An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Bioinspired Mesoporous Chiral Nematic Graphitic Carbon Nitride Photocatalysts modulated by Polarized Light.

PubMed

Lin, Wensheng; Hong, Wei; Sun, Lu; Yu, Di; Yu, Dingshan; Chen, Xudong

2018-01-10

Endowing materials with chirality and exploring the responses of the material under circularly polarized light (CPL) can enable further insight into the physical and chemical properties of the semiconductors to be gained, thus expanding on optoelectronic applications. Herein a bioinspired mesoporous chiral nematic graphitic carbon nitride (g-C 3 N 4 ) for efficient hydrogen evolution with polarized light modulation based on chiral nematic cellulose nanocrystal films prepared through silica templating is described. The mesoporous nematic chiral g-C 3 N 4 exhibits an ultrahigh hydrogen evolution rate of 219.9 μmol h -1 (for 20 mg catalyst), corresponding to a high enhancement factor of 55 when compared to the bulk g-C 3 N 4 under λ>420 nm irradiation. Furthermore, the chiral g-C 3 N 4 material exhibits unique photocatalytic activity modulated by CPL within the absorption region. This CPL-assisted photocatalytic regulation strategy holds great promise for a wide range of applications including optical devices, asymmetric photocatalysis, and chiral recognition/separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

H2 evolution at Si-based metal-insulator-semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover.

PubMed

Esposito, Daniel V; Levin, Igor; Moffat, Thomas P; Talin, A Alec

2013-06-01

Photoelectrochemical (PEC) water splitting represents a promising route for renewable production of hydrogen, but trade-offs between photoelectrode stability and efficiency have greatly limited the performance of PEC devices. In this work, we employ a metal-insulator-semiconductor (MIS) photoelectrode architecture that allows for stable and efficient water splitting using narrow bandgap semiconductors. Substantial improvement in the performance of Si-based MIS photocathodes is demonstrated through a combination of a high-quality thermal SiO2 layer and the use of bilayer metal catalysts. Scanning probe techniques were used to simultaneously map the photovoltaic and catalytic properties of the MIS surface and reveal the spillover-assisted evolution of hydrogen off the SiO2 surface and lateral photovoltage driven minority carrier transport over distances that can exceed 2 cm. The latter finding is explained by the photo- and electrolyte-induced formation of an inversion channel immediately beneath the SiO2/Si interface. These findings have important implications for further development of MIS photoelectrodes and offer the possibility of highly efficient PEC water splitting.

Surfactant-Assisted Phase-Selective Synthesis of New Cobalt MOFs and Their Efficient Electrocatalytic Hydrogen Evolution Reaction.

PubMed

Wu, Ya-Pan; Zhou, Wei; Zhao, Jun; Dong, Wen-Wen; Lan, Ya-Qian; Li, Dong-Sheng; Sun, Chenghua; Bu, Xianhui

2017-10-09

Reported herein are two new polymorphic Co-MOFs (CTGU-5 and -6) that can be selectively crystallized into the pure 2D or 3D net using an anionic or neutral surfactant, respectively. Each polymorph contains a H 2 O molecule, but differs dramatically in its bonding to the framework, which in turn affects the crystal structure and electrocatalytic performance for hydrogen evolution reaction (HER). Both experimental and computational studies find that 2D CTGU-5 which has coordinates water and more open access to the cobalt site has higher electrocatalytic activity than CTGU-6 with the lattice water. The integration with co-catalysts, such as acetylene black (AB) leads to a composite material, AB&CTGU-5 (1:4) with very efficient HER catalytic properties among reported MOFs. It exhibits superior HER properties including a very positive onset potential of 18 mV, low Tafel slope of 45 mV dec -1 , higher exchange current density of 8.6×10 -4  A cm -2 , and long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Hou, Yidong; Abrams, Billie L.; Vesborg, Peter C. K.; Bjørketun, Mårten E.; Herbst, Konrad; Bech, Lone; Seger, Brian; Pedersen, Thomas; Hansen, Ole; Rossmeisl, Jan; Dahl, Søren; Nørskov, Jens K.; Chorkendorff, Ib

2011-10-01

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 evolution, earth-abundant alternatives are needed for largescale use. We show that bio-inspired molecular clusters based on molybdenum sulfides and tungsten sulfides mimic nature's enzymes for hydrogen evolution, molybdenum sulfides evolve hydrogen at a slightly higher overpotential than platinum when 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 part of the spectrum is utilized for hydrogen evolution while the blue part is reserved for the more difficult oxygen evolution. The samples have been illuminated with a simulated red part of the solar spectrum i.e. long wavelength (" > 620 nm) part of simulated AM 1.5G radiation. The current densities 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 into the nature of the active site.

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

PubMed

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

2016-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jinlong, Lv, E-mail: ljltsinghua@126.com; State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084; Tongxiang, Liang, E-mail: txliang@mail.tsinghua.edu.cn

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{submore » 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.« less

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xiaofang; Tang, Chaowan; Zheng, Qun

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 CdSmore » 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.« less

Ionic liquid-assisted synthesis of Br-modified g-C3N4 semiconductors with high surface area and highly porous structure for photoredox water splitting

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Wang, Yanyun; Zhou, Yuming; Qiu, Kaibo; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-12-01

Coping with the gradually increasing worldwide energy and environmental issues, it is urgent to develop efficient, cheap and visible-light-driven photocatalysts for hydrogen production. Here, we present a facile way to synthesize bromine doped graphitic carbon nitride (CN-BrX) with highly porous structure by using ionic liquid (1-butyl-3-vinylimidazolium bromide) as the Br source and soft-template for the first time, which applied in hydrogen evolution under visible light irradiation. A systematic study is conducted on the optimization in the doping amount. The results find that the as-fabricated CN-BrX photocatalysts possess a uniform porous network with thin walls due to the release of volatile domains and decomposition of ionic liquids. The highly porous structure with the large surface area (≤150 m2/g) benefits the exposure of active sites. Moreover, the bromine modification and porous structure can narrow the band gap, enhance the transportation capability of photogenerated electrons, improve the optical and conductive properties of CN, thus contribute to an outstanding H2 evolution rate under visible light irradiation (120 μmol h-1), which is about 3.6 times higher than pure CN. This work provides a new insight for designing the novel g-C3N4 based photocatalysts for hydrogen production, CO2 conversion and environmental remediation.

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

PubMed

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

2016-11-23

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP 4+ ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P 2 Mo 18 O 62 6- and P 2 W 18 O 62 6- anions, and one Keplerate {Mo 132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP 4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P 2 Mo 18 O 62 6- anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P 2 W 18 O 62 6- anion; and (c) the high nuclearity Keplerate {Mo 132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic evolution of the spectrum of long-period fiber Bragg gratings fabricated from hydrogen-loaded optical fiber by ultraviolet laser irradiation.

PubMed

Fujita, Keio; Masuda, Yuji; Nakayama, Keisuke; Ando, Maki; Sakamoto, Kenji; Mohri, Jun-pei; Yamauchi, Makoto; Kimura, Masanori; Mizutani, Yasuo; Kimura, Susumu; Yokouchi, Takashi; Suzaki, Yoshifumi; Ejima, Seiki

2005-11-20

Long-period fiber Bragg gratings fabricated by exposure of hydrogen-loaded fiber to UV laser light exhibit large-scale dynamic evolution for approximately two weeks at room temperature. During this time two distinct features show up in their spectrum: a large upswing in wavelength and a substantial deepening of the transmission minimum. The dynamic evolution of the transmission spectrum is explained quantitatively by use of Malo's theory of UV-induced quenching [Electron. Lett. 30, 442 (1994)] followed by refilling of hydrogen in the fiber core and the theory of hydrogen diffusion in the fiber material. The amount of hydrogen quenched by the UV irradiation is 6% of the loaded hydrogen.

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

DOEpatents

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.

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

PubMed

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.

Recent progress in the development of carbonate-intercalated Zn/Cr LDH as a novel photocatalyst for hydrogen evolution aimed at the utilization of solar light.

PubMed

Parida, Kulamani; Mohapatra, Lagnamayee

2012-01-28

A series of novel photocatalysts Zn/Cr LDH with different Zn/Cr molar ratios (2 : 1, 3 : 1, 4 : 1 and 2 : 1-CO(3)) were fabricated by a co-precipitation method and evaluated for photodecomposition of water using visible light irradiation. Various characterization methods were employed to investigate the structures, morphologies and photocatalytic properties. In comparison to Zn/Cr (2 : 1) LDH, Zn/Cr-CO(3) (2 : 1) LDH extends the absorption edges to the visible region and exhibits good photocatalytic activity, even without the assistance of co-catalysts. The visible light photocatalytic activity is ascribed to the charge transfer spectra of octahedral Cr ions in LDH. Zn/Cr-CO(3) LDH shows enhanced photocatalytic activities compared to Zn/Cr LDH as carbonate ions oxidise by holes to form carbonate radicals, inhibit the rapid recombination of e(-) and h(+) charge carriers and thereby suppress the backward reaction to some extent. This work provides a detailed understanding of the semiconductor properties of LDHs for photocatalytical hydrogen evolution.

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matanovic, Ivana; Garzon, Fernando H.

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

DOE PAGES

Matanovic, Ivana; Garzon, Fernando H.

2018-04-26

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Ni-C-N Nanosheets as Catalyst for Hydrogen Evolution Reaction.

PubMed

Yin, Jie; Fan, Qiaohui; Li, Yuxuan; Cheng, Fangyi; Zhou, Panpan; Xi, Pinxian; Sun, Shouheng

2016-11-09

We report a facile nitrogenation/exfoliation process to prepare hybrid Ni-C-N nanosheets. These nanosheets are <2 nm thin, chemically stable, and metallically conductive. They serve as a robust catalyst for the hydrogen evolution reaction in 0.5 M H 2 SO 4 , or 1.0 M KOH or 1.0 M PBS (pH = 7). For example, they catalyze the hydrogen evolution reaction in 0.5 M H 2 SO 4 at an onset potential of 34.7 mV, an overpotential of 60.9 mV (at j = 10 mA cm -2 ) and with remarkable long-term stability (∼10% current drop after 70 h testing period). They are promising as a non-Pt catalyst for practical hydrogen evolution reaction.

Hydrogen-Assisted Crack Propagation in Austenitic Stainless Steel Fusion Welds

NASA Astrophysics Data System (ADS)

Somerday, B. P.; Dadfarnia, M.; Balch, D. K.; Nibur, K. A.; Cadden, C. H.; Sofronis, P.

2009-10-01

The objective of this study was to characterize hydrogen-assisted crack propagation in gas-tungsten arc (GTA) welds of the nitrogen-strengthened, austenitic stainless steel 21Cr-6Ni-9Mn (21-6-9), using fracture mechanics methods. The fracture initiation toughness and crack growth resistance curves were measured using fracture mechanics specimens that were thermally precharged with 230 wppm (1.3 at. pct) hydrogen. The fracture initiation toughness and slope of the crack growth resistance curve for the hydrogen-precharged weld were reduced by as much as 60 and 90 pct, respectively, relative to the noncharged weld. A physical model for hydrogen-assisted crack propagation in the welds was formulated from microscopy evidence and finite-element modeling. Hydrogen-assisted crack propagation proceeded by a sequence of microcrack formation at the weld ferrite, intense shear deformation in the ligaments separating microcracks, and then fracture of the ligaments. One salient role of hydrogen in the crack propagation process was promoting microcrack formation at austenite/ferrite interfaces and within the ferrite. In addition, hydrogen may have facilitated intense shear deformation in the ligaments separating microcracks. The intense shear deformation could be related to the development of a nonuniform distribution of hydrogen trapped at dislocations between microcracks, which in turn created a gradient in the local flow stress.

Dual organism design cycle reveals small subunit substitutions that improve [NiFe] hydrogenase hydrogen evolution.

PubMed

Yonemoto, Isaac T; Matteri, Christopher W; Nguyen, Thao Amy; Smith, Hamilton O; Weyman, Philip D

2013-07-02

Photosynthetic microorganisms that directly channel solar energy to the production of molecular hydrogen are a potential future biofuel system. Building such a system requires installation of a hydrogenase in the photosynthetic organism that is both tolerant to oxygen and capable of hydrogen production. Toward this end, we have identified the [NiFe] hydrogenase from the marine bacterium Alteromonas macleodii "Deep ecotype" that is able to be heterologously expressed in cyanobacteria and has tolerance to partial oxygen. The A. macleodii enzyme shares sequence similarity with the uptake hydrogenases that favor hydrogen uptake activity over hydrogen evolution. To improve hydrogen evolution from the A. macleodii hydrogenase, we examined the three Fe-S clusters found in the small subunit of many [NiFe] uptake hydrogenases that presumably act as a molecular wire to guide electrons to or from the active site of the enzyme. Studies by others altering the medial cluster of a Desulfovibrio fructosovorans hydrogenase from 3Fe-4S to 4Fe-4S resulted in two-fold improved hydrogen evolution activity. We adopted a strategy of screening for improved hydrogenase constructs using an Escherichia coli expression system before testing in slower growing cyanobacteria. From the A. macleodii enzyme, we created a mutation in the gene encoding the hydrogenase small subunit that in other systems is known to convert the 3Fe-4S medial cluster to 4Fe-4S. The medial cluster substitution did not improve the hydrogen evolution activity of our hydrogenase. However, modifying both the medial cluster and the ligation of the distal Fe-S cluster improved in vitro hydrogen evolution activity relative to the wild type hydrogenase by three- to four-fold. Other properties of the enzyme including thermostability and tolerance to partial oxygen did not appear to be affected by the substitutions. Our results show that substitution of amino acids altering the ligation of Fe-S clusters in the A. macleodii [NiFe] uptake hydrogenase resulted in increased hydrogen evolution activity. This activity can be recapitulated in multiple host systems and with purified protein. These results validate the approach of using an E. coli-cyanobacteria shuttle system for enzyme expression and improvement.

Prereduction of Metal Oxides via Carbon Plasma Treatment for Efficient and Stable Electrocatalytic Hydrogen Evolution.

PubMed

Zhang, Yongqi; Ouyang, Bo; Xu, Kun; Xia, Xinhui; Zhang, Zheng; Rawat, Rajdeep Singh; Fan, Hong Jin

2018-04-01

Prereduction of transition metal oxides is a feasible and efficient strategy to enhance their catalytic activity for hydrogen evolution. Unfortunately, the prereduction via the common H 2 annealing method is unstable for nanomaterials during the hydrogen evolution process. Here, using NiMoO 4 nanowire arrays as the example, it is demonstrated that carbon plasma (C-plasma) treatment can greatly enhance both the catalytic activity and the long-term stability of transition metal oxides for hydrogen evolution. The C-plasma treatment has two functions at the same time: it induces partial surface reduction of the NiMoO 4 nanowire to form Ni 4 Mo nanoclusters, and simultaneously deposits a thin graphitic carbon shell. As a result, the C-plasma treated NiMoO 4 can maintain its array morphology, chemical composition, and catalytic activity during long-term intermittent hydrogen evolution process. This work may pave a new way for simultaneous activation and stabilization of transition metal oxide-based electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel-silver alloy electrocatalysts for hydrogen evolution and oxidation in an alkaline electrolyte.

PubMed

Tang, Maureen H; Hahn, Christopher; Klobuchar, Aidan J; Ng, Jia Wei Desmond; Wellendorff, Jess; Bligaard, Thomas; Jaramillo, Thomas F

2014-09-28

The development of improved catalysts for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) in basic electrolytes remains a major technical obstacle to improved fuel cells, water electrolyzers, and other devices for electrochemical energy storage and conversion. Based on the free energy of adsorbed hydrogen intermediates, theory predicts that alloys of nickel and silver are active for these reactions. In this work, we synthesize binary nickel-silver bulk alloys across a range of compositions and show that nickel-silver alloys are indeed more active than pure nickel for hydrogen evolution and, possibly, hydrogen oxidation. To overcome the mutual insolubility of silver and nickel, we employ electron-beam physical vapor codeposition, a low-temperature synthetic route to metastable alloys. This method also produces flat and uniform films that facilitate the measurement of intrinsic catalytic activity with minimal variations in the surface area, ohmic contact, and pore transport. Rotating-disk-electrode measurements demonstrate that the hydrogen evolution activity per geometric area of the most active catalyst in this study, Ni0.75Ag0.25, is approximately twice that of pure nickel and has comparable stability and hydrogen oxidation activity. Our experimental results are supported by density functional theory calculations, which show that bulk alloying of Ni and Ag creates a variety of adsorption sites, some of which have near-optimal hydrogen binding energy.

Effects of microstructure banding on hydrogen assisted fatigue crack growth in X65 pipeline steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ronevich, Joseph A.; Somerday, Brian P.; San Marchi, Chris W.

Banded ferrite-pearlite X65 pipeline steel was tested in high pressure hydrogen gas to evaluate the effects of oriented pearlite on hydrogen assisted fatigue crack growth. Test specimens were oriented in the steel pipe such that cracks propagated either parallel or perpendicular to the banded pearlite. The ferrite-pearlite microstructure exhibited orientation dependent behavior in which fatigue crack growth rates were significantly lower for cracks oriented perpendicular to the banded pearlite compared to cracks oriented parallel to the bands. Thus the reduction of hydrogen assisted fatigue crack growth across the banded pearlite is attributed to a combination of crack-tip branching and impededmore » hydrogen diffusion across the banded pearlite.« less

Effects of microstructure banding on hydrogen assisted fatigue crack growth in X65 pipeline steels

DOE PAGES

Ronevich, Joseph A.; Somerday, Brian P.; San Marchi, Chris W.

2015-09-10

Banded ferrite-pearlite X65 pipeline steel was tested in high pressure hydrogen gas to evaluate the effects of oriented pearlite on hydrogen assisted fatigue crack growth. Test specimens were oriented in the steel pipe such that cracks propagated either parallel or perpendicular to the banded pearlite. The ferrite-pearlite microstructure exhibited orientation dependent behavior in which fatigue crack growth rates were significantly lower for cracks oriented perpendicular to the banded pearlite compared to cracks oriented parallel to the bands. Thus the reduction of hydrogen assisted fatigue crack growth across the banded pearlite is attributed to a combination of crack-tip branching and impededmore » hydrogen diffusion across the banded pearlite.« less

Exploring Hydrogen Evolution and the Overpotential

ERIC Educational Resources Information Center

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…

Hydrogen Assisted Cracking of High Strength Steel Welds

DTIC Science & Technology

1988-05-01

cracking of high strength steel welds. The microplasticity theory originally proposed by M Beachem is used to explain the effect of hydrogen on the var... microplasticity mechanism rather than embrittlement (B7). He suggests that the hydrogen in the lattice ahead of the crack tip assists whatever...intensity level on the observed fracture mode. This theory postu- lates that hydrogen will promote cracking by a microplasticity mechanism rather than

A Metal-Organic Framework Approach toward Highly Nitrogen-Doped Graphitic Carbon as a Metal-Free Photocatalyst for Hydrogen Evolution.

PubMed

Zhao, Xiuxia; Yang, Hao; Jing, Peng; Shi, Wei; Yang, Guangming; Cheng, Peng

2017-03-01

Zeolitic imidazolate framework-8 (ZIF-8)-derived N-doped graphene analogous polyhedrons (ZNGs) obtained via the direct carbonation of ZIF-8 are applied to photocatalytic hydrogen evolution for the first time. The contents of different types of nitrogen atoms in ZNGs can be fine-tuned via the calcination temperature, which significantly influences the hydrogen evolution rate of the ZNGs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dye-Sensitized Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) Nanofibers for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Gonce, Mehmet Kerem; Aslan, Emre; Ozel, Faruk; Hatay Patir, Imren

2016-03-21

The photocatalytic hydrogen evolution activities of low-cost and noble-metal-free Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofiber catalysts have been investigated using triethanolamine as an electron donor and eosin Y as a photosensitizer under visible-light irradiation. The rates of hydrogen evolution by Cu2 XSnS4 (X=Zn, Ni, Fe, Co, and Mn) nanofibers have been compared with each other and with that of the noble metal Pt. The hydrogen evolution rates for the nanofibers change in the order Cu2 NiSnS4 >Cu2 FeSnS4 >Cu2 CoSnS4 >Cu2 ZnSnS4 >Cu2 MnSnS4 (2028, 1870, 1926, 1420, and 389 μmol g(-1) h(-1) , respectively). The differences between the hydrogen evolution rates of the nanofibers could be attributed to their energy levels. Moreover, Cu2 NiSnS4, Cu2 FeSnS4 , and Cu2 CoSnS4 nanofibers show higher and more stable photocatalytic hydrogen production rates than that of the noble metal Pt under long-term irradiation with visible light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Striving toward noble-metal-free photocatalytic water splitting: The hydrogenated-graphene-TiO 2 prototype

DOE PAGES

Nguyen-Phan, Thuy -Duong; Luo, Si; Liu, Zongyuan; ...

2015-08-20

Graphane, graphone and hydrogenated graphene (HG) have been extensively studied in recent years due to their interesting properties and potential use in commercial and industrial applications. The present study reports investigation of hydrogenated graphene/TiO 2-x (HGT) nanocomposites as photocatalysts for H 2 and O 2 production from water without the assistance of a noble metal co-catalyst. By combination of several techniques, the morphologies, bulk/atomic structure and electronic properties of all the powders were exhaustively interrogated. Hydrogenation treatment efficiently reduces TiO 2 nanoparticles, while the graphene oxide sheets undergo the topotactic transformation from a graphene-like structure to a mixture of graphiticmore » and turbostratic carbon (amorphous/disordered) upon altering the calcination atmosphere from a mildly reducing to a H 2-abundant environment. Remarkably, the hydrogenated graphene-TiO 2-x composite that results upon H 2-rich reduction exhibits the highest photocatalytic H 2 evolution performance equivalent to low loading of Pt (~0.12 wt%), whereas the addition of HG suppresses the O 2 production. As a result, we propose that such an enhancement can be attributed to a combination of factors including the introduction of oxygen vacancies and Ti 3+ states, retarding the recombination of charge carriers and thus, facilitating the charge transfer from TiO 2-x to the carbonaceous sheet.« less

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

DOE PAGES

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; ...

2016-09-16

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

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis.

PubMed

Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang; Cai, Jinyan; Wu, Shaoyang; Kang, Jian; Zhou, Jianbin; Chen, Zhiyan; Zheng, Xusheng; Xiao, Xiangheng; Wang, Gongming

2018-04-12

Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo 2 S 4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm -2 and a Tafel slope of 37 mV dec -1 , which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo 2 S 4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.

Bioinspired Molecular Co-Catalysts Bonded to a Silicon Photocathode for Solar Hydrogen Evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Yidong

2011-11-08

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-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 (Mo{sub 3}S{sub 4}) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor that harvests red photons in the solar spectrum. The current densities atmore » 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 calculations of the Mo{sub 3}S{sub 4} clusters adsorbed on the hydrogen-terminated Si(100) surface, providing insights into the nature of the active site.« less

Dual organism design cycle reveals small subunit substitutions that improve [NiFe] hydrogenase hydrogen evolution

PubMed Central

2013-01-01

Background Photosynthetic microorganisms that directly channel solar energy to the production of molecular hydrogen are a potential future biofuel system. Building such a system requires installation of a hydrogenase in the photosynthetic organism that is both tolerant to oxygen and capable of hydrogen production. Toward this end, we have identified the [NiFe] hydrogenase from the marine bacterium Alteromonas macleodii “Deep ecotype” that is able to be heterologously expressed in cyanobacteria and has tolerance to partial oxygen. The A. macleodii enzyme shares sequence similarity with the uptake hydrogenases that favor hydrogen uptake activity over hydrogen evolution. To improve hydrogen evolution from the A. macleodii hydrogenase, we examined the three Fe-S clusters found in the small subunit of many [NiFe] uptake hydrogenases that presumably act as a molecular wire to guide electrons to or from the active site of the enzyme. Studies by others altering the medial cluster of a Desulfovibrio fructosovorans hydrogenase from 3Fe-4S to 4Fe-4S resulted in two-fold improved hydrogen evolution activity. Results We adopted a strategy of screening for improved hydrogenase constructs using an Escherichia coli expression system before testing in slower growing cyanobacteria. From the A. macleodii enzyme, we created a mutation in the gene encoding the hydrogenase small subunit that in other systems is known to convert the 3Fe-4S medial cluster to 4Fe-4S. The medial cluster substitution did not improve the hydrogen evolution activity of our hydrogenase. However, modifying both the medial cluster and the ligation of the distal Fe-S cluster improved in vitro hydrogen evolution activity relative to the wild type hydrogenase by three- to four-fold. Other properties of the enzyme including thermostability and tolerance to partial oxygen did not appear to be affected by the substitutions. Conclusions Our results show that substitution of amino acids altering the ligation of Fe-S clusters in the A. macleodii [NiFe] uptake hydrogenase resulted in increased hydrogen evolution activity. This activity can be recapitulated in multiple host systems and with purified protein. These results validate the approach of using an E. coli-cyanobacteria shuttle system for enzyme expression and improvement. PMID:23819621

Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

NASA Astrophysics Data System (ADS)

Pan, Hui

2016-02-01

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

Method and System for Hydrogen Evolution and Storage

DOEpatents

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

2008-10-21

A method and system for storing and evolving hydrogen 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.

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.

PubMed

Yuan, Jiangtan; Wu, Jingjie; Hardy, Will J; Loya, Philip; Lou, Minhan; Yang, Yingchao; Najmaei, Sina; Jiang, Menglei; Qin, Fan; Keyshar, Kunttal; Ji, Heng; Gao, Weilu; Bao, Jiming; Kono, Junichiro; Natelson, Douglas; Ajayan, Pulickel M; Lou, Jun

2015-10-07

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterostructured WS2 -MoS2 Ultrathin Nanosheets Integrated on CdS Nanorods to Promote Charge Separation and Migration and Improve Solar-Driven Photocatalytic Hydrogen Evolution.

PubMed

Reddy, D Amaranatha; Park, Hanbit; Ma, Rory; Kumar, D Praveen; Lim, Manho; Kim, Tae Kyu

2017-04-10

Solar-driven photocatalytic hydrogen evolution is important to bring solar-energy-to-fuel energy-conversion processes to reality. However, there is a lack of highly efficient, stable, and non-precious photocatalysts, and catalysts not designed completely with expensive noble metals have remained elusive, which hampers their large-scale industrial application. Herein, for the first time, a highly efficient and stable noble-metal-free CdS/WS 2 -MoS 2 nanocomposite was designed through a facile hydrothermal approach. When assessed as a photocatalyst for water splitting, the CdS/WS 2 -MoS 2 nanostructures exhibited remarkable photocatalytic hydrogen-evolution performance and impressive durability. An excellent hydrogen evolution rate of 209.79 mmol g -1  h -1 was achieved under simulated sunlight irradiation, which is higher than the values for CdS/MoS 2 (123.31 mmol g -1  h -1 ) and CdS/WS 2 nanostructures (169.82 mmol g -1  h -1 ) and the expensive CdS/Pt benchmark catalyst (34.98 mmol g -1  h -1 ). The apparent quantum yield reached 51.4 % at λ=425 nm in 5 h. Furthermore, the obtained hydrogen evolution rate was better than those of several noble-metal-free catalysts reported previously. The observed high rate of hydrogen evolution and remarkable stability may be a result of the ultrafast separation of photogenerated charge carriers and transport between the CdS nanorods and the WS 2 -MoS 2 nanosheets, which thus increases the number of electrons involved in hydrogen production. The proposed designed strategy is believed to potentially open a door to the design of advanced noble-metal-free photocatalytic materials for efficient solar-driven hydrogen production. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method and system for hydrogen evolution and storage

DOEpatents

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.

Selective electrochemical generation of hydrogen peroxide from water oxidation

DOE PAGES

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

2015-10-08

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

Wax: A benign hydrogen-storage material that rapidly releases H2-rich gases through microwave-assisted catalytic decomposition

PubMed Central

Gonzalez-Cortes, S.; Slocombe, D. R.; Xiao, T.; Aldawsari, A.; Yao, B.; Kuznetsov, V. L.; Liberti, E.; Kirkland, A. I.; Alkinani, M. S.; Al-Megren, H. A.; Thomas, J. M.; Edwards, P. P.

2016-01-01

Hydrogen is often described as the fuel of the future, especially for application in hydrogen powered fuel-cell vehicles (HFCV’s). However, its widespread implementation in this role has been thwarted by the lack of a lightweight, safe, on-board hydrogen storage material. Here we show that benign, readily-available hydrocarbon wax is capable of rapidly releasing large amounts of hydrogen through microwave-assisted catalytic decomposition. This discovery offers a new material and system for safe and efficient hydrogen storage and could facilitate its application in a HFCV. Importantly, hydrogen storage materials made of wax can be manufactured through completely sustainable processes utilizing biomass or other renewable feedstocks. PMID:27759014

Hydrothermal growth of two dimensional hierarchical MoS2 nanospheres on one dimensional CdS nanorods for high performance and stable visible photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Chava, Rama Krishna; Do, Jeong Yeon; Kang, Misook

2018-03-01

The visible photocatalytic H2 production from water splitting considered as a clean and renewable energy source could solve the problem of greenhouse gas emission from fossil fuels. Despite tremendous efforts, the development of cost effective, highly efficient and more stable visible photocatalysts for splitting of water remains a great challenge. Here, we report the heteronanostructures consisting of hierarchical MoS2 nanospheres grown on 1D CdS nanorods referred to as CdS-MoS2 HNSs as a high performance visible photocatalyst for H2 evolution. The as-synthesized CdS-MoS2 HNSs exhibited ∼11 fold increment of H2 evolution rate when compared to pure CdS nanorods. This remarkable enhanced hydrogen evolution performance can be assigned to the positive synergetic effect from heteronanostructures formed between the CdS and MoS2 components which assist as an electron sink and source for abundant active edge sites and in turn increases the charge separation. This study presents a low-cost visible photocatalyst for solar energy conversion to achieve efficient H2.

Active Cocatalysts for Photocatalytic Hydrogen Evolution Derived from Nickel or Cobalt Amine Complexes.

PubMed

Huang, Yi; Zhang, Bin

2017-11-20

A cost-effective and robust strategy for the anchoring of molecular hydrogen evolution cocatalysts onto semiconductors has recently been reported. The composite materials were highly efficient and stable towards photocatalytic H 2 evolution. This study provides guidance for the design and construction of highly active heterogeneous photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Preparation of NiS/ZnIn2S4 as a superior photocatalyst for hydrogen evolution under visible light irradiation

PubMed Central

Wei, Liang; Chen, Yongjuan; Zhao, Jialin

2013-01-01

Summary 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. PMID:24455453

Survey of selected seaweeds for simultaneous photoproduction of hydrogen and oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenbaum, E.; Ramus, J.

1983-03-01

Then seaweed species were surveyed for simultaneous photoevolution of hydrogen and oxygen. In an attempt to induce hydrogenase activity (as measured by hydrogen photoproduction) the seaweeds were maintained under anaerobiosis in CO/sub 2/-free seawater for varying lengths of time. Although oxygen evolution was observed in every alga studied, hydrogen evolution was not observed. One conclusion of this research is that, in contrast to the microscopic algae, there is not a single example of a macroscopic alga for which the photoevolution of hydrogen has been observed, in spite of the fact that there are now at least nine macroscopic algal speciesmore » known for which hydrogenase activity has been reported (either by dark hydrogen evolution or light-activated hydrogen uptake). These results are in conflict with the conventional view that algal hydrogenase can catalyze a multiplicity of reactions, one of which is the photoproduction of molecular hydrogen. Two possible explanations for the lack of hydrogen photoproduction in macroscopic algae are presented. It is postulated that electron acceptors other than carbon dioxide can take up reducing equivalents from Photosystem I to the measurable exclusion of hydrogen photoproduction. Alternatively, the hydrogenase system in macroscopic algae may be primarily a hydrogen-uptake system with respect to light-activated reactions. A simple kinetic argument based on recent measurements of the photosynthetic turnover times of simultaneous light-activated hydrogen and oxygen production is presented that supports the second explanation. 25 references, 3 figures, 1 table.« less

A composite of borohydride and super absorbent polymer for hydrogen generation

NASA Astrophysics Data System (ADS)

Li, Z. P.; Liu, B. H.; Liu, F. F.; Xu, D.

To develop a hydrogen source for underwater applications, a composite of sodium borohydride and super absorbent polymer (SAP) is prepared by ball milling sodium borohydride powder with SAP powder, and by dehydrating an alkaline borohydride gel. When sodium polyacrylate (NaPAA) is used as the SAP, the resulting composite exhibits a high rate of borohydride hydrolysis for hydrogen generation. A mechanism of hydrogen evolution from the NaBH 4-NaPAA composite is suggested based on structure analysis by X-ray diffraction and scanning electron microscopy. The effects of water and NiCl 2 content in the precursor solution on the hydrogen evolution behavior are investigated and discussed.

Microbial detection method based on sensing molecular hydrogen

NASA Technical Reports Server (NTRS)

Wilkins, J. R.; Stoner, G. E.; Boykin, E. H.

1974-01-01

An approach involving the measurement of hydrogen evolution by test organisms was used to detect and enumerate various members of the Enterobacteriaceae group. The experimental setup for measuring hydrogen evolution consisted of a test tube containing two electrodes plus broth and organisms. The test tube was kept in a water bath at a temperature of 35 C. It is pointed out that the hydrogen-sensing method, coupled with the pressure transducer technique reported by Wilkins (1974) could be used in various experiments in which gas production by microorganisms is being measured.

CoMoS2/rGO/C3N4 ternary heterojunctions catalysts with high photocatalytic activity and stability for hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Xu, Xuejun; Si, Zhichun; Liu, Liping; Wang, Zehao; Chen, Ze; Ran, Rui; He, Yonghong; Weng, Duan

2018-03-01

Noble metal free MoS2/g-C3N4 catalyst has attracted intense attentions for visible light photocatalytic hydrogen evolution as a result of its earth abundance, low cost and unique heterojunctions stacked with two dimensional sheets. However, the low charge separation efficiency resulted from the poor conductivity of g-C3N4 and MoS2, and lack of abundant active sites from coordinative unsaturated atoms in MoS2, restricts the photocatalytic hydrogen evolution activity and stability enhancement of MoS2/C3N4 composite catalysts. Herein, CoMoS2/rGO/g-C3N4 catalysts with ternary heterojunctions are prepared by facile solvothermal method, which exhibit high visible light photocatalytic activity and stability for hydrogen evolution. The optimal hydrogen evolution rate of CoMoS2/rGO/g-C3N4 catalysts is 684 μmol g-1 h-1 when the content of CoMoS2 is 2% and the content of rGO is 0.5%. The stability of CoMoS2/rGO/C3N4 catalysts just decrease about 3% after 4 cycling runs for 16 h. The good catalytic performances of catalysts are attributed to the synergistic effect among the g-C3N4 nanosheets, rGO nanosheets and CoMoS2 nanosheets. The high conductivity of rGO nanosheets enhances the electron-hole separation and charge transfer, and Co doping increases the active sites for hydrogen evolution due to the increase of unsaturated atoms in CoMoS2 nanosheets.

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

PubMed

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

2015-03-01

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

Membrane contactor assisted water extraction system for separating hydrogen peroxide from a working solution, and method thereof

DOEpatents

Snyder, Seth W [Lincolnwood, IL; Lin, Yupo J [Naperville, IL; Hestekin', Jamie A [Fayetteville, AR; Henry, Michael P [Batavia, IL; Pujado, Peter [Kildeer, IL; Oroskar, Anil [Oak Brook, IL; Kulprathipanja, Santi [Inverness, IL; Randhava, Sarabjit [Evanston, IL

2010-09-21

The present invention relates to a membrane contactor assisted extraction system and method for extracting a single phase species from multi-phase working solutions. More specifically one preferred embodiment of the invention relates to a method and system for membrane contactor assisted water (MCAWE) extraction of hydrogen peroxide (H.sub.2O.sub.2) from a working solution.

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.; Marsik, S. J.

1974-01-01

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

Microstructural characterization of hydrogen induced cracking in TRIP-assisted steel by EBSD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laureys, A., E-mail: Aurelie.Laureys@UGent.be; Depover, T.; Petrov, R.

2016-02-15

The present work evaluates hydrogen induced cracking by performing an elaborate EBSD (Electron BackScatter Diffraction) study in a steel with transformation induced plasticity (TRIP-assisted steel). This type of steel exhibits a multiphase microstructure which undergoes a deformation induced phase transformation. Additionally, each microstructural constituent displays a different behavior in the presence of hydrogen. The aim of this study is to obtain a better understanding on the mechanisms governing hydrogen induced crack initiation and propagation in the hydrogen saturated multiphase structure. Tensile tests on notched samples combined with in-situ electrochemical hydrogen charging were conducted. The tests were interrupted at stresses justmore » after reaching the tensile strength, i.e. before macroscopic failure of the material. This allowed to study hydrogen induced crack initiation and propagation by SEM (Scanning Electron Microscopy) and EBSD. A correlation was found between the presence of martensite, which is known to be very susceptible to hydrogen embrittlement, and the initiation of hydrogen induced cracks. Initiation seems to occur mostly by martensite decohesion. High strain regions surrounding the hydrogen induced crack tips indicate that further crack propagation may have occurred by the HELP (hydrogen-enhanced localized plasticity) mechanism. Small hydrogen induced cracks located nearby the notch are typically S-shaped and crack propagation was dominantly transgranularly. The second stage of crack propagation consists of stepwise cracking by coalescence of small hydrogen induced cracks. - Highlights: • Hydrogen induced cracking in TRIP-assisted steel is evaluated by EBSD. • Tensile tests were conducted on notched hydrogen saturated samples. • Crack initiation occurs by a H-Enhanced Interface DEcohesion (HEIDE) mechanism. • Crack propagation involves growth and coalescence of small cracks. • Propagation is governed by the characteristics of phases on the crack path.« less

Design of catalysts by different substituent groups to the ;cut g-C3N4; single layer

NASA Astrophysics Data System (ADS)

Xu, Weiwei; Tang, Chao; Chen, Chongyang; Li, Youyong; Xu, Lai

2017-09-01

Graphitic carbon nitride has been wildly studied as a kind of promising photocatalysts for hydrogen evolution. However, it has a low intrinsic activity. Herein, we designed new periodic structures "cut g-C3N4", and adding the new substituent groups. We employed density functional theory to calculate the charge distribution and catalytic properties of hydrogen evolution on the structures. We got a theoretical view that introducing conjugate substituents can enhance the catalytic performance for hydrogen evolution. Furthermore, it provided a theoretical guidance for the reasonable design of two dimensional non-metallic photocatalysts, with lower activation barrier of the catalytic reaction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

In situ grown Ni9S8 nanorod/O-MoS2 nanosheet nanocomposite on carbon cloth as a free binder supercapacitor electrode and hydrogen evolution catalyst

NASA Astrophysics Data System (ADS)

Li, Songzhan; Chen, Tian; Wen, Jian; Gui, Pengbin; Fang, Guojia

2017-11-01

Transition metal sulfide nanostructure composites have received significant attention as energy conversion and storage devices. In this work, we report a three-dimension (3D) nanostructure with the Ni9S8 nanorods embedded in oxygen-incorporated MoS2 (O-MoS2) nanosheets for supercapacitors and hydrogen evolution catalysts. The in situ grown Ni9S8/O-MoS2 nanocomposite on carbon cloth can be used as a free binder supercapacitor electrode and hydrogen evolution catalyst. The Ni9S8/O-MoS2 nanocomposite exhibits electrochemical behaviors with a specific capacitance of 907 F g-1 (at 2 A g-1) and good cycle stability after 1200 cycles due to its unique mutual embedding 3D nanostructure. Furthermore, the Ni9S8/O-MoS2 nanocomposite also shows highly electrocatalytic features for hydrogen production with an onset overpotential of ˜150 mV and a low Tafel slope of ˜81 mV dec-1. The oxygen incorporation of MoS2 provides more active sites to participate in the catalytic process for the hydrogen evolution reaction.

Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

DOEpatents

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.

Photosynthetic water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenbaum, E.

1981-01-01

The photosynthetic unit of hydrogen evolution, the turnover time of photosynthetic hydrogen production, and hydrogenic photosynthesis are discussed in the section on previous work. Recent results are given on simultaneous photoproduction of hydrogen and oxygen, kinetic studies, microscopic marine algae-seaweeds, and oxygen profiles.

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

PubMed

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

2012-03-12

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

Graphene quantum dots to enhance the photocatalytic hydrogen evolution efficiency of anatase TiO2 with exposed {001} facet.

PubMed

Yu, Shan; Zhong, Yun-Qian; Yu, Bao-Quan; Cai, Shi-Yi; Wu, Li-Zhu; Zhou, Ying

2016-07-27

Hydrogen evolution through photocatalysis is promising with respect to the environmental problems and challenges of energy shortage that we encounter today. In this paper, we have combined graphene quantum dots (GQDs) and {001} faceted anatase TiO2 (with an exposed percentage of 65-75%) together for effective photocatalytic hydrogen evolution. A series of characterizations including X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy and UV-visible absorption spectroscopy have been carried out to study the structure of the as-prepared GQDs/{001}TiO2 composite. It turns out that GQDs could be effectively decorated on {001}TiO2 sheet without changing its intrinsic structure. With an optimum loading amount of GQDs (0.5 wt% to {001}TiO2), GQDs/{001}TiO2 exhibits a hydrogen evolution efficiency 8 times higher than that of bare {001}TiO2, which is a significantly more obvious improvement than many other photocatalytic systems relevant to GQDs and TiO2 hybrids. In addition, GQDs/{001}TiO2 could stand long-term photocatalytic experiments. Photocurrent tests show that such an improvement of the photocatalytic efficiency over GQDs/{001}TiO2 may originate from a higher charge separation efficiency. The present study could offer reference for the construction of photocatalytic hydrogen evolution systems with low cost and long term stability.

Preparation of Cu-loaded SrTiO3 nanoparticles and their photocatalytic activity for hydrogen evolution from methanol aqueous solution

NASA Astrophysics Data System (ADS)

Bui, Duc-Nguyen; Mu, Jin; Wang, Lei; Kang, Shi-Zhao; Li, Xiangqing

2013-06-01

Cu-loaded SrTiO3 nanoparticles (Cu-SrTiO3) were prepared using a simple in situ photo-deposition method and their photocatalytic activity for hydrogen evolution from methanol aqueous solution was evaluated. The results characterized with XRD, TEM, XPS and EDX indicated that the as-synthesized sample was composed of metallic Cu and cubic SrTiO3, and the metallic Cu was homogeneously loaded on the surface of SrTiO3 nanoparticles. Under UV light irradiation, Cu-SrTiO3 displayed much higher photocatalytic activity for hydrogen evolution and excellent stability in comparison with pure SrTiO3 nanoparticles. The results further confirmed that the efficient separation of photogenerated electron/hole pairs was critical for the enhanced photocatalytic activity of Cu-SrTiO3. Moreover, the rate of hydrogen evolution of 0.5 wt.% Cu-SrTiO3 is comparable with that of 0.5 wt.% Pt-SrTiO3 photocatalyst under optimum conditions, implying that the metallic Cu is an efficient alternative to Pt as a co-catalyst on SrTiO3. The high photocatalytic activity, low cost and chemical stability mean that the Cu-loaded SrTiO3 is a potential catalyst for the photocatalytic hydrogen evolution from methanol aqueous solution.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

Bioelectrochemical sulphate reduction on batch reactors: Effect of inoculum-type and applied potential on sulphate consumption and pH.

PubMed

Gacitúa, Manuel A; Muñoz, Enyelbert; González, Bernardo

2018-02-01

Microbial electrolysis batch reactor systems were studied employing different conditions, paying attention on the effect that biocathode potential has on pH and system performance, with the overall aim to distinguish sulphate reduction from H 2 evolution. Inocula from pure strains (Desulfovibrio paquesii and Desulfobacter halotolerans) were compared to a natural source conditioned inoculum. The natural inoculum possess the potential for sulphate reduction on serum bottles experiments due to the activity of mutualistic bacteria (Sedimentibacter sp. and Bacteroides sp.) that assist sulphate-reducing bacterial cells (Desulfovibrio sp.) present in the consortium. Electrochemical batch reactors were monitored at two different potentials (graphite-bar cathodes poised at -900 and -400mV versus standard hydrogen electrode) in an attempt to isolate bioelectrochemical sulphate reduction from hydrogen evolution. At -900mV all inocula were able to reduce sulphate with the consortium demonstrating superior performance (SO 4 2- consumption: 25.71gm -2 day -1 ), despite the high alkalinisation of the media. At -400mV only the pure Desulfobacter halotolerans inoculated system was able to reduce sulphate (SO 4 2- consumption: 17.47gm -2 day -1 ) and, in this potential condition, pH elevation was less for all systems, confirming direct (or at least preferential) bioelectrochemical reduction of sulphate over H 2 production. Copyright © 2017 Elsevier B.V. All rights reserved.

Fracture mechanics and surface chemistry investigations of environment-assisted crack growth

NASA Technical Reports Server (NTRS)

Wei, R. P.; Klier, K.; Simmons, G. W.; Chou, Y. T.

1984-01-01

It is pointed out that environment-assisted subcritical crack growth in high-strength steels and other high-strength alloys (particularly in hydrogen and in hydrogenous environments) is an important technological problem of long standing. This problem is directly related to issues of structural integrity, durability, and reliability. The terms 'hydrogen embrittlement' and 'stress corrosion cracking' have been employed to describe the considered phenomenon. This paper provides a summary of contributions made during the past ten years toward the understanding of environmentally assisted crack growth. The processes involved in crack growth are examined, and details regarding crack growth and chemical reactions are discussed, taking into account crack growth in steels exposed to water/water vapor, the effect of hydrogen, reactions involving hydrogen sulfide, and aspects of fracture surface morphology and composition. Attention is also given to the modeling of crack growth response, crack growth in gas mixtures, and the interaction of solute atoms with the crack-tip stress field.

Mechanisms of hydrogen-assisted fracture in austenitic stainless steel welds.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balch, Dorian K.; Sofronis, Petros; Somerday, Brian P.

2005-03-01

The objective of this study was to quantify the hydrogen-assisted fracture susceptibility of gas-tungsten arc (GTA) welds in the nitrogen-strengthened, austenitic stainless steels 21Cr-6Ni-9Mn (21-6-9) and 22Cr-13Ni-5Mn (22-13-5). In addition, mechanisms of hydrogen-assisted fracture in the welds were identified using electron microscopy and finite-element modeling. Elastic-plastic fracture mechanics experiments were conducted on hydrogen-charged GTA welds at 25 C. Results showed that hydrogen dramatically lowered the fracture toughness from 412 kJ/m{sup 2} to 57 kJ/m{sup 2} in 21-6-9 welds and from 91 kJ/m{sup 2} to 26 kJ/m{sup 2} in 22-13-5 welds. Microscopy results suggested that hydrogen served two roles in themore » fracture of welds: it promoted the nucleation of microcracks along the dendritic structure and accelerated the link-up of microcracks by facilitating localized deformation. A continuum finite-element model was formulated to test the notion that hydrogen could facilitate localized deformation in the ligament between microcracks. On the assumption that hydrogen decreased local flow stress in accordance with the hydrogen-enhanced dislocation mobility argument, the finite-element results showed that deformation was localized in a narrow band between two parallel, overlapping microcracks. In contrast, in the absence of hydrogen, the finite-element results showed that deformation between microcracks was more uniformly distributed.« less

Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

PubMed

Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

2005-03-28

The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

ULTRASOUND-ASSISTED EPOXIDATION OF OLEFINS AND A,B-UNSATURATED KETONES OVER HYDROTALCITES USING HYDROGEN PEROXIDE

EPA Science Inventory

An efficient ultrasound-assisted epoxidation of olefins and a,B-unsaturated ketones over hydrotacite catalysts in the presence of hydrogen peroxide and acetonitrile is described. This general and selective protocol is relatively fast and is applicable to a wide variety of substra...

Is light-induced degradation of a-Si:H/c-Si interfaces reversible?

DOE Office of Scientific and Technical Information (OSTI.GOV)

El Mhamdi, El Mahdi; Holovsky, Jakub; Demaurex, Bénédicte

2014-06-23

Thin hydrogenated amorphous silicon (a-Si:H) films deposited on crystalline silicon (c-Si) surfaces are sensitive probes for the bulk electronic properties of a-Si:H. Here, we use such samples during repeated low-temperature annealing and visible-light soaking to investigate the long-term stability of a-Si:H films. We observe that during annealing the electronic improvement of the interfaces follows stretched exponentials as long as hydrogen evolution in the films can be detected. Once such evolution is no longer observed, the electronic improvement occurs much faster. Based on these findings, we discuss how the reversibility of light-induced defects depends on (the lack of observable) hydrogen evolution.

Photocatalytic hydrogen evolution over β-iron silicide under infrared-light irradiation.

PubMed

Yoshimizu, Masaharu; Kobayashi, Ryoya; Saegusa, Makoto; Takashima, Toshihiro; Funakubo, Hiroshi; Akiyama, Kensuke; Matsumoto, Yoshihisa; Irie, Hiroshi

2015-02-18

We investigated the ability of β-iron silicide (β-FeSi2) to serve as a hydrogen (H2)-evolution photocatalyst due to the potential of its conduction band bottom, which may allow thermodynamically favorable H2 evolution in spite of its small band-gap of 0.80 eV. β-FeSi2 had an apparent quantum efficiency for H2 evolution of ∼24% up to 950 nm (near infrared light), in the presence of the dithionic acid ion (S2O6(2-)) as a sacrificial agent. It was also sensitive to infrared light (>1300 nm) for H2 evolution.

Hydrogen production by nitrogen-starved cultures of Anabaena cylindrica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weissman, J.C.; Benemann, J.R.

Nitrogen-starved cultures of the alga Anabaena cylindrica 629 produced hydrogen and oxygen continuously for 7 to 19 days. Hydrogen production attained a maximum level after 1 to 2 days of starvation and was followed by a slow decline. The maximum rates were 30 ml of H/sub 2/ evolved per liter of culture per h or 32 ..mu..l of H/sub 2/ per mg of dry weight per h. In 5 to 7 days the rate of H/sub 2/ evolution by the more productive cultures fell to one-half its maximum value. The addition of 10/sup -4/ to 5 x 10/sup -4/ Mmore » ammonium increased the rate of oxygen evolution and the total hydrogen production of the cultures. H/sub 2/-O/sub 2/ ratios were 4:1 under conditions of complete nitrogen starvation and about 1.7:1 after the addition of ammonium. Thus, oxygen evolution was affected by the extent of the nitrogen starvation. Thermodynamic efficiencies of converting incident light energy to free energy of hydrogen via algal photosynthesis were 0.4 percent. Possible factors limiting hydrogen production were decline of reductant supply and filament breakage. Hydrogen production by filamentous, heterocystous blue-green algae could be used for development of a biophotolysis system.« less

Core thermal response and hydrogen generation of the N Reactor hydrogen mitigation design basis accident

DOE Office of Scientific and Technical Information (OSTI.GOV)

White, M.D.; Lombardo, N.J.; Heard, F.J.

1988-04-01

Calculations were performed to determine core heatup, core damage, and subsequent hydrogen production of a hypothetical loss-of-cooling accident at the Department of Energy's N Reactor. The thermal transient response of the reactor core was solved using the TRUMP-BD computer program. Estimates of whole-core thermal damage and hydrogen production were made by weighting the results of multiple half-length pressure tube simulations at various power levels. The Baker-Just and Wilson parabolic rate equations for the metal-water chemical reactions modeled the key phenomena of chemical energy and hydrogen evolution. Unlimited steam was assumed available for continuous oxidation of exposed Zircaloy-2 surfaces and formore » uranium metal with fuel cladding beyond the failure temperature (1038 C). Intact fuel geometry was modeled. Maximum fuel temperatures (1181 C) in the cooled central regions of the core were predicted to occur one-half hour into the accident scenario. Maximum fuel temperatures of 1447 C occurred in the core GSCS-regions at the end of the 10-h transient. After 10-h 26% of the fuel inventory was predicted to have failed. Peak hydrogen evolution equaled 42 g/s, while 10-h integrated hydrogen evolution equaled 167 kg. 12 refs., 12 figs., 2 tabs.« less

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

ERIC Educational Resources Information Center

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…

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

A novel versatile microbiosensor for local hydrogen detection by means of scanning photoelectrochemical microscopy.

PubMed

Zhao, Fangyuan; Conzuelo, Felipe; Hartmann, Volker; Li, Huaiguang; Stapf, Stefanie; Nowaczyk, Marc M; Rögner, Matthias; Plumeré, Nicolas; Lubitz, Wolfgang; Schuhmann, Wolfgang

2017-08-15

The development of a versatile microbiosensor for hydrogen detection is reported. Carbon-based microelectrodes were modified with a [NiFe]-hydrogenase embedded in a viologen-modified redox hydrogel for the fabrication of a sensitive hydrogen biosensor By integrating the microbiosensor in a scanning photoelectrochemical microscope, it was capable of serving simultaneously as local light source to initiate photo(bio)electrochemical reactions while acting as sensitive biosensor for the detection of hydrogen. A hydrogen evolution biocatalyst based on photosystem 1-platinum nanoparticle biocomplexes embedded into a specifically designed redox polymer was used as a model for proving the capability of the developed hydrogen biosensor for the detection of hydrogen upon localized illumination. The versatility and sensitivity of the proposed microbiosensor as probe tip allows simplification of the set-up used for the evaluation of complex electrochemical processes and the rapid investigation of local photoelectrocatalytic activity of biocatalysts towards light-induced hydrogen evolution. Copyright © 2017 Elsevier B.V. All rights reserved.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The anodic surface film and hydrogen evolution on Mg

DOE PAGES

Song, Guang -Ling; Unocic, Kinga A.

2015-06-04

This paper clarifies that the inner and outer layers of the anodic film consist of a nano/micro-porous MgO+Mg(OH) 2 mixture. The film becomes thicker and more porous with increasing potential. It can rupture when potential is too positive in a non-corrosive Mg(OH) 2 solution. Hydrogen evolution becomes more intensive as polarization potential increases, particularly when the potential at the film-covered Mg surface is close to or more positive than the hydrogen equilibrium potential, suggesting that an “anodic hydrogen evolution” (AHE) reaction occurs on the substrate Mg in film pores, and the significantly intensified AHE causes film rupture at high potential.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

Theoretical modeling of the plasma-assisted catalytic growth and field emission properties of graphene sheet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Suresh C.; Gupta, Neha

2015-12-15

A theoretical modeling for the catalyst-assisted growth of graphene sheet in the presence of plasma has been investigated. It is observed that the plasma parameters can strongly affect the growth and field emission properties of graphene sheet. The model developed accounts for the charging rate of the graphene sheet; number density of electrons, ions, and neutral atoms; various elementary processes on the surface of the catalyst nanoparticle; surface diffusion and accretion of ions; and formation of carbon-clusters and large graphene islands. In our investigation, it is found that the thickness of the graphene sheet decreases with the plasma parameters, numbermore » density of hydrogen ions and RF power, and consequently, the field emission of electrons from the graphene sheet surface increases. The time evolution of the height of graphene sheet with ion density and sticking coefficient of carbon species has also been examined. Some of our theoretical results are in compliance with the experimental observations.« less

Influence of degree of ambient medium rarefaction on deformation of copper and aluminum

NASA Technical Reports Server (NTRS)

Lyubarskiy, I. M.; Guslyakov, A. A.; Ashukin, A. V.; Kuleba, V. I.

1974-01-01

The influence of high vacuum 1 x 10 to the minus 9th power torr on the plastic deformation of copper and aluminum was studied. When stretching polycrystalline aluminum and copper specimens in vacuum, it was found that the deformation at failure increases and the ultimate strength decreases. Deformation in vacuum is accompanied by the evolution of hydrogen. For copper, gas evolution is observed only at failure, while for aluminum hydrogen evolution takes place in the initial stage and the gas evolution peaks correspond to small steps on the deformation curve.

Water electrolysis with a conducting carbon cloth: subthreshold hydrogen generation and superthreshold carbon quantum dot formation.

PubMed

Biswal, Mandakini; Deshpande, Aparna; Kelkar, Sarika; Ogale, Satishchandra

2014-03-01

A conducting carbon cloth, which has an interesting turbostratic microstructure and functional groups that are distinctly different from other ordered forms of carbon, such as graphite, graphene, and carbon nanotubes, was synthesized by a simple one-step pyrolysis of cellulose fabric. This turbostratic disorder and surface chemical functionalities had interesting consequences for water splitting and hydrogen generation when such a cloth was used as an electrode in the alkaline electrolysis process. Importantly, this work also gives a new twist to carbon-assisted electrolysis. During electrolysis, the active sites in the carbon cloth allow slow oxidation of its surface to transform the surface groups from COH to COOH and so forth at a voltage as low as 0.2 V in a two-electrode system, along with platinum as the cathode, instead of 1.23 V (plus overpotential), which is required for platinum, steel, or even graphite anodes. The quantity of subthreshold hydrogen evolved was 24 mL cm(-2)  h(-1) at 1 V. Interestingly, at a superthreshold potential (>1.23 V+overpotential), another remarkable phenomenon was found. At such voltages, along with the high rate and quantity of hydrogen evolution, rapid exfoliation of the tiny nanoscale (5-7 nm) units of carbon quantum dots (CQDs) are found in copious amounts due to an enhanced oxidation rate. These CQDs show bright-blue fluorescence under UV light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-12-01

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

Modeling of hydrogen evolution reaction on the surface of GaInP2

NASA Astrophysics Data System (ADS)

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

2012-02-01

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

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand.

PubMed

Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D; Lowry, Gregory V

2017-01-15

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=12K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7×10 -4 Lhr -1 m -2 ) and hydrogen evolution rate constant (1.4 nanomolLhr -1 m -2 ) were independent of nZVI concentration above 10g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10g/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 <5g/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. Copyright © 2016 Elsevier B.V. All rights reserved.

Final Scientifc Report - Hydrogen Education State Partnership Project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leon, Warren

2012-02-03

Under the leadership of the Department of Energy Hydrogen and Fuel Cells program, Clean Energy States Alliance (CESA) educated and worked with state leaders to encourage wider deployment of fuel cell and hydrogen technologies. Through outreach to state policymakers, legislative leaders, clean energy funds, energy agencies, and public utility commissions, CESA worked to accomplish the following objectives of this project: 1. Provide information and technical assistance to state policy leaders and state renewable energy programs in the development of effective hydrogen fuel cell programs. 2. Identify and foster hydrogen program best practices. 3. Identify and promote strategic opportunities for statesmore » and the Department of Energy (DOE) to advance hydrogen technology deployment through partnerships, collaboration, and targeted activities. Over the three years of this project, CESA, with our partner National Conference of State Legislatures (NCSL), was able to provide credible information on fuel cell policies, finance, and technical assistance to hundreds of state officials and other stakeholders. CESA worked with its membership network to effectively educate state clean energy policymakers, program managers, and decision makers about fuel cell and hydrogen technologies and the efforts by states to advance those technologies. With the assistance of NCSL, CESA gained access to an effective forum for outreach and communication with state legislators from all 50 states on hydrogen issues and policies. This project worked to educate policymakers and stakeholders with the potential to develop and deploy stationary and portable fuel cell technologies.« less

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei

2017-01-18

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

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

NASA Astrophysics Data System (ADS)

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.

A theoretical study on the mechanism of hydrogen evolution on non-precious partially oxidized nickel-based heterostructures for fuel cells.

PubMed

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.

A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

DOE PAGES

Liu, Wen; Hu, Enyuan; Jiang, Hong; ...

2016-02-19

Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm –2 and 100 mA cm –2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

PubMed

Feng, Jin-Xian; Tong, Si-Yao; Tong, Ye-Xiang; Li, Gao-Ren

2018-04-18

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H + and hamper the ability of H + to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H + from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Composition and evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Donahue, Thomas (Principal Investigator)

1996-01-01

The contract year started by analyzing Jovian atmospheric data acquired by the Galileo Probe Mass Spectrometer (GPMS). Two Venus hydrogen projects got underway as well. The first study strives to understand how to reconcile the standard treatment of the evolution of the H2O and HDO resevoirs on Venus over 4.5 Gyr in the presence of H and D escape and injection by comets. The second study is calculating the charge exchange contribution to hydrogen loss rates, using realistic models for exospheric H, H(+), D, D(+), and ion temperature from PV data. This report includes the following papers as attachments and supporting data: 'The Galileo Probe Mass Spectrometer: Composition of Jupiter's Atmosphere'; 'Chemical Composition Measurements of the Atmosphere of Jupiter with the Galileo Probe Mass Spectrometer'; 'Ion/Neutral Escape of Hydrogen and Deuterium: Evolution of Water'; 'Hydrogen and Deuterium in the Thermosphere of Venus: Solar Cycle Variations and Escape'; and 'Solar Cycle Variations in H(+) and D(+) Densities in the Venus Ionosphere: Implications for Escape'.

Data on the synthesis processes optimization of novel β-NiS film modified CdS nanoflowers heterostructure nanocomposite for photocatalytic hydrogen evolution.

PubMed

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.

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

One-pot synthesis of MoS2/In2S3 ultrathin nanoflakes with mesh-shaped structure on indium tin oxide as photocathode for enhanced photo-and electrochemical hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Sun, Baoliang; Shan, Fei; Jiang, Xinxin; Ji, Jing; Wang, Feng

2018-03-01

A bifunctional MoS2/In2S3 hybrid composite that has both photo- and electrocatalytic activity toward hydrogen evolution reaction (HER) is prepared by a facile one pot hydrothermal method. The characterizations by scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM) and Photoluminescence (PL) shows that the MoS2/In2S3 hybrid exhibits ultrathin nanoflakes with mesh-shaped structure on transparent conductive substrates, and the as prepared catalyst composite obviously improves the separation of electro-hole pairs. The as prepared hybrid nanosheets with Mo:In of 1/2 integrate In-doped MoS2 to reduce the stacking and increase the active surface area. The novel mesh-shaped nanostructure with a moderate degree of disorder provides not only simultaneously intrinsic conductivity and defects but also higher electrochemically active surface area (ECSA). By electrochemical measurements, such as linear sweep voltammetry (LSV), electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV), we find that the MoS2/In2S3 hybrid possesses much better photo/electrochemical activity than pristine MoS2 or In2S3. MoS2/In2S3 ultrathin nanoflaks are anticipated to be a superior photoelectrocatalyst for PEC cells, and the rational use of the MoS2/In2S3 cathode offers a new avenue toward achieving effective photo-assistant electrocatalytic activity.

Uncertainty propagation in modeling of plasma-assisted hydrogen production from biogas

NASA Astrophysics Data System (ADS)

Zaherisarabi, Shadi; Venkattraman, Ayyaswamy

2016-10-01

With the growing concern of global warming and the resulting emphasis on decreasing greenhouse gas emissions, there is an ever-increasing need to utilize energy-production strategies that can decrease the burning of fossil fuels. In this context, hydrogen remains an attractive clean-energy fuel that can be oxidized to produce water as a by-product. In spite of being an abundant species, hydrogen is seldom found in a form that is directly usable for energy-production. While steam reforming of methane is one popular technique for hydrogen production, plasma-assisted conversion of biogas (carbon dioxide + methane) to hydrogen is an attractive alternative. Apart from producing hydrogen, the other advantage of using biogas as raw material is the fact that two potent greenhouse gases are consumed. In this regard, modeling is an important tool to understand and optimize plasma-assisted conversion of biogas. The primary goal of this work is to perform a comprehensive statistical study that quantifies the influence of uncertain rate constants thereby determining the key reaction pathways. A 0-D chemical kinetics solver in the OpenFOAM suite is used to perform a series of simulations to propagate the uncertainty in rate constants and the resulting mean and standard deviation of outcomes.

Relative Importance of Various Sources of Defect-Producing Hydrogen Introduced into Steel During Application of Vitreous Coatings

NASA Technical Reports Server (NTRS)

Moore, Dwight G; Mason, Mary A; Harrison, William N

1953-01-01

When porcelain enamels or vitreous-type ceramic coatings are applied to ferrous metals, there is believed to be an evolution of hydrogen gas both during and after the firing operation. At elevated temperatures rapid evolution may result in blistering while if hydrogen becomes trapped in the steel during the rapid cooling following the firing operation gas pressures may be generated at the coating-metal interface and flakes of the coating literally blown off the metal. To determine experimentally the relative importance of the principal sources of the hydrogen causing the defects, a procedure was devised in which heavy hydrogen (deuterium) was substituted in turn for regular hydrogen in each of five possible hydrogen-producing operations in the coating process. The findings of the study were as follows: (1) the principal source of the defect-producing hydrogen was the dissolved water present in the enamel frit that was incorporated into the coating. (2) the acid pickling, the milling water, the chemically combined water in the clay, and the quenching water were all minor sources of defect-producing hydrogen under the test conditions used. Confirming experiments showed that fishscaling could be eliminated by using a water-free coating.

Unusual para-substituent effects on the intramolecular hydrogen-bond in hydrazone-based switches.

PubMed

Su, Xin; Lõkov, Märt; Kütt, Agnes; Leito, Ivo; Aprahamian, Ivan

2012-11-04

A "V"-shaped Hammett plot shows that resonance-assisted hydrogen bonding does not dictate the strength of the intramolecular hydrogen bond in the E isomers of hydrazone-based switches because it involves an aromatic pyridyl ring.

Design of a Hydrogen Community for Santa Monica

DTIC Science & Technology

2011-01-01

transportation of hydrogen fuel have been discussed. Cascade simulations were conducted for different compressor capacities and storage bank configurations...been discussed. Cascade simulations were conducted for different compressor capacities and storage bank configurations. Hydrogen dispensing using...tanks (Storage capacity of 198 kg of H2 at 350 and 700 bar), four compressors which assist in dispensing 400 kg of hydrogen in 14 hours, two hydrogen

Thermally induced evolution of hydrogenated amorphous carbon

NASA Astrophysics Data System (ADS)

Mangolini, Filippo; Rose, Franck; Hilbert, James; Carpick, Robert W.

2013-10-01

The thermally induced structural evolution of hydrogenated amorphous carbon (a-C:H) films was investigated in situ by X-ray photoelectron spectroscopy for annealing temperatures up to 500 °C. A model for the conversion of sp3- to sp2-hybridized carbon in a-C:H vs. temperature and time was developed and applied to determine the ranges of activation energies for the thermally activated processes occurring. The energies are consistent with ordering and clustering of sp2 carbon, scission of sp3 carbon-hydrogen bonds and formation of sp2 carbon, and direct transformation of sp3- to sp2-hybridized carbon.

One-pot Synthesis of CdS Irregular Nanospheres Hybridized with Oxygen-Incorporated Defect-Rich MoS2 Ultrathin Nanosheets for Efficient Photocatalytic Hydrogen Evolution.

PubMed

Zhang, Shouwei; Yang, Hongcen; Gao, Huihui; Cao, Ruya; Huang, Jinzhao; Xu, Xijin

2017-07-19

Robust and highly active photocatalysts, CdS@MoS 2 , for hydrogen evolution were successfully fabricated by one-step growth of oxygen-incorporated defect-rich MoS 2 ultrathin nanosheets on the surfaces of CdS with irregular fissures. Under optimized experimental conditions, the CdS@MoS 2 displayed a quantum yield of ∼24.2% at 420 nm and the maximum H 2 generation rate of ∼17203.7 umol/g/h using Na 2 S-Na 2 SO 3 as sacrificial agents (λ ≥ 420 nm), which is ∼47.3 and 14.7 times higher than CdS (∼363.8 μmol/g/h) and 3 wt % Pt/CdS (∼1173.2 μmol/g/h), respectively, and far exceeds all previous hydrogen evolution reaction photocatalysts with MoS 2 as co-catalysts using Na 2 S-Na 2 SO 3 as sacrificial agents. Large volumes of hydrogen bubbles were generated within only 2 s as the photocatalysis started, as demonstrated by the photocatalytic video. The high hydrogen evolution activity is attributed to several merits: (1) the intimate heterojunctions formed between the MoS 2 and CdS can effectively enhance the charge transfer ability and retard the recombination of electron-hole pairs; and (2) the defects in the MoS 2 provide additional active S atoms on the exposed edge sites, and the incorporation of O reduces the energy barrier for H 2 evolution and increases the electric conductivity of the MoS 2 . Considering its low cost and high efficiency, this highly efficient hybrid photocatalysts would have great potential in energy-generation and environment-restoration fields.

In Situ Formation of AgCo Stabilized on Graphitic Carbon Nitride and Concomitant Hydrolysis of Ammonia Borane to Hydrogen.

PubMed

Wang, Qi; Xu, Caili; Ming, Mei; Yang, Yingchun; Xu, Bin; Wang, Yi; Zhang, Yun; Wu, Jie; Fan, Guangyin

2018-04-26

The development of highly-efficient heterogeneous supported catalysts for catalytic hydrolysis of ammonia borane to yield hydrogen is of significant importance considering the versatile usages of hydrogen. Herein, we reported the in situ synthesis of AgCo bimetallic nanoparticles supported on g-C₃N₄ and concomitant hydrolysis of ammonia borane for hydrogen evolution at room temperature. The as-synthesized Ag 0.1 Co 0.9 /g-C₃N₄ catalysts displayed the highest turnover frequency (TOF) value of 249.02 mol H₂·(mol Ag ·min) −1 for hydrogen evolution from the hydrolysis of ammonia borane, which was higher than many other reported values. Furthermore, the Ag 0.1 Co 0.9 /g-C₃N₄ catalyst could be recycled during five consecutive runs. The study proves that Ag 0.1 Co 0.9 /g-C₃N₄ is a potential catalytic material toward the hydrolysis of ammonia borane for hydrogen production.

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

PubMed

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.

Photocatalysts Based on Cobalt-Chelating Conjugated Polymers for Hydrogen Evolution from Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lianwei; Hadt, Ryan G.; Yao, Shiyu

Developing photocatalytic systems for water splitting to generate oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this work, we report the first example of heterogeneous photocatalysts for hydrogen evolution based on in-chain cobalt-chelating conjugated polymers. Four conjugated polymers chelated with earth abundant cobalt ions were synthesized and found to evolve hydrogen photocatalytically from water. These polymers are designed to combine functions of the conjugated backbone as light-harvesting antenna and electron transfer conduit with the in-chain bipyridyl chelated transition metal centers as catalytic active sites. In addition, these polymers are soluble in organic solvents,more » enabling effective interactions with the substrates as well as detailed characterization. We also found a polymer-dependent optimal cobalt chelating concentration at which the highest photocatalytic hydrogen production (PHP) activity can be achieved.« less

Microbial detection method based on sensing molecular hydrogen

NASA Technical Reports Server (NTRS)

Wilkins, J. R.; Stoner, G. E.; Boykin, E. H.

1974-01-01

A simple method for detecting bacteria, based on the time of hydrogen evolution, was developed and tested against various members of the Enterobacteriaceae group. The test system consisted of (1) two electrodes, platinum and a reference electrode, (2) a buffer amplifier, and (3) a strip-chart recorder. Hydrogen evolution was measured by an increase in voltage in the negative (cathodic) direction. A linear relationship was established between inoculum size and the time hydrogen was detected (lag period). Lag times ranged from 1 h for 1 million cells/ml to 7 h for 1 cell/ml. For each 10-fold decrease in inoculum, length of the lag period increased 60 to 70 min. Based on the linear relationship between inoculum and lag period, these results indicate the potential application of the hydrogen-sensing method for rapidly detecting coliforms and other gas-producing microorganisms in a variety of clinical, food, and other samples.

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

NASA Astrophysics Data System (ADS)

Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.; Thomas, Joseph G.; Ding, Qi; Chang, Hung-Chih; Tsai, Meng-Lin; He-Hau, Jr.; Jin, Song

2015-12-01

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 (CoS2), 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-2 at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n+-p-p+ silicon micropyramids achieved photocurrents up to 35 mA cm-2 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.

Hydrodynamic and chemical effects of hydrogen dilution on soot evolution in turbulent nonpremixed bluff body ethylene flames

NASA Astrophysics Data System (ADS)

Deng, Sili; Mueller, Michael E.; Chan, Qing N.; Qamar, Nader H.; Dally, Bassam B.; Alwahabi, Zeyad T.; Nathan, Graham J.

2015-11-01

A turbulent nonpremixed bluff body ethylene/hydrogen (volume ratio 2:1) flame is studied and compared with the ethylene counterpart [Mueller et al., Combust. Flame, 160, 2013]. Similar to the ethylene buff body flame, a low-strain recirculation zone, a high-strain neck region, and a downstream jet-like region are observed. However, the maximum soot volume fraction in the recirculation zone of the hydrogen diluted case is significantly lower than the ethylene case. Large Eddy Simulation is used to further investigate soot evolution in the recirculation zone and to elucidate the role of hydrogen dilution. Since the central jet Reynolds numbers in both cases are the same (approximately 30,900), the jet velocity of the hydrogen diluted case is higher, resulting in a shorter and leaner recirculation zone. In addition, hydrogen dilution chemically suppresses soot formation due to the reduction of C/H ratio. Consequently, the reduction of the soot volume fraction for the hydrogen diluted ethylene flame is attributed to two major effects: hydrodynamic and chemical effects.

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery – Part 1

PubMed Central

Purushothaman, B. K.; Wainright, J. S.

2012-01-01

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H2 storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1st hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body. PMID:22423175

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery - Part 1.

PubMed

Purushothaman, B K; Wainright, J S

2012-05-15

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H(2) storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1(st) hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body.

Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution.

PubMed

Katz, S; Noth, J; Horch, M; Shafaat, H S; Happe, T; Hildebrandt, P; Zebger, I

2016-11-01

[FeFe] hydrogenases are biocatalytic model systems for the exploitation and investigation of catalytic hydrogen evolution. Here, we used vibrational spectroscopic techniques to characterize, in detail, redox transformations of the [FeFe] and [4Fe4S] sub-sites of the catalytic centre (H-cluster) in a monomeric [FeFe] hydrogenase. Through the application of low-temperature resonance Raman spectroscopy, we discovered a novel metastable intermediate that is characterized by an oxidized [Fe I Fe II ] centre and a reduced [4Fe4S] 1+ cluster. Based on this unusual configuration, this species is assigned to the first, deprotonated H-cluster intermediate of the [FeFe] hydrogenase catalytic cycle. Providing insights into the sequence of initial reaction steps, the identification of this species represents a key finding towards the mechanistic understanding of biological hydrogen evolution.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mir, Showkat H.; Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John

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 themore » 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.« less

Hydrogen as a fuel for today and tomorrow: expectations for advanced hydrogen storage materials/systems research.

PubMed

Hirose, Katsuhiko

2011-01-01

History shows that the evolution of vehicles is promoted by several environmental restraints very similar to the evolution of life. The latest environmental strain is sustainability. Transport vehicles are now facing again the need to advance to use sustainable fuels such as hydrogen. Hydrogen fuel cell vehicles are being prepared for commercialization in 2015. Despite intensive research by the world's scientists and engineers and recent advances in our understanding of hydrogen behavior in materials, the only engineering phase technology which will be available for 2015 is high pressure storage. Thus industry has decided to implement the high pressure tank storage system. However the necessity of smart hydrogen storage is not decreasing but rather increasing because high market penetration of hydrogen fuel cell vehicles is expected from around 2025 onward. In order to bring more vehicles onto the market, cheaper and more compact hydrogen storage is inevitable. The year 2025 seems a long way away but considering the field tests and large scale preparation required, there is little time available for research. Finding smart materials within the next 5 years is very important to the success of fuel cells towards a low carbon sustainable world.

Highly sensitive hydrogen detection of catalyst-free ZnO nanorod networks suspended by lithography-assisted growth.

PubMed

Huh, Junghwan; Park, Jonghyurk; Kim, Gyu Tae; Park, Jeong Young

2011-02-25

We have successfully demonstrated a ZnO nanorod-based 3D nanostructure to show a high sensitivity and very fast response/recovery to hydrogen gas. ZnO nanorods have been synthesized selectively over the pre-defined area at relatively low temperature using a simple self-catalytic solution process assisted by a lithographic method. The conductance of the ZnO nanorod device varies significantly as the concentration of the hydrogen is changed without any additive metal catalyst, revealing a high sensitivity to hydrogen gas. Its superior performance can be explained by the porous structure of its three-dimensional network and the enhanced surface reaction of the hydrogen molecules with the oxygen defects resulting from a high surface-to-volume ratio. It was found that the change of conductance follows a power law depending on the hydrogen concentration. A Langmuir isotherm following an ideal power law and a cross-over behavior of the activation energy with respect to hydrogen concentration were observed. This is a very novel and intriguing phenomenon on nanostructured materials, which suggests competitive surface reactions in ZnO nanorod gas sensors.

Liquid-Phase Electrical Discharges: Fundamental Mechanisms and Applications

NASA Astrophysics Data System (ADS)

Franclemont, Joshua

The increased demand in alternative energy in recent decades has generated significant interest in cleaner fuel sources including hydrogen and syngas (hydrogen and carbon monoxide). Hydrogen and syngas are both primarily produced through the steam reforming of hydrocarbons, specifically natural gas. Although other processes are known, the cheapest source of these fuels is currently through the heating of natural gas in the presence of steam and a catalyst. However, due to the emissions associated with the steam reforming of natural gas and the lack of low cost, efficient, and reliable onboard hydrogen storage technologies for fuel cell powered vehicles, attention has been focused on plasma-assisted reforming of hydrocarbons. Plasma processes can be implemented onboard and are able to directly reform liquid hydrocarbons and alcohols without external heating or catalysts. In addition to hydrogen and syngas, the plasma-assisted reforming of hydrocarbons and alcohols offers other desirable products such as C2 gases (ethane, ethylene, and acetylene), methanol and ethanol. The primary goal of this study is to investigate the fundamental chemical reactions occurring during plasma-assisted reforming of liquid hydrocarbons and alcohols using streamer-like pulsed electrical discharges. Due to the relatively unexplored field of chemical reactions in liquid plasmas, the focus of this study is on elucidating chemical pathways responsible for the formation of hydrogen, syngas, and other products during the direct reforming of liquid methanol, glycerol, and pentane as model species.

A ’Hydrogen Partitioning’ Model for Hydrogen Assisted Crack Growth.

DTIC Science & Technology

1984-09-01

the change in Stage II crack growth rate from Region A to Region C in the 18NI maraging steels . It cannot, however, explain the sudden drop off in...Neither partitioning of hydrogen nor adsorption equilibrium can account for the observed "high" temperature response of l8Ni maraging steel in hydrogen...ment and Stress Corrosion Cracking, American Society for Metals, Metals Park, OH, 1984, p. 103 (in press). 11. R. P. Wei: in Hydrogen Effects in

Assessing Hydrogen Assisted Cracking Modes in High Strength Steel Welds

DTIC Science & Technology

1988-12-01

posed theoretical hydrogen assisted cracking mechanisms. It was found that the microplasticity theory of Beachem can best describe how the stress...precludes an internal pressure gradient as the driv- ing force for crack growth. The adsorption theory of Petch and Stables3 and further modifications4...the adsorption theory. In addition, fracture surfaces indicate rapid void formation and coales- cence at low temperatures where the rate of surface

Carbon-Encapsulated WOx Hybrids as Efficient Catalysts for Hydrogen Evolution.

