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Sample records for hydrogen evolution reduction

  1. Lanthanides-based graphene catalysts for high performance hydrogen evolution and oxygen reduction

    International Nuclear Information System (INIS)

    Shinde, S.S.; Sami, Abdul; Lee, Jung-Ho

    2016-01-01

    Highlights: • Facile, scalable in-situ synthesis of lanthanide (La, Eu, Yb) doped graphene frameworks. • Efficient electrocatalytic performance towards HER and ORR. • Eu-Gr hybrid shows HER performance; onset & overpotential (81 & 160 mV), & Tafel slope (52 mV dec −1 ). • Eu-Gr exhibits superior activity of ORR; onset potential (0.92 V), electron transfer number (4.03). • Excellent long-term stability in HER and ORR, comparable to those of commercial Pt/C catalysts. - Abstract: The design of efficient electrocatalysts for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has received enormous consideration due to their effectiveness in modern renewable energy technologies such as fuel cells, electrolyzers, and metal–air batteries. Herein, we present a facile method to fabricate lanthanides (L = La, Eu, Yb)-doped graphene materials as catalyst for the HER and ORR that show desirable electrocatalytic activities as well as long-term stability. The Eu-graphene hybrid has showed unbeatable HER performance such as small values of onset potential (81 mV), overpotential (160 mV), and Tafel slope (52 mV dec −1 ), along with a high exchange current density (7.55 × 10 −6 A cm −2 ). The L-graphenes also exhibit superior electrocatalytic activity for ORR, including small Tafel slopes (96, 66, and 105 mV dec −1 for La-Gr, Eu-Gr, and Yb-Gr, respectively), positive onset potential (∼0.83–0.92 V), high electron transfer numbers (∼3.84–4.03), and excellent enduring strength, analogous to those of viable Pt/C catalysts. The excellent electrocatalytic performance is attributed to the synergistic effect of abundant edges and doping sites, high electrical conductivity, large active surface areas and fast charge transfer; which renders lanthanide-based graphene hybrids as potentially great candidate for energy conversion systems.

  2. Temperature effect on the photoinduced reduction of methyl viologen with several sensitizers and the evolution of hydrogen from water

    Energy Technology Data Exchange (ETDEWEB)

    Nenadovic, M.T.; Micic, O.I.; Rajh, T.; Savic, D.

    1983-01-01

    Irradiation by visible light of an aqueous solution containing a photosensitizer, methyl viologen (MV/sup 2 +/) and ethylenediaminetetraacetic acid leads to the formation of the reduced form of methyl viologen (MV/sup +/). The quantum yield for the formation of MV/sup +/ depends strongly on the time during which the formation is observed owing to the reaction of MV/sup +/ with oxidative products and its reduction to MV/sup 0/. Proflavin, acridine yellow and ruthenium(II)tris(2,2-bipyridyl) were used as photosensitizers and showed the same ability to promote hydrogen evolution. When CdS was used as a sensitizer a factor of 10 less hydrogen was obtained than when the dyes were used. The redox catalysts platinum, Pt-TiO/sub 2/-RuO/sub 2/ and Pt-CdS in colloidal systems showed approximately the same activity towards the reduction of water. The reduction of MV/sup 2 +/ and the evolution of hydrogen were enhanced at higher temperatures (70/sup 0/C). The optimum conditions for water reduction on redox catalysts in colloidal system under continuous illumination are analysed.

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

    Science.gov (United States)

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

    2017-06-21

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

  4. Hydrogen evolution reaction catalyst

    Science.gov (United States)

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

    2016-02-09

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

  5. Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

    2011-06-30

    Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

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

    Science.gov (United States)

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

    2017-11-01

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

  7. 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.

  8. 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 experiment...... catalysts based on this. Suited for upper-level high school and first-year university students, this exercise involves using a basic two-cell electrochemical setup to test multiple electrode materials as catalysts at one applied potential, and then constructing a volcano curve with the resulting currents...

  9. 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...

  10. Hydrogen evolution by a metal-free electrocatalyst

    KAUST Repository

    Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Luhua; Han, Yu; Chen, Ying; Du, Aijun; Jaronieć, Mietek; Qiao, Shizhang

    2014-01-01

    Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All

  11. Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

    Science.gov (United States)

    Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

    2018-05-01

    Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

  12. The interplay between hydrogen evolution reaction and nitrate reduction on boron-doped diamond in aqueous solution: the effect of alkali cations

    International Nuclear Information System (INIS)

    Manzo-Robledo, A.; Lévy-Clément, C.; Alonso-Vante, N.

    2014-01-01

    The nitrate ion reduction was studied on boron-doped diamond (BDD) electrodes by real-time on-line differential electrochemical mass spectrometry (DEMS) coupled with chronoamperometry in K + , Na + cation-containing electrolyte solutions. It was found, via steady state voltammetry, that the hydrogen evolution reaction (HER) was affected by the presence of K + or Na + . A moderate HER occurs in K + -containing electrolyte solution favoring the reaction between NO 3 − and H 2 species, whereas in Na + -containing electrolyte solutions, the HER kinetics was more important leading to a suppression of molecular nitrogen generation. The use of isotope-labeled nitrogen and DEMS confirmed the influence of alkali cations toward the nitrate ion reduction

  13. A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

    Science.gov (United States)

    Kuriki, Ryo; Ichibha, Tom; Hongo, Kenta; Lu, Daling; Maezono, Ryo; Kageyama, Hiroshi; Ishitani, Osamu; Oka, Kengo; Maeda, Kazuhiko

    2018-05-16

    Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N 3- , S 2- ) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb 2 Ti 2 O 5.4 F 1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb 2 Ti 2 O 5.4 F 1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb 2 Ti 2 O 5.4 F 1.2 worked as a stable photocatalyst for visible-light-driven H 2 evolution and CO 2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb 2 Ti 2 O 5.4 F 1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

  14. M3C (M: Fe, Co, Ni) Nanocrystals Encased in Graphene Nanoribbons: An Active and Stable Bifunctional Electrocatalyst for Oxygen Reduction and Hydrogen Evolution Reactions.

    Science.gov (United States)

    Fan, Xiujun; Peng, Zhiwei; Ye, Ruquan; Zhou, Haiqing; Guo, Xia

    2015-07-28

    Transition metal carbide nanocrystalline M3C (M: Fe, Co, Ni) encapsulated in graphitic shells supported with vertically aligned graphene nanoribbons (VA-GNRs) are synthesized through a hot filament chemical vapor deposition (HF-CVD) method. The process is based on the direct reaction between iron group metals (Fe, Co, Ni) and carbon source, which are facilely get high purity carbide nanocrystals (NCs) and avoid any other impurity at relatively low temperature. The M3C-GNRs exhibit superior enhanced electrocatalystic activity for oxygen reduction reaction (ORR), including low Tafel slope (39, 41, and 45 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively), positive onset potential (∼0.8 V), high electron transfer number (∼4), and long-term stability (no obvious drop after 20 000 s test). The M3C-GNRs catalyst also exhibits remarkable hydrogen evolution reaction (HER) activity with a large cathodic current density of 166.6, 79.6, and 116.4 mA cm(-2) at an overpotential of 200 mV, low onset overpotential of 32, 41, and 35 mV, small Tafel slope of 46, 57, and 54 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively, as well as an excellent stability in acidic media.

  15. Facile solvothermal synthesis of monodisperse Pt2.6Co1 nanoflowers with enhanced electrocatalytic activity towards oxygen reduction and hydrogen evolution reactions

    International Nuclear Information System (INIS)

    Jiang, Liu-Ying; Lin, Xiao-Xiao; Wang, Ai-Jun; Yuan, Junhua; Feng, Jiu-Ju; Li, Xin-Sheng

    2017-01-01

    Highlights: • Uniform Pt 2.6 Co 1 nanoflowers were prepared by a simple solvothermal method. • Glucose and CTAC were used as the green reductant and structure director, respectively. • The architectures had the enlarged ECSA. • The architectures exhibited excellent catalytic performances for HER in acid and alkaline media. • The architectures showed highly catalytic performances for ORR in acid media. - Abstract: Herein, uniform Pt 2.6 Co 1 nanoflowers (NFs) were synthesized in oleylamine by a one-pot solvothermal method, using cetyltrimethylammonium chloride (CTAC) and glucose as the capping agent and green reducing agent. The samples were mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The architectures had larger electrochemically active surface area (ECSA) of 23.84 m 2 g −1 Pt than Pt 1.2 Co 1 nanocrystals (NCs, 14.96 m 2 g −1 Pt ), Pt 3.7 Co 1 NCs (16.96 m 2 g −1 Pt ) and commercial Pt black (20.35 m 2 g −1 Pt ). And the as-obtained Pt 2.6 Co 1 catalyst displayed superior catalytic performance and better durability for hydrogen evolution reaction (HER) as compared to Pt 1.2 Co 1 NCs, Pt 3.7 Co 1 NCs, commercial 50% Pt/C and Pt black catalysts in acid and alkaline media. Meanwhile, the electrocatalytic performance of Pt 2.6 Co 1 NFs for oxygen reduction reaction (ORR) is better in acid media as compared with that in alkaline media. It indicates the great potential applications of the as-prepared catalyst in fuel cells.

  16. Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

    Science.gov (United States)

    Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

    2018-08-15

    The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. 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.

  18. 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…

  19. 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.

  20. 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.

  1. Chitosan catalyzes hydrogen evolution at mercury electrodes

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Římánková, Ludmila

    2014-01-01

    Roč. 44, JUL2014 (2014), s. 59-62 ISSN 1388-2481 R&D Projects: GA ČR(CZ) GAP301/11/2055 Institutional support: RVO:68081707 Keywords : Chitosan * Glucosamine-containing polymers * Catalytic hydrogen evolution Subject RIV: BO - Biophysics Impact factor: 4.847, year: 2014

  2. 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.

  3. Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction

    Science.gov (United States)

    Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

    2015-05-01

    Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment

  4. Decomposition and reduction of AUC in hydrogen

    International Nuclear Information System (INIS)

    Ge Qingren; Kang Shifang; Zhou Meng

    1987-01-01

    AUC (Ammonium Uranyl Carbonate) conversion processes have been adopted extensively in nuclear fuel cycle. The kinetics investigation of these processes, however, has not yet been reported in detail at the published literatures. In the present work, the decomposition kinetics of AUC in hydrogen has been determined by non-isothermal method. DSC curves are solved with computer by Ge Qingren method. The results show that the kinetics obeys Avrami-Erofeev equation within 90% conversion. The apparent activation energy and preexponent are found to be 113.0 kJ/mol and 7.11 x 10 11 s -1 respectively. The reduction kinetics of AUC decomposition product in hydrogen at the range of 450 - 600 deg C has been determined by isothermal thermogravimetric method. The results show that good linear relationship can be obtained from the plot of conversion vs time, and that the apparent activation energy is found to be 113.9 kJ/mol. The effects of particle size and partial pressure of hydrogen are examined in reduction of AUC decomposition product. The reduction mechanism and the structure of particle are discussed according to the kinetics behaviour and SEM (scanning electron microscope) photograph

  5. Kinetic Monte Carlo study on the evolution of silicon surface roughness under hydrogen thermal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gang; Wang, Yu; Wang, Junzhuan; Pan, Lijia; Yu, Linwei; Zheng, Youdou; Shi, Yi, E-mail: yshi@nju.edu.cn

    2017-08-31

    Highlights: • The KMC method is adopted to investigate the relationships between surface evolution and hydrogen thermal treatment conditions. • The reduction in surface roughness is divided into two stages at relatively low temperatures, both exhibiting exponential dependence on the time. • The optimized surface structure can be obtained by precisely adjusting thermal treatment temperatures and hydrogen pressures. - Abstract: The evolution of a two-dimensional silicon surface under hydrogen thermal treatment is studied by kinetic Monte Carlo simulations, focusing on the dependence of the migration behaviors of surface atoms on both the temperature and hydrogen pressure. We adopt different activation energies to analyze the influence of hydrogen pressure on the evolution of surface morphology at high temperatures. The reduction in surface roughness is divided into two stages, both exhibiting exponential dependence on the equilibrium time. Our results indicate that a high hydrogen pressure is conducive to obtaining optimized surfaces, as a strategy in the applications of three-dimensional devices.

  6. Low content of Pt supported on Ni-MoC{sub x}/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui, E-mail: diamond_wangyanhui@163.com

    2017-08-01

    Highlights: • Ni-MoC{sub x}/C catalyst support was synthesized by a two-step method. • 10Pt/Ni-MoC{sub x}/C was an active and durable low Pt catalyst for MOR, ORR and HER. • The high stability of 10Pt/Ni-MoC{sub x}/C was ascribed to the anchoring effect of MoC{sub x}. • High activity of 10Pt/Ni-MoC{sub x}/C was due to a synergistic of Pt, Ni, MoO{sub x} and MoC{sub x}. - Abstract: Nickel and molybdenum carbide modified carbon black (Ni-MoC{sub x}/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-MoC{sub x}/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoC{sub x}/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoC{sub x}/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoC{sub x}/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-MoC{sub x}/C reached 68.4 m{sup 2} g{sup −1}, which was higher than that of 20Pt/C (63.2 m{sup 2} g{sup −1}). The enhanced stability and activity of 10Pt/Ni-MoC{sub x}/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoC{sub x} formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoO{sub x} and MoC{sub x}. These findings indicated that 10Pt/Ni-MoC{sub x}/C was a promising electrocatalyst for direct methanol fuel cells.

  7. 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...

  8. 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.

  9. 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

  10. Beyond the top of the volcano? A unified approach to electrocatalytic oxygen reduction and oxygen evolution

    Czech Academy of Sciences Publication Activity Database

    Busch, M.; Halck, N. B.; Kramm, U. I.; Siehrostami, S.; Krtil, Petr; Rossmeisl, J.

    2016-01-01

    Roč. 29, NOV 2016 (2016), s. 126-135 ISSN 2211-2855 Institutional support: RVO:61388955 Keywords : hydrogen evolution * catalytic-activity * Electrocatalysis * Oxygen reduction * Oxygen evolution * Volcano * Density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.343, year: 2016

  11. Hydrogen risk reduction in Nuclear power plant

    International Nuclear Information System (INIS)

    Movahed, M.A.; Travis, J.R.

    1999-01-01

    In case of a severe accident in a nuclear power plant with core melt and hydrogen production, the hydrogen risk is one of the main concerns. It may jeopardize the containment integrity due to violent deflagration that can lead to DDT (Deflagration Detonation Transient) or even detonation of proper hydrogen mitigation means are not available. The design of the EPR (European Pressurized water Reactor) Hydrogen mitigation and control system is based on the lumped parameter code WAVCO and the 3D code GASFLOW. The concept consists of recombiners and igniters to cope with all scenarios including those without steam. The system has been checked to avoid DDT by the 7λ criteria that's implemented in GASFLOW. Future analysis could deal with determining dynamic pressure loads, if appropriate, and some sensitivity studies to check the hydrogen control measures with respect to different source locations and mass flow rates. Also a conditional criterion for determining the likelihood of fast deflagration should be developed. (author)

  12. 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...

  13. Chemical reduction of refractory oxides by atomic hydrogen

    International Nuclear Information System (INIS)

    Dooley, D.; Balooch, M.; Olander, D.R.

    1978-11-01

    The chemical reduction of UO 2 and Al 2 O 3 by atomic hydrogen was studied. Results of the UO 2 /H investigation indicates that reduction of UO 2 by atomic hydrogen proceeds by the production of water vapor and hypostoichiometric urania. Water vapor and aluminum metal are formed in the Al 2 O 3 /H system. The relative ease which UO 2 is reduced by atomic hydrogen compared with Al 2 O 3 is due to two factors. The first is related to the thermochemistry of the reactions. The second factor which favors efficient reduction of UO 2 but not of Al 2 O 3 is the oxygen diffusivity

  14. 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...

  15. Dynamic modelling of hydrogen evolution effects in the all-vanadium redox flow battery

    International Nuclear Information System (INIS)

    Shah, A.A.; Al-Fetlawi, H.; Walsh, F.C.

    2010-01-01

    A model for hydrogen evolution in an all-vanadium redox flow battery is developed, coupling the dynamic conservation equations for charge, mass and momentum with a detailed description of the electrochemical reactions. Bubble formation at the negative electrode is included in the model, taking into account the attendant reduction in the liquid volume and the transfer of momentum between the gas and liquid phases, using a modified multiphase-mixture approach. Numerical simulations are compared to experimental data for different vanadium concentrations and mean linear electrolyte flow rates, demonstrating good agreement. Comparisons to simulations with negligible hydrogen evolution demonstrate the effect of gas evolution on the efficiency of the battery. The effects of reactant concentration, flow rate, applied current density and gas bubble diameter on hydrogen evolution are investigated. Significant variations in the gas volume fraction and the bubble velocity are predicted, depending on the operating conditions.

  16. Cost reductions in nickel-hydrogen battery

    Science.gov (United States)

    Beauchamp, Richard L.; Sindorf, Jack F.

    1987-01-01

    Significant progress was made toward the development of a commercially marketable hydrogen nickel oxide battery. The costs projected for this battery are remarkably low when one considers where the learning curve is for commercialization of this system. Further developmental efforts on this project are warranted as the H2/NiO battery is already cost competitive with other battery systems.

  17. 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.

  18. Ternary alloy nanocatalysts for hydrogen evolution reaction

    Indian Academy of Sciences (India)

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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

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

    International Nuclear Information System (INIS)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

    2015-01-01

    Liquid natural rubber (LNR) with molecular weight of lower than 10 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)

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

    Science.gov (United States)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

    2015-09-01

    Liquid natural rubber (LNR) with molecular weight of lower than 105 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).

  2. 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)

  3. Photocatalytic hydrogen evolution from aqueous solutions of organophosphorous compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kozlova, Ekaterina A.; Vorontsov, Alexander V. [Boreskov Institute of Catalysis and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2010-07-15

    Photocatalytic hydrogen production from water solutions of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), triethyl phosphate (TEP), and radiation protective amine WR 2721, that imitate nerve chemical warfare agents was studied for the first time. Platinized titianium dioxide Degussa P25 was used as catalyst. No significant hydrogen evolution was detected without organic electron donors - sacrificial agents. The hydrogen evolution rate was shown to grow slowly with the rise of initial DMMP concentration. The initial rate vs. DMMP concentration curve is well fitted by Langmuir-Hinshelwood (L-H) equation. The DMMP adsorption constant obtained from the L-H equation fit is markedly higher than that obtained from the Langmuir adsorption isotherm. Reactions of full destruction into inorganic products of the four organophosphorous compounds were conducted. Amounts of evolved hydrogen and carbon dioxide were completely consistent with stoichiometry of proposed reaction. There were no initial compounds and only trace of total organic carbon after the end of the reaction. Complete water purification and production of an amount of valuable hydrogen was achieved. Intermediates of DMMP oxygen-free destruction were identified by means of GC/MS. They were the same as those in the case of DMMP photocatalytic oxidation. A mechanism of hydrogen evolution that explains smaller rates of mineralization compared to photocatalytic oxidation by oxygen was proposed. (author)

  4. 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…

  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 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...

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

    DEFF Research Database (Denmark)

    Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan

    2011-01-01

    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....... 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...... is evaluated with a micro-kinetic model. The analysis reproduces measured Pd-coverage-dependent activities for Pd submonolayers exceeding similar to 0.15 ML and enables the relative contributions from different types of electrocatalytically active sites to be determined. Finally, the implications of surface...

  8. Chemical evolution. XXIX - Pyrimidines from hydrogen cyanide

    Science.gov (United States)

    Ferris, J. P.; Joshi, P. C.; Lawless, J. G.

    1978-01-01

    Compounds obtained by hydrolysis of HCN oligomers formed by allowing pH 9.2, 0.1 M cyanide to stand at room temperature for 4 to 12 months were analyzed. Hydrolysis of HCN oligomers yielded 4,5-dihydroxypyrimidine and 5-hydroxyuracil; orotic acid was detected after hydrolysis at pH 8.5. A unified pathway from diaminofumaronitrile to the pyrimidines observed is suggested. As purines, pyrimidines and amino acids are released by hydrolysis of HCN oligomers in either acidic or mildly basic aqueous solutions, they could have been formed on the primitive earth in spite of fluctuations in pH. 4,5-dihydroxypyrimidines appear to be likely candidates for incorporation into primitive nucleic acids, as they should undergo Watson-Crick hydrogen bonding with adenine.

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

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  10. Hydrogenated graphenes by birch reduction: influence of electron and proton sources on hydrogenation efficiency, magnetism, and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Eng, A.Y.S.; Sofer, Z.; Huber, Š.; Bouša, D.; Maryško, Miroslav; Pumera, M.

    2015-01-01

    Roč. 21, č. 7 (2015), 16828-16838 ISSN 0947-6539 Institutional support: RVO:68378271 Keywords : hydrogenated graphenes * birch reduction * magnetism * electrochemistry * hydrogenation efficiency Subject RIV: CA - Inorganic Chemistry Impact factor: 5.771, year: 2015

  11. Reduction kinetics of zinc and cadmium sulfides with hydrogen

    International Nuclear Information System (INIS)

    Turgenev, I.S.; Kabisov, I.Kh.; Zviadadze, G.N.; Vasil'eva, O.Yu.

    1985-01-01

    Kinetics of reduction processes of zinc sulfide in the temperature range 800-1100 deg C and of cadmium sulfide 600-900 deg C has been stodied. Activation energies and reaction order in terms of hydrogen are calculated. Thermodynamic processes of reduction depend on aggregate state of the metal formed. For vaporous zinc in the temperature range 1050-950 deq C activation energy constitutes 174 kJ/mol, for liquid in the range 900-850 deg - 151 kJ/mol and reaction order in terms of hydrogen is 1.0. For vaporous cadmium in the temperature range 900-700 deg C activation energy constitutes 144 kJ/mol and reaction order in terms of hydrogen is 0.86, for liquid in the range 675-600 deg C 127 kJ/mol and 0.8 respectively. The processes of zinc and cadmium sulfide reduction proceed in kinetic regime and are limited by the rate of chemical reaction

  12. Phosphate-bonded composite electrodes for hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Potvin, E.; Menard, H.; Lalancette, J.M. (Sherbrooke Univ., PQ (Canada). Dept. de Chimie); Brossard, L. (Institut de Recherche d' Hydro-Quebec, Varennes, PQ (Canada))

    1990-03-01

    A new process of cementing metallic powders to produce high surface area cathodes for alkaline water electrolysis is described. The binding compound is a tridimensional polymer of aluminium phosphate (AlPO{sub 4}). Phosphate-bonded composite electrodes give a low-polarization performance for hydrogen evolution in 1 M KOH aqueous solution in the case of 95wt% Pt and 98wt%Ni. When electrode materials are prepared with nickel powder, the electrocatalytic activity for the hydrogen evolution reaction, the chemical stability and the electrical conductivity depend on the Ni content and morphology of the electrode. The best performance and chemical stability with Ni as the starting material are obtained for spiky filamentary particles produced by the decomposition of nickel carbonyl. (author).

  13. Seawater splitting for high-efficiency hydrogen evolution by alloyed PtNix electrocatalysts

    Science.gov (United States)

    Zheng, Jingjing

    2017-08-01

    Robust electrocatalyst is a prerequisite to realize high-efficiency hydrogen evolution by water splitting. Expensive platinum (Pt) is a preferred electrode catalyst for state-of-the-art hydrogen evolution reaction (HER). We present here a category of alloyed PtNix electrocatalysts by a facile green chemical reduction method, which are used to catalyze HER during seawater splitting. The catalytic performances are optimized by tuning stoichiometric Pt/Ni ratio, yielding a maximized catalytic behavior for PtNi5 electrode. The minimized onset potential is as low as -0.38 V and the corresponding Tafel slope is 119 mV dec-1. Moreover, the launched alloy electrodes have remarkable stability at -1.2 V over 12 h. The high efficiency as well as good durability demonstrates the PtNix electrocatalysts to be promising in practical applications.

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

    KAUST Repository

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    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

  15. Kinetics of hydrogen reduction of titanium-doped molybdenum dioxide

    International Nuclear Information System (INIS)

    He, Qian; Marin-Flores, Oscar; Hu, Shuozhen; Scudiero, Louis; Ha, Su; Norton, M. Grant

    2015-01-01

    Ti-doped MoO 2 was synthesized to broaden the oxygen-to-carbon ratio operating range of MoO 2 for partial oxidation of long-chain hydrocarbons by increasing the redox stability. The structure modification causes the hydrogen reduction mechanism to change from three-dimensional nuclei growth with an activation energy of 61.3 kJ mol −1 to a three-dimensional hydrogen diffusion limited model with an activation energy of 317.9 kJ mol −1 . Because of the enhanced redox stability, Ti-doped MoO 2 has potential as an alternative anode in direct liquid-fed solid oxide fuel cells

  16. Effect of hydrogen on reduction of burden materials

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

    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.

  17. 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.

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

    KAUST Repository

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

    2016-01-01

    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.

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

    Science.gov (United States)

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

    2016-12-14

    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.

  20. 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.

  1. Reduction of Large Dynamical Systems by Minimization of Evolution Rate

    Science.gov (United States)

    Girimaji, Sharath S.

    1999-01-01

    Reduction of a large system of equations to a lower-dimensional system of similar dynamics is investigated. For dynamical systems with disparate timescales, a criterion for determining redundant dimensions and a general reduction method based on the minimization of evolution rate are proposed.

  2. 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.

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

    KAUST Repository

    Xia, Chuan; Liang, Hanfeng; Zhu, Jiajie; Schwingenschlö gl, Udo; Alshareef, Husam N.

    2017-01-01

    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

  4. Method and system for hydrogen evolution and storage

    Science.gov (United States)

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

    2012-12-11

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

  5. Evolution of helium rich stars with hydrogen burning

    International Nuclear Information System (INIS)

    Roeser, M.

    1975-08-01

    Evolutionary tracks of stars with an initial chemical composition X = 0.100, Y = 0.8790, Z = 0.021 are calculated for masses of 0.35 M(sun), 0.66 M(sun), 1.00 M(sun), 2.00 M(sun), and 5.00 M(sun) and with X = 0.302, Y = 0.677, Z = 0.021 for masses of 1.00 M(sun), 3.00 M(sun), and 5.00 M(sun). The evolution is followed from hydrogen burning to helium burning and to carbon burning when the occasion arises. The data of evolution are presented and compared with normal Population I-stars. The helium rich stars show higher effective temperatures, much higher luminosities and therefore shorter time scales. They are situated in regions of the HR-diagram where observed helium stars are found. (orig.) [de

  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. Heterogeneous catalysis in fluoride melts - reduction of uranium(V) by hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kelmers, A D; Bennett, M R [Oak Ridge National Lab., Tenn. (USA)

    1976-01-01

    A necessary step in fuel reprocessing for the Molten-Salt Breeder Reactor is the reduction of pentavalent uranium to tetravalent uranium by hydrogen gas. The pentavalent uranium is dissolved in a mixed fluoride melt. Results are presented which show that the hydrogen reduction is rate limited, possibly due to the dissociation of hydrogen molecules to yield active hydrogen atoms; and that by the application of platinum catalysts a 10- to 100-fold increase in the reaction rate can be achieved.

  8. AB/sub 5/-catalyzed hydrogen evolution cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Hall, D E; Sawada, T; Shepard, V R; Tsujikawa, Y

    1984-01-01

    The AB/sub 5/ metal compounds are highly efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Three types of AB/sub 5/-catalyzed cathode structures were made, using the hydride-forming AB/sub 5/ compounds in particulate form. Plastic-bonded cathodes containing >90 w/o AB/sub 5/ (finished-weight basis) were the most efficient, giving hydrogen evolution overpotentials (/eta/ /SUB H2/ ) of about 0.05 V at 200 mA cm/sup -2/. However, they tended to swell and shed material during electrolysis. Pressed, sintered cathodes containing 40-70 w/o catalyst in a nickel binder gave /eta/ /SUB H2/ about0.08 V; catalyst retention was excellent. Porous, sintered cathode coatings were made with 30-70 w/o AB/sub 5/ catalyst loadings. Their overpotentials were similar to those of the pressed, sintered cathodes. However, at catalyst loadings below about 40 w/o, high overpotentials characteristic of the nickel binder were observed. The structural and electrochemical properties of the three AB/sub 5/-catalyzed cathodes are discussed.

  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. Experimental study and modelling of iron ore reduction by hydrogen

    International Nuclear Information System (INIS)

    Wagner, D.

    2008-01-01

    In an effort to find new ways to drastically reduce the CO 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-11-02

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

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

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole

    2016-01-01

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

  14. Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2017-10-01

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

  15. Hydrogen evolution by a thermophilic blue-green alga. Mastigocladus laminosus

    Energy Technology Data Exchange (ETDEWEB)

    Mirua, Y; Yokoyama, H; Kanaoka, K; Saito, S; Iwasa, K; Okazaki, M; Komemushi, S

    1980-01-01

    The thermophillic blue-green alga (cyanobacterium), Mastigocladus laminosus isolated from a hot spring, evolved hydrogen gas under nitrogen-starved conditions in light when algal cells were grown in a nitrate-free medium. Cells grown in a nitrate-medium evolved no detectable hydrogen gas in light. The optimal temperature and pH for hydrogen evolution were 44-49 degrees C and 7.0-7.5. High activity of hydrogen evolution, 1.6 ml H/sub 2//mg chl.hr, was induced when algal cells grown in the nitrate medium were actively forming heterocysts in the nitrate-free medium in air. Hydrogen evolution in light was depressed by nitrogen gas and inhibited by salicylaldoxime or DNP. This hydrogen evolution by M. laminosus is attributed to the action of nitrogenase.

  16. Mechanism of the hydrogen reduction of molybdenum oxides

    International Nuclear Information System (INIS)

    Schulmeyer, W.V.; Ortner, H.M.

    2001-01-01

    The two stages of the hydrogen reduction of MoO 3 to Mo were investigated in a thermal balance under well defined reaction conditions. Starting with different grain and agglomerate sizes for both stages, the influence of a set of parameters (temperature, local partial pressure of H 2 O, gas flow, etc.) on the reaction progress and the final result were studied in detail. Depending on the set of parameters used, different reaction mechanisms like pseudomorphic transformation or chemical vapor transport (CVT) were observed. Taking into account that grains and agglomerates deviate from a spherical shape and a definite grain size, the extent of reaction is well described by standard theoretical gas-solid-reaction models such as the shrinking core model (SCM) or the crackling core model (CCM). Thermo-gravimetric analysis (TGA), x-ray diffraction (XRD), scanning electron microscopy (SEM), surface area measurements (BET-method) and laser diffraction were used for these studies. Under all conditions, the first stage shows a reaction path MoO 3 → Mo 4 O 11 → MoO 2 via chemical vapor transport (CVT). The reaction extent follows the crackling core model (Park/Levenspiel). Depending on the local partial pressure of H 2 O during reduction, the formed Mo 4 O 11 and MoO 2 exhibit different size distributions and shapes of the grains. The extent of reaction of the second stage develops according to the shrinking core model (Yagi/Kunii). Depending on the local dew point, two different reaction paths can occur: pseudomorphic transformation at low dew points and transformation via chemical vapor transport at high dew points. This paper is an extract from the Ph.D. thesis of W.V. Schulmeyer 'Mechanismen der Wasserstoffreduktion von Molybdaenoxiden', 1998, Darmstadt University of Technology, Institute of Material Science, Department of Chemical Analytics, FRG. It therefor focuses on a phenomenological description of the most important results. (author)

  17. 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...

  18. On order reduction in hydrogen isotope distillation models

    International Nuclear Information System (INIS)

    Sarigiannis, D.A.

    1994-01-01

    The design integration of the fuel processing system for the next generation fusion reactor plants (such as ITER and beyond) requires the enhancement of safety features related to the operation of the system. The current drive for inherent safety of hazardous chemical plants warrants the minimization of active toxic or radioactive inventories and the identification of process pathways with minimal risk of accidental or routine releases. New mathematical and numerical tools have been developed for the dynamic simulation and optimization of the safety characteristics related to tritium in all its forms in the fusion fuel processing system. The separation of hydrogen isotopes by cryogenic distillation is a key process therein, due to the importance of the separation performance for the quality of the fuel mixture and the on site inventory, the increased energy requirements for cryogenic operation, and the high order of mathematical complexity required for accurate models, able to predict the transient as well as the steady state behavior of the process. The modeling methodology described here is a part of a new dynamic simulation code that captures the inventory dynamics of all the species in the fusion fuel processing plant. The significant reduction of the computational effort and time required by this code will permit designers to easily explore a variety of design and technology options and assess their impact on the overall power plant safety

  19. NOx reduction and NO2 emission characteristics in rich-lean combustion of hydrogen

    OpenAIRE

    Shudo, Toshio; Omori, Kento; Hiyama, Osamu

    2008-01-01

    Hydrogen is a clean alternative to conventional hydrocarbon fuels, but it is very important to reduce the nitrogen oxides (NOx) emissions generated by hydrogen combustion. The rich-lean combustion or staged combustion is known to reduce NOx emissions from continuous combustion burners such as gas turbines and boilers, and NOx reduction effects have been demonstrated for hydrocarbon fuels. The authors applied rich-lean combustion to a hydrogen gas turbine and showed its NOx reduction effect in...

  20. Hierarchical Layered WS2 /Graphene-Modified CdS Nanorods for Efficient Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Xiang, Quanjun; Cheng, Feiyue; Lang, Di

    2016-05-10

    Graphene-based ternary composite photocatalysts with genuine heterostructure constituents have attracted extensive attention in photocatalytic hydrogen evolution. Here we report a new graphene-based ternary composite consisting of CdS nanorods grown on hierarchical layered WS2 /graphene hybrid (WG) as a high-performance photocatalyst for hydrogen evolution under visible light irradiation. The optimal content of layered WG as a co-catalyst in the ternary CdS/WS2 /graphene composites was found to be 4.2 wt %, giving a visible light photocatalytic H2 -production rate of 1842 μmol h(-1)  g(-1) with an apparent quantum efficiency of 21.2 % at 420 nm. This high photocatalytic H2 -production activity is due to the deposition of CdS nanorods on layered WS2 /graphene sheets, which can efficiently suppress charge recombination, improve interfacial charge transfer, and provide reduction active sites. The proposed mechanism for the enhanced photocatalytic activity of CdS nanorods modified with hierarchical layered WG was further confirmed by transient photocurrent response. This work shows that a noble-metal-free hierarchical layered WS2 /graphene nanosheets hybrid can be used as an effective co-catalyst for photocatalytic water splitting. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    Li, Yuanchao; Nguyen, Trung Van

    2018-04-01

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

  2. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-15

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

  4. 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.

  5. Hydrogenation Reactions in Ionic Liquids. The Efficient Reduction of ...

    African Journals Online (AJOL)

    NJD

    2008-12-09

    Dec 9, 2008 ... Volatile organic solvents such as ethanol, methanol and THF are often used for the ... remained consistently high and only declined markedly on the fifth cycle. ... transferral of the viscous liquid from the hydrogenation reactor.

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

    KAUST Repository

    Bhunia, Manas Kumar; Yamauchi, Kazuo; Takanabe, Kazuhiro

    2014-01-01

    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

  7. An Influence Study of Hydrogen Evolution Characteristics on the Negative Strap Corrosion of Lead Acid Battery

    Directory of Open Access Journals (Sweden)

    Zhong Guobin

    2015-01-01

    Full Text Available Negative strap corrosion is an important reason for the failure of valve regulated lead acid battery. This paper selected the Pb-Sb alloy material and Pb-Sn alloy material, made an investigation on the negative corrosion resistance and hydrogen evolution of these two alloy materials by scanning electron microscope analysis, metallographic analysis, chemical study and linear sweep voltammetry, and discussed the influence of lead alloy hydrogen evolution on the negative strap corrosion. The results showed that the hydrogen evolution reaction rates of the alloys had an impact on the corrosion areas with the maximum thickness of the alloys and the depth of corrosion layers. Greater hydrogen evolution reaction rate can lead to shorter distance between the corrosion area with the maximum thickness and the liquid level; whereas the greater corrosion layer thickness can bring aggravated risk of negative strap corrosion failure.

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

    KAUST Repository

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

    2017-01-01

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

  9. 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

    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...... that harvests red photons in the solar spectrum. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10% (ref. 16). The experimental observations are supported by density functional theory......-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...

  10. Reduction of Aldehydes and Ketones to Corresponding Alcohols Using Diammonium Hydrogen Phosphite and Commercial Zinc Dust

    Directory of Open Access Journals (Sweden)

    K. Anil Kumar

    2011-01-01

    Full Text Available A mild and an efficient system has been developed for the reduction of aromatic aldehydes and ketones to their corresponding alcohols in good yield using inexpensive commercial zinc dust as catalyst and diammonium hydrogen phosphite as a hydrogen donor.

  11. Efficient electroreduction of CO{sub 2} on bulk silver electrode in aqueous solution via the inhibition of hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Quan, Fengjiao; Xiong, Mubing; Jia, Falong, E-mail: fljia@mail.ccnu.edu.cn; Zhang, Lizhi

    2017-03-31

    Highlights: • High Faradic efficiency for CO (95%) is achieved on bulk Ag electrode. • The addition of DTAB contributes to enhanced CO{sub 2} conversion efficiency. • Hydrogen evolution is suppressed by the adsorbed DTAB on Ag electrode. - Abstract: Electrochemical CO{sub 2} reduction provides a desirable pathway to convert greenhouse gas into useful chemicals. It is a great challenge to reduce CO{sub 2} efficiently in aqueous solution, especially on commercial bulk metal electrodes. Here, we report substantial improvement in CO{sub 2} 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 CO{sub 2} 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 CO{sub 2} reduction through the inhibition of proton reduction.

  12. A nano-engineered graphene/carbon nitride hybrid for photocatalytic hydrogen evolution

    Institute of Scientific and Technical Information of China (English)

    Xiaobo Li; Yao Zheng; Anthony F.Masters; Thomas Maschmeyer

    2016-01-01

    A metal-free photocatalytic hydrogen evolution system was successfully fabricated using heteroatom doped graphene materials as electron-transfer co-catalysts and carbon nitride as a semiconductor.The catalytic role of graphene is significantly dependent on the heteroatom dopant of the graphene,such as O,S,B,N doped/undoped graphene co-catalysts,and N-graphene shows the best catalytic hydrogen evolution rate.

  13. 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.

  14. Electrochemical reduction of hydrogen peroxide on stainless steel

    Indian Academy of Sciences (India)

    Administrator

    wide range of industrial processes such as food processing (e.g. in the ... tron transfer effect of mitochondria.4 These radicals. (reactive .... of H2O2 without undergoing fouling or poisoning due to any inter- .... adsorbed OHads species was shown operative at po- tentials of .... Douglass W C 2003 Hydrogen peroxide medical.

  15. Phase Evolution During the Carbothermic Reduction Process of Ilmenite Concentrate

    Science.gov (United States)

    Gou, Hai-Peng; Zhang, Guo-Hua; Chou, Kuo-Chih

    2015-02-01

    The phase evolution during the carbothermic reduction process of Panzhihua ilmenite concentrate was investigated under argon atmosphere. The Panzhihua ilmenite concentrate briquette with graphite powder was reduced at 1473 K, 1573 K, 1673 K, and 1773 K (1200 °C, 1300 °C, 1400 °C, and 1500 °C) respectively, with the molar ratios of C to FeTiO3 being 4:1 and 5:1. The phase transformation of the briquette reduced at different temperatures was investigated by X-ray diffraction and scanning electron microscope. During the carbothermic reduction process from 1473 K to 1773 K (1200 °C to 1500 °C), it was found that main phases were Fe, Ti3O5, Ti2O3, and TiC x O y . The lowest temperature for the generation of TiC x O y was 1573 K (1300 °C) for both kinds of briquettes with different C contents. The rate controlling step for the carbothermic reduction above 1573 K (1300 °C) obeyed the diffusion model. The reduction degree of the ilmenite was increased by increasing the temperature. With the increase of reaction temperature and reaction time, TiC x O y phase would be reduced to TiC phase.

