants. A novel process for the reduction of the H2 concentration in HTF via stripping and gas separation has been simulated for the operation in PT CSP plants. Applying the proposed process, the concentration of H2 in HTF can be reduced down to 1 ppb. A cost comparison between the H2 separation process and frequent PT receivers replacement was conducted and found that proposed H2 removal process is more economic.

  1. Novel Electrochemical Synthesis of Polypyrrole/Ag Nanocomposite and Its Electrocatalytic Performance towards Hydrogen Peroxide Reduction

    Directory of Open Access Journals (Sweden)

    Ruma Gupta

    2015-01-01

    Full Text Available A simple electrochemical method of synthesis of polypyrrole/silver (PPy/Ag nanocomposite is presented. The method is based on potentiodynamic polymerization of pyrrole followed by electrodeposition of silver employing a single potentiostatic pulse. The synthesized PPy film has embedded Ag nanocubes. The morphology and structure of the resulting nanocomposite were characterized by field emission scanning electron microscopy and X-ray diffraction. Electron paramagnetic resonance studies showed that silver nanoparticle deposition on polypyrrole leads to an increase in carrier density, indicative of enhanced conductivity of the resulting composite. Electrocatalytic performance of the prepared composite was examined for reduction of hydrogen peroxide and was compared with corresponding PPy film and bare glassy carbon electrode.

  2. Novel osmium-based electrocatalysts for oxygen reduction and hydrogen oxidation in acid conditions

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Borja-Arco, E.; Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro, Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Av. Cerro Blanco No. 141, Col. Colinas del Cimatario, Queretaro, Qro. 76090 (Mexico)

    2008-03-01

    In this work, novel osmium electrocatalysts for oxygen reduction and hydrogen oxidation in 0.5 M H{sub 2}SO{sub 4}, have been developed. The syntheses were performed by thermolysis of Os{sub 3}(CO){sub 12} and Os{sub 3}(CO){sub 12}/Vulcan {sup registered}, in two reaction media, N{sub 2} (in the absence of solvents) and n-octane, in order to evaluate the effect of these parameters on the electrocatalytic activity of the new materials. In the solvent-free pathway, different reaction temperatures (in the 120-320 C range) and times (5, 7 and 10 h) were explored; the syntheses in n-octane were done at reflux temperature, for 30 and 72 h. The products were characterized structurally by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy, and electrochemically by room temperature rotating disk electrode measurements, using cyclic and linear sweep voltammetry. Some materials prepared in both reaction media can efficiently perform the hydrogen oxidation and/or oxygen reduction reaction, i.e. those prepared by pyrolysis of Os{sub 3}(CO){sub 12}/Vulcan {sup registered} in N{sub 2}, at 180 C/7 h, 320 C/5 h, 320 C/7 h and 320 C/10 h, as well as the materials synthesized in n-octane (from both Os precursors); the latter, in addition, have the important property of being tolerant to carbon monoxide to some extent, in contrast to platinum, which is easily deactivated even by traces of CO. (author)

  3. Effect of gas composition on the kinetics of iron oxide reduction in a hydrogen production process

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Krzysztof; Lorethova, Hana; Stonawski, Lubor; Wiltowski, Tomasz [Coal Research Center, Southern Illinois University Carbondale, Carbondale, IL (United States); Mondal, Kanchan; Szymanski, Tomasz [Department of Mechanical Engineering and Energy Processes, Carbondale, IL (United States)

    2005-12-01

    Fe{sub 2}O{sub 3} is a suitable oxygen transfer agent for converting CO present in syngas to CO{sub 2} for its eventual separation from H{sub 2}. However, H{sub 2} also reacts with iron oxide to form H{sub 2}O. In order to evaluate the reactions for hydrogen enrichment, investigations into Fe{sub 2}O{sub 3} to FeO reduction kinetics in the presence of syngas constituents were conducted. The reaction kinetic parameters were estimated based on the thermogravimetric data. Hancock and Sharp method of comparing the kinetics of isothermal solid-state reactions, based on Johnson-Mehl-Avrami-Erofe'ev equation describing nucleation and growth processes, was applied. The experimental results indicate that the reduction is initially a surface-controlled process, but once a thin layer of lower iron oxides (magnetite, wusite) is formed on the surface, the mechanism shifts to diffusion control. It was concluded that this initial stage of the reaction process could be interpreted as a both phase-boundary-controlled reaction and the two-dimensional nucleation and growth (transformation of the crystallographic lattices of higher oxide to lattices of lower oxide) at the gas/iron oxide interface. Comparison of the reaction courses for both the reducing agents (H{sub 2}, CO) independently and for their mixture was performed. It was found, that the reaction rate increases with, both, temperature and the hydrogen content in inlet gas. The activation energy values were estimated and compared. (author)

  4. A high-performance metal-free hydrogen-evolution reaction electrocatalyst from bacterium derived carbon

    OpenAIRE

    2015-01-01

    We report a sustainable approach to obtain carbon materials with nitrogen and phosphorus dual functionalities from a common bacterium strain (S. aureus) as a highly efficient hydrogen-evolution reaction (HER) catalyst. With mesoporous structure introduced by ZnCl2 salt and cathodic activation, it demonstrates an onset overpotential as low as 76 mV, a Tafel slope of 58.4 mV dec(-1) and a large normalized exchange current density of 1.72 x 10(-2) mA cm(-2), which are comparable to those of hith...

  5. Mesoporous carbon nitride-tungsten oxide composites for enhanced photocatalytic hydrogen evolution.

    Science.gov (United States)

    Kailasam, Kamalakannan; Fischer, Anna; Zhang, Guigang; Zhang, Jinshui; Schwarze, Michael; Schröder, Marc; Wang, Xinchen; Schomäcker, Reinhard; Thomas, Arne

    2015-04-24

    Composites of mesoporous polymeric carbon nitride and tungsten(VI) oxide show very high photocatalytic activity for the evolution of hydrogen from water under visible light and in the presence of sacrificial electron donors. Already addition of very small amounts of WO3 yields up to a twofold increase in the efficiency when compared to bulk carbon nitrides and their composites and more notably even to the best reported mesoporous carbon nitride-based photocatalytic materials. The higher activity can be attributed to the high surface area and synergetic effect of the carbon nitrides and the WO3 resulting in improved charge separation through a photocatalytic solid-state Z-scheme mechanism.

  6. Synthesis of Ni3S2 nanotube arrays on nickel foam by catalysis of thermal reduced graphene for hydrogen evolution reaction

    Science.gov (United States)

    Jinlong, Lv; Miura, Hideo; Meng, Yang; Tongxiang, Liang

    2017-03-01

    The thermal reduced graphene oxide deposition on nickel foam was successfully synthesized by ultrasonic and subsequent thermal reduction process. Ultrathin mesoporous Ni3S2 was formed on the bare nickel foam after hydrothermal process, while Ni3S2 nanotube arrays were formed on the surface of nickel foam with the thermal reduced graphene oxide due to catalysis action of thermal reduced graphene oxide. The resulting Ni3S2 nanotube arrays exhibited higher catalytic activity than ultrathin mesoporous Ni3S2 for hydrogen evolution reaction. In addition, and excellent stability was also obtained in Ni3S2 nanotube arrays.

  7. Computational Fluid Dynamics Simulation of the Hydrogen Reduction of Magnetite Concentrate in a Laboratory Flash Reactor

    Science.gov (United States)

    Fan, De-Qiu; Sohn, H. Y.; Mohassab, Yousef; Elzohiery, Mohamed

    2016-08-01

    A three-dimensional computational fluid dynamics (CFD) model was developed to study the hydrogen reduction of magnetite concentrate particles in a laboratory flash reactor representing a novel flash ironmaking process. The model was used to simulate the fluid flow, heat transfer, and chemical reactions involved. The governing equations for the gas phase were solved in the Eulerian frame of reference while the particles were tracked in the Lagrangian framework. The change in the particle mass was related to the chemical reaction and the particle temperature was calculated by taking into consideration the heat of reaction, convection, and radiation. The stochastic trajectory model was used to describe particle dispersion due to turbulence. Partial combustion of H2 by O2 injected through a non-premixed burner was also simulated in this study. The partial combustion mechanism used in this model consisted of seven chemical reactions involving six species. The temperature profiles and reduction degrees obtained from the simulations satisfactorily agreed with the experimental measurements.

  8. Computational Fluid Dynamics Simulation of the Hydrogen Reduction of Magnetite Concentrate in a Laboratory Flash Reactor

    Science.gov (United States)

    Fan, De-Qiu; Sohn, H. Y.; Mohassab, Yousef; Elzohiery, Mohamed

    2016-12-01

    A three-dimensional computational fluid dynamics (CFD) model was developed to study the hydrogen reduction of magnetite concentrate particles in a laboratory flash reactor representing a novel flash ironmaking process. The model was used to simulate the fluid flow, heat transfer, and chemical reactions involved. The governing equations for the gas phase were solved in the Eulerian frame of reference while the particles were tracked in the Lagrangian framework. The change in the particle mass was related to the chemical reaction and the particle temperature was calculated by taking into consideration the heat of reaction, convection, and radiation. The stochastic trajectory model was used to describe particle dispersion due to turbulence. Partial combustion of H2 by O2 injected through a non-premixed burner was also simulated in this study. The partial combustion mechanism used in this model consisted of seven chemical reactions involving six species. The temperature profiles and reduction degrees obtained from the simulations satisfactorily agreed with the experimental measurements.

  9. Metal diselenide nanoparticles as highly active and stable electrocatalysts for the hydrogen evolution reaction

    Science.gov (United States)

    Liang, Jia; Yang, Yingchao; Zhang, Jing; Wu, Jingjie; Dong, Pei; Yuan, Jiangtan; Zhang, Gengmin; Lou, Jun

    2015-09-01

    In this communication, nickel diselenide (NiSe2) nanoparticles are synthesized by a facile and low-cost hydrothermal method. The synthesis method can be extended to other metal diselenides as well. The electrode made of NiSe2 exhibits superior electrocatalytic activity in the hydrogen evolution reaction (HER). A low Tafel slope of 31.1 mV per decade is achieved for NiSe2, which is comparable to that of platinum (~30 mV per decade). Moreover, the catalytic activity of NiSe2 is very stable and no obvious degradation is found even after 1000 cyclic voltammetric sweeps.In this communication, nickel diselenide (NiSe2) nanoparticles are synthesized by a facile and low-cost hydrothermal method. The synthesis method can be extended to other metal diselenides as well. The electrode made of NiSe2 exhibits superior electrocatalytic activity in the hydrogen evolution reaction (HER). A low Tafel slope of 31.1 mV per decade is achieved for NiSe2, which is comparable to that of platinum (~30 mV per decade). Moreover, the catalytic activity of NiSe2 is very stable and no obvious degradation is found even after 1000 cyclic voltammetric sweeps. Electronic supplementary information (ESI) available: Experimental section, additional figures and tables. See DOI: 10.1039/c5nr03724g

  10. Kinetics of Hydrogen Evolution on Copper Electrode Involving Organic Acids as Proton Donors

    Directory of Open Access Journals (Sweden)

    A. Survila

    2011-01-01

    Full Text Available Linear potential sweep (LPS voltammetry was applied to study the kinetics of hydrogen evolution in solutions containing glycolic, malic, tartaric, and gluconic acids. The CE mechanism of hydrogen evolution was analyzed invoking the 2nd Fick's law equations supplemented by terms that account for chemical interactions between diffusing particles. Acids are considered as components that are capable of releasing hydrated protons taking part in the charge-transfer step. Current peaks observed on LPS voltammograms are in linear dependence on ν (ν is the potential sweep rate. They obey well-known relationships obtained for simple redox processes, provided that the concentration of oxidant is treated as total concentration of proton donors. Determination of surface concentrations as current density functions makes it possible to transform LPS voltammograms into linear Tafel plots normalized with respect to the surface concentration of hydronium ions. Similar kinetic parameters (α≈0.6 and i0≈ 10 μA cm−2 obtained at pH 3 for all OA solutions indicate that the nature of OA has no noticeable influence on the charge-transfer process.

  11. On the mechanism of hydrogen evolution catalysis by proteins: A case study with bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Doneux, Th., E-mail: tdoneux@ulb.ac.b [Chimie Analytique et Chimie des Interfaces, Faculte des Sciences, Universite Libre de Bruxelles, Boulevard du Triomphe 2, CP 255, B-1050 Bruxelles (Belgium); Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic); Ostatna, Veronika [Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic); Palecek, Emil, E-mail: palecek@ibp.cz [Institute of Biophysics, Academy of Sciences of the Czech Republic, Kralovopolska 135, 612 65 Brno (Czech Republic)

    2011-10-30

    Highlights: > Proteins catalyse hydrogen evolution at mercury electrodes. > The adsorbed protein is the mediator and the buffer proton donor is the substrate. > The characteristics of the catalytic peak are connected to the protein properties. - Abstract: The catalysis of the hydrogen evolution reaction (HER) by proteins has been known for decades but was only recently found to be useful for electroanalytical purposes. The mechanism of the catalytic process is investigated at hanging mercury drop electrodes by cyclic voltammetry, with bovine serum albumin as a model system. It is shown that the catalyst is the protein in the adsorbed state. The influence of various parameters such as the accumulation time, scan rate or buffer concentration is studied, and interpreted in the framework of a surface catalytic mechanism. Under the experimental conditions used in the work, a 'total catalysis' phenomenon takes place, the rate of HER being limited by the diffusion of the proton donor. The adequacy of the existing models is discussed, leading to a call for the development of more refined models.

  12. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution.

    Science.gov (United States)

    Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

    2015-08-07

    Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s(-1) at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

  13. Influence of zeolitic structure on photoreduction property and hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chatti, Ravikrishna V.; Dubey, Nidhi; Joshi, Meenal V.; Labhsetwar, Nitin K.; Rayalu, Sadhana S. [National Environmental Engineering Research Institute (NEERI-CSIR), Environmental Materials Unit, Nehru Marg, 440020 Nagpur, Maharashtra (India); Joshi, P.N. [National Chemical Laboratory (NCL-CSIR), Pune (India)

    2010-03-15

    A new photocatalytic material developed by supporting TiO{sub 2} in combination with transition metal ion like cobalt and heteropolyacid (HPA) on the surface is facilitating enhanced photoreduction of water and methyl orange. Zeolites being a solid acid play an important role in the electron transfer reaction, facilitated by the Lewis acid sites in the form of aluminium ions. In the present work, four different zeolite matrices namely, NaY zeolite, ultrastable zeolite Y, beta zeolite and titanium silicate-1 have been used for the synthesis of new photocatalytic materials. These materials have been evaluated for water splitting by an initial screening procedure using methyl orange photoreduction. The photocatalyst containing Na Y has emerged as a potential photocatalyst with hydrogen evolution rate of 2730 {mu}mol/h/g of TiO{sub 2}. Hydrogen evolution was not observed for the composite photocatalysts synthesized using the other zeolite matrices. It has been observed that physico-chemical properties like Si/Al ratio, acidity and basicity of the zeolite support have a tremendous influence on the photoreduction property of these zeolite matrices. (author)

  14. Enhanced Hydrogen Evolution Reactions on Nanostructured Cu2ZnSnS4 (CZTS) Electrocatalyst

    Science.gov (United States)

    Digraskar, Renuka V.; Mulik, Balaji B.; Walke, Pravin S.; Ghule, Anil V.; Sathe, Bhaskar R.

    2017-08-01

    A novel and facile one-step sonochemical method is used to synthesize Cu2ZnSnS4 (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer-Emmett-Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density -130 mA/cm2, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm2, excellent stability (> 500 cycles) and lower charge transfer resistance. This sonochemically fabricated CZTSs nanoparticles are leading to significantly reduce cell cost and simplification of preparation process over existing high efficiency Pt and other nobel metal-free cathode electrocatalyst.

  15. Reductive genome evolution at both ends of the bacterial population size spectrum.

    Science.gov (United States)

    Batut, Bérénice; Knibbe, Carole; Marais, Gabriel; Daubin, Vincent

    2014-12-01

    Bacterial genomes show substantial variations in size. The smallest bacterial genomes are those of endocellular symbionts of eukaryotic hosts, which have undergone massive genome reduction and show patterns that are consistent with the degenerative processes that are predicted to occur in species with small effective population sizes. However, similar genome reduction is found in some free-living marine cyanobacteria that are characterized by extremely large populations. In this Opinion article, we discuss the different hypotheses that have been proposed to account for this reductive genome evolution at both ends of the bacterial population size spectrum.

  16. Efficient Electrocatalyst for the Hydrogen Evolution Reaction Derived from Polyoxotungstate/Polypyrrole/Graphene.

    Science.gov (United States)

    Wang, Xiao-Li; Tang, Yu-Jia; Huang, Wei; Liu, Chun-Hui; Dong, Long-Zhang; Li, Shun-Li; Lan, Ya-Qian

    2017-06-09

    Efficient hydrogen evolution reaction (HER) from water by electrocatalysis using cost-effective materials is critical to realize the clean hydrogen production. Herein, with controlling the structure and composition of polyoxotungstate/conductive polypyrrole/graphene (PCG) precursor precisely and followed by a temperature-programmed reaction, we developed a highly active and stable catalyst: NC@Wx C/NRGO (NC: nitrogen-doped porous carbon, NRGO: nitrogen-doped reduced graphene oxide). The composite presents splendid performance towards HER in acidic media, with a small onset overpotential of 24 mV versus RHE (reversible hydrogen electrode), a low Tafel slope of 58.4 mV dec(-1) , a low overpotential of 100 mV at 10 mA cm(-2) , and remarkable long-term cycle stability. This is one of the highest HER catalysts among the tungsten carbide-based materials ever reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster

    Science.gov (United States)

    Tymoczko, Jakub; Calle-Vallejo, Federico; Schuhmann, Wolfgang; Bandarenka, Aliaksandr S.

    2016-03-01

    Although the hydrogen evolution reaction (HER) is one of the fastest electrocatalytic reactions, modern polymer electrolyte membrane (PEM) electrolysers require larger platinum loadings (~0.5-1.0 mg cm-2) than those in PEM fuel cell anodes and cathodes altogether (~0.5 mg cm-2). Thus, catalyst optimization would help in substantially reducing the costs for hydrogen production using this technology. Here we show that the activity of platinum(111) electrodes towards HER is significantly enhanced with just monolayer amounts of copper. Positioning copper atoms into the subsurface layer of platinum weakens the surface binding of adsorbed H-intermediates and provides a twofold activity increase, surpassing the highest specific HER activities reported for acidic media under similar conditions, to the best of our knowledge. These improvements are rationalized using a simple model based on structure-sensitive hydrogen adsorption at platinum and copper-modified platinum surfaces. This model also solves a long-lasting puzzle in electrocatalysis, namely why polycrystalline platinum electrodes are more active than platinum(111) for the HER.

  18. Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster.

    Science.gov (United States)

    Tymoczko, Jakub; Calle-Vallejo, Federico; Schuhmann, Wolfgang; Bandarenka, Aliaksandr S

    2016-03-10

    Although the hydrogen evolution reaction (HER) is one of the fastest electrocatalytic reactions, modern polymer electrolyte membrane (PEM) electrolysers require larger platinum loadings (∼0.5-1.0 mg cm(-2)) than those in PEM fuel cell anodes and cathodes altogether (∼0.5 mg cm(-2)). Thus, catalyst optimization would help in substantially reducing the costs for hydrogen production using this technology. Here we show that the activity of platinum(111) electrodes towards HER is significantly enhanced with just monolayer amounts of copper. Positioning copper atoms into the subsurface layer of platinum weakens the surface binding of adsorbed H-intermediates and provides a twofold activity increase, surpassing the highest specific HER activities reported for acidic media under similar conditions, to the best of our knowledge. These improvements are rationalized using a simple model based on structure-sensitive hydrogen adsorption at platinum and copper-modified platinum surfaces. This model also solves a long-lasting puzzle in electrocatalysis, namely why polycrystalline platinum electrodes are more active than platinum(111) for the HER.

  19. Surface Roughening of Nickel Cobalt Phosphide Nanowire Arrays/Ni Foam for Enhanced Hydrogen Evolution Activity.

    Science.gov (United States)

    Wang, Xina; Tong, Rui; Wang, Yi; Tao, Hualong; Zhang, Zhihua; Wang, Hao

    2016-12-21

    Development of earth-abundant, efficient, and stable electrocatalysts for hydrogen evolution reactions (HER) in alkaline or even neutral pH electrolyte is very important for hydrogen production from water splitting. Construction of bimetal phosphides via tuning the bonding strength to hydrogen and increasing effective active sites through nanostructuring and surface engineering should lead to high HER activity. Here, ternary NiCoP nanowires (NWs) decorated by homogeneous nanoparticles have been obtained on Ni foam for a highly efficient HER property via long-term cyclic voltammetric (CV) sweeping. The electron density transfer between the positively charged Ni and Co and negatively charged P atoms, one-dimensional electron transfer channel of the NWs, and abundant active sites supplied by the nanoparticles and NWs endow the catalyst with low overpotentials of 43 and 118 mV to achieve the respective current densities of 10 and 100 mA cm(-2) together with long durability for at least 33 h in 1 M KOH. A cycled anodic dissolution-redeposition mechanism is disclosed for the formation of the NiCoP nanoparticles during the CV sweeping process. Such a surface roughening method is found to be adaptable to enhance the HER property of other phosphides, including Ni2P nanoplates/NF, NiCoP nanoparticles/NF, and CoP NW/NF.

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

    KAUST Repository

    Muralikrishna, S.

    2015-10-20

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

  1. Simulation of the Cosmic Evolution of Atomic and Molecular Hydrogen in Galaxies

    CERN Document Server

    Obreschkow, D; De Lucia, G; Khochfar, S; Rawlings, S

    2009-01-01

    We present a simulation of the cosmic evolution of the atomic and molecular phases of the cold hydrogen gas in about 3e7 galaxies, obtained by post-processing the virtual galaxy catalog produced by (De Lucia et al. 2007) on the Millennium Simulation of cosmic structure (Springel et al. 2005). Our method uses a set of physical prescriptions to assign neutral atomic hydrogen (HI) and molecular hydrogen (H2) to galaxies, based on their total cold gas masses and a few additional galaxy properties. These prescriptions are specially designed for large cosmological simulations, where, given current computational limitations, individual galaxies can only be represented by simplistic model-objects with a few global properties. Our recipes allow us to (i) split total cold gas masses between HI, H2, and Helium, (ii) assign realistic sizes to both the HI- and H2-disks, and (iii) evaluate the corresponding velocity profiles and shapes of the characteristic radio emission lines. The results presented in this paper include ...

  2. Efficient Photocatalytic Hydrogen Evolution over Platinum and Boron Co-doped TiO2 Photoatalysts

    Directory of Open Access Journals (Sweden)

    Zhiliang JIN

    2014-12-01

    Full Text Available In this paper, the new photocatalyst, Ptx-/TiO2-yBy was prepared by impregnation method via coupling with a inorganic water splitting system, namely, a ternary system K+,Na+/B4O72- - H2O for hydrogen evolution. The integration process of the preparation for B doping Pt/TiO2 with the significant photocatalytic hydrogen evolution in the ternary system K+,Mg2+/B4O72- - H2O and K+,Na+/B4O72- - H2O were accomplished by impregnation in situ. The photocatalyst Ptx-/TiO2-yBy synthesis and the photocatalytic hydrogen production of the isothermal solubility of the ternary system K+,Mg2+/B4O72- - H2O and K+,Na+/B4O72- - H2O at 25 ºC have been studied. Thus, the present challenge is not only to demonstrate a suitable photocatalytical system that can efficiently produce hydrogen under the borate exsited, but also research that the addition of borate to the suspensions greatly enhanced the stability of the  photocatalysts over semiconductor catalysts.The results show that borate solution is a suitable for B doped TiO2 photocatalysts preparation and a novel photocatalyst Ptx-/TiO2-yBy was successfully prepared by this way. XRD and XPS characterization showed that both anatase and rutile are coexisted and the B is incorporated into the crystal of the TiO2.So the TiO2 can be denoted as TiO2-xBx. The effect of borate on the photocatalytic properties were investigated. The results showed that the amount of hydrogen evolved is enhanced by factors of 4 with the addition of H3BO3 to the ethanol/water reaction solutions. The role of boron anion does not act as a sacrificial electron donors. DOI: http://dx.doi.org/10.5755/j01.ms.20.4.6412

  3. Kinetics of reduction of a RuO2(110) film on Ru by atomic hydrogen

    NARCIS (Netherlands)

    Ugur, D.; Storm, A.J.; Verberk, R.; Brouwer, J.C.; Sloof, W.G.

    2013-01-01

    The kinetics and the mechanism of reduction of a RuO2(110) film, grown thermally on a Ru(0001) surface, has been studied in the temperature range of 60-200 °C by using an atomic hydrogen flux of 2 × 1019 at. H m-2 s-1. The reduction kinetics is dominated by the creation of oxygen vacancies at the su

  4. Effect of Sulfide Removal on Sulfate Reduction at pH 5 in a Hydrogen fed Gas-Lift Bioreactor

    NARCIS (Netherlands)

    Bijmans, M.F.M.; Dopson, M.; Lens, P.N.L.; Buisman, C.J.N.

    2008-01-01

    UNCORRECTED PROOF J. Microbiol. Biotechnol. (2007), 17(4), ¿ Effect of Sulfide Removal on Sulfate Reduction at pH 5 in a Hydrogen fed Gas-Lift Bioreactor Bijmans, Martijn F. M.1*, Mark Dopson2, Frederick Ennin1, Piet N. L. Lens1, and Cees J. N. Buisman1 1Sub Department of Environmental Technology, W

  5. Effect of PdS on Photocatalytic Hydrogen Evolution of Nanostructured CdS under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Qingyun Chen

    2013-01-01

    Full Text Available To investigate the effect of PdS as a cocatalyst for photocatalytic hydrogen evolution, nanostructured PdS/CdS were prepared by an in situ coprecipitation and hydrothermal method, respectively. The as-prepared photocatalysts were characterized by transmission electron microscopy (TEM, X-ray diffraction (XRD, UV-visible absorption spectra, and photoluminescence spectra (PL. With PdS highly dispersed in the CdS nanostructures, the photoactivity was evaluated by hydrogen evolution from aqueous solution containing Na2S/Na2SO3 as sacrificial reagents under visible light irradiation. When the concentration of PdS was 1% by weight, PdS/CdS, prepared by the in situ coprecipitation, showed the highest photocatalytic activity, while that prepared by hydrothermal method showed the most stability for hydrogen evolution. The effect of highly dispersed PdS on the photoactivity was discussed.

  6. Hydrogen production by hyperthermophilic and extremely thermophilic bacteria and archaea: mechanisms for reductant disposal

    NARCIS (Netherlands)

    Verhaart, M.R.A.; Bielen, A.A.M.; Oost, van der J.; Stams, A.J.M.; Kengen, S.W.M.

    2010-01-01

    Hydrogen produced from biomass by bacteria and archaea is an attractive renewable energy source. However, to make its application more feasible, microorganisms are needed with high hydrogen productivities. For several reasons, hyperthermophilic and extremely thermophilic bacteria and archaea are pro

  7. Carbon doped molybdenum disulfide nanosheets stabilized on graphene for the hydrogen evolution reaction with high electrocatalytic ability

    Science.gov (United States)

    Li, Yong; Wang, Jiao; Tian, Xike; Ma, Longlong; Dai, Chu; Yang, Chao; Zhou, Zhaoxin

    2016-01-01

    Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction.Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07370g

  8. Low-Energy Catalytic Electrolysis for Simultaneous Hydrogen Evolution and Lignin Depolymerization.

    Science.gov (United States)

    Du, Xu; Liu, Wei; Zhang, Zhe; Mulyadi, Arie; Brittain, Alex; Gong, Jian; Deng, Yulin

    2017-03-09

    Here, a new proton-exchange-membrane electrolysis is presented, in which lignin was used as the hydrogen source at the anode for hydrogen production. Either polyoxometalate (POM) or FeCl3 was used as the catalyst and charge-transfer agent at the anode. Over 90 % Faraday efficiency was achieved. In a thermal-insulation reactor, the heat energy could be maintained at a very low level for continuous operation. Compared to the best alkaline-water electrolysis reported in literature, the electrical-energy consumption could be 40 % lower with lignin electrolysis. At the anode, the Kraft lignin (KL) was oxidized to aromatic chemicals by POM or FeCl3 , and reduced POM or Fe ions were regenerated during the electrolysis. Structure analysis of the residual KL indicated a reduction of the amount of hydroxyl groups and the cleavage of ether bonds. The results suggest that POM- or FeCl3 -mediated electrolysis can significantly reduce the electrolysis energy consumption in hydrogen production and, simultaneously, depolymerize lignin to low-molecular-weight value-added aromatic chemicals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Hydrogen Isotopic Constraints on the Evolution of Surface and Subsurface Water on Mars

    Science.gov (United States)

    Usui, T.; Kurokawa, H.; Wang, J.; Alexander, C. M. O’D.; Simon, J. I.; Jones, J. H.

    2017-01-01

    The geology and geomorphology of Mars provide clear evidence for the presence of liquid water on its surface during the Noachian and Hesperien eras (i.e., >3 Ga). In contrast to the ancient watery environment, today the surface of Mars is relatively dry. The current desert-like surface conditions, however, do not necessarily indicate a lack of surface or near-surface water/ice. In fact, massive deposits of ground ice and/or icy sediments have been proposed based on subsurface radar sounder observations. Hence, accurate knowledge of both the evolution of the distribution of water and of the global water inventory is crucial to our understanding of the evolution of the climate and near-surface environments and the potential habitability of Mars. This study presents insights from hydrogen isotopes for the interactive evolution of Martian water reservoirs. In particular, based on our new measurement of the D/H ratio of 4 Ga-old Noachian water, we constrain the atmospheric loss and possible exchange of surface and subsurface water through time.

  10. Recent advances in unveiling active sites in molybdenum sulfide-based electrocatalysts for the hydrogen evolution reaction

    Science.gov (United States)

    Seo, Bora; Joo, Sang Hoon

    2017-07-01

    Hydrogen has received significant attention as a promising future energy carrier due to its high energy density and environmentally friendly nature. In particular, the electrocatalytic generation of hydrogen fuel is highly desirable to replace current fossil fuel-dependent hydrogen production methods. However, to achieve widespread implementation of electrocatalytic hydrogen production technology, the development of highly active and durable electrocatalysts based on Earth-abundant elements is of prime importance. In this context, nanostructured molybdenum sulfides (MoS x ) have received a great deal of attention as promising alternatives to precious metal-based catalysts. In this focus review, we summarize recent efforts towards identification of the active sites in MoS x -based electrocatalysts for the hydrogen evolution reaction (HER). We also discuss recent synthetic strategies for the engineering of catalyst structures to achieve high active site densities. Finally, we suggest ongoing and future research challenges in the design of advanced MoS x -based HER electrocatalysts.

  11. Rapid reduction of N-nitrosamine disinfection byproducts in water with hydrogen and porous nickel catalysts.

    Science.gov (United States)

    Frierdich, Andrew J; Shapley, John R; Strathmann, Timothy J

    2008-01-01

    There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 min for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 +/- 13.1 L g(Ni)(-1) h(-1)) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development, Ni-based catalysts may become attractive alternatives to precious metal catalysts.

  12. Catalytic hydrogen evolution in cathodic stripping voltammetry on a mercury electrode in the presence of cobalt(II) ion and phenylthiourea or thiourea.

    Science.gov (United States)

    Spătaru, N; Bănica, F G

    2001-11-01

    The system Co(II)-phenylthiourea (PTU)-borax buffer was investigated by cathodic stripping voltammetry (CSV) at a hanging mercury drop electrode. The results of the voltammetric measurements showed that the presence of both PTU and Co(II) gives rise to a new irreversible peak at about -1.5 V. Based upon our previous results obtained in the study of other sulfur compounds and the sulfide ion itself, the peak was ascribed to the catalytic hydrogen evolution superimposed on the reduction of the coordinated Co(II) ion. The catalyst itself is a Co(II) complex with the sulfide ion produced by the decomposition of the analyte during the deposition step. The influence of PTU and cobalt concentration, accumulation conditions and stripping parameters was investigated and complementary data on thiourea are included. The results showed that the measurement of the catalytic hydrogen evolution peak current can be used as a basis for a simple, accurate and rapid method for the determination of PTU within the concentration range 10-100 nM. The catalytic method is relatively free of interferences and could be a suitable alternative for cases in which the stripping peak due to mercury ion reduction in the accumulated mercury compound is disturbed by some interference.

  13. Destruction of problematic airborne contaminants by hydrogen reduction using a Catalytically Active, Regenerable Sorbent (CARS)

    Science.gov (United States)

    Thompson, John O.; Akse, James R.

    1993-01-01

    Thermally regenerable sorbent beds were demonstrated to be a highly efficient means for removal of toxic airborne trace organic contaminants aboard spacecraft. The utilization of the intrinsic weight savings available through this technology was not realized since many of the contaminants desorbed during thermal regeneration are poisons to the catalytic oxidizer or form highly toxic oxidation by-products in the Trace Contaminant Control System (TCCS). Included in this class of compounds are nitrogen, sulfur, silicon, and halogen containing organics. The catalytic reduction of these problematic contaminants using hydrogen at low temperatures (200-300 C) offers an attractive route for their destruction since the by-products of such reactions, hydrocarbons and inorganic gases, are easily removed by existing technology. In addition, the catalytic oxidizer can be operated more efficiently due to the absence of potential poisons, and any posttreatment beds can be reduced in size. The incorporation of the catalyst within the sorbent bed further improves the system's efficiency. The demonstration of this technology provides the basis for an efficient regenerable TCCS for future NASA missions and can be used in more conventional settings to efficiently remove environmental pollutants.

  14. Reduction of hydrogen peroxide by glutathione peroxidase mimics: reaction mechanism and energetics.

    Science.gov (United States)

    Heverly-Coulson, Gavin S; Boyd, Russell J

    2010-02-04

    The reaction mechanism for the reduction of hydrogen peroxide by N,N-dimethylbenzylamine diselenide, its selenol analogue, and the charged analogues of the diselenide and selenol are elucidated using reliable electronic structure techniques. It is found that the reaction using the diselenide has a large Gibbs energy barrier of 173.5 kJ/mol. The cationic diselenide, with both amines protonated, shows a lower barrier of 103.5 kJ/mol. Both diselenide species show significant Se-Se bond lengthening upon oxidation. An unusual two-step mechanism is found for the selenol with barriers of 136.3 and 141.9 kJ/mol, respectively, showing that it is unlikely that the selenol is the active form. The zwitterion, selenolate, and protonated amine analogues of the selenol show one-step reactions with energy barriers of 82.7, 92.7, and 102.3 kJ/mol, respectively. The zwitterion of the selenol shows the most favorable reaction energies, which is in good agreement with proposed mechanisms for this reaction.

  15. One-pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co-Nx as catalyst.

    Science.gov (United States)

    Zhou, Peng; Zhang, Zehui

    2017-05-09

    A new method was developed for the synthesis of secondary amines through the one-pot reductive amination of carbonyl compounds with nitro compounds using formic acid as the hydrogen donor over a heterogeneous non-noble-metal catalyst (Co-Nx /C-800-AT, generated by the pyrolysis of the cobalt phthalocyanine/silica composite at 800°C under a N2 atmosphere and subsequent etching by HF). Both nitrogen and cobalt were of considerable importance in the transfer hydrogenation reactions with formic acid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Improved hydrogen evolution on glassy carbon electrode modified with novel Pt/cetyltrimethylammonium bromide nanoscale aggregates

    Institute of Scientific and Technical Information of China (English)

    Jahan-Bakhsh Raoof; Sayed Reza Hosseini; Seyedeh Zeinab Mousavi-Sani

    2015-01-01

    A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic CTAB molecules were adsorbed on GCE by immersion in a CTAB solution. The positively charged hydrophilic layer, which consisted of small aggregates of average size less than 100 nm, was used for accumulation and complexation of [PtCl6]2− anions by immersing the electrode in K2PtCl6 solution. The modified electrode was characterized using scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, impedance spectroscopy, and electrochemical methods. The electrocatalytic activity of the Pt particles in the hydrogen evolution reaction (HER) was investigat‐ed. The results show that the CTAB surfactant enhances the electrocatalytic activity of the Pt parti‐cles in the HER in acidic solution.

  17. Monolithic Laser Scribed Graphene Scaffold with Atomic Layer Deposited Platinum for Hydrogen Evolution Reaction

    KAUST Repository

    Nayak, Pranati

    2017-09-01

    The use of three-dimensional (3D) electrode architectures as scaffolds for conformal deposition of catalysts is an emerging research area with significant potential for electrocatalytic applications. In this study, we report the fabrication of monolithic, self-standing, 3D graphitic carbon scaffold with conformally deposited Pt by atomic layer deposition (ALD) as a hydrogen evolution reaction catalyst. Laser scribing is employed to transform polyimide into 3D porous graphitic carbon, which possesses good electronic conductivity and numerous edge plane sites. This laser scribed graphene (LSG) architecture makes it possible to fabricate monolithic electrocatalyst support without any binders or conductive additives. The synergistic effect between ALD of Pt on 3D network of LSG provides an avenue for minimal yet effective Pt usage, leading to an enhanced HER activity. This strategy establish a general approach for inexpensive and large scale HER device fabrication with minimum catalyst cost.

  18. Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction

    Science.gov (United States)

    Cummins, Dustin R.; Martinez, Ulises; Sherehiy, Andriy; Kappera, Rajesh; Martinez-Garcia, Alejandro; Schulze, Roland K.; Jasinski, Jacek; Zhang, Jing; Gupta, Ram K.; Lou, Jun; Chhowalla, Manish; Sumanasekera, Gamini; Mohite, Aditya D.; Sunkara, Mahendra K.; Gupta, Gautam

    2016-01-01

    Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance. PMID:27282871

  19. Polymer Electrolyte Membrane Electrolyzers Utilizing Non-precious Mo-based Hydrogen Evolution Catalysts.

    Science.gov (United States)

    Ng, Jia Wei Desmond; Hellstern, Thomas R; Kibsgaard, Jakob; Hinckley, Allison C; Benck, Jesse D; Jaramillo, Thomas F

    2015-10-26

    The development of low-cost hydrogen evolution reaction (HER) catalysts that can be readily integrated into electrolyzers is critical if H2 from renewable electricity-powered electrolysis is to compete cost effectively with steam reforming. Herein, we report three distinct earth-abundant Mo-based catalysts, namely those based on MoSx , [Mo3 S13 ](2-) nanoclusters, and sulfur-doped Mo phosphide (MoP|S), loaded onto carbon supports. The catalysts were synthesized through facile impregnation-sulfidization routes specifically designed for catalyst-device compatibility. Fundamental electrochemical studies demonstrate the excellent HER activity and stability of the Mo-sulfide based catalysts in an acidic environment, and the resulting polymer electrolyte membrane (PEM) electrolyzers that integrate these catalysts exhibit high efficiency and durability. This work is an important step towards the goal of replacing Pt with earth-abundant catalysts for the HER in commercial PEM electrolyzers.