PubMed

Jing, Shengyu; Lu, Jiajia; Yu, Guangtao; Yin, Shibin; Luo, Lin; Zhang, Zengsong; Ma, Yanfeng; Chen, Wei; Shen, Pei Kang

2018-05-29

Developing non-noble metal catalysts as Pt substitutes, with good activity and stability, remains a great challenge for cost-effective electrochemical evolution of hydrogen. Herein, carbon-encapsulated WO x anchored on a carbon support (WO x @C/C) that has remarkable Pt-like catalytic behavior for the hydrogen evolution reaction (HER) is reported. Theoretical calculations reveal that carbon encapsulation improves the conductivity, acting as an electron acceptor/donor, and also modifies the Gibbs free energy of H* values for different adsorption sites (carbon atoms over the W atom, O atom, WO bond, and hollow sites). Experimental results confirm that WO x @C/C obtained at 900 °C with 40 wt% metal loading has excellent HER activity regarding its Tafel slope and overpotential at 10 and 60 mA cm -2 , and also has outstanding stability at -50 mV for 18 h. Overall, the results and facile synthesis method offer an exciting avenue for the design of cost-effective catalysts for scalable hydrogen generation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of phosphoric acid on the electrochemistry of lead electrodes in sulfuric acid electrolyte containing antimony

NASA Astrophysics Data System (ADS)

Venugopalan, S.

The influence of phosphoric acid (0 to 40 g 1 -1) on the Pb/PbSO 4 reaction and the kinetics of hydrogen evolution on pure, smooth lead and lead alloy electrodes is studied via galvanostatic polarization in the linear and Tafel domains with and without antimony (0 to 10 mg 1 -1) addition to the H 2SO 4 (3 to 10 M) electrolyte. Phosphoric acid is found to offset significantly the adverse effect of antimony. H 3PO 4 is also found to increase the hydrogen overpotential without affecting the Pb/PbSO 4 reaction. This implies that the open-circuit corrosion of lead and the consequent hydrogen evolution rate on lead are reduced in the presence of H 3PO 4. The beneficial effects of H 3PO 4 additive are found to be optimum at around 20 g 1 -1. Suppression of hydrogen evolution on the negative electrode, a crucial criterion for sealed cell operation, can be achieved using a H 3PO 4 additive.

Metal organic framework-derived CoPS/N-doped carbon for efficient electrocatalytic hydrogen evolution.

PubMed

Li, Yuzhi; Niu, Siqi; Rakov, Dmitrii; Wang, Ying; Cabán-Acevedo, Miguel; Zheng, Shijian; Song, Bo; Xu, Ping

2018-04-19

Electrocatalytic hydrogen evolution has attracted a great deal of attention due to the urgent need for clean energy. Herein, we demonstrate the synthesis of ternary pyrite-type cobalt phosphosulphide (CoPS) nanoparticles supported on a nitrogen-doped carbon matrix, CoPS/N-C, through carbonization and subsequent phosphosulfurization of Co-based zeolitic imidazolate frameworks (ZIF-67), as promising hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline solutions. The polyhedral structure of ZIF-67 can be well maintained in the as-prepared CoPS/N-C nanocomposites. In particular, CoPS/N-C provides a geometric catalytic current density of -10 mA cm-2 at overpotentials of -80 and -148 mV vs. a reversible hydrogen electrode (RHE) and a Tafel slope of 68 and 78 mV dec-1 in 0.5 M H2SO4 and 1 M KOH, respectively, which is superior to most of the transition metal phosphosulfide materials. This MOF-derived synthesis of a transition metal phosphosulfide supported heteroatom-doped carbon matrix provides a promising opportunity for the development of highly efficient electrocatalysts for renewable energy devices.

Pre-main Sequence Evolution and the Hydrogen-Burning Minimum Mass

NASA Astrophysics Data System (ADS)

Nakano, Takenori

There is a lower limit to the mass of the main-sequence stars (the hydrogen-burning minimum mass) below which the stars cannot replenish the energy lost from their surfaces with the energy released by the hydrogen burning in their cores. This is caused by the electron degeneracy in the stars which suppresses the increase of the central temperature with contraction. To find out the lower limit we need the accurate knowledge of the pre-main sequence evolution of very low-mass stars in which the effect of electron degeneracy is important. We review how Hayashi and Nakano (1963) carried out the first determination of this limit.

Solar hydrogen production using epitaxial SrTiO 3 on a GaAs photovoltaic

DOE PAGES

Kornblum, L.; Fenning, D. P.; Faucher, J.; ...

2016-12-22

We demonstrate an oxide-stabilized III–V photoelectrode architecture for solar fuel production from water in neutral pH. For this tunable architecture we demonstrate 100% Faradaic efficiency for hydrogen evolution, and incident photon-to-current efficiencies (IPCE) exceeding 50%. High IPCE for hydrogen evolution is a consequence of the low-loss interface achieved via epitaxial growth of a thin oxide on a GaAs solar cell. Developing optimal energetic alignment across the interfaces of the photoelectrode using well-established III–V technology is key to obtaining high performance. This advance constitutes a critical milestone towards efficient, unassisted fuel production from solar energy.

Natural gas-assisted steam electrolyzer

DOEpatents

Pham, Ai-Quoc; Wallman, P. Henrik; Glass, Robert S.

2000-01-01

An efficient method of producing hydrogen by high temperature steam electrolysis that will lower the electricity consumption to an estimated 65 percent lower than has been achievable with previous steam electrolyzer systems. This is accomplished with a natural gas-assisted steam electrolyzer, which significantly reduces the electricity consumption. Since this natural gas-assisted steam electrolyzer replaces one unit of electrical energy by one unit of energy content in natural gas at one-quarter the cost, the hydrogen production cost will be significantly reduced. Also, it is possible to vary the ratio between the electricity and the natural gas supplied to the system in response to fluctuations in relative prices for these two energy sources. In one approach an appropriate catalyst on the anode side of the electrolyzer will promote the partial oxidation of natural gas to CO and hydrogen, called Syn-Gas, and the CO can also be shifted to CO.sub.2 to give additional hydrogen. In another approach the natural gas is used in the anode side of the electrolyzer to burn out the oxygen resulting from electrolysis, thus reducing or eliminating the potential difference across the electrolyzer membrane.

Self-supported three-dimensional Cu/Cu2O-CuO/rGO nanowire array electrodes for an efficient hydrogen evolution reaction.

PubMed

Ye, Lin; Wen, Zhenhai

2018-06-14

We report the fabrication of self-supported Cu/Cu2O-CuO/rGO nanowire arrays on commercial porous copper foam, which exhibit excellent activity and durability for electrochemical hydrogen evolution, presenting a small onset potential of 84 mV and a low overpotential of 105 mV at a current density of 10 mA cm-2.

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

PubMed

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.

Improving the intrinsic electrocatalytic hydrogen evolution activity of few-layer NiPS3 by cobalt doping.

PubMed

Li, Kai; Rakov, Dmitrii; Zhang, Wei; Xu, Ping

2017-07-18

Here we demonstrate the improvement of the intrinsic electrocatalytic hydrogen evolution activity of NiPS 3 by proper cobalt doping. The optimized Ni 0.95 Co 0.05 PS 3 nanosheets display a geometric catalytic current density of -10 mA cm -2 at an overpotential of 71 mV vs. RHE and a Tafel slope of 77 mV dec -1 in 1.0 M KOH.

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

PubMed Central

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

2017-01-01

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

Noble-metal-free g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution under visible light irradiation

NASA Astrophysics Data System (ADS)

Cao, Shao-Wen; Yuan, Yu-Peng; Barber, James; Loo, Say Chye Joachim; Xue, Can

2014-11-01

We report an economic photocatalytic H2 generation system consisting of earth-abundant elements only by coupling graphitic carbon nitride (g-C3N4) with Ni(dmgH)2 sub-microwires that serve as effective co-catalysts for H2 evolution. This composite photocatalyst exhibits efficient hydrogen evolution under visible-light irradiation in the presence of triethanolamine as electron donor. The optimal coupling of 3.5 wt% Ni(dmgH)2 to g-C3N4 (5 mg composite) allows for a steady H2 generation rate of 1.18 μmol/h with excellent stability. This study demonstrates that the combination of polymeric g-C3N4 semiconductor and small proportion of transition-metal-based co-catalyst could serve as a stable, earth-abundant and low-cost system for solar-to-hydrogen conversion.

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

PubMed

Jin, Zhaoyu; Li, Panpan; Xiao, Dan

2017-02-08

Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fracture Kinetics of Hydrogen Embrittled Niobium.

DTIC Science & Technology

1981-03-01

Effects on Hydride Solvus 4...........4 2.3 Subcritical Crack Growth Behavior and Mechanism . . 6 2.4 Crack Propagation Measurements and Techniques... maraging steels in gaseous hydrogen, Hudak and Wei (18) ei has suggested that the KI independence of Stage II velocities is due to a rate limited...lattice decohesion model for hydrogen assisted cracking in steels . The occurrence of three stage behavior in hydrogen embrittled refractory alloys has

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

NASA Astrophysics Data System (ADS)

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.

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

DOE PAGES

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...

2016-08-30

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Effects of Residual Impurities on Hydrogen Assisted Cracking in High Strength Steels. Part II.

DTIC Science & Technology

1982-06-01

source of hydrogen is the corrosion reaction of steel with aqueous hydrogen sulfide solutions encountered either in the production of crude oil and...autoradiography technique, it has been shown that in Armco iron and in maraging steel of hydrogen is trapped at prior austenite grain boundaries. Tritium...also play a deleterious role in hydrogen-induced cracking. In these ultra-high strength steels , the crack-tip stress level and the concomitant stress

Mechanistic investigation of the formation of H2 from HCOOH with a dinuclear Ru model complex for formate hydrogen lyase.

PubMed

Tokunaga, Taisuke; Yatabe, Takeshi; Matsumoto, Takahiro; Ando, Tatsuya; Yoon, Ki-Seok; Ogo, Seiji

2017-01-01

We report the mechanistic investigation of catalytic H 2 evolution from formic acid in water using a formate-bridged dinuclear Ru complex as a formate hydrogen lyase model. The mechanistic study is based on isotope-labeling experiments involving hydrogen isotope exchange reaction.

Iron vs. cobalt clathrochelate electrocatalysts of HER: the first example on a cage iron complex.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Mokhir, Andriy; Bubnov, Yurii N; Voloshin, Yan Z

2013-04-07

New macrobicyclic 2-thiopheneboron-capped iron and cobalt(II) tris-dioximates showed high electrocatalytic activity for hydrogen production from H(+) ions. This is the first example of the hydrogen evolution reaction electrocatalyzed by a clathrochelate iron complex, which catalyzes the hydrogen production at low overpotential.

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

PubMed

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.

Neutral hydrogen in the post-reionization universe

NASA Astrophysics Data System (ADS)

Padmanabhan, Hamsa

2018-05-01

The evolution of neutral hydrogen (HI) across redshifts is a powerful probe of cosmology, large scale structure in the universe and the intergalactic medium. Using a data-driven halo model to describe the distribution of HI in the post-reionization universe (z ~ 5 to 0), we obtain the best-fitting parameters from a rich sample of observational data: low redshift 21-cm emission line studies, intermediate redshift intensity mapping experiments, and higher redshift Damped Lyman Alpha (DLA) observations. Our model describes the abundance and clustering of neutral hydrogen across redshifts 0 - 5, and is useful for investigating different aspects of galaxy evolution and for comparison with hydrodynamical simulations. The framework can be applied for forecasting future observations with neutral hydrogen, and extended to the case of intensity mapping with molecular and other line transitions at intermediate redshifts.

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

PubMed

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

2016-11-01

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

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

PubMed

Lazar, Petr; Otyepka, Michal

2017-04-06

Molybdenum disulfide, in particular its edges, has attracted considerable attention as possible substitute for platinum catalysts in the hydrogen evolution reaction (HER). The complex nature of the reaction complicates its detailed experimental investigations, which are mostly indirect and sample dependent. Therefore, density functional theory calculations were employed to study how the properties of the MoS 2 Mo-edge influence the thermodynamics of hydrogen adsorption onto the edge. The effect of the computational model (one-dimensional nanostripe), border symmetry imposed by its length, sulfur saturation of the edge, and dimensionality of the material are discussed. Hydrogen adsorption was found to depend critically on the coverage of extra sulfur at the Mo edge. The bare Mo-edge and fully sulfur-covered Mo-edge are catalytically inactive. The most favorable hydrogen binding towards HER was found for the Mo-edge covered by sulfur monomers. This edge provides hydrogen adsorption free energies positioned around -0.25 eV at up to 50 % hydrogen coverage, close to the experimental values of overpotential needed for the HER reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Efficient Catalytic Hydrogen Evolution from Ammonia Borane Using the Synergistic Effect of Crystallinity and Size of Noble-Metal-Free Nanoparticles Supported by Porous Metal-Organic Frameworks.

PubMed

Liu, Penglong; Gu, Xiaojun; Kang, Kai; Zhang, Hao; Cheng, Jia; Su, Haiquan

2017-03-29

A series of nonprecious metal nanoparticles (NPs) supported by metal-organic framework MIL-101 were synthesized using four methods and their catalytic performance on hydrogen evolution from ammonia borane (NH 3 BH 3 ) was studied. The results showed that the crystalline Co NPs with size of 4.5-8.5 and 14.5-24.5 nm had low activities featuring the total turnover frequency (TOF) values of 9.9 and 4.5 mol H2 mol cat -1 min -1 , respectively. In contrast, the amorphous Co NPs with size of 1.6-2.6 and 13.5-24.5 nm exhibited high activities featuring the total TOF values of 51.4 and 22.3 mol H2 mol cat -1 min -1 , respectively. The remarkably different activities could be ascribed to the different crystallinity and size of Co NPs in the catalysts. Moreover, the ultrasound-assisted in situ method was also successfully applied to bimetallic systems, and MIL-101-supported amorphous CuCo, FeCo and NiCo NPs had the catalytic activities with total TOF values of 51.7, 50.8, and 44.3 mol H2 mol cat -1 min -1 , respectively, which were the highest in the values of the reported non-noble metal Co-based catalysts. The present approach, namely, using the synergistic effect of crystallinity and size of metal NPs, may offer a new prospect for high-performance and low-cost nanocatalysts.

Photosynthetic production of hydrogen. [Blue-green alga, Anabaena cylindrica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neil, G.; Nicholas, D.J.D.; Bockris, J.O.

A systematic investigation of photosynthetic hydrogen production using a blue-green alga, Anabaena cylindrica, was carried out. The results indicate that there are two important problems which must be overcome for large-scale hydrogen production using photosynthetic processes. These are (a) the development of a stable system, and (b) attainment of at least a fifty-fold increase in the rate of hydrogen evolution per unit area illuminated.

Hydrogen production by recombinant Escherichia coli strains

PubMed Central

Maeda, Toshinari; Sanchez‐Torres, Viviana; Wood, Thomas K.

2012-01-01

Summary The production of hydrogen via microbial biotechnology is an active field of research. Given its ease of manipulation, the best‐studied bacterium Escherichia coli has become a workhorse for enhanced hydrogen production through metabolic engineering, heterologous gene expression, adaptive evolution, and protein engineering. Herein, the utility of E. coli strains to produce hydrogen, via native hydrogenases or heterologous ones, is reviewed. In addition, potential strategies for increasing hydrogen production are outlined and whole‐cell systems and cell‐free systems are compared. PMID:21895995

Large-scale atomistic simulations of helium-3 bubble growth in complex palladium alloys

DOE PAGES

Hale, Lucas M.; Zimmerman, Jonathan A.; Wong, Bryan M.

2016-05-18

Palladium is an attractive material for hydrogen and hydrogen-isotope storage applications due to its properties of large storage density and high diffusion of lattice hydrogen. When considering tritium storage, the material’s structural and mechanical integrity is threatened by both the embrittlement effect of hydrogen and the creation and evolution of additional crystal defects (e.g., dislocations, stacking faults) caused by the formation and growth of helium-3 bubbles. Using recently developed inter-atomic potentials for the palladium-silver-hydrogen system, we perform large-scale atomistic simulations to examine the defect-mediated mechanisms that govern helium bubble growth. Our simulations show the evolution of a distribution of materialmore » defects, and we compare the material behavior displayed with expectations from experiment and theory. In conclusion, we also present density functional theory calculations to characterize ideal tensile and shear strengths for these materials, which enable the understanding of how and why our developed potentials either meet or confound these expectations.« less

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

PubMed Central

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

2016-01-01

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. PMID:27034988

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

PubMed

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.

Minimising hydrogen sulphide generation during steam assisted production of heavy oil

PubMed Central

Montgomery, Wren; Sephton, Mark A.; Watson, Jonathan S.; Zeng, Huang; Rees, Andrew C.

2015-01-01

The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product. PMID:25670085

Minimising hydrogen sulphide generation during steam assisted production of heavy oil

NASA Astrophysics Data System (ADS)

Montgomery, Wren; Sephton, Mark A.; Watson, Jonathan S.; Zeng, Huang; Rees, Andrew C.

2015-02-01

The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product.

Minimising hydrogen sulphide generation during steam assisted production of heavy oil.

PubMed

Montgomery, Wren; Sephton, Mark A; Watson, Jonathan S; Zeng, Huang; Rees, Andrew C

2015-02-11

The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product.

Evidences for Cooperative Resonance-Assisted Hydrogen Bonds in Protein Secondary Structure Analogs

NASA Astrophysics Data System (ADS)

Zhou, Yu; Deng, Geng; Zheng, Yan-Zhen; Xu, Jing; Ashraf, Hamad; Yu, Zhi-Wu

2016-11-01

Cooperative behaviors of the hydrogen bonding networks in proteins have been discovered for a long time. The structural origin of this cooperativity, however, is still under debate. Here we report a new investigation combining excess infrared spectroscopy and density functional theory calculation on peptide analogs, represented by N-methylformamide (NMF) and N-methylacetamide (NMA). Interestingly, addition of the strong hydrogen bond acceptor, dimethyl sulfoxide, to the pure analogs caused opposite effects, namely red- and blue-shift of the N-H stretching infrared absorption in NMF and NMA, respectively. The contradiction can be reconciled by the marked lowering of the energy levels of the self-associates between NMA molecules due to a cooperative effect of the hydrogen bonds. On the contrary, NMF molecules cannot form long-chain cooperative hydrogen bonds because they tend to form dimers. Even more interestingly, we found excellent linear relationships between changes on bond orders of N-H/N-C/C = O and the hydrogen bond energy gains upon the formation of hydrogen bonding multimers in NMA, suggesting strongly that the cooperativity originates from resonance-assisted hydrogen bonds. Our findings provide insights on the structures of proteins and may also shed lights on the rational design of novel molecular recognition systems.

The Role of Hydrogen Sulfide in Evolution and the Evolution of Hydrogen Sulfide in Metabolism and Signaling.

PubMed

Olson, Kenneth R; Straub, Karl D

2016-01-01

The chemical versatility of sulfur and its abundance in the prebiotic Earth as reduced sulfide (H2S) implicate this molecule in the origin of life 3.8 billion years ago and also as a major source of energy in the first seven-eighths of evolution. The tremendous increase in ambient oxygen ∼ 600 million years ago brought an end to H2S as an energy source, and H2S-dependent animals either became extinct, retreated to isolated sulfide niches, or adapted. The first 3 billion years of molecular tinkering were not lost, however, and much of this biochemical armamentarium easily adapted to an oxic environment where it contributes to metabolism and signaling even in humans. This review examines the role of H2S in evolution and the evolution of H2S metabolism and signaling. ©2016 Int. Union Physiol. Sci./Am. Physiol. Soc.

Hydrogen effects on materials for CNG/H2 blends.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farese, David; Keller, Jay O.; Somerday, Brian P.

2010-09-01

No concerns for Hydrogen-Enriched Compressed Natural gas (HCNG) in steel storage tanks if material strength is < 950 MPa. Recommend evaluating H{sub 2}-assisted fatigue cracking in higher strength steels at H{sub 2} partial pressure in blend. Limited fatigue testing on higher strength steel cylinders in H{sub 2} shows promising results. Impurities in Compressed Natural Gas (CNG) (e.g., CO) may provide extrinsic mechanism for mitigating H{sub 2}-assisted fatigue cracking in steel tanks.

Defects Engineered Monolayer MoS 2 for Improved Hydrogen Evolution Reaction

DOE PAGES

Ye, Gonglan; Gong, Yongji; Lin, Junhao; ...

2016-01-13

MoS 2 is a promising, low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. Our work represents an easy method to increase the hydrogen production in electrochemical reaction of MoS 2 via defect engineering, and helps to understand the catalytic properties of MoS 2.

Cellular Automaton Study of Hydrogen Porosity Evolution Coupled with Dendrite Growth During Solidification in the Molten Pool of Al-Cu Alloys

NASA Astrophysics Data System (ADS)

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.

Photosynthesis in Hydrogen-Dominated Atmospheres

PubMed Central

Bains, William; Seager, Sara; Zsom, Andras

2014-01-01

The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life. PMID:25411926

Photosynthesis in hydrogen-dominated atmospheres.

PubMed

Bains, William; Seager, Sara; Zsom, Andras

2014-11-18

The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life.

Counteranion Driven Homochiral Assembly of a Cationic C3-Symmetric Gelator through Ion-Pair Assisted Hydrogen Bond.

PubMed

Maity, Arunava; Gangopadhyay, Monalisa; Basu, Arghya; Aute, Sunil; Babu, Sukumaran Santhosh; Das, Amitava

2016-09-07

The helical handedness in achiral self-assemblies is mostly complex due to spontaneous symmetry breaking or kinetically controlled random assembly formation. Here an attempt has been made to address this issue through chiral anion exchange. A new class of cationic achiral C3-symmetric gelator devoid of any conventional gelation assisting functional units is found to form both right- and left-handed helical structures. A chiral counteranion exchange-assisted approach is successfully introduced to control the chirality sign and thereby to obtain preferred homochiral assemblies. Formation of anion-assisted chiral assembly was confirmed by circular dichroism (CD) spectroscopy, microscopic images, and crystal structure. The X-ray crystal structure reveals the construction of helical assemblies with opposite handedness for (+)- and (-)-chiral anion reformed gelators. The appropriate counteranion driven ion-pair-assisted hydrogen-bonding interactions are found responsible for the helical bias control in this C3-symmetric gelator.

Hydrogen Isotopes Record the History of the Martian Hydrosphere and Atmosphere

NASA Technical Reports Server (NTRS)

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

2015-01-01

The surface geology and geomorphology of Mars indicates that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. This study presents insights from hydrogen isotopes for the origin and evolution of Martian water reservoirs.

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

PubMed

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.

An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

PubMed

Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

2017-08-08

It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

Hydrogen evolution using palladium sulfide (PdS) nanocorals as photoanodes in aqueous solution.

PubMed

Barawi, M; Ferrer, I J; Ares, J R; Sánchez, C

2014-11-26

Palladium sulfide (PdS) nanostructures are proposed to be used as photoanodes in photoelectrochemical cells (PECs) for hydrogen evolution due to their adequate transport and optical properties shown in previous works. Here, a complete morphological and electrochemical characterization of PdS films has been performed by different techniques. PdS flatband potential (Vfb=-0.65±0.05 V vs NHE) was determined by electrochemical impedance spectroscopy measurements in aqueous Na2SO3 electrolyte, providing a description of the energy levels scheme at the electrolyte-semiconductor interface. This energy levels scheme confirms PdS as a compound able to photogenerate hydrogen in a PEC. At last, photogenerated hydrogen rates are measured continuously by mass spectrometry as a function of the external bias potential under illumination, reaching values up to 4.4 μmolH2/h at 0.3 V vs Ag/AgCl.

Evolution behavior of nanohardness after thermal-aging and hydrogen-charging on austenite and strain-induced martensite in pre-strained austenitic stainless steel

NASA Astrophysics Data System (ADS)

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.

Nanoplasmonic hydrogen sensing

NASA Astrophysics Data System (ADS)

Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

2014-09-01

In this review we discuss the evolution of surface plasmon resonance and localized surface plasmon resonance based hydrogen sensors. We put particular focus on how they are used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and the single nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes. However, nanoplasmonic hydrogen sensors are not only of academic interest but may also find more practical use as all-optical gas detectors in industrial and medical applications, as well in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier.

A reagent-assisted method in SERS detection of methyl salicylate

NASA Astrophysics Data System (ADS)

Li, Yali; Li, Qianwen; Wang, Yanan; Oh, Joohee; Jin, Sila; Park, Yeonju; Zhou, Tieli; Zhao, Bing; Ruan, Weidong; Jung, Young Mee

2018-04-01

With the explosive application of methyl salicylate (MS) molecules in food and cosmetics, the further detection of MS molecules becomes particularly important. Here we investigated the detection of MS molecules based on surface-enhanced Raman scattering (SERS) in a novel molecule/assistant/metal system constructed with MS, 4,4‧-(hexafluoroisopropylidene) bis (benzoic acid) and Ag nanoparticles (AgNPs). The minimum detection concentration is 10-4 M. To explore the function of assisted reagent, we also referred another system without assistant molecules. The result demonstrates that SERS signals were not acquired, which proves that the assistant molecules are critical for the capture of MS molecules. Two possible mechanisms of MS/assistant/AgNPs system were speculated through two patterns of hydrogen bonds. The linker molecules acted as the role of the bridge between metallic substrates and target molecules through the molecular recognition. This strategy is very beneficial to the expanding of MS detection techniques and other hydrogen bond based coupling detections with SERS.

Hydrogen-assisted versus hydroxyl-assisted CO dissociation over Co-doped Cu(111): A DFT study

NASA Astrophysics Data System (ADS)

Zha, Hao; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2018-03-01

First principle based density functional theory (DFT) was used to calculate the step-by-step hydrogenation and dissociation reaction network of carbon monoxide (CO) over Co-doped Cu(111) surface as a model for understanding the lateral interaction of surface hydroxyl species (OH) on these reactions. We discussed the Csbnd O bond length and the adsorption energy changes of reaction intermediates under different adsorption circumstances for purpose of making out the effect of surface hydroxyl on the reaction selectivity. Reaction intermediates co-adsorbed with H atom and hydroxyl could undergo H-assisted or OH-assisted routes. The calculations show that the OH-assisted route prefers with the formation of COH, CHOH and CH2OH while general H-assisted route prefers with the formation of HCO, CH2O and CH3O. Considering the rather low activation barrier of COH, CHOH and CH2OH to form CHX, the existence of hydroxyl on the surface is in favor of boosting the CHX and suppressing the methanol.

Fundamental studies of hydrogen attack in carbon-0.5molybdenum steel and weldments applied in petroelum and petrochemical industries

NASA Astrophysics Data System (ADS)

Liu, Peng

High temperature hydrogen attack (HTHA) is a form of surface decarburization, internal decarburization, and/or intergranular cracking in steels exposed to high temperature (>400°F) and high hydrogen pressure. Hydrogen attack is an irreversible process which can cause permanent damage resulting in degradation of mechanical properties and failures such as leakage, bursting, fire, and/or explosion. The continuous progression of hydrogen attack in C-0.5Mo steel and weldments below the C-0.5Mo Nelson Curve has caused a significant concern for the integrity and serviceability of C-0.5Mo steel utilized for pressure vessels and piping in the petroleum refinery and petrochemical industries. A state-of-the-art literature review was implemented to provide a comprehensive overview of the published research efforts on hydrogen attack studies. The evolution of "Nelson Curves" for carbon steel, C-0.5Mo, and Cr-Mo steels was historically reviewed in regard to design applications and limitations. Testing techniques for hydrogen attack assessment were summarized under the categories of hydrogen exposure testing, mechanical evaluation, and dilatometric swelling testing. In accord with the demands of these industries, fundamental studies of hydrogen attack in C-0.5Mo steel and weldments were accomplished in terms of quantitative methodologies for hydrogen damage evaluation; hydrogen damage assessment of service exposed weldments and autoclave exposed materials; effects of carbon and alloying elements, heat treatments, hot and cold working, welding processes and postweld heat treatment (PWHT) on hydrogen attack susceptibility; development of continuous cooling transformation (CCT) diagrams for C-0.5Mo base metals and the coarse grained heat-affected zone (CGHAZ); carbide evaluation for the C-0.5Mo steel after service exposure and heat treatment; methane evolution by the reaction of hydrogen and carbides; hydrogen diffusion and methane pressure through the wall thickness of one-sided hydrogen exposure assembly; hydrogen attack mechanism and hydrogen attack limit modeling.

Hydrogen assisted growth of high quality epitaxial graphene on the C-face of 4H-SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Tuocheng; Jia, Zhenzhao; Yan, Baoming

2015-01-05

We demonstrate hydrogen assisted growth of high quality epitaxial graphene on the C-face of 4H-SiC. Compared with the conventional thermal decomposition technique, the size of the growth domain by this method is substantially increased and the thickness variation is reduced. Based on the morphology of epitaxial graphene, the role of hydrogen is revealed. It is found that hydrogen acts as a carbon etchant. It suppresses the defect formation and nucleation of graphene. It also improves the kinetics of carbon atoms via hydrocarbon species. These effects lead to increase of the domain size and the structure quality. The consequent capping effectmore » results in smooth surface morphology and suppression of multilayer growth. Our method provides a viable route to fine tune the growth kinetics of epitaxial graphene on SiC.« less

Hierarchical Ni-Mo-S nanosheets on carbon fiber cloth: A flexible electrode for efficient hydrogen generation in neutral electrolyte.

PubMed

Miao, Jianwei; Xiao, Fang-Xing; Yang, Hong Bin; Khoo, Si Yun; Chen, Jiazang; Fan, Zhanxi; Hsu, Ying-Ya; Chen, Hao Ming; Zhang, Hua; Liu, Bin

2015-08-01

A unique functional electrode made of hierarchal Ni-Mo-S nanosheets with abundant exposed edges anchored on conductive and flexible carbon fiber cloth, referred to as Ni-Mo-S/C, has been developed through a facile biomolecule-assisted hydrothermal method. The incorporation of Ni atoms in Mo-S plays a crucial role in tuning its intrinsic catalytic property by creating substantial defect sites as well as modifying the morphology of Ni-Mo-S network at atomic scale, resulting in an impressive enhancement in the catalytic activity. The Ni-Mo-S/C electrode exhibits a large cathodic current and a low onset potential for hydrogen evolution reaction in neutral electrolyte (pH ~7), for example, current density of 10 mA/cm(2) at a very small overpotential of 200 mV. Furthermore, the Ni-Mo-S/C electrode has excellent electrocatalytic stability over an extended period, much better than those of MoS2/C and Pt plate electrodes. Scanning and transmission electron microscopy, Raman spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy were used to understand the formation process and electrocatalytic properties of Ni-Mo-S/C. The intuitive comparison test was designed to reveal the superior gas-evolving profile of Ni-Mo-S/C over that of MoS2/C, and a laboratory-scale hydrogen generator was further assembled to demonstrate its potential application in practical appliances.

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

NASA Astrophysics Data System (ADS)

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.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Single cell performance studies on the FE/CR Redox Energy Storage System using mixed reactant solutions at elevated temperature

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Ling, J. S.

1983-01-01

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions, i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluated by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86 percent at 43 ma/sq cm to 75 percent at 129 ma/sq cm with corresponding coulombic efficiencies of 92 percent and 97 percent, respectively. Hydrogen evolution was less than 1 percent of the charge coulumbic capacity during charge-discharge cycling. Bismuth amd bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems. Previously announced in STAR as N83-25042

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Single cell performance studies on the Fe/Cr Redox Energy Storage System using mixed reactant solutions at elevated temperature

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H.; Ling, J. S.

1983-01-01

Experimental studies in a 14.5 sq cm single cell system using mixed reactant solutions at 65 C are described. Systems were tested under isothermal conditions i.e., reactants and the cell were at the same temperature. Charging and discharging performance were evaluted by measuring watt-hour and coulombic efficiencies, voltage-current relationships, hydrogen evolution and membrane resistivity. Watt-hour efficiencies ranged from 86% at 43 ma/sq cm to 75% at 129 ma/sq cm with corresponding coulombic efficiencies of 92% and 97%, respectively. Hydrogen evolution was less than 1% of the charge coulombic capacity during charge-discharge cycling. Bismuth and bismuth-lead catalyzed chromium electrodes maintained reversible performance and low hydrogen evolution under normal and adverse cycling conditions. Reblending of the anode and cathode solutions was successfully demonstrated to compensate for osmotic volume changes. Improved performance was obtained with mixed reactant systems in comparison to the unmixed reactant systems.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

Hydrogen embrittlement in nickel-hydrogen cells

NASA Technical Reports Server (NTRS)

Gross, Sidney

1989-01-01

It was long known that many strong metals can become weakened and brittle as the result of the accumulation of hydrogen within the metal. When the metal is stretched, it does not show normal ductile properties, but fractures prematurely. This problem can occur as the result of a hydrogen evolution reaction such as corrosion or electroplating, or due to hydrogen in the environment at the metal surface. High strength alloys such as steels are especially susceptible to hydrogen embrittlement. Nickel-hydrogen cells commonly use Inconel 718 alloy for the pressure container, and this also is susceptible to hydrogen embrittlement. Metals differ in their susceptibility to embrittlement. Hydrogen embrittlement in nickel-hydrogen cells is analyzed and the reasons why it may or may not occur are discussed. Although Inconel 718 can display hydrogen embrittlement, experience has not identified any problem with nickel-hydrogen cells. No hydrogen embrittlement problem is expected with the 718 alloy pressure container used in nickel-hydrogen cells.

Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions.

PubMed

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.

Photoelectron emission yield experiments on evolution of sub-gap states in amorphous In-Ga-Zn-O thin films with post deposition hydrogen treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayashi, Kazushi, E-mail: hayashi.kazushi@kobelco.com; Hino, Aya; Tao, Hiroaki

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 deducedmore » 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.« less

Comparative amperometric study of uptake hydrogenase and hydrogen photoproduction activities between heterocystous cyanobacterium Anabaena cylindrica B629 and nonheterocystous cyanobacterium Oscillatoria sp. strain Miami BG7

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumazawa, S.; Mitsui, A.

Heterocystous filamentous cyanobacterium Anabaena cylindrica B629 and nonheterocystous filamentous cyanobacterium Oscillatoria sp. strain Miami BG7 were cultured in media with N/sub 2/ as the sole nitrogen source; and activities of oxygen-dependent hydrogen uptake, photohydrogen production photooxygen evolution, and respiration were compared amperometrically under the same or similar experimental conditions for both strains. Distinct differences in these activities were observed in both strains. The rates of hydrogen photoproduction and hydrogen accumulation were significantly higher in Oscillatoria sp. strain BG7 than in A. cylindrica B629 at every light intensity tested. The major reason for the difference was attributable to the fact thatmore » the heterocystous cyanobacterium had a high rate of oxygen-dependent hydrogen consumption activity and the nonheterocystous cyanobacterium did not. The activity of oxygen photoevolution and respiration also contributed to the difference. Oscillatoria sp. strain BG7 had lower O/sub 2/ evolution and higher respiration than did A. cylindrica B629. Thus, the effect of O/sub 2/ on hydrogen photoproduction was minimized in Oscillatoria sp. strain BG7. 32 references, 5 figures.« less

In situ/Operando studies of electrocatalysts using hard X-ray spectroscopy

DOE PAGES

Lassalle-Kaiser, Benedikt; Gul, Sheraz; Kern, Jan; ...

2017-05-02

This review focuses on the use of X-ray absorption and emission spectroscopy techniques using hard X-rays to study electrocatalysts under in situ/operando conditions. The importance and the versatility of methods in the study of electrodes in contact with the electrolytes are described, when they are being cycled through the catalytic potentials during the progress of the oxygen-evolution, oxygen reduction and hydrogen evolution reactions. The catalytic oxygen evolution reaction is illustrated with examples using three oxides, Co, Ni and Mn, and two sulfides, Mo and Co. These are used as examples for the hydrogen evolution reaction. A bimetallic, bifunctional oxygen evolvingmore » and oxygen reducing Ni/Mn oxide is also presented. The various advantages and constraints in the use of these techniques and the future outlook are discussed.« less

World Hydrogen Energy Conference, 5th, Toronto, Canada, July 15-19, 1984, Proceedings

NASA Astrophysics Data System (ADS)

Veziroglu, T. N.; Taylor, J. B.

Among the topics discussed are thermochemical and hybrid processes for hydrogen production, pyrite-assisted water electrolysis, a hydrogen distribution network for industrial use in Western Europe, the combustion of alternative fuels in spark-ignition engines, the use of fuel cells in locomotive propulsion, hydrogen storage by glass microencapsulation, and FeTi compounds' hydriding. Also covered are plasmachemical methods of energy carrier production, synthetic fuels' production in small scale plants, products found in the anodic oxidation of coal, hydrogen embrittlement, and the regulating step in LaNi5 hydride formation.

The influence of H{sub 2}O{sub 2} concentration to the structure of silicon nanowire growth by metal-assisted chemical etching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Omar, Hafsa, E-mail: mrshafsaomar@gmail.com; Jani, Abdul Mutalib Md., E-mail: abdmutalib@perlis.uitm.edu.my; Abdullah, Saifollah, E-mail: saifollah@salam.utm.edu.my

2016-07-06

A simple and low cost method to produce well aligned silicon nanowires at large areas using Ag-assisted chemical etching at room temperature were presented. The structure of silicon nanowires growth by metal-assisted chemical etching was observed. Prior to the etching, the silicon nanowires were prepared by electroless metal deposited (EMD) in solution containing hydrofluoric acid and hydrogen peroxide in Teflon vessel. The silver particle was deposited on substrate by immersion in hydrofluoric acid and silver nitrate solution for sixty second. The silicon nanowires were growth in different hydrogen peroxide concentration which are 0.3M, 0.4M, 0.5M and 0.6M and 0.7M.The influencemore » of hydrogen peroxide concentration to the formation of silicon nanowires was studied. The morphological properties of silicon nanowires were investigated using field emission scanning electron microscopy (FESEM) and Energy Dispersive X-Ray Spectroscopy (EDS).« less

Rhodium-catalyzed asymmetric hydrogenation of unprotected NH imines assisted by a thiourea.

PubMed

Zhao, Qingyang; Wen, Jialin; Tan, Renchang; Huang, Kexuan; Metola, Pedro; Wang, Rui; Anslyn, Eric V; Zhang, Xumu

2014-08-04

Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)-thiourea provided chiral amines with up to 97% yield and 95% ee. (1)H NMR studies, coupled with control experiments, implied that catalytic chloride-bound intermediates were involved in the mechanism through a dual hydrogen-bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

System for the co-production of electricity and hydrogen

DOEpatents

Pham, Ai Quoc; Anderson, Brian Lee

2007-10-02

Described herein is a system for the co-generation of hydrogen gas and electricity, wherein the proportion of hydrogen to electricity can be adjusted from 0% to 100%. The system integrates fuel cell technology for power generation with fuel-assisted steam-electrolysis. A hydrocarbon fuel, a reformed hydrocarbon fuel, or a partially reformed hydrocarbon fuel can be fed into the system.