  16. Hydrogen evolution from aluminium in reactor containment spray solutions

    International Nuclear Information System (INIS)

    Karlberg, G.; Sundvall, S.-B.

    1982-01-01

    Three different aluminium alloys were exposed to conditions similar to BWR and PWR containment spray waters at 50, 100 and 150 0 C. BWR deionized water gives corrosion rates of at most 0.05 mm/year and hydrogen concentrations less than 0.1-1%. On the contrary PWR alkaline solutions give very high corrosion rates and hydrogen contents. (Auth.)

  17. Cathodic over-potential and hydrogen partial pressure coupling in hydrogen evolution reaction of marine steel under hydrostatic pressure

    International Nuclear Information System (INIS)

    Xiong, X.L.; Zhou, Q.J.; Li, J.X.; Volinsky, Alex A.; Su, Y.J.

    2017-01-01

    Highlights: •Hydrostatic pressure increases the Volmer and the Heyrovsky reactions rates. •Hydrostatic pressure decreases the Tafel reaction rate. •Hydrogen adsorption conditions change with pressure under −1.2 and −1.3 V SSE . •Under −1.2 and −1.3 V SSE , the Heyrovsky reaction dominates the hydrogen recombination. •Under −1.0 and −1.1 V SSE , the Tafel reaction dominates the hydrogen recombination. -- Abstract: A new electrochemical impedance spectroscopy (EIS) model, which considers both the Tafel recombination and the Heyrovsky reaction under permeable boundary conditions, was developed to characterize the kinetic parameters of the hydrogen evolution reaction (HER) under hydrostatic pressure. The effect of the hydrostatic pressure on the kinetic parameters of the HER and the permeation of A514 steel in alkaline solution were measured using potentiodynamic polarization, the Devanathan cell hydrogen permeation, and EIS. The hydrostatic pressure accelerates the Volmer reaction and inhibits the Tafel recombination, which increases the number of adsorbed hydrogen atoms. On the other hand, the pressure accelerates the Heyrovsky reaction, which decreases the amount of adsorbed hydrogen atoms. At 10 to 40 MPa hydrostatic pressure within the −1.0 to −1.1 V SSE cathodic potential region, the HER is controlled by hydrogen partial pressure, and hydrogen adsorption is the Langmuir type. Within the −1.2 to −1.3 V SSE cathodic potential region, the HER is controlled by the potential, and hydrogen adsorption gradually transfers from the Langmuir type to the Temkin type with increasing hydrostatic pressure.

  18. Evolution and Reduction of Scour around Offshore Wind Turbines

    Science.gov (United States)

    McGovern, David; Ilic, Suzana

    2010-05-01

    Evolution and Reduction of Scour around Offshore Wind Turbines In response to growing socio-economic and environmental demands, electricity generation through offshore wind turbine farms is a fast growing sector of the renewable energy market. Considerable numbers of offshore wind farms exist in the shallow continental shelf seas of the North-West Europe, with many more in the planning stages. Wind energy is harnessed by large rotating blades that drive an electricity generating turbine placed on top of a long cylindrical monopile that are driven into the sea-bed, well into the bed rock below the sediment. Offshore wind turbines are popular due to consistently higher wind speeds and lower visual impact than their onshore counter parts, but their construction and maintenance is not without its difficulties. The alteration of flow by the presence of the wind turbine monopile results in changes in sedimentary processes and morphology at its base. The increase in flow velocity and turbulence causes an amplification of bed shear stress and this can result in the creation of a large scour hole at the monopile base. Such a scour hole can adversely affect the structural integrity and hence longevity of the monopile. Changes to the sea bed caused by this may also locally affect the benthic habitat. We conducted an extensive series of rigid and mobile bed experiments to examine the process of scour under tidal currents. We also test the effectiveness of a flow-altering collared monopile in reducing scour. Firstly, we used Particle Image Velocimetry (PIV) and Acoustic Doppler Velocimetry (ADV) to visualise and analyse the flow and turbulence properties in the local flow around the monopile and collared monopile over a smooth rigid bed under tidal flow. The measured flow, turbulence and shear stress properties are related to mobile bed tests where a Seatek 5 MHz Ultrasonic Ranging system is used to identify the evolution of scour under reversing tidal currents. The tidal

  19. 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

    The production of fuels directly or indirectly from sunlight represents one of the major challenges to the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and while platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen...... 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...... 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...

  20. Molecular beam studies of oxide reduction by atomic hydrogen

    International Nuclear Information System (INIS)

    Olander, D.R.

    1978-01-01

    The graphite and oxide internals of a CTR are susceptible to chemical corrosion as well as to physical degradation by high-energy particles. Reactions of thermal atomic hydrogen with oxides are being studied. The hydrogen used is at thermal energy (0.22 eV). Typical data are reported for the H/UO 2 system. The reaction probability is plotted as a function of solid temperature at fixed beam intensity and moculation frequency. The reaction probability increases from low temperature to a high-temperature plateau at about 1300 0 C. Here the reaction rate is limited solely by the sticking probability of H on the surface; about one in seven of the incident atoms is chemisorbed by the surface and ultimately returns to the gas phase as water vapor. A reaction model comprising sticking, recombination to H 2 , solution and diffusion of H in the bulk of the UO 2 , surface reaction of adsorbed H with lattice oxygen atoms to produce the hydroxyl radical, and production of water is constructed. The rate constants for the elementary steps in the mechanism are tabulated. 2 figures, 2 tables

  1. 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...... of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

  2. Characteristics of hydrogen evolution and oxidation catalyzed by Desulfovibrio caledoniensis biofilm on pyrolytic graphite electrode

    International Nuclear Information System (INIS)

    Yu Lin; Duan Jizhou; Zhao Wei; Huang Yanliang; Hou Baorong

    2011-01-01

    Highlights: → The sulphate-reducing bacteria (SRB) have the ability to catalyze the hydrogen evolution and oxidation on pyrolytic graphite electrode. → The SRB biofilm decreases the overpotential and electron transfer resistance by the CV and EIS detection. → The SRB biofilm can transfer electrons to the 0.24 V polarized pyrolytic graphite electrode and the maximum current is 0.035 mA, which is attributed to SRB catalyzed hydrogen oxidation. → The SRB biofilm also can obtain electron from the -0.61 V polarized PGE to catalyze the hydrogen evolution. - Abstract: Hydrogenase, an important electroactive enzyme of sulphate-reducing bacteria (SRB), has been discovered having the capacity to connect its activity to solid electrodes by catalyzing hydrogen evolution and oxidation. However, little attention has been paid to similar electroactive characteristics of SRB. In this study, the electroactivities of pyrolytic graphite electrode (PGE) coated with SRB biofilm were investigated. Two corresponding redox peaks were observed by cyclic voltammetry detection, which were related to the hydrogen evolution and oxidation. Moreover, the overpotential for the reactions decreased by about 0.2 V in the presence of the SRB biofilm. When the PGE coated with the SRB biofilm was polarized at 0.24 V (vs. SHE), an oxidation current related to the hydrogen oxidation was found. The SRB biofilm was able to obtain electrons from the -0.61 V (vs. SHE) polarized PGE to form hydrogen, and the electron transfer resistance also decreased with the formation of SRB biofilm, as measured by the non-destructive electrochemical impendence spectroscopy detection. It was concluded that the hydrogen evolution and oxidation was an important way for the electron transfer between SRB biofilm and solid electrode in anaerobic environment.

  3. Thermogravimetric study of the kinetics of lithium titanate reduction by hydrogen

    International Nuclear Information System (INIS)

    Sonak, Sagar; Rakesh, R.; Jain, Uttam; Mukherjee, Abhishek; Kumar, Sanjay; Krishnamurthy, Nagaiyar

    2014-01-01

    Highlights: • Li 2 TiO 3 powder is synthesized by the gel combustion route. • Activation energy of reduction of Li 2 TiO 3 by H 2 found out to be 27.45 kJ/mol H 2 . • Non-stoichiometric phase of Li 2 TiO 3 is formed in hydrogen atmosphere. • One-dimensional diffusion appears to be the most probable mechanism of reduction. - Abstract: The lithium titanate powder was synthesized by gel-combustion route. The mechanism and the kinetics of hydrogen interaction with lithium titanate powder were studied using non-isothermal thermogravimetric technique. Lithium titanate underwent reduction in hydrogen atmosphere which led to the formation of oxygen deficient non-stoichiometric compound in lithium titanate. One-dimensional diffusion appeared to be the most probable reaction mechanism. The activation energy for reduction of lithium titanate under hydrogen atmosphere was found to be 27.4 kJ/mol/K. Structural changes after hydrogen reduction in lithium titanate were observed in X-ray diffraction analysis

  4. Electrocatalytic behavior of carbon paste electrode modified with metal phthalocyanines nanoparticles toward the hydrogen evolution

    International Nuclear Information System (INIS)

    Abbaspour, Abdolkarim; Norouz-sarvestani, Fatemeh; Mirahmadi, Ehsan

    2012-01-01

    Highlights: ► The new construction of a carbon paste electrode impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). ► The decrease overpotential and higher current value obtained in nano ZnPc and nano NiPc compared to bulky ZnPc and bulky NiPc, respectively. ► Types of the catalyst and pH of the solution affect the electro catalytic proton reduction reaction considerably. - Abstract: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of Zn and Ni phthalocyanine (nano ZnPc and nano NiPc). These new electrodes (nano ZnPc-CPE and nano NiPc-CPE) reveal interesting electrocatalytic behavior toward hydrogen evolution reaction (HER). Voltammetric characteristics indicated that the proposed electrodes display better electrocatalytic activity compared to their corresponding bulky modified metal phthalocyanines (MPcs) in minimizing overpotential and increasing the reduction current of HER. Electrocatalytic activities irregularly change with the pH of the solution. However by increasing the pH while nano MPcs are still active, bulky MPcs are almost inactive, and their corresponding ΔE increase by increasing the pH.

  5. Electrochemical reduction of metal ions in dilute solution using hydrogen

    NARCIS (Netherlands)

    Portegies Zwart, I.; Wijnbelt, E.C.W.; Janssen, L.J.J.

    1995-01-01

    Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. A new electrochemical cell has been introduced. This cell - a GBC-cell - is a combination of a gasdiffusion electrode in direct contact with a packed bed of carbon particles.

  6. 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.

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

    KAUST Repository

    Yu, Weili; Isimjan, Tayirjan; Lin, Bin; Takanabe, Kazuhiro

    2014-01-01

    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.

  8. Preparation of the vulcan XC-72R-supported Pt nanoparticles for the hydrogen evolution reaction in PEM water electrolysers

    International Nuclear Information System (INIS)

    Nguyen, Huy Du; Nguyen, T Thuy Luyen; Nguyen, Khac Manh; Ha, Thuc Huy; Nguyen, Quoc Hien

    2015-01-01

    Pt nanoparticles on vulcan XC-72R support (Pt/vulcan XC-72R) were prepared by the impregnation–reduction method. The Pt content, the morphological properties and the electrochemical catalysis of the Pt/vulcan XC 72R materials have been investigated by ICP-OES analysis, FESEM, TEM, and cyclic voltammetry. These materials were then used as catalyst for hydrogen evolution reaction at the cathode of proton exchange membrane (PEM) water electrolysers. The best catalyst was Pt/vulcan XC-72R prepared by the impregnation–reduction method which is conducted in two reducing steps with the reductants of sodium borohydride and ethylene glycol, respectively. The current density of PEM water electrolysers reached 1.0 A cm"−"2 when applying a voltage of 2.0 V at 25 °C. (paper)

  9. Hydrogen evolution from water using solid carbon and light energy

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, T; Sakata, T

    1979-11-15

    Hydrogen is produced from water vapour and solid carbon when mixed powders of TiO2, RuO2 and active carbon exposed to water vapor at room temperature, or up to 80 C, are illuminated. At 80 C, the rate of CO and COat2 formation increased. Therefore solar energy would be useful here as a combination of light energy and heat energy. Oxygen produced on the surface of the photocatalyst has a strong oxidising effect on the carbon. It is suggested that this process could be used for coal gasification and hydrogen production from water, accompanied by storage of solar energy.

  10. Hydrogen evolution under visible light over LaCoO3 prepared by chemical route

    International Nuclear Information System (INIS)

    Meziani, D.; Reziga, A.; Rekhila, G.; Bellal, B.; Trari, M.

    2014-01-01

    Highlights: • Visible-light hydrogen evolution is achieved on the hetero-system LaCoO 3 /SnO 2 . • The crystal field splits the Co 3+ : 3d orbital by a value of 2.05 eV. • The capacitance plot shows p-type conduction with flat band potential of 0 V SCE. • The photo-electrochemistry yields a valence and conduction bands of 3d parentage. - Abstract: The semiconducting properties of the perovskite LaCoO 3 , prepared by nitrate route, are investigated for the first time by the photo-electrochemical technique. The oxide shows a direct optical transition at 1.33 eV, due to Co 3+ : 3d orbital splitting in octahedral site and possesses a chemical stability over a fair pH range (4–14). The conductivity follows an exponential type law with a hole mobility (8.3 × 10 −2 cm 2 V −1 s −1 ), thermally activated. The Mott–Schottky plot in KOH medium is characteristic of p type conduction with a flat band potential of 0 V SCE and a holes density of 1.35 × 10 17 cm −3 . The electrochemical impedance spectroscopy reveals the predominance of the bulk and grains boundaries contributions with a constant phase element and a multi-relaxation type nature. As application, the hydrogen evolution upon visible light is demonstrated on the hetero-junction LaCoO 3 /SnO 2 . The best performance occurs at pH ∼ 12.8 with an evolution rate of 0.25 cm 3 min −1 (mg LaCoO 3 ) −1 and a quantum yield of 0.11%. The improved activity is attributed to the wide depletion width of ∼10 nm and the potential of the conduction band of LaCoO 3 (−1.34 V SCE ), more negative than that of SnO 2 , the latter acts as electrons bridge for the interfacial water reduction. The relevance of 3d orbital of the performance of semi conducting photoelectrode is discussed

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

    Science.gov (United States)

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

    2018-03-09

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

  12. Reduction of friction stress of ethylene glycol by attached hydrogen ions

    Science.gov (United States)

    Li, Jinjin; Zhang, Chenhui; Deng, Mingming; Luo, Jianbin

    2014-01-01

    In the present work, it is shown that the friction stress of ethylene glycol can decrease by an order of magnitude to achieve superlubricity if there are hydrogen ions attached on the friction surfaces. An ultra-low friction coefficient (μ = 0.004) of ethylene glycol between Si3N4 and SiO2 can be obtained with the effect of hydrogen ions. Experimental result indicates that the hydrogen ions adsorbed on the friction surfaces forming a hydration layer and the ethylene glycol in the contact region forming an elastohydrodynamic film are the two indispensable factors for the reduction of friction stress. The mechanism of superlubricity is attributed to the extremely low shear strength of formation of elastohydrodynamic film on the hydration layer. This finding may introduce a new approach to reduce friction coefficient of liquid by attaching hydrogen ions on friction surfaces. PMID:25428584

  13. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

    This work deals with the selective catalytic reduction of nitrogen oxides (NO 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 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 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.)

  14. Nanoplasmonically Engineered Interfaces on Amorphous TiO2 for Highly Efficient Photocatalysis in Hydrogen Evolution.

    Science.gov (United States)

    Liang, Huijun; Meng, Qiuxia; Wang, Xiaobing; Zhang, Hucheng; Wang, Jianji

    2018-04-25

    The nanoplasmonic metal-driven photocatalytic activity depends heavily on the spacing between metal nanoparticles (NPs) and semiconductors, and this work shows that ethylene glycol (EG) is an ideal candidate for interface spacer. Controlling the synthetic systems at pH 3, the composite of Ag NPs with EG-stabilized amorphous TiO 2 (Ag/TiO 2 -3) was synthesized by the facile light-induced reduction. It is verified that EG spacers can set up suitable geometric arrangement in the composite: the twin hydroxyls act as stabilizers to bind Ag NPs and TiO 2 together and the nonconductive alkyl chains consisting only of two CH 2 are able to separate the two building blocks completely and also provide the shortest channels for an efficient transfer of radiation energies to reach TiO 2 . Employed as photocatalysts in hydrogen evolution under visible light, amorphous TiO 2 hardly exhibits the catalytic activity due to high defect density, whereas Ag/TiO 2 -3 represents a remarkably high catalytic efficiency. The enhancement mechanism of the reaction rate is proposed by the analysis of the compositional, structural, and optical properties from a series of Ag/TiO 2 composites.

  15. Effect of sacrificial agents on the dispersion of metal cocatalysts for photocatalytic hydrogen evolution

    Science.gov (United States)

    Cao, Shaowen; Shen, Baojia; Huang, Qian; Chen, Zhe

    2018-06-01

    Surface photodeposition of noble metal cocatalyst has been regarded as an effective approach to facilitate the separation of charge carriers and reduce the over-potential of water reduction, thus to enhance the photocatalytic H2-production activities of semiconductor photocatalyst. Herein, the influences of sacrificial agents used in the photodeposition process on the dispersion of noble metal nanoparticles are investigated, via a series of technique of photocatalytic hydrogen evolution test, microstructure analysis and photoelectrochemical measurement. As a result, the sacrificial agents are found to show large impact on the loading amount, particle size and distribution of different metals on the surface of g-C3N4. The real loading amount of Pt and Au is higher in methanol solution than that in triethanolamine solution. Better distribution and smaller size of Pt nanoparticles are achieved in the presence of methanol; while better distribution and smaller size of Au nanoparticles are achieved in the presence of triethanolamine. As a result, quite different charge transfer ability is achieved for the synthesized Pt and Au decorated g-C3N4, which subsequently leads to disparate photocatalytic activities of the same g-C3N4 photocatalyst under various conditions. The finding in this work indicates that the valid deposition content, particle size and distribution of metal cocatalysts should be carefully taken into account when comparing the photocatalytic activities among various samples.

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

    KAUST Repository

    Takanabe, Kazuhiro; Isimjan, Tayirjan; Yu, Weili; Del Gobbo, Silvano; Xu, Wei

    2015-01-01

    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.

  17. 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.

  18. Kinetics of hydrogen evolution in the thermal dissociation of the hydride ZrNiH /SUB 2.8/

    International Nuclear Information System (INIS)

    Chernavskii, P.A.; Lunin, V.V.

    1985-01-01

    The kinetics of hydrogen evolution in the thermal decomposition of ZrNiH /SUB 2.8/ has been studied. The kinetic curve has two rate maxima. It is presumed that the second maximum is related to the phenomenon of critical inhibition that accompanies the phase transition. Apparent activation energies were determined for hydrogen evolution in argon and argon-ethylene atmospheres. The apparent energy increases in the argon-ethylene mixture. On the basis of the activation energy measurements it is presumed that the rate-determining step in hydrogen evolution is either the formation of hydrogen molecules from atoms on the surface of the lateral diffusion of atomic hydrogen. In the region of hydrogen concentration in the hydride corresponding to the phase transition, the rate-determining step is hydrogen diffusion in the hydride

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

    KAUST Repository

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

    2017-01-01

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

  20. The hydrogen evolution and oxidation kinetics during overdischarging of sealed nickel-metal hydride batteries

    NARCIS (Netherlands)

    Ayeb, A.; Otten, W.M.; Mank, A.J.G.; Notten, P.H.L.

    2006-01-01

    The hydrogen evolution and oxidation kinetics in NiMH batteries have been investigated under temperature-controlled, steady-state, overdischarging conditions within a temperature range of 10 and 50°C and at discharging currents of 1–330 mA (0.0009 to 0.3 C rate). In situ Raman spectroscopic analyses

  1. 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...

  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...

  3. 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.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  5. 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.

  6. Preparation and elementary research on electrocatalytic hydrogen evolution of highly ordered titanium dioxide nanotube arrays

    International Nuclear Information System (INIS)

    Wu Qinglong; Liao Junsheng; Bai Yun

    2010-01-01

    Well ordered and uniform titanium dioxide nanotube arrays were fabricated by anodiaing process from a bath containing 1% NaF, 1mol/L Na 2 SO 4 , 0.5 mol/L H 2 SO 4 at room temperature. Surface morphology of titanium dioxide nanotube arrays were observed with SEM. The formation process of titanium dioxide nanotube arrays was suggested by current-time transient. Its catalytic hydrogen evolution behavior was studied by electrochemical measurements in a 5%(mass fraction) H 2 SO 4 solution. The results showed that the titanium dioxide nanotube arrays on titanium had better hydrogen evolution activity and trace palladium lead to the maximum electrocatalytic activity of hydrogen production. (authors)

  7. High Efficient Reduction of Graphene Oxide via Nascent Hydrogen at Room Temperature

    Directory of Open Access Journals (Sweden)

    Qiqi Zhuo

    2018-02-01

    Full Text Available To develop a green and efficient method to synthesize graphene in relative milder conditions is prerequisite for graphene applications. A chemical reducing method has been developed to high efficiently reduce graphene oxide (GO using Fe2O3 and NH3BH3 as catalyst and reductants, respectively. During the process, environmental and strong reductive nascent hydrogen were generated surrounding the surface of GO sheets by catalyst hydrolysis reaction of NH3BH3 and were used for reduction of GO. The reduction process was studied by ultraviolet absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared spectrum. The structure and morphology of the reduced GO were characterized with scanning electron microscopy and transmission electron microscopy. Compared to metal (Mg/Fe/Zn/Al particles and acid system which also use nascent hydrogen to reduce GO, this method exhibited higher reduction efficiency (43.6%. Also the reduction was carried out at room temperature condition, which is environmentally friendly. As a supercapacitor electrode, the reversible capacity of reduced graphene oxide was 113.8 F g−1 at 1 A g−1 and the capacitance retention still remained at 90% after 200 cycles. This approach provides a new method to reduce GO with high reduction efficiency by green reductant.

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

    Science.gov (United States)

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

    2016-01-01

    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. PMID:27199009

  9. Exfoliated MoS2 nanosheets as efficient catalysts for electrochemical hydrogen evolution

    International Nuclear Information System (INIS)

    Ji, Shanshan; Yang, Zhe; Zhang, Chao; Liu, Zhenyan; Tjiu, Weng Weei; Phang, In Yee; Zhang, Zheng; Pan, Jisheng; Liu, Tianxi

    2013-01-01

    Graphical abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on exfoliation of bulk MoS 2 crystals via a direct dispersion and ultrasonication method. Drop-casting method is used to fabricate the exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings. The E-MoS 2 /GCE with electrode loading of 48 μg cm −1 exhibits high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV). -- Highlights: • Two-dimensional MoS 2 nanosheets have been obtained by exfoliation of bulk MoS 2 crystals. • Exfoliated MoS 2 nanosheets show high electrocatalytic activity for H 2 production. • This study provides a new approach for renewable and economic H 2 production. -- Abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on liquid exfoliation of bulk MoS 2 via a direct dispersion and ultrasonication method. Transmission electron microscopy and atomic force microscopy measurements show that the exfoliated MoS 2 consists of two-dimensional nanosheets. The exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings is fabricated via a drop-casting method. The electrocatalytic activity of E-MoS 2 /GCE toward hydrogen evolution reaction is examined using linear sweep voltammetry. It is shown that the E-MoS 2 /GCE with an electrode loading of 48 μg cm −2 exhibits a high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV)

  10. Effect of hydrogen peroxide and camellia sinensis extract on reduction of oxygen level in graphene oxide

    Science.gov (United States)

    Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.

    2016-10-01

    The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV-vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.

  11. Hazards analyses of hydrogen evolution and ammonium nitrate accumulation in DWPF -- Revision 1

    International Nuclear Information System (INIS)

    Holtzscheiter, E.W.

    1994-01-01

    This revision consists of two reports, the first of which is an analysis of potential ammonium nitrate explosion hazards in the DWPF (Defense Waste Processing Facility). Sections describe the effect of impurities (organic and inorganic (chlorides, chromates, metals and oxides)); the consequences of a hydrogen deflagration or detonation; the role of confinement; the action of heat on ammonium nitrate; the thermal decomposition of ammonium nitrate; the hazard of spontaneous heating; and the explosive decomposition of ammonium nitrate. The second report, Hazard analysis of hydrogen evolution in DWPF: Process vessels and vent system for the late wash/nitric acid flowsheet, contains a description of a revised model for hydrogen generation based on the late wash/nitric acid process. The second part of the report is a sensitivity analysis of the base case conditions and the hydrogen generation model

  12. Hydrogen cyanide formation in selective catalytic reduction of nitrogen oxides over Cu/ZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Radtke, F; Koeppel, R; Baiker, A [Department of Chemical Engineering and Industrial Chemistry, Swiss Federal Institute of Technology, Zurich, (Switzerland)

    1994-01-06

    Hydrogen cyanide is formed over Cu/ZSM-5 during the selective catalytic reduction of NO[sub x] by either propylene or ethylene in the temperature range 450-600 K. Under the reaction conditions used (reactant feed: 973 ppm NO, 907 ppm propene or 1448 ppm ethylene, 2% oxygen, W/F=0.1 g s cm[sup -3]), the concentration of hydrogen cyanide reaches 20, respectively, 30 ppm, depending on whether ethylene or propene are used as hydrocarbons. In addition, significant N[sub 2]O formation is observed at temperatures lower than 700 K, independent of the hydrocarbon used

  13. Visualization of hydrogen gas evolution during deformation and fracture in SCM 440 steel with different tempering conditions

    Energy Technology Data Exchange (ETDEWEB)

    Horikawa, Keitaro, E-mail: horikawa@me.es.osaka-u.ac.jp [Department of Mechanical Science and Bioengineering, School of Engineering Science, Osaka University, Toyonaka 560-8531 (Japan); Ando, Nobuaki; Kobayashi, Hidetoshi [Department of Mechanical Science and Bioengineering, School of Engineering Science, Osaka University, Toyonaka 560-8531 (Japan); Urushihara, Wataru [Surface Design and Corrosion Research Section, Materials Research Laboratory, Kobe Steel, Ltd., Kobe 651-2271 (Japan)

    2012-02-01

    Highlights: Black-Right-Pointing-Pointer We visualize emission sites of hydrogen atoms on the microstructures during deformation. Black-Right-Pointing-Pointer Hydrogen atoms are emitted from slip lines and inclusions when deformed. Black-Right-Pointing-Pointer We show the sequence of hydrogen gas evolution during deformation. Black-Right-Pointing-Pointer Hydrogen evolution amount will increase if the steels with high strength are tested. - Abstract: In the present study, the hydrogen gas evolution behavior was investigated in SCM 440 steel by using a hydrogen microprint technique (HMT) and a testing machine equipped with a quadrupole mass spectrometer (QMS) in a ultrahigh vacuum (UHV) atmosphere. SCM 440 steels prepared by varying the tempering temperature over the range 200-700 Degree-Sign C were evaluated in order to elucidate the relationship between the hydrogen gas evolution and the tempered microstructures in the deformation. Cathodic hydrogen charging was carried out with a current density of 100 A/m{sup 2} for 1 h at room temperature. For comparison, a tensile specimen was prepared without hydrogen charging. The HMT showed that silver particles, which are indicative of the hydrogen emission sites, were present mainly in the matrix as well as on the slip lines after the deformation. It is believed that the silver particles on the slip lines represent the effect of hydrogen transportation due to mobile dislocations. In addition, accumulation of silver particles around non-metallic inclusions such as Al{sub 2}O{sub 3} was also identified. This tendency was observed for different tempering conditions. From the relationship between the stress-strain curves and the hydrogen evolution, determined by using QMS under a UHV atmosphere, it was found that the hydrogen gas evolution behavior varied with the deformation stage.

  14. Visualization of hydrogen gas evolution during deformation and fracture in SCM 440 steel with different tempering conditions

    International Nuclear Information System (INIS)

    Horikawa, Keitaro; Ando, Nobuaki; Kobayashi, Hidetoshi; Urushihara, Wataru

    2012-01-01

    Highlights: ► We visualize emission sites of hydrogen atoms on the microstructures during deformation. ► Hydrogen atoms are emitted from slip lines and inclusions when deformed. ► We show the sequence of hydrogen gas evolution during deformation. ► Hydrogen evolution amount will increase if the steels with high strength are tested. - Abstract: In the present study, the hydrogen gas evolution behavior was investigated in SCM 440 steel by using a hydrogen microprint technique (HMT) and a testing machine equipped with a quadrupole mass spectrometer (QMS) in a ultrahigh vacuum (UHV) atmosphere. SCM 440 steels prepared by varying the tempering temperature over the range 200–700 °C were evaluated in order to elucidate the relationship between the hydrogen gas evolution and the tempered microstructures in the deformation. Cathodic hydrogen charging was carried out with a current density of 100 A/m 2 for 1 h at room temperature. For comparison, a tensile specimen was prepared without hydrogen charging. The HMT showed that silver particles, which are indicative of the hydrogen emission sites, were present mainly in the matrix as well as on the slip lines after the deformation. It is believed that the silver particles on the slip lines represent the effect of hydrogen transportation due to mobile dislocations. In addition, accumulation of silver particles around non-metallic inclusions such as Al 2 O 3 was also identified. This tendency was observed for different tempering conditions. From the relationship between the stress–strain curves and the hydrogen evolution, determined by using QMS under a UHV atmosphere, it was found that the hydrogen gas evolution behavior varied with the deformation stage.

  15. 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.

  16. Vanadium purification by transformation to the tetrachloride and reduction by hydrogen. Study of the reduction mechanism

    International Nuclear Information System (INIS)

    Val, Christian

    1968-01-01

    The problem studied here is the production of very high purity metallic vanadium. By analogy with the method used for silicon or germanium production in electronics, the one employed here involves preparing the tetrachloride from the impure metal, purifying it by distillation, an easy process, and finally reducing this tetrachloride with hydrogen to obtain the pure metal. By this technique it has been possible to reduce the impurity content from about 5000 ppm to under 500 ppm and, in particular, to eliminate almost completely the nitrogen which is not removed by the normal purification methods. The author has studied the changes in the morphology of the deposit obtained as a function of the operational conditions. He has determined in particular the conditions leading to the formation of a compact deposit. He has shown that the deposition kinetics are very probably governed by an adsorbed phase reaction at the metal surface, (author) [fr

  17. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

    International Nuclear Information System (INIS)

    Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.

    2017-01-01

    Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

  18. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates.

    Science.gov (United States)

    Chadderdon, Xiaotong H; Chadderdon, David J; Matthiesen, John E; Qiu, Yang; Carraher, Jack M; Tessonnier, Jean-Philippe; Li, Wenzhen

    2017-10-11

    Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

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

    International Nuclear Information System (INIS)

    Schneider, Julian; Vaneski, Aleksandar; Susha, Andrei S.; Rogach, Andrey L.; Pesch, Georg R.; Yang Teoh, Wey

    2014-01-01

    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

  20. 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.

  1. 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.

  2. Formation of Hydrogen Peroxide by Electrochemical Reduction of Molecular Oxygen using Luminol Chemiluminescence

    International Nuclear Information System (INIS)

    Rana, Sohail

    2005-01-01

    Formation of hydrogen peroxide by electrochemical reduction of molecular oxygen was examined by measuring luminol chemiluminescence and absorption spectrum using flow-injection method. Ferryl porphyrin is widely accepted as responsible species to stimulate the emission in hydrogen peroxide/ iron porphyrin/ luminol system. Emission was observed under cathodic potentials (0.05V at pH2.0 and -0.3V at pH11.0) by the electrochemical reduction of aerated electrolytes solution but emission was observed at anodic potentials. Iron porphyrin solution was added at down stream of the working electrode and was essential for the emission. Removal of the dissolved molecular oxygen resulted in the decrease of emission intensity by more than 70%. In order to examine the life time of reduced active species, delay tubes were introduced between working electrode Fe TMPyP inlet. Experimental results suggested the active species were stable for quite a long period. The emission was quenched considerably (>90%) when hydroperoxy was added at the down stream of working electrode whereas the Superoxide dismutase (SOD) had little effect and mannitol had no effect. The spectra at reduction potential under aerated condition were shifted to the longer wavelength (>430nm) compared to the original spectrum of Fe TMPyP (422nm), indicating that the ferryl species were mixed to some extent. These observations lead to the conclusion that hydrogen peroxide was produced first by electrochemical reduction of molecular oxygen which then converted Fe TMPyP into O=FeTMPyP to activate luminol. Comparing emission intensities with the reference experiments, the current efficiencies for the formation of hydrogen peroxide were estimated as about 30-65% in all over the pH range used. (author)

  3. Biogenic Properties of Deep Waters from the Black Sea Reduction (Hydrogen Sulphide) Zone for Marine Algae

    OpenAIRE

    Polikarpov, Gennady G.; Lazorenko, Galina Е.; Тereschenko, Natalya N.

    2015-01-01

    Abstract Generalized data of biogenic properties investigations of the Black Sea deep waters from its reduction zone for marine algae are presented. It is shown on board and in laboratory that after pre-oxidation of hydrogen sulphide by intensive aeration of the deep waters lifted to the surface of the sea, they are ready to be used for cultivation of the Black Sea unicellular, planktonic, and multicellular, benthic, algae instead of artificial medium. Naturally balanced micro- and macroeleme...

  4. 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.

  5. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

    Science.gov (United States)

    Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

    2017-05-01

    The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

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

    International Nuclear Information System (INIS)

    Li Jina; Zhang Shunli

    2008-01-01

    We exploit higher-order conditional symmetry to reduce initial-value problems for evolution equations to Cauchy 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

  7. Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution

    Directory of Open Access Journals (Sweden)

    Lei Yang

    2017-09-01

    Full Text Available Recently, transition metal dichalcogenides (TMDs, represented by MoS2, have been proven to be a fascinating new class of electrocatalysts in hydrogen evolution reaction (HER. The rich chemical activities, combined with several strategies to regulate its morphologies and electronic properties, make MoS2 very attractive for understanding the fundamentals of electrocatalysis. In this review, recent developments in using MoS2 as electrocatalysts for the HER with high activity are presented. The effects of edges on HER activities of MoS2 are briefly discussed. Then we demonstrate strategies to further enhance the catalytic performance of MoS2 by improving its conductivity or engineering its structure. Finally, the key challenges to the industrial application of MoS2 in electrocatalytic hydrogen evolution are also pointed out.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-01

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

  9. 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.

  10. 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)

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

    Czech Academy of Sciences Publication Activity Database

    Doneux, T.; Ostatná, Veronika; Paleček, Emil

    2011-01-01

    Roč. 56, č. 25 (2011), s. 9337-9343 ISSN 0013-4686 R&D Projects: GA MŠk(CZ) ME09038; GA MŠk(CZ) LC06035 Grant - others:GA ČR(CZ) GAP301/11/2055 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : hydrogen evolution reaction * mediated catalysis * proton transfer Subject RIV: BO - Biophysics Impact factor: 3.832, year: 2011

  12. Visible-light-induced hydrogen evolution reaction with WS x Se 2

    Indian Academy of Sciences (India)

    ... 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 μ mol h − 1 g − 1 for WSSe, which is three times higher than that of WS2 alone (866 μ mol h − 1 g − 1 ). The turnover frequency is also high (0.7 h − 1 ).

  13. Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation.

    Science.gov (United States)

    Zheng, Yi-Wen; Chen, Bin; Ye, Pan; Feng, Ke; Wang, Wenguang; Meng, Qing-Yuan; Wu, Li-Zhu; Tung, Chen-Ho

    2016-08-17

    We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.

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

    Science.gov (United States)

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

    2017-12-01

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

  15. 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.

  16. Fuel hydrogen retention of tungsten and the reduction by inert gas glow discharges

    Energy Technology Data Exchange (ETDEWEB)

    Hino, T., E-mail: tomhino@qe.eng.hokudai.ac.jp [Laboratory of Plasma Physics and Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Yamauchi, Y.; Kimura, Y. [Laboratory of Plasma Physics and Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Nishimura, K. [National Institute for Fusion Science, Toki-shi, Gifu-ken 509-5292 (Japan); Ueda, Y. [Graduate School of Engineering, Osaka University, Suita-shi 565-0872 (Japan)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer The performances of inert gas glow discharges for reduction of fuel hydrogen retention in tungsten were systematically investigated. Black-Right-Pointing-Pointer For the tungsten with rough surface structure, the reduction of fuel hydrogen retention by inert gas discharges is quite small. Black-Right-Pointing-Pointer The deuterium glow discharge is quite useful to reduce the tritium retention in plasma facing walls in fusion reactor. Black-Right-Pointing-Pointer The wall baking with temperature higher than 700-800 K is also useful to reduce the tritium retention in plasma facing walls. - Abstract: Polycrystalline tungsten was exposed to deuterium glow discharge followed by He, Ne or Ar glow discharge. The amount of retained deuterium in the tungsten was measured using residual gas analysis. The amount of desorbed deuterium during the inert gas glow discharge was also measured. The amount of retained deuterium was 2-3 times larger compared with a case of stainless steel. The ratios of desorbed amount of deuterium by He, Ne and Ar glow discharges were 4.6, 3.1 and 2.9%, respectively. These values were one order of magnitude smaller compared with the case of stainless steel. The inert gas glow discharge is not suitable to reduce the fuel hydrogen retention for tungsten walls. However, the wall baking with a temperature higher than 700 K is suitable to reduce the fuel hydrogen retention. It is also shown that the use of deuterium glow discharge is effective to reduce the in-vessel tritium inventory in fusion reactors through the hydrogen isotope exchange.

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

    Science.gov (United States)

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

    2018-01-24

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

  18. Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

    Science.gov (United States)

    Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi

    2018-03-01

    Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.

  19. 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.

  20. TiO{sub 2} nanocomposite with reduced graphene oxide through facile blending and its photocatalytic behavior for hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Pei, Fuyun; Liu, Yingliang; Zhang, Li; Wang, Shengping; Xu, Shengang, E-mail: xusg@zzu.edu.cn; Cao, Shaokui, E-mail: caoshaokui@zzu.edu.cn

    2013-08-01

    Graphical abstract: - Highlights: • TRG-COOH nanocomposite as a photocatalyst for hydrogen evolution is prepared. • The reduction of graphene oxide reconstructs a part of conjugated structure. • The band gap is red-shifted due to the reconstruction of conjugated structure. • RG-COOH covered and anchored by P25 blocks the aggregation and the stacking. • The photocatalytic efficiency of TRG-COOH was increased under 500 W Xenon lamp. - Abstract: TRG-COOH nanocomposite is prepared as a photocatalyst for hydrogen evolution by blending TiO{sub 2} with reduced graphene oxide (RG-COOH). TRG-COOH is characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and photoluminescent spectra. XPS result shows the reduction of monolayer graphene oxide (GO). The band gap is red-shifted from 3.25 eV for P25, which consists of 20% rutile and 80% anatase, to 2.95 eV for TGO and then to 2.80 eV for TRG-COOH due to the introduction of GO and the reconstruction of conjugated structure. TEM image illustrates that RG-COOH in TRG-COOH is covered and anchored by P25, which blocks the aggregation of TiO{sub 2} nanoparticles and the stacking of monolayer graphene. This allows RG-COOH to take a good role of electron-sink and electron-transporting bridge. The photocatalytic efficiency of TRG-COOH is respectively increased under Xenon lamp about 8.9 and 2.7 times compared to P25 and TGO.

  1. Understanding the kinetics of sulfate reduction in brines by hydrogen: Progress report

    International Nuclear Information System (INIS)

    Strachan, D.M.