  20. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-19

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Isolation, purification and characterization of the hydrogen evolution promoting factor of hydrogenase of Spirulina platensis

    Science.gov (United States)

    Gu, Tian-Qing; Zhang, Hui-Miao; Sun, Shi-Hua

    1996-03-01

    A component (s-factor) with obvious promoting effect on hydrogen evolution of hydrogenase has been isolated and extracted from a cell-free preparation of Spirulina platensis. The effect of the s-factor in the reaction system is similar to that of Na2S2O4, but is coupled with light. The s-factor has the maximum absorption peak at 620 nm in the oxidized state, at 590 nm in the reduced state. The partially purified s-factor showed two bands by SDS-PAGE and is distinctly different from phycocyanin, which has no change of oxidized state and reduced state absorption spectra, and also has no promoting effect on hydrogenase of Spirulina platensis under the light.

  2. Multiple phases of molybdenum carbide as electrocatalysts for the hydrogen evolution reaction.

    Science.gov (United States)

    Wan, Cheng; Regmi, Yagya N; Leonard, Brian M

    2014-06-16

    Molybdenum carbide has been proposed as a possible alternative to platinum for catalyzing the hydrogen evolution reaction (HER). Previous studies were limited to only one phase, β-Mo2C with an Fe2N structure. Here, four phases of Mo-C were synthesized and investigated for their electrocatalytic activity and stability for HER in acidic solution. All four phases were synthesized from a unique amine-metal oxide composite material including γ-MoC with a WC type structure which was stabilized for the first time as a phase pure nanomaterial. X-ray photoelectron spectroscopy (XPS) and valence band studies were also used for the first time on γ-MoC. γ-MoC exhibits the second highest HER activity among all four phases of molybdenum carbide, and is exceedingly stable in acidic solution.

  3. Pt-modified molybdenum carbide for the hydrogen evolution reaction: From model surfaces to powder electrocatalysts

    Science.gov (United States)

    Kelly, Thomas G.; Lee, Kevin X.; Chen, Jingguang G.

    2014-12-01

    This work explores the opportunity to substantially reduce the cost of hydrogen evolution reaction (HER) electrocatalysts by supporting one monolayer (ML) of platinum (Pt) on low-cost molybdenum carbide (Mo2C) substrate. These efforts were primarily directed towards scaling a thin-film catalyst to high surface area particles. Electrochemical experiments investigated single-phase Mo2C thin films modified by different coverages of Pt for the HER. The ML Pt-Mo2C thin film showed Pt-like HER activity while displaying excellent stability under HER conditions. The promising results on thin films were then extended to more practical powder catalysts. Samples of various Pt loadings on Mo2C powders were synthesized using the co-impregnation method and were evaluated for HER activity. The ability to successfully link electrochemical activity on thin films and powder catalysts was thus demonstrated.

  4. Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%

    Science.gov (United States)

    Yan, Yong; Crisp, Ryan W.; Gu, Jing; Chernomordik, Boris D.; Pach, Gregory F.; Marshall, Ashley R.; Turner, John A.; Beard, Matthew C.

    2017-04-01

    Multiple exciton generation (MEG) in quantum dots (QDs) has the potential to greatly increase the power conversion efficiency in solar cells and in solar-fuel production. During the MEG process, two electron-hole pairs (excitons) are created from the absorption of one high-energy photon, bypassing hot-carrier cooling via phonon emission. Here we demonstrate that extra carriers produced via MEG can be used to drive a chemical reaction with quantum efficiency above 100%. We developed a lead sulfide (PbS) QD photoelectrochemical cell that is able to drive hydrogen evolution from aqueous Na2S solution with a peak external quantum efficiency exceeding 100%. QD photoelectrodes that were measured all demonstrated MEG when the incident photon energy was larger than 2.7 times the bandgap energy. Our results demonstrate a new direction in exploring high-efficiency approaches to solar fuels.

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

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

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

  6. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  7. Ultrasmall and phase-pure W2C nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution

    Science.gov (United States)

    Gong, Qiufang; Wang, Yu; Hu, Qi; Zhou, Jigang; Feng, Renfei; Duchesne, Paul N.; Zhang, Peng; Chen, Fengjiao; Han, Na; Li, Yafei; Jin, Chuanhong; Li, Yanguang; Lee, Shuit-Tong

    2016-01-01

    Earlier research has been primarily focused on WC as one of the most promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER), whereas the other compound in this carbide family—W2C—has received far less attention. Our theoretical calculations suggest that such a focus is misplaced and W2C is potentially more HER-active than WC. Nevertheless, the preparation of phase pure and sintering-free W2C nanostructures represents a formidable challenge. Here we develop an improved carburization method and successfully prepare ultrasmall and phase-pure W2C nanoparticles. When evaluated for HER electrocatalysis, W2C nanoparticles exhibit a small onset overpotential of 50 mV, a Tafel slope of 45 mV dec−1 and outstanding long-term cycling stability, which are dramatically improved over all existing WC-based materials. In addition, the integration of W2C nanoparticles with p-type Si nanowires enables highly active and sustainable solar-driven hydrogen production. Our results highlight the great potential of this traditionally non-popular material in HER electrocatalysis. PMID:27752046

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

    Science.gov (United States)

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M.

    2016-11-01

    Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH4) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and reactions over a 1 cm2 catalytic surface with aqueous NaBH4 solutions generated rate constants (K) = equal to 4.9 × 10-3 min-1, 4.6 × 10-3 min-1, and 3.3 × 10-3 min-1 for ACoF, NCoF, and copper substrate respectively.

  9. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    Science.gov (United States)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm-2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  10. General Thermal Texturization Process of MoS2 for Efficient Electrocatalytic Hydrogen Evolution Reaction.

    Science.gov (United States)

    Kiriya, Daisuke; Lobaccaro, Peter; Nyein, Hnin Yin Yin; Taheri, Peyman; Hettick, Mark; Shiraki, Hiroshi; Sutter-Fella, Carolin M; Zhao, Peida; Gao, Wei; Maboudian, Roya; Ager, Joel W; Javey, Ali

    2016-07-13

    Molybdenum disulfide (MoS2) has been widely examined as a catalyst containing no precious metals for the hydrogen evolution reaction (HER); however, these examinations have utilized synthesized MoS2 because the pristine MoS2 mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. In order to achieve high HER performance with pristine MoS2, it is essential to activate the basal plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. This texturization is achieved through a simple thermal annealing procedure in a hydrogen environment, removing sulfur from the MoS2 surface to form edge sites. As a result, the process generates high HER catalytic performance in pristine MoS2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially available spray of nanoflake MoS2. The lowest overpotential (η) observed for these samples was η = 170 mV to obtain 10 mA/cm(2) of HER current density.

  11. Interactive Evolution of Multiple Water-Ice Reservoirs on Mars: Insights from Hydrogen Isotope Compositions

    CERN Document Server

    Kurokawa, Hiroyuki; Sato, Masahiko

    2015-01-01

    Remote sensing data from orbiter missions have proposed that ground ice may currently exist on Mars, although the volume is still uncertain. Recent analyses of Martian meteorites have suggested that the water reservoirs have at least three distinct hydrogen isotope compositions (D/H ratios): primordial and high D/H ratios, which are approximately the same and six times that of ocean water on Earth, respectively, and a newly identified intermediate D/H ratio, which is approximately two to three times higher than that in ocean water on Earth. We calculate the evolution of the D/H ratios and the volumes of the water reservoirs on Mars by modeling the exchange of hydrogen isotopes between multiple water reservoirs and the atmospheric escape. The D/H ratio is slightly higher in the topmost thin surface-ice layer than that in the atmosphere because of isotopic fractionation by sublimation, whereas the water-ice reservoir just below the exchangeable topmost surface layer retains the intermediate D/H signature found ...

  12. Bacteria-directed construction of hollow TiO2 micro/nanostructures with enhanced photocatalytic hydrogen evolution activity.

    Science.gov (United States)

    Zhou, Han; Fan, Tongxiang; Ding, Jian; Zhang, Di; Guo, Qixin

    2012-03-12

    A general method has been developed for the synthesis of various hollow TiO2 micro/nanostructures with bacteria as templates to further study the structural effect on photocatalytic hydrogen evolution properties. TiO2 hollow spheres and hollow tubes, served as prototypes, are obtained via a surface sol-gel process using cocci and bacillus as biotemplates, respectively. The formation mechanisms are based on absorption of metal-alkoxide molecules from solution onto functional cell wall surfaces and subsequent hydrolysis to give nanometer-thick oxide layers. The UV-Vis absorption spectrum shows that the porous TiO2 hollow spheres have enhanced light harvesting property compared with the corresponding solid counterpart. This could be attributed to their unique hollow porous micro/nanostructures with microsized hollow cavities and nanovoids which could bring about multiple scattering and rayleigh scattering of light, respectively. The hollow TiO2 structures exhibit superior photocatalytic hydrogen evolution activities under UV and visible light irradiation in the presence of sacrificial reagents. The hydrogen evolution rate of hollow structures is about 3.6 times higher than the solid counterpart and 1.5 times higher than P25-TiO2. This work demonstrates the structural effect on enhancing the photocatalytic hydrogen evolution performance which would pave a new pathway to tailor and improve catalytic properties over a broad range.

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

    DEFF Research Database (Denmark)

    Wiberg, Gustav Karl Henrik; Arenz, Matthias

    2015-01-01

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

  14. Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

    Science.gov (United States)

    Jinlong, Lv; Tongxiang, Liang; Chen, Wang

    2016-03-01

    The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. A large number of gaps between 'cauliflower' like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

  15. The early stage of bacterial genome-reductive evolution in the host.

    Directory of Open Access Journals (Sweden)

    Han Song

    2010-05-01

    Full Text Available The equine-associated obligate pathogen Burkholderia mallei was developed by reductive evolution involving a substantial portion of the genome from Burkholderia pseudomallei, a free-living opportunistic pathogen. With its short history of divergence (approximately 3.5 myr, B. mallei provides an excellent resource to study the early steps in bacterial genome reductive evolution in the host. By examining 20 genomes of B. mallei and B. pseudomallei, we found that stepwise massive expansion of IS (insertion sequence elements ISBma1, ISBma2, and IS407A occurred during the evolution of B. mallei. Each element proliferated through the sites where its target selection preference was met. Then, ISBma1 and ISBma2 contributed to the further spread of IS407A by providing secondary insertion sites. This spread increased genomic deletions and rearrangements, which were predominantly mediated by IS407A. There were also nucleotide-level disruptions in a large number of genes. However, no significant signs of erosion were yet noted in these genes. Intriguingly, all these genomic modifications did not seriously alter the gene expression patterns inherited from B. pseudomallei. This efficient and elaborate genomic transition was enabled largely through the formation of the highly flexible IS-blended genome and the guidance by selective forces in the host. The detailed IS intervention, unveiled for the first time in this study, may represent the key component of a general mechanism for early bacterial evolution in the host.

  16. Significantly Enhanced Hydrogen Evolution Activity of Freestanding Pd-Ru Distorted Icosahedral Clusters with less than 600 Atoms.

    Science.gov (United States)

    Dai, Zhihui; Liu, Suli; Zhang, Qinghua; Bao, Jianchun; Li, Yafei; Gu, Lin

    2017-07-24

    Freestanding metal nanoclusters can tune, precisely and effectively, the Gibbs free energy (ΔGH) of atomic hydrogen on the surface of materials. This enables the enhancement of hydrogen evolution activity. In this paper, we report a study of freestanding Pd-Ru distorted icosahedral clusters (ico-clusters) with less than 600 atoms using a simple one-pot synthesis method. This Pd-Ru ico-cluster can be used as an efficient electrocatalyst for the hydrogen evolution reaction (HER) in acidic water, which is a promising alternative to Pt. The experimental and theoretical results suggest that the fcc freestanding Pd-Ru distorted ico-clusters with less than 600 atoms ensure increased active edges and distorted defect sites that reduce the coordination number for the atoms on the catalyst surface. Furthermore, Ru is a more effective hydrogen dissociation source, while Pd has a better hydrogen storage function. Pd-Ru can tune the ΔGH of atomic hydrogen adsorbed on a catalyst and reach an optimal equilibrium state that improves the HER performance. Our studies represent a robust approach towards the development of freestanding Pd-Ru distorted ico-clusters and advanced catalysts with non-Pt content for HER and many other heterogeneous reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Electrochemical, spectroscopic and theoretical studies of a simple bifunctional cobalt corrole catalyst for oxygen evolution and hydrogen production.

    Science.gov (United States)

    Lei, Haitao; Han, Ali; Li, Fengwang; Zhang, Meining; Han, Yongzhen; Du, Pingwu; Lai, Wenzhen; Cao, Rui

    2014-02-07

    Six cobalt and manganese corrole complexes were synthesized and examined as single-site catalysts for water splitting. The simple cobalt corrole [Co(tpfc)(py)2] (1, tpfc = 5,10,15-tris(pentafluorophenyl)corrole, py = pyridine) catalyzed both water oxidation and proton reduction efficiently. By coating complex 1 onto indium tin oxide (ITO) electrodes, the turnover frequency for electrocatalytic water oxidation was 0.20 s(−1) at 1.4 V (vs. Ag/AgCl, pH = 7), and it was 1010 s(−1) for proton reduction at −1.0 V (vs. Ag/AgCl, pH = 0.5). The stability of 1 for catalytic oxygen evolution and hydrogen production was evaluated by electrochemical, UV-vis and mass measurements, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), which confirmed that 1 was the real molecular catalyst. Titration and UV-vis experiments showed that the pyridine group on Co dissociated at the beginning of catalysis, which was critical to subsequent activation of water. A proton-coupled electron transfer process was involved based on the pH dependence of the water oxidation reaction catalyzed by 1. As for manganese corroles 2–6, although their oxidizing powers were comparable to that of 1, they were not as stable as 1 and underwent decomposition at the electrode. Density functional theory (DFT) calculations indicated that water oxidation by 1 was feasible through a proposed catalytic cycle. The formation of an O–O bond was suggested to be the rate-determining step, and the calculated activation barrier of 18.1 kcal mol(−1) was in good agreement with that obtained from experiments.

  18. Hydrogen evolution reaction on titanium and oxide-covered titanium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, M.W.; Abdel Rahim, M.A. (Cairo Univ., Gizeh (Egypt). Dept. of Chemistry)

    1991-10-01

    The kinetics of hydrogen evolution reaction (HER) on Ti electrodes in H{sub 2}SO{sub 4} of various concentrations in the pH range of 0.24-1.88 was studied. Cathodic Tafel lines were measured potentiodynamically at a scan rate 1.0 mVs{sup -1} within the H{sub 2} evolution potential range. Linear parallel Tafel lines of a slope of 152 mVdecade{sup -1} were obtained. A value of 0.73 was calculated for the reaction order wrt asub(H{sup +})using the exchange cd, i{sub 0}. Tafel lines measured on oxide covered electrodes showed three deviations from linearity. An attempt was made to explain the deviations in terms of hydride formation and chemical oxide dissolution. Tafel slopes of 152 mVdecade{sup -1} were also observed for the HER on oxide-covered electrodes. The nature and compositions of the oxide did not depend on the electrolyte in which the oxides were formed. (orig.).

  19. [Fe]-hydrogenases in green algae: photo-fermentation and hydrogen evolution under sulfur deprivation

    Energy Technology Data Exchange (ETDEWEB)

    Winkler, M.; Hemschemeier, A.; Happe, T. [Botanisches Institut der Universitat Bonn (Germany); Gotor, C. [CSIC y Universidad de Sevilla (Spain). Instituto de Bioquimica Vegetal y Fotosintesis; Melis, A. [University of California, Berkeley, CA (United States). Department of Plant and Microbial Biology

    2002-12-01

    Recent studies indicate that [Fe]-hydrogenases and H{sub 2} metabolism are widely distributed among green algae. The enzymes are simple structured and catalyze H{sub 2} evolution with similar rates than the more complex [Fe]-hydrogenases from bacteria. Different green algal species developed diverse strategies to survive under sulfur deprivation. Chlamydomonas reinhardtii evolves large quantities of hydrogen gas in the absence of sulfur. In a sealed culture of C. reinhardtii, the photosynthetic O{sub 2} evolution rate drops below the rate of respiratory O{sub 2} consumption due to a reversible inhibition of photosystem II, thus leading to an intracellular anaerobiosis. The algal cells survive under these anaerobic conditions by switching their metabolism to a kind of photo-fermentation. Although possessing a functional [Fe]-hydrogenase gene, the cells of Scenedesmus obliquus produce no significant amounts of H{sub 2} under S-depleted conditions. Biochemical analyses indicate that S. obliquus decreases almost the complete metabolic activities while maintaining a low level of respiratory activity. (author)

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

    KAUST Repository

    Li, Zhengxing

    2014-07-01

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

  1. Hydrogen.

    Science.gov (United States)

    Bockris, John O'M

    2011-11-30

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

  2. A molecular copper catalyst for electrochemical water reduction with a large hydrogen-generation rate constant in aqueous solution.

    Science.gov (United States)

    Zhang, Peili; Wang, Mei; Yang, Yong; Yao, Tianyi; Sun, Licheng

    2014-12-08

    The copper complex [(bztpen)Cu](BF4)2 (bztpen=N-benzyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen-generation rate constant (k(obs)) of over 10000 s(-1). A turnover frequency (TOF) of 7000 h(-1) cm(-2) and a Faradaic efficiency of 96% were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu](2+) in pH 2.5 buffer solution at -0.90 V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton-coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu](2+).

  3. Hexadecacarbonylhexarhodium as a novel electrocatalyst for oxygen reduction and hydrogen oxidation in the presence of fuel cell contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro. Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Hernandez-Castellanos, R. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

    2010-11-01

    The electrocatalytic activity for oxygen reduction and hydrogen oxidation of a discrete metal carbonyl cluster with a well defined molecular and crystal structure, Rh{sub 6}(CO){sub 16}, is reported. The exchange current density of this compound for oxygen reduction is one order of magnitude higher than that of platinum, and its resistance degree to PEM fuel cell contaminants such as methanol and CO is as high as 2 mol L{sup -1} and 0.5%, respectively. These properties make the metal complex a potential alternative for use as electrode in polymer electrolyte membrane fuel cells. (author)

  4. Platinum nanocrystals supported by silica, alumina and ceria: metal support interaction due to high-temperature reduction in hydrogen

    Science.gov (United States)

    Penner, S.; Wang, D.; Su, D. S.; Rupprechter, G.; Podloucky, R.; Schlögl, R.; Hayek, K.

    2003-06-01

    Regular Pt nanoparticles, obtained by epitaxial deposition on NaCl surfaces, were supported by thin films of silica, alumina and ceria and subjected to hydrogen reduction at temperatures up to 1073 K. The changes in morphology and composition were followed by (HR)TEM, electron diffraction and EELS, and the results were supported by theoretical calculations. The structural changes of the Pt particles upon reduction at 773 K and above are surprisingly similar despite the differing chemical properties of the three supports. Some platelet- and cube-like geometries exhibit double lattice periodicities in high resolution images and electron diffraction patterns. With increasing reduction larger aggregates of more complex appearance and structure are formed. Surface reconstruction under hydrogen and alloy formation are considered as responsible for this effect. Most likely, the first step is identical on all three systems and consists in the topotactic formation of Pt rich Pt 3Me (Me=Si, Al, Ce) under the influence of hydrogen, followed by transformation into diverging structures of lower Pt content and different crystallography. Density functional calculations were performed for deriving energies of formation of PtMe and Pt 3Me compounds.

  5. Eosin Y/Pt/SiO2催化剂光催化还原水制氢%Photocatalytic Reduction of Water to Hydrogen over Eosin Y/Pt/SiO2 Catalysts

    Institute of Scientific and Technical Information of China (English)

    张晓杰; 汤长青; 靳治良; 吕功煊; 李树本

    2011-01-01

    A novel efficient photoscatalytic system Eosin Y/Pt/SiO2 for photocatalytic reduction of water to hydrogen under visible light irradiation was constructed.The effects of parameters, such as the surface physical property of SiO2 (i.e., specific surface area), method of mixing Eosin Y and SiO2, and light intensity on catalyst properties for hydrogen evolution were investigated systemically.With increase of SiO2 specific surface area, the rate of hydrogen evolution increased.Either over high or low intensive irradiation is detrimental to obtain high quantum efficiency for hydrogen evolution.Compared to the Eosin Y adsorbed on SiO2 by an impregnation method, the composite system in which Eosin Y mixed with SiO2 physically in situ displayed higher rate and superior stability of hydrogen evolution.%构建了具有较高可见光还原水制氢性能的Eosin Y/Pt/SiO2催化体系,详细考察了二氧化硅性质、曙红Y 与二氧化硅的混合方式以及光照强度等因素对光敏化催化剂制氢性能的影响.实验结果表明:二氧化硅的比表面积增大,析氧速率随之提高;光照强度过高或过低都不利于提高光量子效率;与曙红Y浸渍法吸附在二氧化硅表面制备的催化剂相比,原位物理混合制备的催化剂光敏化析氢速率和稳定性均有显著提高.

  6. The hydrogen and the fuel cells in the world. Programs and evolutions; L'hydrogene et les piles a combustibles dans le monde. Programmes et evolutions

    Energy Technology Data Exchange (ETDEWEB)

    Lucchese, P. [CEA Saclay, Dir. des Nouvelles Technologies de l' Energie CEA, 91 - Gif-sur-Yvette (France)

    2008-07-01

    HyPac is a french platform on the hydrogen and fuel cells, created in 2008. The author presents the opportunity of such a platform facing the world research programs and other existing platforms. (A.L.B.)

  7. Reduction and expansion in microsporidian genome evolution: new insights from comparative genomics.

    Science.gov (United States)

    Nakjang, Sirintra; Williams, Tom A; Heinz, Eva; Watson, Andrew K; Foster, Peter G; Sendra, Kacper M; Heaps, Sarah E; Hirt, Robert P; Martin Embley, T

    2013-01-01

    Microsporidia are an abundant group of obligate intracellular parasites of other eukaryotes, including immunocompromised humans, but the molecular basis of their intracellular lifestyle and pathobiology are poorly understood. New genomes from a taxonomically broad range of microsporidians, complemented by published expression data, provide an opportunity for comparative analyses to identify conserved and lineage-specific patterns of microsporidian genome evolution that have underpinned this success. In this study, we infer that a dramatic bottleneck in the last common microsporidian ancestor (LCMA) left a small conserved core of genes that was subsequently embellished by gene family expansion driven by gene acquisition in different lineages. Novel expressed protein families represent a substantial fraction of sequenced microsporidian genomes and are significantly enriched for signals consistent with secretion or membrane location. Further evidence of selection is inferred from the gain and reciprocal loss of functional domains between paralogous genes, for example, affecting transport proteins. Gene expansions among transporter families preferentially affect those that are located on the plasma membrane of model organisms, consistent with recruitment to plug conserved gaps in microsporidian biosynthesis and metabolism. Core microsporidian genes shared with other eukaryotes are enriched in orthologs that, in yeast, are highly expressed, highly connected, and often essential, consistent with strong negative selection against further reduction of the conserved gene set since the LCMA. Our study reveals that microsporidian genome evolution is a highly dynamic process that has balanced constraint, reductive evolution, and genome expansion during adaptation to an extraordinarily successful obligate intracellular lifestyle.

  8. Time-resolved X-Ray Absorption Spectroscopy of a Cobalt-Based Hydrogen Evolution System for Artificial Photosynthesis

    Science.gov (United States)

    Moonshiram, Dooshaye; Gimbert, Carolina; Lehmann, Carl; Southworth, Stephen; Llobet, Antoni; Argonne National Laboratory Team; Institut Català d'Investigació Química Collaboration

    2015-03-01

    Production of cost-effective hydrogen gas through solar power is an important challenge of the Department of Energy among other global industry initiatives. In natural photosynthesis, the oxygen evolving complex(OEC) can carry out four-electron water splitting to hydrogen with an efficiency of around 60%. Although, much progress has been carried out in determining mechanistic pathways of the OEC, biomimetic approaches have not duplicated Nature's efficiency in function. Over the past years, we have witnessed progress in developments of light harvesting modules, so called chromophore/catalytic assemblies. In spite of reportedly high catalytic activity of these systems, quantum yields of hydrogen production are below 40 % when using monochromatic light. Proper understanding of kinetics and bond making/breaking steps has to be achieved to improve efficiency of hydrogen evolution systems. This project shows the timing implementation of ultrafast X-ray absorption spectroscopy to visualize in ``real time'' the photo-induced kinetics accompanying a sequence of redox reactions in a cobalt-based molecular photocatalytic system. Formation of a Co(I) species followed by a Co(III) hydride species all the way towards hydrogen evolution is shown through time-resolved XANES.

  9. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris

    2011-11-01

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

  10. The energetics of the reductive citric acid cycle in the pyrite-pulled surface metabolism in the early stage of evolution.

    Science.gov (United States)

    Kalapos, Miklós Péter

    2007-09-21

    The chemoautotrophic theory concerning the origin of life postulates that a central role is played in the prebiotic chemical machinery by a reductive citric acid cycle operating without enzymes. The crucial point in this scenario is the formation of pyrite from hydrogen sulfide and ferrous sulfide, a reaction suggested to be linked to endergonic reactions, making them exergonic. This mechanism is believed to provide the driving force for the cycle to operate as a carbon dioxide fixation network. The present paper criticizes the thermodynamic calculations and their presentation in the original version of the archaic reductive citric acid cycle [Wächtershäuser, 1990. Evolution of the first metabolic cycles. Proc. Natl Acad. Sci. USA 87, 200-204.]. The most significant differences between the Wächtershäuser hypothesis and the present proposal: Wächtershäuser did not consider individual reactions in his calculations. A particularly questionable feature is the involvement of seven molecules of pyrite which does not emerge as a direct consequence of the chemical reactions presented in the archaic reductive citric acid cycle. The involvement of a considerable number of sulfur-containing organic intermediates as building blocks is also disputed. In the new scheme of the cycle proposed here, less free energy is liberated than hypothesized by Wächtershäuser, but it has the advantages that the free energy changes for the individual reactions can be calculated, the number of pyrite molecules involved in the cycle is reduced, and fewer sulfur-containing intermediates are required for the cycle to operate. In combination with a plausible route for the anaplerotic reactions [Kalapos, 1997a. Possible evolutionary role of methylglyoxalase pathway: anaplerotic route for reductive citric acid cycle of surface metabolists. J. Theor. Biol. 188, 201-206.], this new presentation of the cycle assigns a special meaning to hydrogen sulfide formation in the early stage of biochemical

  11. Hydrogenated TiO2 nanobelts as highly efficient photocatalytic organic dye degradation and hydrogen evolution photocatalyst.

    Science.gov (United States)

    Tian, Jian; Leng, Yanhua; Cui, Hongzhi; Liu, Hong

    2015-12-15

    TiO2 nanobelts have gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Here we report the facile synthesis of hydrogenated TiO2 (H-TiO2) nanobelts, which exhibit excellent UV and visible photocatalytic decomposing of methyl orange (MO) and water splitting for hydrogen production. The improved photocatalytic property can be attributed to the Ti(3+) ions and oxygen vacancies in TiO2 nanobelts created by hydrogenation. Ti(3+) ions and oxygen vacancies can enhance visible light absorption, promote charge carrier trapping, and hinder the photogenerated electron-hole recombination. This work offers a simple strategy for the fabrication of a wide solar spectrum of active photocatalysts, which possesses significant potential for more efficient photodegradation, photocatalytic water splitting, and enhanced solar cells using sunlight as light source. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Mitigation of hydrogen hazard in a fusion reactor by reduction of metallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Arnould, F.; Chaudron, V. [Technicatome, Dir. de l' Ingenierie, SEPS, 13 - Aix-en-Provence (France); Latge, C. [CEA/Cadarache, Dept. d' Etudes des Reacteurs (DER), 13 - Saint-Paul-lez-Durance (France); Laurent, A. [Institut National Polytechnique de Lorraine, Lab. des Sciences du Genie Chimique, 54 - Nancy (France)

    1998-07-01

    Significant quantities of hydrogen could be generated inside a fusion reactor during a loss of coolant accident (LOCA) by chemical reaction between steam released into the torus and plasma-facing components at high temperature. On the basis of functional specifications stemming from ITER accident sequence analyses, it appears that the implementation of an anaerobic hydrogen elimination system inside the torus or its expansion volume is the most advisable mitigation means because it allows removal of the hydrogen at its source of production before it comes into contact with oxygen. After a review of literature data and an experimental evaluation of various types of metallic oxides at laboratory scale, manganese oxide catalyzed by silver compounds was found to be the most efficient hydrogen getter. In order to test this hydrogen mitigation technique in representative fusion plant accident conditions, Technicatome and the CEA designed and built a pilot installation named MIRHABEL (MItigation of the Risk linked to Hydrogen by ABsorption and ELimination). After a short description of MIRHABEL, this paper presents and discusses the test results with respect to ITER accident conditions. (authors)

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

    Science.gov (United States)

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

    2016-04-13

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

  14. Hydrogenated TiO{sub 2} nanobelts as highly efficient photocatalytic organic dye degradation and hydrogen evolution photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Jian [School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Leng, Yanhua [State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Cui, Hongzhi, E-mail: cuihongzhi1965@163.com [School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); Liu, Hong, E-mail: hongliu@sdu.edu.cn [State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

    2015-12-15

    Highlights: • A facile synthesis of hydrogenated TiO{sub 2} nanobelts is reported. • Utilizing UV and visible light in photocatalytic degradation and H{sub 2} production. • The improved photocatalytic property is owe to Ti{sup 3+} ions and oxygen vacancies. - Abstract: TiO{sub 2} nanobelts have gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Here we report the facile synthesis of hydrogenated TiO{sub 2} (H-TiO{sub 2}) nanobelts, which exhibit excellent UV and visible photocatalytic decomposing of methyl orange (MO) and water splitting for hydrogen production. The improved photocatalytic property can be attributed to the Ti{sup 3+} ions and oxygen vacancies in TiO{sub 2} nanobelts created by hydrogenation. Ti{sup 3+} ions and oxygen vacancies can enhance visible light absorption, promote charge carrier trapping, and hinder the photogenerated electron–hole recombination. This work offers a simple strategy for the fabrication of a wide solar spectrum of active photocatalysts, which possesses significant potential for more efficient photodegradation, photocatalytic water splitting, and enhanced solar cells using sunlight as light source.

  15. Nonpoint Symmetry and Reduction of Nonlinear Evolution and Wave Type Equations

    Directory of Open Access Journals (Sweden)

    Ivan Tsyfra

    2015-01-01

    Full Text Available We study the symmetry reduction of nonlinear partial differential equations with two independent variables. We propose new ansätze reducing nonlinear evolution equations to system of ordinary differential equations. The ansätze are constructed by using operators of nonpoint classical and conditional symmetry. Then we find solution to nonlinear heat equation which cannot be obtained in the framework of the classical Lie approach. By using operators of Lie-Bäcklund symmetries we construct the solutions of nonlinear hyperbolic equations depending on arbitrary smooth function of one variable too.

  16. High-performance hydrogen fuel cell using nitrate reduction reaction on a non-precious catalyst.

    Science.gov (United States)

    Han, Sang-Beom; Song, You-Jung; Lee, Young-Woo; Ko, A-Ra; Oh, Jae-Kyung; Park, Kyung-Won

    2011-03-28

    The H(2)-NO(3)(-) electrochemical cell using nitrate reduction on a non-precious cathode catalyst shows much improved efficiency despite ∼75% reduction of Pt metal loading as compared to typical PEMFCs using typical ORR on precious catalysts.

  17. Dispersed conductive polymer nanoparticles on graphitic carbon nitride for enhanced solar-driven hydrogen evolution from pure water.

    Science.gov (United States)

    Sui, Yi; Liu, Jinghai; Zhang, Yuewei; Tian, Xike; Chen, Wei

    2013-10-07

    Developing new methods to improve the photocatalytic activity of graphitic carbon nitride (g-C₃N₄) for hydrogen (H₂) evolution has attracted intensive research interests. Here, we report that the g-C₃N₄ exhibits photocatalytic activity for H₂ evolution from pure water. And, the activity is dramatically improved by loading highly dispersed conductive polymer nanoparticles. The H₂ evolution rate increases up to 50 times for g-C₃N₄ with 1.5 wt% polypyrrole (PPy) nanoparticles on the surface. The reaction proceeding in a pure water system excludes the need for sacrificial agents. The role of the highly conductive PPy in enhancing H₂ evolution is as a surface junction to increase the number of photoinduced electrons, and to facilitate electron transfer to the interface.

  18. Enhancement of the Hydrogen Evolution Reaction from Ni-MoS2 Hybrid Nanoclusters

    Science.gov (United States)

    2016-01-01

    This report focuses on a novel strategy for the preparation of transition metal–MoS2 hybrid nanoclusters based on a one-step, dual-target magnetron sputtering, and gas condensation process demonstrated for Ni-MoS2. Aberration-corrected STEM images coupled with EDX analysis confirms the presence of Ni and MoS2 in the hybrid nanoclusters (average diameter = 5.0 nm, Mo:S ratio = 1:1.8 ± 0.1). The Ni-MoS2 nanoclusters display a 100 mV shift in the hydrogen evolution reaction (HER) onset potential and an almost 3-fold increase in exchange current density compared with the undoped MoS2 nanoclusters, the latter effect in agreement with reported DFT calculations. This activity is only reached after air exposure of the Ni-MoS2 hybrid nanoclusters, suggested by XPS measurements to originate from a Ni dopant atoms oxidation state conversion from metallic to 2+ characteristic of the NiO species active to the HER. Anodic stripping voltammetry (ASV) experiments on the Ni-MoS2 hybrid nanoclusters confirm the presence of Ni-doped edge sites and reveal distinctive electrochemical features associated with both doped Mo-edge and doped S-edge sites which correlate with both their thermodynamic stability and relative abundance.

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

    KAUST Repository

    Zhou, Xiaofeng

    2017-01-07

    There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered as several promising HER candidates. Here, a highly active and stable hybrid electrocatalyst 3D flower-like hierarchical Co9S8 nanosheets incorporated with MoSx has been developed via a one-step sulfurization method. Since the amounts of Co9S8 and MoSx are easily adjustable, we verify that small amounts of MoSx promotes the HER activity of Co9S8, and vise versa. In other words, we validate that symmetric synergy for HER in the Co- and Mo-based sulfide hybrid catalysts, a long-standing question requiring clear experimental proofs. Meanwhile, the best electrocatalyst Co9S8-30@MoSx/CC in this study exhibits excellent HER performance with an overpotential of −98 mV at −10 mA/cm2, a small Tafel slope of 64.8 mV/dec, and prominent electrochemical stability.

  20. Influence of the interfacial peptide organization on the catalysis of hydrogen evolution.

    Science.gov (United States)

    Doneux, Th; Dorcák, V; Palecek, E

    2010-01-19

    The hydrogen evolution reaction is catalyzed by peptides and proteins adsorbed on electrode materials with high overpotentials for this reaction, such as mercury. The catalytic response characteristics are known to be very sensitive to the composition and structure of the investigated biomolecule, opening the way to the implementation of a label-free, reagentless electroanalytical method in protein analysis. Herein, it is shown using the model peptide Cys-Ala-Ala-Ala-Ala-Ala that the interfacial organization significantly influences the catalytic behavior. This peptide forms at the electrode two distinct films, depending on the concentration and accumulation time. The low-coverage film, composed of flat-lying molecules (area per molecule of approximately 250-290 A(2)), yields a well-defined catalytic peak at potentials around -1.75 V. The high-coverage film, made of upright-oriented peptides (area per molecule of approximately 43 A(2)), is catalytically more active and the peak is observed at potentials less negative by approximately 0.4 V. The higher activity, evidenced by constant-current chronopotentiometry and cyclic voltammetry, is attributed to an increase in the acid dissociation constant of the amino acid residues as a result of the low permittivity of the interfacial region, as inferred from impedance measurements. An analogy is made to the known differences in acidic-basic behaviors of solvent-exposed and hydrophobic domains of proteins.

  1. Charge-Transfer Induced High Efficient Hydrogen Evolution of MoS2/graphene Cocatalyst

    Science.gov (United States)

    Li, Honglin; Yu, Ke; Li, Chao; Tang, Zheng; Guo, Bangjun; Lei, Xiang; Fu, Hao; Zhu, Ziqiang

    2015-12-01

    The MoS2 and reduced graphite oxide (rGO) composite has attracted intensive attention due to its favorable performance as hydrogen evolution reaction (HER) catalyst, but still lacking is the theoretical understanding from a dynamic perspective regarding to the influence of electron transfer, as well as the connection between conductivity and the promoted HER performance. Based on the first-principles calculations, we here clearly reveal how an excess of negative charge density affects the variation of Gibbs free energy (ΔG) and the corresponding HER behavior. It is demonstrated that the electron plays a crucial role in the HER routine. To verify the theoretical analyses, the MoS2 and reduced graphite oxide (rGO) composite with well defined 3-dimensional configuration was synthesized via a facile one-step approach for the first time. The experimental data show that the HER performance have a direct link to the conductivity. These findings pave the way for a further developing of 2-dimension based composites for HER applications.