Facile synthesis of polypyrrole functionalized nickel foam with catalytic activity comparable to Pt for the poly-generation of hydrogen and electricity

NASA Astrophysics Data System (ADS)

Tang, Tiantian; Li, Kan; Shen, Zhemin; Sun, Tonghua; Wang, Yalin; Jia, Jinping

2016-01-01

Polypyrrole functionalized nickel foam is facilely prepared through the potentiostatic electrodeposition. The PPy-functionalized Ni foam functions as a hydrogen-evolution cathode in a rotating disk photocatalytic fuel cell, in which hydrogen energy and electric power are generated by consuming organic wastes. The PPy-functionalized Ni foam cathode exhibits stable catalytic activities after thirteen continuous runs. Compared with net or plate structure, the Ni foam with a unique three-dimensional reticulate structure is conducive to the electrodeposition of PPy. Compared with Pt-group electrode, PPy-coated Ni foam shows a satisfactory catalytic performance for the H2 evolution. The combination of PPy and Ni forms a synergistic effect for the rapid trapping and removal of proton from solution and the catalytic reduction of proton to hydrogen. The PPy-functionalized Ni foam could be applied in photocatalytic and photoelectrochemical generation of H2. In all, we report a low cost, high efficient and earth abundant PPy-functionalized Ni foam with a satisfactory catalytic activities comparable to Pt for the practical application of poly-generation of hydrogen and electricity.

Evolution of dislocation loops in austenitic stainless steels implanted with high concentration of hydrogen

NASA Astrophysics Data System (ADS)

Zheng, Zhongcheng; Gao, Ning; Tang, Rui; Yu, Yanxia; Zhang, Weiping; Shen, Zhenyu; Long, Yunxiang; Wei, Yaxia; Guo, Liping

2017-10-01

It has been found that under certain conditions, hydrogen retention would be strongly enhanced in irradiated austenitic stainless steels. To investigate the effect of the retained hydrogen on the defect microstructure, AL-6XN stainless steel specimens were irradiated with low energy (100 keV) H2+ so that high concentration of hydrogen was injected into the specimens while considerable displacement damage dose (up to 7 dpa) was also achieved. Irradiation induced dislocation loops and voids were characterised by transmission electron microscopy. For specimens irradiated to 7 dpa at 290 °C, dislocation loops with high number density were found and the void swelling was observed. At 380 °C, most of dislocation loops were unfaulted and tangled at 7 dpa, and the void swellings were observed at 5 dpa and above. Combining the data from low dose in previous work to high dose, four stages of dislocation loops evolution with hydrogen retention were suggested. Finally, molecular dynamics simulation was made to elucidate the division of large dislocation loops under irradiation.

Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage† †Electronic supplementary information (ESI) available: Experimental and computational details, free energy plots for the NH3 evolution and N2 reduction with Co3N/Co, Fe4N/Fe, Mn5N2/Mn4N, Mo2N/Mo, CrN/Cr2N, TaN/Ta2N, NbN/Nb2N, Li3N/LiH, Ba3N2/BaH2, Sr3N2/SrH2, and Ca3N2/CaH2, surface oxidation energetics, ΔGvac[NH*x, yH*] based on gas phase H2 as hydrogen source, NH3 evolution with Fe-doped Mn4N, NH3 evolution with Mn6N2.58, Ca3N2 and Sr2N after correcting for partial nitride hydrolysis, NH3 yield from Ca3N2vs. time and H2 gas flow rate. See DOI: 10.1039/c5sc00789e

PubMed Central

Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A.

2015-01-01

The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH3), a fertilizer and chemical fuel, from N2 and H2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn6N2.58 to Mn4N and hydrogenation of Ca3N2 and Sr2N to Ca2NH and SrH2, respectively. PMID:29218166

Nanocomposites of AgInZnS and graphene nanosheets as efficient photocatalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Tang, Xiaosheng; Chen, Weiwei; Zu, Zhiqiang; Zang, Zhigang; Deng, Ming; Zhu, Tao; Sun, Kuan; Sun, Lidong; Xue, Junmin

2015-11-01

In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field.In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05145b

Hydrogen assisted cracking and CO2 corrosion behaviors of low-alloy steel with high strength used for armor layer of flexible pipe

NASA Astrophysics Data System (ADS)

Liu, Zhenguang; Gao, Xiuhua; Du, Linxiu; Li, Jianping; Zhou, Xiaowei; Wang, Xiaonan; Wang, Yuxin; Liu, Chuan; Xu, Guoxiang; Misra, R. D. K.

2018-05-01

In this study, hydrogen induced cracking (HIC), sulfide stress corrosion cracking (SSCC) and hydrogen embrittlement (HE) were carried out to study hydrogen assisted cracking behavior (HIC, SSCC and HE) of high strength pipeline steel used for armor layer of flexible pipe in ocean. The CO2 corrosion behavior of designed steel with high strength was studied by using immersion experiment. The experimental results demonstrate that the corrosion resistance of designed steel with tempered martensite to HIC, SSCC and HE is excellent according to specific standards, which contributes to the low concentration of dislocation and vacancies previously formed in cold rolling process. The corrosion mechanism of hydrogen induced cracking of designed steel, which involves in producing process, microstructure and cracking behavior, is proposed. The designed steel with tempered martensite shows excellent corrosion resistance to CO2 corrosion. Cr-rich compound was first formed on the coupon surface exposed to CO2-saturated brine condition and chlorine, one of the corrosion ions in solution, was rich in the inner layer of corrosion products.

HELIUM ATMOSPHERES ON WARM NEPTUNE- AND SUB-NEPTUNE-SIZED EXOPLANETS AND APPLICATIONS TO GJ 436b

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Renyu; Yung, Yuk L.; Seager, Sara, E-mail: renyu.hu@jpl.nasa.gov

2015-07-01

Warm Neptune- and sub-Neptune-sized exoplanets in orbits smaller than Mercury’s are thought to have experienced extensive atmospheric evolution. Here we propose that a potential outcome of this atmospheric evolution is the formation of helium-dominated atmospheres. The hydrodynamic escape rates of Neptune- and sub-Neptune-sized exoplanets are comparable to the diffusion-limited escape rate of hydrogen, and therefore the escape is heavily affected by diffusive separation between hydrogen and helium. A helium atmosphere can thus be formed—from a primordial hydrogen–helium atmosphere—via atmospheric hydrodynamic escape from the planet. The helium atmosphere has very different abundances of major carbon and oxygen species from those ofmore » a hydrogen atmosphere, leading to distinctive transmission and thermal emission spectral features. In particular, the hypothesis of a helium-dominated atmosphere can explain the thermal emission spectrum of GJ 436b, a warm Neptune-sized exoplanet, while also being consistent with the transmission spectrum. This model atmosphere contains trace amounts of hydrogen, carbon, and oxygen, with the predominance of CO over CH{sub 4} as the main form of carbon. With our atmospheric evolution model, we find that if the mass of the initial atmosphere envelope is 10{sup −3} planetary mass, hydrodynamic escape can reduce the hydrogen abundance in the atmosphere by several orders of magnitude in ∼10 billion years. Observations of exoplanet transits may thus detect signatures of helium atmospheres and probe the evolutionary history of small exoplanets.« less

Micro-structured femtosecond laser assisted FBG hydrogen sensor.

PubMed

Karanja, Joseph Muna; Dai, Yutang; Zhou, Xian; Liu, Bin; Yang, Minghong

2015-11-30

We discuss hydrogen sensors based on fiber Bragg gratings (FBGs) micro-machined by femtosecond laser to form microgrooves and sputtered with Pd/Ag composite film. The atomic ratio of the two metals is controlled at Pd:Ag = 3:1. At room temperature, the hydrogen sensitivity of the sensor probe micro-machined by 75 mW laser power and sputtered with 520 nm of Pd/Ag film is 16.5 pm/%H. Comparably, the standard FBG hydrogen sensitivity becomes 2.5 pm/%H towards the same 4% hydrogen concentration. At an ambient temperature of 35°C, the processed sensor head has a dramatic rise in hydrogen sensitivity. Besides, the sensor shows good response and repeatability during hydrogen concentration test.

Atomic hydrogen and diatomic titanium-monoxide molecular spectroscopy in laser-induced plasma

NASA Astrophysics Data System (ADS)

Parigger, Christian G.; Woods, Alexander C.

2017-03-01

This article gives a brief review of experimental studies of hydrogen Balmer series emission spectra. Ongoing research aims to evaluate early plasma evolution following optical breakdown in laboratory air. Of interest is as well laser ablation of metallic titanium and characterization of plasma evolution. Emission of titanium monoxide is discussed together with modeling of diatomic spectra to infer temperature. The behavior of titanium particles in plasma draws research interests ranging from the modeling of stellar atmospheres to the enhancement of thin film production via pulsed laser deposition.

Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

PubMed

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.

A Novel Bimetallic NiMo Carbide Nanowire Array for Efficient Hydrogen Evolution.

PubMed

Guo, Lixia; Wang, Jianying; Teng, Xue; Liu, Yangyang; He, Xiaoming; Chen, Zuofeng

2018-06-12

Design and fabrication of noble metal-free hydrogen evolution electrocatalysts with high activity is significant to future renewable energy systems. In this work, self-supported NiMo carbide nanowires have been developed on carbon cloth (Ni3Mo3C@NPC NWs/CC; NPC is N,P-doped carbon) through an electropolymerization-assisted procedure. During the synthesis process, NiMoO4 nanowires were first grown on CC through a hydrothermal reaction which is free of any polymer binder like Nafion. The as-prepared NiMoO4 NWs/CC was then coated by a layer of polypyrole (PPy) by electropolymerization that serves as carbon source for the subsequent conversion to Ni3Mo3C@NPC NWs/CC by carbothermal reduction. The experimental results indicate that the judicious choices of the amount of coated PPy and the pyrolysis temperature are essential for obtaining pure phase and nanowire array structure of Ni3Mo3C@NPC NWs/CC. Benefitting from the pure phase of bimetallic carbide, the unique architecture of nanowire array and the self-supported merit, the optimized Ni3Mo3C@NPC NWs/CC electrode exhibits excellent HER performance in both acidic and alkaline media. It requires low overpotentials of 161 mV and 215 mV to afford a high current density of 100 mA cm-2 toward the HER in acidic and alkaline media, respectively, and the catalytic activity is maintained for at least 48 h, which makes it among the best HER electrocatalysts based on metallic carbides yet reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets

DOE PAGES

Yin, Ying; Han, Jiecai; Zhang, Yumin; ...

2016-06-07

Molybdenum disulfide (MoS 2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS 2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS 2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS 2 nanosheet samples, including 2H and 1T phase, porous 2H andmore » 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS 2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS 2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS 2 always outperforms the corresponding 2H phase MoS 2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS 2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. Furthermore, this study presents new insights and opens up new avenues for designing electrocatalysts based on MoS 2 or other layered materials with enhanced HER performance.« less

Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Ying; Han, Jiecai; Zhang, Yumin

Molybdenum disulfide (MoS 2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS 2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS 2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS 2 nanosheet samples, including 2H and 1T phase, porous 2H andmore » 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS 2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS 2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS 2 always outperforms the corresponding 2H phase MoS 2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS 2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. Furthermore, this study presents new insights and opens up new avenues for designing electrocatalysts based on MoS 2 or other layered materials with enhanced HER performance.« less

A Review of Fatigue Crack Growth for Pipeline Steels Exposed to Hydrogen

PubMed Central

Nanninga, N.; Slifka, A.; Levy, Y.; White, C.

2010-01-01

Hydrogen pipeline systems offer an economical means of storing and transporting energy in the form of hydrogen gas. Pipelines can be used to transport hydrogen that has been generated at solar and wind farms to and from salt cavern storage locations. In addition, pipeline transportation systems will be essential before widespread hydrogen fuel cell vehicle technology becomes a reality. Since hydrogen pipeline use is expected to grow, the mechanical integrity of these pipelines will need to be validated under the presence of pressurized hydrogen. This paper focuses on a review of the fatigue crack growth response of pipeline steels when exposed to gaseous hydrogen environments. Because of defect-tolerant design principles in pipeline structures, it is essential that designers consider hydrogen-assisted fatigue crack growth behavior in these applications. PMID:27134796

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

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.

An Historical Summary and Prospects for the Future of Spacecraft Batteries

NASA Technical Reports Server (NTRS)

Halpert, Gerald; Surampudi, S.

1998-01-01

Subjects covered in this report include a historical evolution of batteries in space, evolution and status of nickel-cadmium batteries and nickel-hydrogen batteries, present applications, future applications and advanced batteries for future missions.

Evaluating Hydrogen Evolution and Oxidation in Alkaline Media to Establish Baselines

DOE PAGES

Alia, Shaun M.; Pivovar, Bryan S.

2018-04-28

This paper fills a significant gap in the literature for alkaline hydrogen evolution (HER) and oxidation (HOR) baseline performance, while reviewing the different variables that influence observed properties. Although high-performing HER-HOR catalysts in acidic electrolytes are too active to measure kinetic in rotating disk electrode (RDE) half-cells, under alkaline conditions RDE kinetics evaluations are relevant and half-cell performances are comparable to hydrogen pump data. This paper focuses on best practices to ensure that half-cell tests don't unnecessarily lower platinum group metal (PGM) performance or improve non-PGM performance. Specific aspects examined include experiments on PGMs minimizing the impact of impurities (electrolyte,more » cell material) and experiments on non-PGMs minimizing the impact from test protocols (counter electrode).« less

Probing Transition-Metal Silicides as PGM-Free Catalysts for Hydrogen Oxidation and Evolution in Acidic Medium

PubMed Central

Mittermeier, Thomas; Madkikar, Pankaj; Wang, Xiaodong; Gasteiger, Hubert A.; Piana, Michele

2017-01-01

In this experimental study, we investigate various transition-metal silicides as platinum-group-metal-(PGM)-free electrocatalysts for the hydrogen oxidation reaction (HOR), and for the hydrogen evolution reaction (HER) in acidic environment for the first time. Using cyclic voltammetry in 0.1 M HClO4, we first demonstrate that the tested materials exhibit sufficient stability against dissolution in the relevant potential window. Further, we determine the HOR and HER activities for Mo, W, Ta, Ni and Mo-Ni silicides in rotating disk electrode experiments. In conclusion, for the HOR only Ni2Si shows limited activity, and the HER activity of the investigated silicides is considerably lower compared to other PGM-free HER catalysts reported in the literature. PMID:28773022

Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

NASA Astrophysics Data System (ADS)

Fang, Si-Ling; Chou, Tsu-Chin; Samireddi, Satyanarayana; Chen, Kuei-Hsien; Chen, Li-Chyong; Chen, Wei-Fu

2017-03-01

Production of hydrogen from water electrolysis has stimulated the search of sustainable electrocatalysts as possible alternatives. Recently, cobalt phosphide (CoP) and molybdenum phosphide (MoP) received great attention owing to their superior catalytic activity and stability towards the hydrogen evolution reaction (HER) which rivals platinum catalysts. In this study, we synthesize and study a series of catalysts based on hybrids of CoP and MoP with different Co/Mo ratio. The HER activity shows a volcano shape and reaches a maximum for Co/Mo = 1. Tafel analysis indicates a change in the dominating step of Volmer-Hyrovský mechanism. Interestingly, X-ray diffraction patterns confirmed a major ternary interstitial hexagonal CoMoP2 crystal phase is formed which enhances the electrochemical activity.

Silicon oxidation in fluoride solutions

NASA Technical Reports Server (NTRS)

Sancier, K. M.; Kapur, V.

1980-01-01

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Evaluating Hydrogen Evolution and Oxidation in Alkaline Media to Establish Baselines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alia, Shaun M.; Pivovar, Bryan S.

This paper fills a significant gap in the literature for alkaline hydrogen evolution (HER) and oxidation (HOR) baseline performance, while reviewing the different variables that influence observed properties. Although high-performing HER-HOR catalysts in acidic electrolytes are too active to measure kinetic in rotating disk electrode (RDE) half-cells, under alkaline conditions RDE kinetics evaluations are relevant and half-cell performances are comparable to hydrogen pump data. This paper focuses on best practices to ensure that half-cell tests don't unnecessarily lower platinum group metal (PGM) performance or improve non-PGM performance. Specific aspects examined include experiments on PGMs minimizing the impact of impurities (electrolyte,more » cell material) and experiments on non-PGMs minimizing the impact from test protocols (counter electrode).« less

Competitive Adsorption-Assisted Formation of One-Dimensional Cobalt Nanochains with High CO Hydrogenation Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Xin; Ren, Zhibo; Zhu, Xiaolin

In the present work, cobalt nanochains have been successfully synthesized by a novel co assisted self-assembling formation strategy. A dramatic morphology transformation from cobalt nanoparticles to nanochains are observed when co molecules were introduced into the synthetic system. DFT calculations further confirm that competitive co-adsorbed co and oleylamine over the cobalt nanoparticles facilitates the formation of cobalt nanochains, which show higher co hydrogenation performance. The present work provides a new strategic and promising method for controllable synthesis of catalyst nanomaterials with the preferred surface structure and morphology.

The Evolution and Increasing Complexity of the Resident Assistant Role in the United States from Colonial to Modern Times

ERIC Educational Resources Information Center

Boone, Katherine B.; Davidson, Denise L.; Bauman, Mark

2016-01-01

The evolution of the resident assistant position and its history are important to understanding its increasing complexities. In this article we examine how court cases and federal legislation, along with changes in popular culture, have altered and shaped the role of the resident assistant. Our premise is that this role, originally relatively…

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Hays, Charles C. (Inventor)

2015-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor); Narayan, Sri R. (Inventor)

2013-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Self-shielding of hydrogen in the IGM during the epoch of reionization

NASA Astrophysics Data System (ADS)

Chardin, Jonathan; Kulkarni, Girish; Haehnelt, Martin G.

2018-04-01

We investigate self-shielding of intergalactic hydrogen against ionizing radiation in radiative transfer simulations of cosmic reionization carefully calibrated with Lyα forest data. While self-shielded regions manifest as Lyman-limit systems in the post-reionization Universe, here we focus on their evolution during reionization (redshifts z = 6-10). At these redshifts, the spatial distribution of hydrogen-ionizing radiation is highly inhomogeneous, and some regions of the Universe are still neutral. After masking the neutral regions and ionizing sources in the simulation, we find that the hydrogen photoionization rate depends on the local hydrogen density in a manner very similar to that in the post-reionization Universe. The characteristic physical hydrogen density above which self-shielding becomes important at these redshifts is about nH ˜ 3 × 10-3 cm-3, or ˜20 times the mean hydrogen density, reflecting the fact that during reionization photoionization rates are typically low enough that the filaments in the cosmic web are often self-shielded. The value of the typical self-shielding density decreases by a factor of 3 between redshifts z = 3 and 10, and follows the evolution of the average photoionization rate in ionized regions in a simple fashion. We provide a simple parameterization of the photoionization rate as a function of density in self-shielded regions during the epoch of reionization.

Self-shielding of hydrogen in the IGM during the epoch of reionization

NASA Astrophysics Data System (ADS)

Chardin, Jonathan; Kulkarni, Girish; Haehnelt, Martin G.

2018-07-01

We investigate self-shielding of intergalactic hydrogen against ionizing radiation in radiative transfer simulations of cosmic reionization carefully calibrated with Lyα forest data. While self-shielded regions manifest as Lyman limit systems in the post-reionization Universe, here we focus on their evolution during reionization (redshifts z = 6-10). At these redshifts, the spatial distribution of hydrogen-ionizing radiation is highly inhomogeneous, and some regions of the Universe are still neutral. After masking the neutral regions and ionizing sources in the simulation, we find that the hydrogen photoionization rate depends on the local hydrogen density in a manner very similar to that in the post-reionization Universe. The characteristic physical hydrogen density above which self-shielding becomes important at these redshifts is about nH ˜ 3 × 10-3 cm-3, or ˜20 times the mean hydrogen density, reflecting the fact that during reionization photoionization rates are typically low enough that the filaments in the cosmic web are often self-shielded. The value of the typical self-shielding density decreases by a factor of 3 between redshifts z = 3 and 10, and follows the evolution of the average photoionization rate in ionized regions in a simple fashion. We provide a simple parametrization of the photoionization rate as a function of density in self-shielded regions during the epoch of reionization.

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

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

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Active hydrogen evolution through lattice distortion in metallic MoTe2

NASA Astrophysics Data System (ADS)

Seok, Jinbong; Lee, Jun-Ho; Cho, Suyeon; Ji, Byungdo; Kim, Hyo Won; Kwon, Min; Kim, Dohyun; Kim, Young-Min; Oh, Sang Ho; Wng Kim, Sung; Lee, Young Hee; Son, Young-Woo; Yang, Heejun

2017-06-01

Engineering surface atoms of transition metal dichalcogenides (TMDs) is a promising way to design catalysts for efficient electrochemical reactions including the hydrogen evolution reaction (HER). However, materials processing based on TMDs, such as vacancy creation or edge exposure, for active HER, has resulted in insufficient atomic-precision lattice homogeneity and a lack of clear understanding of HER over 2D materials. Here, we report a durable and effective HER at atomically defined reaction sites in 2D layered semimetallic MoTe2 with intrinsic turnover frequency (TOF) of 0.14 s-1 at 0 mV overpotential, which cannot be explained by the traditional volcano plot analysis. Unlike former electrochemical catalysts, the rate-determining step of the HER on the semimetallic MoTe2, hydrogen adsorption, drives Peierls-type lattice distortion that, together with a surface charge density wave, unexpectedly enhances the HER. The active HER using unique 2D features of layered TMDs enables an optimal design of electrochemical catalysts and paves the way for a hydrogen economy.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution.

PubMed

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

2016-12-12

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 H 2 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.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

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.

Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

PubMed Central

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

2016-01-01

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. PMID:27941752

Rationally designed n-n heterojunction with highly efficient solar hydrogen evolution.

PubMed

Xu, Miao; Ye, Tiannan; Dai, Fang; Yang, Jindi; Shen, Jingmei; He, Qingquan; Chen, Wenlong; Liang, Na; Zai, Jiantao; Qian, Xuefeng

2015-04-13

In most of the reported n-n heterojunction photocatalysts, both the conduction and valence bands of one semiconductor are more negative than those of the other semiconductor. In this work, we designed and synthesized a novel n-n heterojunction photocatalyst, namely CdS-ZnWO4 heterojunctions, in which ZnWO4 has more negative conduction band and more positive valence band than those of CdS. The hydrogen evolution rate of CdS-30 mol %-ZnWO4 reaches 31.46 mmol h(-1)  g(-1) under visible light, which is approximately 8 and 755 times higher than that of pure CdS and ZnWO4 under similar conditions, respectively. The location of the surface active sites is researched and a plausible mechanism of performance enhancement by the tuning of the structure is proposed based on the photoelectrochemical characterization. The results illustrate that this kind of nonconventional n-n heterojunctions is also suitable and highly efficient for solar hydrogen evolution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

NASA Astrophysics Data System (ADS)

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-05-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm-2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec-1. Moreover, we achieve 10 mA cm-2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2.

Highly Efficient Photocatalytic H2 Evolution from Water using Visible Light and Structure-Controlled Graphitic Carbon Nitride**

PubMed Central

Martin, David James; Qiu, Kaipei; Shevlin, Stephen Andrew; Handoko, Albertus Denny; Chen, Xiaowei; Guo, Zhengxiao; Tang, Junwang

2014-01-01

The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low-cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g-C3N4) from a low-cost precursor, urea, is reported. The g-C3N4 exhibits an extraordinary hydrogen-evolution rate (ca. 20 000 μmol h−1 g−1 under full arc), which leads to a high turnover number (TON) of over 641 after 6 h. The reaction proceeds for more than 30 h without activity loss and results in an internal quantum yield of 26.5 % under visible light, which is nearly an order of magnitude higher than that observed for any other existing g-C3N4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen-evolution rate is significantly enhanced. PMID:25045013

Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution

PubMed Central

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

2015-01-01

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt–nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt–N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s−1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols. PMID:26250525

Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

NASA Astrophysics Data System (ADS)

Kitagawa, Yuta; Tanabe, Katsuaki

2018-05-01

Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

High Strength Steel Weldment Reliability: Weld Metal Hydrogen Trapping.

DTIC Science & Technology

1998-02-01

Reliability : Weld Metal Hydrogen Trapping submitted to : United States Army Research Office Materials Science Division P.O. Box 12211 Research Triangle...Conf. Proc. of Welding and Related Technologies for the XXIth Century, November 1998, Kiev, Ukraine : "Hydrogen Assisted Cracking in...appendices (see appendix IV). Next TTCP workshop will be held from 6th to 8th October 1998, at CANMET , Ottawa, Ontario, Canada. 20 III. Figures 18

Interface Engineering of Colloidal CdSe Quantum Dot Thin Films as Acid-Stable Photocathodes for Solar-Driven Hydrogen Evolution.

PubMed

Li, Hui; Wen, Peng; Hoxie, Adam; Dun, Chaochao; Adhikari, Shiba; Li, Qi; Lu, Chang; Itanze, Dominique S; Jiang, Lin; Carroll, David; Lachgar, Abdou; Qiu, Yejun; Geyer, Scott M

2018-05-23

Colloidal semiconductor quantum dot (CQD)-based photocathodes for solar-driven hydrogen evolution have attracted significant attention because of their tunable size, nanostructured morphology, crystalline orientation, and band gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM-1.5G, 100 mW/cm 2 ) at a potential of 0 V versus reversible hydrogen electrode (RHE) ( j 0 ) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V versus RHE and long-term stability with negligible degradation. In the acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited because of photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared with 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge-transfer rate, and faster reaction kinetics. We believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.

Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

PubMed

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.

Ultrafast visualization of the structural evolution of dense hydrogen towards warm dense matter

NASA Astrophysics Data System (ADS)

Fletcher, Luke

2016-10-01

Hot dense hydrogen far from equilibrium is ubiquitous in nature occurring during some of the most violent and least understood events in our universe such as during star formation, supernova explosions, and the creation of cosmic rays. It is also a state of matter important for applications in inertial confinement fusion research and in laser particle acceleration. Rapid progress occurred in recent years characterizing the high-pressure structural properties of dense hydrogen under static or dynamic compression. Here, we show that spectrally and angularly resolved x-ray scattering measure the thermodynamic properties of dense hydrogen and resolve the ultrafast evolution and relaxation towards thermodynamic equilibrium. These studies apply ultra-bright x-ray pulses from the Linac Coherent Light (LCLS) source. The interaction of rapidly heated cryogenic hydrogen with a high-peak power optical laser is visualized with intense LCLS x-ray pulses in a high-repetition rate pump-probe setting. We demonstrate that electron-ion coupling is affected by the small number of particles in the Debye screening cloud resulting in much slower ion temperature equilibration than predicted by standard theory. This work was supported by the DOE Office of Science, Fusion Energy Science under FWP 100182.

Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.

Surfactant-assisted coal liquefaction

NASA Technical Reports Server (NTRS)

Hsu, G. C.

1977-01-01

Improved process of coal liquefaction utilizing nonaqueous surfactant has increased oil yield from 50 to about 80%. Asphaltene molecule formation of colloid particles is prevented by surfactant. Separated molecules present more surface area for hydrogenation reaction. Lower requirements for temperature, pressure, and hydrogen lead to reduction in capital and operation costs.

Self-assembled inorganic clusters of semiconducting quantum dots for effective solar hydrogen evolution.

PubMed

Gao, Yu-Ji; Yang, Yichen; Li, Xu-Bing; Wu, Hao-Lin; Meng, Shu-Lin; Wang, Yang; Guo, Qing; Huang, Mao-Yong; Tung, Chen-Ho; Wu, Li-Zhu

2018-05-08

Owing to promoted electron-hole separation, the catalytic activity of semiconducting quantum dots (QDs) towards solar hydrogen (H2) production has been significantly enhanced by forming self-assembled clusters with ZnSe QDs made ex situ. Taking advantage of the favored interparticle hole transfer to ZnSe QDs, the rate of solar H2 evolution of CdSe QDs can be increased to ∼30 000 μmol h-1 g-1 with ascorbic acid as the sacrificial reagent, ∼150-fold higher than that of bare CdSe QDs clusters under the same conditions.

Structural evolution and electronic properties of n-type doped hydrogenated amorphous silicon thin films

NASA Astrophysics Data System (ADS)

He, Jian; Li, Wei; Xu, Rui; Qi, Kang-Cheng; Jiang, Ya-Dong

2011-12-01

The relationship between structure and electronic properties of n-type doped hydrogenated amorphous silicon (a-Si:H) thin films was investigated. Samples with different features were prepared by plasma enhanced chemical vapor deposition (PECVD) at various substrate temperatures. Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy were used to evaluate the structural evolution, meanwhile, electronic-spin resonance (ESR) and optical measurement were applied to explore the electronic properties of P-doped a-Si:H thin films. Results reveal that the changes in materials structure affect directly the electronic properties and the doping efficiency of dopant.

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution.

PubMed

Hua, Wei; Liu, Huanyan; Wang, Jian-Gan; Wei, Bingqing

2017-12-06

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O) x ·MoO x nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O) x and amorphous MoO x , as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm -2 , a low Tafel slope of 54 mV dec -1 , and excellent cycling stability.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution

PubMed Central

Hua, Wei; Liu, Huanyan

2017-01-01

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O)x·MoOx nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O)x and amorphous MoOx, as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm−2, a low Tafel slope of 54 mV dec-1, and excellent cycling stability. PMID:29210991

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

DOE PAGES

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie; ...

2017-09-22

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Structure-Activity Relationships for Pt-Free Metal Phosphide Hydrogen Evolution Electrocatalysts.

PubMed

Owens-Baird, Bryan; Kolen'ko, Yury V; Kovnir, Kirill

2018-05-23

In the field of renewable energy, the splitting of water into hydrogen and oxygen fuel gases using water electrolysis is a prominent topic. Traditionally, these catalytic processes have been performed by platinum-group metal catalysts, which are effective at promoting water electrolysis but expensive and rare. The search for an inexpensive and Earth-abundant catalyst has led to the development of 3d-transition-metal phosphides for the hydrogen evolution reaction. These catalysts have shown excellent activity and stability. In this review, we discuss the electronic and crystal structures of bulk and surface of selected Fe, Co, and Ni phosphides, and their relationships to the experimental catalytic activity. The various synthetic protocols towards the state-of-the-art transition metal phosphide electrocatalysts are also discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gaseous hydrogen embrittlement of high strength steels

NASA Technical Reports Server (NTRS)

Gangloff, R. P.; Wei, R. P.

1977-01-01

The effects of temperature, hydrogen pressure, stress intensity, and yield strength on the kinetics of gaseous hydrogen assisted crack propagation in 18Ni maraging steels were investigated experimentally. It was found that crack growth rate as a function of stress intensity was characterized by an apparent threshold for crack growth, a stage where the growth rate increased sharply, and a stage where the growth rate was unchanged over a significant range of stress intensity. Cracking proceeded on load application with little or no detectable incubation period. Gaseous hydrogen embrittlement susceptibility increased with increasing yield strength.

Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

PubMed

Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

2015-05-11

A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile Synthesis of Vanadium-Doped Ni3S2 Nanowire Arrays as Active Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Qu, Yuanju; Yang, Mingyang; Chai, Jianwei; Tang, Zhe; Shao, Mengmeng; Kwok, Chi Tat; Yang, Ming; Wang, Zhenyu; Chua, Daniel; Wang, Shijie; Lu, Zhouguang; Pan, Hui

2017-02-22

Ni 3 S 2 nanowire arrays doped with vanadium(V) are directly grown on nickel foam by a facile one-step hydrothermal method. It is found that the doping can promote the formation of Ni 3 S 2 nanowires at a low temperature. The doped nanowires show excellent electrocatalytic performance toward hydrogen evolution reaction (HER), and outperform pure Ni 3 S 2 and other Ni 3 S 2 -based compounds. The stability test shows that the performance of V-doped Ni 3 S 2 nanowires is improved and stabilized after thousands of linear sweep voltammetry test. The onset potential of V-doped Ni 3 S 2 nanowire can be as low as 39 mV, which is comparable to platinum. The nanowire has an overpotential of 68 mV at 10 mA cm -2 , a relatively low Tafel slope of 112 mV dec -1 , good stability and high Faradaic efficiency. First-principles calculations show that the V-doping in Ni 3 S 2 extremely enhances the free carrier density near the Fermi level, resulting in much improved catalytic activities. We expect that the doping can be an effective way to enhance the catalytic performance of metal disulfides in hydrogen evolution reaction and V-doped Ni 3 S 2 nanowire is one of the most promising electrocatalysts for hydrogen production.

Bioengineering of the Enterobacter aerogenes strain for biohydrogen production.

PubMed

Zhang, Chong; Lv, Feng-Xiang; Xing, Xin-Hui

2011-09-01

Enterobacter aerogenes is one of the most widely-studied model strains for fermentative hydrogen production. To improve the hydrogen yield of E. aerogenes, the bioengineering on a biomolecular level and metabolic network level is of importance. In this review, the fermentative technology of E. aerogenes for hydrogen production will be first briefly summarized. And then the bioengineering of E. aerogenes for the improvement of hydrogen yield will be thoroughly reviewed, including the anaerobic metabolic networks for hydrogen evolution in E. aerogenes, metabolic engineering for improving hydrogen production in E. aerogenes and mixed culture of E. aerogenes with other hydrogen-producing bacteria to enhance the overall yield in anaerobic cultivation. Finally, a perspective on E. aerogenes as a hydrogen producer including systems bioengineering approach for improving the hydrogen yield and application of the engineered E. aerogenes in mixed culture will be presented. Copyright © 2011 Elsevier Ltd. All rights reserved.

Laser and optical system for laser assisted hydrogen ion beam stripping at SNS

DOE PAGES

Liu, Y.; Rakhman, A.; Menshov, A.; ...

2016-12-01

A high-efficiency laser assisted hydrogen ion (H-) beam stripping was recently successfully carried out in the Spallation Neutron Source (SNS) accelerator. The experiment was not only an important step toward foil-less H- stripping for charge exchange injection, it also set up a first example of using megawatt ultraviolet (UV) laser source in an operational high power proton accelerator facility. This study reports in detail the design, installation, and commissioning result of a macro-pulsed multi-megawatt UV laser system and laser beam transport line for the laser stripping experiment.

Laser and optical system for laser assisted hydrogen ion beam stripping at SNS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Y.; Rakhman, A.; Menshov, A.

A high-efficiency laser assisted hydrogen ion (H-) beam stripping was recently successfully carried out in the Spallation Neutron Source (SNS) accelerator. The experiment was not only an important step toward foil-less H- stripping for charge exchange injection, it also set up a first example of using megawatt ultraviolet (UV) laser source in an operational high power proton accelerator facility. This study reports in detail the design, installation, and commissioning result of a macro-pulsed multi-megawatt UV laser system and laser beam transport line for the laser stripping experiment.

Synthesis of Tapered CdS Nanobelts and CdSe Nanowires with Good Optical Property by Hydrogen-Assisted Thermal Evaporation

PubMed Central

2009-01-01

The tapered CdS nanobelts and CdSe nanowires were prepared by hydrogen-assisted thermal evaporation method. Different supersaturation leads to two different kinds of 1D nanostructures. The PL measurements recorded from the as-prepared tapered CdS nanobelts and CdSe nanowires show only a bandgap emission with relatively narrow full-width half maximum, which means that they possess good optical property. The as-synthesized high-quality tapered CdS nanobelts and CdSe nanowires may be excellent building blocks for photonic devices. PMID:20596418

Hydrogen content and mechanical stress in glow discharge amorphous silicon

NASA Astrophysics Data System (ADS)

Paduschek, P.; Eichinger, P.; Kristen, G.; Mitlehner, H.

1982-08-01

The hydrogen content of plasma deposited amorphous silicon thin films on silicon has been determined as a function of annealing parameters (200-700°C, 12 h) using the proton-proton scattering method. It is shown that hydrogen is released with an activation energy of 1.3 eV. Different deposition temperatures are compared with respect to the hydrogen evolution. The mechanical stress of the layers on silicon substrates has been measured by interferometric techniques for each annealing step. As the hydrogen content decreases monotonically with rising annealing temperature the mechanical stress converts from compressive to tensile. While only a weak correlation exists between the total hydrogen content and the mechanical stress, the bound hydrogen as determined by IR absorption displays a linear relation with the measured mechanical stress.

In situ probing of doping- and stress-mediated phase transitions in a single-crystalline VO2 nanobeam by spatially resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chang, Sung-Jin; Park, Jong Bae; Lee, Gaehang; Kim, Hae Jin; Lee, Jin-Bae; Bae, Tae-Sung; Han, Young-Kyu; Park, Tae Jung; Huh, Yun Suk; Hong, Woong-Ki

2014-06-01

We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress.We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO2 nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO2 nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO2 nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO2 nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO2 nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO2 nanostructures through doping and stress. Electronic supplementary information (ESI) available: Illustration, photograph, Raman data, and EDX spectra. See DOI: 10.1039/c4nr01118j

Is the addition of an assisted driving Hamiltonian always useful for adiabatic evolution?

NASA Astrophysics Data System (ADS)

Sun, Jie; Lu, Songfeng; Li, Li

2017-04-01

It has been known that when an assisted driving item is added to the main system Hamiltonian, the efficiency of the resultant adiabatic evolution can be significantly improved. In some special cases, it can be seen that only through adding an assisted driving Hamiltonian can the resulting adiabatic evolution be made not to fail. Thus the additional driving Hamiltonian plays an important role in adiabatic computing. In this paper, we show that if the driving Hamiltonian is chosen inappropriately, the adiabatic computation may still fail. More importantly, we find that the adiabatic computation can only succeed if the assisted driving Hamiltonian has a relatively fixed form. This may help us understand why in the related literature all of the driving Hamiltonians used share the same form.

[Analysis of the implementation of Nursing Assistance Systematization in a rehabilitation unit].

PubMed

Neves, Rinaldo de Souza; Shimizu, Helena Eri

2010-01-01

This study seeks to analyze the execution of the Infirmary Attendance Systematization Nursing stages through an exploratory, qualitative and retrospective approach. The retrospective analysis took place using 25 medic reports containing 25 historical reports, 12 diagnosis reports, 100 prescriptions and 100 nursing evolution reports. The results demonstrated the many difficulties the nurses faced to make Nursing Assistance Systematization operational. Although all Nursing Assistance Systematization stages were accomplished - historical, diagnosis, prescription, evolution and nursing - it was verified a larger frequency in filling prescription and historical related forms and a lesser one related with evolution and diagnosis related forms. In short, Nursing Assistance Systematization procedures still are fragmentized, showing the need to reorganize this attendance methodology attendance, and, above all, to invest in continuous nursing training to improve the customer care services quality.

The ionisation parameter of star-forming galaxies evolves with the specific star formation rate

NASA Astrophysics Data System (ADS)

Kaasinen, Melanie; Kewley, Lisa; Bian, Fuyan; Groves, Brent; Kashino, Daichi; Silverman, John; Kartaltepe, Jeyhan

2018-04-01

We investigate the evolution of the ionisation parameter of star-forming galaxies using a high-redshift (z ˜ 1.5) sample from the FMOS-COSMOS survey and matched low-redshift samples from the Sloan Digital Sky Survey. By constructing samples of low-redshift galaxies for which the stellar mass (M*), star formation rate (SFR) and specific star formation rate (sSFR) are matched to the high-redshift sample we remove the effects of an evolution in these properties. We also account for the effect of metallicity by jointly constraining the metallicity and ionisation parameter of each sample. We find an evolution in the ionisation parameter for main-sequence, star-forming galaxies and show that this evolution is driven by the evolution of sSFR. By analysing the matched samples as well as a larger sample of z < 0.3, star-forming galaxies we show that high ionisation parameters are directly linked to high sSFRs and are not simply the byproduct of an evolution in metallicity. Our results are physically consistent with the definition of the ionisation parameter, a measure of the hydrogen ionising photon flux relative to the number density of hydrogen atoms.