    1988-07-01

    Experiments were conducted with mixtures of hydrogen gas and each of PBB1 and PBB3 brines to examine the reduction kinetics of sulfate in high ionic strength solutions. Results from the experiments with brines showed that the kinetics of sulfate reduction is slower in high ionic strength solutions than the kinetics in low ionic strength solutions. However, the kinetic mechanism does not seem to alter the slow kinetics, but the addition of much larger quantities of sulfide, about 40 mM, does accelerate the reduction of sulfate. Since the proposed reaction mechanism for the reduction of sulfate by hydrogen gas involves the reaction of sulfide with sulfate, slow initial kinetics in the absence of sulfide is understandable, but also implies an unknown rate-limiting reaction. Precipitation of calcium sulfate(s) and calcium sulfide may limit the sulfide and sulfate concentrations to low values. The coexistence of anhydrite and oldhamite may indicate a part of the Ca-S-H 2 O that has not yet been investigated. 6 refs., 4 figs., 3 tabs

  2. Reduction of sulfate by hydrogen in natural systems: A literature review: Salt Repository Project

    International Nuclear Information System (INIS)

    Mahoney, J.J.; Strachan, D.M.

    1988-01-01

    The results of this literature search indicate that the reduction of sulfate by hydrogen gas can occur in nature, but that temperature appears to be a key factor in the rate of this reaction. At temperatures below 200/degree/C, the key factor in the rate of reaction appears to be extremely slow. At low pH the rate of reaction is faster than at high pH. The solution composition also influences the reaction rate; the most recent research available (Yanisagawa 1983) suggests that the concentration of sulfide in solution influences the rate of this reaction. The reduction reaction appears to proceed through a thiosulfate intermediate, so the presence and distribution of other sulfur species will influence the reaction rate. If the reaction mechanism proposed by Yanisagawa is correct, then higher concentrations of sulfide will result in faster rates of sulfate reduction. In conclusion, the reduction of sulfate by hydrogen to form significant amounts of sulfide is a function of temperature, sulfate and sulfide concentrations, pH, and solution composition. The rate of this reaction appears to be very slow under the conditions anticipated in this repository, but given the length of time required to maintain the integrity of the containers (300 to 1000 years) and the unusual solution compositions present, a better understanding of the reaction mechanism is needed. 16 refs., 1 tab

  3. A study on the kinetics of hydrogen reduction of molybdenum disulphide powders

    International Nuclear Information System (INIS)

    Mehdi Afsahi, M.; Sohrabi, Morteza; Vasant Kumar, R.; Ale Ebrahim, Habib

    2008-01-01

    In order to achieve direct reduction of molybdenite in presence of a sulphur scavenger such as CaO such that SO 2 emission is completely avoided, it is important to maximise the rate of the partial reaction involving molybdenite and hydrogen (without lime) given the low thermodynamic driving force for this reaction. Accordingly, reaction of molybdenum disulphide powders with hydrogen was investigated by thermogravimetric method. Effect of temperature and concentration on the reaction rate was studied under such conditions that resistance to mass transfer arising from external film, between particles and intra-grain was negligible. The operating temperature ranged between 973 and 1173 K while the hydrogen concentration was varied between 30 and 100%. The experimental data obtained under the above conditions were analyzed by applying 'the shrinking unreacted core model'. The reduction reaction was found to be first order with respect to the gaseous reactant. Pre-exponential factor and activation energy have been determined to be 3.91 x 10 3 cm min -1 and 139.0 kJ mol -1 , respectively. Activation energy obtained from a fitted model, agreed well with the values determined from the model-free methods using isothermal measurements

  4. A study on the kinetics of hydrogen reduction of molybdenum disulphide powders

    Energy Technology Data Exchange (ETDEWEB)

    Mehdi Afsahi, M. [Amirkabir University of Technology, Department of Chemical Engineering, Tehran 15914 (Iran, Islamic Republic of); University of Cambridge, Department of Materials Sciences and Metallurgy, Cambridge CB2 3QZ (United Kingdom)], E-mail: mma50@cam.ac.uk; Sohrabi, Morteza [Amirkabir University of Technology, Department of Chemical Engineering, Tehran 15914 (Iran, Islamic Republic of); Vasant Kumar, R. [University of Cambridge, Department of Materials Sciences and Metallurgy, Cambridge CB2 3QZ (United Kingdom); Ale Ebrahim, Habib [Amirkabir University of Technology, Department of Chemical Engineering, Tehran 15914 (Iran, Islamic Republic of)

    2008-07-10

    In order to achieve direct reduction of molybdenite in presence of a sulphur scavenger such as CaO such that SO{sub 2} emission is completely avoided, it is important to maximise the rate of the partial reaction involving molybdenite and hydrogen (without lime) given the low thermodynamic driving force for this reaction. Accordingly, reaction of molybdenum disulphide powders with hydrogen was investigated by thermogravimetric method. Effect of temperature and concentration on the reaction rate was studied under such conditions that resistance to mass transfer arising from external film, between particles and intra-grain was negligible. The operating temperature ranged between 973 and 1173 K while the hydrogen concentration was varied between 30 and 100%. The experimental data obtained under the above conditions were analyzed by applying 'the shrinking unreacted core model'. The reduction reaction was found to be first order with respect to the gaseous reactant. Pre-exponential factor and activation energy have been determined to be 3.91 x 10{sup 3} cm min{sup -1} and 139.0 kJ mol{sup -1}, respectively. Activation energy obtained from a fitted model, agreed well with the values determined from the model-free methods using isothermal measurements.

  5. 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.

  6. 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.

  7. Hydrogen evolution in enzymatic photoelectrochemical cell using modified seawater electrolytes produced by membrane desalination process

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Hyunku; Yoon, Jaekyung [Hydrogen Energy Research Center, New and Renewable Energy Research Division, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon 305-343 (Korea); Bae, Sanghyun [Department of Environmental Engineering, Yonsei University, 234 Maeji-ri, Hungub-myun, Wonju, Gangwon-do 220-710 (Korea); Kim, Chunghwan; Kim, Suhan [Korea Institute of Water and Environment, K-Water, 462-1 Jeonmin-dong, Yuseong-gu, Daejeon 305-730 (Korea)

    2009-09-15

    In the near future, potential water shortages are expected to occur all over the world and this problem will have a significant influence on the availability of water for water-splitting processes, such as photocatalysis and electrolysis, as well as for drinking water. For this reason, it has been suggested that seawater could be used as an alternative for the various water industries including hydrogen production. Seawater contains a large amount of dissolved ion components, thus allowing it to be used as an electrolyte in photoelectrochemical (PEC) systems for producing hydrogen. Especially, the concentrate (retentate) stream shows higher salinity than the seawater fed to the membrane desalination process, because purified water (fresh water) is produced as the permeate stream and the waste brine is more concentrated than the original seawater. In this study, we investigated the hydrogen evolution rate in a photoelectrochemical system, including the preparation and characterization of an anodized tubular TiO{sub 2} electrode (ATTE) as both the photoanode and the cathode with the assistance of an immobilized hydrogenase enzyme and an external bias (solar cell), and the use of various qualities of seawater produced by membrane desalination processes as the electrolyte. The results showed that the rate of hydrogen evolution obtained using the nanofiltration (NF) retentate in the PEC system is ca. 105 {mu}mol/cm{sup 2} h, showing that this is an effective seawater electrolyte for hydrogen production, the optimum amount of enzyme immobilized on the cathode is ca. 3.66 units per geometrical unit area (1 cm x 1 cm), and the optimum external external bias supplied by the solar cell is 2.0 V. (author)

  8. An obligately aerobic soil bacterium activates fermentative hydrogen production to survive reductive stress during hypoxia.

    Science.gov (United States)

    Berney, Michael; Greening, Chris; Conrad, Ralf; Jacobs, William R; Cook, Gregory M

    2014-08-05

    Oxygen availability is a major factor and evolutionary force determining the metabolic strategy of bacteria colonizing an environmental niche. In the soil, conditions can switch rapidly between oxia and anoxia, forcing soil bacteria to remodel their energy metabolism accordingly. Mycobacterium is a dominant genus in the soil, and all its species are obligate aerobes. Here we show that an obligate aerobe, the soil actinomycete Mycobacterium smegmatis, adopts an anaerobe-type strategy by activating fermentative hydrogen production to adapt to hypoxia. This process is controlled by the two-component system DosR-DosS/DosT, an oxygen and redox sensor that is well conserved in mycobacteria. We show that DosR tightly regulates the two [NiFe]-hydrogenases: Hyd3 (MSMEG_3931-3928) and Hyd2 (MSMEG_2719-2718). Using genetic manipulation and high-sensitivity GC, we demonstrate that Hyd3 facilitates the evolution of H2 when oxygen is depleted. Combined activity of Hyd2 and Hyd3 was necessary to maintain an optimal NAD(+)/NADH ratio and enhanced adaptation to and survival of hypoxia. We demonstrate that fermentatively-produced hydrogen can be recycled when fumarate or oxygen become available, suggesting Mycobacterium smegmatis can switch between fermentation, anaerobic respiration, and aerobic respiration. Hydrogen metabolism enables this obligate aerobe to rapidly meet its energetic needs when switching between microoxic and anoxic conditions and provides a competitive advantage in low oxygen environments.

  9. 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

  10. 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...... 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.......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 counter gas at the other electrode. Products of NO reduction (N-2 and H2O) were analyzed by an on-line mass spectrometer. At high NO+H-2+Ar flow rate (17 mL/min; 17 and 354 mL/min, respectively, at atmospheric pressure) the maximum rate enhancement ratio was 4.65. At low NO+H-2+Ar flow rate (17 mL/min; 17...

  11. 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.

  12. Molybdenum sulphides on carbon supports as electrocatalysts for hydrogen evolution in acidic industrial wastewater

    International Nuclear Information System (INIS)

    Kokko, M.; Bayerköhler, F.; Erben, J.; Zengerle, R.; Kurz, Ph.; Kerzenmacher, S.

    2017-01-01

    Highlights: • MoS_x is an efficient and durable catalyst for H_2 evolution in acidic wastewater. • MoS_x outperformed Pt as H_2-catalyst in long term in acidic wastewater. • Improved activity over time was likely due to changes in MoS_x structure. - Abstract: Microbial electrolysis cells (MECs) are an attractive future alternative technology to generate renewable hydrogen and simultaneously treat wastewaters. The thermodynamics of hydrogen evolution in MECs can be greatly improved by operating the cathode at acidic pH in combination with a neutral pH microbial anode. This can easily be achieved with acidic industrial wastewaters that have to be neutralised before discharge. For the hydrogen evolution reaction (HER) in acidic wastewater, efficient and inexpensive catalysts are required that are compatible with the often complex chemical composition of wastewaters. In this study, molybdenum sulphides (MoS_x) on different carbon supports were successfully used for hydrogen evolution in different acidic media. At first, the cathodes were screened by linear sweep voltammetry in sulphuric acid (pH 0) or phosphate buffer (pH 2.2). After this, the overpotentials for H_2 production of the best cathodes and their long term performances (⩾1 week) were determined in acidic industrial wastewater (pH 2.4) obtained from a plant mainly producing cellulose acetate. For the most promising MoS_x cathodes, the overpotentials for HER (at 3 mA cm"−"2) were only ∼40 mV higher than for a platinum electrode. Most importantly, the catalytic efficiency of the MoS_x electrodes improved in the wastewater over time (7–17 days), while Pt electrodes were found to be slowly deactivated. Thus, MoS_x emerges as an affordable, efficient and especially durable electrocatalyst for HER in real acidic wastewaters and this could be an important contribution to take energy production from wastewaters in the form of hydrogen towards practical applications.

  13. Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

    Science.gov (United States)

    Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

    2014-01-01

    The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

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

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

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

  15. Abiotic nitrate reduction in the presence of steel material and hydrogen in cementitious environments

    International Nuclear Information System (INIS)

    Truche, L.; Berger, G.; Albrecht, A.

    2012-01-01

    Document available in extended abstract form only. Abiotic nitrate reduction induced by different electron donors represents a major reaction of interest in the context of disposal of nuclear waste containing such oxyanions (Honda et al., 2006; Katsounaros et al., 2009). These wastes are characterized, amongst others by the coexistence of oxyanions (nitrate, phosphate, sulfate...) and potentially reducing agents such as organic matter, native metals and hydrogen gas formed or from package material via radiolysis or anaerobic corrosion. In addition to the large number of reactants present in the waste itself, the medium-level long-lived (MAVL) waste concept is based on large masses of concrete and steel in part used for primary waste containers as well as armored cement over pack and engineered barrier; a concept that guarantees the mechanical stability of both the waste container and the waste cell. In this experimental study we evaluate the consequences of steel material (carbon steel and 316L stainless steel) from waste canisters and construction material (concrete and Callovo- Oxfordian argillite), as well as magnetite as their possible corrosion by-products, on the reduction of aqueous nitrate in the presence of hydrogen. A parametric study (0 2 ) - ] 2+ , Fe 2+ ) that can act as electron donors. This experimental study demonstrates that abiotic nitrate reduction induced by the combination of steel materials and hydrogen is a likely process under waste cell conditions, thus applicable to cases where nitrate-bearing waste (i.e. nuclear) is disposed in near-surface or in deep geological settings. Depending on the nature of the steel, the reaction may exhibit different kinetic features that would require dedicated assessment. An increase in nitrate concentrat ions above the steel saturation level of 10 mM (Fig. 1; beyond the range of the current study) may also have an influence on reaction processes and kinetics and thus influence nitrate reactivity. (authors)

  16. Automation Activator of Hydrogen Gas Inlet Valve on Reduction Furnace ME-11

    International Nuclear Information System (INIS)

    Achmad Suntoro

    2007-01-01

    Operational of hydrogen inlet valve of the reduction furnace ME-11 was actuated manually by furnace operator if all its requirements have been fulfilled. Automation of the valve has been constructed as an additional option of the furnace operating system, in which any interruption by the existing manual system by the operator is still valid even though the automatic option is being used. This paper describes the information concerning the automation construction and its logical status of control in the form of its finite state machine. This automation system has been tested successfully. (author)

  17. Ag3PO4-TiO2-Graphene Oxide Ternary Composites with Efficient Photodegradation, Hydrogen Evolution, and Antibacterial Properties

    Directory of Open Access Journals (Sweden)

    Fu-Jye Sheu

    2018-02-01

    Full Text Available Ag3PO4-TiO2-graphene oxide ternary composite photocatalysts were fabricated by the photocatalytic reduction and ion exchange methods. The properties and photocatalytic activity of the composites were examined, and the photodegradation mechanism was investigated. More TiO2 nanoparticles in the composites were found to improve light absorption, but caused a larger impedance and inferior charge transport. Excess TiO2 nanoparticles distributed over the surfaces of Ag3PO4 and graphene oxide decreased the specific surface area and thus lowered light absorbance. An appropriate TiO2 content enhanced photocatalytic performance. When the molar ratio of Ag3PO4 to TiO2 was 0.6, the highest efficiency in photodegradation, hydrogen production (with a quantum efficiency of 8.1% and a hydrogen evolution rate of 218.7 μmole·g−1·h−1 and bacterial inactivation was achieved. Trapping experiments demonstrated that superoxide radicals and holes are the major active species involved in the photodegradation process.

  18. Quasistatic evolution of magnetoelastic plates via dimension reduction

    Czech Academy of Sciences Publication Activity Database

    Kružík, Martin; Stefanelli, U.; Zanini, Ch.

    2015-01-01

    Roč. 35, č. 12 (2015), s. 5999-6013 ISSN 1078-0947 R&D Projects: GA ČR GAP201/10/0357; GA ČR GA14-15264S Institutional support: RVO:67985556 Keywords : magnetoelasticity * energetic solution * existence * dimension reduction Subject RIV: BA - General Mathematics Impact factor: 1.127, year: 2015 http://library.utia.cas.cz/separaty/2015/MTR/kruzik-0444502.pdf

  19. 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.

  20. The Evolution of Breast Reduction Publications: A Bibliometric Analysis.

    Science.gov (United States)

    Muslu, Ümran

    2018-06-01

    This study aims to make a bibliometric analysis of the studies on breast reduction (BR) between the years 1980 and 2016 and identify important studies through trend topics as well as active authors, countries, universities, scientific journals, and citation and co-citation analyses about BR. Although BR looks like one of the cosmetic surgeries performed in order to restore the woman's appearance, in fact it is a reconstructive surgery that eliminates back pain, stance disorder, headache, shoulder pain, back and cervical disk hernia, difficulty in breathing, hollowness caused by bra straps, hygiene problems under breasts (e.g., rash or fungal infections), and limitations in some daily activities. However, the related literature has little information about the publications on this issue. Bibliometric analysis was performed by downloading all the documents published between 1980 and 2016 from Thomson Reuters Web of Science (WoS; Thomson Reuters, New York, NY, USA), using the keywords including "breast reduction", "gigantomastia", "reduction mammaplasty", and "reduction mammoplasty". There was a total of 1427 publications in the WoS database. Of these publications, 869 (60.90%) were research articles. The top three research areas of these publications were surgery with 1178 (82.55%) publications, oncology with 78 (5.47%) publications, and obstetrics gynecology with 67 (4.70%) publications. The top three countries that contributed to the literature most were the USA (515), England (147), and Turkey (83), respectively; the top university that contributed most was Harvard University, and the top two authors who contributed most were Drew PJ and Iwuagwu OC (13; 0.91%). The top-cited publication was "A Simplified Vertical Reduction Mammaplasty: Shortening the Learning Curve" written by Hall-Findlay, EJ in 1999. The journals with top numbers of publications were Plastic and Reconstructive Surgery (483; 33.85%), Annals of Plastic Surgery (164; 11.50%) and Aesthetic Plastic

  1. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    KAUST Repository

    Li, Hui

    2018-02-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  2. Titanium-Phosphonate-Based Metal-Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution

    KAUST Repository

    Li, Hui; Sun, Ying; Yuan, Zhong-Yong; Zhu, Yun-Pei; Ma, Tianyi

    2018-01-01

    Photocatalytic hydrogen production is crucial for solar-to-chemical conversion process, wherein high-efficiency photocatalysts lie in the heart of this area. Herein a new photocatalyst of hierarchically mesoporous titanium-phosphonate-based metal-organic frameworks, featuring well-structured spheres, periodic mesostructure and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well-structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemical field.

  3. N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex

    Science.gov (United States)

    Rodriguez, Meghan M.; Bill, Eckhard; Brennessel, William W.; Holland, Patrick L.

    2011-01-01

    The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N2) to ammonia is an iron surface promoted with K+, but soluble iron complexes have neither reduced the N-N bond of N2 to nitride nor produced large amounts of NH3 from N2. We report a molecular iron complex that reacts with N2 and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe3N2 core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H2 to give substantial yields of N2-derived ammonia. These reactions, though not yet catalytic, give structural and spectroscopic insight into N2 cleavage and N-H bond-forming reactions of iron. PMID:22076372

  4. N₂reduction and hydrogenation to ammonia by a molecular iron-potassium complex.

    Science.gov (United States)

    Rodriguez, Meghan M; Bill, Eckhard; Brennessel, William W; Holland, Patrick L

    2011-11-11

    The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron.

  5. PtNi Alloy Cocatalyst Modification of Eosin Y-Sensitized g-C3N4/GO Hybrid for Efficient Visible-Light Photocatalytic Hydrogen Evolution

    Science.gov (United States)

    Wang, Peng; Zong, Lanlan; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

    2018-02-01

    An economic and effective Pt-based alloy cocatalyst has attracted considerable attention due to their excellent catalytic activity and reducing Pt usage. In this study, PtNi alloy cocatalyst was successfully decorated on the g-C3N4/GO hybrid photocatalyst via a facile chemical reduction method. The Eosin Y-sensitized g-C3N4/PtNi/GO-0.5% composite photocatalyst yields about 1.54 and 1178 times higher hydrogen evolution rate than the Eosin Y-sensitized g-C3N4/Pt/GO-0.5% and g-C3N4/Ni/GO-0.5% samples, respectively. Mechanism of enhanced performance for the g-C3N4/PtNi/GO composite was also investigated by different characterization, such as photoluminescence, transient photocurrent response, and TEM. These results indicated that enhanced charge separation efficiency and more reactive sites are responsible for the improved hydrogen evolution performance due to the positive synergetic effect between Pt and Ni. This study suggests that PtNi alloy can be used as an economic and effective cocatalyst for hydrogen evolution reaction. [Figure not available: see fulltext.

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

    Science.gov (United States)

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

    2018-05-01

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

  7. Amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaofang; Tang, Chaowan; Zheng, Qun; Shao, Yu; Li, Danzhen, E-mail: dzli@fzu.edu.cn

    2017-02-15

    Loading cocatalyst on semiconductors was crucially necessary for improving the photocatalytic hydrogen evolution. Amorphous MoS{sub x} as a novel and noble metal-free cocatalyst was loaded on CdS nanorods by a simple photodeposition method. Efficient hydrogen evolution with amount of 15 mmol h{sup −1} g{sup −1} was observed over the MoS{sub x} modified CdS nanorods, which was about 6 times higher than that by using Pt as cocatalyst. Meanwhile, with MoS{sub x} cocatalyst, the efficiency of CdS nanorods was superior to that of CdS nanoparticles and bulk CdS. No deactivation could be observed in the efficiency of MoS{sub x} modified CdS nanorods under irradiation for successive 10 h. Further experimental results indicated that the efficient electrons transfer, low overpotential of hydrogen evolution and active S atoms over the MoS{sub x} modified CdS nanorods were responsible for the higher efficiency. Our results provided guidance for synthesizing noble metal-free materials as cocatalyst for photocatalytic hydrogen evolution. - Graphical abstract: Photodeposition of amorphous MoS{sub x} on CdS nanorods for highly efficient photocatalytic hydrogen evolution. - Highlights: • Amorphous MoSx cocatalyst was loaded on CdS NRs by a simple photodeposition. • MoS{sub x}/CdS NRs exhibited 6 times higher hydrogen evolution efficiency than Pt/CdS NRs. • The hydrogen evolution of MoS{sub x}/CdS NRs linearly increased with prolonging time. • Lower overpotential and efficient electron transfer were observed over MoS{sub x}/CdS NRs.

  8. 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).

  9. Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2018-05-01

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

  10. 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

    phosphoric acid were investigated in a temperature range from 80 to 170°C. A significant dependence of the activities on temperature was observed for all five carbide samples. Through the entire temperature range Group 6 metal carbides showed higher activity than that of the Group 5 metal carbides......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...

  11. Synthesis, characterization, and hydrogen uptake studies of magnesium nanoparticles by solution reduction method

    International Nuclear Information System (INIS)

    Rather, Sami ullah

    2014-01-01

    Graphical abstract: X-ray diffraction (XRD) pattern of magnesium nanoparticles synthesized by solution reduction method with and without TOPO. - Highlights: • Simple and convenient method of preparing Mg nanoparticles. • Characterized by XRD, SEM, FESEM and TEM. • Trioctylphosphine oxide offers a greater control over the size of the particles. • Hydrogen uptake of samples at different temperatures and pressure of 4.5 MPa. - Abstract: Facile and simple, surfactant-mediated solution reduction method was used to synthesize monodisperse magnesium nanoparticles. Little amount of magnesium oxide nanoparticles were also formed due to the presence of TOPO and easy oxidation of magnesium, eventhough, all precautions were taken to avoid oxidation of the sample. Precise size control of particles was achieved by carefully varying the concentration ratio of two different types of surfactants, – trioctylphosphine oxide and hexadecylamine. Recrystallized magnesium nanoparticle samples with and without TOPO were analyzed by X-ray diffraction, scanning electron microscope, field emission scanning electron microscope, and transmission electron microscope. The peak diameters of particles were estimated from size distribution analysis of the morphological data. The particles synthesized in the presence and absence of TOPO found to have diameters 46.5 and 34.8 nm, respectively. This observed dependence of particle size on the presence of TOPO offers a convenient method to control the particle size by simply using appropriate surfactant concentrations. Exceptional enhancement in hydrogen uptake and kinetics in synthesized magnesium nanoparticles as compared to commercial magnesium sample was due to the smaller particle size and improved morphology. Overall hydrogen uptake not affected by the little variation in particle size with and without TOPO

  12. Microbial Fe (III) reduction and hydrogen production by a transposon-mutagenized strain of Pantoea agglomerans BH18

    International Nuclear Information System (INIS)

    Liu, Hongyan; Wang, Guangce

    2015-01-01

    Based on the transposon-mutagenized library of Pantoea agglomerans BH18, mutant screens were conducted to obtain the strain with the highest Fe (III) reduction and hydrogen production. Of these transposon-mutagenized mutants, the mutant strain TB230 was screened for high Fe (III)-reducing efficiency and hydrogen production. The PCR amplification and kanamycin resistance selection results indicated that the transposon insertion of the mutant strain TB230 was stable. Hydrogen production of the mutant strain TB230 was (2.21 ± 0.34) mol H 2 /mol glucose, which increased hydrogen production by over 40% compared with that of the wild type strain. The accumulation concentration of Fe (II) in the medium of the mutant strain TB230 with Fe (OH) 3 as the sole electron acceptor was (7.39 ± 0.49) mmol/l, which was approximately 3-fold greater than that of the wild type strain. The mutant strain TB230 showed high Fe (III)-reducing activity and hydrogen production by adopting glucose and pyruvate as the carbon source. In addition, the mutant strain TB230 was capable of Fe (III) reduction and hydrogen production under fresh or marine conditions. This result indicates that the mutant strain with high microbial Fe (III) reduction and hydrogen production is beneficial for the improvement of anaerobic performance. - Highlights: • The mutant strain TB230 was a transposon-mutagenized strain of Pantoea agglomerans BH18. • Strain TB230 was screened for high Fe (III)-reducing efficiency and hydrogen production. • H 2 yield and Fe (III)-reducing activity were 2.21 ± 0.34 and 7.39 ± 0.49 in marine condition. • Strain TB230 was capable of Fe (III) reduction and hydrogen production in fresh or marine condition

  13. Hydrogen evolution in [NiFe] hydrogenases and related biomimetic systems: similarities and differences.

    Science.gov (United States)

    Das, Ranjita; Neese, Frank; van Gastel, Maurice

    2016-09-21

    In this work, a detailed quantum chemical study of the mechanism of [Ni(bdt)(dppf)] (Ni(II)L) catalyzed hydrogen formation [A. Gan, T. L. Groy, P. Tarakeshwar, S. K. S. Mazinani, J. Shearer, V. Mujica and A. K. Jones, J. Am. Chem. Soc., 2015, 137, 1109-1115] following an electro-chemical-electro-chemical (ECEC) pathway is reported. The complex exclusively catalyzes the reduction of protons to molecular hydrogen. The calculations suggest that the first one-electron reduction of the [Ni(II)L] catalyst is the rate limiting step of the catalytic cycle and hence, the buildup of detectable reaction intermediates is not expected. The catalytic activity of the [Ni(II)L] complex is facilitated by the flexibility of the ligand system, which allows the ligand framework to adapt to changes in the Ni oxidation state over the course of the reaction. Additionally, a comparison is made with the catalytic activity of [NiFe] hydrogenase. It is argued that the directionality of the reversible hydrogen formation reaction is controlled by the ligand field of the nickel ion and the possibility for side-on (η(2)) binding of H2: if the ligand framework does not allow for η(2) binding of H2, as is the case for [Ni(II)L], the catalyst irreversibly reduces protons. If the ligand field allows η(2) binding of H2, the catalyst can in principle work reversibly. The conditions for η(2) binding are discussed.

  14. Potential for greenhouse gas emission reductions using surplus electricity in hydrogen, methane and methanol production via electrolysis

    International Nuclear Information System (INIS)

    Uusitalo, Ville; Väisänen, Sanni; Inkeri, Eero; Soukka, Risto

    2017-01-01

    Highlights: • Greenhouse gas emission reductions using power-to-x processes are studied using life cycle assessment. • Surplus electricity use led to greenhouse gas emission reductions in all studied cases. • Highest reductions can be achieved by using hydrogen to replace fossil based hydrogen. • High reductions are also achieved when fossil transportation fuels are replaced. - Abstract: Using a life cycle perspective, potentials for greenhouse gas emission reductions using various power-to-x processes via electrolysis have been compared. Because of increasing renewable electricity production, occasionally surplus renewable electricity is produced, which leads to situations where the price of electricity approach zero. This surplus electricity can be used in hydrogen, methane and methanol production via electrolysis and other additional processes. Life cycle assessments have been utilized to compare these options in terms of greenhouse gas emission reductions. All of the power-to-x options studied lead to greenhouse gas emission reductions as compared to conventional production processes based on fossil fuels. The highest greenhouse gas emission reductions can be gained when hydrogen from steam reforming is replaced by hydrogen from the power-to-x process. High greenhouse gas emission reductions can also be achieved when power-to-x products are utilized as an energy source for transportation, replacing fossil transportation fuels. A third option with high greenhouse gas emission reduction potential is methane production, storing and electricity conversion in gas engines during peak consumption hours. It is concluded that the power-to-x processes provide a good potential solution for reducing greenhouse gas emissions in various sectors.

  15. Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

    2017-11-16

    The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  18. 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

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

    International Nuclear Information System (INIS)

    Masina, C.J.; Neethling, J.H.; Olivier, E.J.; Ferg, E.; Manzini, S.; Lodya, L.; Mohlala, P.; Ngobeni, M.W.

    2015-01-01

    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 2 . • The presence of SiO 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 2 O) as well as 2-line FeOOH·nH 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 2 O to hematite (α-Fe 2 O 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 2 O and at T ∼ 660 K for 2-line FeOOH·nH 2 O/SiO 2 , i.e., the presence of SiO 2 appears to inhibit the transformation. SiO 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 2 O to metallic iron (α-Fe) are observed: a two-stage process via magnetite (Fe 3 O 4 ) as an intermediate phase for 2-line FeOOH·nH 2 O, a three-step reduction involving Fe 3 O 4 and wüstite (FeO) as intermediate phases for 2-line FeOOH·nH 2 O/SiO 2 and a thermal transformation to α-Fe 2 O 3 followed by a two-step reduction via Fe 3 O 4 intermediate for 6-line FeOOH·nH 2 O. It is inferred that SiO 2 interacts with Fe species to form Fe–O–Fe structures which tend

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

    Science.gov (United States)

    Yuan, Heyang; He, Zhen

    2017-07-01

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

  1. 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.

  2. Microstructural evolution during hydrogen sorption cycling of Mg-FeTi nanolayered composites

    Energy Technology Data Exchange (ETDEWEB)

    Kalisvaart, W.P., E-mail: pkalisvaart@gmail.com [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada); Kubis, Alan; Danaie, Mohsen; Amirkhiz, Babak Shalchi [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada); Mitlin, David, E-mail: dmitlin@ualberta.ca [Chemical and Materials Engineering, University of Alberta and National Research Council Canada, National Institute for Nanotechnology, Edmonton, AB, T6G 2V4 (Canada)

    2011-03-15

    This paper describes the microstructural evolution of Mg-FeTi mutlilayered hydrogen storage materials during extended cycling. A 28 nm Mg-5 nm FeTi multilayer has comparable performance to a cosputtered material with an equivalent composition (Mg-10%Fe-10%Ti), which is included as a baseline case. At 200 deg. C, the FeTi layers act as a barrier, preventing agglomeration of Mg particles. At 300 deg. C, the initial structure of the multilayer is preserved up to 35 cycles, followed by fracturing of the Mg layers in the in-plane direction and progressive delamination of the FeTi layers as observed by electron microscopy. Concurrently, an increase in the Mg grain size was observed from 32 to 76 nm between cycles 35 and 300. As a result, the absorption kinetics deteriorate with cycling, although 90% of the total capacity is still absorbed within 2 min after as many as 300 cycles. The desorption kinetics, on the other hand, remain rapid and stable, and complete desorption of 4.6 wt.% H is achieved in 1.5 min at ambient desorption pressure. In addition to showing good hydrogen storage performance, multilayers are an excellent model system for studying the relation between microstructure and hydrogen absorption/desorption kinetics.

  3. Microstructural evolution during hydrogen sorption cycling of Mg-FeTi nanolayered composites

    International Nuclear Information System (INIS)

    Kalisvaart, W.P.; Kubis, Alan; Danaie, Mohsen; Amirkhiz, Babak Shalchi; Mitlin, David

    2011-01-01

    This paper describes the microstructural evolution of Mg-FeTi mutlilayered hydrogen storage materials during extended cycling. A 28 nm Mg-5 nm FeTi multilayer has comparable performance to a cosputtered material with an equivalent composition (Mg-10%Fe-10%Ti), which is included as a baseline case. At 200 deg. C, the FeTi layers act as a barrier, preventing agglomeration of Mg particles. At 300 deg. C, the initial structure of the multilayer is preserved up to 35 cycles, followed by fracturing of the Mg layers in the in-plane direction and progressive delamination of the FeTi layers as observed by electron microscopy. Concurrently, an increase in the Mg grain size was observed from 32 to 76 nm between cycles 35 and 300. As a result, the absorption kinetics deteriorate with cycling, although 90% of the total capacity is still absorbed within 2 min after as many as 300 cycles. The desorption kinetics, on the other hand, remain rapid and stable, and complete desorption of 4.6 wt.% H is achieved in 1.5 min at ambient desorption pressure. In addition to showing good hydrogen storage performance, multilayers are an excellent model system for studying the relation between microstructure and hydrogen absorption/desorption kinetics.

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

    KAUST Repository

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

    2015-01-01

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

  5. A mathematical model for hydrogen evolution in an electrochemical cell and experimental validation

    International Nuclear Information System (INIS)

    Mahmut D Mat; Yuksel Kaplan; Beycan Ibrahimoglu; Nejat Veziroglu; Rafig Alibeyli; Sadiq Kuliyev

    2006-01-01

    Electrochemical reaction is largely employed in various industrial areas such as hydrogen production, chlorate process, electroplating, metal purification etc. Most of these processes often take place with gas evaluation on the electrodes. Presence of gas phase in the liquid phase makes the problem two-phase flow which is much knowledge available from heat transfer and fluid mechanics studies. The motivation of this study is to investigate hydrogen release in an electrolysis processes from two-phase flow point of view and investigate effect of gas release on the electrolysis process. Hydrogen evolution, flow field and current density distribution in an electrochemical cell are investigated with a two-phase flow model. The mathematical model involves solutions of transport equations for the variables of each phase with allowance for inter phase transfer of mass and momentum. An experimental set-up is established to collect data to validate and improve the mathematical model. Void fraction is determined from measurement of resistivity changes in the system due to the presence of bubbles. A good agreement is obtained between numerical results and experimental data. (authors)

  6. A Facile Method for the Preparation of Colored Bi4Ti3O12−x Nanosheets with Enhanced Visible-Light Photocatalytic Hydrogen Evolution Activity

    Directory of Open Access Journals (Sweden)

    Yizeng Zhang

    2018-04-01

    Full Text Available Bi4Ti3O12−x nanosheet photocatalysts with abundant oxygen vacancies are fabricated by a facile solid-state chemical reduction method for the first time. This method is simple in operation, has short reaction time, and can be conducted at mild temperatures (300~400 °C. The electron paramagnetic resonance, thermogravimetric analysis, X-ray photoelectron spectrometer, and positron annihilation lifetime spectra results indicate that oxygen vacancies are produced in Bi4Ti3O12−x, and they can be adjusted by tuning the reduction reaction conditions. Control experiments show that the reduction time and temperature have great influences on the photocatalytic activities of Bi4Ti3O12−x. The optimal Bi4Ti3O12−x is the sample undergoing the reduction treatment at 350 °C for 60 min and it affords a hydrogen evolution rate of 129 μmol·g−1·h−1 under visible-light irradiation, which is about 3.4 times that of the pristine Bi4Ti3O12. The Bi4Ti3O12−x photocatalysts have good reusability and storage stability and can be used to decompose formaldehyde and formic acid for hydrogen production. The surface oxygen vacancies states result in the broadening of the valence band and the narrowing of the band gap. Such energy level structure variation helps promote the separation of photo-generated electron-hole pairs thus leading to enhancement in the visible-light photocatalytic hydrogen evolution. Meanwhile, the narrowing of the band gap leads to a broader visible light absorption of Bi4Ti3O12−x.

  7. Metal-polypyridyl catalysts for electro- and photochemical reduction of water to hydrogen.

    Science.gov (United States)

    Zee, David Z; Chantarojsiri, Teera; Long, Jeffrey R; Chang, Christopher J

    2015-07-21

    Climate change, rising global energy demand, and energy security concerns motivate research into alternative, sustainable energy sources. In principle, solar energy can meet the world's energy needs, but the intermittent nature of solar illumination means that it is temporally and spatially separated from its consumption. Developing systems that promote solar-to-fuel conversion, such as via reduction of protons to hydrogen, could bridge this production-consumption gap, but this effort requires invention of catalysts that are cheap, robust, and efficient and that use earth-abundant elements. In this context, catalysts that utilize water as both an earth-abundant, environmentally benign substrate and a solvent for proton reduction are highly desirable. This Account summarizes our studies of molecular metal-polypyridyl catalysts for electrochemical and photochemical reduction of protons to hydrogen. Inspired by concept transfer from biological and materials catalysts, these scaffolds are remarkably resistant to decomposition in water, with fast and selective electrocatalytic and photocatalytic conversions that are sustainable for several days. Their modular nature offers a broad range of opportunities for tuning reactivity by molecular design, including altering ancillary ligand electronics, denticity, and/or incorporating redox-active elements. Our first-generation complex, [(PY4)Co(CH3CN)2](2+), catalyzes the reduction of protons from a strong organic acid to hydrogen in 50% water. Subsequent investigations with the pentapyridyl ligand PY5Me2 furnished molybdenum and cobalt complexes capable of catalyzing the reduction of water in fully aqueous electrolyte with 100% Faradaic efficiency. Of particular note, the complex [(PY5Me2)MoO](2+) possesses extremely high activity and durability in neutral water, with turnover frequencies at least 8500 mol of H2 per mole of catalyst per hour and turnover numbers over 600 000 mol of H2 per mole of catalyst over 3 days at an

  8. Abiotic nitrate and sulphate reduction by hydrogen: a comparative experimental study

    International Nuclear Information System (INIS)

    Truche, L.; Berger, G.; Albrecht, A.; Giffaut, E.

    2010-01-01

    Document available in extended abstract form only. The bituminous waste which is part of the intermediate level, long-lived waste (MAVL) is characterised, amongst others, by the coexistence of nitrates, sulphates, organic matter, native metals and hydrogen gas in the waste mixture and package. It can be considered as the most complex example that will be used to discuss redox reactions occurring in such waste mixtures. The evaluation of the redox conditions requires quantification of the amount of electron acceptors and donors and definition of the kinetics of redox reaction. The objectives of an experimental study to unravel some of these reaction complexities are: - to investigate nature and rate of sulphate and nitrate reduction by hydrogen in the presence of different catalysts (stainless steel, hastelloy, magnetite and argillite); - to compare sulphate and nitrate as electron acceptors; - to provide a mechanistic model of these reactions. It is well known that reduction of sulphate and nitrate requires high activation energies, usually supplied either by thermal processes or via bacterial and surface catalysis, of which the latter has been investigated in this study. Preliminary experiments performed at 150 deg. C and under H 2 pressure show that sulphate reduction is enhanced in the presence of magnetite, but essentially under the restricted condition of low sulphate concentration and at a pH below the Point of Zero Charge of magnetite. This suggests that sorption of sulphate contributes to the catalysed reaction (at low pH) but provided that the magnetite surface sites are not saturated with respect to aqueous sulphate (low concentration). On the contrary, nitrate reduction is observed whatever the pH and the nitrate concentration in the presence of both magnetite and hastelloy C276 (Ni, Cr, Mo, W, Fe alloy). The effect of temperature on the rate of nitrate reduction (500 ppm KNO 3 solution) is shown by comparing three different experiments conducted in

  9. Hydrogen Production via Water Dissociation Using Pt–TiO2 Photocatalysts: An Oxidation–Reduction Network

    Directory of Open Access Journals (Sweden)

    J. F. Guayaquil-Sosa

    2017-10-01

    Full Text Available Several TiO2 based semiconductors with different Pt loadings are prepared using incipient impregnation, wet impregnation and the sol-gel method. These photocatalysts are evaluated in the Photo-CREC-Water II Photoreactor for hydrogen production via water dissociation, using an organic renewable scavenger (ethanol. Results obtained show the influence of the photocatalyst preparation in the production of hydrogen and in the observed quantum yields. Furthermore, it is established that the reaction networks leading to hydrogen production, using various photocatalysts, share common features. This analysis is developed by both identifying and quantifying different chemical species and their changes with irradiation time. Key species in this oxidation–reduction network are hydrogen, hydrogen peroxide, ethanol, methane, ethane, acetaldehyde and carbon dioxide. On this basis, it is shown that under an inert gas atmosphere, ethanol consumption is sub-stoichiometric. This points towards simultaneous ethanol consumption and the formation of the ethanol scavenger.