  2. Synthesis of 4H/fcc Noble Multimetallic Nanoribbons for Electrocatalytic Hydrogen Evolution Reaction.

    Science.gov (United States)

    Fan, Zhanxi; Luo, Zhimin; Huang, Xiao; Li, Bing; Chen, Ye; Wang, Jie; Hu, Yanling; Zhang, Hua

    2016-02-03

    Noble multimetallic nanomaterials, if only consisting of Au, Ag, Pt, and Pd, typically adopt the high-symmetry face-centered cubic (fcc) structure. Here for the first time, by using the 4H/fcc Au@Ag nanoribbons (NRBs) as seeds, we report the synthesis of 4H/fcc trimetallic Au@PdAg core-shell NRBs via the galvanic reaction method under ambient conditions. Moreover, this strategy can also be used to synthesize 4H/fcc trimetallic Au@PtAg and quatermetallic Au@PtPdAg core-shell NRBs. Impressively, for the first time, these alloy shells, i.e., PdAg, PtAg, and PtPdAg, epitaxially grown on the 4H/fcc Au core with novel 4H hexagonal phase were successfully synthesized. Remarkably, the obtained 4H/fcc Au@PdAg NRBs exhibit excellent electrocatalytic activity toward the hydrogen evolution reaction, which is even quite close to that of the commercial Pt black. We believe that our findings here may provide a novel strategy for the crystal-structure-controlled synthesis of advanced functional noble multimetallic nanomaterials with various promising applications.

  3. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets.

    Science.gov (United States)

    Lukowski, Mark A; Daniel, Andrew S; Meng, Fei; Forticaux, Audrey; Li, Linsen; Jin, Song

    2013-07-17

    Promising catalytic activity from molybdenum disulfide (MoS2) in the hydrogen evolution reaction (HER) is attributed to active sites located along the edges of its two-dimensional layered crystal structure, but its performance is currently limited by the density and reactivity of active sites, poor electrical transport, and inefficient electrical contact to the catalyst. Here we report dramatically enhanced HER catalysis (an electrocatalytic current density of 10 mA/cm(2) at a low overpotential of -187 mV vs RHE and a Tafel slope of 43 mV/decade) from metallic nanosheets of 1T-MoS2 chemically exfoliated via lithium intercalation from semiconducting 2H-MoS2 nanostructures grown directly on graphite. Structural characterization and electrochemical studies confirmed that the nanosheets of the metallic MoS2 polymorph exhibit facile electrode kinetics and low-loss electrical transport and possess a proliferated density of catalytic active sites. These distinct and previously unexploited features of 1T-MoS2 make these metallic nanosheets a highly competitive earth-abundant HER catalyst.

  4. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction.

    Science.gov (United States)

    Geng, Xiumei; Sun, Weiwei; Wu, Wei; Chen, Benjamin; Al-Hilo, Alaa; Benamara, Mourad; Zhu, Hongli; Watanabe, Fumiya; Cui, Jingbiao; Chen, Tar-Pin

    2016-02-10

    Metallic-phase MoS2 (M-MoS2) is metastable and does not exist in nature. Pure and stable M-MoS2 has not been previously prepared by chemical synthesis, to the best of our knowledge. Here we report a hydrothermal process for synthesizing stable two-dimensional M-MoS2 nanosheets in water. The metal-metal Raman stretching mode at 146 cm(-1) in the M-MoS2 structure, as predicted by theoretical calculations, is experimentally observed. The stability of the M-MoS2 is associated with the adsorption of a monolayer of water molecules on both sides of the nanosheets, which reduce restacking and prevent aggregation in water. The obtained M-MoS2 exhibits excellent stability in water and superior activity for the hydrogen evolution reaction, with a current density of 10 mA cm(-2) at a low potential of -175 mV and a Tafel slope of 41 mV per decade.

  5. Promotion of Electrocatalytic Hydrogen Evolution Reaction on Nitrogen-Doped Carbon Nanosheets with Secondary Heteroatoms.

    Science.gov (United States)

    Qu, Konggang; Zheng, Yao; Zhang, Xianxi; Davey, Ken; Dai, Sheng; Qiao, Shi Zhang

    2017-07-25

    Dual heteroatom-doped carbon materials are efficient electrocatalysts via a synergistic effect. With nitrogen as the primary dopant, boron, sulfur, and phosphorus can be used as secondary elements for co-doped carbons. However, evaluation and analysis of the promotional effect of B, P, and S to N-doped carbons has not been widely researched. Here we report a robust platform that is constructed through polydopamine to prepare N,B-, N,P-, and N,S-co-doped carbon nanosheets, characterized by similar N species content and efficient B, P, and S doping. Systematic investigation reveals S to have the greatest promotional effect in hydrogen evolution reactions (HER) followed by P and that B decreases the activity of N-doped carbons. Experimental and theoretical analyses show the secondary heteroatom promotional effect is impacted by the intrinsic structures and extrinsic surface areas of both materials, i.e., electronic structures exclusively determine the catalytic activity of active sites, while large surface areas optimize apparent HER performance.

  6. Mo2C Nanoparticles Dispersed on Hierarchical Carbon Microflowers for Efficient Electrocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Huang, Yang; Gong, Qiufang; Song, Xuening; Feng, Kun; Nie, Kaiqi; Zhao, Feipeng; Wang, Yeyun; Zeng, Min; Zhong, Jun; Li, Yanguang

    2016-12-27

    The development of nonprecious metal based electrocatalysts for hydrogen evolution reaction (HER) has received increasing attention over recent years. Previous studies have established Mo2C as a promising candidate. Nevertheless, its preparation requires high reaction temperature, which more than often causes particle sintering and results in low surface areas. In this study, we show supporting Mo2C nanoparticles on the three-dimensional scaffold as a possible solution to this challenge and develop a facile two-step preparation method for ∼3 nm Mo2C nanoparticles uniformly dispersed on carbon microflowers (Mo2C/NCF) via the self-polymerization of dopamine. The resulting hybrid material possesses large surface areas and a fully open and accessible structure with hierarchical order at different levels. MoO4(2-) was found to play an important role in inducing the formation of this morphology presumably via its strong chelating interaction with the catechol groups of dopamine. Our electrochemical evaluation demonstrates that Mo2C/NCF exhibits excellent HER electrocatalytic performance with low onset overpotentials, small Tafel slopes, and excellent cycling stability in both acidic and alkaline solutions.

  7. Superior visible light hydrogen evolution of Janus bilayer junctions via atomic-level charge flow steering.

    Science.gov (United States)

    Li, Jie; Zhan, Guangming; Yu, Ying; Zhang, Lizhi

    2016-05-09

    Although photocatalytic hydrogen evolution (PHE) is ideal for solar-to-fuel conversion, it remains challenging to construct a highly efficient PHE system by steering the charge flow in a precise manner. Here we tackle this challenge by assembling 1T MoS2 monolayers selectively and chemically onto (Bi12O17) end-faces of Bi12O17Cl2 monolayers to craft two-dimensional (2D) Janus (Cl2)-(Bi12O17)-(MoS2) bilayer junctions, a new 2D motif different from van der Waals heterostructure. Electrons and holes from visible light-irradiated Bi12O17Cl2 are directionally separated by the internal electric field to (Bi12O17) and (Cl2) end-faces, respectively. The separated electrons can further migrate to MoS2 via Bi-S bonds formed between (Bi12O17) and MoS2 monolayers. This atomic-level directional charge separation endows the Janus bilayers with ultralong carrier lifetime of 3,446 ns and hence a superior visible-light PHE rate of 33 mmol h(-1) g(-1). Our delineated Janus bilayer junctions on the basis of the oriented assembly of monolayers presents a new design concept to effectively steer the charge flow for PHE.

  8. Boron-dependency of molybdenum boride electrocatalysts for the hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T. [Department of Chemistry, University of California, Riverside, CA (United States); Department of Chemical and Environmental Engineering, University of California, Riverside, CA (United States); Scheifers, Jan P.; Zhang, Yuemei [Department of Chemistry, University of California, Riverside, CA (United States)

    2017-05-08

    Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo{sub 2}B, α-MoB, β-MoB, and MoB{sub 2} by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB{sub 2} and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo{sub 2}C phases, while the molybdenum richest phase Mo{sub 2}B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB{sub 2} and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Studies on Structure and Electrocatalytic Hydrogen Evolution of Nanocrystyalline Ni—Mo—Fe Alloy Electrodeposit Electrodes

    Institute of Scientific and Technical Information of China (English)

    黄令; 杨防祖; 孙世刚; 许书楷; 周绍民

    2003-01-01

    Nanocrystalline Ni-Mo-Fe alloy deposits were obtained by electrodeposition.The structures of the alloy deposits were analyzed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).The XRD results of nanocrystalline Ni-Mo-Fe alloy deposit show that many diffraction lines disappear,and that there is only one diffraction peak at 44.0°.The XPS results of nanocrystalline Ni-Mo-Fe alloy deposits indicate that the nickel,molybdenum and iron of the deposits exist in metallic state,and that the binding energy of the alloyed elements increases to some extent.The nanocrystalline Ni-Mo-Fe alloy deposit electrode may offer better electrocatalytic activity than the polycrystalline nickel eletrode and the nanocrystalline Ni-Mo alloy electrode.The electrochemical impedance spectra from the nanocrystalline Ni-Mo-Fe alloy electrode indicate that hydrogen evolution in 30%(m/m) KOH at lower overpotential is in accordance with the Volmer-Tafel mechanism,but with the Volmer-Heyrovsky mechanism at higher overpotential.

  10. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-06-05

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  11. Comparison of cathode catalyst binders for the hydrogen evolution reaction in microbial electrolysis cells

    KAUST Repository

    Ivanov, Ivan

    2017-06-02

    Nafion is commonly used as a catalyst binder in many types of electrochemical cells, but less expensive binders are needed for the cathodes in microbial electrolysis cells (MECs) which are operated in neutral pH buffers, and reverse electrodialysis stacks (RED),which use thermolytic solutions such as ammonium bicarbonate. Six different binders were examined based on differences in ion exchange properties (anionic: Nafion, BPSH20, BPSH40, S-Radel; cationic: Q-Radel; and neutral: Radel, BAEH) and hydrophobicity based on water uptake (0%, Radel; 17–56% for the other binders). BPSH40 had similar performance to Nafion based on steady-state polarization single electrode experiments in a neutral pH phosphate buffer, and slightly better performance in ammonium bicarbonate. Three different Mo-based catalysts were examined as alternatives to Pt, with MoB showing the best performance under steady-state polarization. In MECs, MoB/BPSH40 performed similarly to Pt with Nafion or Radel binders. The main distinguishing feature of the BPSH40 was that it is very hydrophilic, and thus it had a greater water content (56%) than the other binders (0–44%). These results suggest the binders for hydrogen evolution in MECs should be designed to have a high water content without sacrificing ionic or electronic conductivity in the electrode.

  12. Electrocatalytic hydrogen evolution under densely buffered neutral pH conditions

    KAUST Repository

    Shinagawa, Tatsuya

    2015-08-18

    Under buffered neutral pH conditions, solute concentrations drastically influence the hydrogen evolution reaction (HER). The iR-free HER performance as a function of solute concentration was found to exhibit a volcano-shaped trend in sodium phosphate solution at pH 5, with the maximum occurring at 2 M. A detailed microkinetic model that includes calculated activity coefficients, solution resistance, and mass-transport parameters accurately describes the measured values, clarifying that the overall HER performance is predominantly governed by mass-transport of slow phosphate ions (weak acid). In the HER at the optimum concentration of approximately 2 M sodium phosphate at pH 5, our theoretical model predicts that the concentration overpotential accounts for more than half of the required overpotential. The substantial concentration overpotential would originate from the electrolyte property, suggesting that the proper electrolyte engineering will result in an improved apparent HER performances. The significance of concentration overpotential shown in the study is critical in the advancement of electrocatalysis, biocatalysis, and photocatalysis.

  13. Ultrafine Molybdenum Carbide Nanoparticles Composited with Carbon as a Highly Active Hydrogen-Evolution Electrocatalyst.

    Science.gov (United States)

    Ma, Ruguang; Zhou, Yao; Chen, Yongfang; Li, Pengxi; Liu, Qian; Wang, Jiacheng

    2015-12-01

    The replacement of platinum with non-precious-metal electrocatalysts with high efficiency and superior stability for the hydrogen-evolution reaction (HER) remains a great challenge. Herein, we report the one-step synthesis of uniform, ultrafine molybdenum carbide (Mo2C) nanoparticles (NPs) within a carbon matrix from inexpensive starting materials (dicyanamide and ammonium molybdate). The optimized catalyst consisting of Mo2C NPs with sizes lower than 3 nm encapsulated by ultrathin graphene shells (ca. 1-3 layers) showed superior HER activity in acidic media, with a very low onset potential of -6 mV, a small Tafel slope of 41 mV dec(-1), and a large exchange current density of 0.179 mA cm(-2), as well as good stability during operation for 12 h. These excellent properties are similar to those of state-of-the-art 20% Pt/C and make the catalyst one of the most active acid-stable electrocatalysts ever reported for HER.

  14. Surface treatment of zinc anodes to improve discharge capacity and suppress hydrogen gas evolution

    Science.gov (United States)

    Cho, Yung-Da; Fey, George Ting-Kuo

    The shape change and redistribution of zinc anode material over the electrode during repeated cycling have been identified as the main factors that can limit the life of alkaline zinc-air batteries. Li 2O-2B 2O 3 (lithium boron oxide, LBO) glass with high Li + conductivity and stability can be coated on the surface of zinc powders. The structures of the surface-treated and pristine zinc powders were characterized by XRD, SEM, TEM, ESCA and BET analyses. XRD patterns of LBO-coated zinc powders revealed that the coating did not affect the crystal structure. TEM images of LBO-coated on the zinc particles were compact with an average passivation layer of about 250 nm. The LBO layer can prevent zinc from coming into direct contact with the KOH electrolyte and minimize the side reactions within the batteries. The 0.1 wt.% LBO-coated zinc anode material provided an initial discharge capacity of 1.70 Ah at 0.5 V, while the pristine zinc electrode delivered only 1.57 Ah. A surface-treated zinc electrode can increase discharge capacity, decrease hydrogen evolution reaction, and reduce self-discharge. The results indicated that surface treatment should be effective for improving the comprehensive properties of anode materials for zinc-air batteries.

  15. Cobalt-doped graphitic carbon nitride photocatalysts with high activity for hydrogen evolution

    Science.gov (United States)

    Chen, Pei-Wen; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

    2017-01-01

    Cobalt-doped graphitic carbon nitride (Cosbnd CN) was synthesized by one-step thermal polycondensation using cobalt phthalocyanine (CoPc) and melamine as precursors. The π-π interaction between melamine and CoPc promotes cobalt doping into the framework of g-C3N4. The prepared samples were carefully characterized and the results demonstrated that Co-doped graphitic carbon nitride inhibited the crystal growth of graphitic carbon nitride (CN), leading to larger specific surface area (33.1 m2 g-1) and abundant Co-Nx active sites, narrower band gap energy and more efficient separation of photogenerated electrons and holes. 0.46% Cosbnd CN exhibited higher hydrogen evolution rate (28.0 μmol h-1) under visible light irradiation, which is about 3.0 times of that over the pure CN and about 2.2 times of that over cobalt-doped CN using CoCl2 • 6H2O as a cobalt source. This study provides a valuable strategy to modify CN with enhanced photocatalytic performance.

  16. Hydrothermal synthesis of core-shell TiO2 to enhance the photocatalytic hydrogen evolution

    Science.gov (United States)

    Jiang, Jinghui; Zhou, Han; Zhang, Fan; Fan, Tongxiang; Zhang, Di

    2016-04-01

    A hydrothermal approach was designed to synthesize core-shell TiO2 with interior cavity by making sodium dodecyl sulfonate (SDS) as the surfactant and the mixture of water and ethanol as the solvent. The control experiment of solvent reveals ethanol and water are responsible for the formation of sphere and interior cavity, respectively. Besides, SDS can assist the growth of core-shell structure, and the sizes of sphere and interior cavity can be tuned by regulating the reaction time or temperature. UV-vis absorption proves core-shell structure with interior cavity can increase the absorption of incident light to enhance the optical activity of final product. The calculated bandgap and photoluminescence (PL) analyses reveal the coexistence of rutile in final product can optimize the bandgap to 3.03 eV and delay the charge recombination. As a result, an effective photocatalytic hydrogen evolution under full spectrum irradiation can be harvested by the as-synthesized core-shell spheres to reach a quantum yield, approximately 9.57% at 340 nm wavelength.

  17. Molybdenum carbide-carbon nanocomposites synthesized from a reactive template for electrochemical hydrogen evolution

    KAUST Repository

    Alhajri, Nawal Saad

    2014-01-01

    Molybdenum carbide nanocrystals (Mo2C) with sizes ranging from 3 to 20 nm were synthesized within a carbon matrix starting from a mesoporous graphitic carbon nitride (mpg-C3N4) template with confined pores. A molybdenum carbide phase (Mo2C) with a hexagonal structure was formed using a novel synthetic method involving the reaction of a molybdenum precursor with the carbon residue originating from C3N4 under nitrogen at various temperatures. The synthesized nanocomposites were characterized using powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicated that the synthesized samples have different surface structures and compositions, which are accordingly expected to exhibit different electrocatalytic activities toward the hydrogen evolution reaction (HER). Electrochemical measurements demonstrated that the sample synthesized at 1323 K exhibited the highest and most stable HER current in acidic media, with an onset potential of -100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (∼8 nm on average) and accordingly high surface area (308 m2 g-1), with less oxidized surface entrapped within the graphitized carbon matrix. © 2014 the Partner Organisations.

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

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

  19. Hydrogen, metals, bifurcating electrons, and proton gradients: the early evolution of biological energy conservation.

    Science.gov (United States)

    Martin, William F

    2012-03-09

    Life is a persistent, self-specified set of far from equilibrium chemical reactions. In modern microbes, core carbon and energy metabolism are what keep cells alive. In very early chemical evolution, the forerunners of carbon and energy metabolism were the processes of generating reduced carbon compounds from CO(2) and the mechanisms of harnessing energy as compounds capable of doing some chemical work. The process of serpentinization at alkaline hydrothermal vents holds promise as a model for the origin of early reducing power, because Fe(2+) in the Earth's crust reduces water to H(2) and inorganic carbon to methane. The overall geochemical process of serpentinization is similar to the biochemical process of methanogenesis, and methanogenesis is similar to acetogenesis in that both physiologies allow energy conservation from the reduction of CO(2) with electrons from H(2). Electron bifurcation is a newly recognized cytosolic process that anaerobes use generate low potential electrons, it plays an important role in some forms of methanogenesis and, via speculation, possibly in acetogenesis. Electron bifurcation likely figures into the early evolution of biological energy conservation.

  20. Research on the reduction of the hydrogen content in steels treated in vacuum

    Science.gov (United States)

    Magaon, M.; Şerban, S.; Hepuţ, T.

    2017-01-01

    This paper discusses the results of the research on the influence of the vacuuming technological factors on the hydrogen content in the steel produced in an electric furnace type EBT, treated outside the furnice in Ladle-Furnace (LF) and Vacuum Degassing (VD) facilities, and then continuously casted as semi round products designed for pipes manufacturing. Vacumming main parameters were followed such as: the total duration of vacuuming, the duration of advanced vacuuming, the pressure in the vacuum facility, the vacumming temperature drop during the treatment (considered independent parameters) and the amount of hydrogen removed from the metal bath during the vacuuming. The obtained data was processed in the MATLAB calculation program, using three types of equations, the results obtained being presented both in analytical and graphical form. The technological analysis of the correlation equations and the graphical representations allowed to establish the variation limits of the independent parameters in order to advancely reduce the steel hydrogen content.

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

    Directory of Open Access Journals (Sweden)

    Pierożyński Bogusław

    2015-03-01

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

  2. Regulated Synthesis of Mo Sheets and Their Derivative MoX Sheets (X: P, S, or C) as Efficient Electrocatalysts for Hydrogen Evolution Reactions.

    Science.gov (United States)

    Jia, Jin; Zhou, Weijia; Li, Guixiang; Yang, Linjing; Wei, Zhaoqian; Cao, Lindie; Wu, Yisheng; Zhou, Kai; Chen, Shaowei

    2017-03-08

    Electrochemical H2 generation from H2O has been focused on the exploration of non-noble metals as well as earth-rich catalysts. In our practical work, we provide a simple cost-efficient fabrication process to prepare large Mo sheets via the controlled equilibrium between sublimation of MoO3 and reduction of H2. Porous MoP sheets were synthesized from the obtained Mo sheets as the Mo source and template which exhibit notable activity in the hydrogen evolution reaction with a low onset potential of -88 mV vs RHE, small Tafel value of 54.5 mV/dec, and strong catalytic stability. With Mo sheets as the universal Mo source and template, MoS2 and Mo2C sheets were synthesized by a similar process, and the corresponding catalytic activities were calculated by density functional theory.

  3. Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

    Science.gov (United States)

    Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

    2017-01-01

    Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

  4. Correlation of electrical and physical properties of photoanode with hydrogen evolution in enzymatic photo-electrochemical cell

    Science.gov (United States)

    Bae, Sanghyun; Kang, Junwon; Shim, Eunjung; Yoon, Jaekyung; Joo, Hyunku

    2008-05-01

    In this study, the electrical and physical properties, including the current density, open-circuit voltage, morphology and crystalline structure, of an anodized TiO2 electrode on a titanium foil are correlated with the hydrogen production rate in an enzymatic photo-electrochemical system. The effect of light intensity at ca. 74 and ca. 146 mW cm-2 on the properties is also examined. Anodizing (20 V; bath temperature 5 °C; anodizing time 45 min) and subsequent annealing (350-850 °C for 5 h) of the Ti foils in an O2 atmosphere led to the formation of a tube-shaped, or a compact layered, TiO2 film on the Ti substrate depending on the annealing temperature. The annealing temperature has a similar effect on the properties of the sample and the hydrogen evolution rate. The generated electrical value, the chronoamperometry (CA), is +13 to -229 and +13 to -247 μA for light intensities of ca. 74 and ca. 146 mW cm-2, while the corresponding open-circuit voltage (OCV) is in the range of -41 to -687 and -144 to 738 mV, respectively. In the absence of light (dark), the CA is 13-29 μA and the OCV is +258 to -126 mW cm-2. The trend in the electrical properties for the different samples is well matched with the rate of hydrogen evolution. The samples with higher activities (450, 550, and 650 °C) have similar X-ray diffraction (XRD) patterns, which clearly indicates that the samples showing the highest evolution rate are composed of both anatase and rutile, while those showing a lower evolution rate are made of either anatase or rutile. Increasing the intensity of the irradiated light causes a remarkable enhancement in the rate of hydrogen production from 71 to 153 μmol h-1 cm-2.

  5. Influence of substituted benzaldehydes and their derivatives as inhibitors for hydrogen evolution in lead/acid batteries

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, H. [Technische Univ. Dresden, Inst. fuer Physikalische Chemie und Elektrochemie (Germany); Hoogestraat, G. [DETA-Akkumulatorenwerk GmbH, Bad Lauterberg (Germany); Laibach, S. [Kurt-Schwabe-Inst. fuer Mess- und Sensortechnik e.V., Meinsberg (Germany); Borstel, D. von [DETA-Akkumulatorenwerk GmbH, Bad Lauterberg (Germany); Wiesener, K. [Kurt-Schwabe-Inst. fuer Mess- und Sensortechnik e.V., Meinsberg (Germany)

    1995-02-01

    The influence of substituted benzaldehydes and their derivatives (e.g. vanillin) as inhibitors for hydrogen evolution on smooth and porous negative electrodes of the lead/acid system is investigated by cyclic voltammetric measurements. The experiments have been carried out with and without the presence of antimony. The effect of the inhibitors can be distinguished by a moderate and a strong inhibiting action. Use of these inhibitors in flooded lead/acid batteries can reduce water loss during cycling by 50%. (orig.)

  6. High-Performance Hydrogen Evolution from MoS2(1-x) P(x) Solid Solution.

    Science.gov (United States)

    Ye, Ruquan; del Angel-Vicente, Paz; Liu, Yuanyue; Arellano-Jimenez, M Josefina; Peng, Zhiwei; Wang, Tuo; Li, Yilun; Yakobson, Boris I; Wei, Su-Huai; Yacaman, Miguel Jose; Tour, James M

    2016-02-17

    A MoS2(1-x) P(x) solid solution (x = 0 to 1) is formed by thermally annealing mixtures of MoS2 and red phosphorus. The effective and stable electrocatalyst for hydrogen evolution in acidic solution holds promise for replacing scarce and expensive platinum that is used in present catalyst systems. The high performance originates from the increased surface area and roughness of the solid solution.

  7. Sol–gel synthesis of palladium nanoparticles supported on reduced graphene oxide: an active electrocatalyst for hydrogen evolution reaction

    Indian Academy of Sciences (India)

    Fereshteh Chekin

    2015-08-01

    In this work, the synthesis and characterization of palladium nanoparticle-reduced graphene oxide hybrid (Pd–rGO) material is reported. Techniques of X-ray diffraction, transmission electron microscope (TEM), energy-dispersive X-ray, FT-IR spectroscopy, thermogravimetric analysis and cyclic voltammetry were used to characterize the structure and properties of the Pd–rGO. Results demonstrate the effect of Pd on the reduced GO. The average particle size of the Pd nanoparticles supported on rGO obtained from TEM is about 12–18 nm. Moreover, glassy carbon electrode (GCE) modified with palladium nanoparticle–graphene oxide hybrid (Pd–rGO/GCE) was prepared by casting of the Pd–rGO solution on GCE. The electrochemical and catalytic activity of the Pd–rGO/GCE was studied in 0.1 M H2SO4 solution. The Pd–rGO/GCE electrode exhibited remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). At potential more negative than −0.4 V vs. Ag|AgCl|KCl3M, the current is mainly due to hydrogen evolution reaction. Finally, the kinetic parameters of hydrogen evolution reaction are also discussed on the Pd–rGO/GCE.

  8. Reduction of hydrogen peroxide-induced erythrocyte damage by Carica papaya leaf extract

    Institute of Scientific and Technical Information of China (English)

    Tebekeme Okoko; Diepreye Ere

    2012-01-01

    Objective: To investigate the in vitro antioxidant potential of Carica papaya (C. papaya) leaf extract and its effect on hydrogen peroxide-induced erythrocyte damage assessed by haemolysis and lipid peroxidation. Methods: Hydroxyl radical scavenging activities, hydrogen ion scavenging activity, metal chelating activity, and the ferrous ion reducing ability were assessed as antioxidant indices. In the other experiment, human erythrocytes were treated with hydrogen peroxide to induce erythrocyte damage. The extract (at various concentrations) was subsequently incubated with the erythrocytes and later analysed for haemolysis and lipid peroxidation as indices for erythrocyte damage. Results:Preliminary investigation of the extract showed that the leaf possessed significant antioxidant and free radical scavenging abilities using in vitro models in a concentration dependent manner (P<0.05). The extract also reduced hydrogen peroxide induced erythrocyte haemolysis and lipid peroxidation significantly when compared with ascorbic acid (P<0.05). The IC50 values were 7.33 mg/mL and 1.58 mg/mL for inhibition of haemolysis and lipid peroxidation, respectively. In all cases, ascorbic acid (the reference antioxidant) possessed higher activity than the extract. Conclusions:The findings show that C. papaya leaves possess significant bioactive potential which is attributed to the phytochemicals which act in synergy. Thus, the leaves can be exploited for pharmaceutical and nutritional purposes.

  9. Salinity-Gradient Energy Driven Microbial Electrosynthesis of Hydrogen Peroxide from Oxygen Reduction

    DEFF Research Database (Denmark)

    Li, Xiaohu; Zhang, Yifeng; Angelidaki, Irini

    2015-01-01

    Hydrogen peroxide (H2O2) is widely used in various chemical industries and environmental remediation. Recently, bioelectrochemical systems (BES) have gained increasing attention for synthesizing H2O2 with simultaneous wastewater treatment[1]. However, in order to get high-yield H2O2 requires...

  10. Facile Synthesis of Nb3Sn Via a Hydrogen Reduction Process

    Science.gov (United States)

    Zhu, Jun; Jiao, Shuqiang; Zhang, Long; Li, Yanxiang; Zhu, Hongmin

    2016-09-01

    A controllable and facile process for the preparation of Nb3Sn intermetallic compound nanopowders using NbCl5 and SnCl2 vapors reduced by hydrogen has been developed. The vaporizing rates of the two chlorides are controlled by measuring their mass loss as a function of carrier gas (argon) flow rate at certain vaporization temperatures, respectively. X-ray diffraction (XRD) patterns indicate that hydrogenous Nb3Sn products are obtained under the vaporizing rate of 0.155 g min-1 for NbCl5 and 0.036 g min-1 for SnCl2 with the hydrogen flow rate of 2100 ml min-1 at 1273 K (1000 °C). Results of semi-quantitative analysis by X-ray fluorescence (XRF) demonstrate that the atomic ratio of Nb to Sn in the as-synthesized products is 3.48:1, and the content of (Nb + Sn) is taken up to 89.61 wt pct from the total weight of the products. The products can be purified by vacuum heat treatment. Images of transmission electron microscopy (TEM) show that the products are homogenous particles with a mean diameter of 31 nm. In addition, the reaction ratio of the chlorides and the powder yield are controllable by hydrogen flow rate.

  11. Alcohol production through volatile fatty acids reduction with hydrogen as electron donor by mixed cultures

    NARCIS (Netherlands)

    Steinbusch, K.J.J.; Hamelers, H.V.M.; Buisman, C.J.N.

    2008-01-01

    In this research we demonstrated a new method to produce alcohols. It was experimentally feasible to produce ethanol, propanol and butanol from solely volatile fatty acids (VFAs) with hydrogen as electron donor. In batch tests, VFAs such as acetic, propionic and butyric acids were reduced by mixed m

  12. Facile Synthesis of Nb3Sn Via a Hydrogen Reduction Process

    Science.gov (United States)

    Zhu, Jun; Jiao, Shuqiang; Zhang, Long; Li, Yanxiang; Zhu, Hongmin

    2017-02-01

    A controllable and facile process for the preparation of Nb3Sn intermetallic compound nanopowders using NbCl5 and SnCl2 vapors reduced by hydrogen has been developed. The vaporizing rates of the two chlorides are controlled by measuring their mass loss as a function of carrier gas (argon) flow rate at certain vaporization temperatures, respectively. X-ray diffraction (XRD) patterns indicate that hydrogenous Nb3Sn products are obtained under the vaporizing rate of 0.155 g min-1 for NbCl5 and 0.036 g min-1 for SnCl2 with the hydrogen flow rate of 2100 ml min-1 at 1273 K (1000 °C). Results of semi-quantitative analysis by X-ray fluorescence (XRF) demonstrate that the atomic ratio of Nb to Sn in the as-synthesized products is 3.48:1, and the content of (Nb + Sn) is taken up to 89.61 wt pct from the total weight of the products. The products can be purified by vacuum heat treatment. Images of transmission electron microscopy (TEM) show that the products are homogenous particles with a mean diameter of 31 nm. In addition, the reaction ratio of the chlorides and the powder yield are controllable by hydrogen flow rate.

  13. Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

    Science.gov (United States)

    Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

    2016-05-01

    In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

  14. Three-dimensional porous structural MoP2 nanoparticles as a novel and superior catalyst for electrochemical hydrogen evolution

    Science.gov (United States)

    Wu, Tianli; Pi, Mingyu; Zhang, Dingke; Chen, Shijian

    2016-10-01

    Transition metal phosphides (TMPs) are burgeoning as novel electrocatalysts to replace noble metals for electrochemical production of hydrogen. In this work, we propose a novel and cost-effective catalyst, molybdenum diphosphide (MoP2) three-dimensional porous structural nanoparticles with superior activity towards the hydrogen evolution reaction (HER). MoP2 nanoparticles catalyst exhibits an onset overpotential of -38 mV, a Tafel slope of 52 mV dev-1 and an exchange current density of 0.038 mA cm-2. Furthermore, the catalyst only needs low overpotentials of -121 and -193 mV to produce operationally relevant cathodic current densities of -10 and -100 mA cm-2, respectively, and its catalytic activity is maintained for at least 24 h. Comparative study with MoP nanoparticles as electrocatalyst for HER clearly indicates that MoP2 with high phosphor component can potentially improve the electrocatalytic activities. Density functional theory (DFT) calculation shows that the higher electrocatalytic activity of MoP2 over MoP can be attributed to a longer Hsbnd P bond length, lower hydrogen adsorption energy, lower HER energy barrier and luxuriant surface active sites. This work may expand the TMPs family to poly-phosphides as active and cost-effective hydrogen electrode for the large-scale hydrogen production.

  15. Cobalt phosphide nanowall arrays supported on carbon cloth: an efficient monolithic non-noble-metal hydrogen evolution catalyst

    Science.gov (United States)

    Yang, Libin; Wang, Kunyang; Du, Gu; Zhu, Wenxin; Cui, Liang; Zhang, Chengxiao; Sun, Xuping; Asiri, Abdullah M.

    2016-11-01

    Hydrogen has been considered as an ideal energy carrier for replacing fossil fuels to mitigate global energy crises. Hydrolysis of sodium borohydride (NaBH4) is simple and effective for hydrogen production but needs active and durable catalysts to accelerate the kinetics. In this paper, we demonstrate that cobalt phosphide nanowall arrays supported on carbon cloth (CoP NAs/CC) efficiently catalyze the hydrolytic dehydrogenation of NaBH4 with an activation energy of 42.1 kJ mol-1 in alkaline media. These monolithic CoP NAs/CC show a maximum hydrogen generation rate of 5960 {{ml}} {{{\\min }}}-1 {{{{g}}}-1}({{CoP})} and are robust with superior durability and reusability. They are also excellent in activity and durability for electrochemical hydrogen evolution in 1.0 M KOH, with the need of an overpotential of only 80 mV to drive 10 mA cm-2. They offer us a promising low-cost hydrogen-generating catalyst for applications.

  16. Semimetallic MoP2: an active and stable hydrogen evolution electrocatalyst over the whole pH range

    Science.gov (United States)

    Pu, Zonghua; Saana Amiinu, Ibrahim; Wang, Min; Yang, Yushi; Mu, Shichun

    2016-04-01

    Developing efficient non-precious metal hydrogen evolution reaction (HER) electrocatalysts is a great challenge for sustainable hydrogen production from water. In this communication, for the first time, semimetallic MoP2 nanoparticle films on a metal Mo plate (MoP2 NPs/Mo) are fabricated through a facile two-step strategy. When used as a binder-free hydrogen evolution cathode, the as-prepared MoP2 NPs/Mo electrode exhibits superior HER catalytic activity at all pH values. At a current density of 10 mA cm-2, the catalyst displays overpotentials of 143, 211 and 194 mV in 0.5 M H2SO4, 1.0 M phosphate buffer solution and 1.0 M KOH, respectively. Furthermore, it exhibits excellent stability over a wide pH range. Thus, this in situ route opens up a new avenue for the fabrication of highly efficient, cost-effective and binder-free non-precious catalysts for water splitting and other electrochemical devices.Developing efficient non-precious metal hydrogen evolution reaction (HER) electrocatalysts is a great challenge for sustainable hydrogen production from water. In this communication, for the first time, semimetallic MoP2 nanoparticle films on a metal Mo plate (MoP2 NPs/Mo) are fabricated through a facile two-step strategy. When used as a binder-free hydrogen evolution cathode, the as-prepared MoP2 NPs/Mo electrode exhibits superior HER catalytic activity at all pH values. At a current density of 10 mA cm-2, the catalyst displays overpotentials of 143, 211 and 194 mV in 0.5 M H2SO4, 1.0 M phosphate buffer solution and 1.0 M KOH, respectively. Furthermore, it exhibits excellent stability over a wide pH range. Thus, this in situ route opens up a new avenue for the fabrication of highly efficient, cost-effective and binder-free non-precious catalysts for water splitting and other electrochemical devices. Electronic supplementary information (ESI) available: Experimental section and figures. See DOI: 10.1039/c6nr00820h

  17. Evolution of the Busbar Structure in Large-Scale Aluminum Reduction Cells

    Science.gov (United States)

    Zhang, Hongliang; Liang, Jinding; Li, Jie; Sun, Kena; Xiao, Jin

    2017-02-01

    Studies of magnetic field and magneto-hydro-dynamics are regarded as the foundation for the development of large-scale aluminum reduction cells, while due to the direct relationship between the busbar configuration and magnetic compensation, the actual key content is the configuration of the busbar. As the line current has been increased from 160 kA to 600 kA, the configuration of the busbar was becoming more complex. To summarize and explore the evolution of busbar configuration in aluminum reduction cells, this paper has reviewed various representative large-scale pre-baked aluminum reduction cell busbar structures, such as end-to-end potlines, side-by-side potlines and external compensation current. The advantages and disadvantages in the magnetic distribution or technical specifications have also been introduced separately, especially for the configurations of the mainstream 400-kA potlines. In the end, the development trends of the bus structure configuration were prospected, based on the recent successful applications of super-scale cell busbar structures in China (500-600 kA).

  18. Effect of bombardment with iron ions on the evolution of helium, hydrogen, and deuterium blisters in silicon

    Science.gov (United States)

    Reutov, V. F.; Dmitriev, S. N.; Sokhatskii, A. S.; Zaluzhnyi, A. G.

    2017-02-01

    The effect of bombardment with iron ions on the evolution of gas porosity in silicon single crystals has been studied. Gas porosity has been produced by implantation hydrogen, deuterium, and helium ions with energies of 17, 12.5, and 20 keV, respectively, in identical doses of 1 × 1017 cm-2 at room temperature. For such energy of bombarding ions, the ion doping profiles have been formed at the same distance from the irradiated surface of the sample. Then, the samples have been bombarded with iron Fe10+ ions with energy of 150 keV in a dose of 5.9 × 1014 cm-2. Then 30-min isochoric annealing has been carried out with an interval of 50°C in the temperature range of 250-900°C. The samples have been analyzed using optical and electron microscopes. An extremely strong synergetic effect of sequential bombardment of silicon single crystals with gas ions and iron ions at room temperature on the nucleation and growth of gas porosity during postradiation annealing has been observed. For example, it has been shown that the amorphous layer formed in silicon by additional bombardment with iron ions stimulates the evolution of helium blisters, slightly retards the evolution of hydrogen blisters, and completely suppresses the evolution of deuterium blisters. The results of experiments do not provide an adequate explanation of the reason for this difference; additional targeted experiments are required.