Evaluation of advanced propulsion options for the next manned transportation system: Propulsion evolution study

NASA Technical Reports Server (NTRS)

Spears, L. T.; Kramer, R. D.

1990-01-01

The objectives were to examine launch vehicle applications and propulsion requirements for potential future manned space transportation systems and to support planning toward the evolution of Space Shuttle Main Engine (SSME) and Space Transportation Main Engine (STME) engines beyond their current or initial launch vehicle applications. As a basis for examinations of potential future manned launch vehicle applications, we used three classes of manned space transportation concepts currently under study: Space Transportation System Evolution, Personal Launch System (PLS), and Advanced Manned Launch System (AMLS). Tasks included studies of launch vehicle applications and requirements for hydrogen-oxygen rocket engines; the development of suggestions for STME engine evolution beyond the mid-1990's; the development of suggestions for STME evolution beyond the Advanced Launch System (ALS) application; the study of booster propulsion options, including LOX-Hydrocarbon options; the analysis of the prospects and requirements for utilization of a single engine configuration over the full range of vehicle applications, including manned vehicles plus ALS and Shuttle C; and a brief review of on-going and planned LOX-Hydrogen propulsion technology activities.

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

The ionization parameter of star-forming galaxies evolves with the specific star formation rate

NASA Astrophysics Data System (ADS)

Kaasinen, Melanie; Kewley, Lisa; Bian, Fuyan; Groves, Brent; Kashino, Daichi; Silverman, John; Kartaltepe, Jeyhan

2018-07-01

We investigate the evolution of the ionization parameter of star-forming galaxies using a high-redshift (z˜ 1.5) sample from the FMOS-COSMOS (Fibre Multi-Object Spectrograph-COSMic evOlution Survey) and matched low-redshift samples from the Sloan Digital Sky Survey. By constructing samples of low-redshift galaxies for which the stellar mass (M*), star formation rate (SFR), and specific star formation rate (sSFR) are matched to the high-redshift sample, we remove the effects of an evolution in these properties. We also account for the effect of metallicity by jointly constraining the metallicity and ionization parameter of each sample. We find an evolution in the ionization parameter for main-sequence, star-forming galaxies and show that this evolution is driven by the evolution of sSFR. By analysing the matched samples as well as a larger sample of z< 0.3, star-forming galaxies we show that high ionization parameters are directly linked to high sSFRs and are not simply the by-product of an evolution in metallicity. Our results are physically consistent with the definition of the ionization parameter, a measure of the hydrogen ionizing photon flux relative to the number density of hydrogen atoms.

Innovative self-powered submersible microbial electrolysis cell (SMEC) for biohydrogen production from anaerobic reactors.

PubMed

Zhang, Yifeng; Angelidaki, Irini

2012-05-15

A self-powered submersible microbial electrolysis cell (SMEC), in which a specially designed anode chamber and external electricity supply were not needed, was developed for in situ biohydrogen production from anaerobic reactors. In batch experiments, the hydrogen production rate reached 17.8 mL/L/d at the initial acetate concentration of 410 mg/L (5 mM), while the cathodic hydrogen recovery ( [Formula: see text] ) and overall systemic coulombic efficiency (CE(os)) were 93% and 28%, respectively, and the systemic hydrogen yield ( [Formula: see text] ) peaked at 1.27 mol-H(2)/mol-acetate. The hydrogen production increased along with acetate and buffer concentration. The highest hydrogen production rate of 32.2 mL/L/d and [Formula: see text] of 1.43 mol-H(2)/mol-acetate were achieved at 1640 mg/L (20 mM) acetate and 100 mM phosphate buffer. Further evaluation of the reactor under single electricity-generating or hydrogen-producing mode indicated that further improvement of voltage output and reduction of electron losses were essential for efficient hydrogen generation. In addition, alternate exchanging the electricity-assisting and hydrogen-producing function between the two cell units of the SMEC was found to be an effective approach to inhibit methanogens. Furthermore, 16S rRNA genes analysis showed that this special operation strategy resulted same microbial community structures in the anodic biofilms of the two cell units. The simple, compact and in situ applicable SMEC offers new opportunities for reactor design for a microbial electricity-assisted biohydrogen production system. Copyright © 2012 Elsevier Ltd. All rights reserved.

An efficient microwave-assisted synthesis method for the production of water soluble amine-terminated Si nanoparticles.

PubMed

Atkins, Tonya M; Louie, Angelique Y; Kauzlarich, Susan M

2012-07-27

Silicon nanoparticles can be considered a green material, especially when prepared via a microwave-assisted method without the use of highly reactive reducing agents or hydrofluoric acid. A simple solution synthesis of hydrogen-terminated Si- and Mn-doped Si nanoparticles via microwave-assisted synthesis is demonstrated. The reaction of the Zintl salt, Na(4)Si(4), or Mn-doped Na(4)Si(4), Na(4)Si(4(Mn)), with ammonium bromide, NH(4)Br, produces small dispersible nanoparticles along with larger particles that precipitate. Allylamine and 1-amino-10-undecene were reacted with the hydrogen-terminated Si nanoparticles to provide water solubility and stability. A one-pot, single-reaction process and a one-pot, two-step reaction process were investigated. Details of the microwave-assisted process are provided, with the optimal synthesis being the one-pot, two-step reaction procedure and a total time of about 15 min. The nanoparticles were characterized by transmission electron microscopy (TEM), x-ray diffraction, and fluorescence spectroscopies. The microwave-assisted method reliably produces a narrow size distribution of Si nanoparticles in solution.

Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution.

PubMed

Zhao, Li; Dong, Biliang; Li, Shaozhou; Zhou, Lijun; Lai, Linfei; Wang, Zhiwei; Zhao, Shulin; Han, Min; Gao, Kai; Lu, Min; Xie, Xiaoji; Chen, Bo; Liu, Zhengdong; Wang, Xiangjing; Zhang, Hao; Li, Hai; Liu, Juqing; Zhang, Hua; Huang, Xiao; Huang, Wei

2017-06-27

Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti 3 C 2 T x (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm -2 at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec -1 in 0.1 M KOH. These results outperform those obtained by the standard IrO 2 -based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti 3 C 2 T x nanosheets enabled the rapid charge and ion transfer across the well-defined Ti 3 C 2 T x -CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

"A bridge over troubled gaps": up-conversion driven photocatalysis for hydrogen generation and pollutant degradation by near-infrared excitation.

PubMed

Acosta-Mora, P; Domen, K; Hisatomi, T; Lyu, H; Méndez-Ramos, J; Ruiz-Morales, J C; Khaidukov, N M

2018-02-15

Spectral up-conversion (UC) has been attracting growing interest for the effective harvesting of the near-infrared (NIR) part of sunlight for photocatalytic hydrogen production and environmental purification. We present evidence of NIR-to-UV-VIS photon conversion for degradation of organic dyes and hydrogen and oxygen evolution via water-splitting by TiO 2 and Rh-Cr oxide-loaded SrTiO 3 :Al photocatalysts, respectively.

Variable photosynthetic units, energy transfer and light-induced evolution of hydrogen in algae and bacteria.

NASA Technical Reports Server (NTRS)

Gaffron, H.

1971-01-01

The present state of knowledge regarding the truly photochemical reactions in photosynthesis is considered. Nine-tenths of the available knowledge is of a biochemical nature. Questions regarding the activities of the chlorophyll system are examined. The simplest photochemical response observed in living hydrogen-adapted algal cells is the release of molecular hydrogen, which continues even after all other known natural reactions have been eliminated either by heating or the action of poisons.

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Carbon and hydrogen metabolism of green algae in light and dark

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1990-01-01

After adaptation to a hydrogen metabolism, Chlamydomonas reinhardtii can photoanaerobically metabolize acetate with the evolution of H{sub 2} and CO{sub 2}. An enzyme profile of the chloroplastic, cytoplasmic, and mitochondrial fractions were obtained with a cellular fractionation procedure that incorporated cell wall removal by autolysine, digestion of the plasmalemma with digitonin and fractionation by differential centrifugation on a Percoll step gradient. The sequence of events leading to the photo-evolution of H{sub 2} from acetate includes the conversion of acetate into succinate via the extraplastidic glyoxylate cycle, the oxidation of succinate to fumarate by chloroplastic succinic dehydrogenase and the oxidation ofmore » malate to oxaloacetate in the chloroplast by NAD dependent malate dehydrogenase. The level of potential activity of the enzymes was sufficient to accommodate the observed rate of gas evolution. The isolated darkened chloroplast evolves aerobically CO{sub 2} from glucose indicating a chloroplastic respiratory pathway. Evolution of CO{sub 2} is blocked by mitochondrial inhibitors.« less

Crystal structures of 5-amino-N-phenyl-3H-1,2,4-di-thia-zol-3-iminium chloride and 5-amino-N-(4-chloro-phen-yl)-3H-1,2,4-di-thia-zol-3-iminium chloride monohydrate.

PubMed

Yeo, Chien Ing; Tan, Yee Seng; Tiekink, Edward R T

2015-10-01

The crystal and mol-ecular structures of the title salt, C8H8N3S2 (+)·Cl(-), (I), and salt hydrate, C8H7ClN3S2 (+)·Cl(-)·H2O, (II), are described. The heterocyclic ring in (I) is statistically planar and forms a dihedral angle of 9.05 (12)° with the pendant phenyl ring. The comparable angle in (II) is 15.60 (12)°, indicating a greater twist in this cation. An evaluation of the bond lengths in the H2N-C-N-C-N sequence of each cation indicates significant delocalization of π-electron density over these atoms. The common feature of the crystal packing in (I) and (II) is the formation of charge-assisted amino-N-H⋯Cl(-) hydrogen bonds, leading to helical chains in (I) and zigzag chains in (II). In (I), these are linked by chains mediated by charge-assisted iminium-N(+)-H⋯Cl(-) hydrogen bonds into a three-dimensional architecture. In (II), the chains are linked into a layer by charge-assisted water-O-H⋯Cl(-) and water-O-H⋯O(water) hydrogen bonds with charge-assisted iminium-N(+)-H⋯O(water) hydrogen bonds providing the connections between the layers to generate the three-dimensional packing. In (II), the chloride anion and water mol-ecules are resolved into two proximate sites with the major component being present with a site occupancy factor of 0.9327 (18).

A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid.

PubMed

Nguyen, Nga T; Mori, Yuki; Matsumoto, Takahiro; Yatabe, Takeshi; Kabe, Ryota; Nakai, Hidetaka; Yoon, Ki-Seok; Ogo, Seiji

2014-11-11

We report the decomposition of formic acid to hydrogen and carbon dioxide, catalysed by a NiRu complex originally developed as a [NiFe]hydrogenase model. This is the first example of H2 evolution, catalysed by a [NiFe]hydrogenase model, which does not require additional energy.

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

PubMed

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.

Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

NASA Astrophysics Data System (ADS)

Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

2017-05-01

Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

Activating and optimizing MoS 2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies

DOE PAGES

Li, Hong; Tsai, Charlie; Koh, Ai Leen; ...

2015-11-09

As a promising non-precious catalyst for the hydrogen evolution reaction, molybdenum disulphide (MoS 2) is known to contain active edge sites and an inert basal plane. Activating the MoS 2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS 2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bindmore » directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔG H) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Furthermore, proper combinations of S-vacancy and strain yield the optimal ΔG H = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.« less

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

PubMed

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.

In situ photodeposition of cobalt on CdS nanorod for promoting photocatalytic hydrogen production under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Yanhong; Liu, Mei; Gao, Li; Mao, Liqun; Fan, Zeyun; Shangguan, Wenfeng

2018-06-01

Non-noble metal Co were loaded on CdS for enhancing photocatalytic activity of water splitting by a simple and efficient in situ photodeposition method. The Co particles with diameter ca. 5 nm were photoreduced and then loaded on the surface of CdS. The loading of Co can not only effectively promote the separation of electrons and holes photoexcited by CdS, but reduce the overpotential of hydrogen evolution as well, thus enhancing photocatalytic activity of water splitting. The highest photocatalytic H2 evolution rate of Co/CdS reaches up to 1299 μmol h-1 under visible light irradiation(λ > 420 nm) when the amount of loading is 1.0 wt%, which is 17 times of that of pure CdS and achieves 80% of that of 0.5 wt%Pt/CdS. This work not only exhibits a pathway to obtain photocatalysts with high photocatalytic activity for hydrogen production, but provides a possibility for the utilization of low cost Co as a substitute for noble metals in photocatalytic hydrogen production.

Photocatalyzed Hydrogen Evolution from Water by a Composite Catalyst of NH2 -MIL-125(Ti) and Surface Nickel(II) Species.

PubMed

Meyer, Kim; Bashir, Shahid; Llorca, Jordi; Idriss, Hicham; Ranocchiari, Marco; van Bokhoven, Jeroen A

2016-09-19

A composite of the metal-organic framework (MOF) NH 2 -MIL-125(Ti) and molecular and ionic nickel(II) species, catalyzed hydrogen evolution from water under UV light. In 95 v/v % aqueous conditions the composite produced hydrogen in quantities two orders of magnitude higher than that of the virgin framework and an order of magnitude greater than that of the molecular catalyst. In a 2 v/v % water and acetonitrile mixture, the composite demonstrated a TOF of 28 mol H 2  g(Ni) -1  h -1 and remained active for up to 50 h, sustaining catalysis for three times longer and yielding 20-fold the amount of hydrogen. Appraisal of physical mixtures of the MOF and each of the nickel species under identical photocatalytic conditions suggest that similar surface localized light sensitization and proton reduction processes operate in the composite catalyst. Both nickel species contribute to catalytic conversion, although different activation behaviors are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modelling of hydrogen conditioning, retention and release in Tore Supra

NASA Astrophysics Data System (ADS)

Grisolia, C.; Horton, L. D.; Ehrenberg, J. K.

1995-04-01

A model based on a local mixing model has been previously developed at JET to explain the recovery of tritium after the first PTE experiment. This model is extended by a 0D plasma particle balance model and is applied to data from Tore Supra wall saturation experiments. With only two free parameters, representing the diffusion of hydrogen atoms and the volume recombination process between hydrogen atoms into molecules, the model can reproduce experimental data. The time evolution of the after-shot outgassing and the integral amount of particles recovered after the shot (assuming 13 m 2 of interacting surfaces between plasma and walls) are in good agreement with the experimental observations. The same set of parameters allows the model to simulate after-shot outgassing of five consecutive discharges. However, the model fails to predict the observed saturation of the walls by the plasma. Results from helium glow discharge (HeGD) can only be partially described. Good agreement with the experimental hydrogen release and its time evolution during HeGD is observed, but the model fails to describe the stability of a saturated graphite wall.

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide.

DOE PAGES

Chou, Stanley Shihyao; Sai, Na; Lu, Ping; ...

2015-10-07

Establishing processing–structure–property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T' (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T'more » transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Furthermore, we show basal plane activation of 1T' molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T', comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.« less

Hollow core-shell structured Ni-Sn@C nanoparticles: a novel electrocatalyst for the hydrogen evolution reaction.

PubMed

Lang, Leiming; Shi, Yi; Wang, Jiong; Wang, Feng-Bin; Xia, Xing-Hua

2015-05-06

Pt-free electrocatalysts with high activity and low cost are highly pursued for hydrogen production by electrochemically splitting water. Ni-based alloy catalysts are potential candidates for the hydrogen evolution reaction (HER) and have been studied extensively. Here, we synthesized novel hollow core-shell structure Ni-Sn@C nanoparticles (NPs) by sol-gel, chemical vapor deposition, and etching processes. The prepared electrocatalysts with porous hollow carbon layers have a high conductivity and large active area, which exhibit good electrocatalytic activity toward HER. The Tafel slope of ∼35 millivolts per decade measured in acidic solution for Ni-Sn@C NPs is the smallest one to date for the Ni-Sn alloy catalysts, and exceeds those of the most non-noble metal catalysts, indicating a possible Volmer-Heyrovsky reaction mechanism. The synthetic method can be extended to prepare other hollow core-shell structure electrocatalysts for low-temperature fuel cells.

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

PubMed

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.

Summary of FY17 ParaChoice Accomplishments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levinson, Rebecca Sobel; West, Todd H.

As part of analysis support for FCTO, Sandia assesses the factors that influence the future of FCEVs and Hydrogen in the US vehicle fleet. Using ParaChoice, we model competition between FCEVs, conventional vehicles, and other alternative vehicle technologies in order to understand the drivers and sensitivities of adoption of FCEVs. ParaChoice leverages existing tools such as Autonomie (Moawad et al., 2016), AEO (U.S. Energy Information Administration, 2016), and the Macro System Model (Ruth et al., 2009) in order to synthesize a complete picture of the co-evolution of vehicle technology development, energy price evolution, and hydrogen production and pricing, with consumermore » demand for vehicles and fuel. We then assess impacts of FCEV market penetration and hydrogen use on green- house gas (GHG) emissions and petroleum consumption, providing context for the role of policy, technology development, infrastructure, and consumer behavior on the vehicle and fuel mix through parametric and sensitivity analyses.« less

Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values.

PubMed

Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup; Silva, Rafael; Sathe, Bhaskar R; Mikmeková, Eliška; Asefa, Tewodros

2014-04-22

Despite being technically possible, splitting water to generate hydrogen is still practically unfeasible due mainly to the lack of sustainable and efficient catalysts for the half reactions involved. Herein we report the synthesis of cobalt-embedded nitrogen-rich carbon nanotubes (NRCNTs) that 1) can efficiently electrocatalyze the hydrogen evolution reaction (HER) with activities close to that of Pt and 2) function well under acidic, neutral or basic media alike, allowing them to be coupled with the best available oxygen-evolving catalysts-which also play crucial roles in the overall water-splitting reaction. The materials are synthesized by a simple, easily scalable synthetic route involving thermal treatment of Co(2+) -embedded graphitic carbon nitride derived from inexpensive starting materials (dicyandiamide and CoCl2 ). The materials' efficient catalytic activity is mainly attributed to their nitrogen dopants and concomitant structural defects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Versatile Titanium Silicide Monolayers with Prominent Ferromagnetic, Catalytic, and Superconducting Properties: Theoretical Prediction.

PubMed

Wu, Qisheng; Zhang, Jun-Jie; Hao, Peipei; Ji, Zhongyang; Dong, Shuai; Ling, Chongyi; Chen, Qian; Wang, Jinlan

2016-10-06

On the basis of global structure search and density functional theory calculations, we predict a new class of two-dimensional (2D) materials, titanium silicide (Ti 2 Si, TiSi 2 , and TiSi 4 ) monolayers. They are proved to be energetically, dynamically, and thermally stable and own excellent mechanical properties. Among them, Ti 2 Si is a ferromagnetic metal with a magnetic moment of 1.37 μ B /cell, while TiSi 2 is an ideal catalyst for the hydrogen evolution reaction with a nearly zero free energy of hydrogen adsorption. More importantly, electron-phonon coupling calculations suggest that TiSi 4 is a robust 2D phonon-mediated superconductor with a transition temperature of 5.8 K, and the transition temperature can be enhanced up to 11.7 K under a suitable external strain. The versatility makes titanium silicide monolayers promising candidates for spintronic materials, hydrogen evolution catalysts, and 2D superconductors.

Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

2014-12-01

C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Zhongjie; Luo, Wenjia; Ma, Lu

2015-12-07

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

A tunable azine covalent organic framework platform for visible light-induced hydrogen generation

PubMed Central

Vyas, Vijay S.; Haase, Frederik; Stegbauer, Linus; Savasci, Gökcen; Podjaski, Filip; Ochsenfeld, Christian; Lotsch, Bettina V.

2015-01-01

Hydrogen evolution from photocatalytic reduction of water holds promise as a sustainable source of carbon-free energy. Covalent organic frameworks (COFs) present an interesting new class of photoactive materials, which combine three key features relevant to the photocatalytic process, namely crystallinity, porosity and tunability. Here we synthesize a series of water- and photostable 2D azine-linked COFs from hydrazine and triphenylarene aldehydes with varying number of nitrogen atoms. The electronic and steric variations in the precursors are transferred to the resulting frameworks, thus leading to a progressively enhanced light-induced hydrogen evolution with increasing nitrogen content in the frameworks. Our results demonstrate that by the rational design of COFs on a molecular level, it is possible to precisely adjust their structural and optoelectronic properties, thus resulting in enhanced photocatalytic activities. This is expected to spur further interest in these photofunctional frameworks where rational supramolecular engineering may lead to new material applications. PMID:26419805

Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

PubMed

Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

2018-05-09

Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

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

PubMed

Tanabe, Katsuaki

2016-01-01

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

Efficient Electron Transfer across a ZnO-MoS2 -Reduced Graphene Oxide Heterojunction for Enhanced Sunlight-Driven Photocatalytic Hydrogen Evolution.

PubMed

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.

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

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.

One- or two-electron water oxidation, hydroxyl radical, or H 2O 2 evolution

DOE PAGES

Siahrostami, Samira; Li, Guo -Ling; Viswanathan, Venkatasubramanian; ...

2017-02-23

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H 2O 2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O 2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H 2O 2, and O 2.

Pyrite-Induced Hydrogen Peroxide Formation as a Driving Force in the Evolution of Photosynthetic Organisms on an Early Earth

NASA Astrophysics Data System (ADS)

Borda, Michael J.; Elsetinow, Alicia R.; Schoonen, Martin A.; Strongin, Daniel R.

2001-09-01

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.

Promotion effect of nickel loaded on CdS for photocatalytic H2 production in lactic acid solution

NASA Astrophysics Data System (ADS)

Chen, Shu; Chen, Xiaoping; Jiang, Qizhong; Yuan, Jian; Lin, Caifang; Shangguan, Wenfeng

2014-10-01

Low-cost Ni modified CdS was prepared via a hydrothermal reduction method. The hydrogen production activity of CdS loaded with 5 wt% Ni under visible light was even higher than that of the one loaded with 0.5 wt% Pt. The highest H2 evolution rate (3004.8 μmol h-1) occurred when the concentration of sacrificial agent (lactic acid) was 50 vol%. The nickel can quickly transfer excited electrons and enhance the photocatalytic H2 production activity. It was also found that the hydrogen evolution in this system was generated steadily from both water and lactic acid.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

PubMed Central

Li, Haoyi; Chen, Shuangming; Jia, Xiaofan; Xu, Biao; Lin, Haifeng; Yang, Haozhou; Song, Li; Wang, Xun

2017-01-01

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2. PMID:28485395

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ for the hydrogen evolution reaction: beyond van der Waals heterostructures.

PubMed

Chua, Chun Kiang; Sofer, Zdeněk; Jankovský, Ondřej; Pumera, Martin

2015-03-16

Recent research on stable 2D nanomaterials has led to the discovery of new materials for energy-conversion and energy-storage applications. A class of layered heterostructures known as misfit-layered chalcogenides consists of well-defined atomic layers and has previously been applied as thermoelectric materials for use as high-temperature thermoelectric batteries. The performance of such misfit-layered chalcogenides in electrochemical applications, specifically the hydrogen evolution reaction, is currently unexplored. Herein, a misfit-layered chalcogenide consisting of CoO2 layers interleaved with an SrO-BiO-BiO-SrO rock-salt block and having the formula Bi1.85 Sr2 Co1.85 O7.7-δ is synthesized and examined for its structural and electrochemical properties. The hydrogen-evolution performance of misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ , which has an overpotential of 589 mV and a Tafel slope of 51 mV per decade, demonstrates the promising potential of misfit-layered chalcogenides as electrocatalysts instead of classical carbon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical structural analysis of diamondlike carbon films: II. Raman analysis

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The chemical structure of diamondlike carbon (DLC) films, synthesized by photoemission-assisted glow discharge, has been analyzed by Raman spectroscopy. Raman analysis in conjunction with the sp2 cluster model clarified the film structure. The sp2 clusters in DLC films synthesized at low temperature preferred various aliphatic structures. Sufficient argon-ion assist allowed for formation of less strained DLC films containing large amounts of hydrogen. As the synthesis temperature was increased, thermal desorption of hydrogen left carbon dangling bonds with active unpaired electrons in the films, and the reactions that followed created strained films containing aromatic sp2 clusters. In parallel, the desorption of methane molecules from the growing surface by chemisorption of hydrogen radicals prevented the action of argon ions, promoting internal strain of the films. However, in synthesis at very high temperature, where sp2 clusters are sufficiently dominant, the strain was dissolved gradually. In contrast, the DLC films synthesized at low temperature were more stable than other films synthesized at the same temperature because of stable hydrogen-carbon bonds in the films.

Electrical and optical performance of transparent conducting oxide films deposited by electrostatic spray assisted vapour deposition.

PubMed

Hou, Xianghui; Choy, Kwang-Leong; Liu, Jun-Peng

2011-09-01

Transparent conducting oxide (TCO) films have the remarkable combination of high electrical conductivity and optical transparency. There is always a strong motivation to produce TCO films with good performance at low cost. Electrostatic Spray Assisted Vapor Deposition (ESAVD), as a variant of chemical vapour deposition (CVD), is a non-vacuum and low-cost deposition method. Several types of TCO films have been deposited using ESAVD process, including indium tin oxide (ITO), antimony-doped tin oxide (ATO), and fluorine doped tin oxide (FTO). This paper reports the electrical and optical properties of TCO films produced by ESAVD methods, as well as the effects of post treatment by plasma hydrogenation on these TCO films. The possible mechanisms involved during plasma hydrogenation of TCO films are also discussed. Reduction and etching effect during plasma hydrogenation are the most important factors which determine the optical and electrical performance of TCO films.

Water in Earth's mantle: Hydrogen analysis of mantle olivine, pyroxenes and garnet using the SIMS

NASA Technical Reports Server (NTRS)

Kurosawa, Masanori; Yurimoto, Hisayoshi; Sueno, Shigeho

1993-01-01

Hydrogen (or water) in the Earth's interior plays a key role in the evolution and dynamics of the planet. However, the abundance and the existence form of the hydrogen have scarcely been clear in practice. Hydrogen in the mantle was incorporated in the interior during the formation of the Earth. The incorporated hydrogen was hardly possible to concentrate locally inside the Earth considering its high mobility and high reactivity. The hydrogen, preferably, could be distributed homogeneously over the mantle and the core by the subsequent physical and chemical processes. Therefore, hydrogen in the mantle could be present in the form of trace hydrogen in nominally anhydrous mantle minerals. The hydrogen and the other trace elements in mantle olivines, orthopyroxenes, clinopyroxenes, and garnets were determined using secondary ion mass spectrometry (SIMS) for elucidating (1) the exact hydrogen contents, (2) the correlation between the hydrogen and the other trace elements, (3) the dependence of the hydrogen contents on the depth, and (4) the dependence of the whole rock water contents on the depth.

Knowledge Based Software Assistant Conference Proceedings (4th) Held in Syracuse, New York on 12-14 September 1989

DTIC Science & Technology

1990-05-01

Sanders Associates. Inc. A demonstration of knowledge-based support for the evolut ;cnry development of software system requirements uskig mitV/9 text...Conference Commiffee W Douga W~t Spin-Off Technologies 4 AN OVERVIEW OF RADC’S KNOWLEDGE BASED SOFTWARE ASSISTANT PROGRAM Donald M. Elefante Rome Air...Knowledge-Based Software Assistant is a formally based, computer-mediated paradigm for the specification, development, evolution , and Ir ig term

Enormous Hydrogen Bond Strength Enhancement through π-Conjugation Gain: Implications for Enzyme Catalysis.

PubMed

Wu, Chia-Hua; Ito, Keigo; Buytendyk, Allyson M; Bowen, K H; Wu, Judy I

2017-08-22

Surprisingly large resonance-assistance effects may explain how some enzymes form extremely short, strong hydrogen bonds to stabilize reactive oxyanion intermediates and facilitate catalysis. Computational models for several enzymic residue-substrate interactions reveal that when a π-conjugated, hydrogen bond donor (XH) forms a hydrogen bond to a charged substrate (Y - ), XH can become significantly more π-electron delocalized, and this "extra" stabilization may boost the [XH···Y - ] hydrogen bond strength by ≥15 kcal/mol. This reciprocal relationship departs from the widespread pK a concept (i.e., the idea that short, strong hydrogen bonds form when the interacting moieties have matching pK a values), which has been the rationale for enzymic acid-base reactions. The findings presented here provide new insight into how short, strong hydrogen bonds could form in enzymes.

Generalized Synthesis of Ternary Sulfide Hollow Structures with Enhanced Photocatalytic Performance for Degradation and Hydrogen Evolution.

PubMed

Ding, Shuoping; Liu, Xiufan; Shi, Yiqiu; Liu, Ye; Zhou, Tengfei; Guo, Zaiping; Hu, Juncheng

2018-05-17

A series of ternary sulfide hollow structures have been successfully prepared by a facile glutathione (GSH)-assisted one-step hydrothermal route, where GSH acts as the source of sulfur and bubble template. We demonstrate the feasibility and versatility of this in situ gas-bubble template strategy by the fabrication of novel hollow structures of MIn 2 S 4 (M = Cd, Zn, Ca, Mg, and Mn). Interestingly, with the reaction time varying, the hierarchical CdIn 2 S 4 microspheres with controlled internal structures can be regulated from yolk-shell, smaller yolk-shell (yolk-shell with shrunk yolk), hollow, to solid. Under visible-light irradiation, all of our prepared CdIn 2 S 4 samples with different morphologies were photoactivated. In virtue of the appealing hierarchical hollow structure, the yolk-shell-structured CdIn 2 S 4 microspheres exhibited the optimal photocatalytic activity and excellent durability for both the X 3 B degradation and H 2 evolution, which can be ascribed to the synergy-promoting effect of the small crystallite size together with the unique structural advantages of the yolk-shell structure. Thus, we hypothesize that this proof-of-concept strategy paves an example of rational design of hollow structured ternary or multinary sulfides with superior photochemical performance, holding great potential for future multifunctional applications.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Design principles for hydrogen evolution reaction catalyst materials

DOE PAGES

Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan; ...

2016-04-19

Design and synthesis of active, stable and cost-effective materials for efficient hydrogen production (hydrogen evolution reaction, HER) is of paramount importance for the successful deployment of hydrogen -based alternative energy technologies. The HER, seemingly one of the simplest electrochemical reactions, has served for decades to bridge the gap between fundamental electrocatalysis and practical catalyst design. However, there are still many open questions that need to be answered before it would be possible to claim that design principles of catalyst materials are fully developed for the efficient hydrogen production. Here in this review, by summarizing key results for the HER onmore » well-characterized electrochemical interfaces in acidic and alkaline media, we have broadened our understanding of the HER in the whole range of pH by considering three main parameters: the nature of the proton donor (H 3O + in acid and H 2O in alkaline), the energy of adsorption of H ad and OH ad, and the presence of spectator species. Simply by considering these three parameters we show that great deal has already been learned and new trends are beginning to emerge, giving some predictive ability with respect to the nature of electrochemical interface and electrocatalytic activity of the HER.« less

Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

NASA Astrophysics Data System (ADS)

Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

2015-11-01

Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

Nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tashlykova-Bushkevich, Iya I.

2015-12-31

The present work summarizes recent progress in the investigation of nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys foils produced at exceptionally high cooling rates. We focus here on the potential of modification of hydrogen desorption kinetics in respect to weak and strong trapping sites that could serve as hydrogen sinks in Al materials. It is shown that it is important to elucidate the surface microstructure of the Al alloy foils at the submicrometer scale because rapidly solidified microstructural features affect hydrogen trapping at nanostructured defects. We discuss the profound influence of solute atoms on hydrogen−lattice defectmore » interactions in the alloys. with emphasis on role of vacancies in hydrogen evolution; both rapidly solidified pure Al and conventionally processed aluminum samples are considered.« less

Water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2017-12-05

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Polyoxometalate water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2014-09-02

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Trapping hydrogen atoms from a neon-gas matrix: a theoretical simulation.

PubMed

Bovino, S; Zhang, P; Kharchenko, V; Dalgarno, A

2009-08-07

Hydrogen is of critical importance in atomic and molecular physics and the development of a simple and efficient technique for trapping cold and ultracold hydrogen atoms would be a significant advance. In this study we simulate a recently proposed trap-loading mechanism for trapping hydrogen atoms released from a neon matrix. Accurate ab initio quantum calculations are reported of the neon-hydrogen interaction potential and the energy- and angular-dependent elastic scattering cross sections that control the energy transfer of initially cold atoms are obtained. They are then used to construct the Boltzmann kinetic equation, describing the energy relaxation process. Numerical solutions of the Boltzmann equation predict the time evolution of the hydrogen energy distribution function. Based on the simulations we discuss the prospects of the technique.

Comparison of hydrogen production and electrical power generation for energy capture in closed-loop ammonium bicarbonate reverse electrodialysis systems.

PubMed

Hatzell, Marta C; Ivanov, Ivan; Cusick, Roland D; Zhu, Xiuping; Logan, Bruce E

2014-01-28

Currently, there is an enormous amount of energy available from salinity gradients, which could be used for clean hydrogen production. Through the use of a favorable oxygen reduction reaction (ORR) cathode, the projected electrical energy generated by a single pass ammonium bicarbonate reverse electrodialysis (RED) system approached 78 W h m(-3). However, if RED is operated with the less favorable (higher overpotential) hydrogen evolution electrode and hydrogen gas is harvested, the energy recovered increases by as much ~1.5× to 118 W h m(-3). Indirect hydrogen production through coupling an RED stack with an external electrolysis system was only projected to achieve 35 W h m(-3) or ~1/3 of that produced through direct hydrogen generation.

Wolf-Rayet stars in the Small Magellanic Cloud as testbed for massive star evolution

NASA Astrophysics Data System (ADS)

Schootemeijer, A.; Langer, N.

2018-03-01

Context. The majority of the Wolf-Rayet (WR) stars represent the stripped cores of evolved massive stars who lost most of their hydrogen envelope. Wind stripping in single stars is expected to be inefficient in producing WR stars in metal-poor environments such as the Small Magellanic Cloud (SMC). While binary interaction can also produce WR stars at low metallicity, it is puzzling that the fraction of WR binaries appears to be about 40%, independent of the metallicity. Aim. We aim to use the recently determined physical properties of the twelve known SMC WR stars to explore their possible formation channels through comparisons with stellar models. Methods: We used the MESA stellar evolution code to construct two grids of stellar models with SMC metallicity. One of these consists of models of rapidly rotating single stars, which evolve in part or completely chemically homogeneously. In a second grid, we analyzed core helium burning stellar models assuming constant hydrogen and helium gradients in their envelopes. Results: We find that chemically homogeneous evolution is not able to account for the majority of the WR stars in the SMC. However, in particular the apparently single WR star SMC AB12, and the double WR system SMC AB5 (HD 5980) appear consistent with this channel. We further find a dichotomy in the envelope hydrogen gradients required to explain the observed temperatures of the SMC WR stars. Shallow gradients are found for the WR stars with O star companions, while much steeper hydrogen gradients are required to understand the group of hot apparently single WR stars. Conclusions: The derived shallow hydrogen gradients in the WR component of the WR+O star binaries are consistent with predictions from binary models where mass transfer occurs early, in agreement with their binary properties. Since the hydrogen profiles in evolutionary models of massive stars become steeper with time after the main sequence, we conclude that most of the hot (Teff > 60 kK ) apparently single WR stars lost their envelope after a phase of strong expansion, e.g., as the result of common envelope evolution with a lower mass companion. The so far undetected companions, either main sequence stars or compact objects, are then expected to still be present. A corresponding search might identify the first immediate double black hole binary progenitor with masses as high as those detected in GW150914.

Improved efficiency of a large-area Cu(In,Ga)Se₂ solar cell by a nontoxic hydrogen-assisted solid Se vapor selenization process.

PubMed

Wu, Tsung-Ta; Hu, Fan; Huang, Jyun-Hong; Chang, Chia-ho; Lai, Chih-chung; Yen, Yu-Ting; Huang, Hou-Ying; Hong, Hwen-Fen; Wang, Zhiming M; Shen, Chang-Hong; Shieh, Jia-Min; Chueh, Yu-Lun

2014-04-09

A nontoxic hydrogen-assisted solid Se vapor selenization process (HASVS) technique to achieve a large-area (40 × 30 cm(2)) Cu(In,Ga)Se2 (CIGS) solar panel with enhanced efficiencies from 7.1 to 10.8% (12.0% for active area) was demonstrated. The remarkable improvement of efficiency and fill factor comes from improved open circuit voltage (Voc) and reduced dark current due to (1) decreased interface recombination raised from the formation of a widened buried homojunction with n-type Cd(Cu) participation and (2) enhanced separation of electron and hole carriers resulting from the accumulation of Na atoms on the surface of the CIGS film. The effects of microstructural, compositional, and electrical characteristics with hydrogen-assisted Se vapor selenization, including interdiffusion of atoms and formation of buried homojunction, were examined in detail. This methodology can be also applied to CIS (CuInSe2) thin film solar cells with enhanced efficiencies from 5.3% to 8.5% (9.4% for active area) and provides a facile approach to improve quality of CIGS and stimulate the nontoxic progress in the large scale CIGS PV industry.

The microwave-assisted ionic liquid nanocomposite synthesis: platinum nanoparticles on graphene and the application on hydrogenation of styrene

PubMed Central

2013-01-01

The microwave-assisted nanocomposite synthesis of metal nanoparticles on graphene or graphite oxide was introduced in this research. With microwave assistance, the Pt nanoparticles on graphene/graphite oxide were successfully produced in the ionic liquid of 2-hydroxyethanaminium formate [HOCH2CH2NH3][HCO2]. On graphene/graphite oxide, the sizes of Pt nanoparticles were about 5 to 30 nm from transmitted electron microscopy (TEM) results. The crystalline Pt structures were examined by X-ray diffraction (XRD). Since hydrogenation of styrene is one of the important well-known chemical reactions, herein, we demonstrated then the catalytic hydrogenation capability of the Pt nanoparticles on graphene/graphite oxide for the nanocomposite to compare with that of the commercial catalysts (Pt/C and Pd/C, 10 wt.% metal catalysts on activated carbon from Strem chemicals, Inc.). The conversions with the Pt nanoparticles on graphene are >99% from styrene to ethyl benzene at 100°C and under 140 psi H2 atmosphere. However, ethyl cyclohexane could be found as a side product at 100°C and under 1,520 psi H2 atmosphere utilizing the same nanocomposite catalyst. PMID:24103100

Evaluation of Environmentally Assisted Cracking of Armour Wires in Flexible Pipes, Power Cables and Umbilicals

NASA Astrophysics Data System (ADS)

Zhang, Zhiying

Environmentally assisted cracking (EAC) of armour wires in flexible pipes, power cables and umbilicals is a major concern with the development of oil and gas fields and wind farms in harsh environments. Hydrogen induced cracking (HIC) or hydrogen embrittlement (HE) of steel armour wires used in deep-water and ultra-deep-water has been evaluated. Simulated tests have been carried out in simulated sea water, under conditions where the susceptibility is the highest, i.e. at room temperature, at the maximum negative cathodic potential and at the maximum stress level expected in service for 150 hours. Examinations of the tested specimens have not revealed cracking or blistering, and measurement of hydrogen content has confirmed hydrogen charging. In addition, sulphide stress cracking (SSC) and chloride stress cracking (CSC) of nickel-based alloy armour wires used in harsh down-hole environments has been evaluated. Simulated tests have been carried out in simulated solution containing high concentration of chloride, with high hydrogen sulphide partial pressure, at high stress level and at 120 °C for 720 hours. Examinations of the tested specimens have not revealed cracking or blistering. Subsequent tensile tests of the tested specimens at ambient pressure and temperature have revealed properties similar to the as-received specimens.

Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying

Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

DOE PAGES

Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying; ...

2018-01-01

Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

Detecting and measuring metabolic byproducts by electrochemical sensing

NASA Technical Reports Server (NTRS)

Wilkins, J. R.; Stoner, G. E.

1974-01-01

Method of detecting certain groups of bacteria is based on sensing buildup in molecular hydrogen. Apparatus is easy to assemble and use, and it has added advantage that hydrogen evolution by test micro-organisms can be measured automatically and accurately. System has been used to detect and enumerate variety of gram-negative bacteria of enterobacteriaceae group.

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

NASA Astrophysics Data System (ADS)

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.

Safety Sensor Testing Laboratory | Hydrogen and Fuel Cells | NREL

Science.gov Websites

collaborations, trainings and workshops, and academic research and development support. Work in the laboratory (temperature, pressure, and relative humidity) and gas parameters (flow and composition) Quantitative sensor services to assist end-users on sensor selection and use Assist developers in quantitative assessment of

Same-Side Platinum Electrodes for Metal Assisted Etching of Porous Silicon

DTIC Science & Technology

2015-11-01

hydrogen peroxide (H2O2), and ethanol etch solution. The H2O2 reacts with hydrogen ions from the HF at the catalytic metal surface to become water...order to measure the combustion rates of the PSi, bridge wires were photolithographically deposited onto the wafers, prior to PSi etching, using a...

In-situ Probing of Radiation-induced Processing of Organics in Astrophysical Ice Analogs—Novel Laser Desorption Laser Ionization Time-of-flight Mass Spectroscopic Studies

NASA Astrophysics Data System (ADS)

Gudipati, Murthy S.; Yang, Rui

2012-09-01

Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Lyα radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K—close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies—the first glimpses into interstellar ice chemistry through analog studies—show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

Variations on a theme - the evolution of hydrocarbon solids. I. Compositional and spectral modelling - the eRCN and DG models

NASA Astrophysics Data System (ADS)

Jones, A. P.

2012-04-01

Context. The compositional properties of hydrogenated amorphous carbons are known to evolve in response to the local conditions. Aims: We present a model for low-temperature, amorphous hydrocarbon solids, based on the microphysical properties of random and defected networks of carbon and hydrogen atoms, that can be used to study and predict the evolution of their properties in the interstellar medium. Methods: We adopt an adaptable and prescriptive approach to model these materials, which is based on a random covalent network (RCN) model, extended here to a full compositional derivation (the eRCN model), and a defective graphite (DG) model for the hydrogen poorer materials where the eRCN model is no longer valid. Results: We provide simple expressions that enable the determination of the structural, infrared and spectral properties of amorphous hydrocarbon grains as a function of the hydrogen atomic fraction, XH. Structural annealing, resulting from hydrogen atom loss, results in a transition from H-rich, aliphatic-rich to H-poor, aromatic-rich materials. Conclusions: The model predicts changes in the optical properties of hydrogenated amorphous carbon dust in response to the likely UV photon-driven and/or thermal annealing processes resulting, principally, from the radiation field in the environment. We show how this dust component will evolve, compositionally and structurally in the interstellar medium in response to the local conditions. Appendices A and B are available in electronic form at http://www.aanda.org

Nickel sulfide/graphitic carbon nitride/strontium titanate (NiS/g-C3N4/SrTiO3) composites with significantly enhanced photocatalytic hydrogen production activity.

PubMed

Luo, Xiu-Li; He, Gang-Ling; Fang, Yue-Ping; Xu, Yue-Hua

2018-05-15

NiS/g-C 3 N 4 /SrTiO 3 (NS/CN/STO) composites were prepared using a facile hydrothermal method. The synergistic effect of g-C 3 N 4 /SrTiO 3 (CN/STO) heterojunction and NiS cocatalyst enhanced the photocatalytic hydrogen evolution activity of NS/CN/STO. A hydrogen production rate of 1722.7 μmol h -1  g -1 was obtained when the 2%NiS/20%g-C 3 N 4 /SrTiO 3 (2NS/20CN/STO) was used for the photocatalytic hydrogen evolution in the presence of methanol used as a sacrificial agent under UV-vis light irradiation; the photocatalytic hydrogen production rate of 2NS/20CN/STO is 32.8, 8.9 and 4.2 times the value of that obtained with pure g-C 3 N 4 , SrTiO 3 and 20%g-C 3 N 4 /SrTiO 3 (20CN/STO), respectively. Moreover, in photoelectrochemical investigations when compared with 20CN/STO, SrTiO 3 and g-C 3 N 4 , 2NS/20CN/STO exhibited significant photocurrent enhancement. The heterojunction and cocatalyst in NS/CN/STO improved the charge separation efficiency and the lifetime of the charge carriers, leading to the enhanced generation of electrons for photocatalytic hydrogen production. Copyright © 2018 Elsevier Inc. All rights reserved.

Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

DOE PAGES

Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; ...

2015-01-11

Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C 60H 60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C 60 and increased isosteric heats of adsorption for the lithium doped fullerene Li 12C 60. However, despite these improvements the low amount of physisorbedmore » hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.« less

Robotic instrumentation: Evolution and microsurgical applications

PubMed Central

Parekattil, Sijo J.; Moran, Michael E.

2010-01-01

This article presents a review of the history and evolution of robotic instrumentation and its applications in urology. A timeline for the evolution of robotic instrumentation is presented to better facilitate an understanding of our current-day applications. Some new directions including robotic microsurgical applications (robotic assisted denervation of the spermatic cord for chronic orchialgia and robotic assisted vasectomy reversal) are presented. There is a paucity of prospective comparative effectiveness studies for a number of robotic applications. However, right or wrong, human nature has always led to our infatuation with the concept of using tools to meet our needs. This chapter is a brief tribute to where we have come from and where we may be potentially heading in the field of robotic assisted urologic surgery. PMID:21116362

Fullerene-like hydrogenated carbon films with super-low friction and wear, and low sensitivity to environment

NASA Astrophysics Data System (ADS)

Ji, Li; Li, Hongxuan; Zhao, Fei; Quan, Weilong; Chen, Jianmin; Zhou, Huidi

2010-01-01

A novel hydrogenated carbon film containing fullerene-like nanostructure was prepared by pulse bias-assisted plasma enhanced chemical vapour deposition, and the fullerene-like arrangement in the film was characterized by high resolution transmission electron microscopy. The as-prepared hydrogenated carbon film exhibited super-low friction and wear in both dry N2 and humid ambient atmospheres, and was superior to the conventional hydrogenated carbon films. These excellent tribological properties could be attributed to the unique fullerene-like nanostructure, which endows the film with some special chemical and physical features, such as high chemical inertness, hardness and elastic recovery owing to the closed, curved and caged graphite planes, and hence, improves the tribological properties of the hydrogenated carbon film.

Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

2015-10-01

Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

An ultrafine platinum-cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution.

PubMed

Wang, Ziqiang; Ren, Xiang; Luo, Yonglan; Wang, Liang; Cui, Guanwei; Xie, Fengyu; Wang, Hongjing; Xie, Ying; Sun, Xuping

2018-06-22

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Negative impact of surface Ti3+ defects on the photocatalytic hydrogen evolution activity of SrTiO3

NASA Astrophysics Data System (ADS)

Chen, Haidong; Zhang, Feng; Zhang, Weifeng; Du, Yingge; Li, Guoqiang

2018-01-01

Defects play an important and in many cases dominant role in the physical and chemical properties of many oxide materials. In this work, we show that the surface Ti3+ defects in SrTiO3 (STO), characterized by electron paramagnetic resonance and X-ray photoelectron spectroscopy, directly impact the photocatalytic activity of STO. O2 species are found to absorb preferentially on Ti3+ defect sites. Hydrogen evolution under ambient air diminishes with the increase in the concentration of surface Ti3+. This is explained by the over-accumulation of Pt cocatalysts on the site of surface Ti3+ defects after the removal of adsorbed O2.

Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

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.

Multifunctional nanostructured electrocatalysts for energy conversion and storage: current status and perspectives.

PubMed

Ghosh, Srabanti; Basu, Rajendra N

2018-06-21

Electrocatalytic oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) have attracted widespread attention because of their important role in the application of various energy storage and conversion devices, such as fuel cells, metal-air batteries and water splitting devices. However, the sluggish kinetics of the HER/OER/ORR and their dependency on expensive noble metal catalysts (e.g., Pt) obstruct their large-scale application. Hence, the development of efficient and robust bifunctional or trifunctional electrocatalysts in nanodimension for both oxygen reduction/evolution and hydrogen evolution reactions is highly desired and challenging for their commercialization in renewable energy technologies. This review describes some recent developments in the discovery of bifunctional or trifunctional nanostructured catalysts with improved performances for application in rechargeable metal-air batteries and fuel cells. The role of the electronic structure and surface redox chemistry of nanocatalysts in the improvement of their performance for the ORR/OER/HER under an alkaline medium is highlighted and the associated reaction mechanisms developed in the recent literature are also summarized.

MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts

PubMed Central

Li, Hong; Ke, Fei; Zhu, Junfa

2018-01-01

The development of a highly efficient and stable bifunctional electrocatalyst for water splitting is still a challenging issue in obtaining clean and sustainable chemical fuels. Herein, a novel bifunctional catalyst consisting of 2D transition-metal phosphide nanosheets with abundant reactive sites templated by Co-centered metal−organic framework nanosheets, denoted as CoP-NS/C, has been developed through a facile one-step low-temperature phosphidation process. The as-prepared CoP-NS/C has large specific surface area and ultrathin nanosheets morphology providing rich catalytic active sites. It shows excellent electrocatalytic performances for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic and alkaline media, with the Tafel slopes of 59 and 64 mV/dec and a current density of 10 mA/cm2 at the overpotentials of 140 and 292 mV, respectively, which are remarkably superior to those of CoP/C, CoP particles, and comparable to those of commercial noble-metal catalysts. In addition, the CoP-NS/C also shows good durability after a long-term test. PMID:29414838

Co-fermentation of sewage sludge with ryegrass for enhancing hydrogen production: Performance evaluation and kinetic analysis.

PubMed

Yang, Guang; Wang, Jianlong

2017-11-01

The low C/N ratio and low carbohydrate content of sewage sludge limit its application for fermentative hydrogen production. In this study, perennial ryegrass was added as the co-substrate into sludge hydrogen fermentation with different mixing ratios for enhancing hydrogen production. The results showed that the highest hydrogen yield of 60mL/g-volatile solids (VS) added was achieved when sludge/perennial ryegrass ratio was 30:70, which was 5 times higher than that from sole sludge. The highest VS removal of 21.8% was also achieved when sludge/perennial ryegrass ratio was 30:70, whereas VS removal from sole sludge was only 0.7%. Meanwhile, the co-fermentation system simultaneously improved hydrogen production efficiency and organics utilization of ryegrass. Kinetic analysis showed that the Cone model fitted hydrogen evolution better than the modified Gompertz model. Furthermore, hydrogen yield and VS removal increased with the increase of dehydrogenase activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed Central

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

Hydrogen in tungsten as plasma-facing material

NASA Astrophysics Data System (ADS)

Roth, Joachim; Schmid, Klaus

2011-12-01

Materials facing plasmas in fusion experiments and future reactors are loaded with high fluxes (1020-1024 m-2 s-1) of H, D and T fuel particles at energies ranging from a few eV to keV. In this respect, the evolution of the radioactive T inventory in the first wall, the permeation of T through the armour into the coolant and the thermo-mechanical stability after long-term exposure are key parameters determining the applicability of a first wall material. Tungsten exhibits fast hydrogen diffusion, but an extremely low solubility limit. Due to the fast diffusion of hydrogen and the short ion range, most of the incident ions will quickly reach the surface and recycle into the plasma chamber. For steady-state operation the solute hydrogen for the typical fusion reactor geometry and wall conditions can reach an inventory of about 1 kg. However, in short-pulse operation typical of ITER, solute hydrogen will diffuse out after each pulse and the remaining inventory will consist of hydrogen trapped in lattice defects, such as dislocations, grain boundaries and irradiation-induced traps. In high-flux areas the hydrogen energies are too low to create displacement damage. However, under these conditions the solubility limit will be exceeded within the ion range and the formation of gas bubbles and stress-induced damage occurs. In addition, simultaneous neutron fluxes from the nuclear fusion reaction D(T,n)α will lead to damage in the materials and produce trapping sites for diffusing hydrogen atoms throughout the bulk. The formation and diffusive filling of these different traps will determine the evolution of the retained T inventory. This paper will concentrate on experimental evidence for the influence different trapping sites have on the hydrogen inventory in W as studied in ion beam experiments and low-temperature plasmas. Based on the extensive experimental data, models are validated and applied to estimate the contribution of different traps to the tritium inventory in future fusion reactors.

Using a Hands-On Hydrogen Peroxide Decomposition Activity to Teach Catalysis Concepts to K-12 Students

ERIC Educational Resources Information Center

Cybulskis, Viktor J.; Ribeiro, Fabio H.; Gounder, Rajamani

2016-01-01

A versatile and transportable laboratory apparatus was developed for middle and high school (6th-12th grade) students as part of a hands-on outreach activity to estimate catalytic rates of hydrogen peroxide decomposition from oxygen evolution rates measured by using a volumetric displacement method. The apparatus was constructed with inherent…

Early evolution without a tree of life.

PubMed

Martin, William F

2011-06-30

Life is a chemical reaction. Three major transitions in early evolution are considered without recourse to a tree of life. The origin of prokaryotes required a steady supply of energy and electrons, probably in the form of molecular hydrogen stemming from serpentinization. Microbial genome evolution is not a treelike process because of lateral gene transfer and the endosymbiotic origins of organelles. The lack of true intermediates in the prokaryote-to-eukaryote transition has a bioenergetic cause.

Polyethyleneimine functionalized platinum superstructures: enhancing hydrogen evolution performance by morphological and interfacial control† †Electronic supplementary information (ESI) available: Experimental details and additional physical characterization. See DOI: 10.1039/c7sc04109h

PubMed Central

Xu, Guang-Rui; Bai, Juan; Jiang, Jia-Xing

2017-01-01

The electrocatalytic hydrogen evolution reaction (HER) is a highly promising green method for sustainable and efficient hydrogen production. So far, Pt nanocrystals are still the most active electrocatalysts for the HER in acidic media, although a tremendous search for alternatives has been done in the past decade. In this work, we synthesize polyethyleneimine (PEI) functionalized Pt superstructures (Pt-SSs@PEI) with tetragonal, hierarchical, and branched morphologies with a facile wet chemical reduction method. A series of physical characterizations are conducted to investigate the morphology, electronic structure, surface composition, and formation mechanism of Pt-SSs@PEI. Impressively, the as-prepared Pt-SSs@PEI show an unprecedented onset reduction potential (+64.6 mV vs. reversible hydrogen electrode) for the HER in strong acidic media due to the protonation of –NH2 groups in the PEI adlayers on the Pt surface, and they outperform all currently reported HER electrocatalysts. The work highlights a highly effective interface-engineering strategy for improving the electrocatalytic performance of Pt nanocrystals for the HER. PMID:29619188

Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

NASA Astrophysics Data System (ADS)

Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

2018-05-01

Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

Design of active and stable Co-Mo-S x chalcogels as pH-universal catalyst for the hydrogen evolution reaction

DOE PAGES

Staszak-Jirkovský, Jakub; Malliakas, Christos D.; Lopes, Pietro P.; ...

2015-11-30

Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS 2 and MoS 2) and amorphous (CoS x and MoS x) hydrogen evolution catalysts. We propose that Co 2+ and Mo 4+ centers promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoS x materials are more active than MoSmore » x they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. Finally, by combining the higher activity of CoS x building blocks with the higher stability of MoS x units into a compact and robust CoMoS x structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.« less

Freeze drying-assisted synthesis of Pt@reduced graphene oxide nanocomposites as excellent hydrogen sensor

NASA Astrophysics Data System (ADS)

Lu, Xiaojing; Song, Xinjie; Gu, Cuiping; Ren, Haibo; Sun, Yufeng; Huang, Jiarui

2018-05-01

Quick and efficient detection of low concentrations of hydrogen remains a challenge because of the stability of hydrogen. A sensor based on reduced oxide graphene functionalized with Pt nanoparticles is successfully fabricated using a freeze-drying method followed by heat treatment. The structure and morphology of the Pt@rGO nanocomposites are well analyzed by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The as-prepared Pt@rGO nanocomposites show excellent hydrogen gas sensing properties at a low working temperature of 50 °C. The sensitivity toward 0.5% hydrogen is 8%. The response and recovery times of the sensor exposed to 0.5% hydrogen are 63 and 104 s, respectively. The gas-sensing mechanism of Pt@rGO sensor is also discussed.

Hydrodynamic escape from planetary atmospheres

NASA Astrophysics Data System (ADS)

Tian, Feng

Hydrodynamic escape is an important process in the formation and evolution of planetary atmospheres. Due to the existence of a singularity point near the transonic point, it is difficult to find transonic steady state solutions by solving the time-independent hydrodynamic equations. In addition to that, most previous works assume that all energy driving the escape flow is deposited in one narrow layer. This assumption not only results in less accurate solutions to the hydrodynamic escape problem, but also makes it difficult to include other chemical and physical processes in the hydrodynamic escape models. In this work, a numerical model describing the transonic hydrodynamic escape from planetary atmospheres is developed. A robust solution technique is used to solve the time dependent hydrodynamic equations. The method has been validated in an isothermal atmosphere where an analytical solution is available. The hydrodynamic model is applied to 3 cases: hydrogen escape from small orbit extrasolar planets, hydrogen escape from a hydrogen rich early Earth's atmosphere, and nitrogen/methane escape from Pluto's atmosphere. Results of simulations on extrasolar planets are in good agreement with the observations of the transiting extrasolar planet HD209458b. Hydrodynamic escape of hydrogen from other hypothetical close-in extrasolar planets are simulated and the influence of hydrogen escape on the long-term evolution of these extrasolar planets are discussed. Simulations on early Earth suggest that hydrodynamic escape of hydrogen from a hydrogen rich early Earth's atmosphere is about two orders magnitude slower than the diffusion limited escape rate. A hydrogen rich early Earth's atmosphere could have been maintained by the balance between the hydrogen escape and the supply of hydrogen into the atmosphere by volcanic outgassing. Origin of life may have occurred in the organic soup ocean created by the efficient formation of prebiotic molecules in the hydrogen rich early Earth's atmosphere. Simulations show that hydrodynamic escape of nitrogen from Pluto is able to remove a ~3 km layer of ice over the age of the solar system. The escape flux of neutral nitrogen may interact with the solar wind at Pluto's orbit and may be detected by the New Horizon mission.

Effect of laser-assisted bleaching with Nd:YAG and diode lasers on shear bond strength of orthodontic brackets.

PubMed

Mirhashemi, Amirhossein; Emadian Razavi, Elham Sadat; Behboodi, Sara; Chiniforush, Nasim

2015-12-01

The aim of the present study was to assess the effect of laser-assisted bleaching with neodymium:yttrium-aluminum-garnet (Nd:YAG) and diode lasers on shear bond strength (SBS) of orthodontic brackets. One hundred and four extracted human premolars were randomly divided into four groups: group 1: No bleaching applied (control group); group 2: Teeth bleached with 40 % hydrogen peroxide; group 3: Teeth treated with 30 % hydrogen peroxide activated with Nd:YAG laser (1064 nm, 2.5 W, 25 Hz, pulse duration of 100 μs, 6 mm distance); and group 4: Teeth treated with 30 % hydrogen peroxide activated with diode laser (810 nm, 1 W, CW, 6 mm distance). Equal numbers of teeth in groups 2, 3, and 4 were bonded at start, 1 h, 24 h, and 1 week after bleaching. A universal testing machine measured the SBS of the samples 24 h after bonding. After bracket debonding, the amount of residual adhesive on the enamel surface was observed under a stereomicroscope to determine the adhesive remnant index (ARI) scores. The SBS in the unbleached group was significantly higher than that in the bleached groups bonded immediately and 1 h after laser-assisted bleaching (P < 0.05). In groups 3 and 4 at start and group 2 at start and 1 h after laser-assisted bleaching, the SBS was found to be significantly lower than that in the control group. Significant differences in the ARI scores existed among groups as well. The SBS of brackets seems to increase quickly within an hour after laser-assisted bleaching and 24 h after conventional bleaching. Thus, this protocol can be recommended if it is necessary to bond the brackets on the same day of bleaching.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

A new prescription for the mass-loss rates of hydrogen-free WR stars

NASA Astrophysics Data System (ADS)

Tramper, Frank; Sana, Hugues; de Koter, Alex

2017-11-01

We present a new empirical prescription for the mass-loss rates of hydrogen-free Wolf-Rayet stars based on results of detailed spectral analyses of WC and WO stars. Compared to the prescription of Nugis & Lamers (2000), M⊙ is less sensitive to the surface helium abundance, implying a stronger mass loss at the late stages of Wolf-Rayet evolution. The winds of hydrogen-free WN stars have a strong metallicity dependence, while those of WC and WO stars have a very weak metallicity dependence.

Enhanced Hydrogen Evolution Reactions on Nanostructured Cu2ZnSnS4 (CZTS) Electrocatalyst

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

White dwarf stars with carbon atmospheres.

PubMed

Dufour, P; Liebert, J; Fontaine, G; Behara, N

2007-11-22

White dwarfs represent the endpoint of stellar evolution for stars with initial masses between approximately 0.07 and 8-10, where is the mass of the Sun (more massive stars end their life as either black holes or neutron stars). The theory of stellar evolution predicts that the majority of white dwarfs have a core made of carbon and oxygen, which itself is surrounded by a helium layer and, for approximately 80 per cent of known white dwarfs, by an additional hydrogen layer. All white dwarfs therefore have been traditionally found to belong to one of two categories: those with a hydrogen-rich atmosphere (the DA spectral type) and those with a helium-rich atmosphere (the non-DAs). Here we report the discovery of several white dwarfs with atmospheres primarily composed of carbon, with little or no trace of hydrogen or helium. Our analysis shows that the atmospheric parameters found for these stars do not fit satisfactorily in any of the currently known theories of post-asymptotic giant branch evolution, although these objects might be the cooler counterpart of the unique and extensively studied PG 1159 star H1504+65 (refs 4-7). These stars, together with H1504+65, might accordingly form a new evolutionary sequence that follows the asymptotic giant branch.

NASA Hydrogen Research for Spaceport and Space Based Applications

NASA Technical Reports Server (NTRS)

Anderson, Tim

2005-01-01

Project management activities for this grant includes internal oversight, coordination and facilitation among research groups (internal to UF and external); system and/or trade studies to assist in evaluating and prioritizing new hydrogen production processes that may become available for potential research investigations; a technical and programmatic outreach activity; and formal reporting, including periodic technical reviews with the NASA team.

Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution† †Electronic supplementary information (ESI) available: Complementary resonance Raman and infrared spectroscopic data. See DOI: 10.1039/c6sc01098a Click here for additional data file.

PubMed Central

Katz, S.; Noth, J.; Shafaat, H. S.; Happe, T.; Hildebrandt, P.

2016-01-01

[FeFe] hydrogenases are biocatalytic model systems for the exploitation and investigation of catalytic hydrogen evolution. Here, we used vibrational spectroscopic techniques to characterize, in detail, redox transformations of the [FeFe] and [4Fe4S] sub-sites of the catalytic centre (H-cluster) in a monomeric [FeFe] hydrogenase. Through the application of low-temperature resonance Raman spectroscopy, we discovered a novel metastable intermediate that is characterized by an oxidized [FeIFeII] centre and a reduced [4Fe4S]1+ cluster. Based on this unusual configuration, this species is assigned to the first, deprotonated H-cluster intermediate of the [FeFe] hydrogenase catalytic cycle. Providing insights into the sequence of initial reaction steps, the identification of this species represents a key finding towards the mechanistic understanding of biological hydrogen evolution. PMID:28451119

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

PubMed

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.

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

DOE PAGES

Hod, Idan; Deria, Pravas; Bury, Wojciech; ...

2015-09-14

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.

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 assessmore » 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.« less

2D Transition-Metal-Dichalcogenide-Nanosheet-Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions.

PubMed

Lu, Qipeng; Yu, Yifu; Ma, Qinglang; Chen, Bo; Zhang, Hua

2016-03-09

Hydrogen (H2) is one of the most important clean and renewable energy sources for future energy sustainability. Nowadays, photocatalytic and electrocatalytic hydrogen evolution reactions (HERs) from water splitting are considered as two of the most efficient methods to convert sustainable energy to the clean energy carrier, H2. Catalysts based on transition metal dichalcogenides (TMDs) are recognized as greatly promising substitutes for noble-metal-based catalysts for HER. The photocatalytic and electrocatalytic activities of TMD nanosheets for the HER can be further improved after hybridization with many kinds of nanomaterials, such as metals, oxides, sulfides, and carbon materials, through different methods including the in situ reduction method, the hot-injection method, the heating-up method, the hydro(solvo)thermal method, chemical vapor deposition (CVD), and thermal annealing. Here, recent progress in photocatalytic and electrocatalytic HERs using 2D TMD-based composites as catalysts is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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.

Rationally Designed Hierarchically Structured Tungsten Nitride and Nitrogen-Rich Graphene-Like Carbon Nanocomposite as Efficient Hydrogen Evolution Electrocatalyst.

PubMed

Zhu, Yanping; Chen, Gao; Zhong, Yijun; Zhou, Wei; Shao, Zongping

2018-02-01

Practical application of hydrogen production from water splitting relies strongly on the development of low-cost and high-performance electrocatalysts for hydrogen evolution reaction (HER). The previous researches mainly focused on transition metal nitrides as HER catalysts due to their electrical conductivity and corrosion stability under acidic electrolyte, while tungsten nitrides have reported poorer activity for HER. Here the activity of tungsten nitride is optimized through rational design of a tungsten nitride-carbon composite. More specifically, tungsten nitride (WN x ) coupled with nitrogen-rich porous graphene-like carbon is prepared through a low-cost ion-exchange/molten-salt strategy. Benefiting from the nanostructured WN x , the highly porous structure and rich nitrogen dopant (9.5 at%) of the carbon phase with high percentage of pyridinic-N (54.3%), and more importantly, their synergistic effect, the composite catalyst displays remarkably high catalytic activity while maintaining good stability. This work highlights a powerful way to design more efficient metal-carbon composites catalysts for HER.

Hierarchical Heterostructure of ZnO@TiO2 Hollow Spheres for Highly Efficient Photocatalytic Hydrogen Evolution

NASA Astrophysics Data System (ADS)

Li, Yue; Wang, Longlu; Liang, Jian; Gao, Fengxian; Yin, Kai; Dai, Pei

2017-09-01

The rational design and preparation of hierarchical nanoarchitectures are critical for enhanced photocatalytic hydrogen evolution reaction (HER). Herein, well-integrated hollow ZnO@TiO2 heterojunctions were obtained by a simple hydrothermal method. This unique hierarchical heterostructure not only caused multiple reflections which enhances the light absorption but also improved the lifetime and transfer of photogenerated charge carriers due to the potential difference generated on the ZnO-TiO2 interface. As a result, compared to bare ZnO and TiO2, the ZnO@TiO2 composite photocatalyst exhibited higher hydrogen production rated up to 0.152 mmol h-1 g-1 under simulated solar light. In addition, highly repeated photostability was also observed on the ZnO@TiO2 composite photocatalyst even after a continuous test for 30 h. It is expected that this low-cost, nontoxic, and readily available ZnO@TiO2 catalyst could exhibit promising potential in photocatalytic H2 to meet the future fuel needs.

Self-assembly synthesis of precious-metal-free 3D ZnO nano/micro spheres with excellent photocatalytic hydrogen production from solar water splitting

NASA Astrophysics Data System (ADS)

Guo, Si-yao; Zhao, Tie-jun; Jin, Zu-quan; Wan, Xiao-mei; Wang, Peng-gang; Shang, Jun; Han, Song

2015-10-01

A simple and straightforward solution growth routine is developed to prepare microporous 3D nano/micro ZnO microsphere with a large BET surface area of 288 m2 g-1 at room temperature. The formation mechanism of the hierarchical 3D nano/micro ZnO microsphere and its corresponding hydrogen evolution performance has been deeply discussed. In particular, this novel hierarchical 3D ZnO microspheres performs undiminished hydrogen evolution for at least 24 h under simulated solar light illumination, even under the condition of no precious metal as cocatalyst. Since the complex production process of photocatalysts and high cost of precious metal cocatalyst remains a major constraint that hinders the application of solar water splitting, this 3D nano/micro ZnO microspheres could be expected to be applicable in the precious-metal-free solar water splitting system due to its merits of low cost, simple procedure and high catalytic activity.

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

PubMed Central

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

2015-01-01

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

On the Role of Dissolved Gases in the Atmosphere Retention of Low-mass Low-density Planets

NASA Astrophysics Data System (ADS)

Chachan, Yayaati; Stevenson, David J.

2018-02-01

Low-mass low-density planets discovered by Kepler in the super-Earth mass regime typically have large radii for their inferred masses, implying the presence of H2–He atmospheres. These planets are vulnerable to atmospheric mass loss due to heating by the parent star’s XUV flux. Models coupling atmospheric mass loss with thermal evolution predicted a bimodal distribution of planetary radii, which has gained observational support. However, a key component that has been ignored in previous studies is the dissolution of these gases into the molten core of rock and iron that constitute most of their mass. Such planets have high temperatures (>2000 K) and pressures (∼kbars) at the core-envelope boundary, ensuring a molten surface and a subsurface reservoir of hydrogen that can be 5–10 times larger than the atmosphere. This study bridges this gap by coupling the thermal evolution of the planet and the mass loss of the atmosphere with the thermodynamic equilibrium between the dissolved H2 and the atmospheric H2 (Henry’s law). Dissolution in the interior allows a planet to build a larger hydrogen repository during the planet formation stage. We show that the dissolved hydrogen outgasses to buffer atmospheric mass loss. The slow cooling of the planet also leads to outgassing because solubility decreases with decreasing temperature. Dissolution of hydrogen in the interior therefore increases the atmosphere retention ability of super-Earths. The study highlights the importance of including the temperature- and pressure-dependent solubility of gases in magma oceans and coupling outgassing to planetary evolution models.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hui; Wen, Peng; Hoxie, Adam

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

DOE PAGES

Li, Hui; Wen, Peng; Hoxie, Adam; ...

2018-04-30

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Results of a technical analysis of the Hubble Space Telescope nickel-cadmium and nickel-hydrogen batteries

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

1991-01-01

The Hubble Space Telescope (HST) Program Office requested the expertise of the NASA Aerospace Flight Battery Systems Steering Committee (NAFBSSC) in the conduct of an independent assessment of the HST's battery system to assist in their decision of whether to fly nickel-cadmium or nickel-hydrogen batteries on the telescope. In response, a subcommittee to the NAFBSSC was organized with membership comprised of experts with background in the nickel-cadmium/nickel-hydrogen secondary battery/power systems areas. The work and recommendations of that subcommittee are presented.

Nanosized zero-valent iron as Fenton-like reagent for ultrasonic-assisted leaching of zinc from blast furnace sludge.

PubMed

Mikhailov, Ivan; Komarov, Sergey; Levina, Vera; Gusev, Alexander; Issi, Jean-Paul; Kuznetsov, Denis

2017-01-05

Ultrasonic-assisted sulphuric acid leaching combined with a Fenton-like process, utilizing nanoscale zero-valent iron (nZVI), was investigated to enhance the leaching of zinc from the blast furnace sludge (BFS). The leaching of iron (Fe) and zinc (Zn) from the sludge was investigated using Milli-Q water/BFS ratio of 10 and varying the concentration of hydrogen peroxide, sulphuric acid, the temperature, the input energy for ultrasound irradiation, and the presence or absence of nZVI as a Fenton reagent. The results showed that with 1g/l addition of nZVI and 0.05M of hydrogen peroxide, the kinetic rate of Zn leaching increased with a maximum dissolution degree of 80.2%, after 5min treatment. In the absence of nZVI, the maximum dissolution degree of Zn was 99.2%, after 15min treatment with 0.1M of hydrogen peroxide. The rate of Zn leaching at several concentrations of hydrogen peroxide is accelerated in the presence of nZVI although a reduction in efficiency was observed. The loss of Fe was no more than 3%. On the basis of these results, the possible route for BFS recycling has been proposed (BFS slurry mixed with sulphuric acid and hydrogen peroxide is recirculated under ultrasonic irradiation then separated). Copyright © 2016 Elsevier B.V. All rights reserved.

Surface hydrogenation regulated wrinkling and torque capability of hydrogenated graphene annulus under circular shearing.

PubMed

Li, Yinfeng; Liu, Silin; Datta, Dibakar; Li, Zhonghua

2015-11-12

Wrinkles as intrinsic topological feature have been expected to affect the electrical and mechanical properties of atomically thin graphene. Molecular dynamics simulations are adopted to investigate the wrinkling characteristics in hydrogenated graphene annulus under circular shearing at the inner edge. The amplitude of wrinkles induced by in-plane rotation around the inner edge is sensitive to hydrogenation, and increases quadratically with hydrogen coverage. The effect of hydrogenation on mechanical properties is investigated by calculating the torque capability of annular graphene with varying hydrogen coverage and inner radius. Hydrogenation-enhanced wrinkles cause the aggregation of carbon atoms towards the inner edge and contribute to the critical torque strength of annulus. Based on detailed stress distribution contours, a shear-to-tension conversion mechanism is proposed for the contribution of wrinkles on torque capacity. As a result, the graphane annulus anomalously has similar torque capacity to pristine graphene annulus. The competition between hydrogenation caused bond strength deterioration and wrinkling induced local stress state conversion leads to a U-shaped evolution of torque strength relative to the increase of hydrogen coverage from 0 to 100%. Such hydrogenation tailored topological and mechanical characteristics provides an innovative mean to develop novel graphene-based devices.

Chemical structural analysis of diamondlike carbon films: I. Surface growth model

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The surface growth mechanisms of diamondlike carbon (DLC) films has been clarified. DLC films were synthesized in atmospheres with a fixed methane-to-argon ratio at different temperatures up to 700 °C by the photoemission-assisted glow discharge of photoemission-assisted plasma-enhanced chemical vapor deposition. The electrical resistivity of the films decreased logarithmically as the synthesis temperature was increased. Conversely, the dielectric constant of the films increased and became divergent at high temperature. However, the very high electrical resistivity of the film synthesized at 150 °C was retained even after post-annealing treatments at temperatures up to 500 °C, and divergence of the dielectric constant was not observed. Such films exhibited excellent thermal stability and retained large amounts of hydrogen, even after post-annealing treatments. These results suggest that numerous hydrogen atoms were incorporated into the DLC films during synthesis at low temperatures. Hydrogen atoms terminate carbon dangling bonds in the films to restrict π-conjugated growth. During synthesis at high temperature, hydrogen was desorbed from the interior of the growing films and π-conjugated conductive films were formed. Moreover, hydrogen radicals were chemisorbed by carbon atoms at the growing DLC surface, leading to removal of carbon atoms from the surface as methane gas. The methane molecules decomposed into hydrocarbons and hydrogen radicals through the attack of electrons above the surface. Hydrogen radicals contributed to the etching reaction cycle of the film; the hydrocarbon radicals were polymerized by reacting with other radicals and the methane source. The polymer radicals remained above the film, preventing the supply of the methane source and disrupting the action of argon ions. At high temperatures, the resultant DLC films were rough and thin.

Hydrogen peroxide-assisted synthesis of novel three-dimensional octagonal-like CuO nanostructures with enhanced visible-light-driven photocatalytic activity

NASA Astrophysics Data System (ADS)

Chen, Xiangyu; Chu, Deqing; Wang, Limin; Hu, Wenhui; Yang, Huifang; Sun, Jingjing; Zhu, Shaopeng; Wang, Guowei; Tao, Jian; Zhang, Songsong

2018-04-01

Novel three-dimensional octagonal-like CuO micro-/nanostructures with diameters ranging from 10 to 15 μm have been successfully prepared by hydrogen peroxide-assisted hydrothermal method and subsequent calcination. The product morphology can be changed by simply ordering the amount of hydrogen peroxide (H2O2). When the amounts of H2O2 is increased, the length of the corner portion is increased and the width is narrower. The obtained octagonal CuO nanostructures were evaluated for their ability for the degradation of hazardous organic contaminants in water under visible-light irradiation. Comparing with commercial CuO and other CuO products, the CuO octagonal nanostructures exhibit excellent performance for photocatalytic decomposition of RhB (Rhodamine B). It is well established that effective photocatalytic performance results from its unique 3D octagonal nanostructures. We believe that the present work will provide some ideas for further fabrication of other novel nanostructures and exploration of their applications.

Sulfide stress corrosion study of a super martensitic stainless steel in H2S sour environments: Metallic sulfides formation and hydrogen embrittlement

NASA Astrophysics Data System (ADS)

Monnot, Martin; Nogueira, Ricardo P.; Roche, Virginie; Berthomé, Grégory; Chauveau, Eric; Estevez, Rafael; Mantel, Marc

2017-02-01

Thanks to their high corrosion resistance, super martensitic stainless steels are commonly used in the oil and gas industry, particularly in sour environments. Some grades are however susceptible to undergo hydrogen and mechanically-assisted corrosion processes in the presence of H2S, depending on the pH. The martensitic stainless steel EN 1.4418 grade exhibits a clear protective passive behavior with no sulfide stress corrosion cracking when exposed to sour environments of pH ≥ 4, but undergoes a steep decrease in its corrosion resistance at lower pH conditions. The present paper investigated this abrupt loss of corrosion resistance with electrochemical measurements as well as different physicochemical characterization techniques. Results indicated that below pH 4.0 the metal surface is covered by a thick (ca 40 μm) porous and defect-full sulfide-rich corrosion products layer shown to be straightforwardly related to the onset of hydrogen and sulfide mechanically-assisted corrosion phenomena.

Ultrasonic pilot-scale reactor for enzymatic bleaching of cotton fabrics.

PubMed

Gonçalves, Idalina; Herrero-Yniesta, Victor; Perales Arce, Iratxe; Escrigas Castañeda, Monica; Cavaco-Paulo, Artur; Silva, Carla

2014-07-01

The potential of ultrasound-assisted technology has been demonstrated by several laboratory scale studies. However, their successful industrial scaling-up is still a challenge due to the limited pilot and commercial sonochemical reactors. In this work, a pilot reactor for laccase-hydrogen peroxide cotton bleaching assisted by ultrasound was scaled-up. For this purpose, an existing dyeing machine was transformed and adapted by including piezoelectric ultrasonic devices. Laboratory experiments demonstrated that both low frequency, high power (22 kHz, 2100 W) and high frequency, low power ultrasounds (850 kHz, 400 W) were required to achieve satisfactory results. Standard half (4 g/L H2O2 at 90 °C for 60 min) and optical (8 g/L H2O2 at 103 °C for 40 min) cotton bleaching processes were used as references. Two sequential stages were established for cotton bleaching: (1) laccase pretreatment assisted by high frequency ultrasound (850 kHz, 400 W) and (2) bleaching using high power ultrasound (22 kHz, 2100 W). When compared with conventional methods, combined laccase-hydrogen peroxide cotton bleaching with ultrasound energy improved the whitening effectiveness. Subsequently, less energy (temperature) and chemicals (hydrogen peroxide) were needed for cotton bleaching thus resulting in costs reduction. This technology allowed the combination of enzyme and hydrogen peroxide treatment in a continuous process. The developed pilot-scale reactor offers an enhancement of the cotton bleaching process with lower environmental impact as well as a better performance of further finishing operations. Copyright © 2014 Elsevier B.V. All rights reserved.