  10. Density evaluation of remotely-supplied hydrogen radicals produced via tungsten filament method for SiCl4 reduction

    Science.gov (United States)

    Zohra Dahmani, Fatima; Okamoto, Yuji; Tsutsumi, Daiki; Ishigaki, Takamasa; Koinuma, Hideomi; Hamzaoui, Saad; Flazi, Samir; Sumiya, Masatomo

    2018-05-01

    Effect of the hydrogen radical on the reduction of a silicon tetrachloride (SiCl4) source was studied. The hydrogen radicals were generated using a tungsten (W) filament in a generation chamber, and were remotely supplied to another reaction chamber. The density of the hydrogen radical was estimated from the optical transmittance of 600-nm-wavelength light through phosphate glass doped with tungsten oxide (WO3). Lifetime of the hydrogen radical seemed sufficiently long, and its density as supplied to the reaction chamber was estimated to be on the order of 1012 cm‑3. Signal intensity of the peak corresponding to SiCl4 (m/z = 170) detected by quadrupole-mass measurement was confirmed to decrease owing to the reaction with the remotely-supplied hydrogen radical. This indicates the possibility that chemically-stable SiCl4, as one of the by-products of the Siemens process, can be reduced to produce silicon.

  11. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. An insight on hydrogen fuel injection techniques with SCR system for NO{sub X} reduction in a hydrogen-diesel dual fuel engine

    Energy Technology Data Exchange (ETDEWEB)

    Saravanan, N. [ERC Engines, Hall 11A, Tata Motors, Pimpri, Pune 411019, Maharashtra (India); Nagarajan, G. [Department of Mechanical Engineering, ICE Division, College of Engineering, Guindy, Anna University-Chennai, Chennai 600 025 (India)

    2009-11-15

    Internal combustion engines continue to dominate in many fields like transportation, agriculture and power generation. Among the various alternative fuels, hydrogen is a long-term renewable and less polluting fuel (Produced from renewable energy sources). In the present experimental investigation, the performance and emission characteristics were studied on a direct injection diesel engine in dual fuel mode with hydrogen inducted along with air adopting carburetion, timed port and manifold injection techniques. Results showed that in timed port injection, the specific energy consumption reduces by 15% and smoke level by 18%. The brake thermal efficiency and NO{sub X} increases by 17% and 34% respectively compared to baseline diesel. The variation in performance between port and manifold injection is not significant. The unburnt hydrocarbons and carbon monoxide emissions are lesser in port injection. The oxides of nitrogen are higher in hydrogen operation (both port and manifold injection) compared to diesel engine. In order to reduce the NO{sub X} emissions, a selective catalytic converter was used in hydrogen port fuel injection. The NO{sub X} emission reduced upto a maximum of 74% for ANR (ratio of flow rate of ammonia to the flow rate of NO) of 1.1 with a marginal reduction in efficiency. Selective catalytic reduction technique has been found to be effective in reducing the NO{sub X} emission from hydrogen fueled diesel engines. (author)

  13. 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.

  14. Greenhouse gas reduction benefits and costs of a large-scale transition to hydrogen in the USA

    International Nuclear Information System (INIS)

    Dougherty, William; Kartha, Sivan; Lazarus, Michael; Fencl, Amanda; Rajan, Chella; Bailie, Alison; Runkle, Benjamin

    2009-01-01

    Hydrogen is an energy carrier able to be produced from domestic, zero-carbon sources and consumed by zero-pollution devices. A transition to a hydrogen-based economy could therefore potentially respond to climate, air quality, and energy security concerns. In a hydrogen economy, both mobile and stationary energy needs could be met through the reaction of hydrogen (H 2 ) with oxygen (O 2 ). This study applies a full fuel cycle approach to quantify the energy, greenhouse gas emissions (GHGs), and cost implications associated with a large transition to hydrogen in the United States. It explores a national and four metropolitan area transitions in two contrasting policy contexts: a 'business-as-usual' (BAU) context with continued reliance on fossil fuels, and a 'GHG-constrained' context with policies aimed at reducing greenhouse gas emissions. A transition in either policy context faces serious challenges, foremost among them from the highly inertial investments over the past century or so in technology and infrastructure based on petroleum, natural gas, and coal. A hydrogen transition in the USA could contribute to an effective response to climate change by helping to achieve deep reductions in GHG emissions by mid-century across all sectors of the economy; however, these reductions depend on the use of hydrogen to exploit clean, zero-carbon energy supply options. (author)

  15. Greenhouse gas reduction benefits and costs of a large-scale transition to hydrogen in the USA

    Energy Technology Data Exchange (ETDEWEB)

    Dougherty, William; Kartha, Sivan; Lazarus, Michael; Fencl, Amanda [Stockholm Environment Institute - US Center, 11 Curtis Avenue, Somerville, MA 02143 (United States); Rajan, Chella [Indian Institute of Technology Madras, I.I.T. Post Office, Chennai 600 036 (India); Bailie, Alison [The Pembina Institute, 200, 608 - 7th Street, S.W. Calgary, AB (Canada); Runkle, Benjamin [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

    2009-01-15

    Hydrogen is an energy carrier able to be produced from domestic, zero-carbon sources and consumed by zero-pollution devices. A transition to a hydrogen-based economy could therefore potentially respond to climate, air quality, and energy security concerns. In a hydrogen economy, both mobile and stationary energy needs could be met through the reaction of hydrogen (H{sub 2}) with oxygen (O{sub 2}). This study applies a full fuel cycle approach to quantify the energy, greenhouse gas emissions (GHGs), and cost implications associated with a large transition to hydrogen in the United States. It explores a national and four metropolitan area transitions in two contrasting policy contexts: a 'business-as-usual' (BAU) context with continued reliance on fossil fuels, and a 'GHG-constrained' context with policies aimed at reducing greenhouse gas emissions. A transition in either policy context faces serious challenges, foremost among them from the highly inertial investments over the past century or so in technology and infrastructure based on petroleum, natural gas, and coal. A hydrogen transition in the USA could contribute to an effective response to climate change by helping to achieve deep reductions in GHG emissions by mid-century across all sectors of the economy; however, these reductions depend on the use of hydrogen to exploit clean, zero-carbon energy supply options. (author)

  16. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

    Science.gov (United States)

    Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

    2018-01-31

    The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

  17. Determination of factor of hydrogen permeation reduction (PRF) for different protective coatings over vanadium

    International Nuclear Information System (INIS)

    Afanasyev, S.; Kulsartov, T.; Shestakov, V.; Chikhray, Y.; Smith, D.

    2002-01-01

    Selection of structural materials for liquid-metal system as well as for another system and constructions of nuclear energy plants must be carried out and based on specified demands depending on conditions of these materials functioning. Specific demand is its compatibility with liquid metals. Design of reactors with liquid-metal coolant (Li, PbLi 17 ) which reproduces tritium arise additional demand to structural materials. This demand is a creation of structural material or protective barrier with minimum acceptable value of tritium permeation through itself or with maximum permeation reduction factor (PRF). Vanadium and vanadium alloys are supposed to be use as a blanket structural material in such nuclear energy plants. Worked out at first stage of studies vanadium coatings should have stability of its characteristics at temperature 800 deg. C under influence of hydrogen. Given work shows the experimental results on testing of protective coatings over vanadium: glass-ceramic coating and CaO-base coating. PRF for every coating and its changes depending on thermo-capacity of vanadium sample with coating was determined by method of hydrogen permeation. The results of experiments would be used at the development of cooling loops of reactor core protection with liquid-metal coolant

  18. Natural spectroscopic hydrogen isotope transfer in alcohol dehydrogenase-catalysed reduction

    International Nuclear Information System (INIS)

    Ben-Li Zhang; Pionnier, S.

    2002-01-01

    The enantiomeric purity of natural α-mono deuterated enantiomers, (R) and (S)ethanol-1-d 1 , in the alcohol produced by sugar fermentation with yeast was studied by 2 H NMR using their esters derived from optical mandelic acid. The results of isotope tracing experiments show that the transfer pathways of the two eantiotopic hydrogens of the methylene group are different. It was observed that (S)-deuterium comes only from the medium water. The (R)-deuterium transferred by NADH in alcohol dehydrogenase reduction of the acetaldehyde is complex origin. Some of them originates from carbon bound hydrogen of the sugar, especially from C(4) position of glucose and most of them comes from water. Only a small portion of the NADH deuterium is incorporated indirectly from water through enzyme catalysed exchange between the pro-S site of NADH and flavin. When a carbonyl compound (ethyl acetoacetate) was reduced under the same conditions during the alcoholic fermentation, among the NADH-transferred deuterium, only a small portion comes from water while most comes from the unexchangeable positions of the glucose. (author)

  19. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    DEFF Research Database (Denmark)

    Hansen, Thomas Søndergaard; Barta, Katalin; Anastas, Paul T.

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hyd......Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions....... The hydrogen equivalents needed for the reductive deoxygenation of HMF originate from the solvent itself upon its reforming. Dimethylfuran, dimethyltetrahydrofuran and 2-hexanol were obtained in good yields. At milder reaction temperatures, a combined yield (DMF + DMTHF) of 58% was achieved. Notably...

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

    Science.gov (United States)

    Stolbov, Sergey; Alcántara Ortigoza, Marisol

    2012-02-01

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

  1. Reduction of tungstates and molybdates by hydrogen and thermodynamic properties of these salts

    International Nuclear Information System (INIS)

    Gerasimov, Ya.I.; Rezukhina, T.N.; Simanov, Yu.P.; Vasil'eva, I.A.; Kurshakova, R.D.

    1988-01-01

    Study of thermodynamic properties of a series of tungstates of bivalent metals (Mg, Ca, Sr, Ba, Mn, Co, Fe, Ni, Cu, Zn, Cd and Pb) as well as of some molybdates- of Mg, Ca, Sr, Ba is carried out. The obtained values are compared with magnetic characteristics of compounds and parameters of their crystal lattices. Thermodynamic properties were studied by measuring constants of their reduction with hydrogen in the 500-1350 deg C temperature range. It is concluded that dependence of thermodynamic values on geometric parameters of the lattice is not definitive. Comparison of salt formation atomic entropies with deviations of salt magnetic moments from theoretical ionic moments points to the fact of existence of some accordance between these two series of values. 25 refs.; 10 figs.; 6 tabs

  2. Simulation of uranium oxides reduction kinetics by hydrogen. Reactivities of germination and growth

    International Nuclear Information System (INIS)

    Brun, C.

    1997-01-01

    The aim of this work is to simulate the reduction by hydrogen of the tri-uranium octo-oxide U 3 O 8 (obtained by uranium trioxide calcination) into uranium dioxide. The kinetics curves have been obtained by thermal gravimetric analysis, the hydrogen and steam pressures being defined. The geometrical modeling which has allowed to explain the trend of the kinetics curves and of the velocity curves is an anisotropic germination-growth modeling. The powder is supposed to be formed of spherical grains with the same radius. The germs of the new UO 2 phase appear at the surface of the U 3 O 8 grains with a specific germination frequency. The growth reactivity is anisotropic and is very large in the tangential direction to the grains surface. Then, the uranium dioxide growths inside the grain and the limiting step is the grain surface. The variations of the growth reactivity and of the germination specific frequency in terms of the gases partial pressures and of the temperature have been explained by two different mechanisms. The limiting step of the growth mechanism is the desorption of water in the uranium dioxide surface. Concerning the germination mechanism the limiting step is a water desorption too but in the tri-uranium octo-oxide surface. The same geometrical modeling and the same germination and growth mechanisms have been applied to the reduction of a tri-uranium octo-oxide obtained by calcination of hydrated uranium trioxide. The values of the germination specific frequency of this solid are nevertheless weaker than those of the solid obtained by direct calcination of the uranium trioxide. (O.M.)

  3. Unified reduction principle for the evolution of mutation, migration, and recombination

    Science.gov (United States)

    Altenberg, Lee; Liberman, Uri; Feldman, Marcus W.

    2017-01-01

    Modifier-gene models for the evolution of genetic information transmission between generations of organisms exhibit the reduction principle: Selection favors reduction in the rate of variation production in populations near equilibrium under a balance of constant viability selection and variation production. Whereas this outcome has been proven for a variety of genetic models, it has not been proven in general for multiallelic genetic models of mutation, migration, and recombination modification with arbitrary linkage between the modifier and major genes under viability selection. We show that the reduction principle holds for all of these cases by developing a unifying mathematical framework that characterizes all of these evolutionary models. PMID:28265103

  4. 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.)

  5. 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.

  6. Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

    2017-09-19

    This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  8. Impedance and hydrogen evolution studies on magnesium alloy in oxalic acid solution containing different anions

    Energy Technology Data Exchange (ETDEWEB)

    Fekry, A.M. [Chemistry Department, Faculty of Science, Cairo University, Giza 12613 (Egypt)

    2010-12-15

    The corrosion behavior of AZ31E alloy was investigated in oxalic acid solution using different electrochemical techniques. The effect of concentration was studied, where the corrosion rate was found to increase with increasing oxalic acid concentration and hydrogen evolution. The effect of adding Cl{sup -}, F{sup -} or PO{sub 4}{sup 3-} ions on the electrochemical behavior of AZ31E electrode was studied in 0.01 M oxalic acid solution at 298 K. It was found that the corrosion rate increases with increasing Cl{sup -} or F{sup -} ion concentration, however, it decreases with increasing PO{sub 4}{sup 3-} ion concentration. Good agreement was observed between the results obtained from electrochemical techniques and confirmed by Scanning electron micrographs. (author)

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

    KAUST Repository

    Yu, Weili; Isimjan, Tayirjan T.; Del Gobbo, Silvano; Anjum, Dalaver Hussain; Abdel-Azeim, Safwat; Cavallo, Luigi; Garcia Esparza, Angel T.; Domen, Kazunari; Xu, Wei; Takanabe, Kazuhiro

    2014-01-01

    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.

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

    KAUST Repository

    Nayak, Pranati; Jiang, Qiu; Kurra, Narendra; Buttner, Ulrich; Wang, Xianbin; Alshareef, Husam N.

    2017-01-01

    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.

  11. Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

    Science.gov (United States)

    Sprick, Reiner Sebastian; Bonillo, Baltasar; Clowes, Rob; Guiglion, Pierre; Brownbill, Nick J; Slater, Benjamin J; Blanc, Frédéric; Zwijnenburg, Martijn A; Adams, Dave J; Cooper, Andrew I

    2016-01-26

    Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H 2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO 2 , but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co-polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

  12. Nanoporous niobium nitride (Nb2N) with enhanced electrocatalytic performance for hydrogen evolution

    Science.gov (United States)

    Li, Yan; Zhang, Jianli; Qian, Xingyue; Zhang, Yue; Wang, Yining; Hu, Rudan; Yao, Chao; Zhu, Junwu

    2018-01-01

    The transition metal nitrides (TMNs) with nanoporous structure have shown great promise as potential electrocatalysts for the hydrogen evolution reaction (HER). Herein, self-organized nanoporous Nb2N was first successfully synthesized through the anodization of niobium in mixed oxalic acid/HF electrolyte, followed by a simple annealing treatment in the ammonia atmosphere. Due to the highly ordered nanoporous structure with abundant active sites and the enhanced electrical conductivity, the Nb2N exhibits a high catalytic current (326.3 mA cm-2) and low onset potential (96.3 mV), which is almost 3.9 times and 4.2 times better than that of Nb2O5, respectively. Meanwhile, the Nb2N also presents low Tafel slope (92 mV dec-1), and excellent cycling durability. More importantly, this study will provide more opportunities for designing and fabricating niobium compounds as an innovative HER catalysts.

  13. Engineering Pt/Pd Interfacial Electronic Structures for Highly Efficient Hydrogen Evolution and Alcohol Oxidation.

    Science.gov (United States)

    Fan, Jinchang; Qi, Kun; Zhang, Lei; Zhang, Haiyan; Yu, Shansheng; Cui, Xiaoqiang

    2017-05-31

    Tailoring the interfacial structure of Pt-based catalysts has emerged as an effective strategy to improve catalytic activity. However, little attention has been focused on investigating the relationship between the interfacial facets and their catalytic activity. Here, we design and implement Pd-Pt interfaces with controlled heterostructure features by epitaxially growing Pt nanoparticles on Pd nanosheets. On the basis of both density functional theory calculation and experimental results, we demonstrate that charge transfer from Pd to Pt is highly dependent on the interfacial facets of Pd substrates. Therefore, the Pd-Pt heterostructure with Pd(100)-Pt interface exhibits excellent activity and long-term stability for hydrogen evolution and methanol/ethanol oxidation reactions in alkaline medium, much better than that with Pd (111)-Pt interface or commercial Pt/C. Interfacial crystal facet-dependent electronic structural modulation sheds a light on the design and investigation of new heterostructures for high-activity catalysts.

  14. 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.

  15. 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.

  16. Amorphous nickel/cobalt tungsten sulfide electrocatalysts for high-efficiency hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lun [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Wu, Xinglong, E-mail: hkxlwu@nju.edu.cn [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Department of Physics, NingBo University, NingBo 315001 (China); Zhu, Xiaoshu [Center for Analysis and Testing, Nanjing Normal University, Nanjing 210093 (China); He, Chengyu; Meng, Ming; Gan, Zhixing [Key Laboratory of Modern Acoustics, MOE, Institute of Acoustics and Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Chu, Paul K. [Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

    2015-06-30

    Graphical abstract: - Highlights: • Amorphous nickel/cobalt tungsten sulfides were synthesized by a thermolytic process. • Amorphous NiWS and CoWS could realize hydrogen evolution efficiently. • Ni/Co promotion and annealing alter the porous structure and chemical bonding states. • Active sites on the surface of amorphous WS{sub x} are increased with Ni or Co doping. • Amorphous NiWS and CoWS have immense potentials in water splitting devices. - Abstract: The hydrogen evolution reaction (HER), an appealing solution for future energy supply, requires efficient and inexpensive electrocatalysts with abundant active surface sites. Although crystalline MoS{sub 2} and WS{sub 2} are promising candidates, their activity is dominated by edge sites. Amorphous tungsten sulfide prepared so far lacks the required active sites and its application has thus been hampered. In this work, nickel and cobalt incorporated amorphous tungsten sulfide synthesized by a thermolytic process is demonstrated to enhance the HER efficiency dramatically. The amorphous nickel tungsten sulfide (amorphous NiWS) annealed at 210 °C delivers the best HER performance in this system boasting a Tafel slope of 55 mV per decade and current density of 8.6 mA cm{sup −2} at 250 mV overpotential in a sustained test for 24 h. The introduction of Ni or Co into the catalyst and subsequent thermal treatment alters the porous structure and chemical bonding states thereby increasing the density of active sites on the surface.

  17. Surface spintronics enhanced photo-catalytic hydrogen evolution: Mechanisms, strategies, challenges and future

    Science.gov (United States)

    Zhang, Wenyan; Gao, Wei; Zhang, Xuqiang; Li, Zhen; Lu, Gongxuan

    2018-03-01

    Hydrogen is a green energy carrier with high enthalpy and zero environmental pollution emission characteristics. Photocatalytic hydrogen evolution (HER) is a sustainable and promising way to generate hydrogen. Despite of great achievements in photocatalytic HER research, its efficiency is still limited due to undesirable electron transfer loss, high HER over-potential and low stability of some photocatalysts, which lead to their unsatisfied performance in HER and anti-photocorrosion properties. In recent years, many spintronics works have shown their enhancing effects on photo-catalytic HER. For example, it was reported that spin polarized photo-electrons could result in higher photocurrents and HER turn-over frequency (up to 200%) in photocatalytic system. Two strategies have been developed for electron spin polarizing, which resort to heavy atom effect and magnetic induction respectively. Both theoretical and experimental studies show that controlling spin state of OHrad radicals in photocatalytic reaction can not only decrease OER over-potential (even to 0 eV) of water splitting, but improve stability and charge lifetime of photocatalysts. A convenient strategy have been developed for aligning spin state of OHrad by utilizing chiral molecules to spin filter photo-electrons. By chiral-induced spin filtering, electron polarization can approach to 74%, which is significantly larger than some traditional transition metal devices. Those achievements demonstrate bright future of spintronics in enhancing photocatalytic HER, nevertheless, there is little work systematically reviewing and analysis this topic. This review focuses on recent achievements of spintronics in photocatalytic HER study, and systematically summarizes the related mechanisms and important strategies proposed. Besides, the challenges and developing trends of spintronics enhanced photo-catalytic HER research are discussed, expecting to comprehend and explore such interdisciplinary research in

  18. Highly efficient and stable MoP-RGO nanoparticles as electrocatalysts for hydrogen evolution

    International Nuclear Information System (INIS)

    Wu, Zexing; Wang, Jie; Zhu, Jing; Guo, Junpo; Xiao, Weiping; Xuan, Cuijuan; Lei, Wen; Wang, Deli

    2017-01-01

    Graphical abstract: Graphene supported MoP (MoP-RGO) was synthesized through a facile solvothermal reaction followed by high-temperature phosphating treatment method. The material exhibits an outstanding HER performance in both acid and alkaline media. RGO act as a substrate which can not only avoid the nanoparticles aggregation, but also facilitate the electron transfer during the electrocatalytic process. - Abstract: Electrochemical splitting of water to obtain hydrogen plays a vital role in high energy density devices, especially for fuel cells. In this work, reduced graphene oxide supported molybdenum phosphide nanoparticles (MoP-RGO) were prepared via a facile solvothermal reaction followed by high-temperature phosphating treatment. The electrochemical measurement results indicate that the MoP-RGO nanocomposite obtained at 900 °C exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER) with overpotentials of 117 mV and 150 mV at a current density of 10 mA cm"−"2 in acid and alkaline media, respectively. Furthermore, the instability of the catalyst in basic medium was systemically investigated. This work provides a facile strategy for the synthesis of cost-effective carbon supported metal phosphide as HER electrocatalyst.

  19. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang

    2017-01-01

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  20. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun

    2017-12-27

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  1. Dispersive kinetic model for the non-isothermal reduction of nickel oxide by hydrogen

    International Nuclear Information System (INIS)

    Adnadevic, Borivoj; Jankovic, Bojan

    2008-01-01

    The kinetics of the non-isothermal reduction process of powder nickel oxide samples using hydrogen was investigated by temperature-programmed experiments at the different constant heating rates. The new procedure for the determination of density distribution function of activation energies (ddfE a ), evaluated from the experimentally obtained non-isothermal conversion curves, was developed. The analytical relationships between the corresponding thermo-kinetic parameters for the investigated reduction process were established. From the influence of heating rate on the basic characteristics of ddfE a 's, it was concluded that the evaluated ddfE a 's are completely independent of the heating rate (v h ). It was found that the value of activation energy at the peak of the distribution curve (E a,max ), at all considered heating rates, is in good agreement with the value of E a,0 (96.6 kJ mol -1 ) calculated from the isoconversional dependence of activation energy, in the conversion range of 0.20≤α≤0.60. From the appearances of the true compensation effect, it was concluded that the factor that produces the changes of kinetic parameter values is a conversion fraction (α). Using the model prediction, the experimentally obtained conversion curves are completely described by the evaluated distribution curves (g(E a ) vhj ) at all considered heating rates. It was concluded that the assumption about the distribution of potential energies of oxygen vacancies presented in NiO samples leads to the distribution of activation energies, which determine the kinetics of non-isothermal reduction processes

  2. Hydrogen-Induced Phase Transformation and Microstructure Evolution for Ti-6Al-4V Parts Produced by Electron Beam Melting

    Directory of Open Access Journals (Sweden)

    Natalia Pushilina

    2018-04-01

    Full Text Available In this paper, phase transitions and microstructure evolution in titanium Ti-6Al-4V alloy parts produced by electron beam melting (EBM under hydrogenation was investigated. Hydrogenation was carried out at the temperature of 650 °C to the absolute hydrogen concentrations in the samples of 0.29, 0.58, and 0.90 wt. %. Comparative analysis of microstructure changes in Ti-6Al-4V alloy parts was performed using scanning electron microscopy (SEM, transmission electron microscopy (TEM, and X-ray diffraction (XRD. Furthermore, in-situ XRD was used to investigate the phase transitions in the samples during hydrogenation. The structure of Ti-6Al-4V parts produced by EBM is represented by the α phase plates with the transverse length of 0.2 μm, the β phase both in the form of plates and globular grains, and metastable α″ and ω phases. Hydrogenation to the concentration of 0.29 wt. % leads to the formation of intermetallic Ti3Al phase. The dimensions of intermetallic Ti3Al plates and their volume fraction increase significantly with hydrogen concentration up to 0.58 wt. % along with precipitation of nano-sized crystals of titanium δ hydrides. Individual Ti3Al plates decay into nanocrystals with increasing hydrogen concentration up to 0.9 wt. % accompanied by the increase of proportion and size of hydride plates. Hardness of EBM Ti-6Al-4V alloy decreases with hydrogen content.

  3. Design of Copper and Titanium Dioxide Nanoparticles Doped with Reduced Graphene Oxide for Hydrogen Evolution by Water Splitting

    Science.gov (United States)

    Yang, Yuhao; Huang, Wenhuan

    2018-05-01

    TiO2-graphene (P25-GR, PG) nanocomposite was fabricated from P25 titania and graphite oxide by hydrothermal method, and then Cu nanoparticles (Cu NPs) were assembled in P25-GR composite (Cu- P25-GR, CPG) under microwave-assisted chemical reduction. The prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-Vis absorption (UV-Vis) and Raman spectroscopies. Cu NPs were well dispersed on the surface of PG and are in metallic state. The ternary Cu-P25-GR (CPG) nanocomposites show an extended light absorption range and more efficient charge separation properties compared to binary P25-GR (PG) composite. Methylene blue photodegradation experiment proved that surface plasmon resonance (SPR) phenomenon had an effect on photoreaction efficiency. The corresponding hydrogen evolution rate for CPG prepared using 0.002 M Cu(NO3)2 solution was 10 times higher than with pure P25, and 2.3 times higher than with PG in the same test conditions. The improved photocatalytic performance can be attributed to the presence of GR in the prepared composite and to the SPR effect, leading to the longer lifetime of photogenerated electronhole pairs and faster interfacial charge transfer rate. We expect that our work would be useful for the further exploration of GR-based nanocomposites.

  4. Boron-Doped Diamond (BDD) Coatings Protect Underlying Silicon in Aqueous Acidic Media–Application to the Hydrogen Evolution Reaction

    International Nuclear Information System (INIS)

    Halima, A.F.; Rana, U.A.; MacFarlane, D.R.

    2014-01-01

    Abstract: Silicon has potential application as a functional semiconductor electrode in proposed solar water splitting cells. It is abundant and has excellent photovoltaic attributes, however it is extremely susceptible to corrosion, even in the dark, resulting in the formation of an electrochemically passive oxide upon interaction with aqueous media. This work investigates the potential for conductive, inert and transparent boron doped diamond (BDD) coatings to protect p-type Silicon (p-Si). The stability and electrochemical performance of p-Si and p-Si|BDD were investigated using voltammetric techniques in 1 M H 2 SO 4 , before and after long-term exposure to the acidic medium (up to 280 hours) under no applied potential bias. Unprotected Si degraded very rapidly whilst BDD was shown to protect the underlying Si, as evident from I-V curves that indicated no increased resistance across the Si-diamond interface. Furthermore, BDD supported facile proton reduction at significantly lower onset potential for the hydrogen evolution reaction (up to -500 mV vs. SCE) compared with bare Si cathode (-850 mV vs. SCE). The activity of the BDD electrode/electrolyte interface was further improved by coating with platinum catalyst particles, to produce a p-Si|BDD|Pt strucure, which reduced the HER onset to nearly zero overpotential. Tafel analysis indicated that desirable electrochemical activity and stability were achieved for p-Si|BDD|Pt, making this a promising electrode for application in water splitting cells

  5. Evolution of the structure and hydrogen bonding configuration in annealed hydrogenated a-Si/a-Ge multilayers and layers

    International Nuclear Information System (INIS)

    Frigeri, C.; Nasi, L.; Serenyi, M.; Khanh, N.Q.; Csik, A.; Szekrenyes, Zs.; Kamaras, K.

    2012-01-01

    Complete text of publication follows. Among the present available renewable energy sources, energy harvesting from sunlight by means of photovoltaic cells is the most attractive one. In order to win over the traditional energy resources both efficiency and cost effectiveness of photovoltaic conversion must be optimized as far as possible. Efficiency is basically improved by the use of multijunction cells containing semiconductors with different band-gap. In this respect, the III-V compounds guarantee the highest efficiency, up to 41.6 %, but they are quite expensive. The latter drawback also affects other compounds like CdTe and CuIn 1-x Ga x Se 2 (CIGS). Si based solar devices have lower efficiency but are much more cost effective. They can use either crystalline or amorphous Si thin layers or Si nanoparticles. As to the thin films, amorphous Si (a-Si) is preferred to crystalline Si as it has a wider band-gap (1.7 instead of 1.1 eV) thus harvesting a larger portion of solar energy. A tandem cell is formed by using a-SiGe which has a smaller band-gap tunable between 1.1 and 1.7 eV depending on the Ge content. The best value should be 1.4 eV since the material properties seem to degrade below this value whilst the photo-conductivity drops after light soaking if the band gap exceeds 1.4 eV. A key issue of amorphous Si, Ge and SiGe is the high density of defects in the band-gap mostly due to dangling bonds whose density is particularly high (even up to 5 x10 19 cm -3 ) since the lattice is significantly disordered with distorted bond angles and lengths. This increases the probability of rupture of the Si-Si (Ge-Ge) bonds, i.e., formation of dangling bonds. Owing to the fact that hydrogen with its single electron structure can close the dangling bonds, their density can be reduced even by 4 orders of magnitude by doping with hydrogen. However, H is unstable in the host lattice. In fact, several findings showed its evolution from the thin layer upon annealing and that

  6. [NiFe] hydrogenase structural and functional models: new bio-inspired catalysts for hydrogen evolution

    International Nuclear Information System (INIS)

    Oudart, Y.

    2006-09-01

    Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)

  7. 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

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

    KAUST Repository

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

    2015-01-01

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

  9. 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...

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

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  11. 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,

  12. Fabrication of efficient TiO2-RGO heterojunction composites for hydrogen generation via water-splitting: Comparison between RGO, Au and Pt reduction sites

    Science.gov (United States)

    El-Bery, Haitham M.; Matsushita, Yoshihisa; Abdel-moneim, Ahmed

    2017-11-01

    A facile one-step synthesis approach of M/TiO2/RGO (M = Au or Pt) ternary composite by hydrothermal treatment for hydrogen generation via water-splitting was investigated. Photocurrent response measurements revealed that TiO2 (P25) nanoparticles anchored on the reduced graphene oxide (RGO) surface exhibited a p-n heterojunction interface by changing the photocurrent direction with the applied bias from reverse to forward potential. H2 evolution rate of TiO2/RGO (5 wt.%) composite was substantially enhanced by 12-fold in comparison to bare TiO2 under simulated solar light irradiation. Cyclic volatmmetry measurements manifested, that the optimized 0.3 wt.% of platinum metal loaded on TiO2/RGO composite was the most active catalytic reduction sites for hydrogen generation reaction with an initial hydrogen rate of 670 μmol h-1. This study sheds the light on the tunable semiconductor type of TiO2/RGO composite fabricated by solution mixing pathway and its merits to improve the photocatalytic activity.

  13. Searching for magnetism in hydrogenated graphene: Using highly hydrogenated graphene prepared via birch reduction of graphite oxides

    Czech Academy of Sciences Publication Activity Database

    Eng, A.Y.S.; Poh, H. L.; Šaněk, F.; Maryško, Miroslav; Matějková, Stanislava; Šofer, Z.; Pumera, M.

    2013-01-01

    Roč. 7, č. 7 (2013), s. 5930-5939 ISSN 1936-0851 R&D Projects: GA ČR GA13-20507S Institutional support: RVO:68378271 ; RVO:61388963 Keywords : hydrogenated graphene * graphane * graphite oxide * ferromagnetism Subject RIV: BM - Solid Matter Physics ; Magnetism; CF - Physical ; Theoretical Chemistry (UOCHB-X) Impact factor: 12.033, year: 2013

  14. 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 the present study, using Density Functional Theory (DFT) calculations, we show that several widely available low index crystal facets on Ni2P have better properties for a high catalytic activity. DFT calculations were used to identify moderately bonding nickel bridge sites and nickel hollow sites for hydrogen...... adsorption and to calculate barriers for the Tafel pathway. The investigated surfaces in this study were the (10 (1) over bar0), ((1) over bar(1) over bar 20), (11 (2) over bar0), (11 (2) over bar1) and (0001) facets of the hexagonal Ni2P crystal. In addition to the DFT results, we present experiments on Ni2...

  15. [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)

  16. 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

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

    International Nuclear Information System (INIS)

    Trasatti, S.

    1975-01-01

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

  18. A coarse grained description of time evolution: Irreversible state reduction and time-energy relation

    International Nuclear Information System (INIS)

    Bonifacio, R.; Milan Univ.

    1983-05-01

    We show that a proper coarse-grained description of time evolution leads to a finite difference equation with step tau for the density operator. This implies state reduction to the diagonal form in the energy representation and a quasi ergodic behaviour of quantum mechanical ensemble averages. An intrinsic time-energy relation tauΔE>=(h/2π)/2 is proposed, and its equivalence to a time quantization is discussed. (author)

  19. Defect engineering: reduction effect of hydrogen atom impurities in HfO2-based resistive-switching memory devices

    International Nuclear Information System (INIS)

    Kim, Seonghyun; Park, Jubong; Jung, Seungjae; Lee, Wootae; Shin, Jungho; Hwang, Hyunsang; Lee, Daeseok; Woo, Jiyong; Choi, Godeuni

    2012-01-01

    In this study, we propose a new and effective methodology for improving the resistive-switching performance of memory devices by high-pressure hydrogen annealing under ambient conditions. The reduction effect results in the uniform creation of oxygen vacancies that in turn enable forming-free operation and afford uniform switching characteristics. In addition, H + and mobile hydroxyl (OH − ) ions are generated, and these induce fast switching operation due to the higher mobility compared to oxygen ions. Defect engineering, specifically, the introduction of hydrogen atom impurities, improves the device performance for metal–oxide-based resistive-switching random access memory devices. (paper)

  20. 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.)

  1. Electrochemical preparation and characteristics of Ni-Co-LaNi{sub 5} composite coatings as electrode materials for hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-02-15

    Electrocatalytic activity for the hydrogen evolution reaction on Ni-Co-LaNi{sub 5} composite electrodes prepared by electrochemical codeposition technique was evaluated. The relationship between the current density for hydrogen evolution reaction and the amount of LaNi{sub 5} particles in Ni-Co baths is like the well-known 'volcano plot'. The Surface morphology and microstructure of Ni-Co-LaNi{sub 5} coatings were determined by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The kinetic parameters were determined from electrochemical steady-state Tafel polarization and electrochemical impedance spectroscopy technology in 1 M NaOH solution. The values obtained for the apparent energies of activation are 32.48, 46.29 and 57.03 kJ mol{sup -1} for the Ni-Co-LaNi{sub 5}, Ni-Co and Ni electrodes, respectively. The hydrogen evolution reaction on Ni-Co-LaNi{sub 5} proceeds via Volmer-Tafel reaction route with the mixed rate determining characteristics. The composite coating Ni-Co-LaNi{sub 5} is catalytically more active than Ni and Ni-Co electrodes due to the increase in its real surface areas and the decrease in the apparent free energy of activation caused by the electrocatalytic synergistic effect of the Ni-Co alloys and the hydrogen storage intermetallic particles on the electrode surface.

  2. Electrochemical preparation and characteristics of Ni-Co-LaNi5 composite coatings as electrode materials for hydrogen evolution

    International Nuclear Information System (INIS)

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-01-01

    Electrocatalytic activity for the hydrogen evolution reaction on Ni-Co-LaNi 5 composite electrodes prepared by electrochemical codeposition technique was evaluated. The relationship between the current density for hydrogen evolution reaction and the amount of LaNi 5 particles in Ni-Co baths is like the well-known 'volcano plot'. The Surface morphology and microstructure of Ni-Co-LaNi 5 coatings were determined by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The kinetic parameters were determined from electrochemical steady-state Tafel polarization and electrochemical impedance spectroscopy technology in 1 M NaOH solution. The values obtained for the apparent energies of activation are 32.48, 46.29 and 57.03 kJ mol -1 for the Ni-Co-LaNi 5 , Ni-Co and Ni electrodes, respectively. The hydrogen evolution reaction on Ni-Co-LaNi 5 proceeds via Volmer-Tafel reaction route with the mixed rate determining characteristics. The composite coating Ni-Co-LaNi 5 is catalytically more active than Ni and Ni-Co electrodes due to the increase in its real surface areas and the decrease in the apparent free energy of activation caused by the electrocatalytic synergistic effect of the Ni-Co alloys and the hydrogen storage intermetallic particles on the electrode surface

  3. 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.

  4. Hydrogen systems : a Canadian strategy for greenhouse gas reduction and economic growth

    International Nuclear Information System (INIS)

    2005-01-01

    Rising concerns about the depletion of fossil fuels and climate change have led to the search for new energy sources. This paper outlines the mission of the Canadian Hydrogen Association, which is to build on Canada's energy resource base and expertise in hydrogen technologies in order to deploy sustainable hydrogen energy systems. Basic strategies needed to develop hydrogen systems in Canada were outlined, with specific reference to the establishment of low cost energy sources with low life-cycle emissions. The current hydrogen infrastructure produces marginal life-cycle emissions benefits, particularly when compared with improvements in technologies expected in the next 10 years. It was noted that regional development of hydrogen systems was likely to be an effective strategy, due to high transportation costs. Several potential locations were discussed for the development of a hydrogen energy infrastructure. Opportunities arising from hydrogen vehicle penetration of consumer markets and the broad commercialization of fuel cells were examined. Feasible transition strategies were reviewed, to be built in the near term around pathways such as hydrogen internal combustion engines and fuel cell vehicles designed for high-value niche applications. Strategies addressing the preparation of the market to express the value proposition for hydrogen were discussed, with reference to the fact that the existing energy market places no value on environmental factors. Several recommendations were made to conclude the discussion, and included: the necessity of government action to establish national goals; the creation of a stakeholder base for hydrogen systems; a government and industry partnership towards the development of a near-term commercialization plan; and the establishment of a long-term direction for the development of hydrogen systems in terms of advancing technology and public education. refs., tabs., figs

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

    International Nuclear Information System (INIS)

    Ahmed, Jahangeer; Mao, Yuanbing

    2016-01-01

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

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

    International Nuclear Information System (INIS)

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

    1986-01-01

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

  7. 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.

  8. 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.

  9. Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

    Science.gov (United States)

    Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

    2018-05-22

    Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

  10. 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.

  11. 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)

  12. 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.

  13. 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.

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

    KAUST Repository

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

    2017-01-01

    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.

  15. Hydrothermal synthesis of core–shell TiO_2 to enhance the photocatalytic hydrogen evolution

    International Nuclear Information System (INIS)

    Jiang, Jinghui; Zhou, Han; Zhang, Fan; Fan, Tongxiang; Zhang, Di

    2016-01-01

    Graphical abstract: Core–shell TiO_2 with interior cavity was synthesized by a hydrothermal approach to enhance the photocatalytic performance. - Highlights: • Core–shell TiO_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_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.