  19. INFLUENCE OF SOLVENT ON INTRAMOLECULAR PROTON-TRANSFER IN HYDROGEN MALONATE - MOLECULAR-DYNAMICS SIMULATION STUDY OF TUNNELING BY DENSITY-MATRIX EVOLUTION AND NONEQUILIBRIUM SOLVATION

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC; VANGUNSTEREN, WF

    1993-01-01

    A density matrix evolution (DME) method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. the preceding paper in this issue) in combination with classical molecular dynamics simulation was applied to calculate the rate of proton tunneling in the intramolecular double-well hydrogen bond of hydrogen malo

  20. Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)

    Energy Technology Data Exchange (ETDEWEB)

    Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos

    2014-10-03

    Reaction pathways are explored for low temperature (e.g., 400 K) reduction of nitric oxide by hydrogen on Pt(111). First-principles electronic structure calculations based on periodic, self-consistent density functional theory(DFT-GGA, PW91) are employed to obtain thermodynamic and kinetic parameters for proposed reaction schemes on Pt(111). The surface of Pt(111) during NO reduction by H₂ at low temperatures is predicted to operate at a high NO coverage, and this environment is explicitly taken into account in the DFT calculations. Maximum rate analyses are performed to assess the most likely reaction mechanisms leading to formation of N₂O, the major product observed experimentally at low temperatures. The results of these analyses suggest that the reaction most likely proceeds via the addition of at least two H atoms to adsorbed NO, followed by cleavage of the N-O bond.

  1. Analysis of the Hydrogen Reduction Rate of Magnetite Concentrate Particles in a Drop Tube Reactor Through CFD Modeling

    Science.gov (United States)

    Fan, Deqiu; Mohassab, Yousef; Elzohiery, Mohamed; Sohn, H. Y.

    2016-06-01

    A computational fluid dynamics (CFD) approach, coupled with experimental results, was developed to accurately evaluate the kinetic parameters of iron oxide particle reduction. Hydrogen reduction of magnetite concentrate particles was used as a sample case. A detailed evaluation of the particle residence time and temperature profile inside the reactor is presented. This approach eliminates the errors associated with assumptions like constant particle temperature and velocity while the particles travel down a drop tube reactor. The gas phase was treated as a continuum in the Eulerian frame of reference, and the particles are tracked using a Lagrangian approach in which the trajectory and velocity are determined by integrating the equation of particle motion. In addition, a heat balance on the particle that relates the particle temperature to convection and radiation was also applied. An iterative algorithm that numerically solves the governing coupled ordinary differential equations was developed to determine the pre-exponential factor and activation energy that best fit the experimental data.

  2. Novel atmospheric pressure plasma device releasing atomic hydrogen: reduction of microbial-contaminants and OH radicals in the air

    Science.gov (United States)

    Nojima, Hideo; Park, Rae-Eun; Kwon, Jun-Hyoun; Suh, Inseon; Jeon, Junsang; Ha, Eunju; On, Hyeon-Ki; Kim, Hye-Ryung; Choi, Kyoung Hui; Lee, Kwang-Hee; Seong, Baik-Lin; Jung, Hoon; Kang, Shin Jung; Namba, Shinichi; Takiyama, Ken

    2007-01-01

    A novel atmospheric pressure plasma device releasing atomic hydrogen has been developed. This device has specific properties such as (1) deactivation of airborne microbial-contaminants, (2) neutralization of indoor OH radicals and (3) being harmless to the human body. It consists of a ceramic plate as a positive ion generation electrode and a needle-shaped electrode as an electron emission electrode. Release of atomic hydrogen from the device has been investigated by the spectroscopic method. Optical emission of atomic hydrogen probably due to recombination of positive ions, H+(H2O)n, generated from the ceramic plate electrode and electrons emitted from the needle-shaped electrode have been clearly observed in the He gas (including water vapour) environment. The efficacy of the device to reduce airborne concentrations of influenza virus, bacteria, mould fungi and allergens has been evaluated. 99.6% of airborne influenza virus has been deactivated with the operation of the device compared with the control test in a 1 m3 chamber after 60 min. The neutralization of the OH radical has been investigated by spectroscopic and biological methods. A remarkable reduction of the OH radical in the air by operation of the device has been observed by laser-induced fluorescence spectroscopy. The cell protection effects of the device against OH radicals in the air have been observed. Furthermore, the side effects have been checked by animal experiments. The harmlessness of the device has been confirmed.

  3. Life cycle assessment of processes for hydrogen production. Environmental feasibility and reduction of greenhouse gases emissions

    Energy Technology Data Exchange (ETDEWEB)

    Dufour, J.; Moreno, J. [Department of Chemical and Environmental Technology, ESCET, Universidad Rey Juan Carlos, c/Tulipan s/n, 28933 Mostoles, Madrid (Spain); Serrano, D.P. [Department of Chemical and Environmental Technology, ESCET, Universidad Rey Juan Carlos, c/Tulipan s/n, 28933 Mostoles, Madrid (Spain)]|[IMDEA Energia, c/Tulipan s/n, 28933 Mostoles, Madrid (Spain); Galvez, J.L.; Garcia, C. [National Institute of Aerospace Technology (INTA), Renewable Energies Area, Crtra. Ajalvir Km 4, 28850 Torrejon de Ardoz, Madrid (Spain)

    2009-02-15

    Decomposition of CH{sub 4} (natural gas) is one of the alternatives under study to achieve the sustainable production of hydrogen. No CO{sub 2} or other greenhouse gases emissions are produced in this route and carbon is obtained as a solid co-product at the end of the reaction (CH{sub 4}<-> C+2 H{sub 2}). This process can be thermally or catalytically conducted and recent studies have demonstrated that the carbon obtained in the reaction can also show catalytic activity. In this work, thermal and autocatalytic decomposition of methane were studied and compared with the steam reforming with and without CO{sub 2} capture and storage from an environmental point of view, using life cycle assessment (LCA) tools. As well, different energetic scenarios were included in the study. The selected functional unit was 1 Nm{sup 3} of hydrogen and the LCA was focused on material and raw materials acquisition and manufacturing stages. The assessment was carried out with SimaPro 7.1 software by using Eco-indicator 95 method. Results showed that autocatalytic decomposition is the most environmental-friendly process for hydrogen production since presented the lowest total environmental impact and CO{sub 2} emissions. Also, steam reforming with CO{sub 2} capture and storage led to lower CO{sub 2} emissions but higher total environmental impact than conventional steam reforming. (author)

  4. Genome Size and GC Content Evolution of Festuca: Ancestral Expansion and Subsequent Reduction

    Science.gov (United States)

    Šmarda, Petr; Bureš, Petr; Horová, Lucie; Foggi, Bruno; Rossi, Graziano

    2008-01-01

    Background and Aims Plant evolution is well known to be frequently associated with remarkable changes in genome size and composition; however, the knowledge of long-term evolutionary dynamics of these processes still remains very limited. Here a study is made of the fine dynamics of quantitative genome evolution in Festuca (fescue), the largest genus in Poaceae (grasses). Methods Using flow cytometry (PI, DAPI), measurements were made of DNA content (2C-value), monoploid genome size (Cx-value), average chromosome size (C/n-value) and cytosine + guanine (GC) content of 101 Festuca taxa and 14 of their close relatives. The results were compared with the existing phylogeny based on ITS and trnL-F sequences. Key Results The divergence of the fescue lineage from related Poeae was predated by about a 2-fold monoploid genome and chromosome size enlargement, and apparent GC content enrichment. The backward reduction of these parameters, running parallel in both main evolutionary lineages of fine-leaved and broad-leaved fescues, appears to diverge among the existing species groups. The most dramatic reductions are associated with the most recently and rapidly evolving groups which, in combination with recent intraspecific genome size variability, indicate that the reduction process is probably ongoing and evolutionarily young. This dynamics may be a consequence of GC-rich retrotransposon proliferation and removal. Polyploids derived from parents with a large genome size and high GC content (mostly allopolyploids) had smaller Cx- and C/n-values and only slightly deviated from parental GC content, whereas polyploids derived from parents with small genome and low GC content (mostly autopolyploids) generally had a markedly increased GC content and slightly higher Cx- and C/n-values. Conclusions The present study indicates the high potential of general quantitative characters of the genome for understanding the long-term processes of genome evolution, testing evolutionary

  5. Pilot Study to Evaluate Hydrogen Injection for Stimulating Reduction and Immobilization of Uranium in Groundwater at an ISR Mining Site

    Science.gov (United States)

    Clapp, L. W.; Cabezas, J.; Gamboa, Y.; Fernandez, W.

    2011-12-01

    State and federal regulations require that groundwater at in-situ recovery (ISR) uranium mining operations be restored to pre-mining conditions. Reverse osmosis (RO) filtration of several pore volumes of the post-leached groundwater and reinjection of the clean permeate is the most common technology currently used for restoring groundwater at uranium ISR sites. However, this approach does not revert the formation back to its initial reducing conditions, which can potentially impede timely groundwater restoration. In-situ biostimulation of indigenous iron- and sulfate reducing bacteria by injection of organic electron donors (e.g., ethanol, acetate, and lactate) to promote soluble uranium reduction and immobilization has been the subject of previous studies. However, injection of organic substrates has been observed to cause aquifer clogging near the injection point. In addition, U(VI) solubility may be enhanced through complexation with carbonate generated by organic carbon oxidation. An alternative approach that may overcome these problems involves the use of hydrogen as a reductant to promote microbial reduction and immobilization of U(VI) in situ. To test this approach, approximately 100,000 scf of compressed hydrogen gas was injected into a leached unconsolidated sand zone over two months at an ISR mining site. During this time groundwater was recirculated between injection and extraction wells (separated by 130 ft) at a rate of about 40 gpm and bromide was coinjected as a conservative tracer. A well monitoring program has been executed since June 2009 to evaluate the performance of the hydrogen injection. Current results show that U(VI) has been reduced from 4.2 to 0.05 ppm in the area surrounding the injection well and to 2.0 ± 0.3 ppm in the area surrounding the extraction well and two intermediate monitoring wells. Other water quality changes near the injection well include significant decreases in concentrations of Mo, sulfate, Fe, Mn, bicarbonate, Ca

  6. Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

    Science.gov (United States)

    Lee, Il-Su; Bae, Jae-Ho; McCarty, Perry L.

    2007-10-01

    Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H 2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H 2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H 2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H 2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.

  7. Ruthenium nanoparticles for oxygen reduction and/or hydrogen oxidation, prepared by pyrolysis in a reducing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Altamirano-Gutierrez, A.; Villagran-Naredo, J.L.A.; Jimenez-Sandoval, O. [Inst. Politecnico Nacional (Mexico). Centro de Investigacion y de Estudios Avanzados; Hernandez-Castellanos, R. [Centro de Investigacion y Desarrollo Technologic en Electroquimica (Mexico)

    2006-07-01

    An investigation of the synthesis, structural and electrochemical characterization of ruthenium-based materials prepared by pyrolysis was presented. Ru{sub 3}(CO){sub 12} materials were pyrolized in a hydrogen atmosphere at 80, 140, 360 and 460 degrees C. The materials were then characterized using Fourier Transform Infrared (FTIR) spectroscopy; X-ray diffraction (XRD) and scanning electron microscopy (SEM). Oxygen reduction reactions (ORR) and hydrogen oxidation reactions (HOR) were evaluated through the use of rotating disk electrode measurements in a 0.5 M hydrogen peroxide (H{sub 2}SO{sub 4}) electrolyte at room temperature. Results of the investigation indicated that the Ru{sub 3}(CO){sub 12} precursor was completely decarbonylated in H{sub 2} at 140 degrees C. Carbonyl group bands were observed when the materials were prepared at 80 degrees C due to the formation of an inactive Ru cluster resulting from a structural rearrangement of the cluster. Polarization curves indicated that the materials prepared at 140 degrees C were able to perform the ORR and HOR in an acid medium similar to the medium present in proton exchange (PE) fuel cells. The electrokinetic parameters indicated that the exchange current densities were of the same order as platinum (Pt) current densities, and that the ORR occurred via 4 electrons due to the direct formation of water. Tafel slope values for the HOR suggested that the mechanism of the reaction was related to Herovsky/Volmer types. It was concluded that the use of a reductive atmosphere in the preparation process of ruthenium-based materials prevents the formation of undesirable ruthenium oxides. The nano-sized materials prepared during the experiment did not exhibit loss of their catalytic properties after being exposed to air for several weeks. 4 refs., 2 figs.

  8. Predicting the minimal translation apparatus: lessons from the reductive evolution of mollicutes.

    Directory of Open Access Journals (Sweden)

    Henri Grosjean

    2014-05-01

    Full Text Available Mollicutes is a class of parasitic bacteria that have evolved from a common Firmicutes ancestor mostly by massive genome reduction. With genomes under 1 Mbp in size, most Mollicutes species retain the capacity to replicate and grow autonomously. The major goal of this work was to identify the minimal set of proteins that can sustain ribosome biogenesis and translation of the genetic code in these bacteria. Using the experimentally validated genes from the model bacteria Escherichia coli and Bacillus subtilis as input, genes encoding proteins of the core translation machinery were predicted in 39 distinct Mollicutes species, 33 of which are culturable. The set of 260 input genes encodes proteins involved in ribosome biogenesis, tRNA maturation and aminoacylation, as well as proteins cofactors required for mRNA translation and RNA decay. A core set of 104 of these proteins is found in all species analyzed. Genes encoding proteins involved in post-translational modifications of ribosomal proteins and translation cofactors, post-transcriptional modifications of t+rRNA, in ribosome assembly and RNA degradation are the most frequently lost. As expected, genes coding for aminoacyl-tRNA synthetases, ribosomal proteins and initiation, elongation and termination factors are the most persistent (i.e. conserved in a majority of genomes. Enzymes introducing nucleotides modifications in the anticodon loop of tRNA, in helix 44 of 16S rRNA and in helices 69 and 80 of 23S rRNA, all essential for decoding and facilitating peptidyl transfer, are maintained in all species. Reconstruction of genome evolution in Mollicutes revealed that, beside many gene losses, occasional gains by horizontal gene transfer also occurred. This analysis not only showed that slightly different solutions for preserving a functional, albeit minimal, protein synthetizing machinery have emerged in these successive rounds of reductive evolution but also has broad implications in guiding the

  9. Driving electrocatalytic activity by interface electronic structure control in a metalloprotein hybrid catalyst for efficient hydrogen evolution.

    Science.gov (United States)

    Behera, Sushant Kumar; Deb, Pritam; Ghosh, Arghya

    2016-08-17

    The rational design of metalloprotein hybrid structures and precise calculations for understanding the role of the interfacial electronic structure in regulating the HER activity of water splitting sites and their microscopic effect for obtaining robust hydrogen evolution possess great promise for developing highly efficient nano-bio hybrid HER catalysts. Here, we employ high-accuracy linear-scaling density functional theory calculations using a near-complete basis set and a minimal parameter implicit solvent model within the self-consistent calculations, on silver (Ag) ions assimilated on bacteriorhodopsin (bR) at specific binding sites. Geometry optimization indicates the formation of active sites at the interface of the metalloprotein complex and the density of states reflects the metallic nature of the active sites. The reduced value of the canonical orbital gap indicates the state of dynamic nature after Ag ion assimilation on active sites and smooth electron transfer. These incorporated active protein sites are more efficient in electrolytic splitting of water than pristine sites due to their low value of Gibbs free energy for the HER in terms of hydrogen coverages. Volcano plot analysis and the free energy diagram are compared for understanding the hydrogen evolution efficiency. Moreover, the essential role of the interfacial electronic properties in regulating the HER catalytic activity of water splitting sites and enhancing the efficiency is elucidated.

  10. Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support.

    Science.gov (United States)

    Youn, Duck Hyun; Han, Suenghoon; Kim, Jae Young; Kim, Jae Yul; Park, Hunmin; Choi, Sun Hee; Lee, Jae Sung

    2014-05-27

    Highly active and stable electrocatalysts for hydrogen evolution have been developed on the basis of molybdenum compounds (Mo2C, Mo2N, and MoS2) on carbon nanotube (CNT)-graphene hybrid support via a modified urea-glass route. By a simple modification of synthetic variables, the final phases are easily controlled from carbide, nitride to sulfide with homogeneous dispersion of nanocrystals on the CNT-graphene support. Among the prepared catalysts, Mo2C/CNT-graphene shows the highest activity for hydrogen evolution reaction with a small onset overpotential of 62 mV and Tafel slope of 58 mV/dec as well as an excellent stability in acid media. Such enhanced catalytic activity may originate from its low hydrogen binding energy and high conductivity. Moreover, the CNT-graphene hybrid support plays crucial roles to enhance the activity of molybdenum compounds by alleviating aggregation of the nanocrystals, providing a large area to contact with electrolyte, and facilitating the electron transfer.

  11. Ultrathin CoS2 shells anchored on Co3O4 nanoneedles for efficient hydrogen evolution electrocatalysis

    Science.gov (United States)

    Li, Tongtong; Niu, Kaili; Yang, Minghe; Shrestha, Nabeen K.; Gao, Zhida; Song, Yan-Yan

    2017-07-01

    Designing new earth-abundant and low-cost catalysts toward the hydrogen evolution reaction (HER) plays a key role in realization of hydrogen economy. In this study, we demonstrate that excellent HER activity is achieved with core-shell Co3O4@CoS2 nanoneedle arrays synthesized by an instantaneous thermal treatment of nanoneedle precursor in H2S atmosphere. The Co3O4@CoS2 structures thus obtained exhibit the current density of 100 mA cm-2 at a remarkably small overpotential of 210 mV with a small Tafel slope of 45.8 mV decade-1 in an acidic medium. The outstanding HER performance is achieved particularly from the unique core-shell nanostructure which offers enough electric conductivity and abundant active sites at the grain boundaries and stacking misalignments between two neighbouring cobalt nanostructures. This instantaneous thermal treatment strategy is compatible with the traditional long-time sulfur vapor to prepare transition metal chalcogenides with significant hydrogen evolution reaction activities.

  12. Noble-metal-free tungsten oxide/carbon (WOx/C) hybrid manowires for highly efficient hydrogen evolution.

    Science.gov (United States)

    Liu, Changhai; Qiu, Yangyang; Xia, Yujian; Wang, Fang; Liu, Xiaocun; Sun, Xuhui; Liang, Qian; Chen, Zhidong

    2017-08-14

    Developing active, stable, and low-cost electrocatalysts to generate hydrogen is a great challenge in the fields of chemistry and energy. Nonprecious metal catalysts comprised of inexpensive and earth-abundant transition metals are regarded as a promising substitute for noble metal catalysts used in hydrogen evolution reaction (HER), but are still practically unfeasible mainly due to unsatisfactory activity and durability. Here we report a facile two-step preparation method for WOx nanowires with high concentration of oxygen vacancies (OVs) via calcination of W-polydopamine compound precursors. The resulting hybrid material possesses a uniform and ultralong 1D nanowires structure and a rough and raised surface, which can effectively improve the specific surface area. The products exhibit excellent performance for H2 generation: the required overpotentials for 1 and 10 mA cm(-2) are 18 and 108 mV, the Tafel slope is 46 mV/decade, and the electrochemically active surface area is estimated to be ∼77.0 m(2) g(-1). After 1000 cycles, the catalyst works well without significant current density drop. Our experimental results verified metallic transition metal oxides as superior non-Pt electrocatalysts for practical hydrogen evolution reactions.

  13. Telomere-centric genome repatterning determines recurring chromosome number reductions during the evolution of eukaryotes.

    Science.gov (United States)

    Wang, Xiyin; Jin, Dianchuan; Wang, Zhenyi; Guo, Hui; Zhang, Lan; Wang, Li; Li, Jingping; Paterson, Andrew H

    2015-01-01

    Whole-genome duplication (WGD) is central to the evolution of many eukaryotic genomes, in particular rendering angiosperm (flowering plant) genomes much less stable than those of animals. Following repeated duplication/triplication(s), angiosperm chromosome numbers have usually been restored to a narrow range, as one element in a 'diploidization' process that re-establishes diploid heredity. In several angiosperms affected by WGD, we show that chromosome number reduction (CNR) is best explained by intra- and/or inter-chromosomal crossovers to form new chromosomes that utilize the existing telomeres of 'invaded' and centromeres of 'invading' chromosomes, the alternative centromeres and telomeres being lost. Comparison with the banana (Musa acuminata) genome supports a 'fusion model' for the evolution of rice (Oryza sativa) chromosomes 2 and 3, implying that the grass common ancestor had seven chromosomes rather than the five implied by a 'fission model.' The 'invading' and 'invaded' chromosomes are frequently homoeologs, originating from duplication of a common ancestral chromosome and with greater-than-average DNA-level correspondence to one another. Telomere-centric CNR following recursive WGD in plants is also important in mammals and yeast, and may be a general mechanism of restoring small linear chromosome numbers in higher eukaryotes. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  14. Evaluation of Biofuel Cells with Hemoglobin as Cathodic Electrocatalysts for Hydrogen Peroxide Reduction on Bare Indium-Tin-Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Yusuke Ayato

    2013-12-01

    Full Text Available A biofuel cell (BFC cathode has been developed based on direct electron transfer (DET of hemoglobin (Hb molecules with an indium-tin-oxide (ITO electrode and their electrocatalysis for reduction of hydrogen peroxide (H2O2. In this study, the ITO-coated glass plates or porous glasses were prepared by using a chemical vapor deposition (CVD method and examined the electrochemical characteristics of the formed ITO in pH 7.4 of phosphate buffered saline (PBS solutions containing and not containing Hb. In half-cell measurements, the reduction current of H2O2 due to the electrocatalytic activity of Hb increased with decreasing electrode potential from around 0.1 V versus Ag|AgCl|KCl(satd. in the PBS solution. The practical open-circuit voltage (OCV on BFCs utilizing H2O2 reduction at the Hb-ITO cathode with a hydrogen (H2 oxidation anode at a platinum (Pt electrode was expected to be at least 0.74 V from the theoretical H2 oxidation potential of −0.64 V versus Ag|AgCl|KCl(satd. in pH 7.4. The assembled single cell using the ITO-coated glass plate showed the OCV of 0.72 V and the maximum power density of 3.1 µW cm−2. The maximum power per single cell was recorded at 21.5 µW by using the ITO-coated porous glass.

  15. Electrochemical interfacial influences on deoxygenation and hydrogenation reactions in CO reduction on a Cu(100) surface.

    Science.gov (United States)

    Sheng, Tian; Lin, Wen-Feng; Sun, Shi-Gang

    2016-06-01

    Electroreduction of CO2 to hydrocarbons on a copper surface has attracted much attention in the last few decades for providing a sustainable way for energy storage. During the CO2 and further CO electroreduction processes, deoxygenation that is C-O bond dissociation, and hydrogenation that is C-H bond formation, are two main types of surface reactions catalyzed by the copper electrode. In this work, by performing the state-of-the-art constrained ab initio molecular dynamics simulations, we have systematically investigated deoxygenation and hydrogenation reactions involving two important intermediates, COHads and CHOads, under various conditions of (i) on a Cu(100) surface without water molecules, (ii) at the water/Cu(100) interface and (iii) at the charged water/Cu(100) interface, in order to elucidate the electrochemical interfacial influences. It has been found that the electrochemical interface can facilitate considerably the C-O bond dissociation via changing the reaction mechanisms. However, C-H bond formation has not been affected by the presence of water or electrical charge. Furthermore, the promotional roles of an aqueous environment and negative electrode potential in deoxygenation have been clarified, respectively. This fundamental study provides an atomic level insight into the significance of the electrochemical interface towards electrocatalysis, which is of general importance for understanding electrochemistry.

  16. Molecular development of fibular reduction in birds and its evolution from dinosaurs.

    Science.gov (United States)

    Botelho, João Francisco; Smith-Paredes, Daniel; Soto-Acuña, Sergio; O'Connor, Jingmai; Palma, Verónica; Vargas, Alexander O

    2016-03-01

    Birds have a distally reduced, splinter-like fibula that is shorter than the tibia. In embryonic development, both skeletal elements start out with similar lengths. We examined molecular markers of cartilage differentiation in chicken embryos. We found that the distal end of the fibula expresses Indian hedgehog (IHH), undergoing terminal cartilage differentiation, and almost no Parathyroid-related protein (PTHrP), which is required to develop a proliferative growth plate (epiphysis). Reduction of the distal fibula may be influenced earlier by its close contact with the nearby fibulare, which strongly expresses PTHrP. The epiphysis-like fibulare however then separates from the fibula, which fails to maintain a distal growth plate, and fibular reduction ensues. Experimental downregulation of IHH signaling at a postmorphogenetic stage led to a tibia and fibula of equal length: The fibula is longer than in controls and fused to the fibulare, whereas the tibia is shorter and bent. We propose that the presence of a distal fibular epiphysis may constrain greater growth in the tibia. Accordingly, many Mesozoic birds show a fibula that has lost its distal epiphysis, but remains almost as long as the tibia, suggesting that loss of the fibulare preceded and allowed subsequent evolution of great fibulo-tibial disparity.

  17. THE DATA REDUCTION PIPELINE FOR THE APACHE POINT OBSERVATORY GALACTIC EVOLUTION EXPERIMENT

    Energy Technology Data Exchange (ETDEWEB)

    Nidever, David L. [Department of Astronomy, University of Michigan, Ann Arbor, MI 48109 (United States); Holtzman, Jon A. [New Mexico State University, Las Cruces, NM 88003 (United States); Prieto, Carlos Allende; Mészáros, Szabolcs [Instituto de Astrofísica de Canarias, Via Láctea s/n, E-38205 La Laguna, Tenerife (Spain); Beland, Stephane [Laboratory for Atmospheric and Space Sciences, University of Colorado at Boulder, Boulder, CO (United States); Bender, Chad; Desphande, Rohit [Department of Astronomy and Astrophysics, The Pennsylvania State University, University Park, PA 16802 (United States); Bizyaev, Dmitry [Apache Point Observatory and New Mexico State University, P.O. Box 59, sunspot, NM 88349-0059 (United States); Burton, Adam; García Pérez, Ana E.; Hearty, Fred R.; Majewski, Steven R.; Skrutskie, Michael F.; Sobeck, Jennifer S.; Wilson, John C. [Department of Astronomy, University of Virginia, Charlottesville, VA 22904-4325 (United States); Fleming, Scott W. [Computer Sciences Corporation, 3700 San Martin Dr, Baltimore, MD 21218 (United States); Muna, Demitri [Department of Astronomy and the Center for Cosmology and Astro-Particle Physics, The Ohio State University, Columbus, OH 43210 (United States); Nguyen, Duy [Department of Astronomy and Astrophysics, University of Toronto, Toronto, Ontario, M5S 3H4 (Canada); Schiavon, Ricardo P. [Gemini Observatory, 670 N. A’Ohoku Place, Hilo, HI 96720 (United States); Shetrone, Matthew, E-mail: dnidever@umich.edu [University of Texas at Austin, McDonald Observatory, Fort Davis, TX 79734 (United States)

    2015-12-15

    The Apache Point Observatory Galactic Evolution Experiment (APOGEE), part of the Sloan Digital Sky Survey III, explores the stellar populations of the Milky Way using the Sloan 2.5-m telescope linked to a high resolution (R ∼ 22,500), near-infrared (1.51–1.70 μm) spectrograph with 300 optical fibers. For over 150,000 predominantly red giant branch stars that APOGEE targeted across the Galactic bulge, disks and halo, the collected high signal-to-noise ratio (>100 per half-resolution element) spectra provide accurate (∼0.1 km s{sup −1}) RVs, stellar atmospheric parameters, and precise (≲0.1 dex) chemical abundances for about 15 chemical species. Here we describe the basic APOGEE data reduction software that reduces multiple 3D raw data cubes into calibrated, well-sampled, combined 1D spectra, as implemented for the SDSS-III/APOGEE data releases (DR10, DR11 and DR12). The processing of the near-IR spectral data of APOGEE presents some challenges for reduction, including automated sky subtraction and telluric correction over a 3°-diameter field and the combination of spectrally dithered spectra. We also discuss areas for future improvement.

  18. Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Longlu; Duan, Xidong; Liu, Chengbin; Zhang, Shuqu; Zeng, Yunxiong [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha (China); Liu, Xia; Pei, Yong [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University (China); Luo, Jinming; Crittenden, John [Brook Byers Institute for Sustainable Systems and School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA (United States); Duan, Xiangfeng [Department of Chemistry and Biochemistry, University of California, Los Angeles, CA (United States)

    2017-06-19

    The metallic 1T-MoS{sub 2} has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS{sub 2} and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS{sub 2} by hydrothermal exfoliation of MoS{sub 2} nanosheets vertically rooted into rigid one-dimensional TiO{sub 2} nanofibers. The 1T-MoS{sub 2} can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a ''catalytic site self-optimization''. Hydrogen atom adsorption is the major driving force for this phase transition. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Mechanical bending induced catalytic activity enhancement of monolayer 1 T'-MoS2 for hydrogen evolution reaction

    Science.gov (United States)

    Shi, Wenwu; Wang, Zhiguo; Fu, Yong Qing

    2017-09-01

    In this paper, mechanisms behind enhancement of catalytic activity of MoS2 mono-layer (three atomic layers) for hydrogen evolution reaction (HER) by mechanically applying bending strain were investigated using density functional theory. Results showed that with the increase of bending strains, the Gibbs free energy for hydrogen adsorption on the MoS2 mono-layer was decreased from 0.18 to -0.04 eV and to 0.13 eV for the bend strains applied along the zigzag and armchair directions, respectively. The mechanism for the enhanced catalytic activity comes from the changes of density of electronic states near the Fermi energy level, which are induced by the changes of the Mo-S and Mo-Mo bonds upon bending. This report provides a new design methodology to improve the catalytic activity of catalysts based on two-dimensional transition metal dichalcogenides through a simple mechanical bending.

  20. Mechanistic Switching by Hydronium Ion Activity for Hydrogen Evolution and Oxidation over Polycrystalline Platinum Disk and Platinum/Carbon Electrodes

    KAUST Repository

    Shinagawa, Tatsuya

    2014-07-22

    Fundamental electrochemical reactions, namely the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), are re-evaluated under various pH conditions over polycrystalline Pt disk electrodes and Pt/C electrodes to investigate the overpotential and Tafel relations. Kinetic trends are observed and can be classified into three pH regions: acidic (1-5), neutral (5-9), and alkaline (9-13). Under neutral conditions, in which H2O becomes the primary reactant, substantial overpotential, which is not affected by pH and the supporting electrolyte type, is required for electrocatalysis in both directions. This ion independence, including pH, suggests that HER/HOR performance under neutral conditions solely reflects the intrinsic electrocatalytic activity of Pt in the rate determining steps, which involve electron transfer with water molecules. A global picture of the HER/HOR, resulting from mechanistic switching accompanied by change in pH, is detailed.

  1. Non-noble metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Song, Jun-Ling, E-mail: s070054@e.ntu.edu.sg [China-Australia Joint Research Centre for Functional Molecular Materials, School of Chemical & Material Engineering, Jiangnan University, Wuxi 214122 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China); Zhang, Jian-Han; Mao, Jiang-Gao [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)

    2016-05-15

    We reported the synthesis and crystal structures of alkali metal and alkali-earth metal phosphite, namely, CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} (1), and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} (2). Both compounds were prepared by hydrothermal reactions and feature unique new structures. They both exhibit 3D complicated frameworks based on VO{sub 6} octahedra which are connected by HPO{sub 3} tetrahedra via corner-sharing. Alkali or alkali earth metal cations are filled in the different channels of the frameworks. Topological analysis shows that the framework of CsV{sub 2}(H{sub 3}O) (HPO{sub 3}){sub 4} (1) is a new 3,3,3,4,5-connected network with the Schläfli symbol of {4.6"2}{sub 2}{4"2.6"6.8"2}{6"3}{6"5.8}. The investigations of X-ray photoelectron spectroscopy (XPS) and magnetic measurement on CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} suggest a +3 oxidation state of the vanadium ions in compound 1. Photocatalytic performance was evaluated by photocatalytic H{sub 2} evolution and degradation of methylene blue, which shows that both compounds exhibit activity under visible-light irradiation. IR spectrum, UV–vis-NIR spectrum and thermogravimetric analysis (TGA) of compounds were also investigated. - Graphical abstract: Metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution and the degradation of methylene blue aqueous solution. - Highlights: • Two new vanadium phosphites, CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6}, are reported. • CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} feature complicated 3D framework structures with different channels. • CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} exhibit strong and broad absorptions in the visible and Near IR region. • Photocatalytic properties of CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} are investigated. • The magnetic

  2. The influence of reduction methods and conditions on the activity of alumina-supported platinum catalysts for the liquid phase hydrogenation of benzaldehyde in ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Arai, M.; Obata, A.; Nishiyama, Y. [Tohoku Univ., Sendai (Japan)

    1997-02-01

    The activities of supported metal catalysts depend on various preparation variables, including the method of reduction. A variety of reduction procedures can be applied to the preparation of supported metal catalysts. Previously, the authors used a solid-liquid reduction by sodium tetrahydroborate solution for preparing supported platinum catalysts. In this reduction, platinum precursors adsorbed on supports were brought into contact with the reducing solution. The alumina-supported platinum catalysts prepared in this way were found to display interesting activities in the liquid-phase hydrogenation of {alpha},{beta}-unsaturated aldehydes; they were highly selective to the formation of unsaturated alcohols. The selective hydrogenation of C=O bonds of {alpha},{beta}-unsaturated aldehydes is difficult to achieve with platinum catalysts without using some additives like tin and iron. The maximum temperature that the supported platinum catalysts went through was 110{degrees}C, required for the removal of water. This thermal history is a possible reason for the catalytic activity observed. Following those observations, in the present work, the authors have further examined the influence of reduction procedures by using hydrazine as well as sodium tetrahydroborate and different temperatures common during gas-phase reduction with hydrogen. The catalytic activity has been tested by the liquid-phase hydrogenation of benzaldehyde (BAL) in ethanol under mild conditions. 12 refs., 3 figs.

  3. Aerobic evolution of hydrogen by Enterobacter aerogenes for hydrogen production accompanied with sewage treatment; Suiso seizo wo tomonau haisui syori sisutemu no tameno Enterobacter aerogenes ni yoru kokiteki suiso hassei

    Energy Technology Data Exchange (ETDEWEB)

    Tanisho, S.; Sasaki, Y. [Yokohama National Univaersity, Kanagawa (Japan)

    1997-06-01

    Enterobacter aerogenes react via the path of NADH (nicotinamide adenine dinucleotide) to evolve hydrogen. Aerobic evolution of hydrogen by E. aerogenes under the conditions of unsuitable nutrient and pH for growth is investigated. Hydrogenase maintains activity for longer than 40 minutes even in oxygen containing atmosphere. It is shown that bacteria held under anaerobic condition for a few hours consume oxygen immediately when placed in aerobic condition. As a result, it becomes clear that TCA cycle and electron-transfer chain are maintained even under anaerobic condition. Inactivation of hydrogen production under oxygen containing atmosphere is caused by re-oxidation of NADH utilizing mainly electron-transfer chain having better efficiency. It is considered that yield can be improved by interrupting electron transfer in NADH/oxidase composite because hydrogen evolution is possible even under aerobic condition, but the verification is postponed for future study. 12 refs., 5 figs., 4 tabs.

  4. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  5. Synthesis and Characterization of Iodine laden Graphene Nano Platelets via reduction of Graphene Oxide Using Hydrogen Iodide

    Science.gov (United States)

    Sundararaj, Joe Livingston

    This research thesis proposes a novel method for the synthesis, analysis and characterization of Iodinated X-Ray contrast agents using Graphene Nanoplatelets (GNPs) for Computed Tomographic Imaging. Graphene Oxide was synthesized using the Hummers Method of Oxidation [1] through oxidative treatment of Graphite with Potassium Permanganate (KMnO4). The resulting Graphene Oxide was chemically reduced using varying concentrations of Hydrogen Iodide or Hydroiodic acid (HI), rather than the conventionally used highly toxic Hydrazine Hydrate (N2H4) to strip off the oxygen functionalities. In the process of chemical reduction using Hydrogen Iodide, we hypothesized that this would result in the incorporation of Iodine into the Graphitic structure. Raman Spectroscopy, EDS along with XRD analysis provided evidence for the reduction of GO. Raman spectra for reduced GNPs showed an increase in ID/IG ratio from that of graphene oxide and also a peak at 154cm-1 attributed to I5 -. EDS/EDX spectra for HI reduced GO showed a peak at X-ray energy level 3.94KeV characteristic of Iodine. Further analysis using Ion-Selective Electrode measurements confirmed the presence of about 10% Iodine in the Hydroiodic acid reduced samples. SEM and TEM images showed a brief morphology of the Graphene Nanoplatelets. Finally, to elucidate the possibility of Iodinated GNPs to be developed into potential CT contrast agents in the near or far future, CT Phantoms of Iodine loaded GNPs at a concentration of 40mg/ml in water showed excellent contrast density with water and dilute Hydroiodic acid as controls.

  6. Effect of Pt promotion on Ni/Al2O3 for the selective catalytic reduction of NO with hydrogen

    Science.gov (United States)

    Mihet, Maria; Lazar, Mihaela D.; Borodi, G.; Almasan, V.

    2013-11-01

    Ni/Al2O3 (10 wt.% Ni) and Ni-Pt/Al2O3 (10 wt.% Ni, 0.5 wt.% Pt) were comparatively tested in the hydrogen selective catalytic reduction process (H2-SCR), at reaction temperatures below 350°C. Catalytic activity tests consisted in temperature programmed reactions (TPRea) under plug flow conditions from 50 to 350°C, with a temperature rate of 5°C/min, using a feed stream with a reactant ratio NO:H2 = 1:1.3 and a GHSV of 4500 h-1. Promotion with Pt increases the catalytic performances of the Ni based catalyst, in respect to NO conversion, N2 selectivity and N2 yield. The reaction temperatures for NO conversion above 95% decrease significantly due to Pt addition, from 250°C for Ni/Al2O3 to 125°C for Ni-Pt/Al2O3. Characterization of catalysts was performed by: X ray powder diffraction (XRD) for the estimation of Ni crystallite size, temperature programmed reduction (TPR) for the catalyst reducibility, temperature programmed desorption of hydrogen (H2-TPD) for the investigation of active sites and metal dispersion on the support, N2 adsorption-desorption isotherms at -196°C for the determination of total specific surface area and pore size distribution, and H/D isotopic exchange on the catalyst surface. At the request of the Proceedings Editor, and all authors of the paper, an updated version of this article was published on 14 January 2014. Data presented in Table 1 of the original paper contained errors which have been corrected in the updated and re-published article. The Corrigendum attached to the corrected article PDF file explains the errors in more detail.