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

DOE PAGES

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.; ...

2017-10-16

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

Carbon-coated ceramic membrane reactor for the production of hydrogen by aqueous-phase reforming of sorbitol.

PubMed

Neira D'Angelo, M F; Ordomsky, V; Schouten, J C; van der Schaaf, J; Nijhuis, T A

2014-07-01

Hydrogen was produced by aqueous-phase reforming (APR) of sorbitol in a carbon-on-alumina tubular membrane reactor (4 nm pore size, 7 cm long, 3 mm internal diameter) that allows the hydrogen gas to permeate to the shell side, whereas the liquid remains in the tube side. The hydrophobic nature of the membrane serves to avoid water loss and to minimize the interaction between the ceramic support and water, thus reducing the risks of membrane degradation upon operation. The permeation of hydrogen is dominated by the diffusivity of the hydrogen in water. Thus, higher operation temperatures result in an increase of the flux of hydrogen. The differential pressure has a negative effect on the flux of hydrogen due to the presence of liquid in the larger pores. The membrane was suitable for use in APR, and yielded 2.5 times more hydrogen than a reference reactor (with no membrane). Removal of hydrogen through the membrane assists in the reaction by preventing its consumption in undesired reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative analysis of hydrogen in SiO{sub 2}/SiN/SiO{sub 2} stacks using atom probe tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kunimune, Yorinobu, E-mail: yorinobu.kunimune.vz@renesas.com; Shimada, Yasuhiro; Sakurai, Yusuke

2016-04-15

We have demonstrated that it is possible to reproducibly quantify hydrogen concentration in the SiN layer of a SiO{sub 2}/SiN/SiO{sub 2} (ONO) stack structure using ultraviolet laser-assisted atom probe tomography (APT). The concentration of hydrogen atoms detected using APT increased gradually during the analysis, which could be explained by the effect of hydrogen adsorption from residual gas in the vacuum chamber onto the specimen surface. The amount of adsorbed hydrogen in the SiN layer was estimated by analyzing another SiN layer with an extremely low hydrogen concentration (<0.2 at. %). Thus, by subtracting the concentration of adsorbed hydrogen, the actualmore » hydrogen concentration in the SiN layer was quantified as approximately 1.0 at. %. This result was consistent with that obtained by elastic recoil detection analysis (ERDA), which confirmed the accuracy of the APT quantification. The present results indicate that APT enables the imaging of the three-dimensional distribution of hydrogen atoms in actual devices at a sub-nanometer scale.« less

Metal-mediated DNA base pairing: alternatives to hydrogen-bonded Watson-Crick base pairs.

PubMed

Takezawa, Yusuke; Shionoya, Mitsuhiko

2012-12-18

With its capacity to store and transfer the genetic information within a sequence of monomers, DNA forms its central role in chemical evolution through replication and amplification. This elegant behavior is largely based on highly specific molecular recognition between nucleobases through the specific hydrogen bonds in the Watson-Crick base pairing system. While the native base pairs have been amazingly sophisticated through the long history of evolution, synthetic chemists have devoted considerable efforts to create alternative base pairing systems in recent decades. Most of these new systems were designed based on the shape complementarity of the pairs or the rearrangement of hydrogen-bonding patterns. We wondered whether metal coordination could serve as an alternative driving force for DNA base pairing and why hydrogen bonding was selected on Earth in the course of molecular evolution. Therefore, we envisioned an alternative design strategy: we replaced hydrogen bonding with another important scheme in biological systems, metal-coordination bonding. In this Account, we provide an overview of the chemistry of metal-mediated base pairing including basic concepts, molecular design, characteristic structures and properties, and possible applications of DNA-based molecular systems. We describe several examples of artificial metal-mediated base pairs, such as Cu(2+)-mediated hydroxypyridone base pair, H-Cu(2+)-H (where H denotes a hydroxypyridone-bearing nucleoside), developed by us and other researchers. To design the metallo-base pairs we carefully chose appropriate combinations of ligand-bearing nucleosides and metal ions. As expected from their stronger bonding through metal coordination, DNA duplexes possessing metallo-base pairs exhibited higher thermal stability than natural hydrogen-bonded DNAs. Furthermore, we could also use metal-mediated base pairs to construct or induce other high-order structures. These features could lead to metal-responsive functional DNA molecules such as artificial DNAzymes and DNA machines. In addition, the metallo-base pairing system is a powerful tool for the construction of homogeneous and heterogeneous metal arrays, which can lead to DNA-based nanomaterials such as electronic wires and magnetic devices. Recently researchers have investigated these systems as enzyme replacements, which may offer an additional contribution to chemical biology and synthetic biology through the expansion of the genetic alphabet.

Improving MAVEN-IUVS Lyman-Alpha Apoapsis Images

NASA Astrophysics Data System (ADS)

Chaffin, M.; AlMannaei, A. S.; Jain, S.; Chaufray, J. Y.; Deighan, J.; Schneider, N. M.; Thiemann, E.; Mayyasi, M.; Clarke, J. T.; Crismani, M. M. J.; Stiepen, A.; Montmessin, F.; Epavier, F.; McClintock, B.; Stewart, I. F.; Holsclaw, G.; Jakosky, B. M.

2017-12-01

In 2013, the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission was launched to study the Martian upper atmosphere and ionosphere. MAVEN orbits through a very thin cloud of hydrogen gas, known as the hydrogen corona, that has been used to explore the planet's geologic evolution by detecting the loss of hydrogen from the atmosphere. Here we present various methods of extracting properties of the hydrogen corona from observations using MAVEN's Imaging Ultraviolet Spectograph (IUVS) instrument. The analysis presented here uses the IUVS Far Ultraviolet mode apoapase data. From apoapse, IUVS is able to obtain images of the hydrogen corona by detecting the Lyman-alpha airglow using a combination of instrument scan mirror and spacecraft motion. To complete one apoapse observation, eight scan swaths are performed to collect the observations and construct a coronal image. However, these images require further processing to account for the atmospheric MUV background that hinders the quality of the data. Here, we present new techniques for correcting instrument data. For the background subtraction, a multi-linear regression (MLR) routine of the first order MUV radiance was used to improve the images. A flat field correction was also applied by fitting a polynomial to periapse radiance observations. The apoapse data was re-binned using this fit.The results are presented as images to demonstrate the improvements in the data reduction. Implementing these methods for more orbits will improve our understanding of seasonal variability and H loss. Asymmetries in the Martian hydrogen corona can also be assessed to improve current model estimates of coronal H in the Martian atmosphere.

Local potential evolutions during proton exchange membrane fuel cell operation with dead-ended anode - Part II: Aging mitigation strategies based on water management and nitrogen crossover

NASA Astrophysics Data System (ADS)

Abbou, S.; Dillet, J.; Maranzana, G.; Didierjean, S.; Lottin, O.

2017-02-01

Proton exchange membrane (PEM) fuel cells operate with dead-ended anode in order to reduce system cost and complexity when compared with hydrogen re-circulation systems. In the first part of this work, we showed that localized fuel starvation events may occur, because of water and nitrogen accumulation in the anode side, which could be particularly damaging to the cell performance. To prevent these degradations, the anode compartment must be purged which may lead to an overall system efficiency decrease because of significant hydrogen waste. In the second part, we present several purge strategies in order to minimize both hydrogen waste and membrane-electrode assembly degradations during dead-ended anode operation. A linear segmented cell with reference electrodes was used to monitor simultaneously the current density distribution along the gas channel and the time evolution of local anode and cathode potentials. To asses MEA damages, Platinum ElectroChemical Surface Area (ECSA) and cell performance were periodically measured. The results showed that dead-end mode operation with an anode plate maintained at a temperature 5 °C hotter than the cathode plate limits water accumulation in the anode side, reducing significantly purge frequency (and thus hydrogen losses) as well as MEA damages. As nitrogen contribution to hydrogen starvation is predominant in this thermal configuration, we also tested a microleakage solution to discharge continuously most the nitrogen accumulating in the anode side while ensuring low hydrogen losses and minimum ECSA losses provided the right microleakage flow rate is chosen.

High-temperature effect of hydrogen on sintered alpha-silicon carbide

NASA Technical Reports Server (NTRS)

Hallum, G. W.; Herbell, T. P.

1986-01-01

Sintered alpha-silicon carbide was exposed to pure, dry hydrogen at high temperatures for times up to 500 hr. Weight loss and corrosion were seen after 50 hr at temperatures as low as 1000 C. Corrosion of SiC by hydrogen produced grain boundary deterioration at 1100 C and a mixture of grain and grain boundary deterioration at 1300 C. Statistically significant strength reductions were seen in samples exposed to hydrogen for times greater than 50 hr and temperatures above 1100 C. Critical fracture origins were identified by fractography as either general grain boundary corrision at 1100 C or as corrosion pits at 1300 C. A maximum strength decrease of approximately 33 percent was seen at 1100 and 1300 C after 500 hr exposure to hydrogen. A computer assisted thermodynamic program was also used to predict possible reaction species of SiC and hydrogen.

Effect of high-temperature hydrogen exposure on sintered alpha-SiC

NASA Technical Reports Server (NTRS)

Hallum, Gary W.; Herbell, Thomas P.

1988-01-01

Sintered alpha-silicon carbide was exposed to pure, dry hydrogen at high temperatures for times up to 500 hr. Weight loss and corrosion were seen after 50 hr at temperatures as low as 1000 C. Corrosion of SiC by hydrogen produced grain boundary deterioration at 1100 C and a mixture of grain and grain boundary deterioration at 1300 C. Statistically significant strength reductions were seen in samples exposed to hydrogen for times greater than 50 hr and temperatures above 1100 C. Critical fracture origins were identified by fractography as either general grain boundary corrosion at 1100 C or as corrosion pits at 1300 C. A maximum strength decrease of approximately 33 percent was seen at 1100 and 1300 C after 500 hr exposure to hydrogen. A computer assisted thermodynamic program was also used to predict possible reaction species of SiC and hydrogen.

Dust evolution, a global view: II. Top-down branching, nanoparticle fragmentation and the mystery of the diffuse interstellar band carriers

PubMed Central

2016-01-01

The origin of the diffuse interstellar bands (DIBs), one of the longest-standing mysteries of the interstellar medium (ISM), is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS). The likely nature of the DIB carriers and their evolution is here explored within the framework of the structures and sub-structures inherent to doped hydrogenated amorphous carbon grains in the ISM. Based on the natural aromatic-rich moieties (asphaltenes) recovered from coal and oil, the likely structure of their interstellar analogues is investigated within the context of the diffuse band problem. It is here proposed that the top-down evolution of interstellar carbonaceous grains, and, in particular, a-C(:H) nanoparticles, is at the heart of the formation and evolution of the DIB carriers and their associations with small molecules and radicals, such as C2, C3, CH and CN. It is most probable that the DIBs are carried by dehydrogenated, ionized, hetero-cyclic, olefinic and aromatic-rich moieties that form an integral part of the contiguous structure of hetero-atom-doped hydrogenated amorphous carbon nanoparticles and their daughter fragmentation products. Within this framework, it is proposed that polyene structures in all their variants could be viable DIB carrier candidates. PMID:28083089

Dust evolution, a global view: II. Top-down branching, nanoparticle fragmentation and the mystery of the diffuse interstellar band carriers

NASA Astrophysics Data System (ADS)

Jones, A. P.

2016-12-01

The origin of the diffuse interstellar bands (DIBs), one of the longest-standing mysteries of the interstellar medium (ISM), is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS). The likely nature of the DIB carriers and their evolution is here explored within the framework of the structures and sub-structures inherent to doped hydrogenated amorphous carbon grains in the ISM. Based on the natural aromatic-rich moieties (asphaltenes) recovered from coal and oil, the likely structure of their interstellar analogues is investigated within the context of the diffuse band problem. It is here proposed that the top-down evolution of interstellar carbonaceous grains, and, in particular, a-C(:H) nanoparticles, is at the heart of the formation and evolution of the DIB carriers and their associations with small molecules and radicals, such as C2, C3, CH and CN. It is most probable that the DIBs are carried by dehydrogenated, ionized, hetero-cyclic, olefinic and aromatic-rich moieties that form an integral part of the contiguous structure of hetero-atom-doped hydrogenated amorphous carbon nanoparticles and their daughter fragmentation products. Within this framework, it is proposed that polyene structures in all their variants could be viable DIB carrier candidates.

Cell-Free Synthetic Biology Chassis for Nanocatalytic Photon-to-Hydrogen Conversion.

PubMed

Wang, Peng; Chang, Angela Y; Novosad, Valentyn; Chupin, Vladimir V; Schaller, Richard D; Rozhkova, Elena A

2017-07-25

We report on an entirely man-made nano-bio architecture fabricated through noncovalent assembly of a cell-free expressed transmembrane proton pump and TiO 2 semiconductor nanoparticles as an efficient nanophotocatalyst for H 2 evolution. The system produces hydrogen at a turnover of about 240 μmol of H 2 (μmol protein) -1 h -1 and 17.74 mmol of H 2 (μmol protein) -1 h -1 under monochromatic green and white light, respectively, at ambient conditions, in water at neutral pH and room temperature, with methanol as a sacrificial electron donor. Robustness and flexibility of this approach allow for systemic manipulation at the nanoparticle-bio interface toward directed evolution of energy transformation materials and artificial systems.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

PubMed Central

Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

2017-01-01

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

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

NASA Astrophysics Data System (ADS)

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

1996-03-01

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

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

Microalgal hydrogen production - A review.

PubMed

Khetkorn, Wanthanee; Rastogi, Rajesh P; Incharoensakdi, Aran; Lindblad, Peter; Madamwar, Datta; Pandey, Ashok; Larroche, Christian

2017-11-01

Bio-hydrogen from microalgae including cyanobacteria has attracted commercial awareness due to its potential as an alternative, reliable and renewable energy source. Photosynthetic hydrogen production from microalgae can be interesting and promising options for clean energy. Advances in hydrogen-fuel-cell technology may attest an eco-friendly way of biofuel production, since, the use of H 2 to generate electricity releases only water as a by-product. Progress in genetic/metabolic engineering may significantly enhance the photobiological hydrogen production from microalgae. Manipulation of competing metabolic pathways by modulating the certain key enzymes such as hydrogenase and nitrogenase may enhance the evolution of H 2 from photoautotrophic cells. Moreover, biological H 2 production at low operating costs is requisite for economic viability. Several photobioreactors have been developed for large-scale biomass and hydrogen production. This review highlights the recent technological progress, enzymes involved and genetic as well as metabolic engineering approaches towards sustainable hydrogen production from microalgae. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties.

PubMed

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

2016-09-30

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS 2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

Hydrogen quantitative risk assessment workshop proceedings.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Groth, Katrina M.; Harris, Aaron P.

2013-09-01

The Quantitative Risk Assessment (QRA) Toolkit Introduction Workshop was held at Energetics on June 11-12. The workshop was co-hosted by Sandia National Laboratories (Sandia) and HySafe, the International Association for Hydrogen Safety. The objective of the workshop was twofold: (1) Present a hydrogen-specific methodology and toolkit (currently under development) for conducting QRA to support the development of codes and standards and safety assessments of hydrogen-fueled vehicles and fueling stations, and (2) Obtain feedback on the needs of early-stage users (hydrogen as well as potential leveraging for Compressed Natural Gas [CNG], and Liquefied Natural Gas [LNG]) and set priorities for %E2%80%9CVersionmore » 1%E2%80%9D of the toolkit in the context of the commercial evolution of hydrogen fuel cell electric vehicles (FCEV). The workshop consisted of an introduction and three technical sessions: Risk Informed Development and Approach; CNG/LNG Applications; and Introduction of a Hydrogen Specific QRA Toolkit.« less

A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Zou, J.; Ren, Y. X.

2017-06-01

To eliminate the adverse impacts of hydrogen evolution on the capacity of iron-chromium redox flow batteries (ICRFBs) during the long-term operation and ensure the safe operation of the battery, a rebalance cell that reduces the excessive Fe(III) ions at the positive electrolyte by using the hydrogen evolved from the negative electrolyte is designed, fabricated and tested. The effects of the flow field, hydrogen concentration and H2/N2 mixture gas flow rate on the performance of the hydrogen-ferric ion rebalance cell have been investigated. Results show that: i) an interdigitated flow field based rebalance cell delivers higher limiting current densities than serpentine flow field based one does; ii) the hydrogen utilization can approach 100% at low hydrogen concentrations (≤5%); iii) the apparent exchange current density of hydrogen oxidation reaction in the rebalance cell is proportional to the square root of the hydrogen concentration at the hydrogen concentration from 1.3% to 50%; iv) a continuous rebalance process is demonstrated at the current density of 60 mA cm-2 and hydrogen concentration of 2.5%. Moreover, the cost analysis shows that the rebalance cell is just approximately 1% of an ICRFB system cost.

Hydrogen pickup mechanism of zirconium alloys

NASA Astrophysics Data System (ADS)

Couet, Adrien

Although the optimization of zirconium based alloys has led to significant improvements in hydrogen pickup and corrosion resistance, the mechanisms by which such alloy improvements occur are still not well understood. In an effort to understand such mechanisms, a systematic study of the alloy effect on hydrogen pickup is conducted, using advanced characterization techniques to rationalize precise measurements of hydrogen pickup. The hydrogen pick-up fraction is accurately measured for a specially designed set of commercial and model alloys to investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. Two different techniques to measure hydrogen concentrations were used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results indicate that hydrogen pickup varies not only from alloy to alloy but also during the corrosion process for a given alloy. For instance Zircaloy type alloys show high hydrogen pickup fraction and sub-parabolic oxidation kinetics whereas ZrNb alloys show lower hydrogen pickup fraction and close to parabolic oxidation kinetics. Hypothesis is made that hydrogen pickup result from the need to balance charge during the corrosion reaction, such that the pickup of hydrogen is directly related to (and indivisible of) the corrosion mechanism and decreases when the rate of electron transport or oxide electronic conductivity sigmao xe through the protective oxide increases. According to this hypothesis, alloying elements (either in solid solution or in precipitates) embedded in the oxide as well as space charge variations in the oxide would impact the hydrogen pick-up fraction by modifying sigmaox e, which drives oxidation and hydriding kinetics. Dedicated experiments and modelling were performed to assess and validate these hypotheses. In-situ electrochemical impedance spectroscopy (EIS) experiments were performed on Zircaloy-4 tubes to directly measure the evolution of sigma oxe as function of exposure time. The results show that sigmao xe decreases as function of exposure time and that its variations are directly correlated to the instantaneous hydrogen pickup fraction variations. The electron transport through the oxide layer is thus altered as the oxide grows, reasons for which are yet to be exactly determined. Preliminary results also show that sigma oxe of ZrNb alloys would be much higher compared with Zircaloy-4. Thus, it is confirmed that sigmaox e is a key parameter in the hydrogen and oxidation mechanism. Because the mechanism whereby alloying elements are incorporated into the oxide layer is critical to changing sigmao xe, the evolution of the oxidation state of two common alloying elements, Fe and Nb, when incorporated into the growing oxide layers is investigated using X-Ray Absorption Near-Edge Spectroscopy (XANES) using micro-beam synchrotron radiation on cross sectional oxide samples. The results show that the oxidation of both Fe and Nb is delayed in the oxide layer compared to that of Zr, and that this oxidation delay is related to the variations of the instantaneous hydrogen pick-up fraction with exposure time. The evolution of Nb oxidation as function of oxide depth is also compatible with space charge compensation in the oxide and with an increase in sigmaox e of ZrNb alloys compared to Zircaloys. Finally, various successively complex models from the well-known Wagner oxidation theory to the more complex effect of space charge on oxidation kinetics have been developed. The general purpose of the modeling effort is to provide a rationale for the sub-parabolic oxidation kinetics and demonstrate the correlation with hydrogen pickup fraction. It is directly demonstrated that parabolic oxidation kinetics is associated with high sigmao xe and low space charges in the oxide whereas sub-parabolic oxidation kinetics is associated with lower sigmaox e and higher space charge in the oxide. All these observations helped us to propose a general corrosion mechanism of zirconium alloys involving both oxidation and hydrogen pickup mechanism to better understand and predict the effect of alloying additions on the behavior of zirconium alloys.

Postassembly Transformation of a Catalytically Active Composite Material, Pt@ZIF-8, via Solvent-Assisted Linker Exchange.

PubMed

Stephenson, Casey J; Hupp, Joseph T; Farha, Omar K

2016-02-15

2-Methylimidazolate linkers of Pt@ZIF-8 are exchanged with imidazolate using solvent-assisted linker exchange (SALE) to expand the apertures of the parent material and create Pt@SALEM-2. Characterization of the material before and after SALE was performed. Both materials are active as catalysts for the hydrogenation of 1-octene, whereas the hydrogenation of cis-cyclohexene occurred only with Pt@SALEM-2, consistent with larger apertures for the daughter material. The largest substrate, β-pinene, proved to be unreactive with H2 when either material was employed as a candidate catalyst, supporting the contention that substrate molecules, for both composites, must traverse the metal-organic framework component in order to reach the catalytic nanoparticles.

Temperature and density evolution during decay in a 2.45 GHz hydrogen electron cyclotron resonance plasma: off-resonant and resonant cases.

PubMed

Cortázar, O D; Megía-Macías, A; Vizcaíno-de-Julián, A

2013-09-01

Time resolved electron temperature and density measurements during the decay stage in a hydrogen electron cyclotron resonance (ECR) plasma are presented for a resonance and off-resonance magnetic field configurations. The measurements are conducted on a ECR plasma generator excited at 2.45 GHz denominated test-bench for ion-sources plasma studies at ESS Bilbao. The plasma parameters evolution is studied by Langmuir probe diagnostic with synchronized sample technique developed for repetitive pulsed plasmas with a temporal resolution of 200 ns in typical decay processes of about 40 μs. An afterglow transient is clearly observed in the reflected microwave power signal from the plasma. Simultaneously, the electron temperature evolution shows rebounding peaks that may be related to the interplay between density drop and microwave coupling with deep impact on the Electron Energy Distribution Function. The correlation of such structures with the plasma absorbed power and the coupling quality is also reported.

Catalytic activity in lithium-treated core–shell MoO x/MoS 2 nanowires

DOE PAGES

Cummins, Dustin R.; Martinez, Ulises; Kappera, Rajesh; ...

2015-09-22

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoO x/MoS 2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H 2 evolution. The 1D nanowires exhibit significant improvement in H 2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS 2 layersmore » in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).« less

Evolution of massive stars in very young clusters and associations

NASA Technical Reports Server (NTRS)

Stothers, R. B.

1985-01-01

Statistics concerning the stellar content of young galactic clusters and associations which show well defined main sequence turnups have been analyzed in order to derive information about stellar evolution in high-mass galaxies. The analytical approach is semiempirical and uses natural spectroscopic groups of stars on the H-R diagram together with the stars' apparent magnitudes. The new approach does not depend on absolute luminosities and requires only the most basic elements of stellar evolution theory. The following conclusions are offered on the basis of the statistical analysis: (1) O-tupe main-sequence stars evolve to a spectral type of B1 during core hydrogen burning; (2) most O-type blue stragglers are newly formed massive stars burning core hydrogen; (3) supergiants lying redward of the main-sequence turnup are burning core helium; and most Wolf-Rayet stars are burning core helium and originally had masses greater than 30-40 solar mass. The statistics of the natural spectroscopic stars in young galactic clusters and associations are given in a table.

Electrodeposition of Rhodium Nanowires Arrays and Their Morphology-Dependent Hydrogen Evolution Activity

PubMed Central

Zhang, Liqiu; Liu, Lichun; Wang, Hongdan; Shen, Hongxia; Cheng, Qiong; Yan, Chao; Park, Sungho

2017-01-01

This work reports on the electrodeposition of rhodium (Rh) nanowires with a controlled surface morphology synthesized using an anodic aluminum oxide (AAO) template. Vertically aligned Rh nanowires with a smooth and coarse morphology were successfully deposited by adjusting the electrode potential and the concentration of precursor ions and by involving a complexing reagent in the electrolyte solution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses were used to follow the morphological evolution of Rh nanowires. As a heterogeneous electrocatalyst for hydrogen evolution reactions (HER), the coarse Rh nanowire array exhibited an enhanced catalytic performance respect to smooth ones due to the larger surface area to mass ratio and the higher density of catalytically active defects, as evidenced by voltammetric measurements and TEM. Results suggest that the morphology of metallic nanomaterials could be readily engineered by electrodeposition. The controlled electrodeposition offers great potential for the development of an effective synthesis tool for heterogeneous catalysts with a superior performance for wide applications. PMID:28467375

Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

PubMed

Zhang, Yun-Xiao; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

2018-09-15

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS 2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS 2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS 2 /CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS 2 /CNTs/CN catalyst exhibits high performance for H 2 evolution and the optimized rate is 309.9 μmol·h -1 ·g -1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost. Copyright © 2018 Elsevier Inc. All rights reserved.

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

PubMed Central

Asakawa, Daiki

2013-01-01

The matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) of peptides and glycans was studied using an oxidizing chemical, 5-nitrosalicylic acid (5-NSA) as the matrix. The use of 5-NSA for the MALDI-ISD of peptides and glycans promoted fragmentation pathways involving “hydrogen-deficient” radical precursors. Hydrogen abstraction from peptides resulted in the production of a “hydrogen-deficient” peptide radical that contained a radical site on the amide nitrogen in the peptide backbone with subsequent radical-induced cleavage at the Cα–C bonds. Cleavage at the Cα–C bond leads to the production of an a•/x fragment pair and the radical a• ions then undergo further hydrogen abstraction to form a ions after Cα–C bond cleavage. Since the Pro residue does not contain a nitrogen-centered radical site, Cα–C bond cleavage does not occur at this site. Alternatively, the specific cleavage of CO−N bonds leads to a b•/y fragment pair at Xxx−Pro which occurs via hydrogen abstraction from the Cα−H in the Pro residue. In contrast, “hydrogen-deficient” glycan radicals were generated by hydrogen abstraction from hydroxyl groups in glycans. Both glycosidic and cross-ring cleavages occurred as the result of the degradation of “hydrogen-deficient” glycan radicals. Cross-ring cleavage ions are potentially useful in linkage analysis, one of the most critical steps in the characterization of glycans. Moreover, isobaric glycans could be distinguished by structure specific ISD ions, and the molar ratio of glycan isomers in a mixture can be estimated from their fragment ions abundance ratios. MALDI-ISD with 5-NSA could be a useful method for the sequencing of peptides including the location of post-translational modifications, identification and semi-quantitative analysis of mixtures of glycan isomers. PMID:24860709

Spectroscopy and reactions of molecules important in chemical evolution

NASA Technical Reports Server (NTRS)

Becker, R. S.

1974-01-01

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Aerobic Hydrogen Production via Nitrogenase in Azotobacter vinelandii CA6

PubMed Central

Noar, Jesse; Loveless, Telisa; Navarro-Herrero, José Luis; Olson, Jonathan W.

2015-01-01

The diazotroph Azotobacter vinelandii possesses three distinct nitrogenase isoenzymes, all of which produce molecular hydrogen as a by-product. In batch cultures, A. vinelandii strain CA6, a mutant of strain CA, displays multiple phenotypes distinct from its parent: tolerance to tungstate, impaired growth and molybdate transport, and increased hydrogen evolution. Determining and comparing the genomic sequences of strains CA and CA6 revealed a large deletion in CA6's genome, encompassing genes related to molybdate and iron transport and hydrogen reoxidation. A series of iron uptake analyses and chemostat culture experiments confirmed iron transport impairment and showed that the addition of fixed nitrogen (ammonia) resulted in cessation of hydrogen production. Additional chemostat experiments compared the hydrogen-producing parameters of different strains: in iron-sufficient, tungstate-free conditions, strain CA6's yields were identical to those of a strain lacking only a single hydrogenase gene. However, in the presence of tungstate, CA6 produced several times more hydrogen. A. vinelandii may hold promise for developing a novel strategy for production of hydrogen as an energy compound. PMID:25911479

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

Pathways to Earth-like atmospheres. Extreme ultraviolet (EUV)-powered escape of hydrogen-rich protoatmospheres.

PubMed

Lammer, Helmut; Kislyakova, K G; Odert, P; Leitzinger, M; Schwarz, R; Pilat-Lohinger, E; Kulikov, Yu N; Khodachenko, M L; Güdel, M; Hanslmeier, M

2011-12-01

We discuss the evolution of the atmosphere of early Earth and of terrestrial exoplanets which may be capable of sustaining liquid water oceans and continents where life may originate. The formation age of a terrestrial planet, its mass and size, as well as the lifetime in the EUV-saturated early phase of its host star play a significant role in its atmosphere evolution. We show that planets even in orbits within the habitable zone of their host stars might not lose nebular- or catastrophically outgassed initial protoatmospheres completely and could end up as water worlds with CO2 and hydrogen- or oxygen-rich upper atmospheres. If an atmosphere of a terrestrial planet evolves to an N2-rich atmosphere too early in its lifetime, the atmosphere may be lost. We show that the initial conditions set up by the formation of a terrestrial planet and by the evolution of the host star's EUV and plasma environment are very important factors owing to which a planet may evolve to a habitable world. Finally we present a method for studying the discussed atmosphere evolution hypotheses by future UV transit observations of terrestrial exoplanets.

Design of a genetic algorithm for the simulated evolution of a library of asymmetric transfer hydrogenation catalysts.

PubMed

Vriamont, Nicolas; Govaerts, Bernadette; Grenouillet, Pierre; de Bellefon, Claude; Riant, Olivier

2009-06-15

A library of catalysts was designed for asymmetric-hydrogen transfer to acetophenone. At first, the whole library was submitted to evaluation using high-throughput experiments (HTE). The catalysts were listed in ascending order, with respect to their performance, and best catalysts were identified. In the second step, various simulated evolution experiments, based on a genetic algorithm, were applied to this library. A small part of the library, called the mother generation (G0), thus evolved from generation to generation. The goal was to use our collection of HTE data to adjust the parameters of the genetic algorithm, in order to obtain a maximum of the best catalysts within a minimal number of generations. It was namely found that simulated evolution's results depended on the selection of G0 and that a random G0 should be preferred. We also demonstrated that it was possible to get 5 to 6 of the ten best catalysts while investigating only 10 % of the library. Moreover, we developed a double algorithm making this result still achievable if the evolution started with one of the worst G0.

3D-hierarchical MoSe2 nanoarchitecture as a highly efficient electrocatalyst for hydrogen evolution

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu; Qi, Fei; Wang, Xinqiang; Zhang, Wanli; Li, Yanrong; Li, Xuesong

2017-06-01

Clean hydrogen split from water by hydrogen evolution reaction (HER) is significant for sustainability, environmental emissions, and energy security. So far, it is still a big challenge to develop highly efficient noble metal-free electrocatalysts with comparable HER efficiency to platinum-based catalysts, which are mainly hindered by the intrinsic electrocatalytic property and particularly the reasonable nanostructure design of the electrocatalyst. Here we report a newly-designed three-dimensional hierarchical MoSe2 nanoarchitecture (3D-MoSe2) with outstanding HER performance. The 3D-MoSe2 is grown by chemical vapor deposition method with using perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt as a seeding promoter. The as-grown 3D-MoSe2 nanoarchitecture is highly crystalline and constructed with curly few-layered vertical nanosheets onto the horizontal layer, which has much larger (~12 times) electrochemically active area and much smaller (only 2%) charge transfer resistance compared to conventional horizontal MoSe2 layer. With these advantages, the Tafel slope of 3D-MoSe2 can be as small as 47.3 mV/dev, which is the smallest record ever reported for pure MoSe2, even for pure two-dimensional transition metal dichalcogenides (2D-TMDs) catalysts. Furthermore, when 3D-MoSe2 is grown on the multiwall carbon nanotube film, its Tafel slope can be further reduced down to 32.5 mV/dec, which is close to the theoretical limit (29 mV/dec) of HER, and comparable to platinum-based electrocatalysts, making it promising as a highly efficient electrocatalyst for hydrogen evolution.

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

PubMed Central

Zhang, Yizeng; Chen, Zhiwu; Lu, Zhenya

2018-01-01

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. PMID:29690518

Three dimensional simulation of hydrogen chloride and hydrogen fluoride during the Airborne Arctic Stratospheric Expedition

NASA Technical Reports Server (NTRS)

Kaye, Jack A.; Rood, Richard B.; Stolarski, Richard S.; Douglass, Anne R.; Newman, Paul A.; Allen, Dale J.; Larson, Edmund M.; Coffey, Michael T.; Mankin, William G.; Toon, Geoffrey C.

1990-01-01

Simulations of the evolution of stratospheric distributions of hydrogen chloride (HCl) and hydrogen fluoride (HF) have been carried out for the period of the Airborne Arctic Stratospheric Expedition (AASE) with a three-dimensional chemistry-transport model. Simulations were performed assuming only homogeneous gas phase chemistry for HF and both homogeneous gas phase and heterogeneous chemistry for HCl. Results show heterogeneous loss of HCl is needed to provide agreement with infrared column measurements. Estimates of the impact of heterogeneous loss on the global HCl distribution are obtained from the model. Reductions of HCl due to heterogeneous loss are calculated to be localized to regions of high vorticity, even after more than a month of integration.

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

PubMed

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.

Effect of annealing ambience on the formation of surface/bulk oxygen vacancies in TiO2 for photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Hou, Lili; Zhang, Min; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

2018-01-01

The surface and bulk oxygen vacancy have a prominent effect on the photocatalytic performance of TiO2. In this study, TiO2 possessing different types and concentration of oxygen vacancies were prepared by annealing nanotube titanic acid (NTA) at various temperatures in air or vacuum atmosphere. TiO2 with the unitary bulk single-electron-trapped oxygen vacancies (SETOVs) formed when NTA were calcined in air. Whereas, TiO2 with both bulk and surface oxygen vacancies were obtained when NTA were annealed in vacuum. The series of TiO2 with different oxygen vacancies were systematically characterized by TEM, XRD, PL, XPS, ESR, and TGA. The PL and ESR analysis verified that surface oxygen vacancies and more bulk oxygen vacancies could form in vacuum atmosphere. Surface oxygen vacancies can trap electron and hinder the recombination of photo-generated charges, while bulk SETOVs act as the recombination center. The surface or bulk oxygen vacancies attributed different roles on the photo-absorbance and activity, leading that the sample of NTA-A400 displayed higher hydrogen evolution rate under UV light, whereas NTA-V400 displayed higher hydrogen evolution rate under visible light because bulk SETOVs can improve visible light absorption because sub-band formed by bulk SETOVs prompted the secondary transition of electron excited.

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

NASA Astrophysics Data System (ADS)

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.

Photocatalytic water splitting—The untamed dream: A review of recent advances

DOE PAGES

Jafari, Tahereh; Moharreri, Ehsan; Amin, Alireza Shirazi; ...

2016-07-09

Here, photocatalytic water splitting using sunlight is a promising technology capable of providing high energy yield without pollutant byproducts. Herein, we review various aspects of this technology including chemical reactions, physiochemical conditions and photocatalyst types such as metal oxides, sulfides, nitrides, nanocomposites, and doped materials followed by recent advances in computational modeling of photoactive materials. As the best-known catalyst for photocatalytic hydrogen and oxygen evolution, TiO 2 is discussed in a separate section, along with its challenges such as the wide band gap, large overpotential for hydrogen evolution, and rapid recombination of produced electron-hole pairs. Various approaches are addressed tomore » overcome these shortcomings, such as doping with different elements, heterojunction catalysts, noble metal deposition, and surface modification. Development of a photocatalytic corrosion resistant, visible light absorbing, defect-tuned material with small particle size is the key to complete the sunlight to hydrogen cycle efficiently. Computational studies have opened new avenues to understand and predict the electronic density of states and band structure of advanced materials and could pave the way for the rational design of efficient photocatalysts for water splitting. Future directions are focused on developing innovative junction architectures, novel synthesis methods and optimizing the existing active materials to enhance charge transfer, visible light absorption, reducing the gas evolution overpotential and maintaining chemical and physical stability« less

Molybdenum Carbide Nanoparticles Coated into the Graphene Wrapping N-Doped Porous Carbon Microspheres for Highly Efficient Electrocatalytic Hydrogen Evolution Both in Acidic and Alkaline Media.

PubMed

Wei, Huifang; Xi, Qiaoya; Chen, Xi'an; Guo, Daying; Ding, Feng; Yang, Zhi; Wang, Shun; Li, Juan; Huang, Shaoming

2018-03-01

Molybdenum carbide (Mo 2 C) is recognized as an alternative electrocatalyst to noble metal for the hydrogen evolution reaction (HER). Herein, a facile, low cost, and scalable method is provided for the fabrication of Mo 2 C-based eletrocatalyst (Mo 2 C/G-NCS) by a spray-drying, and followed by annealing. As-prepared Mo 2 C/G-NCS electrocatalyst displays that ultrafine Mo 2 C nanopartilces are uniformly embedded into graphene wrapping N-doped porous carbon microspheres derived from chitosan. Such designed structure offer several favorable features for hydrogen evolution application: 1) the ultrasmall size of Mo 2 C affords a large exposed active sites; 2) graphene-wrapping ensures great electrical conductivity; 3) porous structure increases the electrolyte-electrode contact points and lowers the charge transfer resistance; 4) N-dopant interacts with H + better than C atoms and favorably modifies the electronic structures of adjacent Mo and C atoms. As a result, the Mo 2 C/G-NCS demonstrates superior HER activity with a very low overpotential of 70 or 66 mV to achieve current density of 10 mA cm -2 , small Tafel slope of 39 or 37 mV dec -1 , respectively, in acidic and alkaline media, and high stability, indicating that it is a great potential candidate as HER electrocatalyst.

ZnO-dotted porous ZnS cluster microspheres for high efficient, Pt-free photocatalytic hydrogen evolution.

PubMed

Wu, Aiping; Jing, Liqiang; Wang, Jianqiang; Qu, Yang; Xie, Ying; Jiang, Baojiang; Tian, Chungui; Fu, Honggang

2015-03-09

The Pt-free photocatalytic hydrogen evolution (PHE) has been the focus in the photocatalysis field. Here, the ZnO-dotted porous ZnS cluster microsphere (PCMS) is designed for high efficient, Pt-free PHE. The PCMS is designed through an easy "controlling competitive reaction" strategy by selecting the thiourea as S(2-) source and Zn(Ac)₂·2H₂O as Zn source in ethylene glycol medium. Under suitable conditions, one of the PCMS, named PCMS-1, with high SBET specific area of 194 m(2)g(-1), microsphere size of 100 nm and grain size of 3 nm can be obtained. The formation of PCMS is verified by TEM, XAES, XPS, Raman and IR methods. Importantly, a series of the experiments and theoretical calculation demonstrate that the dotting of ZnO not only makes the photo-generated electrons/hole separate efficiently, but also results in the formation of the active catalytic sites for PHE. As a result, the PCMS-1 shows the promising activity up to 367 μmol h(-1) under Pt-free condition. The PHE activity has no obvious change after addition 1 wt.% Pt, implying the presence of active catalytic sites for hydrogen evolution in the PCMS-1. The easy synthesis process, low preparation cost of the PCMS makes their large potential for Pt-free PHE.