  16. WS{sub 2} nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yan-Ru; Hu, Wen-Hui [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2015-11-01

    WS{sub 2} nanosheets (WS{sub 2} NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS{sub 2} (E-WS{sub 2}). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS{sub 2} consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS{sub 2}, with a low overpotential of 80 mV and high current density (10 mA cm{sup −2}, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS{sub 2} for HER. • E-WS{sub 2} shows the better electrocatalytic activity than bulk WS{sub 2}. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  17. Dealloyed Pt3Co nanoparticles with higher geometric strain for superior hydrogen evolution reaction

    Science.gov (United States)

    Saquib, Mohammad; Halder, Aditi

    2018-06-01

    In the present work, the effect of surface strain in the carbon supported Pt3Co dealloy catalyst towards hydrogen evolution reaction (HER) has been reported. Dealloying process is adopted to generate the geometric strain in Pt3Co/C alloy by preferential dissolution of non-noble metal (Co) from the alloy. The developed geometric strain has been estimated by different microstructural characterization techniques. Electrochemical studies showed that the highest current density for HER was obtained for Pt3Co/C dealloy catalyst and it was nearly 2 and 5 times higher than Pt3Co/C alloy and Pt/C respectively. Tafel slope for HER was improved from 49 (Pt/C) to 34 mV dec-1 (Pt3Co/C dealloy), indicating that the surface strain plays important role in the improvement of the catalytic activity of Pt3Co catalyst. The chronoamperometry data, LSV curves and ECSA values before and after chronoamperometry confirmed that Pt3Co/C dealloy catalyst was a stable as well as a durable electrocatalyst for HER.

  18. Electrolytic Synthesis of Ni-W-MWCNT Composite Coating for Alkaline Hydrogen Evolution Reaction

    Science.gov (United States)

    Elias, Liju; Hegde, A. Chitharanjan

    2018-03-01

    Nickel-tungsten multi-walled carbon nanotube (Ni-W-MWCNT) composite films were fabricated by an electrodeposition technique, and their electrocatalytic activity toward hydrogen evolution reaction (HER) was studied. Ni-W-MWCNT composite films with a homogeneous dispersion of MWCNTs were deposited from an optimal Ni-W plating bath containing functionalized MWCNTs, under galvanostatic condition. The presence of functionalized MWCNT was found to enhance the induced codeposition of the reluctant metal W and resulted in a W-rich composite coating with improved properties. The electrocatalytic behaviors of Ni-W-MWCNT composite coating toward HER were studied by cyclic voltammetry (CV) and chronopotentiometry techniques in 1.0 M KOH medium. Further, Tafel polarization and electrochemical impedance spectroscopy (EIS) studies were carried out to establish the kinetics of HER on the alloy and composite electrodes. The experimental results revealed that the addition of MWCNTs (having a diameter of around 10-15 nm) into the alloy plating bath has a significant effect on the electrocatalytic behavior of Ni-W alloy deposit. The Ni-W-MWCNT composite coating was found to show better HER activity than the conventional Ni-W alloy coating. The enhanced electrocatalytic activity of Ni-W-MWCNT composite coating is attributed to the MWCNT intersticed in the deposit matrix, evidenced by surface morphology, composition and phase structure of the coating through SEM, EDS and XRD analyses, respectively.

  19. Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst.

    Science.gov (United States)

    Chen, Zhe; Lu, Jinfeng; Ai, Yuejie; Ji, Yongfei; Adschiri, Tadafumi; Wan, Lijun

    2016-12-28

    Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H 2 SO 4 solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications.

  20. 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.

  1. Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

    Science.gov (United States)

    Li, Maoguo; Yu, Muping; Li, Xiang

    2018-05-01

    Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

  2. WS_2 nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Han, Guan-Qun; Liu, Yan-Ru; Hu, Wen-Hui; Dong, Bin; Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

    2015-01-01

    WS_2 nanosheets (WS_2 NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS_2 (E-WS_2). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS_2 consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS_2, with a low overpotential of 80 mV and high current density (10 mA cm"−"2, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS_2 for HER. • E-WS_2 shows the better electrocatalytic activity than bulk WS_2. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

  3. Extended space expectation values of position related operators for hydrogen-like quantum system evolutions

    International Nuclear Information System (INIS)

    Kalay, Berfin; Demiralp, Metin

    2014-01-01

    The expectation value definitions over an extended space from the considered Hilbert space of the system under consideration is given in another paper of the second author in this symposium. There, in that paper, the conceptuality rather than specification is emphasized on. This work uses that conceptuality to investigate the time evolutions of the position related operators' expectation values not in its standard meaning but rather in a new version of the definition over not the original Hilbert space but in the space obtained by extensions via introducing the images of the given initial wave packet under the positive integer powers of the system Hamiltonian. These images may not be residing in the same space of the initial wave packet when certain singularities appear in the structure of the system Hamiltonian. This may break down the existence of the integrals in the definitions of the expectation values. The cure is the use of basis functions in the abovementioned extended space and the sandwiching of the target operator whose expectation value is under questioning by an appropriately chosen operator guaranteeing the existence of the relevant integrals. Work specifically focuses on the hydrogen-like quantum systems whose Hamiltonians contain a polar singularity at the origin

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

    International Nuclear Information System (INIS)

    Park, Hyounmyung; Encinas, Andrew; Fokwa, Boniface P.T.; Scheifers, Jan P.; Zhang, Yuemei

    2017-01-01

    Molybdenum-based materials have been considered as alternative catalysts to noble metals, such as platinum, for the hydrogen evolution reaction (HER). We have synthesized four binary bulk molybdenum borides Mo_2B, α-MoB, β-MoB, and MoB_2 by arc-melting. All four phases were tested for their electrocatalytic activity (linear sweep voltammetry) and stability (cyclic voltammetry) with respect to the HER in acidic conditions. Three of these phases were studied for their HER activity and by X-ray photoelectron spectroscopy (XPS) for the first time; MoB_2 and β-MoB show excellent activity in the same range as the recently reported α-MoB and β-Mo_2C phases, while the molybdenum richest phase Mo_2B show significantly lower HER activity, indicating a strong boron-dependency of these borides for the HER. In addition, MoB_2 and β-MoB show long-term cycle stability in acidic solution. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

    Science.gov (United States)

    Chen, Qianjin; Luo, Long

    2018-04-17

    We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

  6. 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.

  7. 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.

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

    KAUST Repository

    Ivanov, Ivan; Ahn, YongTae; Poirson, Thibault; Hickner, Michael A.; Logan, Bruce

    2017-01-01

    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.

  9. Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Kunchan; Xia, Ming [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Xiao, Tao [2nd Xiangya Hospital, Central South University, Changsha 410011 (China); Lei, Ting, E-mail: tlei@mail.csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Yan, Weishan [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China)

    2017-01-15

    Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.

  10. Electrocatalytic hydrogen evolution under densely buffered neutral pH conditions

    KAUST Repository

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2015-01-01

    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.

  11. Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Wang, Kunchan; Xia, Ming; Xiao, Tao; Lei, Ting; Yan, Weishan

    2017-01-01

    Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.

  12. 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.

  13. Reduction of greenhouse gas emission on a medium-pressure boiler using hydrogen-rich fuel control

    International Nuclear Information System (INIS)

    Hsieh, S.-C.; Jou, Chih-Ju G.

    2007-01-01

    The increasing emission of greenhouse gases from the combustion of fossil fuel is believed to be responsible for global warming. A study was carried out to probe the influence of replacing fuel gas with hydrogen-rich refinery gas (R.G.) on the reduction of gas emission (CO 2 and NO x ) and energy saving. Test results show that the emission of CO 2 can be reduced by 16.4% annually (or 21,500 tons per year). The NO x emission can be 8.2% lower, or 75 tons less per year. Furthermore, the use of refinery gas leads to a saving of NT$57 million (approximately US$1.73 million) on fuel costs each year. There are no CO 2 , CO, SO x , unburned hydrocarbon, or particles generated from the combustion of added hydrogen. The hydrogen content in R.G. employed in this study was between 50 and 80 mol%, so the C/H ratio of the feeding fuel was reduced. Therefore, the use of hydrogen-rich fuel has practical benefits for both energy saving and the reduction of greenhouse gas emission

  14. Application of microscopy methods to the understanding of mechanisms involved in ilmenite reduction by hydrogen

    International Nuclear Information System (INIS)

    De Vries, M.; Grey, I.; Fitzgerald, J.

    2003-01-01

    Full text: Titania pigment is one of the major drivers of the mineral sands industry with production of over 4 million tpa in 2002 for paints, plastics, paper and ceramics applications. The main feedstock for titania pigment production is ilmenite, FeTiO 3 . It is used either directly or after it has been upgraded to a higher titania content. The major commercial upgrading processes are electro smelting (titania slag) or high temperature char reduction followed by iron removal (synthetic rutile SR). Future ilmenite upgrading processes are likely to use low temperature hydrogen reduction according to reaction, followed by aeration of the metallic iron and acid leaching to produce a high grade SR (Nicholson et al, 2000). The commercial application of such a process requires a detailed knowledge of the kinetics of reaction. FeTiO 3 + H 2 = Fe(m) + TiO 2 + H 2 O. The kinetics of ilmenite reduction has been studied at CSIRO Minerals using a specially designed thermogravimetric apparatus built around a Cahn pressurised symmetrical beam balance. The kinetics have been measured as a function of different operating parameters such as temperature, gas velocity and pressure. The parameters were set so as to minimise mass transport effects and increase chemical reaction control and to ensure the reduction kinetics are outside the gas starvation region. Small samples were used that had been sintered at close to melting point to form large grains with low unconnected porosity. High flow rates of reactant gas were also used. The application of a range of microscopy techniques to the reduced samples at various stages of reaction conversion has been critical to the development of an understanding of the reaction mechanisms. From analysis of TEM, IFESEM and optical microscopy results it appears that initially, chemical reaction is rate controlling at the surface and as the reaction proceeds topochemically inwards then diffusion mechanisms increase their control. Reaction proceeds

  15. 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. © 2016 The Author(s). Evolution published by Wiley Periodicals, Inc. on behalf of The Society for the Study of Evolution.

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

    Science.gov (United States)

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

    2018-05-01

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

  17. 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.

  18. 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. Copyright © 2011. Published by Elsevier B.V.

  19. Macroporous Inverse Opal-like MoxC with Incorporated Mo Vacancies for Significantly Enhanced Hydrogen Evolution.

    Science.gov (United States)

    Li, Feng; Zhao, Xianglong; Mahmood, Javeed; Okyay, Mahmut Sait; Jung, Sun-Min; Ahmad, Ishfaq; Kim, Seok-Jin; Han, Gao-Feng; Park, Noejung; Baek, Jong-Beom

    2017-07-25

    The hydrogen evolution reaction (HER) is one of the most important pathways for producing pure and clean hydrogen. Although platinum (Pt) is the most efficient HER electrocatalyst, its practical application is significantly hindered by high-cost and scarcity. In this work, an Mo x C with incorporated Mo vacancies and macroporous inverse opal-like (IOL) structure (Mo x C-IOL) was synthesized and studied as a low-cost efficient HER electrocatalyst. The macroporous IOL structure was controllably fabricated using a facile-hard template strategy. As a result of the combined benefits of the Mo vacancies and structural advantages, including appropriate hydrogen binding energy, large exposed surface, robust IOL structure and fast mass/charge transport, the synthesized Mo x C-IOL exhibited significantly enhanced HER electrocatalytic performance with good stability, with performance comparable or superior to Pt wire in both acidic and alkaline solutions.

  20. 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)

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

    Science.gov (United States)

    Verhaart, Marcel R A; Bielen, Abraham A M; van der Oost, John; Stams, Alfons J M; Kengen, Servé 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 promising is this respect. In addition to the high polysaccharide-hydrolysing capacities of many of these organisms, an important advantage is their ability to use most of the reducing equivalents (e.g. NADH, reduced ferredoxin) formed during glycolysis for the production of hydrogen, enabling H2/hexose ratios of between 3.0 and 4.0. So, despite the fact that the hydrogen-yielding reactions, especially the one from NADH, are thermodynamically unfavourable, high hydrogen yields are obtained. In this review we focus on three different mechanisms that are employed by a few model organisms, viz. Caldicellulosiruptor saccharolyticus and Thermoanaerobacter tengcongensis, Thermotoga maritima, and Pyrococcus furiosus, to efficiently produce hydrogen. In addition, recent developments to improve hydrogen production by hyperthermophilic and extremely thermophilic bacteria and archaea are discussed.

  2. The hydrogen energy economy: its long-term role in greenhouse gas reduction

    Energy Technology Data Exchange (ETDEWEB)

    Geoff Dutton; Abigail Bristow; Matthew Page; Charlotte Kelly; Jim Watson; Alison Tetteh [CCLRC Rutherford Appleton Laboratory, Didcot (United Kingdom). Energy Research Unit (ERU)

    2005-01-15

    The potential contribution and viability of the hydrogen energy economy towards reducing UK carbon dioxide emissions in the time horizon to 2050 has been assessed using a quantitative model of the UK energy system in the context of a set of diverse socio-economic scenarios. It is argued that different sets of prevailing circumstances are likely to result in very different opportunities for hydrogen and hence very different transition pathways and ultimate penetration levels. The decision on whether to strategically encourage a transition to the hydrogen economy and the ultimate environmental benefits of such a transformation will depend on the outcome of a number of important political and social decisions. These include the acceptability of large scale carbon dioxide sequestration (hydrogen derived from fossil fuels), decisions about land-use (hydrogen from biomass), a possible doubling (or more) of the current electricity production capacity with a high penetration of renewable electricity (hydrogen from electrolysis of water), and/or the public acceptability of a large scale nuclear renaissance (hydrogen from electrolysis of water or from thermo-chemical cycles). Any rapid transition to a fully developed hydrogen economy would require a contribution from at least some and possibly all of these sources. Such a transition could result in a marked decrease in carbon dioxide emissions over the long term, but might even result in increased emissions within the shorter term (due to the initial use of hydrogen derived from fossil fuels without carbon dioxide sequestration or from the bulk grid electricity supply resulting in increased load factors and lifetimes of old fossil-fired power plant to meet the increased overall demand). 47 refs., 45 figs., 19 tabs., 3 apps.

  3. Reduction of Compton background from hydrogen in prompt gamma-ray analysis by multiple photon detection

    International Nuclear Information System (INIS)

    Toh, Y.; Oshima, M.; Kimura, A.; Koizumi, M.; Furutaka, K.; Hatsukawa, Y.

    2008-01-01

    Low-energy photons produced by the Compton scattering from hydrogen increase the background in the lower-energy region of the gamma-ray spectrum. This results in an increase in the detection limit for trace elements. In multiple photon detection prompt gamma-ray analysis (MPGA), only those elements that simultaneously emit two or more prompt gamma-rays, which have cascade relation and are emitted within a short interval, can be measured. Therefore, the influence of hydrogen can be reduced. In this study, standard polymer and food samples are measured. The hydrogen background is reduced in MPGA. (author)

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

    Science.gov (United States)

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

    2017-04-05

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

  5. Non-noble metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution

    International Nuclear Information System (INIS)

    Song, Jun-Ling; Zhang, Jian-Han; Mao, Jiang-Gao

    2016-01-01

    We reported the synthesis and crystal structures of alkali metal and alkali-earth metal phosphite, namely, CsV 2 (H 3 O)(HPO 3 ) 4 (1), and Ba 3 V 2 (HPO 3 ) 6 (2). Both compounds were prepared by hydrothermal reactions and feature unique new structures. They both exhibit 3D complicated frameworks based on VO 6 octahedra which are connected by HPO 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 2 (H 3 O) (HPO 3 ) 4 (1) is a new 3,3,3,4,5-connected network with the Schläfli symbol of {4.6 2 } 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 2 (H 3 O)(HPO 3 ) 4 suggest a +3 oxidation state of the vanadium ions in compound 1. Photocatalytic performance was evaluated by photocatalytic H 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 2 (H 3 O)(HPO 3 ) 4 and Ba 3 V 2 (HPO 3 ) 6 , are reported. • CsV 2 (H 3 O)(HPO 3 ) 4 and Ba 3 V 2 (HPO 3 ) 6 feature complicated 3D framework structures with different channels. • CsV 2 (H 3 O)(HPO 3 ) 4 and Ba 3 V 2 (HPO 3 ) 6 exhibit strong and broad absorptions in the visible and Near IR region. • Photocatalytic properties of CsV 2 (H 3 O)(HPO 3 ) 4 and Ba 3 V 2 (HPO 3 ) 6 are investigated. • The magnetic measurement of CsV 2 (H 3 O)(HPO 3 ) 4 was performed in the temperature range of 2–300 K.

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

    Science.gov (United States)

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

    2016-03-01

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

  7. The Validation of Vapor Phase Hydrogen Peroxide Microbial Reduction for Planetary Protection and a Proposed Vacuum Process Specification

    Science.gov (United States)

    Chung, Shirley; Barengoltz, Jack; Kern, Roger; Koukol, Robert; Cash, Howard

    2006-01-01

    The Jet Propulsion Laboratory, in conjunction with the NASA Planetary Protection Officer, has selected the vapor phase hydrogen peroxide sterilization process for continued development as a NASA approved sterilization technique for spacecraft subsystems and systems. The goal is to include this technique, with an appropriate specification, in NPR 8020.12C as a low temperature complementary technique to the dry heat sterilization process.To meet microbial reduction requirements for all Mars in-situ life detection and sample return missions, various planetary spacecraft subsystems will have to be exposed to a qualified sterilization process. This process could be the elevated temperature dry heat sterilization process (115 C for 40 hours) which was used to sterilize the Viking lander spacecraft. However, with utilization of such elements as highly sophisticated electronics and sensors in modern spacecraft, this process presents significant materials challenges and is thus an undesirable bioburden reduction method to design engineers. The objective of this work is to introduce vapor hydrogen peroxide (VHP) as an alternative to dry heat microbial reduction to meet planetary protection requirements.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 properties. Our goal for this study was to determine the minimum VHP process conditions to achieve microbial reduction levels acceptable for planetary protection.

  8. Facile Synthesis of In–Situ Nitrogenated Graphene Decorated by Few–Layer MoS2 for Hydrogen Evolution Reaction

    International Nuclear Information System (INIS)

    Dai, Xiaoping; Li, Zhanzhao; Du, Kangli; Sun, Hui; Yang, Ying; Zhang, Xin; Ma, Xingyu; Wang, Jie

    2015-01-01

    Graphical abstract: In–situ nitrogenated graphene–few layer MoS 2 composites are fabricated by combinating chemical and hydrothermal reduction. The resulting MoS 2 /N–rGO–HA by N 2 H 4 ·H 2 O and NH 3 ·H 2 O as co-reductant exhibits high activity and remarkable stability for hydrogen evolution reaction (HER). The excellent electro-catalytic performance is ascribed to the synergistic effects, confinement effects and highly dispersed MoS 2 nanosheets on N-doping rGO. Display Omitted -- Highlights: • In–situ nitrogenated graphene–few layer MoS 2 composites are fabricated by combinating chemical and hydrothermal co-reduction. • The resulting MoS 2 /N–rGO–HA exhibits high activity and remarkable stability for HER. • The excellent electro-catalytic performance is ascribed to the synergistic effects, confinement effects and highly dispersed MoS 2 nanosheets on N-doping rGO. -- Abstract: A facile one–step synthetic strategy by combinating chemical and hydrothermal reduction of graphene oxide and Mo precursor is proposed to fabricate in–situ nitrogenated graphene–few layer MoS 2 composite (MoS 2 /N–rGO–HA) for hydrogen evolution reaction (HER). The N–doping graphene nanosheets and highly dispersed MoS 2 nanosheets by ammonia and hydrozine as co–reductant have greatly promoted the N content, concentrations of pyridinic and graphitic N, the electron transport in electrodes, and assure high catalytic efficiency. The MoS 2 /N–rGO–HA composite exhibits extremely high activity in acidic solutions with a small onset potential of 100 mV and Tafel slope of 45 mV/dec, as well as a current density about 32.4 mA cm −2 at overpotential about 0.2 V. Moreover, such MoS 2 /N–rGO–HA electroncatalyst also shows an excellent stability during 1000 cycles with negligible loss of the cathodic current. This facile hydrothermal method could provide a promising strategy for the synthesis of in–situ nitrogen–doping graphene sheets and few

  9. On the evolution of morphology of zirconium sponge during reduction and distillation

    International Nuclear Information System (INIS)

    Kapoor, K.; Padmaprabu, C.; Nandi, D.

    2008-01-01

    High purity zirconium metal is produced by magnesio-thermic reduction of zirconium tetrachloride followed by vacuum distillation. The reduction process is carried out in a batch giving metal sponge and magnesium chloride in the reduced mass. The sponge is purified to using by vacuum distillation. The morphology of the sponge formed during the reduction and its influence on further processing has significant importance. In the present study, a detailed investigation involving evolution of the morphology of sponge particles and its implication during the vacuum distillation was carried out. The study of the microstructure was done using scanning electron microscopy and X-ray diffraction. It is observed that the nascent sponge formed is highly unstable which transforms to a needle-like morphology almost immediately, which further transforms to rounded and finally to a bulk shape. Faceting of the surface and needle-shape formation were observed in these particles, this is probably due to anisotropy in the surface energy. The morphology of the sponge formed during the reduction influences the distillation process. The fine needle-like shape sponge morphology leads to particle ejection, which is explained to be due to curvature effect. This is responsible for the formation of unwanted mass during distillation. XRD line broadening analysis indicates that the individual sponge particles are free from structural defects (dislocation) and are nearly single crystalline in nature

  10. Performances of helium, neon and argon glow discharges for reduction of fuel hydrogen retention in tungsten, stainless steel and graphite

    International Nuclear Information System (INIS)

    Hino, T.; Yamauchi, Y.; Kimura, Y.; Matsumoto, A.; Nishimura, K.; Ueda, Y.

    2012-11-01

    It is quite important to investigate the performance of glow discharge conditionings for controls of in-vessel tritium (T) inventory and hydrogen recycling. For this purpose, first, the deuterium (D) retentions in tungsten (W), graphite (C) and stainless steel (SS) were measured. The retention in W was not small as expected, several times larger than that of SS, although the retention in SS was one order smaller than that of C. Such the large retention in W is owing to the growth of rough surface structure produced by plasma irradiations. For reduction of deuterium retention in W, SS and C, second, inert gas (He, Ne, Ar) glow discharges were conducted under the same condition, and these performances were compared. The removal ratio of deuterium retention was highest in He discharge, and lowest in Ar discharge. These values are well explained by the numerical analyses using SRIM code. The removal ratios for SS and C were significantly large, but quite small for W. This reason is again owing to the rough surface structure in W. For W, thirdly, the hydrogen isotope exchange and the wall baking experiments were conducted. It is found that the wall backing with a temperature higher than 700 K can well reduce the retention, and the hydrogen isotope exchange using deuterium glow discharge is also useful to reduce the tritium retention in the wall. The present results significantly contribute to control the fuel hydrogen retention and to reduce the in-vessel tritium inventory in fusion reactors. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-15

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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  13. Time evolution of cascade processes of muonic atoms in hydrogen-helium mixtures

    International Nuclear Information System (INIS)

    Bystritskij, V.; Czaplinski, W.; Filipowicz, M.; Gula, E.; Popov, N.

    1999-01-01

    Time dependence of population of muonic hydrogen states in hydrogen-helium mixtures is calculated for principal quantum number n. Number of muons transferred to helium nuclei is also determined. Dependence of population of the ground state of muonic hydrogen q ls He on time and target density and helium concentration is also considered. The results are in agreement with recent experimental data. The comparison of the calculated yield of K lines of x-ray in pure hydrogen and deuterium with experimental data indicates on essential role of Coulomb de-excitation process. Possible Stark mixing is also analyzed

  14. Influence of hydrogen reduction on photoelectro-chemical behavior of anodic oxidized n-TiO2 layers

    Energy Technology Data Exchange (ETDEWEB)

    Hartig, K J; Getoff, N

    1983-07-01

    The behavior of polycrystalline n-TiO2 photoanodes produced by anodic oxidation of Ti metal foils and subsequently reduced in hydrogen atmosphere at various temperatures and different times was investigated. The employed methods for their characterization were: scanning electron microscopy, X-ray diffraction, thickness determination, open-circuit voltage and capacitance/voltage studies as well as photoelectrochemical measurements. The reduction process results in an increase of oxygen deficiencies and a decrease of the amount of recombination centers and of grain-boundary energy barriers between the crystallites. All these parameters lead to a significant increase of the photoefficiency. The best photoanodes were obtained when the anodically oxidized samples were reduced under hydrogen at 800-850 C for 15 min (conversion of anatase to rutile crystal structures). 17 references.

  15. Experimental investigation of hydrogen energy share improvement in a compression ignition engine using water injection and compression ratio reduction

    International Nuclear Information System (INIS)

    Chintala, V.; Subramanian, K.A.

    2016-01-01

    Highlights: • Energy efficiency (EE) increased with increase in hydrogen (H_2) energy share. • H_2 energy share increased from 19% to 79% with combined CR reduction and water. • In-cylinder temperature decreased significantly with water addition and CR reduction. • HC, CO, smoke and NO_x emissions with water and CR are lower than base diesel. - Abstract: This study deals with the effect of water addition on enhancement of maximum hydrogen energy share in a compression ignition engine (7.4 kW rated power at 1500 rpm) under dual fuel mode. The specific water consumption (SWC) was varied from 130 to 480 g/kW h in step of 70 g/kW h using manifold and port injection methods. Subsequently, the combined effect of reduction of compression ratio (CR) of the engine (from 19.5:1 (base) to 16.5:1 and 15.4:1) along with water addition on further enhancement of hydrogen energy share is investigated. The hydrogen energy share was limited to 18.8% with conventional dual fuel mode due to knocking. However, the energy share increased to 66.5% with water addition (maximum SWC: 480 g/kW h), and 79% with combined control strategies (SWC of 340 g/kW h and CR reduction to 16.5:1). Thermal efficiency of the engine under water added dual fuel mode is higher than base diesel mode (single fuel mode), but it is lower than the conventional dual fuel mode without water. The efficiency of the engine with reduced CR and water addition is lower than the conventional dual fuel mode, however at the CR of 16.5:1 and SWC of 340 g/kW h, the efficiency is comparable with base diesel mode efficiency. Hydrocarbon, carbon monoxide, smoke, and oxides of nitrogen emissions of the engine with water addition (340 g/kW h) and CR reduction (to 16.5:1) decreased significantly as compared to base diesel mode, but slightly higher than conventional dual fuel mode.

  16. Microstructure and kinetics evolution in MgH2–TiO2 pellets after hydrogen cycling

    International Nuclear Information System (INIS)

    Mirabile Gattia, D.; Di Girolamo, G.; Montone, A.

    2014-01-01

    Highlights: • MgH 2 was ball milled with TiO 2 anatase phase and expanded graphite to prepare pellets. • Different pellets have been prepared at different compression load. • Pellets were repeatedly cycled under hydrogen pressure to simulate tank exercise and verify their stability. • The compression load highly affects the stability of the pellets to cycling. • Microstructural evolution of the particles due to cycling have been observed. - Abstract: The interest in Mg-based hydrides for solid state hydrogen storage is associated to their capability to reversibly absorb and desorb large amounts of hydrogen. In this work MgH 2 powder with 5 wt.% TiO 2 was ball milled for 10 h. The as-milled nanostructured powder was enriched with 5 wt.% of Expanded Natural Graphite (ENG) and then compacted in cylindrical pellets by cold pressing using different loads. Both the powder and the pellets were subjected to kinetic and thermodynamic tests using a Sievert’s type gas reaction controller, in order to study the microstructural and kinetic changes which took place during repeated H 2 absorption and desorption cycles. The pellets exhibited good kinetic performance and durability, even if the pressure of compaction revealed to be an important parameter for their mechanical stability. Scanning Electron Microscopy observations of as-prepared and cycled pellets were carried out to investigate the evolution of their microstructure. In turn the phase composition before and after cycling was analyzed by X-ray diffraction

  17. Treatment of simulated high-level radioactive waste with formic acid: Bench-scale study on hydrogen evolution

    International Nuclear Information System (INIS)

    Hsu, C.L.W.; Ritter, J.A.

    1996-01-01

    At the Savannah River Site, the Defense Waste Processing Facility (DWPF) was constructed to vitrify high-level radioactive liquid waste in borosilicate glass for permanent storage. Formic acid, which serves as both an acid and a reducing agent, is used to treat the washed alkaline sludge during melter feed preparation primarily to improve the processability of the feed and to reduce mercury to its zero state for steam stripping. The high-level sludge is composed of many transition metal hydroxides. Among them, there are small quantities of platinum group metals. During the treatment of simulated sludge with formic acid, significant amounts of hydrogen were generated when the platinum group metals were included in the sludge. Apparently the noble metals in the sludge were reduced to their zero states and caused formic acid to decompose catalytically into hydrogen and carbon dioxide, usually with an induction period. The production of hydrogen gas presented the DWPF with a safety issue. Therefore, the objective of this research was to gain a fundamental understanding of what controlled the hydrogen evolution so that a practical solution to the safety issue could be obtained. A bench-scale parametric study revealed the following: increasing the amount of formic acid added to the sludge increased the hydrogen generation rate dramatically; once the catalysts were activated, the hydrogen generation rate decreased significantly with a lowering of the temperature of the sludge; the relative catalytic activities of the noble metals in the sludge decreased in the following order: rhodium > ruthenium much-gt palladium; ammonium ions were generated catalytically from the reaction between formic acid and nitrate; and when present, the noble metals caused higher upward drifts of the sludge pH

  18. Experimental reduction of simulated lunar glass by carbon and hydrogen and implications for lunar base oxygen production

    International Nuclear Information System (INIS)

    Mckay, D.S.; Morris, R.V.; Jurewicz, A.J.

    1991-01-01

    The most abundant element in lunar rocks and soils is oxygen which makes up approximately 45 percent by weight of the typical lunar samples returned during the Apollo missions. This oxygen is not present as a gas but is tightly bound to other elements in mineral or glass. When people return to the Moon to explore and live, the extraction of this oxygen at a lunar outpost may be a major goal during the early years of operation. Among the most studied processes for oxygen extraction is the reduction of ilmenite by hydrogen gas to form metallic iron, titanium oxide, and oxygen. A related process is proposed which overcomes some of the disadvantages of ilmenite reduction. It is proposed that oxygen can be extracted by direct reduction of native lunar pyroclactic glass using either carbon, carbon monoxide, or hydrogen. In order to evaluate the feasibility of this proposed process a series of experiments on synthetic lunar glass are presented. The results and a discussion of the experiments are presented

  19. Carbon and Mo transformations during the synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction

    Science.gov (United States)

    Wang, Haiyan; Liu, Shida; Liu, Bing; Montes, Vicente; Hill, Josephine M.; Smith, Kevin J.

    2018-02-01

    The synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction is reported. Petroleum coke (petcoke) was activated with KOH at 800 °C to obtain high surface area microporous activated petcoke (APC; 2000 m2/g). The APC was wet impregnated with ammonium heptamolybdate (AHM: 10 wt% Mo), dried and reduced in H2 at temperatures from 400 to 800 °C, to yield Mo2C/APC catalysts. Increased reduction temperature increased the Mo2C yield and the mesoporous volume of the Mo2C/APC. At a reduction temperature of 750 °C the mesopore volume of the catalyst doubled compared to the APC support and accounted for 37% of the total pore volume. Maintaining the final CHR temperature for 90 min further increased the Mo2C yield and mesoporosity of the catalyst. The role of Mo2C in the catalytic hydrogenation of the APC and mesopore generation is demonstrated. The activity of the Mo2C/carbon catalysts in the hydrodeoxygenation of 4-methyl phenol increased with increased CHR temperature and catalyst mesoporosity.

  20. Electrochemical Fluorographane: Hybrid Electrocatalysis of Biomarkers, Hydrogen Evolution, and Oxygen Reduction

    Czech Academy of Sciences Publication Activity Database

    Gusmao, R.; Sofer, Z.; Šembera, Filip; Janoušek, Zbyněk; Pumera, M.

    2015-01-01

    Roč. 21, č. 46 (2015), s. 16474-16478 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA15-09001S Institutional support: RVO:61388963 Keywords : electrochemistry * fluorine * graphene * sensors * synthesis design Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

  1. 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...

  2. Potentials of NO{sub X} emission reduction methods in SI hydrogen engines: Simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Safari, H.; Jazayeri, S.A. [Department of Mechanical Engineering, K.N. Toosi University of Technology, No.15, Pardis Street, Vanak Square, Tehran (Iran); Ebrahimi, R. [Department of Aerospace Engineering, K.N. Toosi University of Technology, 4th Tehranpars Square, East Vafadar Street, Tehran (Iran)

    2009-01-15

    The ever increasing cost of hydrocarbon fuels and more stringent emission standards may resolve challenges in producing hydrogen and using it as an alternative fuel in industries. Internal combustion engines are well-established technology and hydrogen fuel in such engines is considered as an attractive choice in exploiting clean, efficient and renewable hydrogen energy. This work presents an improved thermo-kinetics model for simulation of hydrogen combustion in SI engines. The turbulent propagating flame is modeled using turbulent burning velocity model. During combustion the charge is divided into three zones containing unburned charge, flame and burned gas. The adiabatic flame is assumed to be in thermodynamic equilibrium while the detailed chemical kinetics scheme is considered for burned and unburned zones. The results were first validated against published experiments. Good agreements were obtained between simulation and experiment for varying equivalence ratio, ignition timing and compression ratio. Detailed analysis of engine NO{sub X} emission was performed afterward. The lean-burn and EGR strategies' potentials were examined by the current model. The effects of different amounts of cooled dry EGR and hot wet EGR on the NO{sub X} emission, engine power output and indicated thermal efficiency were investigated and compared theoretically. (author)

  3. Newly emerging opportunity for pollution reduction using hydrogen as vehicular fuel

    International Nuclear Information System (INIS)

    Krepec, T.; Hong, H.

    1998-01-01

    There is a new important development in automotive technology in recent years which is aimed towards more efficient and less polluting vehicles. This is one of the goals of the Partnership for a New Generation of Vehicles (PNGV) launched in 1993 by the USA Government in cooperation with the three big auto makers Chrysler, Ford and General Motors. The objective is to achieve 80 miles per gallon of gasoline by a mid size sedan, i.e. to triple the existing mileage and to reduce proportionally the emissions. Similar activity was undertaken in Europe with the goal of a 3 liter/100 km car, and also in Japan. The recent demonstration results are confirming the feasibility of such a car in the near future. This is creating new opportunity for hydrogen fueled cars where the hydrogen storage limitations could be overcome with an acceptable size of hydrogen tank and additional energy from the electric battery. Such hybrid hydrogen electric vehicle would be a zero emission vehicle. Still, the commercialization of such a car, which would also provide the customer with adequate performance, drive ability and comfort, requires several advanced solutions which are already emerging from the R and D work initiated by the PNGV. (author)

  4. 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

  5. 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).

  6. 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)

  7. 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.

  8. Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

    Science.gov (United States)

    Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

    2018-02-22

    Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

  9. On the Spectral Evolution of Helium-atmosphere White Dwarfs Showing Traces of Hydrogen

    Science.gov (United States)

    Rolland, B.; Bergeron, P.; Fontaine, G.

    2018-04-01

    We present a detailed spectroscopic analysis of 115 helium-line (DB) and 28 cool, He-rich hydrogen-line (DA) white dwarfs based on atmosphere fits to optical spectroscopy and photometry. We find that 63% of our DB population show hydrogen lines, making them DBA stars. We also demonstrate the persistence of pure DB white dwarfs with no detectable hydrogen feature at low effective temperatures. Using state-of-the art envelope models, we next compute the total quantity of hydrogen, M H, that is contained in the outer convection zone as a function of effective temperature and atmospheric H/He ratio. We find that some (T eff, M H) pairs cannot physically exist as a homogeneously mixed structure; such a combination can only occur as stratified objects of the DA spectral type. On that basis, we show that the values of M H inferred for the bulk of the DBA stars are too large and incompatible with the convective dilution scenario. We also present evidence that the hydrogen abundances measured in DBA and cool, helium-rich white dwarfs cannot be globally accounted for by any kind of accretion mechanism onto a pure DB star. We suggest that cool, He-rich DA white dwarfs are most likely created by the convective mixing of a DA star with a thin hydrogen envelope; they are not cooled down DBAs. We finally explore several scenarios that could account for the presence of hydrogen in DBA stars.

  10. Reaction Mechanism of Tar Evolution in Biomass Steam Gasification for Hydrogen Production

    International Nuclear Information System (INIS)

    Shingo Katayama; Masahiro Suzuki; Atsushi Tsutsumi

    2006-01-01

    Reaction mechanism of tar evolution in steam gasification of biomass was investigated with a continuous cross-flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. We estimated that time profile of tar and gas evolution in the gasification of cellulose, xylan, and lignin, and compared it with experimental product time profile of real biomass gasification. The experimental tar evolution rate is different from estimated tar evolution rate. The estimated tar evolution rate has a peak at 20 s. On the other hand, the experimental tar evolution rate at 20 s is little, and tar at initial stage includes more water-soluble and water-insoluble compounds. It can be concluded that in the real biomass steam gasification the evolution of tar from cellulose and lignin component was found to be precipitated by that from hemi-cellulose component. (authors)

  11. Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

    Science.gov (United States)

    Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

    2015-09-01

    The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Plutonium(IV) peroxide formation in nitric medium and kinetics Pu(VI) reduction by hydrogen peroxide

    International Nuclear Information System (INIS)

    Maillard, C.; Adnet, J.M.

    2001-01-01

    Reduction of plutonium (VI) to Pu(IV) with hydrogen peroxide is a step in industrial processes used to purify plutonium nitrate solutions. This operation must be carefully controlled, in order to avoid any formation of the Pu(IV) peroxide green precipitate and to obtain exclusively Pu(IV). This led us to study the acidity and Pu and H 2 O 2 concentrations influences on the precipitate appearance and to perform a Pu(VI) reduction kinetic study on a wide range of acidities ([HNO 3 ]: 0.5 to 8 M), plutonium concentrations ([Pu(VI)]: 0.1 to 0.8 M) and [H 2 O 2 ]/[Pu(VI)] ratio (from 1 to 8). Thus, the domain of Pu(IV) peroxide formation and the reactional paths were established. With the exception of 0.5 M nitric acid medium, the kinetic curves show two distinct regims: the first one corresponds to an induction period where the Pu(VI) concentration doesn't change, the second corresponds to a linear decrease of Pu(VI). An increase of the temperature greatly accelerates the Pu(VI) reduction rate while [H 2 O 2 ]/[Pu(VI)] has almost no influence. The Pu(VI) total reduction time decreases when initial concentration of plutonium increases. By increasing nitric acid concentration from 0.5 M to 6 M, the total Pu(VI) reduction time decreases. This time increases when [HNO 3 ] varies from 6 M to 8 M. (orig.)

  13. Self-assembled monolayers of n-alkanethiols suppress hydrogen evolution and increase the efficiency of rechargeable iron battery electrodes.