  7. Neighboring Hetero-Atom Assistance of Sacrificial Amines to Hydrogen Evolution Using Pt-Loaded TiO2-Photocatalyst

    Directory of Open Access Journals (Sweden)

    Masahide Yasuda

    2014-05-01

    Full Text Available Photocatalytic H2 evolution was examined using Pt-loaded TiO2-photocatalyst in the presence of amines as sacrificial agents. In the case of amines with all of the carbon attached to the hetero-atom such as 2-aminoethanol, 1,2-diamonoethane, 2-amino-1,3-propanediol, and 3-amino-1,2-propanediol, they were completely decomposed into CO2 and water to quantitatively evolve H2. On the other hand, the amines with both hetero-atoms and one methyl group at the β-positions (neighboring carbons of amino group such as 2-amino-1-propanol and 1,2-diaminopropane were partially decomposed. Also, the photocatalytic H2 evolution using amines without the hetero-atoms at the β-positions such as ethylamine, propylamine, 1-butylamine, 1,3-diaminopropane, 2-propylamine, and 2-butylamine was inefficient. Thus, it was found that the neighboring hetero-atom strongly assisted the degradation of sacrificial amines. Moreover, rate constants for H2 evolution were compared among amines. In conclusion, the neighboring hetero-atom did not affect the rate constants but enhanced the yield of hydrogen evolution.

  8. Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-15

    Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

  9. Combining in silico evolution and nonlinear dimensionality reduction to redesign responses of signaling networks

    Science.gov (United States)

    Prescott, Aaron M.; Abel, Steven M.

    2016-12-01

    The rational design of network behavior is a central goal of synthetic biology. Here, we combine in silico evolution with nonlinear dimensionality reduction to redesign the responses of fixed-topology signaling networks and to characterize sets of kinetic parameters that underlie various input-output relations. We first consider the earliest part of the T cell receptor (TCR) signaling network and demonstrate that it can produce a variety of input-output relations (quantified as the level of TCR phosphorylation as a function of the characteristic TCR binding time). We utilize an evolutionary algorithm (EA) to identify sets of kinetic parameters that give rise to: (i) sigmoidal responses with the activation threshold varied over 6 orders of magnitude, (ii) a graded response, and (iii) an inverted response in which short TCR binding times lead to activation. We also consider a network with both positive and negative feedback and use the EA to evolve oscillatory responses with different periods in response to a change in input. For each targeted input-output relation, we conduct many independent runs of the EA and use nonlinear dimensionality reduction to embed the resulting data for each network in two dimensions. We then partition the results into groups and characterize constraints placed on the parameters by the different targeted response curves. Our approach provides a way (i) to guide the design of kinetic parameters of fixed-topology networks to generate novel input-output relations and (ii) to constrain ranges of biological parameters using experimental data. In the cases considered, the network topologies exhibit significant flexibility in generating alternative responses, with distinct patterns of kinetic rates emerging for different targeted responses.

  10. Hydrogen sulfide (H2S) emission control by aerobic sulfate reduction in landfill

    Science.gov (United States)

    Long, Yuyang; Fang, Yuan; Shen, Dongsheng; Feng, Huajun; Chen, Ting

    2016-12-01

    H2S emissions from landfill sites resulting from sulfate reduction has become a serious human health and ecological safety issue. This study investigated H2S emission behavior and sulfate metabolism occurring in simulated landfills under different operating conditions. Under aerobic conditions, great attenuation of the original sulfate content (from around 6000 mg kg‑1 dropped to below 800 mg kg‑1) with corresponding accumulation of sulfides and elemental sulfur were observed, indicating that sulfate reduction processes were intense under such conditions. Analysis of the bacterial community in these landfills showed great abundance (1.10%) and diversity of sulfur reducing types, confirming their active involvement in this process. In particular, the total abundance of sulfate-reducing bacteria increased nearly 30 times under aerobic conditions, leading to the transformation of sulfate to sulfide and other reduced sulfur species. Although exposure to air promoted the accumulation of sulfide, it did not lead to an increase in H2S release in these landfills.

  11. Designing Photocatalysts for Hydrogen Evolution: Are Complex Preparation Strategies Necessary to Produce Active Catalysts?

    Science.gov (United States)

    Grewe, Tobias; Tüysüz, Harun

    2015-09-21

    A facile synthetic route for the preparation of highly active photocatalysts was developed. The protocol involves the preparation of a photocatalyst through the direct injection of metal alkoxide precursors into solutions in a photoreactor. As a proof of concept, a tantalum oxide based photocatalyst was chosen as a model system. Tantalum ethoxide [Ta(OEt)5 ] was injected rapidly into a photoreactor filled with a water/methanol mixture, and a TaOx (OH)y composite formed and was able to produce hydrogen under light illumination. Compared to commercial and mesostructured Ta2 O5 and NaTaO3 materials, TaOx (OH)y produced by direct injection shows superior hydrogen production activity. Notably, the samples prepared by direct injection are amorphous; however, their photocatalytic performance is much higher than those of their crystalline equivalents. If Ta(OEt)5 was dispersed in methanol before injection, an amorphous framework with higher surface area and larger pore volume was formed, and the hydrogen production rate increased further. The addition of a sodium precursor during the injection further boosted the photocatalytic activity. Furthermore, this concept has also been applied to a titanium-based photocatalyst, and a much better hydrogen production rate has been obtained in comparison with that of commercial TiO2 (P25-Degussa); therefore, the direct-injection synthesis is a flexible method that opens the door to the facile preparation of highly active nanostructured photocatalysts for hydrogen production.

  12. Highly Efficient Photocatalytic Hydrogen Evolution in Ternary Hybrid TiO2/CuO/Cu Thoroughly Mesoporous Nanofibers.

    Science.gov (United States)

    Hou, Huilin; Shang, Minghui; Gao, Fengmei; Wang, Lin; Liu, Qiao; Zheng, Jinju; Yang, Zuobao; Yang, Weiyou

    2016-08-10

    Development of novel hybrid photocatalysts with high efficiency and durability for photocatalytic hydrogen generation is highly desired but still remains a grand challenge currently. In the present work, we reported the exploration of ternary hybrid TiO2/CuO/Cu thoroughly mesoporous nanofibers via a foaming-assisted electrospinning technique. It is found that by adjusting the Cu contents in the solutions, the unitary (TiO2), binary (TiO2/CuO, TiO2/Cu), and ternary (TiO2/CuO/Cu) mesoporous products can be obtained, enabling the growth of TiO2/CuO/Cu ternary hybrids in a tailored manner. The photocatalytic behavior of the as-synthesized products as well as P25 was evaluated in terms of their hydrogen evolution efficiency for the photodecomposition water under Xe lamp irradiation. The results showed that the ternary TiO2/CuO/Cu thoroughly mesoporous nanofibers exhibit a robust stability and the most efficient photocatalytic H2 evolution with the highest release rate of ∼851.3 μmol g(-1) h(-1), which was profoundly enhanced for more than 3.5 times with respect to those of the pristine TiO2 counterparts and commercial P25, suggesting their promising applications in clean energy production.

  13. Ni nanoparticles supported on graphene layers: An excellent 3D electrode for hydrogen evolution reaction in alkaline solution

    Science.gov (United States)

    Wang, Lixin; Li, Yao; Xia, Meirong; Li, Zhiping; Chen, Zhouhao; Ma, Zhipeng; Qin, Xiujuan; Shao, Guangjie

    2017-04-01

    Metal Ni is a plentiful resource that can actively split water toward hydrogen evolution reaction (HER) in alkaline solution, but exploiting high-efficiency Ni-based composite catalysts is still a significant assignment. Therefore, we design a catalytic material with one-step approach to co-electrodeposit Ni nanoparticles and reduced graphene oxide (rGO) sheets on a three-dimensional Ni foam. When the carbon content existed in Ni-rGO composite catalyst is 3.335 at%, the catalyst exhibits excellent activity on HER with a low Tafel slope (b = 77 mV dec-1), a high exchange current density (j0 = 3.408 mA cm-2), small overpotentials of only 36, 129, and 183 mV to drive 10, 60, and 100 mA cm-2 respectively, and high stability under the different current densities. Such remarkable hydrogen evolution performance is attributed to good electrical conductivity, large specific surface area and harmonious synergistic effect between Ni particles and rGO sheets. In addition, density functional theory (DFT) calculations explain that Ni-rGO composite material presents superior interfacial activity in adsorption/desorption of H* compared with pure Ni and rGO sheet.

  14. TiO2/ZnS/CdS Nanocomposite for Hydrogen Evolution and Orange II Dye Degradation

    Directory of Open Access Journals (Sweden)

    Václav Štengl

    2011-01-01

    Full Text Available TiO2/ZnS/CdS composites for photocatalytic hydrogen production from water were prepared by homogeneous hydrolysis of aqueous solutions mixture of TiOSO4, ZnSO4, and CdSO4 with thioacetamide. Hydrogen evolution was observed in the presence of palladium and platinum nanoparticles deposited on TiO2/ZnS/CdS composites. The morphology was obtained by scanning electron microscopy, the nitrogen adsorption-desorption was used for determination of surface area (BET and porosity. The method of UV-VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies of prepared TiO2/ZnS/CdS nano-composites. The photocatalytic activity of the prepared samples were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV irradiation at 365 nm wavelength and visible light up to 400 nm wavelength. Doped titanium dioxide by the CdS increased band-gap energy and doping with ZnS increased photocatalytic activity. The best photocatalytic activity for H2 evolution shows sample named TiZnCd7 on surface deposited with palladium, which contains 20.21% TiO2, 78.5% ZnS, and 1.29% CdS.

  15. Fabrication of platinum coated nanoporous gold film electrode: A nanostructured ultra low-platinum loading electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kiani, Abolfazl; Hatami, Somayeh [Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan (Iran)

    2010-06-15

    The electrolytic hydrogen evolution reaction (HER) on platinum coated nanoporous gold film (PtNPGF) electrode is demonstrated. The deposition of platinum occurred as a spontaneous redox process in which a copper layer, obtained by underpotential deposition, was oxidized by platinum ions, which were reduced and simultaneously deposited. The present method could provide a very low Pt-loading electrode and the results demonstrated that ultra thin Pt coating effected efficiently and behaved as the nanostructured Pt for electrocatalytic hydrogen evolution reaction. The loading of Pt was calculated as 4.2 x 10{sup -3} {mu}g cm{sup -2} for PtNPGF electrode. The current density at -0.4 V and -0.8 V vs. Ag/AgCl was as high as 0.66 A {mu}g{sup -1} Pt and 3 A {mu}g{sup -1} Pt, respectively and the j{sub 0} was evaluated as 0.03 mA cm{sup -2} or 8 mA {mu}g{sup -1} Pt. The results indicated that increasing electrode area had no catalytic effect, but the nanostructure nature of as-fabricated electrode and submonolayer deposition of copper resulted in electrocatalytic activity for PtNPGF electrode. (author)

  16. Enhanced hydrogen evolution performance of ultra thin nanoslice/nanopetal structured XS2 (X = W, Mo): From experiment to theory

    Science.gov (United States)

    Li, Honglin; Yu, Ke; Tang, Zheng; Zhu, Ziqiang

    2016-07-01

    The production of H2 through water splitting to make the reaction process economical and friendly has attracted a lot attention. In this work, we synthesized the novel well-defined nanostructured WS2/MoS2 composite for using as the electrocatalyst of hydrogen evolution. The final obtained nanoslice/nanopetal nanostructured WS2/MoS2 composite possessed massive active sites that originated from its well-defined hierarchical structure with densely stacked MoS2 nanopetals. The synthesized composite exhibited significantly enhanced hydrogen evolution reaction (HER) activity and clearly superior to the pristine MoS2/WS2. With the purpose to give a theoretical explanation of the corresponding enhancement mechanism, the first-principles investigation based on the density functional theory was further employed to survey the electronic properties of different structures. Charge density difference and Bader charge analyses revealed that electrons could directional transfer from WS2 to MoS2 and provided an "electron-rich" environment, which was beneficial to the improvement of HER efficiency. These analytical methods will necessarily offer new angles to explain the enhancement mechanism of HER processes regarding the interaction between WS2 and MoS2, which can accurately elucidate the reason why composite structure exhibits a better HER performance based on the experimental results.

  17. Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

    Science.gov (United States)

    Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J.; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco

    2016-12-01

    Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ~130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.

  18. Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS2 Nanosheets: The Dual Interfacial Effect.

    Science.gov (United States)

    Zhao, Shuo; Jin, Renxi; Song, Yongbo; Zhang, Hui; House, Stephen D; Yang, Judith C; Jin, Rongchao

    2017-07-24

    Hydrogen generation via electrocatalytic water splitting holds great promise for future energy revolution. It is desirable to design abundant and efficient catalysts and achieve mechanistic understanding of hydrogen evolution reaction (HER). Here, this paper reports a strategy for improving HER performance of molybdenum disulfide (MoS2 ) via introducing gold nanoclusters as a cocatalyst. Compared to plain MoS2 nanosheets, the Au25 (SR)18 /MoS2 nanocomposite exhibits enhanced HER activity with a small onset potential of -0.20 V (vs reversible hydrogen electrode) and a higher current density of 59.3 mA cm(-2) at the potential of -0.4 V. In addition to the interfacial interaction between nanoclusters and MoS2 , the interface between the Au25 core and the surface ligands (thiolate vs selenolate) is also discovered to distinctly affect the catalytic performance. This work highlights the promise of metal nanoclusters in boosting the HER performance via tailoring the interfacial electronic interactions between gold nanoclusters and MoS2 nanosheets, as well as the interface between metal core and surface ligands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt-like Activity for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Jana, Rajkumar; Bhim, Anupam; Bothra, Pallavi; Pati, Swapan K; Peter, Sebastian C

    2016-10-20

    Manipulating the d-band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (ΔGH ) close to the optimal adsorption energy (ΔGH =0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine-mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd-rich PdCu (ΔGH =0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm(-2) at ∼69 mV overpotential) as an alternative to Pt for HER. The first-principle calculation suggests that formation of low coordination number Pd active sites alters the d-band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt-free highly active and robust electrocatalysts. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis and characterization of 3D Ni nanoparticle/carbon nanotube cathodes for hydrogen evolution in alkaline electrolyte

    Science.gov (United States)

    McArthur, M. A.; Jorge, L.; Coulombe, S.; Omanovic, S.

    2014-11-01

    Renewable alternative energy sources are required to decrease or eliminate the use of environmentally unfriendly fossil fuels. Hydrogen produced by electrolysis has been identified as one such renewable energy carrier. In the current work, Ni nanoparticle (NP)-decorated multiwall carbon nanotube (MWCNT) electrocatalyst cathodes are prepared by a simple two-step procedure. MWCNTs are grown on stainless steel meshes by thermal-chemical vapour deposition (t-CVD) and then decorated with Ni NPs by pulsed laser ablation (PLA). The morphological and electrochemical properties of the produced Ni NP/MWCNT cathodes were characterized through electron microscopy and linear Tafel polarization (LTP)/electrochemical impedance spectroscopy (EIS), respectively. SEM and TEM imaging revealed that the Ni NPs deposited by PLA are on the order of 4 nm in diameter with a narrow size distribution. The LTP measurements showed that the electrocatalytic activity of the Ni NP/MWCNT cathodes towards the hydrogen evolution reaction (HER) is dependent on PLA time and shows a maximum at tPLA = 40 min. EIS measurements revealed that the HER response is characterized by a two time constants process representing HER kinetics and adsorption of hydrogen.

  1. Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

    Science.gov (United States)

    Pan, Yuan; Yang, Na; Chen, Yinjuan; Lin, Yan; Li, Yanpeng; Liu, Yunqi; Liu, Chenguang

    2015-11-01

    Development of hybrid catalysts with high activity, good stability and low cost is extremely desirable for hydrogen production by electrolysis of water. In this work, a hybrid composed of Ni2P nanoparticles (NPs) on N-doped reduced graphene oxide (NRGO) is synthesized via an in situ thermal decomposition approach for the first time and investigated as a catalyst for the hydrogen evolution reaction (HER). The as-synthesized Ni2P/NRGO hybrid exhibits an enhanced catalytic activity with low onset overpotential (37 mV), a small Tafel slope (59 mV dec-1), a much larger exchange current density (4.9 × 10-5 A cm-2), and lower HER activation energy (46.9 kJ mol-1) than Ni2P/RGO hybrid. In addition, the Ni2P/NRGO hybrid maintains its catalytic activity for at least 60‧000 s in acidic media. The enhanced catalytic activity is attributed to the synergistic effect of N-doped RGO and Ni2P NPs, the charged natures of Ni and P, as well as the high electrical conductivity of Ni2P/NRGO hybrid. This study may offer a new strategy for improving the electrocatalytic activity for hydrogen production.

  2. Fabrication of Low Adsorption Energy Ni-Mo Cluster Cocatalyst in Metal-Organic Frameworks for Visible Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Zhen, Wenlong; Gao, Haibo; Tian, Bin; Ma, Jiantai; Lu, Gongxuan

    2016-05-04

    An effective cocatalyst is crucial for enhancing the visible photocatalytic performance of the hydrogen generation reaction. By using density-functional theory (DFT) and frontier molecular orbital (FMO) theory calculation analysis, the hydrogen adsorption free energy (ΔGH) of Ni-Mo alloy (458 kJ·mol(-1)) is found to be lower than that of Ni itself (537 kJ·mol(-1)). Inspired by these results, the novel, highly efficient cocatalyst NiMo@MIL-101 for photocatalysis of the hydrogen evolution reaction (HER) was fabricated using the double solvents method (DSM). In contrast with Ni@MIL-101 and Mo@MIL-101, NiMo@MIL-101 exhibited an excellent photocatalytic performance (740.2 μmol·h(-1) for HER), stability, and high apparent quantum efficiency (75.7%) under 520 nm illumination at pH 7. The NiMo@MIL-101 catalyst also showed a higher transient photocurrent, lower overpotential (-0.51 V), and longer fluorescence lifetime (1.57 ns). The results uncover the dependence of the photocatalytic activity of HER on the ΔGH of Ni-Mo (MoNi4) alloy nanoclusters, i.e., lower ΔGH corresponding to higher HER activity for the first time. The NiMo@MIL-101 catalyst could be a promising candidate to replace precious-metal catalysts of the HER.

  3. Electrocatalysts Derived from Metal-Organic Frameworks for Oxygen Reduction and Evolution Reactions in Aqueous Media.

    Science.gov (United States)

    Qian, Yuhong; Khan, Inayat Ali; Zhao, Dan

    2017-07-28

    Electrochemical energy conversion and storage devices such as fuel cells and metal-air batteries have been extensively studied in recent decades for their excellent conversion efficiency, high energy capacity, and low environmental impact. However, sluggish kinetics of the oxygen-related reactions at air cathodes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are still worth improving. Noble metals such as platinum (Pt), iridium (Ir), ruthenium (Ru) and their oxides are considered as the benchmark ORR and OER electrocatalysts, but they are expensive and prone to be poisoned due to the fuel crossover effect, and may suffer from agglomeration and leaching after long-term usage. To mitigate these limits, it is highly desirable to design alternative ORR/OER electrocatalysts with prominent performance. Metal-organic frameworks (MOFs) are a class of porous crystalline materials consisting metal ions/clusters coordinated by organic ligands. Their crystalline structure, tunable pore size and high surface area afford them wide opportunities as catalytic materials. This Review covers MOF-derived ORR/OER catalysts in electrochemical energy conversion, with a focus on the different strategies of material design and preparation, such as composition control and nanostructure fabrication, to improve the activity and durability of MOF-derived electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Electronic Coupling of Cobalt Nanoparticles to Nitrogen-Doped Graphene for Oxygen Reduction and Evolution Reactions.

    Science.gov (United States)

    Xu, Chaohe; Lu, Meihua; Yan, Binggong; Zhan, Yi; Balaya, Palani; Lu, Li; Lee, Jim Yang

    2016-11-09

    The rational design of nonprecious-metal electrocatalysts with activities comparable to or greater than that of platinum is extremely valuable to the development of high energy density metal-air batteries. Herein, the two-step preparation of a highly active oxygen electrocatalyst based on ultrasmall cobalt nanoparticles stabilized in a nitrogen-doped graphene matrix is reported. The catalyst performs as well as the commercial Pt/C catalyst in the oxygen reduction reaction, and better than the Pt/C catalyst in the oxygen evolution reaction. This particular electrocatalyst could significantly lower the overpotentials of oxygen electrochemical reactions in aqueous lithium-air batteries to attain a round-trip efficiency of about 79.0 % at a current density of 0.1 mA cm(-2) , thereby surpassing the performance of the commercial Pt/C catalyst. The good performance may be attributed to strong metal-support interactions, maximized by a high dispersion of ultrasmall cobalt nanocrystals in a nitrogen-doped graphene matrix, which yields electrocatalytic properties greater than the sum of its parts. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    Science.gov (United States)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  6. Photoelectrochemical hydrogen-evolution over p-type chalcopyrite CuInSe{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Djellal, L. [Laboratoire des Solutions Solides, Faculte de Physique, (USTHB) BP 32 El Alia 16111, Algiers (Algeria); Omeiri, S.; Bouguelia, A. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, (USTHB) BP 32 El Alia 16111, Algiers (Algeria); Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, (USTHB) BP 32 El Alia 16111, Algiers (Algeria)], E-mail: mtrari@caramail.com

    2009-05-12

    Photocatalytic H{sub 2}-production has been realized over active CuInSe{sub 2}, synthesized by the fusion technique. The material crystallizes in the chalcopyrite structure and exhibits p-type conductivity ascribed to copper deficiency. An optical gap of 0.95 eV was determined from the reflectance diffuse spectrum. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polaron hopping. The slope and the intercept of the Mott-Schottky plot gave a holes density N{sub A} of 5.9 x 10{sup 18} cm{sup -3} and a flat band potential of -0.36V{sub SCE}, in perfect agreement with the photo-onset potential V{sub on} (-0.35V{sub SCE}). Hence, the conduction band, located at -1.29V{sub SCE}, allows a spontaneous H{sub 2} liberation upon visible light. In aqueous solutions, the material is stabilized by hole consumption involving X{sup 2-} species (=S{sup 2-} and SO{sub 3}{sup 2-}). H{sub 2} formation would become thermodynamically easy in alkaline media and the best photoactivity was obtained in thiosulfate electrolyte (10{sup -2} M S{sub 2}O{sub 3}{sup 2-}, 0.5 M KOH) with an evolution rate of 0.009 ml mg{sup -1} h{sup -1}. The light induced electron transfer through the interface involves two steps mechanism where S{sub 2}O{sub 3}{sup 2-} is oxidized to SO{sub 3}{sup 2-} and SO{sub 4}{sup 2-} by successive reactions. Such results are corroborated by the semi logarithmic plots and photocurrent-photopotential characteristics. The influence of pH was studied with S{sub 2}O{sub 3}{sup 2-} The tendency towards saturation for prolonged irradiation is attributed to competitive reductions of the end products S{sub n}{sup 2-} and S{sub 2}O{sub 6}{sup 2-} with water and to the yellow color of polysulfide S{sub n}{sup 2-}.

  7. Hydrogen photo-evolution over the spinel CuCr{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Boumaza, Souhila [Laboratoire de Chimie de Gaz Naturel, USTHB, BP 32 16111 Algiers (Algeria); Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (C.R.A.P.C) BP248 Algiers RP, 16004 (Algeria); Bouarab, Rabah [Laboratoire de Chimie de Gaz Naturel, USTHB, BP 32 16111 Algiers (Algeria); Trari, Mohamed; Bouguelia, Aissa [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, USTHB, BP 32 Bab Ezzouar, 16111 Algiers (Algeria)

    2009-01-15

    The photocatalytic H{sub 2} evolution over CuCr{sub 2}O{sub 4} has been studied in connection with some physical properties. The black oxide is classified as a narrow band gap semiconductor crystallizing in the normal spinel structure. The photoactivity is dependent on the preparative conditions through the surface area of the powder and CuCr{sub 2}O{sub 4} has been synthesized by nitrate route. The conductivity varies exponentially with temperature indicating an extrinsic conductivity between mixed valences states Cr{sup 3+/4+} located in octahedra sharing common corners. The oxide exhibits p-type conductivity with an activation energy of 0.20 eV and a hole mobility of 2.14 x 10{sup -8} cm{sup 2}/V s thermally activated. CuCr{sub 2}O{sub 4} shows an excellent chemical stability, a corrosion potential of -0.775 V{sub SCE} and an exchange current density of 16 {mu}A cm{sup -2} have been determined from the semilogarithm plot. The capacitance measurement (C{sup -2}-V), performed in basic electrolyte, exhibits a linear behavior from which a flat band potential of 0.48 V{sub SCE} was obtained. CuCr{sub 2}O{sub 4} is photoelectrochemically stable by hole consumption reactions involving X{sup 2-} (=SO{sub 3}{sup 2-} and S{sub 2} O{sub 3}{sup 2-}) as hole scavengers. The best catalytic performance for H{sub 2}-photoproduction was obtained in (NaOH 0.5 M, Na{sub 2}S{sub 2}O{sub 3} 0.025 M) with an average rate of 0.013 cm{sup 3} h{sup -1} (mg catalyst){sup -1} and a quantum efficiency of 0.2% under polychromatic light. S{sub 2} O{sub 3}{sup 2-} is oxidized to SO{sub 3}{sup 2-} and subsequently to SO{sub 4}{sup 2-} as proven by the dual slopes in the Tafel plot. The system shows a tendency towards saturation whose deceleration is the result of the competitive reductions of the end products namely S{sub 2} O{sub 6}{sup 2-} and S{sub 2} O{sub 4}{sup 2-} with the water discharge. (author)

  8. Hydrogen evolution by fermentation using seaweed as substrates and the contribution to the clean energy production

    Energy Technology Data Exchange (ETDEWEB)

    Tanisho, S.; Suganuma, T.; Yamaguchi, A. [Yokohama National Univ. (Japan). Dept. of Environmental Sciences

    2001-07-01

    It is an important theme in Japan to use the sea for energy production, because Japan is surrounded by seas on all sides. Brown algae such as Laminaria have high value as the substrate of fermentative hydrogen production, since they have very high growth rate and also have high ability on the productivity of mannitol. I would like to present about the affection of salt concentration on the hydrogen production of Enterobacter aerogenes, and also the contribution on clean energy production by the seaweed cultivation in Japan. (orig.)

  9. Electrochemical hydrogen evolution of multi-walled carbon nanotube/micro-hybrid composite decorated with Ni nanoparticles as catalyst through electroless deposition process.

    Science.gov (United States)

    Rahimi, Nazanin; Doroodmand, Mohammad Mahdi; Sabbaghi, Samad; Sheikhi, Mohammad Hossein

    2013-08-01

    Hydrogen evolution of multi-walled nanotube (MWCNT)/micro-hybrid polymer composite, decorated with Ni nanoparticles through electroless deposition process is studied by the electrochemical method. Cyclic voltammetry (CV) is utilized to clearly study the electrochemical hydrogen storage/evolution behavior of the composite through a potential window ranging from -1.60 to +0.60 V (vs. Ag/AgCl). Hydrogen adsorption/desorption peaks are positioned at -1.52 and -0.05 V, respectively. Chronoamperometry is also applied to estimate active surface area (0.145 m(2)g(-1)) of the composite as well as the diffusion coefficient (3.4×10(-11) m(2) s(-1)) of adsorbed hydrogen process. According to the chrono-charge/discharge technique, the capacity of fabricated Ni-MWCNT/micro-hybrid composite is estimated to be 2.98 wt.% during charging for a certain time (40 min).

  10. A hydrogen-bond facilitated cycle for oxygen reduction by an acid- and base-compatible iron platform.

    Science.gov (United States)

    Soo, Han Sen; Komor, Alexis C; Iavarone, Anthony T; Chang, Christopher J

    2009-11-02

    We report a hydrogen-bond functionalized N4Py ligand platform (N,N-bis(2-R-6-pyridylmethyl)-N-bis(2-pyridyl)methylamine; R = neopentyl-NH, N4Py(2NpNH), 9; R = phenyl-NH, N4Py(2PhNH), 10) and the ability of its iron(II)-triflate [N4Py(2R)Fe(II)(OTf)][OTf] complexes (R = NpNH, 11; R = PhNH, 12) to activate and reduce dioxygen in a synthetic cycle by coupled proton and electron transfer. A pair of iron(III)-hydroxide [N4Py(2R)Fe(III)(OH)][OTf](2) complexes (R = NpNH, 13; R = PhNH, 14) are isolated and structurally and spectroscopically characterized after exposure of the iron(II)-triflate precursors to 1 atm of O(2) at ambient temperature. The stability of this system to acids and bases allows regeneration of the labile iron(II)-triflate starting materials by sequential electron and proton transfer with cobaltocene and triflic acid, respectively, or through direct proton-coupled reduction with ascorbic acid. In the stepwise process, reduction of the iron(III)-hydroxide complexes with cobaltocene gives structurally homologous iron(II)-hydroxide [N4Py(2R)Fe(II)(OH)][OTf] congeners (R = NpNH, 15; R = PhNH, 16) that can be prepared independently from 11 and 12 with 20% aq. NaOH. Additions of triflic acid to complexes 15 and 16 furnish the starting compounds 11 and 12, respectively, to complete the synthetic cycle. The combined data establish a synthetic cycle for O(2) reduction by an iron platform that manages proton and electron transfer through its first and second coordination spheres.

  11. The non-metathetic role of Grubbs' carbene complexes: from hydrogen-free reduction of α,β-unsaturated alkenes to solid-supported sequential cross-metathesis/reduction.

    Science.gov (United States)

    Poeylaut-Palena, Andrés A; Testero, Sebastián A; Mata, Ernesto G

    2011-02-07

    An efficient and high-yielding "hydrogen-free" reduction of α,β-unsaturated alkenes was carried out employing Grubbs' catalyst in a non-metathetic role and Et(3)SiH. Conditions were optimized under microwave irradiation. Application to the solid-phase organic synthesis allows a facile construction of sp(3)-sp(3) carbon bonds through a sequential cross metathesis/olefin reduction.

  12. Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

    NARCIS (Netherlands)

    Kluwer, A.M.; Kapre, R.; Hartl, F.; Lutz, M.; Spek, A.L.; Brouwer, A.M.; van Leeuwen, P.W.N.M.; Reek, J.N.H.

    2009-01-01

    The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a su

  13. Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer.

    Science.gov (United States)

    Symes, Mark D; Cronin, Leroy

    2013-05-01

    Hydrogen is essential to several key industrial processes and could play a major role as an energy carrier in a future 'hydrogen economy'. Although the majority of the world's hydrogen supply currently comes from the reformation of fossil fuels, its generation from water using renewables-generated power could provide a hydrogen source without increasing atmospheric CO₂ levels. Conventional water electrolysis produces H₂ and O₂ simultaneously, such that these gases must be generated in separate spaces to prevent their mixing. Herein, using the polyoxometalate H₃PMo₁₂O₄₀, we introduce the concept of the electron-coupled-proton buffer (ECPB), whereby O₂ and H₂ can be produced at separate times during water electrolysis. This could have advantages in preventing gas mixing in the headspaces of high-pressure electrolysis cells, with implications for safety and electrolyser degradation. Furthermore, we demonstrate that temporally separated O₂ and H₂ production allows greater flexibility regarding the membranes and electrodes that can be used in water-splitting cells.

  14. Complete bromate and nitrate reduction using hydrogen as the sole electron donor in a rotating biofilm-electrode reactor

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Yu; Li, Xin [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Advanced Water Management Centre, The University of Queensland, QLD 4072 (Australia); Yao, Fubing [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Li, Xiaoming, E-mail: xmli@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Zhao, Jianwei; Xu, Qiuxiang; Zhang, Chang; Zeng, Guangming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

    2016-04-15

    Graphical abstract: Main mechanism of simultaneous bromate and nitrate removal in the RBER. - Highlights: • Cathode of RBER was designed to automatically rotate. • Simultaneous bromate and nitrate removal was achieved by auto-hydrogenotrophic reduction. • The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h. • An electron transfer process and main reaction mechanism in RBER was explored. - Abstract: Simultaneous reduction of bromate and nitrate was investigated using a rotating biofilm-electrode reactor (RBER) with graphite carbon (GC) rods as anode and activated carbon fiber (ACF) bonded with steel ring as cathode. In RBER, the community of denitrifying bacteria immobilized on the cathode surface could completely utilize hydrogen (H{sub 2}) as the electron donor, which was internally produced by the electrolysis of water. The short-term test confirmed that the RBER system could reduce 150–800 μg/L bromate to below 10 μg/L under autotrophic conditions. The reduced bromate was considered to be roughly equivalent to the amount of bromide in effluent, indicating that bromate was completely reduced to bromide without accumulation of by-products. The long-term test (over 120 days) showed that the removal fluxes of bromate and nitrate could be improved by increasing the electric current and decreasing the hydraulic retention time (HRT). But nitrite in effluent was significantly accumulated when the electric current was beyond 10 mA and the HRT was less than 6 h. The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h when the electric current was 10 mA and HRT was 12 h. It was proposed that the electron transfer process in RBER produced H{sub 2} on the surface of the ACF cathode, and the microbial cultures attached closely on the cathode which could completely utilize H{sub 2} as electron donors for reduction of bromate and nitrate.

  15. Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

    2016-03-21

    The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light.

  16. High Surface Area Tungsten Carbides: Synthesis, Characterization and Catalytic Activity towards the Hydrogen Evolution Reaction in Phosphoric Acid at Elevated Temperatures

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Li, Qingfeng; Jensen, Jens Oluf

    2014-01-01

    Tungsten carbide powders were synthesized as a potential electrocatalyst for the hydrogen evolution reaction in phosphoric acid at elevated temperatures. With ammonium metatungstate as the precursor, two synthetic routes with and without carbon templates were investigated. Through the intermediate...... nitride route and with carbon black as template, the obtained tungsten carbide samples had higher BET area. In 100% H3PO4 at temperatures up to 185°C, the carbide powders showed superior activity towards the hydrogen evolution reaction. A deviation was found in the correlation between the BET area...

  17. Catalytic reduction of nitrate and nitrite ions by hydrogen : investigation of the reaction mechanism over Pd and Pd-Cu catalysts

    NARCIS (Netherlands)

    Ilinitch, OM; Nosova, LV; Gorodetskii, VV; Ivanov, VP; Trukhan, SN; Gribov, EN; Bogdanov, SV; Cuperus, FP

    2000-01-01

    The catalytic behavior of mono- and bimetallic catalysts with Pd and/or Cu supported over gamma-Al2O3 in the reduction of aqueous nitrate and nitrite ions by hydrogen was investigated. The composition of the supported metal catalysts was analysed using secondary ion mass spectroscopy (SIMS) and X-ra

  18. Effect of Hydrogen Reduction of Silver Ions on the Performance and Structure of New Solid Polymer Electrolyte PEI/Pebax2533/AgBF4 Composite Membranes

    Institute of Scientific and Technical Information of China (English)

    WANG Yanbei; REN Jizhong; LI Hui; DENG Maicun

    2013-01-01

    In this paper,the effect of hydrogen reduction of silver ions on the performance and structure of new solid polymer electrolyte polyetherimide (PEI)/Pebax2533 (Polynylon12/tetramethylene oxide block copolymer,PA12-PTMO)/AgBF4 composite membranes is investigated.For PEI/Pebax2533/AgBF4 composite membranes prepared with different AgBF4 concentration,the permeances of propylene and ethylene increase with the increase of AgBF4 concentration due to the carrier-facilitated transport,resulting in a high selectivity.But for propylene/propane mixture,the mixed-gas selectivity is lower than its ideal selectivity.The hydrogen reduction strongly influences the membrane performance,which causes the decrease of propylene permeance and the increase of propane permeance.With the increase of hydrogen reduction time,the membranes show a clearly color change from white to brow0n,yielding a great selectivity loss.The data of X-ray diffraction and FT-IR prove that silver ions are reduced to Ag after hydrogen reduction,and aggregated on the surface of PEI/Pebax2533/AgBF4 composite membranes.

  19. A rationally designed amino-borane complex in a metal organic framework: A novel reusable hydrogen storage and size-selective reduction material

    KAUST Repository

    Wang, Xinbo

    2015-01-01

    A novel amino-borane complex inside a stable metal organic framework was synthesized for the first time. It releases hydrogen at a temperature of 78 °C with no volatile contaminants and can be well reused. Its application as a size-selective reduction material in organic synthesis was also demonstrated. © The Royal Society of Chemistry 2015.

  20. Photocatalytic hydrogen evolution from glycerol and water over nickel-hybrid cadmium sulfide quantum dots under visible-light irradiation.

    Science.gov (United States)

    Wang, Jiu-Ju; Li, Zhi-Jun; Li, Xu-Bing; Fan, Xiang-Bing; Meng, Qing-Yuan; Yu, Shan; Li, Cheng-Bo; Li, Jia-Xin; Tung, Chen-Ho; Wu, Li-Zhu

    2014-05-01

    Natural photosynthesis offers the concept of storing sunlight in chemical form as hydrogen (H2), using biomass and water. Herein we describe a robust artificial photocatalyst, nickel-hybrid CdS quantum dots (Nih-CdS QDs) made in situ from nickel salts and CdS QDs stabilized by 3-mercaptopropionic acid, for visible-light-driven H2 evolution from glycerol and water. With visible light irradiation for 20 h, 403.2 μmol of H2 was obtained with a high H2 evolution rate of approximately 74.6 μmol h(-1)  mg(-1) and a high turnover number of 38 405 compared to MPA-CdS QDs (mercaptopropionic-acid-stabilized CdS quantum dots). Compared to CdTe QDs and CdSe QDs, the modified CdS QDs show the greatest affinity toward Ni(2+) ions and the highest activity for H2 evolution. X-ray photoelectron spectroscopy (XPS), inductively-coupled plasma atomic emission spectrometry (ICP-AES), and photophysical studies reveal the chemical nature of the Nih-CdS QDs. Electron paramagnetic resonance (EPR) and terephthalate fluorescence measurements clearly demonstrate water splitting to generate ⋅OH radicals. The detection of DMPO-H and DMPO-C radicals adduct in EPR also indicate that ⋅H radicals and ⋅C radicals are the active species in the catalytic cycle.