    Science.gov (United States)

    Malkhandi, Souradip; Yang, Bo; Manohar, Aswin K; Prakash, G K Surya; Narayanan, S R

    2013-01-09

    Iron-based rechargeable batteries, because of their low cost, eco-friendliness, and durability, are extremely attractive for large-scale energy storage. A principal challenge in the deployment of these batteries is their relatively low electrical efficiency. The low efficiency is due to parasitic hydrogen evolution that occurs on the iron electrode during charging and idle stand. In this study, we demonstrate for the first time that linear alkanethiols are very effective in suppressing hydrogen evolution on alkaline iron battery electrodes. The alkanethiols form self-assembled monolayers on the iron electrodes. The degree of suppression of hydrogen evolution by the alkanethiols was found to be greater than 90%, and the effectiveness of the alkanethiol increased with the chain length. Through steady-state potentiostatic polarization studies and impedance measurements on high-purity iron disk electrodes, we show that the self-assembly of alkanethiols suppressed the parasitic reaction by reducing the interfacial area available for the electrochemical reaction. We have modeled the effect of chain length of the alkanethiol on the surface coverage, charge-transfer resistance, and double-layer capacitance of the interface using a simple model that also yields a value for the interchain interaction energy. We have verified the improvement in charging efficiency resulting from the use of the alkanethiols in practical rechargeable iron battery electrodes. The results of battery tests indicate that alkanethiols yield among the highest faradaic efficiencies reported for the rechargeable iron electrodes, enabling the prospect of a large-scale energy storage solution based on low-cost iron-based rechargeable batteries.

  14. Self-Assembled Monolayers of n-Alkanethiols Suppress Hydrogen Evolution and Increase the Efficiency of Rechargeable Iron Battery Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Malkhandi, S; Yang, B; Manohar, AK; Prakash, GKS; Narayanan, SR

    2013-01-09

    Iron-based rechargeable batteries, because of their low cost, eco-friendliness, and durability, are extremely attractive for large-scale energy storage. A principal challenge in the deployment of these batteries is their relatively low electrical efficiency. The low efficiency is due to parasitic hydrogen evolution that occurs on the iron electrode during charging and idle stand. In this study, we demonstrate for the first time that linear alkanethiols are very effective in suppressing hydrogen evolution on alkaline iron battery electrodes. The alkanethiols form self-assembled monolayers on the iron electrodes. The degree of suppression of hydrogen evolution by the alkanethiols was found to be greater than 90%, and the effectiveness of the alkanethiol increased with the chain length. Through steady-state potentiostatic polarization studies and impedance measurements on high-purity iron disk electrodes, we show that the self-assembly of alkanethiols suppressed the parasitic reaction by reducing the interfacial area available for the electrochemical reaction. We have modeled the effect of chain length of the alkanethiol on the surface coverage, charge-transfer resistance, and double-layer capacitance of the interface using a simple model that also yields a value for the interchain interaction energy. We have verified the improvement in charging efficiency resulting from the use of the alkanethiols in practical rechargeable iron battery electrodes. The results of battery tests indicate that alkanethiols yield among the highest faradaic efficiencies reported for the rechargeable iron electrodes, enabling the prospect of a large-scale energy storage solution based on low-cost iron-based rechargeable batteries.

  15. Cathodic Electrodeposition of Ni-Mo on Semiconducting NiFe2 O4 for Photoelectrochemical Hydrogen Evolution in Alkaline Media.

    Science.gov (United States)

    Wijten, Jochem H J; Jong, Ronald P H; Mul, Guido; Weckhuysen, Bert M

    2018-04-25

    Photocathodes for hydrogen evolution from water were made by electrodeposition of Ni-Mo layers on NiFe 2 O 4 substrates, deposited by spin coating on F:SnO 2 -glass. Analysis confirmed the formation of two separate layers, without significant reduction of NiFe 2 O 4 . Bare NiFe 2 O 4 was found to be unstable under alkaline conditions during (photo)electrochemistry. To improve the stability significantly, the deposition of a bifunctional Ni-Mo layer through a facile electrodeposition process was performed and the composite electrodes showed stable operation for at least 1 h. Moreover, photocurrents up to -2.1 mA cm -2 at -0.3 V vs. RHE were obtained for Ni-Mo/NiFe 2 O 4 under ambient conditions, showing that the new combination functions as both a stabilizing and catalytic layer for the photoelectrochemical evolution of hydrogen. The photoelectrochemical response of these composite electrodes decreased with increasing NiFe 2 O 4 layer thickness. Transient absorption spectroscopy showed that the lifetime of excited states is short and on the ns timescale. An increase in lifetime was observed for NiFe 2 O 4 of large layer thickness, likely explained by decreasing the defect density in the primary layer(s), as a result of repetitive annealing at elevated temperature. The photoelectrochemical and transient absorption spectroscopy results indicated that a short charge carrier lifetime limits the performance of Ni-Mo/NiFe 2 O 4 photocathodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Mitochondrial genome evolution in Alismatales: Size reduction and extensive loss of ribosomal protein genes

    DEFF Research Database (Denmark)

    Petersen, Gitte; Cuenca, Argelia; Zervas, Athanasios

    2017-01-01

    The order Alismatales is a hotspot for evolution of plant mitochondrial genomes characterized by remarkable differences in genome size, substitution rates, RNA editing, retrotranscription, gene loss and intron loss. Here we have sequenced the complete mitogenomes of Zostera marina and Stratiotes...... aloides, which together with previously sequenced mitogenomes from Butomus and Spirodela, provide new evolutionary evidence of genome size reduction, gene loss and transfer to the nucleus. The Zostera mitogenome includes a large portion of DNA transferred from the plastome, yet it is the smallest known...... mitogenome from a non-parasitic plant. Using a broad sample of the Alismatales, the evolutionary history of ribosomal protein gene loss is analyzed. In Zostera almost all ribosomal protein genes are lost from the mitogenome, but only some can be found in the nucleus....

  17. Electrocatalytic behavior of thin Co-Te-O films in oxygen evolution and reduction reactions

    International Nuclear Information System (INIS)

    Rashkova, V.; Kitova, S.; Vitanov, T.

    2007-01-01

    Co-Te-O catalytic films, obtain by vacuum co-evaporation of Co and TeO 2 are investigated as electrocatalysts for oxygen reactions in alkaline media. Bifunctional gas-diffusion oxygen electrodes (gde) are prepared by direct deposition of catalyst films on gas-diffusion membranes (gdm) consisting of hydrophobized carbon blacks or hydrophobized 'Ebonex' (suboxides of titanium dioxide). Thus obtained electrodes with different atomic ratio R Co/Te of the catalyst, treated at different temperatures were electrochemically tested by means of cyclic voltammetry and steady-state voltammetry. It is shown that the electrodes exhibit high catalytic activity toward oxygen evolution and reduction reaction despite very low catalyst loading of about 0.05-0.5 mg cm -2

  18. Spark Ignition LPG for Hydrogen Gas Combustion the Reduction Furnace ME-11 Process

    International Nuclear Information System (INIS)

    Achmad Suntoro

    2007-01-01

    Reverse engineering method for automatic spark-ignition system of LPG to burn hydrogen gaseous in the reducing process of ME-11 furnace has been successfully implemented using local materials. A qualitative study to the initial behaviour of the LPG flame system has created an idea by modification to install an automatic spark-ignition of the LPG on the reducing furnace ME-11. The automatic spark-ignition system has been tested and proved working well. (author)

  19. Iodide-photocatalyzed reduction of carbon dioxide to formic acid with thiols and hydrogen sulfide

    OpenAIRE

    Berton, Mateo Otao; Mello, Rossella C. C.; González Núñez, María Elena

    2016-01-01

    The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO2 capture coupled with H2S removal may have been relevant as a prebiotic carbon dioxide fixation.

  20. Renewable Molecular Flasks with NADH Models: Combination of Light-Driven Proton Reduction and Biomimetic Hydrogenation of Benzoxazinones.

    Science.gov (United States)

    Zhao, Liang; Wei, Jianwei; Lu, Junhua; He, Cheng; Duan, Chunying

    2017-07-17

    Using small molecules with defined pockets to catalyze chemical transformations resulted in attractive catalytic syntheses that echo the remarkable properties of enzymes. By modulating the active site of a nicotinamide adenine dinucleotide (NADH) model in a redox-active molecular flask, we combined biomimetic hydrogenation with in situ regeneration of the active site in a one-pot transformation using light as a clean energy source. This molecular flask facilitates the encapsulation of benzoxazinones for biomimetic hydrogenation of the substrates within the inner space of the flask using the active sites of the NADH models. The redox-active metal centers provide an active hydrogen source by light-driven proton reduction outside the pocket, allowing the in situ regeneration of the NADH models under irradiation. This new synthetic platform, which offers control over the location of the redox events, provides a regenerating system that exhibits high selectivity and efficiency and is extendable to benzoxazinone and quinoxalinone systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Novel atmospheric pressure plasma device releasing atomic hydrogen: reduction of microbial-contaminants and OH radicals in the air

    International Nuclear Information System (INIS)

    Nojima, Hideo; Park, Rae-Eun; Kwon, Jun-Hyoun; Suh, Inseon; Jeon, Junsang; Ha, Eunju; On, Hyeon-Ki; Kim, Hye-Ryung; Choi, KyoungHui; 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 + (H 2 O)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 m 3 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

  2. Correlation of electrical and physical properties of photoanode with hydrogen evolution in enzymatic photo-electrochemical cell

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Sanghyun; Kang, Junwon [Department of Environmental Engineering, Yonsei University, 234 Maeji-ri, Hungub-myun, Wonju, Gangwon-do 220-710 (Korea); Shim, Eunjung [Department of Chemistry, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764 (Korea); Yoon, Jaekyung; Joo, Hyunku [Fossil Energy and Environment Research Department, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon 305-343 (Korea)

    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 TiO{sub 2} 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{sup -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 O{sub 2} atmosphere led to the formation of a tube-shaped, or a compact layered, TiO{sub 2} 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 {mu}A for light intensities of ca. 74 and ca. 146 mW cm{sup -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 {mu}A and the OCV is +258 to -126 mW cm{sup -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 {mu}mol h{sup -1} cm{sup -2}. (author)

  3. 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

  4. Reduction in Recombination Current Density in Boron Doped Silicon Using Atomic Hydrogen

    Science.gov (United States)

    Young, Matthew Garett

    The solar industry has grown immensely in recent years and has reached a point where solar energy has now become inexpensive enough that it is starting to emerge as a mainstream electrical generation source. However, recent economic analysis has suggested that for solar to become a truly wide spread source of electricity, the costs still need to plummet by a factor of 8x. This demands new and innovative concepts to help lower such cost. In pursuit of this goal, this dissertation examines the use of atomic hydrogen to lessen the recombination current density in the boron doped region of n-type silicon solar cells. This required the development of a boron diffusion process that maintained the bulk lifetime of n-type silicon such that the recombination current density could be extracted by photoconductance spectroscopy. It is demonstrated that by hydrogenating boron diffusions, the majority carrier concentration can be controlled. By using symmetrically diffused test structures with quinhydrone-methanol surface passivation the recombination current density of a hydrogenated boron profile is shown to be less than that of a standard boron profile, by as much as 30%. This is then applied to a modified industrial silicon solar cell process to demonstrate an efficiency enhancement of 0.4%.

  5. The hydrogen and the fuel cells in the world. Programs and evolutions

    International Nuclear Information System (INIS)

    Lucchese, P.

    2008-01-01

    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.)

  6. A study of the thermostimulated evolution of labelled hydrogen sulfide from the leached basalt fibers

    International Nuclear Information System (INIS)

    Zheleznov, A.V.; Zyuzin, A.Yu.; Bekman, I.N.

    1991-01-01

    Thermostimulated separation of labelled hydrogen sulfide from basalt fibers leached by hydrochloric acid is investigated by the method of radioactive tracers. It is shown that the type of H 2 35 S thermosorption spectrum depends on the presence of water traces in a fibrous adsrobent. Formal order and activation energy of thermodesorption of labelled hydrogen sulfide as well as inhomogeneity of porous structure of adsorbents based on basalt fibers are established

  7. Hydrogen: it's now. Hydrogen, essential today, indispensable tomorrow. Power-to-Gas or how to meet the challenge of electricity storage. To develop hydrogen mobility. Hydrogen production modes and scope of application of the IED directive - Interview. Regulatory evolutions needed for an easier deployment of hydrogen energy technologies for a clean mobility. Support of the Community's policy to hydrogen and to fuel cells

    International Nuclear Information System (INIS)

    Mauberger, Pascal; Boucly, Philippe; Quint, Aliette; Pierre, Helene; Lucchese, Paul; Bouillon-Delporte, Valerie; Chauvet, Bertrand; Ferrari, Fabio; Boivin, Jean-Pierre

    2015-01-01

    Published by the French Association for Hydrogen and Fuel Cells (AFHYPAC), this document first outlines how hydrogen can reduce our dependence on fossil energies, how it supports the development of electric mobility to reduce CO 2 emissions by transports, how it enables a massive storage of energy as a support to renewable energies deployment and integration, and how hydrogen can be a competitiveness driver. Then two contributions address technical solutions, the first one being Power-to-Gas as a solution to energy storage (integration of renewable energies, a mean for massive storage of electricity, economic conditions making the first deployments feasible, huge social and economical benefits, necessity of creation of an adapted legal and economic framework), and the second one being the development of hydrogen-powered mobility (a major societal concern for air quality, strategies of car manufacturers in the world, necessity of a favourable framework, the situation of recharging infrastructures). Two contributions address the legal framework regarding hydrogen production modes and the scope of application of the European IED directive on industrial emissions, and the needed regulatory evolutions for an easier deployment of Hydrogen-energy technologies for a clean mobility. A last article comments the evolution of the support of European policies to hydrogen and fuel cells through R and d programs, presents the main support program (FCH JU) and its results, other European financing and support policy, and discusses perspectives, notably for possible financing mechanisms

  8. Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

    Science.gov (United States)

    Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

    2018-01-01

    Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Bi{sub 2}O{sub 3} cocatalyst improving photocatalytic hydrogen evolution performance of TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan, E-mail: hslra@tom.com

    2017-04-01

    Highlights: • Bi-Bi{sub 2}O{sub 3}-anatase-rutile TiO{sub 2} multijunction photocatalyst was prepared. • Bi{sub 2}O{sub 3} quantum dots with size of 2–3 nm were uniformly distributed. • Improved H{sub 2} evolution was noticed in glycerol-water mixture. • Optimal amount of Bi{sub 2}O{sub 3} was found to be 0.89 mol%. - Abstract: Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi{sub 2}O{sub 3}-TiO{sub 2} composite photocatalysts presented as Bi-Bi{sub 2}O{sub 3}-anatase-rutile TiO{sub 2} multijunction were first fabricated by a simple impregnation-calcination method using Bi{sub 2}O{sub 3} as H{sub 2}-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H{sub 2} evolution activity in the presence of glycerol. The effect of Bi{sub 2}O{sub 3} amount on H{sub 2}-evolution activity of TiO{sub 2} was investigated and the optimal Bi{sub 2}O{sub 3} content was found to be 0.89 mol%, achieving a H{sub 2}-production rate of 920 μmol h{sup −1}, exceeding that of pure TiO{sub 2} by more than 73 times. The enhanced mechanism of photocatalytic H{sub 2}-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO{sub 2}-based hydrogen-production photocatalysts using low-cost Bi{sub 2}O{sub 3} as cocatalyst.

  10. Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe?N?C Catalysts

    OpenAIRE

    Choi, Chang Hyuck; Choi, Won Seok; Kasian, Olga; Mechler, Anna K.; Sougrati, Moulay Tahar; Br?ller, Sebastian; Strickland, Kara; Jia, Qingying; Mukerjee, Sanjeev; Mayrhofer, Karl J. J.; Jaouen, Fr?d?ric

    2017-01-01

    Abstract Fe?N?C catalysts with high O2 reduction performance are crucial for displacing Pt in low?temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H2O2 reduction, a key intermediate during indirect O2 reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeN x C y moieties and Fe particles encapsu...

  11. THE DATA REDUCTION PIPELINE FOR THE APACHE POINT OBSERVATORY GALACTIC EVOLUTION EXPERIMENT

    International Nuclear Information System (INIS)

    Nidever, David L.; Holtzman, Jon A.; Prieto, Carlos Allende; Mészáros, Szabolcs; Beland, Stephane; Bender, Chad; Desphande, Rohit; Bizyaev, Dmitry; Burton, Adam; García Pérez, Ana E.; Hearty, Fred R.; Majewski, Steven R.; Skrutskie, Michael F.; Sobeck, Jennifer S.; Wilson, John C.; Fleming, Scott W.; Muna, Demitri; Nguyen, Duy; Schiavon, Ricardo P.; Shetrone, Matthew

    2015-01-01

    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 −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

  12. Optical performance evolutions of reductive glutathione coated CdSe quantum dots in different environments

    International Nuclear Information System (INIS)

    Wang Lili; Jiang Jisen

    2011-01-01

    Optical performances of reductive glutathione coated CdSe quantum dots were studied under different ageing conditions. The enhancements of luminescence were obviously occurred for the samples ageing under illumination. The quantum yield of CdSe was enhanced continuously over 44 days at room temperature, and reached as high as 36.6%. O 2 was proved to make a certain contribute to the enhancement. The evolutions of the systems during the ageing time were deduced according to the variations of pH values with ageing time and the XRD results of the samples ageing in air with illumination. We conferred that the reduction of surface defects resulted from the photo-induced decomposition of CdSe quantum dots was the main reason for the enhancement of fluorescence. The production of CdO as a result of the surface reaction with O 2 made contributions to the enhancement for a certain extent. The curves of quantum yield versus ageing time were fitted with a stretched exponential function. It was found that the course of fluorescence enhancement accorded with the dynamics of system with strongly coupled hierarchical degrees of freedom.

  13. 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.

  14. 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.

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

    International Nuclear Information System (INIS)

    Jinlong, Lv; Tongxiang, Liang; Chen, Wang

    2016-01-01

    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_2SO_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_2SO_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.

  16. 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.

  17. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    Science.gov (United States)

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  18. Iodide-Photocatalyzed Reduction of Carbon Dioxide to Formic Acid with Thiols and Hydrogen Sulfide.

    Science.gov (United States)

    Berton, Mateo; Mello, Rossella; González-Núñez, María Elena

    2016-12-20

    The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO 2 capture coupled with H 2 S removal may have been relevant as a prebiotic carbon dioxide fixation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  20. 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.

  1. 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.

  2. In situ photodeposition of amorphous CoSx on the TiO2 towards hydrogen evolution

    Science.gov (United States)

    Chen, Feng; Luo, Wei; Mo, Yanping; Yu, Huogen; Cheng, Bei

    2018-02-01

    Cocatalyst modification of photocatalysts is an important strategy to enhance the photocatalytic performance by promoting effective separation of photoinduced electron-hole pairs and providing abundant active sites. In this study, a facile in situ photodeposition method was developed to prepare amorphous CoSx-modified TiO2 photocatalysts. It was found that amorphous CoSx nanoparticles were solidly loaded on the TiO2 surface, resulting in a greatly improved photocatalytic H2-evolution performance. When the amount of amorphous CoSx was 10 wt%, the hydrogen evolution rate of the CoSx/TiO2 reached 119.7 μmol h-1, which was almost 16.7 times that of the pure TiO2. According to the above experimental results, a reasonable mechanism of improved photocatalytic performance is proposed for the CoSx/TiO2 photocatalysts, namely, the photogenerated electrons of TiO2 can rapidly transfer to amorphous CoSx nanoparticles due to the solid contact between them, and then amorphous CoSx can provide plenty of sulfur active sites to rapidly adsorb protons from solution to produce hydrogen by the photogenerated electrons. Considering the facile synthesis method, the present cheap and highly efficient amorphous CoSx-modified TiO2 photocatalysts would have great potential for practical use in photocatalytic H2 production.

  3. 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.

  4. Microstructure and kinetics evolution in MgH{sub 2}–TiO{sub 2} pellets after hydrogen cycling

    Energy Technology Data Exchange (ETDEWEB)

    Mirabile Gattia, D., E-mail: daniele.mirabile@enea.it; Di Girolamo, G.; Montone, A.

    2014-12-05

    Highlights: • MgH{sub 2} was ball milled with TiO{sub 2} anatase phase and expanded graphite to prepare pellets. • Different pellets have been prepared at different compression load. • Pellets were repeatedly cycled under hydrogen pressure to simulate tank exercise and verify their stability. • The compression load highly affects the stability of the pellets to cycling. • Microstructural evolution of the particles due to cycling have been observed. - Abstract: The interest in Mg-based hydrides for solid state hydrogen storage is associated to their capability to reversibly absorb and desorb large amounts of hydrogen. In this work MgH{sub 2} powder with 5 wt.% TiO{sub 2} was ball milled for 10 h. The as-milled nanostructured powder was enriched with 5 wt.% of Expanded Natural Graphite (ENG) and then compacted in cylindrical pellets by cold pressing using different loads. Both the powder and the pellets were subjected to kinetic and thermodynamic tests using a Sievert’s type gas reaction controller, in order to study the microstructural and kinetic changes which took place during repeated H{sub 2} absorption and desorption cycles. The pellets exhibited good kinetic performance and durability, even if the pressure of compaction revealed to be an important parameter for their mechanical stability. Scanning Electron Microscopy observations of as-prepared and cycled pellets were carried out to investigate the evolution of their microstructure. In turn the phase composition before and after cycling was analyzed by X-ray diffraction.

  5. 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.)

  6. Evolution of the near-UV emission spectrum associated with the reduction process in microwave iron making.

    Science.gov (United States)

    Matsubara, Akihiro; Takayama, Sadatsugu; Okajima, Shigeki; Sato, Motoyasu

    2008-01-01

    The structure of the emission spectrum in the near-UV range (240 nm-310 nm) changes drastically from the continuous spectrum to a discrete line spectrum with increasing sample temperature during the carbothermic reduction of magnetite in a 2.45 GHz microwave multimode furnace. The continuous spectrum can be assigned as a cathodoluminescence of magnetite. The dynamic evolution of the spectrum from continuous to discrete represents the progress of the reduction from magnetite to iron.

  7. Investigation of hydrogen peroxide reduction reaction on graphene and nitrogen doped graphene nanoflakes in neutral solution

    Science.gov (United States)

    Amirfakhri, Seyed Javad; Binny, Dustin; Meunier, Jean-Luc; Berk, Dimitrios

    2014-07-01

    H2O2 reduction reaction (HPRR) is studied on both graphene (GNF) and nitrogen doped graphene nanoflakes in 0.1 M Na2SO4 solution by rotating disk electrode. The XPS results indicate that N-doped graphene nanoflakes with high nitrogen content, 32 at%N (N-GNF32), are synthesised successfully by an inductively-coupled thermal plasma (ICP) reactor. Pyridinic, pyrrolic and graphitic N species contribute up to 67% of the total nitrogen. Kinetic parameters such as Tafel slope and stoichiometric number suggest that HPRR occurs by the same mechanism on both GNF and N-GNF32. Although nitrogen does not change the mechanism of HPRR, the results indicate that the reaction rate of H2O2 reduction is enhanced on N-GNF32. The exchange current density of H2O2 reduction based on the active surface area of N-GNF32 is (8.3 ± 0.3) × 10-9 A cm-2, which is 6 times higher than the value determined for GNF. The apparent number of electrons involved in the process suggests that H2O2 decomposition competes with H2O2 reduction on both catalysts. Evaluation of the apparent heterogeneous reaction rate constant and the Tafel slope indicate that simultaneous reduction of O2 and H2O2 is negligible on the N-GNF32. On the other hand, the reduction of O2 and H2O2 occurs simultaneously on the GNF surface.

  8. Simulation of uranium oxides reduction kinetics by hydrogen. Reactivities of germination and growth; Modelisation de la cinetique de reduction d`oxydes d`uranium par l`hydrogene. Reactivites de germination et de croissance

    Energy Technology Data Exchange (ETDEWEB)

    Brun, C

    1997-12-04

    The aim of this work is to simulate the reduction by hydrogen of the tri-uranium octo-oxide U{sub 3}O{sub 8} (obtained by uranium trioxide calcination) into uranium dioxide. The kinetics curves have been obtained by thermal gravimetric analysis, the hydrogen and steam pressures being defined. The geometrical modeling which has allowed to explain the trend of the kinetics curves and of the velocity curves is an anisotropic germination-growth modeling. The powder is supposed to be formed of spherical grains with the same radius. The germs of the new UO{sub 2} phase appear at the surface of the U{sub 3}O{sub 8} grains with a specific germination frequency. The growth reactivity is anisotropic and is very large in the tangential direction to the grains surface. Then, the uranium dioxide growths inside the grain and the limiting step is the grain surface. The variations of the growth reactivity and of the germination specific frequency in terms of the gases partial pressures and of the temperature have been explained by two different mechanisms. The limiting step of the growth mechanism is the desorption of water in the uranium dioxide surface. Concerning the germination mechanism the limiting step is a water desorption too but in the tri-uranium octo-oxide surface. The same geometrical modeling and the same germination and growth mechanisms have been applied to the reduction of a tri-uranium octo-oxide obtained by calcination of hydrated uranium trioxide. The values of the germination specific frequency of this solid are nevertheless weaker than those of the solid obtained by direct calcination of the uranium trioxide. (O.M.) 45 refs.

  9. Definitive proof of graphene hydrogenation by Clemmensen reduction: use of deuterium labeling

    Czech Academy of Sciences Publication Activity Database

    Sofer, Z.; Jankovský, O.; Libánská, A.; Šimek, P.; Nováček, M.; Sedmidubský, D.; Macková, Anna; Mikšová, Romana; Pumera, M.

    2015-01-01

    Roč. 7, č. 23 (2015), s. 10535-10543 ISSN 2040-3364 R&D Projects: GA ČR(CZ) GA15-09001S; GA MŠk LM2011019 Institutional support: RVO:61389005 Keywords : graphite oxide * chemical reduction * graphene Subject RIV: BG - Nuclear , Atomic and Molecular Physics, Colliders Impact factor: 7.760, year: 2015

  10. Uranium- and Thorium-Doped Graphene for Efficient Oxygen and Hydrogen Peroxide Reduction

    Czech Academy of Sciences Publication Activity Database

    Sofer, Z.; Jankovský, O.; Šimek, P.; Klimová, K.; Macková, Anna; Pumera, M.

    2014-01-01

    Roč. 8, č. 7 (2014), s. 7106-7114 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:61389005 Keywords : graphene * actinides * electrochemistry * oxygen reduction * uranium Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 12.881, year: 2014

  11. Complete bromate and nitrate reduction using hydrogen as the sole electron donor in a rotating biofilm-electrode reactor

    International Nuclear Information System (INIS)

    Zhong, Yu; Li, Xin; Yang, Qi; Wang, Dongbo; Yao, Fubing; Li, Xiaoming; Zhao, Jianwei; Xu, Qiuxiang; Zhang, Chang; Zeng, Guangming

    2016-01-01

    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 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 2 on the surface of the ACF cathode, and the microbial cultures attached closely on the cathode which could completely utilize H 2 as electron donors for reduction of bromate and nitrate.

  12. Remarkably enhanced photocatalytic hydrogen evolution over MoS2 nanosheets loaded on uniform CdS nanospheres

    Science.gov (United States)

    Chai, Bo; Xu, Mengqiu; Yan, Juntao; Ren, Zhandong

    2018-02-01

    The MoS2/CdS composites with layered MoS2 loaded on uniform CdS nanospheres were synthesized by a two-step process combination hydrothermal and solvothermal treatments, and then applied in photocatalytic hydrogen evolution under visible light irradiation. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Raman spectra, UV-vis diffuse reflectance absorption spectra (UV-DRS), nitrogen adsorption-desorption measurement, photoluminescence spectra (PL) and photoelectrochemical tests. The effects of loading contents of MoS2 in the composites on the photocatalytic H2 evolution activity were comparatively investigated with 0.45 mol L-1 Na2S and 0.55 mol L-1 Na2SO3 as sacrificial agents. The results showed that the 5 wt% MoS2/CdS composite could achieve the highest photocatalytic H2 evolution rate of 372 μmol h-1 and apparent quantum efficiency (AQE) about 7.31% under 420 nm monochromatic light irradiation. The remarkably enhanced photocatalytic activity of MoS2/CdS composite could be attributed to the effective transfer and separation of photogenerated charge carriers, and MoS2 being as a cocatalyst to facilitating photocatalytic H2 evolution reaction. A tentative mechanism of MoS2/CdS composites as photocatalysts for H2 evolution was proposed.

  13. Hail hydrogen

    International Nuclear Information System (INIS)

    Hairston, D.

    1996-01-01

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

  14. Vectorial electron transfer for improved hydrogen evolution by mercaptopropionic-acid-regulated CdSe quantum-dots-TiO2 -Ni(OH)2 assembly.

    Science.gov (United States)

    Yu, Shan; Li, Zhi-Jun; Fan, Xiang-Bing; Li, Jia-Xin; Zhan, Fei; Li, Xu-Bing; Tao, Ye; Tung, Chen-Ho; Wu, Li-Zhu

    2015-02-01

    A visible-light-induced hydrogen evolution system based on a CdSe quantum dots (QDs)-TiO2 -Ni(OH)2 ternary assembly has been constructed under an ambient environment, and a bifunctional molecular linker, mercaptopropionic acid, is used to facilitate the interaction between CdSe QDs and TiO2 . This hydrogen evolution system works effectively in a basic aqueous solution (pH 11.0) to achieve a hydrogen evolution rate of 10.1 mmol g(-1)  h(-1) for the assembly and a turnover frequency of 5140 h(-1) with respect to CdSe QDs (10 h); the latter is comparable with the highest value reported for QD systems in an acidic environment. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and control experiments demonstrate that Ni(OH)2 is an efficient hydrogen evolution catalyst. In addition, inductively coupled plasma optical emission spectroscopy and the emission decay of the assembly combined with the hydrogen evolution experiments show that TiO2 functions mainly as the electron mediator; the vectorial electron transfer from CdSe QDs to TiO2 and then from TiO2 to Ni(OH)2 enhances the efficiency for hydrogen evolution. The assembly comprises light antenna CdSe QDs, electron mediator TiO2 , and catalytic Ni(OH)2 , which mimics the strategy of photosynthesis exploited in nature and takes us a step further towards artificial photosynthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Development of a market penetration forecasting model for Hydrogen Fuel Cell Vehicles considering infrastructure and cost reduction effects

    International Nuclear Information System (INIS)

    Park, Sang Yong; Kim, Jong Wook; Lee, Duk Hee

    2011-01-01

    In order to cope with climate change, the development and deployment of Hydrogen Fuel Cell Vehicles (HFCVs) is becoming more important. In this study, we developed a forecasting model for HFCVs based on the generalized Bass diffusion model and a simulation model using system dynamics. Through the developed model, we could forecast that the saturation of HFCVs in Korea can be moved up 12 years compared with the US. A sensitivity analysis on external variables such as price reduction rates of HFCVs and number of hydrogen refueling stations is also conducted. The results of this study can give insights on the effects of external variables on the market penetration of HFCVs, and the developed model can also be applied to other studies in analyzing the diffusion effects of HFCVs. - Highlights: → A forecasting model for HFCVs was developed using the generalized Bass diffusion model. → A simulation model using system dynamics was also developed. → The empirical study shows that the infrastructure is an important factor to the initial purchase. → The results of this study can promote research related to the diffusion of innovation.

  16. 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.

  17. The Effect of Metal and Oxide Additions on the Reduction of Chalcocite by Hydrogen

    OpenAIRE

    Balsalobre Casares, Carmen

    2011-01-01

    Copper is widely known as a very important material due to its applications in our daily life, such as electrical devices and heating appliances. It is not so common knowledge that copper is not found in its metallic form, but mixed with other metals and elements like sulphur and oxygen. The process to obtain pure copper nowadays implies a strong impact on the environment. Regarding copper sulphides, its reduction to metallic copper is based in the oxidation of the ore products which forms...

  18. The evolution and anatomy of the horse manus with an emphasis on digit reduction

    Science.gov (United States)

    Danowitz, Melinda; Stachtiaris, Elizabeth; Khurana, Abhilasha; Araim, Marwan; Sayegh, Marc; Natale, Jessica

    2018-01-01

    We revisit digit reduction in the horse and propose that all five digits are partially present in the modern adult forelimb. Osteological descriptions of selected tetradactyl, tridactyl and monodactyl equids demonstrate the evolution of the forelimb. Histological, osteological and palaeontological evidence suggest that the Equus distal forelimb is more complex than traditionally conceived. The current understanding is that the horse distal forelimb consists of one complete digit (III) and two reduced splint metacarpals (II and IV). Metacarpals II and IV each exhibit a ventral ridge, which we suggest represents the undifferentiated digits I and V. These ridges are present in the tridactyl Mesohippus, but are absent in the tetradactyl Hyracotherium. The carpal articulations of the five metacarpals match those of pentadactyl taxa. Distally, the frog, a V-shaped structure on the ventral hoof represents digits II and IV, and the wings and hoof cartilages of the distal phalanx are digits I and V. We relate this revised interpretation of the Equus forelimb to Laetoli footprints, and suggest the Hipparion side impressions are created from the hooves of I and V, rather than from II and IV. We show shades of pentadactyly within the Equus manus. PMID:29410871

  19. Acidogenesis driven by hydrogen partial pressure towards bioethanol production through fatty acids reduction

    International Nuclear Information System (INIS)

    Sarkar, Omprakash; Butti, Sai Kishore; Venkata Mohan, S.

    2017-01-01

    H 2 partial pressure drives the reduction of carboxylic acid (short chain fatty acids) formed as primary metabolites in acidogenic fermentation to form bioalcohols. Microbial catalysis under the influence of H 2 partial pressure was evaluated in comparison with a reactor operated at atmospheric pressure under identical conditions. Carboxylic acid reduction gets regulated selectively by the influence of elevated pressures and redox conditions, resulting in the formation of alcohols. The non-equilibrium of the intra and extracellular H 2 ions causes the anaerobic bacteria to alter their pathways as a function of interspecies H 2 transfer. Ethanol production was quantified, as acetic acid was the major carboxylic acid synthesised during acidogenesis. H 2 pressure influenced the electrochemical activity which was reflected in the distinct variation of the electron transfer rates and the catalytic activity of redox mediators (NAD + /NADH, flavoproteins and iron-sulphur clusters). The bioprocess depicted in this communication depicted a non-genetic regulation of product formation, understanding the acidogenic metabolism and alternate route for alcohol production. - Highlights: • H 2 partial pressure in HPR aided in the reduction of carboxylic acids to alcohols. • Production and consumption rate of VFAs were correlating with alcohol formation. • Metabolic shift was evident with bioelectrochical analysis. • NADH/NAD + ratio and H 2 partial pressure coupled in enhanced solventogenesis.

  20. Improvement of performance and reduction of pollutant emission of a four stroke spark ignition engine fueled with hydrogen-gasoline fuel mixture

    Energy Technology Data Exchange (ETDEWEB)

    Al-Baghdadi, Maher Abdul-Resul Sadiq; Al-Janabi, Haroun Abdul-Kadim Shahad [Babylon Univ., Dept. of Mechanical Engineering, Babylon (Iraq)

    2000-07-01

    The effect of the amount of hydrogen/ethyl alcohol addition on the performance and pollutant emissions of a four stroke spark ignition engine has been studied. A detailed model to simulate a four stroke cycle of a spark ignition engine fueled with hydrogen-ethyl alcohol-gasoline has been used to study the effect of hydrogen and ethyl alcohol blending on the thermodynamic cycle of the engine. The results of the study show that all engine performance parameters have been improved when operating the gasoline S.I.E. with dual addition of hydrogen and ethyl alcohol. It has been found that 4% of hydrogen and 30% of ethyl alcohol blending causes a 49% reduction in CO emission, a 39% reduction in NO{sub x} emission, a 49% reduction in specific fuel consumption and increases in the thermal efficiency and output power by 5 and 4%, respectively. When ethyl alcohol is increased over 30%, it causes unstable engine operation which can be related to the fact that the fuel is not vaporised, and this causes a reduction in both the brake power and efficiency. (Author)

  1. Hydrogen peroxide reduction in the oxygen vacancies of ZnO nanotubes

    International Nuclear Information System (INIS)

    Peyghan, Ali Ahmadi; Laeen, Shima Parizad; Aslanzadeh, Saeed Amir; Moradi, Morteza

    2014-01-01

    The adsorption of a H 2 O 2 molecule on the pristine and O-vacancy defected ZnO nanotubes was investigated by means of density functional calculations. It was found that the molecule prefers to attach to two zinc atoms of the tube from its two oxygen atoms with the adsorption energy of 254.1 kJ/mol. Attachment of the H 2 O 2 to the wall of the tube does not have any significant influence on its highest occupied molecular orbital/lowest unoccupied molecular orbital gap (E g ). The presence of oxygen vacancy defect causes a decrease in the E g of the tube and, as a consequence, may cause an increase in the conductivity of the tube. The zinc atoms of the defect are more reactive toward H 2 O 2 reduction to H 2 O than perfect ones with the adsorption energy of 617.4 kJ/mol. During the adsorption process, the H 2 O 2 was reoriented in such a way that its O atom has diffused into vacancy site, so that O-O and O-H bonds of the molecule were dissociated and an H 2 O is formed. Thus, we think that ZnO-NTs may be a candidate for electrochemical reduction and detection of H 2 O 2 . - Highlights: • H 2 O 2 adsorption on pristine and O-vacancy defected ZnO nanotubes was studied by DFT. • H 2 O 2 does not have any significant influence on the gap of the tube. • Presence of oxygen vacancy defect causes a decrease in the gap of the tube. • ZnO nanotubes may be a candidate for electrochemical reduction and detection of H 2 O 2

  2. 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

    The coastal upwelling system off central Namibia is one of the most productive regions of the oceans and is characterized by frequently occurring shelf anoxia with severe effects for the benthic life and fisheries. We present data on water column dissolved oxygen, sulfide, nitrate and nitrite, pore......-depleted bottom waters, the oxygen minimum zone on the continental slope, and the lower continental slope below the oxygen minimum zone. High concentrations of dissolved sulfide, up to 22 mM, in the near-surface sediments of the inner shelf result from extremely high rates of bacterial sulfate reduction...

  3. Symbiotic N2 fixation by legumes growing in pots. 2. Uptake of VN-labelled NO3 , C2H2 reduction and H2 evolution by Trifolium subterraneum L. , Medicago truncatula Gaertn. and Acacia dealbata Link

    Energy Technology Data Exchange (ETDEWEB)

    Hopmans, P.; Chalk, P.M.; Douglas, L.A.

    1983-01-01

    The objectives of this study were to estimate symbiotic nitrogen fixation by two common pasture legumes, Trifolium subterraneum L. and Medicago truncatula Gaertn., and an Australian native legume, Acacia dealbata Link, growing in pots using an indirect isotopic method. This method was also used to calibrate the C2H2 reduction assay of the intact plants. In addition, hydrogen evolution was measured in an attempt to explain the variations in C2H2:N2 ratios between the species. 25 refs.; 1 figure; 4 tabs.

  4. 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

  5. Microstructural evaluation of ceria-samaria-gadolinia-nickel oxide composite after reduction in hydrogen atmosphere

    International Nuclear Information System (INIS)

    Arakaki, A. R.; Yoshito, W.K.; Ussui, V.; Lazar, D.R.R.

    2012-01-01

    The ceria-samaria-gadolinia-nickel composite (Ni-SGDC), used as Solid Oxide Fuel Cell (SOFC) anode, was obtained by 'in situ' reduction of NiO-SGDC, with composition Ce 0,8 (SmGd) 0,2 O 1,9 /NiO and mass proportion 40:60%. The composite was produced by hydroxides coprecipitation using CTAB surfactant, followed by solvothermal treatment in butanol, calcination at 600 deg C, pressing and sintering at 1350 deg C for 1 h. The composite reduction kinetic was evaluated in a tubular furnace under dynamic atmosphere of 4% H2 /Air, fixing the temperature at 900 deg C and time between 10 and 120 minutes. The microstructural characterization was performed by optical and scanning electron microscopy. The samples were characterized either by X-ray diffraction and density measurements by immersion technique in water. It was verified that the NiO reduced fraction reached values between 80 and 90% and the achieved porosity (about 30%) is acceptable to a good anode performance (author)

  6. Electrodeposition and characterization of Fe–Mo alloys as cathodes for hydrogen evolution in the process of chlorate

    Directory of Open Access Journals (Sweden)

    B. N. GRGUR

    2005-06-01

    Full Text Available Fe–Mo alloys were electrodeposited from a pyrophosphate bath using a single diode rectified AC current. Their composition and morphology were investigated by SEM, optical microscopy and EDS, in order to determine the influence of the deposition conditions on the morphology and composition of these alloys. It was shown that the electrodeposition parameters, such as: chemical bath composition and current density, influenced both the composition of the Fe–Mo alloys and the current efficiency for their deposition, while the micro and macro-morphology did not change significantly with changing conditions of alloy electrodeposition. It was found that the electrodeposited Fe–Mo alloys possessed a 0.15 V to 0.30 V lower overvoltage than mild steel for hydrogen evolution in an electrolyte commonly used in commercial chlorate production, depending on the alloy composition, i.e., the conditions of alloy electrodeposition.