  1. 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

  2. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ˜1,663 m2 g-1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn-1 (corresponding to an energy density of 835 Wh kgZn-1), a peak power density of 55 mW cm-2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm-2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

  3. A vertical-oriented WS2 nanosheet sensitized by graphene: an advanced electrocatalyst for hydrogen evolution reaction

    Science.gov (United States)

    Shifa, Tofik Ahmed; Wang, Fengmei; Cheng, Zhongzhou; Zhan, Xueying; Wang, Zhenxing; Liu, Kaili; Safdar, Muhammad; Sun, Lianfeng; He, Jun

    2015-08-01

    Electrocatalytic hydrogen production at low overpotential is a promising route towards a clean and sustainable energy. Layered transition metal dichalcogenides (LTMDs) have attracted copious attention for their outstanding activities in hydrogen evolution reaction (HER). However, the horizontally laid nanosheets suffer from a paucity of active edge sites. Herein, we report the successful synthesis of vertical-oriented WS2 nanosheets through a hydrothermal method followed by a facile sulfurization process. Furthermore, the surface of synthesized WS2 nanosheets was decorated by ultrathin reduced graphene oxide (rGO) nanoplates. This is achieved for the first time by bringing the rGO on the surface of vertical-oriented WS2 nanosheets, which is conducive to rapid electron transport during the HER process. Significantly, the as-synthesized rGO/WS2 nanosheets exhibit improved HER activity as compared to the undecorated ones. It needs a low overpotential of only 229 mV vs. RHE to afford a current density of 10 mA cm-2. We believe that this hybrid structure demonstrated remarkable HER activity brought about by a compatible synergism between rGO and WS2.Electrocatalytic hydrogen production at low overpotential is a promising route towards a clean and sustainable energy. Layered transition metal dichalcogenides (LTMDs) have attracted copious attention for their outstanding activities in hydrogen evolution reaction (HER). However, the horizontally laid nanosheets suffer from a paucity of active edge sites. Herein, we report the successful synthesis of vertical-oriented WS2 nanosheets through a hydrothermal method followed by a facile sulfurization process. Furthermore, the surface of synthesized WS2 nanosheets was decorated by ultrathin reduced graphene oxide (rGO) nanoplates. This is achieved for the first time by bringing the rGO on the surface of vertical-oriented WS2 nanosheets, which is conducive to rapid electron transport during the HER process. Significantly, the as

  4. Reduction of aldehydes and hydrogen cyanide yields in mainstream cigarette smoke using an amine functionalised ion exchange resin

    Directory of Open Access Journals (Sweden)

    Duke Martin G

    2011-04-01

    Full Text Available Abstract Background Cigarette smoking is a well recognized cause of diseases such as lung cancer, chronic obstructive pulmonary disease and cardiovascular disease. Of the more than 5000 identified species in cigarette smoke, at least 150 have toxicological activity. For example, formaldehyde and acetaldehyde have been assigned as Group 1 and Group 2B carcinogens by IARC, and hydrogen cyanide has been identified as a respiratory and cardiovascular toxicant. Active carbon has been shown to be an effective material for the physical adsorption of many of the smoke volatile species. However, physical adsorption of acetaldehyde, formaldehyde and also hydrogen cyanide from smoke is less effective using carbon. Alternative methods for the removal of these species from cigarette smoke are therefore of interest. A macroporous, polystyrene based ion-exchange resin (Diaion®CR20 with surface amine group functionality has been investigated for its ability to react with aldehydes and HCN in an aerosol stream, and thus selectively reduce the yields of these compounds (in particular formaldehyde in mainstream cigarette smoke. Results Resin surface chemistry was characterized using vapour sorption, XPS, TOF-SIMS and 15N NMR. Diaion®CR20 was found to have structural characteristics indicating weak physisorption properties, but sufficient surface functionalities to selectively remove aldehydes and HCN from cigarette smoke. Using 60 mg of Diaion®CR20 in a cigarette cavity filter gave reductions in smoke formaldehyde greater than 50% (estimated to be equivalent to >80% of the formaldehyde present in the smoke vapour phase independent of a range of flow rates. Substantial removal of HCN (>80% and acetaldehyde (>60% was also observed. The performance of Diaion®CR20 was found to be consistent over a test period of 6 months. The overall adsorption for the majority of smoke compounds measured appeared to follow a pseudo-first order approximation to second order

  5. Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

    Science.gov (United States)

    Becker, R. S.; Hong, K.; Hong, J. H.

    1974-01-01

    Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

  6. The urchin-like sphere arrays Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction

    Science.gov (United States)

    Li, Ruchun; Zhou, Dan; Luo, Jiaxian; Xu, Weiming; Li, Jingwei; Li, Shuoshuo; Cheng, Pengpeng; Yuan, Dingsheng

    2017-02-01

    Electrochemical water splitting has attracted great interest because of the growing demand for sustainable energy and increasing concerns for the environment. We present a facile strategy to design the three-dimensional (3D) urchin-like sphere arrays Co3O4 as an effective bifunctional catalyst for electrochemical water splitting. The 3D urchin-like Co3O4 was directly grown on Ni foam by a hydrothermal reaction and annealing treatment at a low temperature. This process offers several advantages including facile synthesis, binder-free, and low cost. The 3D urchin-like Co3O4 as a catalyst for hydrogen evolution reaction exhibits a low onset potential (-130 mV vs. RHE) and good cycling stability in an alkaline electrolyte. When urchin-like Co3O4 is used as a catalyst for oxygen evolution reaction, the onset potential is at 1.46 V (vs. RHE) with a low overpotential of only 230 mV. The good catalytic activity can be attributed to the unique urchin-like nanostructure, abundant mesopores, and low charge-transfer resistance (compared with Co3O4 NPs). In addition, H2 and O2 generation was performed using Co3O4 as both cathode and anode catalysts with a potential of 1.64 V to reach a current density of 10 mA cm-2.

  7. The Transition from Atomic to Molecular Hydrogen in Interstellar Clouds: 21cm Signature of the Evolution of Cold Atomic Hydrogen in Dense Clouds

    CERN Document Server

    Goldsmith, P F; Krco, M; Goldsmith, Paul F.; Li, Di; Krco, Marko

    2006-01-01

    We have investigated the time scale for formation of molecular clouds by examining the conversion of HI to H2 using a time-dependent model. H2 formation on dust grains and cosmic ray and photo destruction are included in one-dimensional model slab clouds which incorporate time-independent density and temperature distributions. We calculate 21cm spectral line profiles seen in absorption against a background provided by general Galactic HI emission, and compare the model spectra with HI Narrow Self-Absorption, or HINSA, profiles absorbed in a number of nearby molecular clouds. The time evolution of the HI and H2 densities is dramatic, with the atomic hydrogen disappearing in a wave propagating from the central, denser regions which have a shorter H2 formation time scale, to the edges, where the density is lower and the time scale for H2 formation longer. The model 21cm spectra are characterized by very strong absorption at early times, when the HI column density through the model clouds is extremely large. The ...

  8. Photoinduced hydrogen evolution with new tetradentate cobalt(ii) complexes based on the TPMA ligand.

    Science.gov (United States)

    Natali, Mirco; Badetti, Elena; Deponti, Elisa; Gamberoni, Marta; Scaramuzzo, Francesca A; Sartorel, Andrea; Zonta, Cristiano

    2016-10-07

    Hydrogen production from water splitting is nowadays recognized as a target, fundamental reaction for the production of clean fuels. Indeed, tremendous efforts have been devoted towards the research of suitable catalysts capable of performing this reaction. With respect to heterogeneous systems, molecular catalysts such as metal complexes are amenable to chemical functionalization in order to fine tune the catalytic properties. In this paper a new class of tris(2-pyridylmethyl)-amine (TPMA) cobalt(ii) complexes (CoL0-4) has been synthesized and employed as hydrogen evolving catalysts under photochemical conditions taking advantage of Ru(bpy)3(2+) (where bpy is 2,2'-bipyridine) as a light-harvesting sensitizer and ascorbic acid as a sacrificial electron donor. Tuning of the photocatalytic activity has been attempted through the introduction of different substituents at the catalyst periphery rather than through a direct chemical modification of the chelating TPMA ligand. The results show that CoL0-4 behave as competent hydrogen evolving catalysts (HECs), although the effects played by the different substituents on the catalysis are relatively modest. Possible reasons supporting the observed behavior as well as possible improvements of the aforementioned tuning approach are discussed.

  9. Rhodium-doped barium titanate perovskite as a stable p-type semiconductor photocatalyst for hydrogen evolution under visible light.

    Science.gov (United States)

    Maeda, Kazuhiko

    2014-02-12

    Rhodium-doped barium titanate (BaTiO3:Rh) powder was prepared by the polymerized complex (PC) method, and the photocatalytic activity for H2 evolution from water was examined. BaTiO3 is a wide-gap n-type semiconductor having a band gap of 3.0 eV. Doping Rh species into the lattice of BaTiO3 resulted in the formation of new absorption bands in visible light region. Upon visible light (λ > 420 nm), BaTiO3:Rh modified with nanoparticulate Pt as a water reduction promoter was capable of producing H2 from water containing an electron donor such as methanol and iodide. The best material prepared by the PC method exhibited higher activity than that made by a conventional solid-state reaction method. Visible-light-driven Z-scheme water splitting was also accomplished using Pt/BaTiO3:Rh as a building block for H2 evolution in combination with PtOx-loaded WO3 as an O2 evolution photocatalyst in the presence of an IO3(-)/I(-) shuttle redox mediator. Photoelectrochemical analysis indicated that a porous BaTiO3:Rh electrode exhibited cathodic photoresponse due to water reduction in a neutral aqueous Na2SO4 solution upon visible light.

  10. Continuous hydrogen evolution by an immobilized combined system of Phormidium valderianum, Halobacterium halobium and Escherichia coli in a packed bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Patel, S.; Madamwar, D. [Sardar Patel Univ., Vallabh Vidyanagar (India)

    1995-12-01

    Long-term hydrogen evolution (11 days) was obtained when Phormidium valderianum was coupled with a mixture of halophilic Halobacterium halobium and salt tolerant Escherichia coli under a cyclic illumination on/off cycle of 18 h dark and 6 h light in an immobilized packed bed reactor. Various conditions such as flow rate, temperature and pH have been optimized for maximum continuous evolution. (author)

  11. Nanoscal design of molybdenum sulfides for more efficient electro- and photoelectrocatalytic hydrogen evolution

    DEFF Research Database (Denmark)

    Laursen, Anders Bo

    . The electrochemical oxidation behavior of MoSx was investigated compared to that of MoS2, and MoS3. It was found that the MoSx demonstrated a unique oxidation behavior indicating that the active sites were not MoS2 or MoS3-like - further experiments are needed to clarify the relation between oxidation behavior and H2...... of active molybdenum sulfide based H2 evolution catalysts. This demonstrated the potential of molybdenum sulfides as electro- and photoelectrochemical catalysts for the H2 evolution reaction....

  12. Reduction Kinetics of Magnetite Concentrate Particles with Hydrogen at 1150-1600 °C Relevant to a Novel Flash Ironmaking Process

    Science.gov (United States)

    Elzohiery, Mohamed; Mohassab, Yousef; Abdelghany, Amr; Zhang, Shengqin; Chen, Feng; Sohn, Hong Yong

    A novel ironmaking process is under development at the University of Utah aimed at producing iron directly from iron oxide concentrate in a flash reactor. This process will reduce hazardous emissions and save energy. The kinetics of magnetite reduction with hydrogen was previously investigated in our laboratory in the temperature range 1150 to 1400 °C at large temperature increments ( 100 °C increments). Due to the significant melting that occurs above 1350 °C, the reduction kinetics was measured and analyzed in two distinct temperature ranges of 1150 to 1350 °C and 1350 to 1600 °C ( 50 °C increments). Experiments were performed using magnetite concentrate particles of different sizes under various hydrogen partial pressures and residence times. Reduction degrees of more than 90 % were achieved in a few seconds at temperatures as low as 1250 °G Different rate expressions were needed to obtain reliable agreement with experimental data.

  13. Ammonia intercalated flower-like MoS2 nanosheet film as electrocatalyst for high efficient and stable hydrogen evolution

    Science.gov (United States)

    Wang, F. Z.; Zheng, M. J.; Zhang, B.; Zhu, C. Q.; Li, Q.; Ma, L.; Shen, W. Z.

    2016-08-01

    Ammonia intercalated flower-like MoS2 electrocatalyst film assembled by vertical orientated ultrathin nanosheet on graphite sheethas been successfully synthesized using one-step hydrothermal method. In this strategy, ammonia can effectively insert into the parallel plane of the MoS2 nanosheets, leading to the expansion of lattice and phase transfer from 2H to 1T, generating more active unsaturated sulfur atoms. The flower-like ammoniated MoS2 electrocatalysts with more active sites and large surface area exhibited excellent HER activity with a small Tafel slope and low onset overpotential, resulting a great enhancement in hydrogen evolution. The high efficient activity and recyclable utilization, as well as large-scale, indicate that it is a very promising electrocatalyst to replace Pt in industry application.

  14. Metallic Iron-Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media.

    Science.gov (United States)

    Long, Xia; Li, Guixia; Wang, Zilong; Zhu, HouYu; Zhang, Teng; Xiao, Shuang; Guo, Wenyue; Yang, Shihe

    2015-09-23

    We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor. The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst. The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm(2) and a smaller Tafel slope of 40 mV/dec. With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H(+) adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER.

  15. Interfacial engineering of MoS2/TiO2 hybrids for enhanced electrocatalytic hydrogen evolution reaction

    Science.gov (United States)

    Song, Xiaolin; Chen, Guifeng; Guan, Lixiu; Zhang, Hui; Tao, Junguang

    2016-09-01

    Herein, we show that the synergistic effect between MoS2 and TiO2 enhances the hydrogen evolution reaction (HER) performance of their hybrids, which is tunable via interface engineering. Among several interfaces, MoS2/TiO2-H complexes exhibit the best HER activity. The observed Tafel slope of 66.9 mV/dec is well in range of previous literature reports, suggesting a Volmer-Heyrovsky mechanism. Enhanced activities were attributed to abundant active sites at the interfaces, as well as improved charge transfer efficiency. Our results emphasize the roles that interfaces play in enhancing the HER activities of MoS2-based heterogeneous catalysts.

  16. Nanoporous FeP nanorods grown on Ti plate as an enhanced binder-free hydrogen evolution cathode

    Science.gov (United States)

    Gao, J. J.; Luo, P.; Qiu, H.-J.; Wang, Y.

    2017-03-01

    A porous and interconnected nanorod-like FeP structure on titanium plate has been fabricated by a simple hydrothermal method and followed by a calcination process. The nanorod is assembled by many paralleled FeP nanowires with a porous structure. With the porous surface structure of FeP nanorods and the synergetic effect from the electronic conductive Ti support, this binder-free FeP electrode brings about a desirable electrocatalytic activity for the hydrogen evolution reaction (HER), showing a low onset overpotential of 23 mV and a small Tafel slope of 39 mV dec‑1. Meanwhile, its catalytic activity could be maintained almost unchanged for at least 12 h in an acidic solution. This work provides us an effective HER electrocatalyst which can be easily produced on a large scale and at low cost.

  17. 2D Transition Metal Dichalcogenides and Graphene-Based Ternary Composites for Photocatalytic Hydrogen Evolution and Pollutants Degradation

    Science.gov (United States)

    Chen, Ying; Sun, Hongqi; Peng, Wenchao

    2017-01-01

    Photocatalysis have attracted great attention due to their useful applications for sustainable hydrogen evolution and pollutants degradation. Transition metal dichalcogenides (TMDs) such as MoS2 and WS2 have exhibited great potential as cocatalysts to increase the photo-activity of some semiconductors. By combination with graphene (GR), enhanced cocatalysts of TMD/GR hybrids could be synthesized. GR here can act as a conductive electron channel for the transport of the photogenerated electrons, while the TMDs nanosheets in the hybrids can collect electrons and act as active sites for photocatalytic reactions. This mini review will focus on the application of TMD/GR hybrids as cocatalysts for semiconductors in photocatalytic reactions, by which we hope to provide enriched information of TMD/GR as a platform to develop more efficient photocatalysts for solar energy utilization. PMID:28336898

  18. Embedding Metal in the Interface of a p-n Heterojunction with a Stack Design for Superior Z-Scheme Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Yin, Wenjie; Bai, Lijie; Zhu, Yuzhen; Zhong, Shuxian; Zhao, Leihong; Li, Zhengquan; Bai, Song

    2016-09-07

    The construction of a p-n heterojunction is an efficient strategy to resolve the limited light absorption and serious charge-carrier recombination in semiconductors and enhance the photocatalytic activity. However, the promotion effect is greatly limited by poor interfacial charge transfer efficiency as well as reduced redox ability of charge carriers. In this work, we demonstrate that the embedding of metal Pd into the interface between n-type C3N4 and p-type Cu2O can further enhance the interfacial charge transfer and increase the redox ability of charge carriers through the design of the C3N4-Pd-Cu2O stack nanostructure. The embedded Pd nanocubes in the stack structure not only trap the charge carriers from the semiconductors in promoting the electron-hole separation but also act as a Z-scheme "bridge" in keeping the strong reduction/oxidation ability of the electrons/holes for surface reactions. Furthermore, Pd nanocubes also increase the bonding strength between the two semiconductors. Enabled by this unique design, the hydrogen evolution achieved is dramatically higher than that of its counterpart C3N4-Cu2O structure without Pd embedding. The apparent quantum efficiency (AQE) is 0.9% at 420 nm for the designed C3N4-Pd-Cu2O. This work highlights the rational interfacial design of heterojunctions for enhanced photocatalytic performance.

  19. Three-Dimensional Heterostructures of MoS 2 Nanosheets on Conducting MoO 2 as an Efficient Electrocatalyst To Enhance Hydrogen Evolution Reaction

    KAUST Repository

    Nikam, Revannath Dnyandeo

    2015-10-05

    Molybdenum disulfide (MoS) is a promising catalyst for hydrogen evolution reaction (HER) because of its unique nature to supply active sites in the reaction. However, the low density of active sites and their poor electrical conductivity have limited the performance of MoS in HER. In this work, we synthesized MoS nanosheets on three-dimensional (3D) conductive MoO via a two-step chemical vapor deposition (CVD) reaction. The 3D MoO structure can create structural disorders in MoS nanosheets (referred to as 3D MoS/MoO), which are responsible for providing the superior HER activity by exposing tremendous active sites of terminal disulfur of S2 (in MoS) as well as the backbone conductive oxide layer (of MoO) to facilitate an interfacial charge transport for the proton reduction. In addition, the MoS nanosheets could protect the inner MoO core from the acidic electrolyte in the HER. The high activity of the as-synthesized 3D MoS/MoO hybrid material in HER is attributed to the small onset overpotential of 142 mV, a largest cathodic current density of 85 mA cm, a low Tafel slope of 35.6 mV dec, and robust electrochemical durability.

  20. Three-Dimensional Heterostructures of MoS2 Nanosheets on Conducting MoO2 as an Efficient Electrocatalyst To Enhance Hydrogen Evolution Reaction.

    Science.gov (United States)

    Nikam, Revannath Dnyandeo; Lu, Ang-Yu; Sonawane, Poonam Ashok; Kumar, U Rajesh; Yadav, Kanchan; Li, Lain-Jong; Chen, Yit-Tsong

    2015-10-21

    Molybdenum disulfide (MoS2) is a promising catalyst for hydrogen evolution reaction (HER) because of its unique nature to supply active sites in the reaction. However, the low density of active sites and their poor electrical conductivity have limited the performance of MoS2 in HER. In this work, we synthesized MoS2 nanosheets on three-dimensional (3D) conductive MoO2 via a two-step chemical vapor deposition (CVD) reaction. The 3D MoO2 structure can create structural disorders in MoS2 nanosheets (referred to as 3D MoS2/MoO2), which are responsible for providing the superior HER activity by exposing tremendous active sites of terminal disulfur of S2(-2) (in MoS2) as well as the backbone conductive oxide layer (of MoO2) to facilitate an interfacial charge transport for the proton reduction. In addition, the MoS2 nanosheets could protect the inner MoO2 core from the acidic electrolyte in the HER. The high activity of the as-synthesized 3D MoS2/MoO2 hybrid material in HER is attributed to the small onset overpotential of 142 mV, a largest cathodic current density of 85 mA cm(-2), a low Tafel slope of 35.6 mV dec(-1), and robust electrochemical durability.

  1. A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

    Science.gov (United States)

    Ma, Juanjuan; Liu, Lin; Chen, Qian; Yang, Min; Wang, Danping; Tong, Zhiwei; Chen, Zhong

    2017-03-01

    Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.

  2. Rh nanoparticles supported on ultrathin carbon nanosheets for high-performance oxygen reduction reaction and catalytic hydrogenation.

    Science.gov (United States)

    Lin, Chong; Wu, Guanghao; Li, Huiqin; Geng, Yanmin; Xie, Gang; Yang, Jianhui; Liu, Bin; Jin, Jian

    2017-02-02

    We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphous carbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10(-3), which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.

  3. Effect of sulfide removal on sulfate reduction at pH 5 in a hydrogen fed gas-lift bioreactor.

    Science.gov (United States)

    Bijmans, Martijn F M; Dopson, Mark; Ennin, Frederick; Lens, Piet N L; Buisman, Cees J N

    2008-11-01

    Biotechnological treatment of sulfate- and metal-ionscontaining acidic wastewaters from mining and metallurgical activities utilizes sulfate-reducing bacteria to produce sulfide that can subsequently precipitate metal ions. Reducing sulfate at a low pH has several advantages above neutrophilic sulfate reduction. This study describes the effect of sulfide removal on the reactor performance and microbial community in a high-rate sulfidogenic gas-lift bioreactor fed with hydrogen at a controlled internal pH of 5. Under sulfide removal conditions, 99% of the sulfate was converted at a hydraulic retention time of 24 h, reaching a volumetric activity as high as 51 mmol sulfate/l/d. Under nonsulfide removal conditions, sulfide removal at a hydraulic retention time of 24 h resulted in an average H2S concentration of 18.2 mM (584 mg S/l). The incomplete sulfate removal was probably due to sulfide inhibition. Molecular phylogenetic analysis identified 11 separate 16S rRNA bands under sulfide stripping conditions, whereas under nonsulfide removal conditions only 4 separate 16S rRNA bands were found. This shows that a less diverse population was found in the presence of a high sulfide concentration.

  4. Hydrogenation of Furfural to Furfuryl Alcohol over Co-B Amorphous Catalysts Prepared by Chemical Reduction in Variable Media

    Institute of Scientific and Technical Information of China (English)

    LI, Hui; CHAI, Wei-Mei; LUO, Hong-Shan; LI, He-Xing

    2006-01-01

    Five Co-B amorphous alloy catalysts were prepared by chemical reduction in different media, including pure water and pure ethanol as well as the mixture of ethanol and water with variable ethanol content. Their catalytic properties were evaluated using liquid phase furfural hydrogenation to furfuryl alcohol as the probe reaction. It was found that the reaction media had no significant influence on either the amorphous structure of the Co-B catalyst or the electronic interaction between metallic Co and alloying B. This could successfully account for the fact that all the as-prepared Co-B catalysts exhibited almost the same selectivity to furfuryl alcohol and the same activity per surface area ( RSH ), which could be considered as the intrinsic activity, since the nature of active sites remained unchanged. However, the activity per gram of Co ( RmH ) of the as-prepared Co-B catalysts increased rapidly when the ethanol content in the water-ethanol mixture used as the reaction medium for catalyst preparation increased. This could be attributed to the rapid increase in the surface area possibly owing to the presence of more oxidized boron species which could serve as a support for dispersing the Co-B amorphous alloy particles.

  5. In situ long-term reductive bioimmobilization of Cr(VI) in groundwater using hydrogen release compound.

    Science.gov (United States)

    Faybishenko, Boris; Hazen, Terry C; Long, Philip E; Brodie, Eoin L; Conrad, Mark E; Hubbard, Susan S; Christensen, John N; Joyner, Dominique; Borglin, Sharon E; Chakraborty, Romy; Williams, Kenneth H; Peterson, John E; Chen, Jinsong; Brown, Shaun T; Tokunaga, Tetsu K; Wan, Jiamin; Firestone, Mary; Newcomer, Darrell R; Resch, Charles T; Cantrell, Kirk J; Willett, Anna; Koenigsberg, Stephen

    2008-11-15

    The results of a field experiment designed to test the effectiveness of a novel approach for long-term, in situ bioimmobilization of toxic and soluble Cr(VI) in groundwater using a hydrogen release compound (HRC)--a slow release glycerol polylactate--are described. The field experiment was conducted at the Hanford Site (Washington), a U.S. Department of Energy nuclear production facility, using a combination of hydrogeological, geophysical, geochemical, and microbiological measurements and analyses of water samples and sediments. The results of this experiment show that a single HRC injection into groundwater stimulates an increase in biomass, a depletion of terminal electron acceptors O2, NO3-, and SO4(2-), and an increase in Fe2+, resulting in a significant decrease in soluble Cr(VI). The Cr(VI) concentration has remained below the background concentration in the downgradient pumping/ monitoring well, and below the detection limit in the injection well for more than 3 years after the HRC injection. The degree of sustainability of Cr(VI) reductive bioimmobilization under different redox conditions at this and other contaminated sites is currently under study.

  6. Hydrogen evolution at nanoporous gold/tungsten sulfide composite film and its optimization

    DEFF Research Database (Denmark)

    Xiao, Xinxin; Engelbrekt, Christian; Li, Zheshen

    2015-01-01

    Development of efficient and economical electrochemical systems for water splitting is a key part of renewable energy technology. Amorphous films of tungsten sulfide have been deposited by electrochemical reduction of tetrathiotungstate ions (WS42-) on dealloyed nanoporous gold (NPG) for electroc......Development of efficient and economical electrochemical systems for water splitting is a key part of renewable energy technology. Amorphous films of tungsten sulfide have been deposited by electrochemical reduction of tetrathiotungstate ions (WS42-) on dealloyed nanoporous gold (NPG...

  7. Features in chemical kinetics. I. Signatures of self-emerging dimensional reduction from a general format of the evolution law

    Science.gov (United States)

    Nicolini, Paolo; Frezzato, Diego

    2013-06-01

    Simplification of chemical kinetics description through dimensional reduction is particularly important to achieve an accurate numerical treatment of complex reacting systems, especially when stiff kinetics are considered and a comprehensive picture of the evolving system is required. To this aim several tools have been proposed in the past decades, such as sensitivity analysis, lumping approaches, and exploitation of time scales separation. In addition, there are methods based on the existence of the so-called slow manifolds, which are hyper-surfaces of lower dimension than the one of the whole phase-space and in whose neighborhood the slow evolution occurs after an initial fast transient. On the other hand, all tools contain to some extent a degree of subjectivity which seems to be irremovable. With reference to macroscopic and spatially homogeneous reacting systems under isothermal conditions, in this work we shall adopt a phenomenological approach to let self-emerge the dimensional reduction from the mathematical structure of the evolution law. By transforming the original system of polynomial differential equations, which describes the chemical evolution, into a universal quadratic format, and making a direct inspection of the high-order time-derivatives of the new dynamic variables, we then formulate a conjecture which leads to the concept of an "attractiveness" region in the phase-space where a well-defined state-dependent rate function ω has the simple evolution dot{ω }= - ω ^2 along any trajectory up to the stationary state. This constitutes, by itself, a drastic dimensional reduction from a system of N-dimensional equations (being N the number of chemical species) to a one-dimensional and universal evolution law for such a characteristic rate. Step-by-step numerical inspections on model kinetic schemes are presented. In the companion paper [P. Nicolini and D. Frezzato, J. Chem. Phys. 138, 234102 (2013)], 10.1063/1.4809593 this outcome will be naturally

  8. Exploring the Role of La Codoping beyond Charge Compensation for Enhanced Hydrogen Evolution by Rh-SrTiO3.

    Science.gov (United States)

    Modak, Brindaban; Ghosh, Swapan K

    2015-08-27

    In this theoretical study, we investigate recent observation of enhancement of hydrogen evolution efficiency of Rh-doped SrTiO3 due to codoping with La at the Sr lattice site. Using hybrid density functional theory, we have systematically studied the electronic structure of (Rh, La)-codoped SrTiO3 and compared with that of Rh-doped SrTiO3, La-doped SrTiO3, and undoped SrTiO3. The aim of the present study has been to explore the role of different factors toward the observed enhanced photoactivity of (Rh, La)-codoped SrTiO3. Doping with only Rh significantly reduces the photoabsorption energy by introducing localized acceptor states between the valence band and conduction band. Unfortunately, these states act as efficient sources for charge carrier trapping. Besides, the oxygen vacancy found to be present in the Rh-doped SrTiO3 as a charge compensating defect also accelerates the electron-hole recombination rate. We have shown that codoping with La and Rh leads to the formation of clean band structure without encountering any midgap states. Introduction of La into the Rh-doped SrTiO3 not only reduces the quantity of Rh(4+) species but also suppresses the oxygen vacancy due to formation of a charge-compensated system. The presence of La favors Rh doping into the crystal structure of SrTiO3 by reducing the formation energy. Moreover, the conduction band minima are found to be shifted in the upward direction significantly due to codoping with Rh and La, thereby increasing the reducing behavior at the conduction band. This leads to enhancement of hydrogen evolution activity of SrTiO3 during photocatalytic water splitting under visible light.

  9. Fabrication of Carbon-Platinum Interdigitated Array Electrodes and Their Application for Investigating Homogeneous Hydrogen Evolution Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fei; Divan, Ralu; Parkinson, Bruce A.

    2015-06-29

    Carbon interdigitated array (IDA) electrodes have been applied to study the homogeneous hydrogen evolution electrocatalyst [Ni(PPh2NBn2)2]2+ (where PPh2NBn2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane). The existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. The currents on IDA electrodes for an EC’ (electron transfer reaction followed by a catalytic reaction) mechanism are derived from the number of redox cycles and the contribution of non-catalytic currents. The catalytic reaction rate constant was then extracted from the IDA current equations. Applying the IDA current and kinetic equations to the electrochemical response of the [Ni(PPh2NBn2)2]2+ catalyst yielded a rate constant of 0.10 s-1 for the hydrogen evolution reaction that agrees with the literature value. The quantitative analysis of IDA cyclic voltammetry can be used as a simple and straightforward method for determining rate constants in other catalytic systems. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE. Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

  10. The genome of the obligate intracellular parasite Trachipleistophora hominis: new insights into microsporidian genome dynamics and reductive evolution.

    Science.gov (United States)

    Heinz, Eva; Williams, Tom A; Nakjang, Sirintra; Noël, Christophe J; Swan, Daniel C; Goldberg, Alina V; Harris, Simon R; Weinmaier, Thomas; Markert, Stephanie; Becher, Dörte; Bernhardt, Jörg; Dagan, Tal; Hacker, Christian; Lucocq, John M; Schweder, Thomas; Rattei, Thomas; Hall, Neil; Hirt, Robert P; Embley, T Martin

    2012-01-01

    The dynamics of reductive genome evolution for eukaryotes living inside other eukaryotic cells are poorly understood compared to well-studied model systems involving obligate intracellular bacteria. Here we present 8.5 Mb of sequence from the genome of the microsporidian Trachipleistophora hominis, isolated from an HIV/AIDS patient, which is an outgroup to the smaller compacted-genome species that primarily inform ideas of evolutionary mode for these enormously successful obligate intracellular parasites. Our data provide detailed information on the gene content, genome architecture and intergenic regions of a larger microsporidian genome, while comparative analyses allowed us to infer genomic features and metabolism of the common ancestor of the species investigated. Gene length reduction and massive loss of metabolic capacity in the common ancestor was accompanied by the evolution of novel microsporidian-specific protein families, whose conservation among microsporidians, against a background of reductive evolution, suggests they may have important functions in their parasitic lifestyle. The ancestor had already lost many metabolic pathways but retained glycolysis and the pentose phosphate pathway to provide cytosolic ATP and reduced coenzymes, and it had a minimal mitochondrion (mitosome) making Fe-S clusters but not ATP. It possessed bacterial-like nucleotide transport proteins as a key innovation for stealing host-generated ATP, the machinery for RNAi, key elements of the early secretory pathway, canonical eukaryotic as well as microsporidian-specific regulatory elements, a diversity of repetitive and transposable elements, and relatively low average gene density. Microsporidian genome evolution thus appears to have proceeded in at least two major steps: an ancestral remodelling of the proteome upon transition to intracellular parasitism that involved reduction but also selective expansion, followed by a secondary compaction of genome architecture in some, but

  11. Tuning the Photoelectrocatalytic Hydrogen Evolution of Pt-Decorated Silicon Photocathodes by the Temperature and Time of Electroless Pt Deposition.

    Science.gov (United States)

    Fabre, Bruno; Li, Gaozeng; Gouttefangeas, Francis; Joanny, Loic; Loget, Gabriel

    2016-11-15

    The electroless deposition of Pt nanoparticles (NPs) on hydrogen-terminated silicon (H-Si) surfaces is studied as a function of the temperature and the immersion time. It is demonstrated that isolated Pt structures can be produced at all investigated temperatures (between 22 and 75 °C) for short deposition times, typically within 1-10 min if the temperature is 45 °C or less than 5 min at 75 °C. For longer times, dendritic metal structures start to grow, ultimately leading to highly rough interconnected Pt networks. Upon increasing the temperature from 22 to 75 °C and for an immersion time of 5 min, the average size of the observed Pt NPs monotonously increases from 120 to 250 nm, and their number density calculated using scanning electron microscopy decreases from (4.5 ± 1.0) × 10(8) to (2.0 ± 0.5) × 10(8) Pt NPs cm(-2). The impact of both the morphology and the distribution of the Pt NPs on the photoelectrocatalytic activity of the resulting metallized photocathodes is then analyzed. Pt deposited at 45 °C for 5 min yields photocathodes with the best electrocatalytic activity for the hydrogen evolution reaction. Under illumination at 33 mW cm(-2), this optimized photoelectrode shows a fill factor of 45%, an efficiency (η) of 9.7%, and a short-circuit current density (|Jsc|) at 0 V versus a reversible hydrogen electrode of 15.5 mA cm(-2).

  12. Co,N-codoped graphene as efficient electrocatalyst for hydrogen evolution reaction: Insight into the active centre

    Science.gov (United States)

    Wang, Shumin; Zhang, Lei; Qin, Yong; Ding, Dong; Bu, Yunfei; Chu, Fuqiang; Kong, Yong; Liu, Meilin

    2017-09-01

    Co and N co-doped carbon (CNC) material is one of the most promising precious-metal-free catalyst for hydrogen evolution reaction (HER), however, widespread application of CNC will require continuous innovation and optimization of fabrication to maximize electrocatalytic performance, which is always a challenge. Herein, two types of three-dimensional (3D) graphene materials synthesized by one-step of simultaneous doping (Co,N/3DG-1) and two-step of sequential doping (Co,N/3DG-2) respectively, are evaluated and correlated their electrocatalytic activity for HER with experimental parameters. The results indicate that Co,N/3DG-2 exhibits significantly better electrocatalytic activity than Co,N/3DG-1. The structure analysis reveals that Co,N/3DG-2 has more moderate Co-N coordinated number than Co,N/3DG-1. Density functional theory calculations unravels that the equilibrium C and N around Co atom is more favorable to the adsorption and desorption of hydrogen. The results shed new light on the rational design of dual hetero-atom co-doped carbon materials, which may be applicable to other energy conversion and storage systems.

  13. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene

    Science.gov (United States)

    Jiao, Yan; Zheng, Yao; Davey, Kenneth; Qiao, Shi-Zhang

    2016-10-01

    The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion through water splitting to produce hydrogen. Effective candidates for HER are often based on noble metals or transition metal dichalcogenides, while carbon-based metal-free electrocatalysts generally demonstrate poorer activity. Here we report evaluation of a series of heteroatom-doped graphene materials as efficient HER electrocatalysts by combining spectroscopic characterization, electrochemical measurements, and density functional theory calculations. Results of theoretical computations are shown to be in good agreement with experimental observations regarding the intrinsic electrocatalytic activity and the HER reaction mechanism. As a result, we establish a HER activity trend for graphene-based materials, and explore their reactivity origin to guide the design of more efficient electrocatalysts. We predict that by rationally modifying particular experimentally achievable physicochemical characteristics, a practically realizable graphene-based material will have the potential to exceed the performance of the metal-based benchmark for HER.

  14. Chemical vapor deposition of monolayer WS2 nano- sheets on Au foils toward direct application in hydrogen evolution

    Institute of Scientific and Technical Information of China (English)

    Yanshuo Zhang[1; Jianping Shi[1; Gaofeng Han[3; Minjie Li[2; Qingqing Ji[2; Donglin Ma[2; Yu Zhang[1,2; Cong Li[1,2; Xingyou Lang[3; Yanfeng Zhang[1,2; Zhongfan Liu[2

    2015-01-01

    Monolayer tungsten disulfide (WS2), a typical member of the semiconducting transition metal dichalcogenide family has drawn considerable interest because of its unique properties. Intriguingly the edge of WS2 exhibits an ideal hydrogen binding energy which makes WS2 a potential alternative to Pt-based electrocatalysts for the hydrogen evolution reaction (HER). Here, we demonstrate for the first time the successful synthesis of uniform monolayer WS2 nanosheets on centimeter- scale Au foils using a facile, low-pressure chemical vapor deposition method. The edge lengths of the universally observed triangular WS2 nanosheets are tunable from -100 to N1,000 nm. The WS2 nanosheets on Au foils featuring abundant edges were then discovered to be efficient catalysts for the HER, exhibiting a rather high exchange current density of -30.20 μA/cm2 and a small onset potential of Nl10 mV. The effects of coverage and domain size (which correlate closely with the active edge density of WS2) on the electrocatalytic activity were investigated. This work not only provides a novel route toward the batch-production of monolayer WS2 via the introduction of metal foil substrates but also opens up its direct application for facile HER.