  7. Edge-rich MoS_2 Naonosheets Rooting into Polyaniline Nanofibers as Effective Catalyst for Electrochemical Hydrogen Evolution

    International Nuclear Information System (INIS)

    Zhang, Nan; Ma, Weiguang; Wu, Tongshun; Wang, Haoyu; Han, Dongxue; Niu, Li

    2015-01-01

    Graphical abstract: For the first time polyaniline (PANI) was employed as an admirable substrate to construct the hierarchical integrative hybrid with MoS_2 (MoS_2/PANI) for hydrogen evolution reaction (HER), which achieved great active edges exposure and excellent HER performance. - Highlights: • PANI is first applied as the support of MoS_2 for enhanced HER performance. • Great active edges exposure of the hybrid significantly benefits the HER activity. • Superior HER activity and excellent stability of MoS_2/PANI have been achieved. - Abstract: Conductive polymer polyaniline (PANI) with abundant protonated sites which are beneficial to hydrogen evolution reaction (HER), was applied as the support of MoS_2 for enhanced HER performance for the first time. The novel three dimensional (3D) HER catalyst (MoS_2/PANI) was constructed with two dimensional (2D) MoS_2 building blocks rooting into the integrative nanowires. PANI nanofibers acted as excellent substrates for the uniform, dense and approximate vertical growth of MoS_2 nanosheets exposing abundant active edges. Consequently, excellent HER performance has been achieved with a low onset overpotential of 100 mV and a small Tafel slope of 45 mV dec"−"1. Most importantly, it only needed 200 and 247 mV overpotential to reach the current density of 30 and 100 mA/cm"2 respectively. Additionally, MoS_2/PANI has achieved superior stability over other MoS_2-polymer-based HER electrocatalyst. In general, for the first time, employing PANI for the construction of the edge-rich integrative hybrid has successfully achieved an outstanding HER performance.

  8. In situ electrodeposition of CoP nanoparticles on carbon nanomaterial doped polyphenylene sulfide flexible electrode for electrochemical hydrogen evolution

    Science.gov (United States)

    Wang, Tingxia; Jiang, Yimin; Zhou, Yaxin; Du, Yongling; Wang, Chunming

    2018-06-01

    Active and durable electrocatalyst for hydrogen evolution reaction (HER) is pivotal to generate molecular hydrogen more energy-efficient, but directly grafting electrocatalyst on electrode material by a single-step method without compromising the catalytic activity and stability remains a challenge. Herein, an intriguing electrode, reduced graphene oxide modified carbon nanotube/reduced graphene oxide/polyphenylene sulfide (RGO-CNT/RGO/PPS) film, is used to replace conventional electrodes. In situ electrodeposition is proposed to fabricate CoP on the RGO-CNT/RGO/PPS (CoP-RGO-CNT/RGO/PPS) electrode and achieves a favorably electrical contact between CoP nanoparticles and RGO-CNT/RGO/PPS electrode due to without any polymer binder. Additionally, the coupling of different electrodeposition stages with scanning electron microscope (SEM) can investigate the nanostructure evolution of CoP nanoparticles, which gives valuable insights into the optimized electrodeposition cycles. The rational integration of RGO onto CNT/RGO/PPS film is an effective approach for enhancing its intrinsic electrical conductivity and favoring the formation of a high density of dispersive CoP nanoparticles. The CoP-RGO-CNT/RGO/PPS film has shown outstanding HER electrocatalytic behaviors performed a current density of 10 mA cm-2 at a relatively low overpotential of 160 mV with a Tafel slope of 60 mV dec-1 in acidic medium, which can be mainly attributed to the synergistic effect between optimized morphology and accelerated kinetics. Additionally, this film electrocatalyst exhibits a good HER activity and stability under both neutral and basic conditions.

  9. Effects of sequential helium and hydrogen ion irradiation on the nucleation and evolution of bubbles in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Zhenyu; Zheng, Zhongcheng [Hubei Nuclear Solid Physics Key Laboratory, Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, 430072 (China); Luo, Fengfeng [Hubei Nuclear Solid Physics Key Laboratory, Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, 430072 (China); Institute of Applied Physics, Jiangxi Academy of Science, Nanchang, 330029 (China); Hu, Wenhui [Hubei Nuclear Solid Physics Key Laboratory, Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, 430072 (China); Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, 230031 (China); Zhang, Weiping [Hubei Nuclear Solid Physics Key Laboratory, Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, 430072 (China); Guo, Liping, E-mail: guolp@whu.edu.cn [Hubei Nuclear Solid Physics Key Laboratory, Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan, 430072 (China); Ren, Yaoyao [Center for Electron Microscopy, Wuhan University, Wuhan, 430072 (China)

    2017-02-15

    Highlights: • The effect of H{sup +} irradiation on formation and evolution of helium bubbles is explored. • The growth of hydrogen bubbles under He{sup +} irradiation is observed. • Mechanism of synergistic effect between He and H is discussed. - Abstract: Irradiations of He{sup +} and H{sup +} have been performed to investigate the effect of H{sup +} irradiation on existing helium bubbles and the effect of pre-irradiation of H{sup +} on the formation of helium bubbles in tungsten. The specimens were irradiated at 800 °C with either 10kev-H{sup +}, 20kev-He{sup +}, or sequentially irradiated with both H{sup +} and He{sup +}. After H{sup +} irradiation, the growth of existing helium bubbles was observed. It was also found that pre- or post- irradiation of H{sup +} enhanced the nucleation of helium bubbles. The growth of hydrogen bubbles was also observed after post irradiation of He{sup +}. The possible mechanism is discussed.

  10. Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

    Science.gov (United States)

    Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

    2012-01-21

    Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

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

    Science.gov (United States)

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

    2018-03-01

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

  12. Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution

    Science.gov (United States)

    Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

    2018-06-01

    Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

  13. Hydrogen reduction in GaAsN thin films by flow rate modulated chemical beam epitaxy

    International Nuclear Information System (INIS)

    Saito, K.; Nishimura, K.; Suzuki, H.; Ohshita, Y.; Yamaguchi, M.

    2008-01-01

    The amount of residual H in the GaAsN film grown by chemical beam epitaxy (CBE) can be decreased by flow rate modulation growth. Many H atoms in the films grown by CBE exist as N-H or N-H 2 structures. Although a higher growth temperature was required for decreasing the H concentration ([H]), it caused a decrease in the N concentration ([N]). A reduction in [H] while keeping [N] constant was necessary. By providing an intermittent supply of Ga source while continuously supplying As and N sources, [H] effectively decreased in comparison with the [H] value in the film grown at the same temperature by conventional CBE without reducing [N

  14. General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

    Science.gov (United States)

    Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

    2018-04-25

    Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

  15. 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.

  16. A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Juanjuan, E-mail: majj0518@hotmail.com [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Liu, Lin; Chen, Qian; Yang, Min [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Wang, Danping [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Tong, Zhiwei [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Chen, Zhong, E-mail: aszchen@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore)

    2017-03-31

    Highlights: • Crumpled CoTMPyP/ERGO hybrid was successfully prepared by a facile two-step process. • CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. • CoTMPyP/ERGO hybrid film shows good electrocatalytic activity and stability for HER. - Abstract: 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.

  17. 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; Lu, Ang-Yu; Sonawane, Poonam Ashok; Kumar, U. Rajesh; Yadav, Kanchan; Li, Lain-Jong; Chen, Yit Tsong

    2015-01-01

    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.

  18. Highly efficient electrochemical hydrogen evolution based on nickel diselenide nanowall film

    Science.gov (United States)

    Tang, Chun; Xie, Lisi; Sun, Xuping; Asiri, Abdullah M.; He, Yuquan

    2016-05-01

    In this letter, we report on hydrothermal growth of nickel diselenide nanowall film on carbon cloth (NiSe2 NW/CC) through topotactic transformation from a Ni(OH)2 precursor based on anion exchange reactions. When tested as an integrated 3D hydrogen-evolving cathode in strongly acidic media, NiSe2 NW/CC exhibits outstanding catalytic activity superior to its powder counterpart and strong long-term durability. It displays 10 and 100 mA cm-2 at overpotentials of 145 and 183 mV, respectively, with its catalytic activity being retained for 40 h.

  19. Hydrogen energy share improvement along with NOx (oxides of nitrogen) emission reduction in a hydrogen dual-fuel compression ignition engine using water injection

    International Nuclear Information System (INIS)

    Chintala, V.; Subramanian, K.A.

    2014-01-01

    Highlights: • H 2 energy share increased from 20% without water to 39% with SWC 270 g/kWh. • Specific water consumption (SWC) 200 g/kWh was selected as the optimum quantity. • NO x decreased about 24% with the optimum water quantity at 20% H 2 energy share. • At 20% H 2 share, energy efficiency decreased about 5.5% with the optimum water. • HC, CO and smoke emissions increased 38%, 100% and 69% with optimum water at 20% H 2 share. - Abstract: The study aims at enhancement of Hydrogen (H 2 ) energy share and reduction of Oxides of Nitrogen (NO x ) emission in a 7.4 kW-CI engine at 1500 rpm using water injection. The test engine was modified to run under dual-fuel operation with diesel–biodiesel blend (B20) and H 2 fuels for different Specific Water Consumption (SWC) of 130, 200, and 270 g/kWh. Under conventional H 2 dual-fuel mode, energy efficiency and NO x emission increased significantly while Hydrocarbon (HC), Carbon Monoxide (CO) and smoke emissions decreased. The maximum H 2 energy share increased from 20% without water to 32%, 36%, and 39% with SWC of 130, 200, and 270 g/kWh respectively. However, SWC of 200 g/kWh was selected as an optimum water quantity for knock free operation, better performance and lower emissions. At the optimum SWC with 20% H 2 energy share, the NO x emission and energy efficiency decreased about 24% and 5.7%, while HC and smoke emissions increased about 38% and 69%. At 20% H 2 energy share, the CO emission increased from 0.0 g/kWh without water to 1.2 g/kWh with the optimum SWC. However, reduction of these HC and CO emissions using oxidation catalysts needs to be studied further. A new methodology for determining heat release rate with consideration of crevice gas was proposed in the study

  20. 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.

  1. Surface Functionalization of g-C 3 N 4 : Molecular-Level Design of Noble-Metal-Free Hydrogen Evolution Photocatalysts

    KAUST Repository

    Chen, Yin; Lin, Bin; Yu, Weili; Yang, Yong; Bashir, Shahid M.; Wang, Hong; Takanabe, Kazuhiro; Idriss, Hicham; Basset, Jean-Marie

    2015-01-01

    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

  2. Gold nanoparticles embedded in Ta 2 O 5 /Ta 3 N 5 as active visible-light plasmonic photocatalysts for solar hydrogen evolution

    KAUST Repository

    Luo, Yujing; Liu, Xiaoming; Tang, Xinghua; Luo, Yan; Zeng, Qianyao; Deng, Xiaolei; Ding, Shaolei; Sun, Yiqun

    2014-01-01

    Here, we demonstrate a new recreating photocatalytic activity of a Nano Au/Ta2O5 composite for hydrogen evolution from water as a visible-light-responsive plasmonic photocatalyst by embedding Au nanoparticles in a Ta2O5 host lattice. The Nano Au/Ta2

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-01

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

  4. Photocatalytic hydrogen evolution of palladium nanoparticles decorated black TiO2 calcined in argon atmosphere

    Science.gov (United States)

    Wu, Ming-Chung; Hsiao, Kai-Chi; Chang, Yin-Hsuan; Chan, Shun-Hsiang

    2018-02-01

    Black TiO2 nanoparticles (BTN) was prepared by sol-gel derived precursor calcined in an argon atmosphere. The synthesized BTN with trivalent titanium ion, structural defect, and oxygen vacancy shows a remarkably high absorbance in the visible light spectrum. BTN thus behaves a higher visible-active nanoreactor than white TiO2 nanoparticles (WTN) in the aqueous solution for organic pollutant degradation. Moreover, palladium decoration on the BTN surface (Pd-BTN) demonstrates a fascinating clean energy application. The obtained Pd-BTN fulfills a satisfied green material demand in the photocatalytic hydrogen production application. Pd-BTN calcined at 400 °C (Pd-BTN-400) shows the high photocatalytic hydrogen generation rate of 5200 μmol/g h under UV-A irradiation and 9300 μmol/g h under UV-B irradiation, respectively. The well-developed material, Pd-BTN-400, could be one of the best solutions in the concern of clean energy and water-purification with regard to the continuous environmental issue.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. Characterization of LaNiO3 prepared by sol–gel: Application to hydrogen evolution under visible light

    International Nuclear Information System (INIS)

    Khettab, M.; Omeiri, S.; Sellam, D.; Ladjouzi, M.A.; Trari, M.

    2012-01-01

    Highlights: ► Photoactive LaNiO 3 was prepared by sol–gel. ► LaNiO 3 exhibits n type conductivity it due to slight oxygen deficiency. ► LaNiO 3 was successfully for hydrogen evolution upon visible light. - Abstract: The semi conducting properties of LaNiO 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 SCE ) and the exchange current density (0.103 mA cm −2 ), determined from the semi logarithmic plot, indicate long lived oxide. The slope and the intercept to C −2 = 0 of the Mott Schottky plot, characteristic of n type behaviour, gave respectively an electron density (N D ) of 2.3 × 10 19 cm −3 and a flat band potential (V fb ) of −0.61 V SCE . The nature of the Nyquist plot, measured over a wide frequency range (10 −3 –10 5 Hz), shows the predominance of the bulk contribution. The arc is not centred on the real axis (−6.3°), 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 3 –CB with a potential (−0.62 V SCE ) sufficient to reduce water (−0.50 V SCE ). As application, the oxide has been tested successfully for hydrogen evolution upon visible light with a rate evolution of 1.73 μmol min −1 (g catalyst) −1 and a quantum efficiency of 0.042% under full light (29 mW cm −2 ).

  10. 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

    2013-06-21

    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 ω[over dot]=-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)] this outcome will be naturally related to the

  11. Microstructural evolution in tungsten and copper probes under hydrogen irradiation at ISTTOK

    International Nuclear Information System (INIS)

    Nunes, D.; Mateus, R.; Nogueira, I.D.; Carvalho, P.A.; Correia, J.B.; Shohoji, N.; Gomes, R.B.; Fernandes, H.; Silva, C.; Franco, N.; Alves, E.

    2009-01-01

    Commercially pure tungsten and copper wires acting as Langmuir probes to estimate edge parameters of ISTTOK plasma have been investigated for long term hydrogen migration. The microstructure of both materials revealed recrystallization and strong grain growth at the most severely exposed regions. A low number of large bubbles was observed at the most severely exposed regions, whereas a high density of small intergranular bubbles was found at more moderately exposed regions. Bubble distribution, lattice parameter, grain size, Young's modulus and microhardness were assessed across longitudinal sections of the probes. The results indicate that bubble formation in tungsten and copper first wall components can be expected to occur and strategies for minimization of this retention phenomenon need to be implemented.

  12. Room temperature synthesis of heptazine-based microporous polymer networks as photocatalysts for hydrogen evolution.

    Science.gov (United States)

    Kailasam, Kamalakannan; Schmidt, Johannes; Bildirir, Hakan; Zhang, Guigang; Blechert, Siegfried; Wang, Xinchen; Thomas, Arne

    2013-06-25

    Two emerging material classes are combined in this work, namely polymeric carbon nitrides and microporous polymer networks. The former, polymeric carbon nitrides, are composed of amine-bridged heptazine moieties and showed interesting performance as a metal-free photocatalyst. These materials have, however, to be prepared at high temperatures, making control of their chemical structure difficult. The latter, microporous polymer networks have received increasing interest due to their high surface area, giving rise to interesting applications in gas storage or catalysis. Here, the central building block of carbon nitrides, a functionalized heptazine as monomer, and tecton are used to create microporous polymer networks. The resulting heptazine-based microporous polymers show high porosity, while their chemical structure resembles the ones of carbon nitrides. The polymers show activity for the photocatalytic production of hydrogen from water, even under visible light illumination. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis of tantalum carbide and nitride nanoparticles using a reactive mesoporous template for electrochemical hydrogen evolution

    KAUST Repository

    Alhajri, Nawal Saad; Yoshida, Hiroshi; Anjum, Dalaver H.; Garcia Esparza, Angel T.; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

    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.

  14. 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......-term stability. The measured Tafel slope of 74 mV dec-1 implies an underlying Volmer-Heyrovsky HER mechanism....

  15. The genome of the obligate intracellular parasite Trachipleistophora hominis: new insights into microsporidian genome dynamics and reductive evolution.

    Directory of Open Access Journals (Sweden)

    Eva Heinz

    Full Text Available 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

  16. Electro-activity of cobalt and nickel complexes for the reduction of protons into di-hydrogen. Application to PEM water electrolysis

    International Nuclear Information System (INIS)

    Pantani, O.; Anxolabehere, E.; Aukauloo, A.; Millet, P.

    2006-01-01

    Proton exchange membrane (PEM) water electrolysis is a safe and efficient way to perform water splitting into di-hydrogen and di-oxygen. In a PEM water electrolyser, platinum is commonly used as electro-catalyst on the cathodic side of the cells, mostly because of its efficiency for hydrogen evolution. But for cost considerations, there is a need to find alternative low-cost electrocatalysts. Molecular chemistry offers the possibility of synthesizing new compounds for this purpose, such as transition metal complexes. Results obtained with nickel- and cobalt-oximes compounds are presented in this paper. They have been chemically (1H NMR, EPR) and electrochemically (voltametry, spectro-electrochemistry) characterized. Their ability to electrochemically reduce protons into di-hydrogen when they are either dissolved in solution or immobilized at the surface of a solid electrode is discussed. (authors)

  17. Photoelectron emission yield experiments on evolution of sub-gap states in amorphous In-Ga-Zn-O thin films with post deposition hydrogen treatment

    International Nuclear Information System (INIS)

    Hayashi, Kazushi; Hino, Aya; Tao, Hiroaki; Ochi, Mototaka; Goto, Hiroshi; Kugimiya, Toshihiro

    2015-01-01

    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

  18. 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.

  19. Wrinkle-free atomically thin CdS nanosheets for photocatalytic hydrogen evolution

    Science.gov (United States)

    Pan, Ziwei; Li, Junnan; Zhou, Kebin

    2018-05-01

    Two-dimensional (2D) nanosheets of atomic thickness have attracted extensive research interest recently. In this work, atomically thin (0.7 nm) flat CdS (F-CdS) nanosheets of several tens of micrometers in lateral size were synthesized by a solvent-thermal method. The as-synthesized F-CdS could maintain flat morphology well in solution, while irreversible wrinkles could be generated after drying, forming wrinkled CdS (W-CdS) samples. It was revealed that the formation of wrinkles could reduce light absorbance, narrow the band gap, move down the conduction band position and accelerate electron–hole recombination. As photocatalysts, the F-CdS achieved a photocatalytic H2 evolution rate of 138.7 mmol g‑1 h‑1 without any co-catalyst under visible light, which was much higher than that of the W-CdS sample (with an H2 evolution rate of only 52.8 mmol g‑1 h‑1). This work demonstrates that great attention should be paid to the wrinkles in 2D materials as photocatalysts.

  20. Preliminary investigation of air bubbling and dietary sulfur reduction to mitigate hydrogen sulfide and odor from swine waste.

    Science.gov (United States)

    Clark, O Grant; Morin, Brent; Zhang, Yongcheng; Sauer, Willem C; Feddes, John J R

    2005-01-01

    When livestock manure slurry is agitated, the sudden release of hydrogen sulfide (H(2)S) can raise concentrations to dangerous levels. Low-level air bubbling and dietary S reduction were evaluated as methods for reducing peak H(2)S emissions from swine (Sus scrofa) manure slurry samples. In a first experiment, 15-L slurry samples were stored in bench-scale digesters and continuously bubbled with air at 0 (control), 5, or 10 mL min(-1) for 28 d. The 5-L headspace of each digester was also continuously ventilated at 40 mL min(-1) and the mean H(2)S concentration in the outlet air was 120 microL L(-1)) from the control treatment, and was 47 and 3.4 microL L(-1) for the 5 and 10 mL min(-1) treatments, respectively. In a second experiment, individually penned barrows were fed rations with dietary S concentrations of 0.34, 0.24, and 0.15% (w/w). Slurry derived from each diet was bubbled with air in bench-scale digesters, as before, at 10 mL min(-1) for 12 d and the mean H(2)S concentration in the digester outlet air was 11 microL L(-1). On Day 12, the slurry was agitated but the H(2)S emissions did not change significantly. Both low-level bubbling of air through slurry and dietary S reduction appear to be viable methods for reducing peak H(2)S emissions from swine manure slurry at a bench scale, but these approaches must be validated at larger scales.

  1. Reduction of hydrogen desorption temperature of ball-milled MgH2 by NbF5 addition

    International Nuclear Information System (INIS)

    Recham, N.; Bhat, V.V.; Kandavel, M.; Aymard, L.; Tarascon, J.-M.; Rougier, A.

    2008-01-01

    Enhanced sorption properties of ball-milled MgH 2 are reported by adding NbF 5 . Among various catalyst amounts, 2 mol% of NbF 5 reveals to be the optimum concentration leading to significant reduction of the desorption temperature as well as faster kinetics of ball-milled MgH 2 . At 200 deg. C, temperature at which MgH 2 does not show any activity, MgH 2NbF 5 /2mol% composite desorbs 3.2 wt.% of H 2 in 50 mins. Interestingly, the addition of NbF 5 is also associated with an increase in the desorption pressure. At 300 deg. C, MgH 2NbF 5 /2mol% composite starts to desorb hydrogen at 600 mbar in comparison with 1 mbar for MgH 2 . Further improvements were successfully achieved by pre-grinding NbF 5 prior to ball-milling the catalyst with MgH 2 . Such pre-ground NbF 5 catalyzed MgH 2 composite desorbs 3 wt.% of H 2 at 150 deg. C. Improved properties are associated with smaller activation energies down to values close to the enthalpy of formation of MgH 2 . Finally, the mechanism at the origin of the enhancement is discussed in terms of catalyst stability, MgF 2 formation and electronic density localization

  2. Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

    Science.gov (United States)

    Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

    2017-09-01

    Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  3. Interface passivation and trap reduction via hydrogen fluoride for molybdenum disulfide on silicon oxide back-gate transistors

    Science.gov (United States)

    Hu, Yaoqiao; San Yip, Pak; Tang, Chak Wah; Lau, Kei May; Li, Qiang

    2018-04-01

    Layered semiconductor molybdenum disulfide (MoS2) has recently emerged as a promising material for flexible electronic and optoelectronic devices because of its finite bandgap and high degree of gate control. Here, we report a hydrogen fluoride (HF) passivation technique for improving the carrier mobility and interface quality of chemical vapor deposited monolayer MoS2 on a SiO2/Si substrate. After passivation, the fabricated MoS2 back-gate transistors demonstrate a more than double improvement in average electron mobility, a reduced gate hysteresis gap of 3 V, and a low interface trapped charge density of ˜5.8 × 1011 cm-2. The improvements are attributed to the satisfied interface dangling bonds, thus a reduction of interface trap states and trapped charges. Surface x-ray photoelectron spectroscopy analysis and first-principles simulation were performed to verify the HF passivation effect. The results here highlight the necessity of a MoS2/dielectric passivation strategy and provides a viable route for enhancing the performance of MoS2 nano-electronic devices.

  4. 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...

  5. 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.

  6. 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.

  7. Rague-Like FeP Nanocrystal Assembly on Carbon Cloth: An Exceptionally Efficient and Stable Cathode for Hydrogen Evolution

    KAUST Repository

    Yang, Xiulin; Lu, Ang-Yu; Zhu, Yihan; Min, Shixiong; Hedhili, Mohamed N.; Han, Yu; Huang, Kuo-Wei; Li, Lain-Jong

    2015-01-01

    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.

  8. 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.

  9. Rapid evolution of troglomorphic characters suggests selection rather than neutral mutation as a driver of eye reduction in cave crabs.

    Science.gov (United States)

    Klaus, Sebastian; Mendoza, José C E; Liew, Jia Huan; Plath, Martin; Meier, Rudolf; Yeo, Darren C J

    2013-04-23

    This study asked whether reductive traits in cave organisms evolve at a slower pace (suggesting neutral evolution under relaxed selection) than constructive changes, which are likely to evolve under directional selection. We investigated 11 subterranean and seven surface populations of Sundathelphusa freshwater crabs on Bohol Island, Philippines, and examined constructive traits associated with improved food finding in darkness (increased leg and setae length) and reductive traits (reduced cornea size and eyestalk length). All changes occurred rapidly, given that the age of the most recent common ancestor was estimated to be 722-271 ka based on three mitochondrial markers. In order to quantify the speed of character change, we correlated the degree of morphological change with genetic distances between surface and subterranean individuals. The temporal pattern of character change following the transition to subterranean life was indistinguishable for constructive and reductive traits, characterized by an immediate onset and rapid evolutionary change. We propose that the evolution of these reductive traits-just like constructive traits-is most likely driven by strong directional selection.

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

    Science.gov (United States)

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

    2018-02-01

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

  11. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  12. 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.

  13. Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization.

    Science.gov (United States)

    Benson, Eric E; Zhang, Hanyu; Schuman, Samuel A; Nanayakkara, Sanjini U; Bronstein, Noah D; Ferrere, Suzanne; Blackburn, Jeffrey L; Miller, Elisa M

    2018-01-10

    We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2 ) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3 CH 2 ) 2 NPh-MoS 2 ) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2 . The p-(CH 3 CH 2 ) 2 NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

  14. 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

  15. Improving corrosion resistance of magnesium-based alloys by surface modification with hydrogen by electrochemical ion reduction (EIR) and by plasma immersion ion implantation (PIII)

    Energy Technology Data Exchange (ETDEWEB)

    Bakkar, A. [Institut fuer Materialpruefung und Werkstofftechnik, Dr. Doelling und Dr. Neubert GmbH, Freiberger Strasse 1, 38678 Clausthal (Germany); Department of Metallurgy and Materials Engineering, Suez Canal University, P.O. Box 43721, Suez (Egypt); Neubert, V. [Institut fuer Materialpruefung und Werkstofftechnik, Dr. Doelling und Dr. Neubert GmbH, Freiberger Strasse 1, 38678 Clausthal (Germany)]. E-mail: volkmar.neubert@tu-clausthal.de

    2005-05-01

    Magnesium-based hydrides are well known that they have a high hydrogen-storage capacity. In this study, two different methods have been provided for hydrogen surface modification of high purity magnesium (hp Mg) and AZ91 magnesium alloy. One was electrochemical ion reduction (EIR) of hydrogen from an alkaline electrolyte on such Mg-based cathode. The other was plasma immersion ion implantation (PIII or PI{sup 3}) into Mg-based substrate. The depth profile of H-modified surfaces was described by Auger electron spectroscopy (AES) and by secondary ion mass spectrometry (SIMS) measurements. Corrosion testing was carried out in Avesta cell by potentiodynamic polarisation in chloride-containing aqueous solutions of pH 7 and pH 12. A greatly significant improvement in the corrosion resistance of H-modified surfaces was verified.

  16. Improving corrosion resistance of magnesium-based alloys by surface modification with hydrogen by electrochemical ion reduction (EIR) and by plasma immersion ion implantation (PIII)

    International Nuclear Information System (INIS)

    Bakkar, A.; Neubert, V.

    2005-01-01

    Magnesium-based hydrides are well known that they have a high hydrogen-storage capacity. In this study, two different methods have been provided for hydrogen surface modification of high purity magnesium (hp Mg) and AZ91 magnesium alloy. One was electrochemical ion reduction (EIR) of hydrogen from an alkaline electrolyte on such Mg-based cathode. The other was plasma immersion ion implantation (PIII or PI 3 ) into Mg-based substrate. The depth profile of H-modified surfaces was described by Auger electron spectroscopy (AES) and by secondary ion mass spectrometry (SIMS) measurements. Corrosion testing was carried out in Avesta cell by potentiodynamic polarisation in chloride-containing aqueous solutions of pH 7 and pH 12. A greatly significant improvement in the corrosion resistance of H-modified surfaces was verified

  17. Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

    Science.gov (United States)

    Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

    2016-10-01

    Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.

  18. Facile synthesis of stable structured MoS{sub 2}-Mo-CNFs heteroarchitecture with enhanced hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Qionghua [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Faculty of Material and Energy, South West University, Chongqing 400700 (China); Yao, Yucen [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Liu, Bitao, E-mail: liubitao007@163.com [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Peng, Lingling; Yan, Hengqing; Hou, Zhupei; Wang, Jun [Research Institute for New Materials Technology, Chongqing University of Arts and Sciences, Chongqing 402160 (China); Lin, Yue, E-mail: linyue@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Anhui 230026 (China)

    2017-06-01

    3D structured MoS{sub 2} are grown in-situ on Mo particles embedded carbon nanofibers (CNFs) via a hydrothermal method. Due to this special structure, the bonding and effective electron delivery between CNFs and MoS{sub 2} are both enhanced, and which will exhibits a better hydrogen evolution activity. The onset potential of this MoS{sub 2}-Mo-CNFs catalyst will decreased to 60 mV compared to the 90 mV for the MoS{sub 2}-CNFs. And its current density nearly no change with 5000 cycles which is better than the 32.3% decrease of MoS{sub 2}-CNFs at η = 300 mV (V vs RHE). - Highlights: • Newly structured MoS{sub 2}-Mo-CNFs with effectively connection between MoS{sub 2} and CNFs successfully synthesized. • This structure can enhance the charge transfer and significantly increase electrocatalytic efficiency. • Nearly no HER activity loss after 5000 CV cycles.

  19. WC Nanocrystals Grown on Vertically Aligned Carbon Nanotubes: An Efficient and Stable Electrocatalyst for Hydrogen Evolution Reaction.

    Science.gov (United States)

    Fan, Xiujun; Zhou, Haiqing; Guo, Xia

    2015-05-26

    Single nanocrystalline tungsten carbide (WC) was first synthesized on the tips of vertically aligned carbon nanotubes (VA-CNTs) with a hot filament chemical vapor deposition (HF-CVD) method through the directly reaction of tungsten metal with carbon source. The VA-CNTs with preservation of vertical structure integrity and alignment play an important role to support the nanocrystalline WC growth. With the high crystallinity, small size, and uniform distribution of WC particles on the carbon support, the formed WC-CNTs material exhibited an excellent catalytic activity for hydrogen evolution reaction (HER), giving a η10 (the overpotential for driving a current of 10 mA cm(-2)) of 145 mV, onset potential of 15 mV, exchange current density@ 300 mV of 117.6 mV and Tafel slope values of 72 mV dec(-1) in acid solution, and η10 of 137 mV, onset potential of 16 mV, exchange current density@ 300 mV of 33.1 mV and Tafel slope values of 106 mV dec(-1) in alkaline media, respectively. Electrochemical stability test further confirms the long-term operation of the catalyst in both acidic and alkaline media.

  20. Self-Supported Biocarbon-Fiber Electrode Decorated with Molybdenum Carbide Nanoparticles for Highly Active Hydrogen-Evolution Reaction.

    Science.gov (United States)

    Xiao, Jian; Zhang, Yan; Zhang, Zheye; Lv, Qiying; Jing, Feng; Chi, Kai; Wang, Shuai

    2017-07-12

    Devising and facilely synthesizing an efficient noble metal-free electrocatalyst for the acceleration of the sluggish kinetics in the hydrogen-evolution reaction (HER) is still a big challenge for electrolytic water splitting. Herein, we present a simple one-step approach for constructing self-supported biocarbon-fiber cloth decorated with molybdenum carbide nanoparticles (BCF/Mo 2 C) electrodes by a direct annealing treatment of the Mo oxyanions loaded cotton T-shirt. The Mo 2 C nanoparticles not only serve as the catalytic active sites toward the HER but also enhance the hydrophilicity and conductivity of resultant electrodes. As an integrated three-dimensional HER cathode catalyst, the BCF/Mo 2 C exhibits outstanding electrocatalytic performance with extremely low overpotentials of 88 and 115 mV to drive a current density of 20 mA cm -2 in alkaline and acidic media, respectively. In addition, it can continuously work for 50 h with little decrease in the cathodic current density in both alkaline and acidic solutions. Even better, self-supported tungsten carbide and vanadium carbide based electrodes also can be prepared by a similar synthesis process. This work will illuminate an entirely new avenue for the preparation of various self-supported three-dimensional electrodes made of transition-metal carbides for various applications.

  1. Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction

    KAUST Repository

    Chen, Yen-Chang; Lu, Ang-Yu; Lu, Ping; Yang, Xiulin; Jiang, Chang-Ming; Mariano, Marina; Kaehr, Brian; Lin, Oliver; Taylor, André ; Sharp, Ian D.; Li, Lain-Jong; Chou, Stanley S.; Tung, Vincent

    2017-01-01

    The emerging molybdenum disulfide (MoS2) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.

  2. CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity

    Science.gov (United States)

    Chen, Yajie; Kang, Chuanhong; Wang, Ruihong; Ren, Zhiyu; Fu, Huiying; Xiao, Yuting; Tian, Guohui

    2018-06-01

    The CoP/WS2 nanoflake composites were synthesized via the sulfuration and subsequent phosphidation using the pre-prepared WO2.72 nanowires as precursors. Originally, WO2.72 nanowires were prepared and followed by sulfuration to obtain WS2 nanoflakes. The as-prepared WS2 nanoflakes were used as substrates, on which the Co3O4 nanoparticles were uniformly anchored to construct the Co3O4/WS2 nanoflakes. Finally, the Co3O4/WS2 composites were subjected to phosphidation and in-situ converted into CoP/WS2 nanoflakes. Because of the dual functionalities of both CoP and WS2, the abundant interfaces as well as their synergy, the CoP/WS2 nanoflakes exhibited much higher electrocatalytic activity, smaller overpotential (-81 mV), lower Tafel slope (62 mV decade-1), and higher stability toward hydrogen-evolution reaction than those for the single CoP and WS2.

  3. MoS2 nanosheets direct supported on reduced graphene oxide: An advanced electrocatalyst for hydrogen evolution reaction.

    Directory of Open Access Journals (Sweden)

    Jiamu Cao

    Full Text Available Molybdenum disulfide nanosheets/reduced graphene oxide (MoS2 NSs/rGO nanohybrid as a highly effective catalyst for hydrogen evolution reaction (HER have been successfully synthesized by a facile microwave-assisted method. The results clearly reveal that direct grown of MoS2 NSs on rGO have been achieved. Electrochemical tests show that the as-prepared hybrid material exhibited excellent HER activity, with a small Tafel slope of 57 mV dec-1, an overpotential of 130 mV and remarkable cycling stability. After analysis, the observed outstanding catalytic performance can be attributed to the uniform distribution of the MoS2 NSs, which are characterized by the presence of multiple active sites as well as the effective electron transport route provided by the conductive rGO substrate. Moreover, according to the classic theory, the mechanism governing of the catalytic HER on the MoS2 NSs/rGO nanohybrid has been clarified.

  4. Incorporation of tantalum ions enhances the electrocatalytic activity of hexagonal WO3 nanowires for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Xie, Xiang; Mu, Wanjun; Li, Xingliang; Wei, Hongyuan; Jian, Yuan; Yu, Qianhong; Zhang, Rui; Lv, Kai; Tang, Hui; Luo, Shunzhong

    2014-01-01

    WO 3 has been identified as a promising candidate electrocatalyst for hydrogen evolution reaction (HER), because it can form a tungsten bronze (HxWO 3 ) which is highly electron and proton conducting. In this paper, we report that the electrocatalytic activity of WO 3 for HER can be enhanced by incorporation of tantalum ions (Ta 5+ ) into the lattice of WO 3 . The most active performance is achieved with the molar ratio of Ta/W being 0.01, which is two times more active than that of undoped WO 3 at an overpotential of -0.52 V. It is shown that incorporation of proper Ta 5+ into WO 3 can induce moderate defects and oxygen vacancies, as well as intercalate a higher amount of protons, which enhance the electron transfer and short the protons diffusion paths. These changes correlated positively with the enhanced catalytic HER activity. This study demonstrates, for the first time, that metal ions-doped WO 3 nanowires are promising electrocatalysts for HER

  5. The self-activation and synergy of amorphous Re nanoparticle – Si nanowire composites for the electrocatalytic hydrogen evolution

    International Nuclear Information System (INIS)

    Yang, Lulu; Lu, Shunkai; Wang, Hui; Shao, Qi; Liao, Fan; Shao, Mingwang

    2017-01-01

    Highlights: • Amorphous Re nanoparticle modified Si nanowire nanocomposites were prepared. • An interesting self-activation phenomenon was observed in HER process. • Re/SiNW showed synergy in HER process. • The optimal mass ratio of Re: Si was determined to be 31.1: 68.9. - Abstract: Amorphous rhenium nanoparticles modified silicon nanowires were prepared via reducing Re ion by Si−H bonds, which were employed to electrocatalysize the hydrogen evolution reaction because amorphous structure may have excellent catalytic activity. It is interesting that an obvious self-activation for Re/Si catalysts was observed with the current density enhanced by 2.2 times its previous value at 400 mV after a 3,000 s of continuous cyclic voltammetry scanning, and the catalytic performance remained steady thereafter. The optimal electrocatalytic performance was found with the Re: Si mass ratio of 31.1: 68.9, resulting in a Tafel slope of 81 mV·dec −1 and overpotential of 100 mV at current density of 10 mA·cm −2 .

  6. Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction

    KAUST Repository

    Chen, Yen-Chang

    2017-10-12

    The emerging molybdenum disulfide (MoS2) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.

  7. Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

    Science.gov (United States)

    Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

    2017-12-11

    The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. 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.

  10. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    Science.gov (United States)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  11. 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%H 2(g) -N 2(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 Mn 2 O 3 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.

  12. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  13. A fault tree analysis (FTA) of hydrogen explosion potentiality on reduction furnace ME-11 in nuclear power fuel element fabrication process

    International Nuclear Information System (INIS)

    Achmad Suntoro

    2012-01-01

    Fault Tree Analysis (FTA) diagrams for the potentiality of hydrogen gas explosion in reduction furnace of ME-11 has been created after modification of its logic control. These FTA diagrams can be used as additional information in designing preventive maintenance program and operational steps of the furnace. The encountering of two conditions, i.e. explosion ignition and the potentially explosive of hydrogen gas, is the search focus of the FTA, and it may be done by breaking and tracing down to any possibility of initial causes for these two conditions to occur coincidently. Two locations of the potentially explosive area were identified: furnace chamber and combustion chamber of the exhaust gas. The possible explosion ignitions for the furnace are only from spark, fire and hot material because the operation of the furnace does not use high-pressure hydrogen. However, these explosion ignitions are part of the on going reduction process, therefore it is important that the hydrogen gas volume composition during the process always be supervised. (author)

  14. 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.

  15. Data on the synthesis processes optimization of novel β-NiS film modified CdS nanoflowers heterostructure nanocomposite for photocatalytic hydrogen evolution.

    Science.gov (United States)

    Zhang, Yu; Peng, Zhijian; Guan, Shundong; Fu, Xiuli

    2018-02-01

    The data presented in this article are related to a research article entitled 'Novel β-NiS film modified CdS nanoflowers heterostructure nanocomposite: extraordinarily highly efficient photocatalysts for hydrogen evolution' (Zhang et al., 2018) [1]. In this article, we report original data on the synthesis processes optimization of the proposed nanocomposite on the basis of their optimum photocatalytic performance together with the comparison on the results of literatures and comparative experiments. The composition, microstructure, morphology, photocatalytic hydrogen evolution and photocatalytic stability of the corresponding samples are included in this report. The data are presented in this format in order to facilitate comparison with data from other researchers in the field and understanding the mechanism of similar catalysts.

  16. Formation of multilayer-Eosin Y-sensitized TiO{sub 2} via Fe{sup 3+} coupling for efficient visible-light photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yuexiang; Guo, Miaomiao; Peng, Shaoqin [Department of Chemistry, Nanchang University, Nanchang 330031 (China); Lu, Gongxuan; Li, Shuben [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2009-07-15

    An efficient visible-light active photocatalyst of multilayer-Eosin Y-sensitized TiO{sub 2} is prepared through linkage of Fe{sup 3+} between not only TiO{sub 2} and Eosin Y but also different Eosin Y molecules to form three-dimensional polymeric dye structure. The multilayer-dye-sensitized photocatalyst is found to have high light harvesting efficiency and photocatalytic activity for hydrogen evolution under visible light irradiation ({lambda} > 420 nm). On the optimum conditions (1:1 initial molar ratio of Eosin Y to Fe(NO{sub 3}){sub 3}, initial 10 x 10{sup -3} M Eosin Y, and 1.0 wt% Pt deposited by in situ photoreduction), its maximal apparent quantum yield for hydrogen evolution is 19.1% from aqueous triethanolamine solution (TEOA aq). The present study highlights linking between dye molecules via metal ions as a general way to develop efficient visible-light photocatalyst. (author)

  17. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin; Lin, Bin; Wang, Hong; Yang, Yong; Zhu, Haibo; Yu, Weili; Basset, Jean-Marie

    2015-01-01

    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.

  18. Evolution behavior of nanohardness after thermal-aging and hydrogen-charging on austenite and strain-induced martensite in pre-strained austenitic stainless steel

    Science.gov (United States)

    Zheng, Yuanyuan; Zhou, Chengshuang; Hong, Yuanjian; Zheng, Jinyang; Zhang, Lin

    2018-05-01

    Nanoindentation has been used to study the effects of thermal-aging and hydrogen on the mechanical property of the metastable austenitic stainless steel. Thermal-aging at 473 K decreases the nanohardness of austenite, while it increases the nanohardness of strain-induced ɑ‧ martensite. Hydrogen-charging at 473 K increases the nanohardness of austenite, while it decreases the nanohardness of strain-induced ɑ‧ martensite. The opposite effect on austenite and ɑ‧ martensite is first found in the same pre-strained sample. This abnormal evolution behavior of hardness can be attributed to the interaction between dislocation and solute atoms (carbon and hydrogen). Carbon atoms are difficult to move and redistribute in austenite compared with ɑ‧ martensite. Therefore, the difference in the diffusivity of solute atoms between austenite and ɑ‧ martensite may result in the change of hardness.

  19. 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.

  20. 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.

  1. Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

    International Nuclear Information System (INIS)

    Maciel, Adriana Veloso; Job, Aldo Eloizo; Nova Mussel, Wagner da; Brito, Walter de; Duarte Pasa, Vanya Marcia

    2011-01-01

    The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor-solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H 2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N 2 atmosphere, at temperatures up to 900 o C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

  2. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-15

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

  4. A theoretical study on the mechanism of hydrogen evolution on non-precious partially oxidized nickel-based heterostructures for fuel cells.

    Science.gov (United States)

    Pan, Xinju; Zhou, Gang

    2018-03-28

    It is desirable, yet challenging, to utilize non-precious metals instead of noble-metals as efficient catalysts in the renewable energy manufacturing industry. Using first principles calculations, we study the structural characteristics of partially oxidized nickel-based nanoheterostructures (NiO/Ni NHSs), and the interfacial effects on hydrogen evolution. The origin of the enhanced hydrogen evolution performance is discussed at the microscopic level. This study identifies two types of active sites of the exposed Ni surface available for the hydrogen evolution reaction (HER). One is the hcp-hollow sites near the perimeter boundary that exhibit a more excellent HER performance than platinum (Pt), and the other the second nearest neighbor fcc-hollow sites away from the boundary that exhibit a similar performance to Pt. The interfacial effects result from the competitive charge transfer between NiO and Ni surfaces in NHSs, and enhance the reactivity of NiO/Ni NHSs by shifting the d-states of surface atoms down in energy. The illumination of the mechanism would be helpful for the design of more efficient and cheap transition metal-based catalysts.

  5. 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.)

  6. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction

    Science.gov (United States)

    Rowley-Neale, Samuel J.; Brownson, Dale A. C.; Smith, Graham C.; Sawtell, David A. G.; Kelly, Peter J.; Banks, Craig E.

    2015-10-01

    We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode

  7. Holey Reduced Graphene Oxide Coupled with an Mo2 N-Mo2 C Heterojunction for Efficient Hydrogen Evolution.

    Science.gov (United States)

    Yan, Haijing; Xie, Ying; Jiao, Yanqing; Wu, Aiping; Tian, Chungui; Zhang, Xiaomeng; Wang, Lei; Fu, Honggang

    2018-01-01

    An in situ catalytic etching strategy is developed to fabricate holey reduced graphene oxide along with simultaneous coupling with a small-sized Mo 2 N-Mo 2 C heterojunction (Mo 2 N-Mo 2 C/HGr). The method includes the first immobilization of H 3 PMo 12 O 40 (PMo 12 ) clusters on graphite oxide (GO), followed by calcination in air and NH 3 to form Mo 2 N-Mo 2 C/HGr. PMo 12 not only acts as the Mo heterojunction source, but also provides the Mo species that can in situ catalyze the decomposition of adjacent reduced GO to form HGr, while the released gas (CO) and introduced NH 3 simultaneously react with the Mo species to form an Mo 2 N-Mo 2 C heterojunction on HGr. The hybrid exhibits superior activity towards the hydrogen evolution reaction with low onset potentials of 11 mV (0.5 m H 2 SO 4 ) and 18 mV (1 m KOH) as well as remarkable stability. The activity in alkaline media is also superior to Pt/C at large current densities (>88 mA cm -2 ). The good activity of Mo 2 N-Mo 2 C/HGr is ascribed to its small size, the heterojunction of Mo 2 N-Mo 2 C, and the good charge/mass-transfer ability of HGr, as supported by a series of experiments and theoretical calculations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synthesis and characterization of Ni-P-Ag composite coating as efficient electrocatalyst for alkaline hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Elias, Liju; Hegde, A. Chitharanjan

    2016-01-01

    Highlights: • Electrocatalytic activity of Ni-P alloy is improved by Ag nanoparticle incorporation. • Ni-P-Ag electrode is developed through sol-enhanced electrodeposition. • Ni-P-Ag composite coating shows better electrocatalytic efficiency for HER. - Abstract: The effect of addition of silver nanoparticle sol (SNS) into Ni-P plating bath was studied in terms of the variation in electrocatalytic behavior of the developed coatings in 1.0 M KOH. Ni-P-Ag composite coating was achieved through direct electrolysis by adding a known quantity of the conventionally prepared SNS into Ni-P bath. Ni-P-Ag coatings electrodeposited galvanostatically on copper under different conditions of the bath was used as electrode material for alkaline hydrogen evolution reaction (HER). The optimal concentration of the SNS required for maximum electrocatalytic activity towards HER was obtained by adding different volumes of SNS (from 0 to 50 mL L −1 ) into the bath. The HER efficiency of the test electrodes in 1.0 M KOH medium was examined using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. The kinetics of HER on the alloy and composite electrodes were established through Tafel polarization and electrochemical impedance spectroscopy (EIS) analyses. Energy dispersive spectroscopy (EDS) was used to confirm the incorporation of Ag nanoparticles into the Ni-P alloy matrix. The microstructure and morphology of the alloy and composite coatings were analyzed by Scanning Electron Microscopy (SEM). A significant improvement in the electrocatalytic property of nano-Ag derived composite coatings was found, and was attributed to the enhanced electroactive sites of Ag particles. Deposition conditions to maximize the electrocatalytic activity of Ni-P-Ag nanocomposite coatings in relation to traditional Ni-P alloy coatings was arrived, and results are discussed.

  9. Determination of the level of DNA modification with cisplatin by catalytic hydrogen evolution at mercury-based electrodes.

    Science.gov (United States)

    Horáková, Petra; Tesnohlídková, Lucie; Havran, Ludek; Vidláková, Pavlína; Pivonková, Hana; Fojta, Miroslav

    2010-04-01

    Electrochemical methods proved useful as simple and inexpensive tools for the analysis of natural as well as chemically modified nucleic acids. In particular, covalently attached metal-containing groups usually render the DNA well-pronounced electrochemical activity related to redox processes of the metal moieties, which can in some cases be coupled to catalytic hydrogen evolution at mercury or some types of amalgam electrodes. In this paper we used voltammetry at the mercury-based electrodes for the monitoring of DNA modification with cis-diamminedichloroplatinum (cisplatin), a representative of metallodrugs used in the treatment of various types of cancer or being developed for such purpose. In cyclic voltammetry at the mercury electrode, the cisplatin-modified DNA yielded catalytic currents the intensity of which reflected DNA modification extent. In square-wave voltammetry, during anodic polarization after prereduction of the cisplatinated DNA, a well-developed, symmetrical signal (peak P) was obtained. Intensity of the peak P linearly responded to the extent of DNA modification at levels relevant for biochemical studies (rb = 0.01-0.10, where rb is the number of platinum atoms bound per DNA nucleotide). We demonstrate a correlation between the peak P intensity and a loss of sequence-specific DNA binding by tumor suppressor protein p53, as well as blockage of DNA digestion by a restriction endonuclease Msp I (both caused by the DNA cisplatination). Application of the electrochemical technique in studies of DNA reactivity with various anticancer platinum compounds, as well as for an easy determination of the extent of DNA platination in studies of its biochemical effects, is discussed.

  10. 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.

  11. 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

  12. Morphological Evolution of Pit-Patterned Si(001) Substrates Driven by Surface-Energy Reduction

    Science.gov (United States)

    Salvalaglio, Marco; Backofen, Rainer; Voigt, Axel; Montalenti, Francesco

    2017-09-01

    Lateral ordering of heteroepitaxial islands can be conveniently achieved by suitable pit-patterning of the substrate prior to deposition. Controlling shape, orientation, and size of the pits is not trivial as, being metastable, they can significantly evolve during deposition/annealing. In this paper, we exploit a continuum model to explore the typical metastable pit morphologies that can be expected on Si(001), depending on the initial depth/shape. Evolution is predicted using a surface-diffusion model, formulated in a phase-field framework, and tackling surface-energy anisotropy. Results are shown to nicely reproduce typical metastable shapes reported in the literature. Moreover, long time scale evolutions of pit profiles with different depths are found to follow a similar kinetic pathway. The model is also exploited to treat the case of heteroepitaxial growth involving two materials characterized by different facets in their equilibrium Wulff's shape. This can lead to significant changes in morphologies, such as a rotation of the pit during deposition as evidenced in Ge/Si experiments.

  13. Holocephalan embryos provide evidence for gill arch appendage reduction and opercular evolution in cartilaginous fishes

    Science.gov (United States)

    Gillis, J. Andrew; Rawlinson, Kate A.; Bell, Justin; Lyon, Warrick S.; Baker, Clare V. H.; Shubin, Neil H.

    2011-01-01

    Chondrichthyans possess endoskeletal appendages called branchial rays that extend laterally from their hyoid and gill-bearing (branchial) arches. Branchial ray outgrowth, like tetrapod limb outgrowth, is maintained by Sonic hedgehog (Shh) signaling. In limbs, distal endoskeletal elements fail to form in the absence of normal Shh signaling, whereas shortened duration of Shh expression correlates with distal endoskeletal reduction in naturally variable populations. Chondrichthyans also exhibit natural variation with respect to branchial ray distribution—elasmobranchs (sharks and batoids) possess a series of ray-supported septa on their hyoid and gill arches, whereas holocephalans (chimaeras) possess a single hyoid arch ray-supported operculum. Here we show that the elongate hyoid rays of the holocephalan Callorhinchus milii grow in association with sustained Shh expression within an opercular epithelial fold, whereas Shh is only transiently expressed in the gill arches. Coincident with this transient Shh expression, branchial ray outgrowth is initiated in C. milii but is not maintained, yielding previously unrecognized vestigial gill arch branchial rays. This is in contrast to the condition seen in sharks, where sustained Shh expression corresponds to the presence of fully formed branchial rays on the hyoid and gill arches. Considered in light of current hypotheses of chondrichthyan phylogeny, our data suggest that the holocephalan operculum evolved in concert with gill arch appendage reduction by attenuation of Shh-mediated branchial ray outgrowth, and that chondrichthyan branchial rays and tetrapod limbs exhibit parallel developmental mechanisms of evolutionary reduction. PMID:21220324

  14. Determination of hydrogen in milligram quantities of titanium and its alloys

    Science.gov (United States)

    Otterson, D. A.; Smith, R. J.

    1973-01-01

    An accurate, versatile, and sensitive method for the determination of hydrogen in milligram-size titanium samples is presented. It involves extraction of hydrogen at 1070 K while a mercury diffusion pump transfers the evolved gases into the inlet of a mass spectrometer. All the evolved gases may then be positively identified and determined. This method can be readily adapted for use with other metals and for the study of the slow evolution of hydrogen. Reduction of interferences due to the evolution of hydrogen by reactions involving vapors such as those of water, acetone, and vacuum grease is discussed.

  15. Evolution of thermal stress and failure probability during reduction and re-oxidation of solid oxide fuel cell

    Science.gov (United States)

    Wang, Yu; Jiang, Wenchun; Luo, Yun; Zhang, Yucai; Tu, Shan-Tung

    2017-12-01

    The reduction and re-oxidation of anode have significant effects on the integrity of the solid oxide fuel cell (SOFC) sealed by the glass-ceramic (GC). The mechanical failure is mainly controlled by the stress distribution. Therefore, a three dimensional model of SOFC is established to investigate the stress evolution during the reduction and re-oxidation by finite element method (FEM) in this paper, and the failure probability is calculated using the Weibull method. The results demonstrate that the reduction of anode can decrease the thermal stresses and reduce the failure probability due to the volumetric contraction and porosity increasing. The re-oxidation can result in a remarkable increase of the thermal stresses, and the failure probabilities of anode, cathode, electrolyte and GC all increase to 1, which is mainly due to the large linear strain rather than the porosity decreasing. The cathode and electrolyte fail as soon as the linear strains are about 0.03% and 0.07%. Therefore, the re-oxidation should be controlled to ensure the integrity, and a lower re-oxidation temperature can decrease the stress and failure probability.

  16. Cellular Automaton Study of Hydrogen Porosity Evolution Coupled with Dendrite Growth During Solidification in the Molten Pool of Al-Cu Alloys

    Science.gov (United States)

    Gu, Cheng; Wei, Yanhong; Yu, Fengyi; Liu, Xiangbo; She, Lvbo

    2017-09-01

    Welding porosity defects significantly reduce the mechanical properties of welded joints. In this paper, the hydrogen porosity evolution coupled with dendrite growth during solidification in the molten pool of Al-4.0 wt pct Cu alloy was modeled and simulated. Three phases, including a liquid phase, a solid phase, and a gas phase, were considered in this model. The growth of dendrites and hydrogen gas pores was reproduced using a cellular automaton (CA) approach. The diffusion of solute and hydrogen was calculated using the finite difference method (FDM). Columnar and equiaxed dendrite growth with porosity evolution were simulated. Competitive growth between different dendrites and porosities was observed. Dendrite morphology was influenced by porosity formation near dendrites. After solidification, when the porosities were surrounded by dendrites, they could not escape from the liquid, and they made pores that existed in the welded joints. With the increase in the cooling rate, the average diameter of porosities decreased, and the average number of porosities increased. The average diameter of porosities and the number of porosities in the simulation results had the same trend as the experimental results.

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

    Science.gov (United States)

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

    2017-02-01

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

  18. Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

    Science.gov (United States)

    Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

    2018-08-15

    In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. Evolution of oxygen reduction current and biofilm on stainless steels cathodically polarised in natural aerated seawater

    Energy Technology Data Exchange (ETDEWEB)

    Faimali, Marco [ISMAR-CNR, Via De Marini 6, 16149 Genoa (Italy)], E-mail: marco.faimali@ismar.cnr.it; Chelossi, Elisabetta; Garaventa, Francesca; Corra, Christian; Greco, Giuliano; Mollica, Alfonso [ISMAR-CNR, Via De Marini 6, 16149 Genoa (Italy)

    2008-12-01

    The aim of a series of works recently performed at ISMAR was to provide new useful information for a better understanding of the mechanisms by which bacteria settlement causes corrosion on Stainless Steels (SS) and similar active-passive alloys exposed to seawater. In this work, the evolutions of cathodic current, bacteria population, and electronic structure of the passive layer were investigated on SS samples polarised at fixed potentials during their exposure to natural seawater. It was found that, during the first phase of biofilm growth, cathodic current increase is proportional to the number of settled bacteria at each fixed potential. However, the proportionality factor between settled bacteria and cathodic current depends on imposed potential. In particular, the proportionality factor strongly decreases when the potential is increased above a critical value close to -150 mV Ag/AgCl. This effect seems to be correlated with the electronic structure of the passive layer. Indeed, the outer part of the passive layer on tested SS was found to behave like a conductor at potentials more active than -150 mV Ag/AgCl, and like an n-type semiconductor at more noble potentials.

  20. Evolution of oxygen reduction current and biofilm on stainless steels cathodically polarised in natural aerated seawater

    International Nuclear Information System (INIS)

    Faimali, Marco; Chelossi, Elisabetta; Garaventa, Francesca; Corra, Christian; Greco, Giuliano; Mollica, Alfonso

    2008-01-01

    The aim of a series of works recently performed at ISMAR was to provide new useful information for a better understanding of the mechanisms by which bacteria settlement causes corrosion on Stainless Steels (SS) and similar active-passive alloys exposed to seawater. In this work, the evolutions of cathodic current, bacteria population, and electronic structure of the passive layer were investigated on SS samples polarised at fixed potentials during their exposure to natural seawater. It was found that, during the first phase of biofilm growth, cathodic current increase is proportional to the number of settled bacteria at each fixed potential. However, the proportionality factor between settled bacteria and cathodic current depends on imposed potential. In particular, the proportionality factor strongly decreases when the potential is increased above a critical value close to -150 mV Ag/AgCl. This effect seems to be correlated with the electronic structure of the passive layer. Indeed, the outer part of the passive layer on tested SS was found to behave like a conductor at potentials more active than -150 mV Ag/AgCl, and like an n-type semiconductor at more noble potentials

  1. Borax and Octabor Treatment of Stored Swine Manure: Reduction in Hydrogen Sulfide Emissions and Phytotoxicity to Agronomic Crops

    Science.gov (United States)

    Gaseous emissions from stored manure have become environmental and health issues for humans and animals as the livestock industry becomes specialized and concentrated. Of particular concern is hydrogen sulfide, which is being targeted for regulatory control in concentrated animal farm operations. ...

  2. 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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Data on the synthesis processes optimization of novel β-NiS film modified CdS nanoflowers heterostructure nanocomposite for photocatalytic hydrogen evolution

    Directory of Open Access Journals (Sweden)

    Yu Zhang

    2018-02-01

    Full Text Available The data presented in this article are related to a research article entitled ‘Novel β-NiS film modified CdS nanoflowers heterostructure nanocomposite: extraordinarily highly efficient photocatalysts for hydrogen evolution’ (Zhang et al., 2018 [1]. In this article, we report original data on the synthesis processes optimization of the proposed nanocomposite on the basis of their optimum photocatalytic performance together with the comparison on the results of literatures and comparative experiments. The composition, microstructure, morphology, photocatalytic hydrogen evolution and photocatalytic stability of the corresponding samples are included in this report. The data are presented in this format in order to facilitate comparison with data from other researchers in the field and understanding the mechanism of similar catalysts. Keywords: NiS/CdS nanoflowers heterostructure, Photocatalysts, Water splitting, Hydrothermal synthesis, Optimization

  4. Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand

    International Nuclear Information System (INIS)

    Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D.; Lowry, Gregory V.

    2017-01-01

    Highlights: • Reactivity of nZVI increased linearly with nZVI concentration above 10 g/L, but was non-linear below 10 g/L. • nZVI reactivity with PCE is more sensitive to solution redox potential than solution pH. • Mass transfer limits the reactivity of emplaced nZVI under typical groundwater flow velocity. • Lowering pH increases H_2 evolution from nZVI more than reactivity with PCE. • Design of nZVI remediation strategies should consider mass loading and flow velocity on performance and lifetime. - Abstract: The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW = 12 K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7 × 10"−"4 L hr"−"1 m"−"2) and hydrogen evolution rate constant (1.4 nanomol L hr"−"1 m"−"2) were independent of nZVI concentration above 10 g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10 g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H_2 evolution was explained by differences in pH and E_h at each nZVI mass loading; PCE reactivity increased when solution E_h decreased, and the H_2 evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5 g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime.

  5. Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hye-Jin [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Chemical Research Division, Environmental Health Research Department, National Institute of Environmental Research, Incheon 404-708 (Korea, Republic of); Leitch, Megan [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Naknakorn, Bhanuphong [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Tilton, Robert D. [Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Biomedical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Lowry, Gregory V., E-mail: glowry@cmu.edu [Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States); Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, PA 15213-3890 (United States)

    2017-01-15

    Highlights: • Reactivity of nZVI increased linearly with nZVI concentration above 10 g/L, but was non-linear below 10 g/L. • nZVI reactivity with PCE is more sensitive to solution redox potential than solution pH. • Mass transfer limits the reactivity of emplaced nZVI under typical groundwater flow velocity. • Lowering pH increases H{sub 2} evolution from nZVI more than reactivity with PCE. • Design of nZVI remediation strategies should consider mass loading and flow velocity on performance and lifetime. - Abstract: The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW = 12 K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7 × 10{sup −4} L hr{sup −1} m{sup −2}) and hydrogen evolution rate constant (1.4 nanomol L hr{sup −1} m{sup −2}) were independent of nZVI concentration above 10 g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10 g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H{sub 2} evolution was explained by differences in pH and E{sub h} at each nZVI mass loading; PCE reactivity increased when solution E{sub h} decreased, and the H{sub 2} evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5 g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime.

  6. Reductive de-polymerization of kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source.

    Science.gov (United States)

    Huang, Shanhua; Mahmood, Nubla; Tymchyshyn, Matthew; Yuan, Zhongshun; Xu, Chunbao Charles

    2014-11-01

    In this study, formic acid (FA) was employed as an in-situ hydrogen donor for the reductive de-polymerization of kraft lignin (KL). Under the optimum operating conditions, i.e., 300 °C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water-ethanol medium with FA at a FA-to-lignin mass ratio of 0.7, KL (Mw∼10,000 g/mol) was effectively de-polymerized, producing de-polymerized lignin (DL, Mw 1270 g/mol) at a yield of ∼90 wt.% and polymerization of KL. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Synthesis carbon-encapsulated NiZn ferrite nanocomposites by in-situ starch coating route combined with hydrogen thermal reduction

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fuming [Department of Materials Chemistry, Nanchang Hangkong University, Nanchang 330063 (China); Xie, Yu, E-mail: xieyu_121@163.com [Department of Materials Chemistry, Nanchang Hangkong University, Nanchang 330063 (China); Key Laboratory of Photochemical Conversion and Optoelectronic Materials, TIPC, Chinese Academy of Sciences, Beijing 100190 (China); Duan, Junhong; Hua, Helin [Department of Materials Chemistry, Nanchang Hangkong University, Nanchang 330063 (China); Yu, Changlin, E-mail: yuchanglinjx@163.com [School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000 (China); Gao, Yunhua [Key Laboratory of Photochemical Conversion and Optoelectronic Materials, TIPC, Chinese Academy of Sciences, Beijing 100190 (China); Huang, Yan; Pan, Jianfei; Ling, Yun [Department of Materials Chemistry, Nanchang Hangkong University, Nanchang 330063 (China)

    2015-05-05

    Carbon-encapsulated NiZn ferrite magnetic nanocomposites were successfully synthesized by an inexpensive and environment-friendly method of in-situ starch coating route combined with hydrogen thermal reduction. The nanocomposites were characterized in detail by X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and vibrate sample magnetometer (VSM) and so on techniques. XRD, FT-IR, TGA and TEM images indicate the formation of carbon-encapsulated NiZn ferrite magnetic nanocomposites. XRD patterns reveal that the crystalline structure of the nanocomposites is cubic spinel and taenite emerges under the hydrogen thermal reductive ambient. FT-IR spectra suggest that there are interactions on the NiZn ferrite nanocomposites and a spinel-type structure corresponding to NiZn ferrite has formed. TGA shows that the weight loss of the nanocomposites can be divided into three stages in the course of heat decomposition. TEM observations reveal that the carbon-encapsulated NiZn ferrite magnetic nanocomposites have an intact core–shell structure. Under the magnetic field, the nanocomposites exhibited the ferrimagnetic behavior. The saturated magnetization (M{sub s}) of carbon-encapsulated NiZn ferrite nanocomposites calcined at 400 °C can reach a high value up to 72.67 emu/g, and the saturated magnetization (M{sub s}) decreases as the annealing temperature goes up, while the coercivity (Hc), magnetic residual (Mr) magnetic parameters practically fixed on 115.15 Oe and 7.85 emu/g. - Graphical abstract: Carbon-encapsulated NiZn ferrite magnetic nanocomposites were successfully synthesized by an inexpensive and environment-friendly method of in-situ starch coating route combined with hydrogen thermal reduction (Fig. 1). The nanocomposites were characterized and the experimental results were discussed. Under applied magnetic field, the nanocomposites exhibited the ferromagnetic behavior

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

    Science.gov (United States)

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

    2018-03-01

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

  9. Gold nanoparticles embedded in Ta 2 O 5 /Ta 3 N 5 as active visible-light plasmonic photocatalysts for solar hydrogen evolution

    KAUST Repository

    Luo, Yujing

    2014-07-10

    Here, we demonstrate a new recreating photocatalytic activity of a Nano Au/Ta2O5 composite for hydrogen evolution from water as a visible-light-responsive plasmonic photocatalyst by embedding Au nanoparticles in a Ta2O5 host lattice. The Nano Au/Ta2O 5 composite samples were prepared through a simple Pechini-type sol-gel process. Further nitridating Nano Au/Ta2O5 composite samples in ammonia flow at 1123 K yielded Nano Au/Ta3N 5 composite samples. The obtained Nano Au/Ta3N5 composite exhibited a significantly enhanced photocatalytic activity in the visible region for hydrogen evolution from water compared with blank Ta 3N5 nanoparticles. UV-visible diffuse reflectance spectra and photocatalytic activity measurements indicated that the excitation of surface plasmon resonance of Au nanoparticles is responsible for the new recreating photocatalytic activity of the Nano Au/Ta2O5 composite and significantly enhanced photocatalytic activity of the Nano Au/Ta3N5 composite for hydrogen evolution in the visible region, which might be ascribed to the charge transfer effect in Nano Au/Ta 2O5 composite and the synergetic effect of charge transfer and near-field electromagnetic effect in Nano Au/Ta3N5 composite induced by surface plasmon resonance of embedded Au nanoparticles. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems for photocatalytic, photovoltaic and other optoelectronic devices. © the Partner Organisations 2014.

  10. A Hybrid Optimization Framework with POD-based Order Reduction and Design-Space Evolution Scheme

    Science.gov (United States)

    Ghoman, Satyajit S.

    The main objective of this research is to develop an innovative multi-fidelity multi-disciplinary design, analysis and optimization suite that integrates certain solution generation codes and newly developed innovative tools to improve the overall optimization process. The research performed herein is divided into two parts: (1) the development of an MDAO framework by integration of variable fidelity physics-based computational codes, and (2) enhancements to such a framework by incorporating innovative features extending its robustness. The first part of this dissertation describes the development of a conceptual Multi-Fidelity Multi-Strategy and Multi-Disciplinary Design Optimization Environment (M3 DOE), in context of aircraft wing optimization. M 3 DOE provides the user a capability to optimize configurations with a choice of (i) the level of fidelity desired, (ii) the use of a single-step or multi-step optimization strategy, and (iii) combination of a series of structural and aerodynamic analyses. The modularity of M3 DOE allows it to be a part of other inclusive optimization frameworks. The M 3 DOE is demonstrated within the context of shape and sizing optimization of the wing of a Generic Business Jet aircraft. Two different optimization objectives, viz. dry weight minimization, and cruise range maximization are studied by conducting one low-fidelity and two high-fidelity optimization runs to demonstrate the application scope of M3 DOE. The second part of this dissertation describes the development of an innovative hybrid optimization framework that extends the robustness of M 3 DOE by employing a proper orthogonal decomposition-based design-space order reduction scheme combined with the evolutionary algorithm technique. The POD method of extracting dominant modes from an ensemble of candidate configurations is used for the design-space order reduction. The snapshot of candidate population is updated iteratively using evolutionary algorithm technique of

  11. Host-symbiont co-speciation and reductive genome evolution in gut symbiotic bacteria of acanthosomatid stinkbugs

    Directory of Open Access Journals (Sweden)

    Kamagata Yoichi

    2009-01-01

    Full Text Available Abstract Background Host-symbiont co-speciation and reductive genome evolution have been commonly observed among obligate endocellular insect symbionts, while such examples have rarely been identified among extracellular ones, the only case reported being from gut symbiotic bacteria of stinkbugs of the family Plataspidae. Considering that gut symbiotic communities are vulnerable to invasion of foreign microbes, gut symbiotic associations have been thought to be evolutionarily not stable. Stinkbugs of the family Acanthosomatidae harbor a bacterial symbiont in the midgut crypts, the lumen of which is completely sealed off from the midgut main tract, thereby retaining the symbiont in the isolated cryptic cavities. We investigated histological, ecological, phylogenetic, and genomic aspects of the unique gut symbiosis of the acanthosomatid stinkbugs. Results Phylogenetic analyses showed that the acanthosomatid symbionts constitute a distinct clade in the γ-Proteobacteria, whose sister groups are the obligate endocellular symbionts of aphids Buchnera and the obligate gut symbionts of plataspid stinkbugs Ishikawaella. In addition to the midgut crypts, the symbionts were located in a pair of peculiar lubricating organs associated with the female ovipositor, by which the symbionts are vertically transmitted via egg surface contamination. The symbionts were detected not from ovaries but from deposited eggs, and surface sterilization of eggs resulted in symbiont-free hatchlings. The symbiont-free insects suffered retarded growth, high mortality, and abnormal morphology, suggesting important biological roles of the symbiont for the host insects. The symbiont phylogeny was generally concordant with the host phylogeny, indicating host-symbiont co-speciation over evolutionary time despite the extracellular association. Meanwhile, some local host-symbiont phylogenetic discrepancies were found, suggesting occasional horizontal symbiont transfers across the host

  12. Insights from the Genome Sequence of Mycobacterium lepraemurium: Massive Gene Decay and Reductive Evolution

    Directory of Open Access Journals (Sweden)

    Andrej Benjak

    2017-10-01

    Full Text Available Mycobacterium lepraemurium is the causative agent of murine leprosy, a chronic, granulomatous disease similar to human leprosy. Due to the similar clinical manifestations of human and murine leprosy and the difficulty of growing both bacilli axenically, Mycobacterium leprae and M. lepraemurium were once thought to be closely related, although it was later suggested that M. lepraemurium might be related to Mycobacterium avium. In this study, the complete genome of M. lepraemurium was sequenced using a combination of PacBio and Illumina sequencing. Phylogenomic analyses confirmed that M. lepraemurium is a distinct species within the M. avium complex (MAC. The M. lepraemurium genome is 4.05 Mb in length, which is considerably smaller than other MAC genomes, and it comprises 2,682 functional genes and 1,139 pseudogenes, which indicates that M. lepraemurium has undergone genome reduction. An error-prone repair homologue of the DNA polymerase III α-subunit was found to be nonfunctional in M. lepraemurium, which might contribute to pseudogene formation due to the accumulation of mutations in nonessential genes. M. lepraemurium has retained the functionality of several genes thought to influence virulence among members of the MAC.

  13. Hydrogen Embrittlement

    Science.gov (United States)

    Woods, Stephen; Lee, Jonathan A.

    2016-01-01

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

  14. Modeling evolution of hydrogen bonding and stabilization of transition states in the process of cocaine hydrolysis catalyzed by human butyrylcholinesterase.

    Science.gov (United States)

    Gao, Daquan; Zhan, Chang-Guo

    2006-01-01

    Molecular dynamics (MD) simulations and quantum mechanical/molecular mechanical (QM/MM) calculations were performed on the prereactive enzyme-substrate complex, transition states, intermediates, and product involved in the process of human butyrylcholinesterase (BChE)-catalyzed hydrolysis of (-)-cocaine. The computational results consistently reveal a unique role of the oxyanion hole (consisting of G116, G117, and A199) in BChE-catalyzed hydrolysis of cocaine, compared to acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylcholine. During BChE-catalyzed hydrolysis of cocaine, only G117 has a hydrogen bond with the carbonyl oxygen (O31) of the cocaine benzoyl ester in the prereactive BChE-cocaine complex, and the NH groups of G117 and A199 are hydrogen-bonded with O31 of cocaine in all of the transition states and intermediates. Surprisingly, the NH hydrogen of G116 forms an unexpected hydrogen bond with the carboxyl group of E197 side chain and, therefore, is not available to form a hydrogen bond with O31 of cocaine in the acylation. The NH hydrogen of G116 is only partially available to form a weak hydrogen bond with O31 of cocaine in some structures involved in the deacylation. The change of the estimated hydrogen-bonding energy between the oxyanion hole and O31 of cocaine during the reaction process demonstrates how the protein environment can affect the energy barrier for each step of the BChE-catalyzed hydrolysis of cocaine. These insights concerning the effects of the oxyanion hole on the energy barriers provide valuable clues on how to rationally design BChE mutants with a higher catalytic activity for the hydrolysis of (-)-cocaine. 2005 Wiley-Liss, Inc.

  15. Hydrogen Evolution Facilitates Reduction of DNA Guanine Residues at the Hanging Mercury Drop Electrode: Evidence for a Chemical Mechanism

    Czech Academy of Sciences Publication Activity Database

    Daňhel, Aleš; Havran, Luděk; Trnková, L.; Fojta, Miroslav

    2016-01-01

    Roč. 28, č. 11 (2016), s. 2785-2790 ISSN 1040-0397 R&D Projects: GA ČR GAP206/11/1638; GA ČR(CZ) GA16-01625S Institutional support: RVO:68081707 Keywords : central trinucleotide sequences * cyclic voltammetry * cisplatin Subject RIV: BO - Biophysics Impact factor: 2.851, year: 2016

  16. Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

    Science.gov (United States)

    Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

    2018-02-01

    In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

  17. Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

    Science.gov (United States)

    Chen, Qian-Qian; Hou, Chun-Chao; Wang, Chuan-Jun; Yang, Xiao; Shi, Rui; Chen, Yong

    2018-06-06

    NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

  18. Facile preparation of water dispersible polypyrrole nanotube-supported silver nanoparticles for hydrogen peroxide reduction and surface-enhanced Raman scattering

    International Nuclear Information System (INIS)

    Peng Yingjing; Qiu Lihua; Pan Congtao; Wang Cancan; Shang Songmin; Yan Feng

    2012-01-01

    Water dispersible polypyrrole nanotube/silver nanoparticle hybrids (PPyNT-COOAgNP) were synthesized via a cation-exchange method. The approach involves the surface functionalization of PPyNTs with carboxylic acid groups (-COOH), and cation-exchange with silver ions (Ag + ) and followed by the reduction of metal ions. The morphology and optical properties of the produced PPyNT-COOAgNP nanohybrids were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectrometer, and UV–vis spectroscopy. The as-prepared PPyNT-COOAgNP nanohybrids exhibited well-defined response to the reduction of hydrogen peroxide, and as extremely suitable substrates for surface-enhanced Raman spectroscopy (SERS) with a high enhancement factor of 6.0 × 10 7 , and enabling the detection of 10 −12 M Rhodamine 6G solution.

  19. Efficient Electron Transfer across a ZnO-MoS2 -Reduced Graphene Oxide Heterojunction for Enhanced Sunlight-Driven Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Kumar, Suneel; Reddy, Nagappagari Lakshmana; Kushwaha, Himmat Singh; Kumar, Ashish; Shankar, Muthukonda Venkatakrishnan; Bhattacharyya, Kaustava; Halder, Aditi; Krishnan, Venkata

    2017-09-22

    The development of noble metal-free catalysts for hydrogen evolution is required for energy applications. In this regard, ternary heterojunction nanocomposites consisting of ZnO nanoparticles anchored on MoS 2 -RGO (RGO=reduced graphene oxide) nanosheets as heterogeneous catalysts show highly efficient photocatalytic H 2 evolution. In the photocatalytic process, the catalyst dispersed in an electrolytic solution (S 2- and SO 3 2- ions) exhibits an enhanced rate of H 2 evolution, and optimization experiments reveal that ZnO with 4.0 wt % of MoS 2 -RGO nanosheets gives the highest photocatalytic H 2 production of 28.616 mmol h -1  g cat -1 under sunlight irradiation; approximately 56 times higher than that on bare ZnO and several times higher than those of other ternary photocatalysts. The superior catalytic activity can be attributed to the in situ generation of ZnS, which leads to improved interfacial charge transfer to the MoS 2 cocatalyst and RGO, which has plenty of active sites available for photocatalytic reactions. Recycling experiments also proved the stability of the optimized photocatalyst. In addition, the ternary nanocomposite displayed multifunctional properties for hydrogen evolution activity under electrocatalytic and photoelectrocatalytic conditions owing to the high electrode-electrolyte contact area. Thus, the present work provides very useful insights for the development of inexpensive, multifunctional catalysts without noble metal loading to achieve a high rate of H 2 generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. FT-IR spectroelectrochemical study of the reduction of 1,4-dinitrobenzene on Au electrode: Hydrogen bonding and protonation in proton donor mixed media

    International Nuclear Information System (INIS)

    Tian Dexiang; Jin Baokang

    2011-01-01

    Highlights: → 1,4-Dinitrobenzene electrochemical reduction on the Au electrode is explored. → Radical anion (PNB· - ) is found both in aprotic media and in proton donors mixed media. → The H-bonding forming between PNB· - , PNB 2- and proton donors in low donors concentration. → The protonation of PNB 2- occurs in high concentration proton donor mixed media. - Abstract: The electrochemical behavior of 1,4-dinitrobenzene (1,4-PNB) on the Au electrode was investigated by cyclic voltammetry (CV), in situ FT-IR spectroelectrochemistry, cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. In aprotic media, 1,4-dinitrobenzene is reversibly reduced in two-step one-electron transfer. A series of IR absorption bands at 1056, 1210, 1341, 1356, 1464 and 1549 cm -1 , tracing to PNB; PNB· - and PNB 2- are observed. In the presence of proton donors mixed media, with increasing concentrations of proton donors, hydrogen-bonding and protonation process are found successively. The values of combining proton donors with per PNB 2- to form hydrogen-bonding are estimated by using electrochemical parameters. The result of forming aromatic nitroso compound is supported by tracing the change of IR absorption bands at 1149 and 1587 cm -1 at high concentration of proton donors. Based on CVA and DCVA techniques, it is clearly distinguished that the mechanisms of electrochemical reduction of PNB are elaborated in different systems.