  15. BEHAVIOR OF POLYPYRROLE MODIFIED GRAPHITE ELECTRODE DURING HYDROGEN EVOLUTION PROCESS%电解析氢过程中聚吡咯修饰电极的行为

    Institute of Scientific and Technical Information of China (English)

    莫笑萍; 王纪孝; 王志; 王世昌

    2003-01-01

    @@ 1 INTRODUCTION Hydrogen evolution reaction is an important reaction to produce high purity hydrogen for use in applications such as fertilizers (synthesis of ammonia),food (hydrogenation of fats and oils),petrochemical industry(hydrocracking of petroleum), metallurgical industry (reducing agent in the metallurgical and semiconductors industries) and alkaline production. The main operating cost of the process is the cost of electricity.

  16. Active and Durable Hydrogen Evolution Reaction Catalyst Derived from Pd-Doped Metal-Organic Frameworks.

    Science.gov (United States)

    Chen, Jitang; Xia, Guoliang; Jiang, Peng; Yang, Yang; Li, Ren; Shi, Ruohong; Su, Jianwei; Chen, Qianwang

    2016-06-01

    The water electrolysis is of critical importance for sustainable hydrogen production. In this work, a highly efficient and stable PdCo alloy catalyst (PdCo@CN) was synthesized by direct annealing of Pd-doped metal-organic frameworks (MOFs) under N2 atmosphere. In 0.5 M H2SO4 solution, PdCo@CN displays remarkable electrocatalytic performance with overpotential of 80 mV, a Tafel slope of 31 mV dec(-1), and excellent stability of 10 000 cycles. Our studies reveal that noble metal doped MOFs are ideal precursors for preparing highly active alloy electrocatalysts with low content of noble metal.

  17. Biogenic hydrogen conversion of de-oiled jatropha waste via anaerobic sequencing batch reactor operation: process performance, microbial insights, and CO2 reduction efficiency.

    Science.gov (United States)

    Kumar, Gopalakrishnan; Lin, Chiu-Yue

    2014-01-01

    We report the semicontinuous, direct (anaerobic sequencing batch reactor operation) hydrogen fermentation of de-oiled jatropha waste (DJW). The effect of hydraulic retention time (HRT) was studied and results show that the stable and peak hydrogen production rate of 1.48 L/L ∗ d and hydrogen yield of 8.7 mL H2/g volatile solid added were attained when the reactor was operated at HRT 2 days (d) with a DJW concentration of 200 g/L, temperature 55 °C, and pH 6.5. Reduced HRT enhanced the production performance until 1.75 d. Further reduction has lowered the process efficiency in terms of biogas production and hydrogen gas content. The effluent from hydrogen fermentor was utilized for methane fermentation in batch reactors using pig slurry and cow dung as seed sources. The results revealed that pig slurry was a feasible seed source for methane generation. Peak methane production rate of 0.43 L CH4/L ∗ d and methane yield of 20.5 mL CH4/g COD were observed at substrate concentration of 10 g COD/L, temperature 30 °C, and pH 7.0. PCR-DGGE analysis revealed that combination of cellulolytic and fermentative bacteria were present in the hydrogen producing ASBR.

  18. Biogenic Hydrogen Conversion of De-Oiled Jatropha Waste via Anaerobic Sequencing Batch Reactor Operation: Process Performance, Microbial Insights, and CO2 Reduction Efficiency

    Directory of Open Access Journals (Sweden)

    Gopalakrishnan Kumar

    2014-01-01

    Full Text Available We report the semicontinuous, direct (anaerobic sequencing batch reactor operation hydrogen fermentation of de-oiled jatropha waste (DJW. The effect of hydraulic retention time (HRT was studied and results show that the stable and peak hydrogen production rate of 1.48 L/L*d and hydrogen yield of 8.7 mL H2/g volatile solid added were attained when the reactor was operated at HRT 2 days (d with a DJW concentration of 200 g/L, temperature 55°C, and pH 6.5. Reduced HRT enhanced the production performance until 1.75 d. Further reduction has lowered the process efficiency in terms of biogas production and hydrogen gas content. The effluent from hydrogen fermentor was utilized for methane fermentation in batch reactors using pig slurry and cow dung as seed sources. The results revealed that pig slurry was a feasible seed source for methane generation. Peak methane production rate of 0.43 L CH4/L*d and methane yield of 20.5 mL CH4/g COD were observed at substrate concentration of 10 g COD/L, temperature 30°C, and pH 7.0. PCR-DGGE analysis revealed that combination of celluloytic and fermentative bacteria were present in the hydrogen producing ASBR.

  19. Mechanistic study on the electrochemical reduction of 9,10-anthraquinone in the presence of hydrogen-bond and proton donating additives.

    Science.gov (United States)

    Katsumi, Jiro; Nakayama, Tatsushi; Esaka, Yukihiro; Uno, Bunji

    2012-01-01

    The electrochemical reduction of 9,10-anthraquinone (AQ) was investigated in CH(3)CN in both the absence and presence of the hydrogen-bond and proton donating additives, CH(3)OH, CH(CF(3))(2)OH, phenol, 4-methoxyphenol, 4-cyanophenol, 2,4,6-trichlorophenol, and benzoic acid (BA). Three clearly different types of electrochemical behavior were observed with increasing concentrations of the additives, and were simulated to analyze the reaction mechanisms. Type I was observed for weakly interacting additives, such as CH(3)OH, characterized by positive shifts of the two well-separated reduction waves, corresponding to the formation of AQ(•-) and AQ(2-), with no loss of reversibility. The second wave shifted more strongly, and finally merged with the first. These behaviors are explained by the association of AQ(2-) with the additives via strong hydrogen-bonding. Type II is attributed to a reduction mechanism involving quantitative formation of strong hydrogen-bonded complexes of AQ(2-) with additives, such as CH(CF(3))(2)OH, phenol and 4-methoxyphenol, showing a reversible or quasireversible two-electron reduction wave with increasing concentrations of the additives. The behavior of Type III, observed in the presence of strongly interacting additives, such as 2,4,6-trichlorophenol and BA, is characterized by a voltammogram composed of the 2-electorn cathodic and the broad anodic waves without keeping reversibility, facilitated by proton transfer in the hydrogen-bonded complexes, AQ(•-)-BA and AQ(2-)-BA. The effects of hydrogen-bonding and protonation on the electrochemistry of AQ have been systematically demonstrated in terms of the potentials and reaction pathways of the various species, which appear in quinone-hydroquinone systems.

  20. Preparation of Cu-loaded SrTiO{sub 3} nanoparticles and their photocatalytic activity for hydrogen evolution from methanol aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bui, Duc-Nguyen [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China); Mu, Jin, E-mail: mujin@sit.edu.cn [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); Wang, Lei [School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China); Kang, Shi-Zhao; Li, Xiangqing [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China)

    2013-06-01

    Cu-loaded SrTiO{sub 3} nanoparticles (Cu–SrTiO{sub 3}) were prepared using a simple in situ photo-deposition method and their photocatalytic activity for hydrogen evolution from methanol aqueous solution was evaluated. The results characterized with XRD, TEM, XPS and EDX indicated that the as-synthesized sample was composed of metallic Cu and cubic SrTiO{sub 3}, and the metallic Cu was homogeneously loaded on the surface of SrTiO{sub 3} nanoparticles. Under UV light irradiation, Cu–SrTiO{sub 3} displayed much higher photocatalytic activity for hydrogen evolution and excellent stability in comparison with pure SrTiO{sub 3} nanoparticles. The results further confirmed that the efficient separation of photogenerated electron/hole pairs was critical for the enhanced photocatalytic activity of Cu–SrTiO{sub 3}. Moreover, the rate of hydrogen evolution of 0.5 wt.% Cu–SrTiO{sub 3} is comparable with that of 0.5 wt.% Pt–SrTiO{sub 3} photocatalyst under optimum conditions, implying that the metallic Cu is an efficient alternative to Pt as a co-catalyst on SrTiO{sub 3}. The high photocatalytic activity, low cost and chemical stability mean that the Cu-loaded SrTiO{sub 3} is a potential catalyst for the photocatalytic hydrogen evolution from methanol aqueous solution.

  1. Preparation of NiS/ZnIn2S4 as a superior photocatalyst for hydrogen evolution under visible light irradiation

    Directory of Open Access Journals (Sweden)

    Liang Wei

    2013-12-01

    Full Text Available In this study, NiS/ZnIn2S4 nanocomposites were successfully prepared via a facile two-step hydrothermal process. The as-prepared samples were characterized by X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and high-resolution transmission electron microscopy (HRTEM. Their photocatalytic performance for hydrogen evolution under visible light irradiation was also investigated. It was found that the photocatalytic hydrogen evolution activity over hexagonal ZnIn2S4 can be significantly increased by loading NiS as a co-catalyst. The formation of a good junction between ZnIn2S4 and NiS via the two step hydrothermal processes is beneficial for the directional migration of the photo-excited electrons from ZnIn2S4 to NiS. The highest photocatalytic hydrogen evolution rate (104.7 μmol/h, which is even higher than that over Pt/ZnIn2S4 nanocomposite (77.8 μmol/h, was observed over an optimum NiS loading amount of 0.5 wt %. This work demonstrates a high potential of the developing of environmental friendly, cheap noble-metal-free co-catalyst for semiconductor-based photocatalytic hydrogen evolution.

  2. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin

    2015-06-12

    A stable noble-metal-free hydrogen evolution photocatalyst based on graphite carbon nitride (g-C3N4) was developed by a molecular-level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g-C3N4. This catalyst family (with less than 0.1 wt% of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt% platinum as co-catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Complex-Mediated Synthesis of Tantalum Oxyfluoride Hierarchical Nanostructures for Highly Efficient Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Xu, Leilei; Gong, Haotian; Deng, Li; Long, Fei; Gu, Yu; Guan, Jianguo

    2016-04-13

    In this work, we have, for the first time, developed a facile wet-chemical route to obtain a novel photocatalytic material of tantalum oxyfluoride hierarchical nanostructures composed of amorphous cores and single crystalline TaO2F nanorod shells (ACHNs) by regulating the one-step hydrothermal process of TaF5 in a mixed solution of isopropanol (i-PrOH) and H2O. In this approach, elaborately controlling the reaction temperature and volume ratio of i-PrOH and H2O enabled TaF5 to transform into intermediate coordination complex ions of [TaOF3·2F](2-) and [TaF7](2-), which subsequently produced tantalum oxyfluoride ACHNs via a secondary nucleation and growth due to a stepwise change in hydrolysis rates of the two complex ions. Because of the unique chemical composition, crystal structure and micromorphology, the as-prepared tantalum oxyfluoride ACHNs show a more negative flat band potential, an accelerated charge transfer, and a remarkable surface area of 152.4 m(2) g(-1) contributing to increased surface reaction sites. As a result, they exhibit a photocatalytic activity for hydrogen production up to 1.95 mmol h(-1) g(-1) under the illumination of a simulated solar light without any assistance of co-catalysts, indicating that the as-prepared tantalum oxyfluoride ACHNs are a novel promising photocatalytic material for hydrogen production.

  4. Tri-s-triazine-Based Crystalline Carbon Nitride Nanosheets for an Improved Hydrogen Evolution.

    Science.gov (United States)

    Ou, Honghui; Lin, Lihua; Zheng, Yun; Yang, Pengju; Fang, Yuanxing; Wang, Xinchen

    2017-06-01

    Tri-s-triazine-based crystalline carbon nitride nanosheets (CCNNSs) have been successfully extracted via a conventional and cost-effective sonication-centrifugation process. These CCNNSs possess a highly defined and unambiguous structure with minimal thickness, large aspect ratios, homogeneous tri-s-triazine-based units, and high crystallinity. These tri-s-triazine-based CCNNSs show significantly enhanced photocatalytic hydrogen generation activity under visible light than g-C3 N4 , poly (triazine imide)/Li(+) Cl(-) , and bulk tri-s-triazine-based crystalline carbon nitrides. A highly apparent quantum efficiency of 8.57% at 420 nm for hydrogen production from aqueous methanol feedstock can be achieved from tri-s-triazine-based CCNNSs, exceeding most of the reported carbon nitride nanosheets. Benefiting from the inherent structure of 2D crystals, the ultrathin tri-s-triazine-based CCNNSs provide a broad range of application prospects in the fields of bioimaging, and energy storage and conversion. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Dramatic effect of pore size reduction on the dynamics of hydrogen adsorbed in metal–organic materials

    KAUST Repository

    Nugent, Patrick

    2014-07-21

    The effects of pore size reduction on the dynamics of hydrogen sorption in metal-organic materials (MOMs) were elucidated by studying SIFSIX-2-Cu and its doubly interpenetrated polymorph SIFSIX-2-Cu-i by means of sorption, inelastic neutron scattering (INS), and computational modeling. SIFSIX-2-Cu-i exhibits much smaller pore sizes, which possess high H2 sorption affinity at low loadings. Experimental H2 sorption measurements revealed that the isosteric heat of adsorption (Qst) for H2 in SIFSIX-2-Cu-i is nearly two times higher than that for SIFSIX-2-Cu (8.6 vs. 4.6 kJ mol-1). The INS spectrum for H2 in SIFSIX-2-Cu-i is rather unique for a porous material, as only one broad peak appears at low energies near 6 meV, which simply increases in intensity with loading until the pores are filled. The value for this rotational transition is lower than that in most neutral metal-organic frameworks (MOFs), including those with open Cu sites (8-9 meV), which is indicative of a higher barrier to rotation and stronger interaction in the channels of SIFSIX-2-Cu-i than the open Cu sites in MOFs. Simulations of H2 sorption in SIFSIX-2-Cu-i revealed two hydrogen sorption sites in the MOM: direct interaction with the equatorial fluorine atom (site 1) and between two equatorial fluorine atoms on opposite walls (site 2). The calculated rotational energy levels and rotational barriers for the two sites in SIFSIX-2-Cu-i are in good agreement with INS data. Furthermore, the rotational barriers and binding energies for site 2 are slightly higher than that for site 1, which is consistent with INS results. The lowest calculated transition for the primary site in SIFSIX-2-Cu is also in good agreement with INS data. In addition, this transition in the non-interpenetrating material is higher than any of the sites in SIFSIX-2-Cu-i, which indicates a significantly weaker interaction with the host as a result of the larger pore size. This journal is © the Partner Organisations 2014.

  6. Oxygen and hydrogen evolution reaction on oriented single crystals of ruthenium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Berger, L I; Pollak, F H; Canivez, Y; O& #x27; Grady, W

    1979-01-01

    A novel design for water electrolysis using a solid polymer electrolyte is being developed by General Electric. Ruthenium is one of the best electrocatalysts for the oxygen evolution reaction. There are problems connected with the significant loss in electrocatalytic activity with time. This performance degradation is presumably due to the gradual formation of an RuO/sub 2/ film. We have performed electrochemical measurements on (100), (110) and (111) oriented single crystals of RuO/sub 2/ in order to elucidate the mechanism of the electrocatalytic process. Large single crystals were grown by the vapor transport method. Our investigation has revealed several interesting differences for the various orientations. This study indicates that RuO/sub 3/ may be an important intermediate species prior to oxygen evolution and that the formation of the RuO/sub 3/ is the rate limiting process. Similar results were previously obtained for IrO/sub 2/.

  7. Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

    Science.gov (United States)

    Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

    2016-01-01

    An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study. PMID:27703212

  8. Evolution of infrared spectra and optical emission spectra in hydrogenated silicon thin films prepared by VHF-PECVD

    Science.gov (United States)

    Hou, Guo-Fu; Geng, Xin-Hua; Zhang, Xiao-Dan; Sun, Jian; Zhang, Jian-Jun; Zhao, Ying

    2011-07-01

    A series of hydrogenated silicon thin films with varying silane concentrations have been deposited by using very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) method. The deposition process and the silicon thin films are studied by using optical emission spectroscopy (OES) and Fourier transfer infrared (FTIR) spectroscopy, respectively. The results show that when the silane concentration changes from 10% to 1%, the peak frequency of the Si-H stretching mode shifts from 2000 cm-1 to 2100 cm-1, while the peak frequency of the Si—H wagging—rocking mode shifts from 650 cm-1 to 620 cm-1. At the same time the SiH/Hα intensity ratio in the plasma decreases gradually. The evolution of the infrared spectra and the optical emission spectra demonstrates a morphological phase transition from amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H). The structural evolution and the μc-Si:H formation have been analyzed based on the variation of Hα and SiH intensities in the plasma. The role of oxygen impurity during the plasma process and in the silicon films is also discussed in this study.

  9. Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

    Science.gov (United States)

    Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

    2016-10-01

    An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study.

  10. Characterization of LaNiO{sub 3} prepared by sol-gel: Application to hydrogen evolution under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Khettab, M. [Laboratoire Electrochimie-Corrosion, Metallurgie et Chimie Minerale (Faculty of Chemistry), USTHB, BP 32, 16111 Algiers (Algeria); Omeiri, S. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, BP 32, 16111 Algiers (Algeria); Sellam, D.; Ladjouzi, M.A. [Laboratoire Electrochimie-Corrosion, Metallurgie et Chimie Minerale (Faculty of Chemistry), USTHB, BP 32, 16111 Algiers (Algeria); Trari, M., E-mail: solarchemistry@gmail.com [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, BP 32, 16111 Algiers (Algeria)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Photoactive LaNiO{sub 3} was prepared by sol-gel. Black-Right-Pointing-Pointer LaNiO{sub 3} exhibits n type conductivity it due to slight oxygen deficiency. Black-Right-Pointing-Pointer LaNiO{sub 3} was successfully for hydrogen evolution upon visible light. - Abstract: The semi conducting properties of LaNiO{sub 3}, elaborated by sol-gel, have been investigated for the first time by the photocurrent technique and capacitance measurements. The oxide crystallizes in a distorted perovskite structure and the transport properties indicate degenerate conductivity with activation energy of 18 meV. The infrared spectrum allowed us to evaluate the band gap at 88 meV. The electrochemical behaviour has been studied in alkaline electrolyte (KOH, 0.5 M). The corrosion potential (-0.204 V{sub SCE}) and the exchange current density (0.103 mA cm{sup -2}), determined from the semi logarithmic plot, indicate long lived oxide. The slope and the intercept to C{sup -2} = 0 of the Mott Schottky plot, characteristic of n type behaviour, gave respectively an electron density (N{sub D}) of 2.3 Multiplication-Sign 10{sup 19} cm{sup -3} and a flat band potential (V{sub fb}) of -0.61 V{sub SCE}. The nature of the Nyquist plot, measured over a wide frequency range (10{sup -3}-10{sup 5} Hz), shows the predominance of the bulk contribution. The arc is not centred on the real axis (-6.3 Degree-Sign ), an evidence of a constant phase element. The straight line at low frequencies is due to Warburg diffusion and the data are interpreted thanks to the Randles model. The absorption of light promotes electrons into LaNiO{sub 3}-CB with a potential (-0.62 V{sub SCE}) sufficient to reduce water (-0.50 V{sub SCE}). As application, the oxide has been tested successfully for hydrogen evolution upon visible light with a rate evolution of 1.73 {mu}mol min{sup -1} (g catalyst){sup -1} and a quantum efficiency of 0.042% under full light (29 mW cm{sup -2}).

  11. Beyond the top of the volcano? - A unified approach to electrocatalytic oxygen reduction and oxygen evolution

    DEFF Research Database (Denmark)

    Busch, Michael; Halck, Niels Bendtsen; Kramm, Ulrike I.;

    2016-01-01

    gives rise to a double volcano for ORR and OER, with a region in between, forbidden by the scaling relations. The reversible perfect catalyst for both ORR and OER would fall into this "forbidden region". Previously, we have found that hydrogen acceptor functionality on oxide surfaces can improve...

  12. Synthesis of tantalum carbide and nitride nanoparticles using a reactive mesoporous template for electrochemical hydrogen evolution

    KAUST Repository

    Alhajri, Nawal Saad

    2013-01-01

    Tantalum carbide and nitride nanocrystals were prepared through the reaction of a tantalum precursor with mesoporous graphitic (mpg)-C 3N4. The effects of the reaction temperature, the ratio of the Ta precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2 and NH3) on the resultant crystal phases and structures were investigated. The produced samples were characterized using powder X-ray diffraction (XRD), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, a temperature-programmed reaction with mass spectroscopy (MS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicate that the different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen when formed at different temperatures. The Ta3N5 phase with a Ta5+ oxidation state was solely obtained at 1023 K under a flow of ammonia, which gasified the C 3N4 template and was confirmed by detecting the decomposed gaseous products via MS. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C 3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen. The high C3N4/Ta precursor ratio generally resulted in high carbide content rather than a nitride one, consistent with the role of mpg-C3N4 as a carbon source. Electrochemical measurements revealed that the synthesized nanomaterials were consistently able to produce hydrogen under acidic conditions (pH 1). The obtained Tafel slope indicates that the rate-determining step is the Volmer discharge step, which is consistent with adsorbed hydrogen being weakly bound to the surface during electrocatalysis. © 2013 The Royal Society of Chemistry.

  13. Investigation of zinc recovery by hydrogen reduction assisted pyrolysis of alkaline and zinc-carbon battery waste.

    Science.gov (United States)

    Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

    2017-10-01

    Zinc (Zn) recovery from alkaline and zinc-carbon (Zn-C) battery waste were studied by a laboratory scale pyrolysis process at a reaction temperature of 950°C for 15-60min residence time using 5%H2(g)-N2(g) mixture at 1.0L/min gas flow rate. The effect of different cooling rates on the properties of pyrolysis residue, manganese oxide particles, were also investigated. Morphological and structural characterization of the produced Zn particles were performed. The battery black mass was characterized with respect to the properties and chemical composition of the waste battery particles. The thermodynamics of the pyrolysis process was studied using the HSC Chemistry 5.11 software. A hydrogen reduction reaction of the battery black mass (washed with Milli-Q water) takes place at the chosen temperature and makes it possible to produce fine Zn particles by rapid condensation following the evaporation of Zn from the pyrolysis batch. The amount of Zn that can be separated from the black mass increases by extending the residence time. Recovery of 99.8% of the Zn was achieved at 950°C for 60min residence time using 1.0L/min gas flow rate. The pyrolysis residue contains MnO and Mn2O3 compounds, and the oxidation state of manganese can be controlled by cooling rate and atmosphere. The Zn particles exhibit spherical and hexagonal particle morphology with a particle size varying between 200nm and 3µm. However the particles were formed by aggregation of nanoparticles which are primarily nucleated from the gas phase. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Photoelectron emission yield experiments on evolution of sub-gap states in amorphous In-Ga-Zn-O thin films with post deposition hydrogen treatment

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, Kazushi, E-mail: hayashi.kazushi@kobelco.com; Hino, Aya; Tao, Hiroaki; Ochi, Mototaka; Goto, Hiroshi; Kugimiya, Toshihiro [Electronics Research Laboratory, Kobe Steel, Ltd., 1-5-5 Takatsuka-dai, Nishi-ku, Kobe 651-2271 (Japan)

    2015-09-14

    Total photoyield emission spectroscopy (TPYS) was applied to study the evolution of sub-gap states in hydrogen-treated amorphous In-Ga-Zn-O (a-IGZO) thin films. The a-IGZO thin films were subjected to hydrogen radicals and subsequently annealed in ultra-high vacuum (UHV) conditions. A clear onset of the electron emission was observed at around 4.3 eV from the hydrogen-treated a-IGZO thin films. After successive UHV annealing at 300 °C, the onset in the TPYS spectra was shifted to 4.15 eV, and the photoelectron emission from the sub-gap states was decreased as the annealing temperature was increased. In conjunction with the results of thermal desorption spectrometer, it was deduced that the hydrogen atoms incorporated in the a-IGZO thin films induced metastable sub-gap states at around 4.3 eV from vacuum level just after the hydrogenation. It was also suggested that the defect configuration was changed due to the higher temperature UHV annealing, and that the hydrogen atoms desorbed with the involvement of Zn atoms. These experiments produced direct evidence to show the formation of sub-gap states as a result of hydrogen incorporation into the a-IGZO thin films.

  15. Hydrogen-treated commercial WO3 as an efficient electrocatalyst for triiodide reduction in dye-sensitized solar cells.

    Science.gov (United States)

    Cheng, Ling; Hou, Yu; Zhang, Bo; Yang, Shuang; Guo, Jian Wei; Wu, Long; Yang, Hua Gui

    2013-07-07

    The electrocatalytically inactive commercial WO3 can be transformed into an efficient counter electrode (CE) material for dye-sensitized solar cells (DSCs) via facile hydrogen treatment. The energy conversion efficiency of the DSCs with the hydrogen-treated WO3 CE was 5.43%, while the corresponding value for commercial WO3 with the stoichiometric surface was only 0.63%.

  16. Low temperature hydrogen reduction of high surface area anatase and anatase/β-TiO₂ for high-charging-rate batteries.

    Science.gov (United States)

    Ventosa, Edgar; Tymoczko, Anna; Xie, Kunpeng; Xia, Wei; Muhler, Martin; Schuhmann, Wolfgang

    2014-09-01

    There are several strategies to improve the electrochemical performance of TiO2 as negative electrode material for Li-ion batteries. Introducing oxygen vacancies through hydrogen reduction leads to an enhancement in electrical conductivity. However, this strategy does not improve the low lithium-ion mobility. Herein, we show that by decreasing the temperature of hydrogen annealing the improved lithium-ion mobility of high-surface-area TiO2 and β-TiO2 can be combined with the enhanced electrical conductivity of oxygen deficiencies. Annealing at only 275-300 °C in pure hydrogen atmosphere successfully creates oxygen vacancies in TiO2, as confirmed by UV/Vis spectroscopy, whereas the temperature is low enough to maintain a high specific surface area and prevent β-to-anatase phase transformation. The hydrogen reduction of high-surface-area anatase or anatase/β-TiO2 at these temperatures leads to improvements in the performance, achieving charge capacities of 142 or 152 mAh g(-1) at 10C, respectively.

  17. Ultrathin graphitic carbon nitride nanosheets: a low-cost, green, and highly efficient electrocatalyst toward the reduction of hydrogen peroxide and its glucose biosensing application

    Science.gov (United States)

    Tian, Jingqi; Liu, Qian; Ge, Chenjiao; Xing, Zhicai; Asiri, Abdullah M.; Al-Youbi, Abdulrahman O.; Sun, Xuping

    2013-09-01

    In this communication, we demonstrate for the first time that ultrathin graphitic carbon nitride (g-C3N4) nanosheets can serve as a low-cost, green, and highly efficient electrocatalyst toward the reduction of hydrogen peroxide. We further demonstrate its application for electrochemical glucose biosensing in both buffer solution and human serum medium with a detection limit of 11 μM and 45 μM, respectively.In this communication, we demonstrate for the first time that ultrathin graphitic carbon nitride (g-C3N4) nanosheets can serve as a low-cost, green, and highly efficient electrocatalyst toward the reduction of hydrogen peroxide. We further demonstrate its application for electrochemical glucose biosensing in both buffer solution and human serum medium with a detection limit of 11 μM and 45 μM, respectively. Electronic supplementary information (ESI) available: Experimental section and supplementary figures. See DOI: 10.1039/c3nr02031b

  18. Dual function photocatalysis of cyano-bridged heteronuclear metal complexes for water oxidation and two-electron reduction of dioxygen to produce hydrogen peroxide as a solar fuel.

    Science.gov (United States)

    Aratani, Yusuke; Suenobu, Tomoyoshi; Ohkubo, Kei; Yamada, Yusuke; Fukuzumi, Shunichi

    2017-03-25

    The photocatalytic production of hydrogen peroxide from water and dioxygen under visible light irradiation was made possible by using polymeric cyano-bridged heteronuclear metal complexes (M(II)[Ru(II)(CN)4(bpy)]; M(II) = Ni(II), Fe(II) and Mn(II)), where the photocatalytic two-electron reduction of O2 and water oxidation were catalysed by the Ru and M(II) moieties, respectively.

  19. Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

    OpenAIRE

    2016-01-01

    Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared ...

  20. Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

    OpenAIRE

    Dongil, Ana Belén; Pastor Pérez, Laura; Fierro, Jose L. G.; Escalona, Néstor; Sepúlveda Escribano, Antonio

    2016-01-01

    Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared ...

  1. Shape Optimization for Drag Reduction in Linked Bodies using Evolution Strategies and the Hybrid Wavelet Collocation - Brinkman Penalization Method

    Science.gov (United States)

    Vasilyev, Oleg V.; Gazzola, Mattia; Koumoutsakos, Petros

    2010-11-01

    In this talk we discuss preliminary results for the use of hybrid wavelet collocation - Brinkman penalization approach for shape optimization for drag reduction in flows past linked bodies. This optimization relies on Adaptive Wavelet Collocation Method along with the Brinkman penalization technique and the Covariance Matrix Adaptation Evolution Strategy (CMA-ES). Adaptive wavelet collocation method tackles the problem of efficiently resolving a fluid flow on a dynamically adaptive computational grid, while a level set approach is used to describe the body shape and the Brinkman volume penalization allows for an easy variation of flow geometry without requiring body-fitted meshes. We perform 2D simulations of linked bodies in order to investigate whether flat geometries are optimal for drag reduction. In order to accelerate the costly cost function evaluations we exploit the inherent parallelism of ES and we extend the CMA-ES implementation to a multi-host framework. This framework allows for an easy distribution of the cost function evaluations across several parallel architectures and it is not limited to only one computing facility. The resulting optimal shapes are geometrically consistent with the shapes that have been obtained in the pioneering wind tunnel experiments for drag reduction using Evolution Strategies by Ingo Rechenberg.

  2. Rague-Like FeP Nanocrystal Assembly on Carbon Cloth: An Exceptionally Efficient and Stable Cathode for Hydrogen Evolution

    KAUST Repository

    Yang, Xiulin

    2015-05-25

    There is a strong demand to replace expensive Pt catalysts with cheap metal sulfides or phosphides for hydrogen generation in water electrolysis. The earth-abundant Fe can be electroplated on carbon cloth (CC) to form high surface area rague-like FeOOH assembly. Subsequent gas phase phosphidation converts the FeOOH to FeP or FeP2 and the morphology of the crystal assembly is controlled by the phosphidation temperature. The FeP prepared at 250 oC presents lower crystallinity and those prepared at higher temperatures 400 oC and 500 oC possess higher crystallinity but lower surface area. The phosphidation at 300 oC produces nanocrystalline FeP and preserves the high-surface area morphology; thus it exhibits the highest HER efficiency in 0.5 M H2SO4; i.e. the required overpotential to reach 10 and 20 mA/cm2 is 34 and 43 mV respectively. These values are lowest among the reported non-precious metal phosphides on CC. The Tafel slope for the FeP prepared at 300 oC is around 29.2 mV/dec comparable to that of Pt/CC, indicating that the hydrogen evolution for our best FeP is limited by Tafel reaction (same as Pt). Importantly, the FeP/CC catalyst exhibits much better stability in a wide range working current density (up to 1 V/cm2), suggesting that it is a promising replacement of Pt for HER.

  3. Influence of temperature on the hydrogen evolution reaction on stainless steels in LiBr solution by means of polarization techniques

    Energy Technology Data Exchange (ETDEWEB)

    Guinon Pina, V.; Igual-Munoz, A.; Garcia-Anton, J. [Valencia Univ. Politecnica, Dept. de Ingenieria Quimica y Nuclear. ETSI Industriales, Valencia (Spain)

    2009-07-01

    Lithium Bromide aqueous solutions used as absorbent in refrigeration machines can cause serious corrosion problems which also facilitate the hydrogen evolution reaction (HER) in the cathodic regions. Hydrogen formation is an important problem in the operating conditions of adsorption machines because they operate under low pressure conditions. Hydrogen generation makes pressure to increase and as a consequence efficiency decreases. Duplex Stainless Steels (DSS) are iron-based alloys with a two-phase microstructure: austenite and delta ferrite in approximately similar percentages. DSS find increasing use as an alternative to austenitic stainless steels, particularly where aggressive anions such as bromide are present in high concentrations. The objective of the present work is to study the effect of temperature on the hydrogen evolution reaction (HER) of two different stainless steels, Austenitic and Duplex steels, using different electrochemical techniques: Open Circuit Potential (OCP), potentiodynamic and galvano-static measurements and image digital analysis. The HER was studied in 992 g/l LiBr at three different temperatures (25, 50 and 75 C). The results showed that the electrocatalytic activity for the HER increased with temperature. The energy consumption for hydrogen generation on Austenitic Stainless Steel, UNS N08031, is lower than on Duplex Stainless Steel, EN 1.4462, at the studied temperatures. (authors)

  4. Molecular Hydrogen Emission from Protoplanetary Disks II. Effects of X-ray Irradiation and Dust Evolution

    CERN Document Server

    Nomura, H; Tsujimoto, M; Nakagawa, Y; Millar, T J

    2007-01-01

    Detailed models for the density and temperature profiles of gas and dust in protoplanetary disks are constructed by taking into account X-ray and ultraviolet (UV) irradiation from a central T Tauri star, as well as dust size growth and settling toward the disk midplane. The spatial and size distributions of dust grains in the disks are numerically computed by solving the coagulation equation for settling dust particles. The level populations and line emission of molecular hydrogen are calculated using the derived physical structure of the disks. X-ray irradiation is the dominant heating source of the gas in the inner disk region and in the surface layer, while the far UV heating dominates otherwise. If the central star has strong X-ray and weak UV radiation, the H2 level populations are controlled by X-ray pumping, and the X-ray induced transition lines could be observable. If the UV irradiation is strong, the level populations are controlled by thermal collisions or UV pumping, depending on the properties of...

  5. Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight

    Directory of Open Access Journals (Sweden)

    Hiroyuki Kaneko

    2015-07-01

    Full Text Available Copper chalcopyrite is a promising candidate for a photocathode material for photoelectrochemical (PEC water splitting because of its high half-cell solar-to-hydrogen conversion efficiency (HC-STH, relatively simple and low-cost preparation process, and chemical stability. This paper reviews recent advances in copper chalcopyrite photocathodes. The PEC properties of copper chalcopyrite photocathodes have improved fairly rapidly: HC-STH values of 0.25% and 8.5% in 2012 and 2015, respectively. On the other hand, the onset potential remains insufficient, owing to the shallow valence band maximum mainly consisting of Cu 3d orbitals. In order to improve the onset potential, we explored substituting Cu for Ag and investigate the PEC properties of silver gallium selenide (AGSe thin film photocathodes for varying compositions, film growth atmospheres, and surfaces. The modified AGSe photocathodes showed a higher onset potential than copper chalcopyrite photocathodes. It was demonstrated that element substitution of copper chalcopyrite can help to achieve more efficient PEC water splitting.

  6. Evolution of Water Reservoirs on Mars: Constraints from Hydrogen Isotopes in Martian Meteorites

    CERN Document Server

    Kurokawa, Hiroyuki; Ushioda, Masashi; Matsuyama, Takeshi; Moriwaki, Ryota; Dohm, James M; Usui, Tomohiro

    2014-01-01

    Martian surface morphology implies that Mars was once warm enough to maintain persistent liquid water on its surface. While the high D/H ratios (~6 times the Earth's ocean water) of the current martian atmosphere suggest that significant water has been lost from the surface during martian history, the timing, processes, and the amount of the water loss have been poorly constrained. Recent technical developments of ion-microprobe analysis of martian meteorites have provided accurate estimation of hydrogen isotope compositions (D/H) of martian water reservoirs at the time when the meteorites formed. Based on the D/H data from the meteorites, this study demonstrates that the water loss during the pre-Noachian (>41-99 m global equivalent layers, GEL) was more significant than in the rest of martian history (>10-53 m GEL). Combining our results with geological and geomorphological evidence for ancient oceans, we propose that undetected subsurface water/ice (~100-1000 m GEL) should have existed, and it exceeds the ...

  7. Multiwalled Carbon Nanotube-TiO2 Nanocomposite for Visible-Light-Induced Photocatalytic Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Ke Dai

    2014-01-01

    Full Text Available Multiwalled carbon nanotube- (MWCNT- TiO2 nanocomposite was synthesized via hydrothermal process and characterized by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, field emission scanning electron microscope, thermogravimetry analysis, and N2 adsorption-desorption isotherms. Appropriate pretreatment on MWCNTs could generate oxygen-containing groups, which is beneficial for forming intimate contact between MWCNTs and TiO2 and leads to a higher thermal stability of MWCNT-TiO2 nanocomposite. Modification with MWCNTs can extend the visible-light absorption of TiO2. 5 wt% MWCNT-TiO2 derived from hydrothermal treatment at 140°C exhibiting the highest hydrogen generation rate of 15.1 μmol·h−1 under visible-light irradiation and a wide photoresponse range from 350 to 475 nm with moderate quantum efficiency (4.4% at 420 nm and 3.7% at 475 nm. The above experimental results indicate that the MWCNT-TiO2 nanocomposite is a promising photocatalyst with good stability and visible-light-induced photoactivity.

  8. Metallic WO2-Carbon Mesoporous Nanowires as Highly Efficient Electrocatalysts for Hydrogen Evolution Reaction.

    Science.gov (United States)

    Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Liu, Dali; Zhang, Bin

    2015-06-10

    The development of electrocatalysts to generate hydrogen, with good activity and stability, is a great challenge in the fields of chemistry and energy. Here we demonstrate a "hitting three birds with one stone" method to synthesize less toxic metallic WO2-carbon mesoporous nanowires with high concentration of oxygen vacancies (OVs) via calcination of inorganic/organic WO3-ethylenediamine hybrid precursors. The products exhibit excellent performance for H2 generation: the onset overpotential is only 35 mV, the required overpotentials for 10 and 20 mA/cm(2) are 58 and 78 mV, the Tafel slope is 46 mV/decade, the exchange current density is 0.64 mA/cm(2), and the stability is over 10 h. Further studies, in combination with density functional theory, demonstrate that the unusual electronic structure and the large amount of active sites, generated by the high concentration of OVs, as well as the closely attached carbon materials, were key factors for excellent performance. Our results experimentally and theoretically establish metallic transition metal oxides (TMOs) as intriguing novel electrocatalysts for H2 generation. Such TMOs with OVs might be promising candidates for other energy storage and conversion applications.

  9. The redshift evolution of escape fraction of hydrogen ionizing photons from galaxies

    CERN Document Server

    Khaire, Vikram; Choudhury, Tirthankar Roy; Gaikwad, Prakash

    2015-01-01

    Using our cosmological radiative transfer code, we study the implications of the updated QSO emissivity and star formation history for the escape fraction (f_esc) of hydrogen ionizing photons from galaxies. We estimate the f_esc that is required to reionize the Universe and to maintain the ionization state of the intergalactic medium in the post-reionization era. At z>5.5, we show that a constant f_esc of 0.14 to 0.22 is sufficient to reionize the Universe. At z3 together with a nearly constant measured H I photoionization rates at 34. In addition, a simple extrapolation of the contribution of such QSOs to high-z suggests that QSOs alone can reionize the Universe. This implies, at z>3.5, that either the properties of galaxies should evolve rapidly to increase the f_esc or most of the low mass galaxies should host massive blackholes and sustain accretion over a prolonged period. These results motivate a careful investigation of theoretical predictions of these alternate scenarios that can be distinguished usin...

  10. Formation and evolution of molecular hydrogen in disk galaxies with different masses and Hubble types

    CERN Document Server

    Bekki, Kenji

    2014-01-01

    We investigate the physical properties of molecular hydrogen (H2) in isolated and interacting disk galaxies with different masses and Hubble types by using chemodynamical simulations with H2 formation on dust grains and dust growth and destruction in interstellar medium (ISM). We particularly focus on the dependences of H2 gas mass fractions (f_H2), spatial distributions of HI and H2, and local H2-scaling relations on initial halo masses (M_h), baryonic fractions (f_bary), gas mass fractions (f_g), and Hubble types. The principal results are as follows. The final f_H2 can be larger in disk galaxies with higher M_h, f_bary, and f_g. Some low-mass disk models with M_h smaller than 10^10 M_sun show extremely low f_H2 and thus no/little star formation, even if initial f_g is quite large (>0.9). Big galactic bulges can severely suppress the formation of H2 from HI on dust grains whereas strong stellar bars can not only enhance f_H2 but also be responsible for the formation of H2-dominated central rings. The projec...

  11. Hydrogen Infrastructure Market Readiness: Opportunities and Potential for Near-term Cost Reductions; Proceedings of the Hydrogen Infrastructure Market Readiness Workshop and Summary of Feedback Provided through the Hydrogen Station Cost Calculator

    Energy Technology Data Exchange (ETDEWEB)

    Melaina, M. W.; Steward, D.; Penev, M.; McQueen, S.; Jaffe, S.; Talon, C.

    2012-08-01

    Recent progress with fuel cell electric vehicles (FCEVs) has focused attention on hydrogen infrastructure as a critical commercialization barrier. With major automakers focused on 2015 as a target timeframe for global FCEV commercialization, the window of opportunity is short for establishing a sufficient network of hydrogen stations to support large-volume vehicle deployments. This report describes expert feedback on the market readiness of hydrogen infrastructure technology from two activities.

  12. FeP nanoparticles film grown on carbon cloth: an ultrahighly active 3D hydrogen evolution cathode in both acidic and neutral solutions.

    Science.gov (United States)

    Tian, Jingqi; Liu, Qian; Liang, Yanhui; Xing, Zhicai; Asiri, Abdullah M; Sun, Xuping

    2014-12-10

    In this Letter, we demonstrate the direct growth of FeP nanoparticles film on carbon cloth (FeP/CC) through low-temperature phosphidation of its Fe3O4/CC precursor. Remarkably, when used as an integrated 3D hydrogen evolution cathode, this FeP/CC electrode exhibits ultrahigh catalytic activity comparable to commercial Pt/C and good stability in acidic media. This electrode also performs well in neutral solutions. This work offers us the most cost-effective and active 3D cathode toward electrochemical water splitting for large-scale hydrogen fuel production.

  13. Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions.

    Science.gov (United States)

    Busser, G Wilma; Mei, Bastian; Muhler, Martin

    2012-11-01

    The deposition of hydrogen evolution sites on photocatalysts is a crucial step in the multistep process of synthesizing a catalyst that is active for overall photocatalytic water splitting. An alternative approach to conventional photodeposition was developed, applying the photocatalytic reforming of aqueous methanol solutions to deposit metal particles on semiconductor materials such as Ga₂O₃ and (Ga₀.₆ Zn₀.₄)(N₀.₆O₀.₄). The method allows optimizing the loading of the co-catalysts based on the stepwise addition of their precursors and the continuous online monitoring of the evolved hydrogen. Moreover, a synergetic effect between different co-catalysts can be directly established.

  14. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane; Reduction catalytique selective des oxydes d'azote (NO{sub x}) provenant d'effluents gazeux industriels par l'hydrogene ou le methane

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

    This work deals with the selective catalytic reduction of nitrogen oxides (NO{sub x}), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N{sub 2}, in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO{sub 3}, on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  15. In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

    Science.gov (United States)

    Jin, Haiyan; Wang, Jing; Su, Diefeng; Wei, Zhongzhe; Pang, Zhenfeng; Wang, Yong

    2015-02-25

    Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.

  16. Metal hydrides as electrode/catalyst materials for oxygen evolution/reduction in electrochemical devices

    Science.gov (United States)

    Bugga, Ratnakumar V. (Inventor); Halpert, Gerald (Inventor); Fultz, Brent (Inventor); Witham, Charles K. (Inventor); Bowman, Robert C. (Inventor); Hightower, Adrian (Inventor)

    1997-01-01

    An at least ternary metal alloy of the formula, AB.sub.(5-Y)X(.sub.y), is claimed. In this formula, A is selected from the rare earth elements, B is selected from the elements of groups 8, 9, and 10 of the periodic table of the elements, and X includes at least one of the following: antimony, arsenic, and bismuth. Ternary or higher-order substitutions, to the base AB.sub.5 alloys, that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

  17. Session 6: The remarkable effect of hydrogen on the NO{sub x} SCR reaction mechanism over Ag/Al{sub 2}O{sub 3} at low temperatures using a combination of hydrogen and octane as reductants

    Energy Technology Data Exchange (ETDEWEB)

    Breen, J.P.; Burch, R.; Hill, C.J.; Meunier, F.C. [Belfast Queen' s Univ., School of Chemistry (Ireland); Krutzsch, B.; Konrad, B. [DaimlerChrysler AG, Research Body and Powertrain, Combustion Engines - Exhaust Gas Aftertreatment, Stuttgart (Germany); Jobson, E.; Cider, L. [Volvo Technology Corporation AB, Dept 06130, Goteborg (Sweden); Eranen, K.; Klingstedt, F.; Lindfors, L.E. [Abo Akademi Univ., Lab. of Industrial Chemistry (Finland)

    2004-07-01

    For automotive applications lean burn engines represent a method for significantly lowering fuel consumption. However, combustion processes produce substantial quantities of nitrogen oxides (NO + NO{sub 2}, collectively referred to as NO{sub x}). The reduction of NO{sub x} to N{sub 2} under such oxidising conditions is a very challenging scientific problem because it requires catalysts that will selectively cause the reductant to react with the NO{sub x} rather than O{sub 2}. One of the most promising systems under realistic conditions uses hydrocarbon reductants with a Ag/Al{sub 2}O{sub 3} catalyst. One drawback of these catalysts is the very poor activity below ca. 350 C. Satsuma and co-workers have shown that the addition of H{sub 2} can significantly improve the level of NO{sub x} reduction. On the basis of UV spectroscopy, they have concluded that the role of H{sub 2} is to reduce Ag{sup +} ions embedded in the Al{sub 2}O{sub 3} surface to produce small metallic Ag clusters. These Ag clusters are thought to promote the reaction mainly through the activation of the hydrocarbon. The purpose of the present investigation is to offer an additional proposal in which a critical role of H{sub 2} is proposed to be a direct involvement in the reaction mechanism. Details of catalyst preparation, characterisation and kinetic tests can be found elsewhere. Fig. 1(A) shows that the remarkable effect of addition of hydrogen to the HC-SCR reaction first noted by Satokawa et al. for C1 to C4 hydrocarbons can be extended to higher hydrocarbons such as octane. The results also show that for the simple reaction of NO + O{sub 2}, hydrogen can promote the oxidation of NO to NO{sub 2}. It was also evident that hydrogen could promote the reaction of octane and oxygen, decreasing by {>=}200 C the temperature at which the octane started to combust (Fig. 1(B)). Transient experiments gave further insight into the role of hydrogen in the reaction. In these experiments, the introduction of

  18. Non-noble metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution

    Science.gov (United States)

    Song, Jun-Ling; Zhang, Jian-Han; Mao, Jiang-Gao

    2016-05-01

    We reported the synthesis and crystal structures of alkali metal and alkali-earth metal phosphite, namely, CsV2(H3O)(HPO3)4 (1), and Ba3V2(HPO3)6 (2). Both compounds were prepared by hydrothermal reactions and feature unique new structures. They both exhibit 3D complicated frameworks based on VO6 octahedra which are connected by HPO3 tetrahedra via corner-sharing. Alkali or alkali earth metal cations are filled in the different channels of the frameworks. Topological analysis shows that the framework of CsV2(H3O) (HPO3)4 (1) is a new 3,3,3,4,5-connected network with the Schläfli symbol of {4.62}2{42.66.82}{63}{65.8}. The investigations of X-ray photoelectron spectroscopy (XPS) and magnetic measurement on CsV2(H3O)(HPO3)4 suggest a +3 oxidation state of the vanadium ions in compound 1. Photocatalytic performance was evaluated by photocatalytic H2 evolution and degradation of methylene blue, which shows that both compounds exhibit activity under visible-light irradiation. IR spectrum, UV-vis-NIR spectrum and thermogravimetric analysis (TGA) of compounds were also investigated.

  19. Study and modeling of the reduction of sulfur dioxide, nitrogen oxides and hydrogen chloride by dry injection technologies

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wuyin

    1997-05-01

    The potential and mechanism to reduce acid gases, such as sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}) and hydrogen chloride (HCl), by dry Ca-based sorbents have been studied to improve the efficiency of the process and sorbent utilization. Several natural limestones were tested for SO{sub 2} removal. Calcium conversion as high as 45 % was achieved in the first 0.3 s at 1000 deg C, 1000 ppm SO{sub 2} and Ca/S=1. A SO{sub 2} removal efficiency of 95 % was reached at Ca/S=2. Two models for estimating the sulfation of CaO at high temperature are presented. Short-residence-time sulfation is described by a pore size distribution model and long-residence-time sulfation by a particle expansion model. The pore size distribution model explains the effects of particle size, pore size distribution and partial pressure of SO{sub 2}, suggesting these three factors be the most important for CaO conversion. For particles larger than 1-2 {mu}m in furnace sorbent injection, pore diameters of 50-300 Aa are desirable. When large particles or long residence times are used, as in fluidized bed combustion, the particle expansion model shows the particle size and the sorbent type to be the main factors affecting the reaction. By using the selected limestone and additives the simultaneous SO{sub 2}/NO{sub x} removal was also measured. Several ammonium salts as well as urea were tested. Urea was found to give the highest NO{sub x} removal efficiency. To fully utilize the unreacted Ca-based sorbents, the spent sorbents from SO{sub 2} reduction processes were tested in a fixed-bed reactor to measure the capacity for HCl removal at 150-600 deg C. The results showed that all spent materials could react with HCl to some extent. After being calcined and slaked, they even showed the same reactivity as pure Ca(OH){sub 2}. A shrinking core model was derived for fixed-bed reactor. For the best sorbent tested, the multiple sorbent utilization reached about 80 %. 100 refs, 42 figs, 12 tabs

  20. Microstructural evolution of Cu-1at% Ti alloy aged in a hydrogen atmosphere and its relation with the electrical conductivity

    KAUST Repository

    Semboshi, Satoshi

    2009-04-01

    Copper alloys with titanium additions between 1 and 6 at% Ti emerge currently as attractive conductive materials for electrical and electronic commercial products, since they exhibit superior mechanical and electrical properties. However, their electrical conductivity is reduced owing to the residual amount of Ti solutes in the Cu solid solution (Cu(ss)) phase. Since Cu shows only poor reactivity with hydrogen (H), while Ti exhibits high affinity to it, we were inspired by the idea that hydrogenation of Cu-Ti alloys would influence their microstructure, resulting in a significant change of their properties. In this contribution, the influence of aging under a deuterium (D(2)) atmosphere of Cu-1 at% Ti alloys on their microstructure is investigated to explore the effects on the electrical conductivity. The specimens were investigated by means of transmission electron microscopy (TEM), field ion microscopy (FIM), computer-aided field ion image tomography (cFIIT), and atom probe tomography (APT). At an early aging stage at 623 K in a D(2) atmosphere of 0.08 Wit, ellipsoidal alpha-Cu(4)Ti precipitates are formed in the alloy, and during subsequent aging, delta-TiD(2) is competitively nucleated instead of growth of alpha-Cu(4)Ti particles. The co-precipitation of alpha-Cu(4)Ti and delta-TiD(2) efficiently reduces the Ti concentration of Cuss matrix, particularly in the later aging stages in comparison to the aging in vacuum conditions. The electrical conductivity of the alloy aged in the D(2) atmosphere increases steeply up to 48% International Annealed Copper Standard (IACS) after 1030 It, while it saturates to approximately 20% IACS in the alloy aged in vacuum. The outstanding increase of electrical conductivity during aging in D2 atmosphere can be basically explained by the reduction of Ti solute concentration in Cuss matrix. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

  1. Dendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activity

    KAUST Repository

    Bhunia, Manas Kumar

    2015-11-23

    Developing stable, ubiquitous and efficient water-splitting photocatalyst material that has extensive absorption in the visible-light range is desired for a sustainable solar energy-conversion device. We herein report a triazine-based carbon nitride (CN) material with different C/N ratios achieved by varying the monomer composition ratio between melamine (Mel) and 2,4,6-triaminopyrimidine (TAP). The CN material with a different C/N ratio was obtained through a two-step synthesis protocol: starting with the solution state dispersion of the monomers via hydrogen-bonding supramolecular aggregate, followed by a salt-melt high temperature polycondensation. This protocol ensures the production of a highly crystalline polytriazine imide (PTI) structure con-sisting of a copolymerized Mel-TAP network. The observed bandgap narrowing with an increasing TAP/Mel ratio is well simulated by density functional theory (DFT) calculations, revealing a positive shift in the valence band upon substitution of N with CH in the aromatic rings. Increasing the TAP amount could not maintain the crystalline PTI structure, consistent with DFT calculation showing the repulsion associated with additional C-H introduced in the aromatic rings. Due to the high exciton binding energy calculated by DFT for the obtained CN, the cocatalyst must be close to any portion of the material to assist the separation of excit-ed charge carriers for an improved photocatalytic performance. The photocatalytic activity was improved by providing a dendritic tip-on-like shape grown on a porous fibrous silica KCC-1 spheres, and highly dispersed Pt nanoparticles (<5 nm) were photodepos-ited to introduce heterojunction. As a result, the Pt/CN/KCC-1 photocatalyst exhibited an apparent quantum efficiency (AQE) as high as 22.1 ± 3% at 400 nm and the silica was also beneficial for improving photocatalytic stability. The results obtained by time-resolved transient absorption spectroscopy measurements were consistent with

  2. Phase- and morphology-controlled synthesis of cobalt sulfide nanocrystals and comparison of their catalytic activities for hydrogen evolution

    Science.gov (United States)

    Pan, Yuan; Liu, Yunqi; Liu, Chenguang

    2015-12-01

    Colalt sulfide nanocrystals (NCs), including dandelion-like Co9S8 and sphere-like Co3S4, have been synthesized via a thermal decomposition approach using cobalt acetylacetonate as the cobalt source, 1-dodecanethiol as the sulfur source and oleic acid or oleylamine as the high boiling organic solvent. It is found that the molar ratio of the Co:S precursor and the species of solvent play an important role in the control of phase and morphology of cobalt sulfide nanostructures. The phase structure and morphology of the as-synthesized nickel sulfide NCs are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), energy dispersive spectrum (EDS) mapping, X-ray photoelectron spectroscopy (XPS) and N2 adsorption-desorption. Then we further compare the electrocatalytic activity and stability of as-synthesized cobalt sulfide NCs for hydrogen evolution reaction (HER). The results show that sphere-like Co3S4 exhibits better electrocatalytic activity than the dandelion-like Co9S8 NCs for HER, which can be attributed to the difference of phase structure and morphology. The sphere-like Co3S4 NCs have large surface area and high electrical conductivity, both are beneficial to enhance the catalytic activity. This study indicates that the crystalline phase structure and morphology of cobalt sulfide NCs are important for designing HER electrocatalysts with high efficiency and good stability.

  3. Synthesis of Cobalt Phosphide Nanoparticles Supported on Pristine Graphene by Dynamically Self-Assembled Graphene Quantum Dots for Hydrogen Evolution.

    Science.gov (United States)

    Wang, Xiaoyan; Yuan, Weiyong; Yu, Yanan; Li, Chang Ming

    2017-03-09

    A highly active, durable, and low-cost hydrogen evolution reaction (HER) catalyst is desirable for energy storage through water splitting but its fabrication presents great challenges. Herein, mediated by dynamically self-assembled graphene quantum dots (GQDs), small, uniform, high-density, and well-dispersed CoP nanoparticles were grown in situ on pristine graphene for the first time. This hybrid nanostructure was then employed as HER electrocatalyst, showing an onset potential of 7 mV, an overpotential of 91.3 mV to achieve 10 mA cm(-2) , a Tafel slope of 42.6 mV dec(-1) , and an exchange current density of 0.1225 mA cm(-2) , all of which compare favorably to those of most reported non-noble-metal catalysts. The developed catalyst also exhibits excellent durability with negligible current loss after 2000 cyclic voltammetry cycles (+0.01 to -0.17 V vs. RHE) or 34 h of chronoamperometric measurement at an overpotential of 91.3 mV. This work not only develops a new strategy for the fabrication of high-performance and inexpensive electrocatalysts for HER but also provides scientific insight into the mechanism of the dynamically self-assembled GQDsmediated synthesis process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  5. Facile solvent-thermal synthesis of ultrathin MoSe2 nanosheets for hydrogen evolution and organic dyes adsorption

    Science.gov (United States)

    Jiang, Qingqing; Lu, Yongfeng; Huang, Zhengxi; Hu, Juncheng

    2017-04-01

    The flower-like MoSe2 nanospheres with average size of 200 nm which composed of ultrathin nanosheets were synthesized by facile solvent-thermal method. AFM analysis indicated that the thickness of the MoSe2 nanosheets could be changed from 3.4 to 6.4 nm by changing the chains of n-alcohol solvent. The as prepared MoSe2 nanosheets in ethanol solvent exhibited the best electrochemical performance and the highest adsorption capability as compared to samples synthesized in other n-alcohol solvent with longer chains. It was due to MoSe2 synthesized in ethanol exhibited higher crystallinity and better wettability than other samples. The maximum adsorption capability of Rhodamine B (RhB) on MoSe2 nanosheets reached 133 mg g-1 in 5 min, while the same adsorption capabilities on activated carbon need 20 min. Electrochemical results exhibited a relatively small onset potential (120 mV), small Tafel slope (71 mV/dec), and long term stability for MoSe2 synthesized in ethanol which making it a promising candidate for hydrogen evolution reaction.

  6. Highly efficient hydrogen evolution reaction using crystalline layered three-dimensional molybdenum disulfides grown on graphene film.

    Energy Technology Data Exchange (ETDEWEB)

    Behranginia, Amirhossein; Asadi, Mohammad; Liu, Cong; Yasaei, Poya; Kumar, Bijandra; Phillips, Patrick; Foroozan, Tara; Waranius, Joseph C.; Kim, Kibum; Abiade, Jeremiah; Klie, Robert F.; Curtiss, Larry A.; Salehi-Khojin, Amin

    2016-01-26

    Electrochemistry is central to applications in the field of energy storage and generation. However, it has advanced far more slowly over the last two decades, mainly because of a lack of suitable and affordable catalysts. Here, we report the synthesis of highly crystalline layered three-dimensional (3D) molybdenum disulfide (MoS2) catalysts with bare Mo-edge atoms and demonstrate their remarkable performance for the hydrogen evolution reaction (HER). We found that Mo-edge-terminated 3D MoS2 directly grown on graphene film exhibits a remarkable exchange current density (18.2 mu A cm(-2)) and turnover frequency (>4 S-1) for HER. The obtained exchange current density is 15.2 and 2.3 times higher than that of MoS2/graphene and MoS2/Au catalysts, respectively, both with sulfided Mo-edge atoms. An easily scalable and robust growth process on a wide variety of substrates, along with prolonged stability, suggests that this material is a promising catalyst in energy-related applications.

  7. Hydrothermal synthesis of core–shell TiO{sub 2} to enhance the photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Jinghui; Zhou, Han; Zhang, Fan; Fan, Tongxiang, E-mail: txfan@sjtu.edu.cn; Zhang, Di

    2016-04-15

    Graphical abstract: Core–shell TiO{sub 2} with interior cavity was synthesized by a hydrothermal approach to enhance the photocatalytic performance. - Highlights: • Core–shell TiO{sub 2} with interior cavity can be synthesized by hydrothermal approach. • Multiple reflection of incident light in cavity can increase the absorption. • Rutile can optimize the bandgap and delay the charge recombination. - Abstract: A hydrothermal approach was designed to synthesize core–shell TiO{sub 2} with interior cavity by making sodium dodecyl sulfonate (SDS) as the surfactant and the mixture of water and ethanol as the solvent. The control experiment of solvent reveals ethanol and water are responsible for the formation of sphere and interior cavity, respectively. Besides, SDS can assist the growth of core–shell structure, and the sizes of sphere and interior cavity can be tuned by regulating the reaction time or temperature. UV–vis absorption proves core–shell structure with interior cavity can increase the absorption of incident light to enhance the optical activity of final product. The calculated bandgap and photoluminescence (PL) analyses reveal the coexistence of rutile in final product can optimize the bandgap to 3.03 eV and delay the charge recombination. As a result, an effective photocatalytic hydrogen evolution under full spectrum irradiation can be harvested by the as-synthesized core–shell spheres to reach a quantum yield, approximately 9.57% at 340 nm wavelength.

  8. Evolution of Minor Phases in a 9PctCr Steel: Effect of Tempering Temperature and Relation with Hydrogen Trapping

    Science.gov (United States)

    Hurtado-Noreña, Carolina; Danón, Claudio Ariel; Luppo, María Inés; Bruzzoni, Pablo

    2015-09-01

    The evolution of minor phases in ASTM A335 P91 steel has been studied on specimens submitted to different thermal treatments including a tempering step. Particular emphasis has been put on the tempering temperature range 573 K to 873 K (300 °C to 600 °C), which has not been yet intensively studied. The techniques used in this investigation were X-ray diffraction with synchrotron light, scanning electron microscopy with field emission gun and transmission electron microscopy. In the low tempering temperature range [573 K to 673 K (300 °C to 400 °C)], retained austenite, Fe3C and MX precipitates are observed. In the high tempering temperature range [773 K to 1053 K (500 °C to 780 °C)], M23C6-type carbides, MX-type carbonitrides and M2X precipitates are observed. The effect of the microstructure on hydrogen trapping is analyzed. The distorted matrix around the M2X and MX particles provides the most important trap sites in the P91 steel.

  9. Reductive evolution of architectural repertoires in proteomes and the birth of the tripartite world.

    Science.gov (United States)

    Wang, Minglei; Yafremava, Liudmila S; Caetano-Anollés, Derek; Mittenthal, Jay E; Caetano-Anollés, Gustavo

    2007-11-01

    The repertoire of protein architectures in proteomes is evolutionarily conserved and capable of preserving an accurate record of genomic history. Here we use a census of protein architecture in 185 genomes that have been fully sequenced to generate genome-based phylogenies that describe the evolution of the protein world at fold (F) and fold superfamily (FSF) levels. The patterns of representation of F and FSF architectures over evolutionary history suggest three epochs in the evolution of the protein world: (1) architectural diversification, where members of an architecturally rich ancestral community diversified their protein repertoire; (2) superkingdom specification, where superkingdoms Archaea, Bacteria, and Eukarya were specified; and (3) organismal diversification, where F and FSF specific to relatively small sets of organisms appeared as the result of diversification of organismal lineages. Functional annotation of FSF along these architectural chronologies revealed patterns of discovery of biological function. Most importantly, the analysis identified an early and extensive differential loss of architectures occurring primarily in Archaea that segregates the archaeal lineage from the ancient community of organisms and establishes the first organismal divide. Reconstruction of phylogenomic trees of proteomes reflects the timeline of architectural diversification in the emerging lineages. Thus, Archaea undertook a minimalist strategy using only a small subset of the full architectural repertoire and then crystallized into a diversified superkingdom late in evolution. Our analysis also suggests a communal ancestor to all life that was molecularly complex and adopted genomic strategies currently present in Eukarya.

  10. Radiolytic hydrogen production from process vessels in HB line - production rates compared to evolution rates and discussion of LASL reviews

    Energy Technology Data Exchange (ETDEWEB)

    Bibler, N.E.

    1992-11-12

    Hydrogen production from radiolysis of aqueous solutions can create a safety hazard since hydrogen is flammable. At times this production can be significant, especially in HB line where nitric acid solutions containing high concentrations of Pu-238, an intense alpha emitter, are processed. The hydrogen production rates from these solutions are necessary for safety analyses of these process systems. The methods and conclusions of hydrogen production rate tests are provided in this report.

  11. Evolution of defect and hydrogen-related low temperature photoluminescence spectra with annealing for hydrogen or helium implanted 6H SiC

    Energy Technology Data Exchange (ETDEWEB)

    Yan, F.; Devaty, R.P.; Choyke, W.J. [Dept. of Physics and Astronomy, Univ. of Pittsburgh, Pittsburgh (United States); Gali, A. [Dept. of Atomic Physics, Budapest Univ. of Technology and Economics, Budapest (Hungary); Schmid, F.; Pensl, G. [Inst. of Applied Physics, Univ. of Erlangen-Nuernberg, Erlangen (Germany); Wagner, G. [Inst. fuer Kristallforschung, Berlin (Germany)

    2005-07-01

    A set of four lightly p-type 6H SiC boule samples was implanted with H or He and annealed in isochronal stages from 950 C to 1500 C. Differences in the hydrogen, D{sub I} and D{sub II} low temperature photoluminescence spectra are observed and compared. Surprisingly, the hydrogen spectrum appears after a 1300 C anneal in the He implanted samples. A number of unidentified damage lines are also reported. (orig.)

  12. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin

    2015-11-02

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  13. NiP₂ nanosheet arrays supported on carbon cloth: an efficient 3D hydrogen evolution cathode in both acidic and alkaline solutions.

    Science.gov (United States)

    Jiang, Ping; Liu, Qian; Sun, Xuping

    2014-11-21

    Designing efficient and stable hydrogen evolution catalysts made from earth-abundant elements is essential to the development of solar-driven water-splitting devices. In this communication, we develop a two-step strategy for constructing NiP2 nanosheet arrays on carbon cloth (NiP2 NS/CC). As a novel 3D hydrogen evolution cathode, the NiP2 NS/CC electrode is highly active in acidic solutions and needs an overpotential of 75 and 204 mV to achieve current densities of 10 and 100 mA cm(-2), respectively, and it preserves its catalytic activity for at least 57 h. Moreover, it also operates efficiently under alkaline conditions.

  14. Therapeutic effects of hydrogen saturated saline on rat diabetic model and insulin resistant model via reduction of oxidative stress

    Institute of Scientific and Technical Information of China (English)

    WANG Qi-jin; ZHA Xiao-juan; KANG Zhi-min; XU Mao-jin; HUANG Qin; ZOU Da-jin

    2012-01-01

    Background Molecular hydrogen,as a novel antioxidant,has been proven effective in treating many diseases.This study aimed to evaluate the therapeutic effects of hydrogen saturated saline in treatment of a rat model of diabetes mellitus and a rat model of insulin resistant.Methods A rat diabetes mellitus model was established by feeding a high fat/high carbohydrate diet followed by injection of a small dose of streptozotocin,and an insulin resistant model was induced with a high glucose and high fat diet.Hydrogen saturated saline was administered to rats with both models conditions on a daily basis for eight weeks.A pioglitazone-treated group and normal saline-treated group served as positive and negative controls.The general condition,body weight,blood glucose,blood lipids,and serum insulin levels of rats were examined at the 8th week after treatment.The oxidative stress indices,including serum superoxide dismutase (SOD),glutathione (GSH) and malondialdehyde (MDA) were also evaluated after eight weeks of treatment using the commercial kits.Results Hydrogen saturated saline showed great efficiency in improving the insulin sensitivity and lowering blood glucose and lipids.Meanwhile,the therapeutic effects of hydrogen saturated saline were superior to those of pioglitazone.Hydrogen saturated saline markedly attenuated the MDA level and elevated the levels of antioxidants SOD and GSH.Conclusion Hydrogen saturated saline may improve the insulin resistance and alleviate the symptoms of diabetes mellitus by reducing the oxidative stress and enhancing the anti-oxidant system.

  15. Strain-dependent Damage Evolution and Velocity Reduction in Fault Zones Induced by Earthquake Rupture

    Science.gov (United States)

    Zhong, J.; Duan, B.

    2009-12-01

    Low-velocity fault zones (LVFZs) with reduced seismic velocities relative to the surrounding wall rocks are widely observed around active faults. The presence of such a zone will affect rupture propagation, near-field ground motion, and off-fault damage in subsequent earth-quakes. In this study, we quantify the reduction of seismic velocities caused by dynamic rup-ture on a 2D planar fault surrounded by a low-velocity fault zone. First, we implement the damage rheology (Lyakhovsky et al. 1997) in EQdyna (Duan and Oglesby 2006), an explicit dynamic finite element code. We further extend this damage rheology model to include the dependence of strains on crack density. Then, we quantify off-fault continuum damage distribution and velocity reduction induced by earthquake rupture with the presence of a preexisting LVFZ. We find that the presence of a LVFZ affects the tempo-spatial distribu-tions of off-fault damage. Because lack of constraint in some damage parameters, we further investigate the relationship between velocity reduction and these damage prameters by a large suite of numerical simulations. Slip velocity, slip, and near-field ground motions computed from damage rheology are also compared with those from off-fault elastic or elastoplastic responses. We find that the reduction in elastic moduli during dynamic rupture has profound impact on these quantities.

  16. Integration of Multiple Plasmonic and Co-Catalyst Nanostructures on TiO2 Nanosheets for Visible-Near-Infrared Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Jiang, Wenya; Bai, Song; Wang, Limin; Wang, Xijun; Yang, Li; Li, Yanrui; Liu, Dong; Wang, Xiaonong; Li, Zhengquan; Jiang, Jun; Xiong, Yujie

    2016-03-23

    Utilization of visible and near-infrared light has always been the pursuit of photocatalysis research. In this article, an approach is developed to integrate dual plasmonic nanostructures with TiO2 semiconductor nanosheets for photocatalytic hydrogen production in visible and near-infrared spectral regions. Specifically, the Au nanocubes and nanocages used in this work can harvest visible and near-infrared light, respectively, and generate and inject hot electrons into TiO2 . Meanwhile, Pd nanocubes that can trap the energetic electrons from TiO2 and efficiently participate in the hydrogen evolution reaction are employed as co-catalysts for improved catalytic activity. Enabled by this unique integration design, the hydrogen production rate achieved is dramatically higher than those of its counterpart structures. This work represents a step toward the rational design of semiconductor-metal hybrid structures for broad-spectrum photocatalysis.

  17. A Facile and Waste-Free Strategy to Fabricate Pt-C/TiO2 Microspheres: Enhanced Photocatalytic Performance for Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Hui Li

    2014-01-01

    Full Text Available A facile and waste-free flame thermal synthesis method was developed for preparing Pt modified C/TiO2 microspheres (Pt-C/TiO2. The photocatalysts were characterized with X-ray diffraction, field emission scanning electron microscopy, transmission electron microscope, ultraviolet-visible (UV-vis diffuse reflectance spectra, X-ray photoelectron spectroscopy, and thermogravimetry analysis. The photocatalytic activity was evaluated by hydrogen evolution from water splitting under UV-vis light illumination. Benefitting from the electron-hole separation behavior and reduced overpotential of H+/H2, remarkably enhanced hydrogen production was demonstrated and the photocatalytic hydrogen generation from 0.4 wt% Pt-C/TiO2 increased by 22 times. This study also demonstrates that the novel and facile method is highly attractive, due to its easy operation, requiring no post treatment and energy-saving features.

  18. Sulfur poisoning of emergent and current electrocatalysts: vulnerability of MoS2, and direct correlation to Pt hydrogen evolution reaction kinetics

    Science.gov (United States)

    Tan, Shu Min; Sofer, Zdeněk; Pumera, Martin

    2015-05-01

    The recent surge in interest in the utilisation of transition metal dichalcogenides for the hydrogen evolution reaction (HER), as well as the long-standing problem of sulfur poisoning suffered by the established Pt HER electrocatalyst, motivated us to examine the impacts of sulfur poisoning on both emergent and current electrocatalysts. Through a comparative study between MoS2 and Pt/C on the effects of sulfur poisoning, we demonstrate that MoS2 is not invulnerable to poisoning. Additionally, using X-ray photoelectron spectroscopy, correlations have also been established between the atomic percentages of Pt-S bonds and normalised HER parameters e.g. Tafel slope and potential at -10 mA cm-2. These findings are of high importance for potential hydrogen evolution catalysis.The recent surge in interest in the utilisation of transition metal dichalcogenides for the hydrogen evolution reaction (HER), as well as the long-standing problem of sulfur poisoning suffered by the established Pt HER electrocatalyst, motivated us to examine the impacts of sulfur poisoning on both emergent and current electrocatalysts. Through a comparative study between MoS2 and Pt/C on the effects of sulfur poisoning, we demonstrate that MoS2 is not invulnerable to poisoning. Additionally, using X-ray photoelectron spectroscopy, correlations have also been established between the atomic percentages of Pt-S bonds and normalised HER parameters e.g. Tafel slope and potential at -10 mA cm-2. These findings are of high importance for potential hydrogen evolution catalysis. Electronic supplementary information (ESI) available: Survey scan XPS spectra, HER LSV curves and surface atomic compositions of poisoned and unpoisoned Pt/C and MoS2 nanoparticles. See DOI: 10.1039/c5nr01378j

  19. WS2 as an Effective Noble-Metal Free Cocatalyst Modified TiSi2 for Enhanced Photocatalytic Hydrogen Evolution under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Dongmei Chu

    2016-09-01

    Full Text Available A noble-metal free photocatalyst consisting of WS2 and TiSi2 being used for hydrogen evolution under visible light irradiation, has been successfully prepared by in-situ formation of WS2 on the surface of TiSi2 in a thermal reaction. The obtained samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray spectrometry (EDX, transmission electron microscopy (TEM, and X-ray photoelectron spectroscopy (XPS. The results demonstrate that WS2 moiety has been successfully deposited on the surface of TiSi2 and some kind of chemical bonds, such as Ti-S-W and Si-S-W, might have formed on the interface of the TiSi2 and WS2 components. Optical and photoelectrochemical investigations reveal that WS2/TiSi2 composite possesses lower hydrogen evolution potential and enhanced photogenerated charge separation and transfer efficiency. Under 6 h of visible light (λ > 420 nm irradiation, the total amount of hydrogen evolved from the optimal WS2/TiSi2 catalyst is 596.4 μmol·g−1, which is around 1.5 times higher than that of pure TiSi2 under the same reaction conditions. This study shows a paradigm of developing the effective, scalable and inexpensive system for photocatalytic hydrogen generation.

  20. Enhanced hydrogen evolution from water splitting using Fe-Ni codoped and Ag deposited anatase TiO{sub 2} synthesized by solvothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Tao [School of Chemical Engineering, Northwest University, No. 229 Taibai North Road, Xi’an, Shaanxi 710069 (China); School of Chemistry & Chemical Engineering, Nanjing University, No. 22 Hankou Road, Nanjing, Jiangsu 210093 (China); Liu, Enzhou; Liang, Xuhua [School of Chemical Engineering, Northwest University, No. 229 Taibai North Road, Xi’an, Shaanxi 710069 (China); Hu, Xiaoyun [Department of Physics, Northwest University, No. 229 Taibai North Road, Xi’an, Shaanxi 710069 (China); Fan, Jun, E-mail: fanjun@nwu.edu.cn [School of Chemical Engineering, Northwest University, No. 229 Taibai North Road, Xi’an, Shaanxi 710069 (China)

    2015-08-30

    Graphical abstract: - Highlights: • Fe-Ni/Ag/TiO{sub 2} nanocomposites displayed a higher hydrogen evolution rate. • TiO{sub 2} showed well optical property of light absorption by Fe, Ni and Ag modified. • More surface vacancies on TiO{sub 2} generated by the low cost metal introduced. • The separation rate of photoinduced electro-hole pairs was considerable improved. - Abstract: In this paper, the Fe-Ni co-doped and Ag deposited anatase TiO{sub 2} (Fe-Ni/Ag/TiO{sub 2}) nanocomposites were successfully prepared by a simple one-pot solvothermal approach. The investigations indicated that all as-prepared TiO{sub 2} samples were single anatase phase, and the impurity level was generated due to the Fe{sup 3+} or Ni{sup 2+} being located in the intrinsic band gap of TiO{sub 2}, while the Ag{sup +} ions could be transformed into metallic silver due to the reduction reaction and then loaded onto the surface of TiO{sub 2}. Compared with pure TiO{sub 2}, Fe-Ni/Ag/TiO{sub 2} composites with the sizes of Ag nanoparticles from 1.0 to 3.0 nm displayed the well optical property including higher visible light absorption activity and lower electron-hole pair recombination rate, and its absorption wavelength edge moved remarkably with a red shift to 700 nm. The photocatalytic water splitting was performed to produce H{sub 2} over the samples, and the experimental results indicate that Fe-Ni/Ag/TiO{sub 2} composites presented the highest H{sub 2} evolution rate, it can reach up to 793.86 μmol h{sup −1} g{sub cat}{sup −1} (λ > 400 nm for 6 h, energy efficiency is 0.25%), which was much higher than that of pure TiO{sub 2} for 9.57 μmol h{sup −1} g{sub cat}{sup −1}. In addition, a tentative photocatalytic mechanism is proposed to understand the enhancement mechanism over Fe-Ni codoped and Ag deposited anatase TiO{sub 2}.