ZnO-dotted porous ZnS cluster microspheres for high efficient, Pt-free photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Wu, Aiping; Jing, Liqiang; Wang, Jianqiang; Qu, Yang; Xie, Ying; Jiang, Baojiang; Tian, Chungui; Fu, Honggang

2015-03-01

The Pt-free photocatalytic hydrogen evolution (PHE) has been the focus in the photocatalysis field. Here, the ZnO-dotted porous ZnS cluster microsphere (PCMS) is designed for high efficient, Pt-free PHE. The PCMS is designed through an easy ``controlling competitive reaction'' strategy by selecting the thiourea as S2- source and Zn(Ac)2.2H2O as Zn source in ethylene glycol medium. Under suitable conditions, one of the PCMS, named PCMS-1, with high SBET specific area of 194 m2g-1, microsphere size of 100 nm and grain size of 3 nm can be obtained. The formation of PCMS is verified by TEM, XAES, XPS, Raman and IR methods. Importantly, a series of the experiments and theoretical calculation demonstrate that the dotting of ZnO not only makes the photo-generated electrons/hole separate efficiently, but also results in the formation of the active catalytic sites for PHE. As a result, the PCMS-1 shows the promising activity up to 367 μmol h-1 under Pt-free condition. The PHE activity has no obvious change after addition 1 wt.% Pt, implying the presence of active catalytic sites for hydrogen evolution in the PCMS-1. The easy synthesis process, low preparation cost of the PCMS makes their large potential for Pt-free PHE.

A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

PubMed

Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

2017-07-18

The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

Shaping thin film growth and microstructure pathways via plasma and deposition energy: a detailed theoretical, computational and experimental analysis.

PubMed

Sahu, Bibhuti Bhusan; Han, Jeon Geon; Kersten, Holger

2017-02-15

Understanding the science and engineering of thin films using plasma assisted deposition methods with controlled growth and microstructure is a key issue in modern nanotechnology, impacting both fundamental research and technological applications. Different plasma parameters like electrons, ions, radical species and neutrals play a critical role in nucleation and growth and the corresponding film microstructure as well as plasma-induced surface chemistry. The film microstructure is also closely associated with deposition energy which is controlled by electrons, ions, radical species and activated neutrals. The integrated studies on the fundamental physical properties that govern the plasmas seek to determine their structure and modification capabilities under specific experimental conditions. There is a requirement for identification, determination, and quantification of the surface activity of the species in the plasma. Here, we report a detailed study of hydrogenated amorphous and crystalline silicon (c-Si:H) processes to investigate the evolution of plasma parameters using a theoretical model. The deposition processes undertaken using a plasma enhanced chemical vapor deposition method are characterized by a reactive mixture of hydrogen and silane. Later, various contributions of energy fluxes on the substrate are considered and modeled to investigate their role in the growth of the microstructure of the deposited film. Numerous plasma diagnostic tools are used to compare the experimental data with the theoretical results. The film growth and microstructure are evaluated in light of deposition energy flux under different operating conditions.

Understanding Combustion of H2/O2 Gases inside Nanobubbles Generated by Water Electrolysis Using Reactive Molecular Dynamic Simulations.

PubMed

Jain, S; Qiao, L

2018-06-21

This work explored the mechanism of spontaneous combustion of hydrogen-oxygen mixtures inside nanobubbles (which were generated by water electrolysis) using reactive molecular dynamic simulations based on the first-principles derived reactive force field ReaxFF. The effects of surface-assisted dissociation of H 2 and O 2 gases that produced H and O radicals were examined. Additionally, the ignition outcome and species evolution as a function of the initial system pressure (or bubble size) were studied. A significant amount of hydrogen peroxide (H 2 O 2 ), 6-140 times water (H 2 O), was observed in the combustion products. This was attributed to the low-temperature (∼300 K) and high-pressure (2-80 atm) conditions at which the chemical reactions were taking place. In addition, the rate of consumption of H 2 and O 2 molecules was found to increase with an increase in added H and O radical concentrations and initial system pressure. The rate at which heat was being lost from the combustion chamber (nanobubbles) was also compared to the rate at which heat was being released from the chemical reactions. Only a slight rise in the reaction temperature was observed (∼68 K), signifying that, at such small scales, heat losses dominate. The resulting chemistry was quite different from macroscopic combustion, which usually takes place at a much higher temperatures of above 1000 K.

Dilute alkali and hydrogen peroxide treatment of microwave liquefied rape straw residue for the extraction of cellulose nanocrystals

Treesearch

Xingyan Huang; Cornelis F. De Hoop; Feng Li; Jiulong Xie; Chung-Yun Hse; Jinqiu Qi; Yongze Jiang; Yuzhu Chen

2017-01-01

Microwave-assisted liquefaction of rape straw in methanol was conducted to collect the liquefied residues for the extraction of cellulose nanocrystals (CNCs).The liquefied residue with content of 23.44% from 180∘C/7.5 min was used to fibrillate CNCs with dilute alkali (2% NaOH) and hydrogen peroxide (5% H2O2...

Determination of trace nickel in hydrogenated cottonseed oil by electrothermal atomic absorption spectrometry after microwave-assisted digestion.

PubMed

Zhang, Gai

2012-01-01

Microwave digestion of hydrogenated cottonseed oil prior to trace nickel determination by electrothermal atomic absorption spectrometry (ETAAS) is proposed here for the first time. Currently, the methods outlined in U.S. Pharmacopeia 28 (USP28) or British Pharmacopeia (BP2003) are recommended as the official methods for analyzing nickel in hydrogenated cottonseed oil. With these methods the samples may be pre-treated by a silica or a platinum crucible. However, the samples were easily tarnished during sample pretreatment when using a silica crucible. In contrast, when using a platinum crucible, hydrogenated cottonseed oil acting as a reducing material may react with the platinum and destroy the crucible. The proposed microwave-assisted digestion avoided tarnishing of sample in the process of sample pretreatment and also reduced the cycle of analysis. The programs of microwave digestion and the parameters of ETAAS were optimized. The accuracy of the proposed method was investigated by analyzing real samples. The results were compared with the ones by pressurized-PTFE-bomb acid digestion and ones obtained by the U.S. Pharmacopeia 28 (USP28) method. The new method involves a relatively rapid matrix destruction technique compared with other present methods for the quantification of metals in oil. © 2011 Institute of Food Technologists®

Plasma-assisted oxide removal from ruthenium-coated EUV optics

NASA Astrophysics Data System (ADS)

Dolgov, A.; Lee, C. J.; Bijkerk, F.; Abrikosov, A.; Krivtsun, V. M.; Lopaev, D.; Yakushev, O.; van Kampen, M.

2018-04-01

An experimental study of oxide reduction at the surface of ruthenium layers on top of multilayer mirrors and thin Ru/Si films is presented. Oxidation and reduction processes were observed under conditions close to those relevant for extreme ultraviolet lithography. The oxidized ruthenium surface was exposed to a low-temperature hydrogen plasma, similar to the plasma induced by extreme ultraviolet radiation. The experiments show that hydrogen ions are the main reducing agent. Furthermore, the addition of hydrogen radicals increases the reduction rate beyond that expected from simple flux calculations. We show that low-temperature hydrogen plasmas can be effective for reducing oxidized top surfaces. Our proof-of-concept experiments show that an in situ, EUV-generated plasma cleaning technology is feasible.

Hydrogen-assisted stable crack growth in iron-3 wt% silicon steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marrow, T.J.; Prangnell, P.; Aindow, M.

1996-08-01

Observations of internal hydrogen cleavage in Fe-3Si are reported. Hydrogen-assisted stable crack growth (H-SCG) is associated with cleavage striations of a 300 nm spacing, observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). High resolution SEM revealed finer striations, previously undetected, with a spacing of approximately 30 nm. These were parallel to the coarser striations. Scanning tunneling microscopy (STM) also showed the fine striation spacing, and gave a striation height of approximately 15 nm. The crack front was not parallel to the striations. Transmission electron microscopy (TEM) of crack tip plastic zones showed {l_brace}112{r_brace} and {l_brace}110{r_brace} slip, withmore » a high dislocation density (around 10{sup 14}m{sup {minus}2}). The slip plane spacing was approximately 15--30 nm. Parallel arrays of high dislocation density were observed in the wake of the hydrogen cleavage crack. It is concluded that H-ScG in Fe-3Si occurs by periodic brittle cleavage on the {l_brace}001{r_brace} planes. This is preceded by dislocation emission. The coarse striations are produced by crack tip blunting and the fine striations by dislocations attracted by image forces to the fracture surface after cleavage. The effects of temperature, pressure and yield strength on the kinetics of H-SCG can be predicted using a model for diffusion of hydrogen through the plastic zone.« less

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage.

PubMed

Wang, Xianfu; Xie, Yiming; Tang, Kai; Wang, Chao; Yan, Chenglin

2018-05-11

Hydrogen ions are ideal charge carriers for rechargeable batteries due to their small ionic radius and wide availability. However, little attention has been paid to hydrogen-ion storage devices because they generally deliver relatively low Coulombic efficiency as a result of the hydrogen evolution reaction that occurs in an aqueous electrolyte. Herein, we successfully demonstrate that hydrogen ions can be electrochemically stored in an inorganic molybdenum trioxide (MoO 3 ) electrode with high Coulombic efficiency and stability. The as-obtained electrode exhibits ultrafast hydrogen-ion storage properties with a specific capacity of 88 mA hg -1 at an ultrahigh rate of 100 C. The redox reaction mechanism of the MoO 3 electrode in the hydrogen-ion cell was investigated in detail. The results reveal a conversion reaction of the MoO 3 electrode into H 0.88 MoO 3 during the first hydrogen-ion insertion process and reversible intercalation/deintercalation of hydrogen ions between H 0.88 MoO 3 and H 0.12 MoO 3 during the following cycles. This study reveals new opportunities for the development of high-power energy storage devices with lightweight elements. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V.; Shukla, S.

2016-01-15

Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows thatmore » 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.« less

Effect of fermentation temperature on hydrogen production from cow waste slurry by using anaerobic microflora within the slurry.

PubMed

Yokoyama, Hiroshi; Waki, Miyoko; Moriya, Naoko; Yasuda, Tomoko; Tanaka, Yasuo; Haga, Kiyonori

2007-02-01

We examined hydrogen production from a dairy cow waste slurry (13.4 g of volatile solids per liter) by batch cultures in a temperature range from 37 to 85 degrees C, using microflora naturally present within the slurry. Without the addition of seed bacteria, hydrogen was produced by simply incubating the slurry, using the microflora within the slurry. Interestingly, two peaks of fermentation temperatures for hydrogen production from the slurry were observed at 60 and 75 degrees C (392 and 248 ml H2 per liter of slurry, respectively). After the termination of the hydrogen evolution, the microflora cultured at 60 degrees C displayed hydrogen-consuming activity, but hydrogen-consuming activity of the microflora cultured at 75 degrees C was not detected, at least for 24 days. At both 60 and 75 degrees C, the main by-product was acetate, and the optimum pH of the slurry for hydrogen production was around neutral. Bacteria related to hydrogen-producing moderate and extreme thermophiles, Clostridium thermocellum and Caldanaerobacter subterraneus, were detected in the slurries cultured at 60 and 75 degrees C, respectively, by denaturing gradient gel electrophoresis analyses, using the V3 region of 16S rDNA.

The Evolution of Instructional Design Principles for Intelligent Computer-Assisted Instruction.

ERIC Educational Resources Information Center

Dede, Christopher; Swigger, Kathleen

1988-01-01

Discusses and compares the design and development of computer assisted instruction (CAI) and intelligent computer assisted instruction (ICAI). Topics discussed include instructional systems design (ISD), artificial intelligence, authoring languages, intelligent tutoring systems (ITS), qualitative models, and emerging issues in instructional…

Strategic Communication in Pursuit of National Interests

DTIC Science & Technology

2012-03-22

the tsunami-induced loss of electricity triggered a hydrogen explosion at Fukushima Daiichi Nuclear Power Plant, further compounding the disaster .38...assistance and disaster relief. Operation Tomodachi conducted in Japan after the devastating earthquake and tsunami in spring of 2011 provided an...humanitarian assistance and disaster relief. Operation Tomodachi conducted in Japan after the devastating earthquake and tsunami in spring of 2011 provided

Characterization and evaluation of cadmium indate photocatalysts for solar hydrogen conversion

NASA Astrophysics Data System (ADS)

Thornton, Jason M.

Alternative energy sources are needed to respond to the continued increase in the global energy needs and a potential decrease in the future supplies of fossil fuels. Solar hydrogen conversion in which sunlight is harnessed to split water into H2 fuel and O2 is a promising source of energy because it is renewable and produces no CO2. A number of semiconducting oxide materials have shown promise for overall water splitting for the generation of hydrogen over the years. In this work we focus on the synthesis and analysis of undoped and C-doped cadmium indate (CdIn2O 4) thin films and nanoparticle powders, and their evaluation for hydrogen evolution via water splitting. The catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis, scanning electron microscopy (SEM), and BET surface adsorption measurements. Spray and sol-gel pyrolysis methods were used for the synthesis of the materials. Doping C into CdIn 2O4 leads to enhancement in light absorption and the band gap was determined to be 2.3 eV in the nanoparticle powders. Carbon doping improves the photocurrent density by 33% and the H2 evolution rate by a factor of two. The performance of C-doped CdIn2O4 were optimized with respect to several synthetic parameters, including the In:Cd molar ratio and glucose concentration, calcination temperature, and the film thickness while the nanoparticles were additionally optimized to F127 concentration and platinum cocatalyst loading. Hydrogen generation activity was evaluated under UV-visible irradiation without the use of a sacrificial reagent and using bandpass filters the quantum efficiency was determined. Compared to platinized TiO2 in methanol C-CdIn2O4 showed a 4-fold increase in hydrogen production. The material was capable of hydrogen generation using visible light only and with good efficiency even at 510 nm. Using natural sunlight illumination, the material evolved hydrogen at a rate of 17 micromol h-1. These studies show carbon-doped cadmium indate to be a promising catalyst for solar hydrogen conversion.

Superior performance of borocarbonitrides, BxCyNz , as stable, low-cost metal-free electrocatalysts for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Chakraborty, Himanshu; Chhetri, Manjeet; Maitra, Somak; Waghmare, Umesh; Rao, C. N. R.

We report superior hydrogen evolution activity of metal-free borocarbonitride (BCN) catalysts. The highly positive onset potential (-56 mV vs. RHE) and the current density of 10 mAcm2 at an overpotential of 70 mV exhibited by a carbon-rich BCN with the composition BC7N2 demonstrates the extraordinary electrocatalytic activity at par with Pt. Theoretical studies throw light on the cause of high activity of this composition. The high activity and good stability of BCN's surpass the characteristics of other metal-free catalysts reported in recent literature. an Energy Frontier Research Centre funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0012575.

Conjugated Polymers: Catalysts for Photocatalytic Hydrogen Evolution.

PubMed

Zhang, Guigang; Lan, Zhi-An; Wang, Xinchen

2016-12-19

Conjugated polymers, comprising fully π-conjugated systems, present a new generation of heterogeneous photocatalysts for solar-energy utilization. They have three key features, namely robustness, nontoxicity, and visible-light activity, for photocatalytic processes, thus making them appealing candidates for scale-up. Presented in this Minireview, is a brief summary on the recent development of various promising polymer photocatalysts for hydrogen evolution from aqueous solutions, including linear polymers, planarized polymers, triazine/heptazine polymers, and other related organic conjugated semiconductors, with a particular focus on the rational manipulation in the composition, architectures, and optical and electronic properties that are relevant to photophysical and photochemical properties. Some future trends and prospects for organic conjugated photocatalysts in artificial photosynthesis, by water splitting, are also envisaged. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-cost industrially available molybdenum boride and carbide as "platinum-like" catalysts for the hydrogen evolution reaction in biphasic liquid systems.

PubMed

Scanlon, Micheál D; Bian, Xiaojun; Vrubel, Heron; Amstutz, Véronique; Schenk, Kurt; Hu, Xile; Liu, BaoHong; Girault, Hubert H

2013-02-28

Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

Biomass-derived high-performance tungsten-based electrocatalysts on graphene for hydrogen evolution

DOE PAGES

Meng, Fanke; Hu, Enyuan; Zhang, Lihua; ...

2015-08-05

We report a new class of highly active and stable tungsten-based catalysts to replace noble metal materials for the hydrogen evolution reaction (HER) in an acidic electrolyte. The catalyst is produced by heating an earth-abundant and low-cost mixture of ammonium tungstate, soybean powder and graphene nanoplatelets (WSoyGnP). The catalyst compound consists of tungsten carbide (W₂C and WC) and tungsten nitride (WN) nanoparticles decorated on graphene nanoplatelets. The catalyst demonstrates an overpotential (η₁₀, the potential at a current density of 10 mA cm⁻²) of 0.105 V, which is the smallest among tungsten-based HER catalysts in acidic media. The coupling with graphenemore » significantly reduces the charge transfer resistance and increases the active surface area of the product, which are favorable for enhancing the HER activity. Therefore, the approach of employing biomass and other less expensive materials as precursors for the production of catalysts with high HER activity provides a new path for the design and development of efficient catalysts for the hydrogen production industry.« less

Heterogeneous Bimetallic Phosphide/Sulfide Nanocomposite for Efficient Solar-Energy-Driven Overall Water Splitting.

PubMed

Xin, Yanmei; Kan, Xiang; Gan, Li-Yong; Zhang, Zhonghai

2017-10-24

Solar-driven overall water splitting is highly desirable for hydrogen generation with sustainable energy sources, which need efficient, earth-abundant, robust, and bifunctional electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, we propose a heterogeneous bimetallic phosphide/sulfide nanocomposite electrocatalyst of NiFeSP on nickel foam (NiFeSP/NF), which shows superior electrocatalytic activity of low overpotentials of 91 mV at -10 mA cm -2 for HER and of 240 mV at 50 mA cm -2 for OER in 1 M KOH solution. In addition, the NiFeSP/NF presents excellent overall water splitting performance with a cell voltage as low as 1.58 V at a current density of 10 mA cm -2 . Combining with a photovoltaic device of a Si solar cell or integrating into photoelectrochemical (PEC) systems, the bifunctional NiFeSP/NF electrocatalyst implements unassisted solar-driven water splitting with a solar-to-hydrogen conversion efficiency of ∼9.2% and significantly enhanced PEC performance, respectively.

On the derivation of a simple dynamic model of anaerobic digestion including the evolution of hydrogen.

PubMed

Giovannini, Giannina; Sbarciog, Mihaela; Steyer, Jean-Philippe; Chamy, Rolando; Vande Wouwer, Alain

2018-05-01

Hydrogen has been found to be an important intermediate during anaerobic digestion (AD) and a key variable for process monitoring as it gives valuable information about the stability of the reactor. However, simple dynamic models describing the evolution of hydrogen are not commonplace. In this work, such a dynamic model is derived using a systematic data driven-approach, which consists of a principal component analysis to deduce the dimension of the minimal reaction subspace explaining the data, followed by an identification of the kinetic parameters in the least-squares sense. The procedure requires the availability of informative data sets. When the available data does not fulfill this condition, the model can still be built from simulated data, obtained using a detailed model such as ADM1. This dynamic model could be exploited in monitoring and control applications after a re-identification of the parameters using actual process data. As an example, the model is used in the framework of a control strategy, and is also fitted to experimental data from raw industrial wine processing wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Structure and evolution of Uranus and Neptune

NASA Technical Reports Server (NTRS)

Hubbard, W. B.; Macfarlane, J. J.

1980-01-01

Three-layer interior models of Uranus and Neptune with central rocky cores, mantles of water, methane, and ammonia (the 'ices'), and outer envelopes primarily composed of hydrogen and helium are presented. The models incorporate a new H2O equation of state based on experimental data which is considerably 'softer' than previous H2O equations of state. Corrections for interior temperatures approximately 5000 K are included in the models, and the thermal evolution of both planets is investigated using recent heat flow measurements. It is found that the evolutionary considerations are consistent with gravitational field data in supporting models with approximately solar abundances of 'ice' and 'rock'. Evolutionary considerations indicate that initial temperatures and luminosities for Uranus and Neptune were not substantially higher than the present value. Both planets apparently have relatively small approximately 1-2 earth masses) hydrogen-helium envelopes, with Neptune's envelope smaller than Uranus'. A monotonic trend is evident among the Jovian planets: all have central rock-ice cores of approximately 15 earth masses, but with hydrogen-helium envelopes which decrease in mass from Jupiter to Saturn to Uranus to Neptune.

3D ordered porous MoxC (x = 1 or 2) for advanced hydrogen evolution and Li storage.

PubMed

Yu, Hong; Fan, Haosen; Wang, Jiong; Zheng, Yun; Dai, Zhengfei; Lu, Yizhong; Kong, Junhua; Wang, Xin; Kim, Young Jin; Yan, Qingyu; Lee, Jong-Min

2017-06-01

3D ordered porous structures of Mo x C are prepared with different Mo to C ratios and tested for two possible promising applications: hydrogen evolution reaction (HER) through water splitting and lithium ion batteries (LIBs). Mo 2 C and MoC with 3D periodic ordered structures are prepared with a similar process but different precursors. The 3D ordered porous MoC exhibits excellent cycling stability and rate performance as an anode material for LIBs. A discharge capacity of 450.9 mA h g -1 is maintained up to 3000 cycles at 10.0 A g -1 . The Mo 2 C with a similar ordered porous structure shows impressive electrocatalytic activity for the HER in neutral, alkaline and acidic pH solutions. In particular, Mo 2 C shows an onset potential of only 33 mV versus a reversible hydrogen electrode (RHE) and a Tafel slope of 42.5 mV dec -1 in a neutral aqueous solution (1.0 M phosphate buffer solution), which is approaching that of the commercial Pt/C catalyst.

Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions.

PubMed

Gnanakumar, Edwin S; Ng, Wesley; Coşkuner Filiz, Bilge; Rothenberg, Gadi; Wang, Sheng; Xu, Hualong; Pastor-Pérez, Laura; Pastor-Blas, M Mercedes; Sepúlveda-Escribano, Antonio; Yan, Ning; Shiju, N Raveendran

2017-11-23

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO 2 supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

TAC Evaluation Assistance: A Ten-Year Evolution from Accountability to Program Improvement.

ERIC Educational Resources Information Center

Yap, Kim O.

The Title I/Chapter 1 Technical Assistance Centers (TACs) were originally created to provide assistance to state and local education agencies in implementing the Title I evaluation and reporting system. However, over a 10-year period, TAC role has changed significantly. Its service foci have evolved from providing evaluation assistance to helping…

Volcano plots in hydrogen electrocatalysis - uses and abuses.

PubMed

Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth; Schmickler, Wolfgang

2014-01-01

Sabatier's principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier's principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst.

Volcano plots in hydrogen electrocatalysis – uses and abuses

PubMed Central

Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth

2014-01-01

Summary Sabatier’s principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier’s principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst. PMID:24991521

DOE Office of Scientific and Technical Information (OSTI.GOV)

García, Abraham; Cotto, María; Duconge, José

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

New Photocatalysts for Hydrogen Production; Nuevos Fotocatalizadores para la Producción de Hidrógeno

DOE PAGES

García, Abraham; Cotto, María; Duconge, José; ...

2014-06-10

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

Gas-phase evolution of Ar/H2O and Ar/CH4 dielectric barrier discharge plasmas

NASA Astrophysics Data System (ADS)

Barni, Ruggero; Riccardi, Claudia

2018-04-01

We present some experimental results of an investigation aimed to hydrogen production with atmospheric pressure plasmas, based on the use of dielectric barrier discharges, fed with a high-voltage alternating signal at frequency 30-50 kHz, in mixtures of methane or water vapor diluted in argon. The plasma gas-phase of the discharge was investigated by means of optical and electrical diagnostics. The emission spectra of the discharges was measured with a wide band spectrometer and a photosensor module, based on a photomultiplier tube. A Rogowski coil allowed to measure the electric current flowing into the circuit and a high voltage probe was employed for evaluating the voltage at the electrodes. The analysis of the signals of voltage and current shows the presence of microdischarges between the electrodes in two alternating phases during the period of oscillation of the applied voltage. The hydrogen concentration in the gaseous mixture was measured too. Besides this experimental campaign, we present also results from a numerical modeling of chemical kinetics in the gas-phase of Ar/H2O and Ar/CH4 plasmas. The simulations were conducted under conditions of single discharge to study the evolution of the system and of fixed frequency repeated discharging. In particular in Ar/H2O mixtures we could study the evolution from early atomic dissociation in the discharge, to longer time scales, when chemical reactions take place producing an increase of the density of species such as OH, H2O2 and subsequently of H and H2. The results of numerical simulations provide some insights into the evolution happening in the plasma gas-phase during the hydrogen reforming process.

Synthesis, characterization and electrocatalytic properties of delafossite CuGaO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Jahangeer; Department of Chemistry, College of Science, King Saud University, Riyadh 11451; Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu

2016-10-15

Delafossite CuGaO{sub 2} has been employed as photocatalysts for solar cells, but their electrocatalytic properties have not been extensively studied, especially no comparison among samples made by different synthesis routes. Herein, we first reported the successful synthesis of delafossite CuGaO{sub 2} particles with three different morphologies, i.e. nanocrystalline hexagons, sub-micron sized plates and micron–sized particles by a modified hydrothermal method at 190 °C for 60 h [1–3], a sono-chemical method followed by firing at 850 °C for 48 h, and a solid state route at 1150 °C, respectively. Morphology, composition and phase purity of the synthesized samples was confirmed bymore » powder X-ray diffraction and Raman spectroscopic studies, and then their electrocatalytic performance as active and cost effective electrode materials to the oxygen and hydrogen evolution reactions in 0.5 M KOH electrolyte versus Ag/AgCl was investigated and compared under the same conditions for the first time. The nanocrystalline CuGaO{sub 2} hexagons show enhanced electrocatalytic activity than the counterpart sub-micron sized plates and micron-sized particles. - Graphical abstract: Representative delafossite CuGaO2 samples with sub-micron sized plate and nanocrystalline hexagon morphologies accompanying with chronoamperometric voltammograms for oxygen evolution reaction and hydrogen evolution reaction in 0.5 M KOH electrolyte after purged with N{sub 2} gas. - Highlights: • Delafossite CuGaO{sub 2} with three morphologies has been synthesized. • Phase purity of the synthesized samples was confirmed. • Comparison on their electrocatalytic properties was made for the first time. • Their use as electrodes for oxygen and hydrogen evolution reactions was evaluated. • Nanocrystalline CuGaO{sub 2} hexagons show highest electrocatalytic activity.« less

Ultraviolet Light-Assisted Copper Oxide Nanowires Hydrogen Gas Sensor

NASA Astrophysics Data System (ADS)

Sihar, Nabihah; Tiong, Teck Yaw; Dee, Chang Fu; Ooi, Poh Choon; Hamzah, Azrul Azlan; Mohamed, Mohd Ambri; Majlis, Burhanuddin Yeop

2018-05-01

We fabricated copper oxide nanowires (CuO NWs) ultraviolet (UV) light-assisted hydrogen gas sensor. The fabricated sensor shows promising sensor response behavior towards 100 ppm of H2 at room temperature and elevated temperature at 100 °C when exposed to UV light (3.0 mW/cm2). One hundred-cycle device stability test has been performed, and it is found that for sample elevated at 100 °C, the UV-activated sample achieved stability in the first cycle as compared to the sample without UV irradiation which needed about 10 cycles to achieve stability at the initial stage, whereas the sample tested at room temperature was able to stabilize with the aid of UV irradiation. This indicates that with the aid of UV light, after some "warming up" time, it is possible for the conventional CuO NW sensor which normally work at elevated temperature to function at room temperature because UV source is speculated to play a dominant role to increase the interaction of the surface of CuO NWs and hydrogen gas molecules absorbed after the light exposure.

Hydrogenation-assisted graphene origami and its application in programmable molecular mass uptake, storage, and release.

PubMed

Zhu, Shuze; Li, Teng

2014-03-25

The malleable nature of atomically thin graphene makes it a potential candidate material for nanoscale origami, a promising bottom-up nanomanufacturing approach to fabricating nanobuilding blocks of desirable shapes. The success of graphene origami hinges upon precise and facile control of graphene morphology, which still remains as a significant challenge. Inspired by recent progresses on functionalization and patterning of graphene, we demonstrate hydrogenation-assisted graphene origami (HAGO), a feasible and robust approach to enabling the formation of unconventional carbon nanostructures, through systematic molecular dynamics simulations. A unique and desirable feature of HAGO-enabled nanostructures is the programmable tunability of their morphology via an external electric field. In particular, we demonstrate reversible opening and closing of a HAGO-enabled graphene nanocage, a mechanism that is crucial to achieve molecular mass uptake, storage, and release. HAGO holds promise to enable an array of carbon nanostructures of desirable functionalities by design. As an example, we demonstrate HAGO-enabled high-density hydrogen storage with a weighted percentage exceeding the ultimate goal of US Department of Energy.

Ultraviolet Light-Assisted Copper Oxide Nanowires Hydrogen Gas Sensor.

PubMed

Sihar, Nabihah; Tiong, Teck Yaw; Dee, Chang Fu; Ooi, Poh Choon; Hamzah, Azrul Azlan; Mohamed, Mohd Ambri; Majlis, Burhanuddin Yeop

2018-05-15

We fabricated copper oxide nanowires (CuO NWs) ultraviolet (UV) light-assisted hydrogen gas sensor. The fabricated sensor shows promising sensor response behavior towards 100 ppm of H 2 at room temperature and elevated temperature at 100 °C when exposed to UV light (3.0 mW/cm 2 ). One hundred-cycle device stability test has been performed, and it is found that for sample elevated at 100 °C, the UV-activated sample achieved stability in the first cycle as compared to the sample without UV irradiation which needed about 10 cycles to achieve stability at the initial stage, whereas the sample tested at room temperature was able to stabilize with the aid of UV irradiation. This indicates that with the aid of UV light, after some "warming up" time, it is possible for the conventional CuO NW sensor which normally work at elevated temperature to function at room temperature because UV source is speculated to play a dominant role to increase the interaction of the surface of CuO NWs and hydrogen gas molecules absorbed after the light exposure.

Hole-Accepting-Ligand-Modified CdSe QDs for Dramatic Enhancement of Photocatalytic and Photoelectrochemical Hydrogen Evolution by Solar Energy.

PubMed

Li, Xu-Bing; Liu, Bin; Wen, Min; Gao, Yu-Ji; Wu, Hao-Lin; Huang, Mao-Yong; Li, Zhi-Jun; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

2016-04-01

Solar H 2 evolution of CdSe QDs can be significantly enhanced simply by introducing a suitable hole-accepting-ligand for achieving efficient hole extraction and transfer at the nanoscale interfaces, which opens an effective pathway for dissociation of excitons to generate long-lived charge separation, thus improving the solar-to-fuel conversion efficiency.

SSME - Materials and Methods for Addressing High-Pressure Hydrogen Embrittlement

NASA Technical Reports Server (NTRS)

Matejczk, Daniel; Russell, Dale; Frandsen, Jon; Swanson, Greg

2010-01-01

From the humid, corrosion-friendly atmosphere of KSC, to the extreme heat of ascent, to the cold vacuum of space, the Space Shuttle faced one hostile environment after another. One of those harsh environments the hydrogen environment existed within the shuttle itself. Liquid hydrogen was the fuel that powered the shuttle s complex, powerful, and reusable main engine. Hydrogen provided the high specific impulse the bang per pound of fuel needed to perform the shuttle s heavy lifting duties. Hydrogen, however, was also a potential threat to the very metal of the propulsion system that used it. The diffusion of hydrogen atoms into a metal can make it more brittle and prone to cracking a process called hydrogen embrittlement. This effect can reduce the toughness of carefully selected and prepared materials. A concern that exposure to hydrogen might encourage crack growth was present from the beginning of the Space Shuttle Program, but the rationale for using hydrogen was compelling. This paper outlines the material characterization, anomaly resolution, and path to understanding of hydrogen embrittlement on superalloys through the course of the SSME program. Specific examples of nickel alloy turbine housings and single crystal turbine blades are addressed. The evolution of fracture mechanics analytical methods is also addressed.

Mechanical behavior of NiTi arc wires under pseudoelastic cycling and cathodically hydrogen charging

NASA Astrophysics Data System (ADS)

Sarraj, R.; Hassine, T.; Gamaoun, F.

2018-01-01

NiTi wires are mainly used to design orthodontic devices. However, they may be susceptible to a delayed fracture while they are submitted to cyclic loading with the presence of hydrogen in the oral cavity. Hydrogen may cause the embrittlement of the structure, leading to lower ductility and to a change in transformation behavior. The aim of the present study is to predict the NiTi behavior under cyclic loading with hydrogen charging. One the one hand, samples are submitted to superelastic cyclic loading, which results in investigating their performance degradations. On the other hand, after hydrogen charging, cyclic tensile aging tests are carried out on NiTi orthodontic wires at room temperature in the air. During cyclic loading, we notice that the critical stress for the martensite transformation evolves, the residual strain is accumulated in the structure and the hysteresis loop changes. Thus, via this work, we can assume that the embrittlement is due to the diffusion of hydrogen and the generation of dislocations after aging. The evolution of mechanical properties of specimens becomes more significant with hydrogen charging rather than without it.

Cyanobacterial Hydrogenases and Hydrogen Metabolism Revisited: Recent Progress and Future Prospects

PubMed Central

Khanna, Namita; Lindblad, Peter

2015-01-01

Cyanobacteria have garnered interest as potential cell factories for hydrogen production. In conjunction with photosynthesis, these organisms can utilize inexpensive inorganic substrates and solar energy for simultaneous biosynthesis and hydrogen evolution. However, the hydrogen yield associated with these organisms remains far too low to compete with the existing chemical processes. Our limited understanding of the cellular hydrogen production pathway is a primary setback in the potential scale-up of this process. In this regard, the present review discusses the recent insight around ferredoxin/flavodoxin as the likely electron donor to the bidirectional Hox hydrogenase instead of the generally accepted NAD(P)H. This may have far reaching implications in powering solar driven hydrogen production. However, it is evident that a successful hydrogen-producing candidate would likely integrate enzymatic traits from different species. Engineering the [NiFe] hydrogenases for optimal catalytic efficiency or expression of a high turnover [FeFe] hydrogenase in these photo-autotrophs may facilitate the development of strains to reach target levels of biohydrogen production in cyanobacteria. The fundamental advancements achieved in these fields are also summarized in this review. PMID:26006225

Isotope composition and volume of Earth's early oceans.

PubMed

Pope, Emily C; Bird, Dennis K; Rosing, Minik T

2012-03-20

Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

SEMICONDUCTOR TECHNOLOGY: Influence of hydrogenation on the dark current mechanism of HgCdTe photovoltaic detectors

NASA Astrophysics Data System (ADS)

Hui, Qiao; Weida, Hu; Zhenhua, Ye; Xiangyang, Li; Haimei, Gong

2010-03-01

The influence of hydrogenation on the dark current mechanism of HgCdTe photovoltaic detectors is studied. The hydrogenation is achieved by exposing samples to a H2/Ar plasma atmosphere that was produced during a reactive ion etching process. A set of variable-area photomask was specially designed to evaluate the hydrogenation effect. It was found that the current-voltage characteristics were gradually improved when detectors were hydrogenated by different areas. The fitting results of experimental results at reverse bias conditions sustained that the improvement of current-voltage curves was due to the suppression of trap assisted tunneling current and the enhancement of minority lifetime in the depletion region. It was also found that the dominative forward current was gradually converted from a generation-recombination current to a diffusion current with the enlargement of the hydrogenation area, which was infered from the ideality factors by abstraction of forward resistance-voltage curves of different detectors.

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound.

PubMed

González-García, José; Banks, Craig E; Sljukić, Biljana; Compton, Richard G

2007-04-01

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Hydrogen production from alcohol reforming in a microwave ‘tornado’-type plasma

NASA Astrophysics Data System (ADS)

Tatarova, E.; Bundaleska, N.; Dias, F. M.; Tsyganov, D.; Saavedra, R.; Ferreira, C. M.

2013-12-01

In this work, an experimental investigation of microwave plasma-assisted reforming of different alcohols is presented. A microwave (2.45 GHz) ‘tornado’-type plasma with a high-speed tangential gas injection (swirl) at atmospheric pressure is applied to decompose alcohol molecules, namely methanol, ethanol and propanol, and to produce hydrogen-rich gas. The reforming efficiency is investigated both in Ar and Ar+ water vapor plasma environments. The hydrogen yield dependence on the partial alcohol flux is analyzed. Mass spectrometry and Fourier transform infrared spectroscopy are used to detect the outlet gas products from the decomposition process. Hydrogen, carbon monoxide, carbon dioxide and solid carbon are the main decomposition by-products. A significant increase in the hydrogen production rate is observed with the addition of a small amount of water. Furthermore, optical emission spectroscopy is applied to detect the radiation emitted by the plasma and to estimate the gas temperature and electron density.

Equilibrium and diffusion studies of metal-hydrogen systems

NASA Astrophysics Data System (ADS)

Maroevic, Petar

Several new methods and models have been developed pertaining to equilibrium properties of hydrogen in random binary substitutional alloys at room and lower temperatures, describing both statistics and kinetics of hydrogen in them. They represent a solution to the problem of the complete Fermi-Dirac description which is physically appropriate for these systems. Hydrogen diffusion which proceeds via lattice assisted quantum tunneling at room and lower temperatures requires a new and different description from the one based on the thermal hopping picture, which pertains only to relatively high temperatures. It is also shown that the analogs of the solution to the Fermi-Dirac problem of hydrogen can be successfully applied to the description of vacancies in a hydrogenated system, a phenomena known to occur due to high hydrogen-vacancy binding energies and the creation of hydrogen-vacancy clusters. The solution based on this model applies to much lower temperatures and higher concentrations than the tradition alone. This methodology has also been applied to the surface problem where very large vacancy and hydrogen concentrations occur. This is of special importance since mechanical properties are known to be greatly affected by the surface. As another consequence of hydrogen induced vacancies, hydrogen induced lattice migration (HILM) occurs. This has been demonstrated in our electrical resistivity study of palladium wires where recrystallization and annealing effects were observed upon hydrogen-heat-treatment (HHT).

Enhanced photo-assistant electrocatalysis of anodization TiO2 nanotubes via surrounded surface decoration with MoS2 for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Tian, Yuanyuan; Song, Ye; Dou, Meiling; Ji, Jing; Wang, Feng

2018-03-01

A highly ordered TiO2 nanotube array covered with MoS2 is fabricated through a facile anodization of a metallic Ti followed by electrochemical deposition approach. The morphologies characterization of v-TiO2@MoS2 indicate that a whole scale of 1D TiO2nanotube uniformly covered with the MoS2 layer inside and outside, and the pathway inside the TiO2nanotube is kept flow-through. The as-synthesized v-TiO2@MoS2 hybrid exhibits higher efficient and stable visible light activities than that of either pure TiO2 nanotubes or nv-TiO2@MoS2 nanostructures. By electrochemical measurements such as linear sweep voltammetry(LSV) and electrochemical impedance spectroscope (EIS) under light illumination or in dark, we find that the v-TiO2@MoS2hybrid shows markedly enhanced photoelectrochemical performance. Furthermore, we compare the electrocatalytic behavior of v-TiO2@MoS2under illumination in H2SO4/Lactic acid within Na2S/NaSO3 solution. The results show that the photo-assistant electrocatalytic activity in acidic environment is much better than in alkaline environment. The highly directional and orthogonal separation of charge carriers between TiO2 nanotubes and MoS2 layer, together with maximally exposed MoS2 edges, light harvesting and junctions formed between TiO2 and MoS2 is supposed to be mainly responsible for the enhanced photo-assistant electrocatalytic activity of v-TiO2@MoS2.

Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

DOEpatents

Kunz, Harold R.; Breault, Richard D.

1993-01-01

An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

Ortho- and para-hydrogen in dense clouds, protoplanets, and planetary atmospheres

NASA Technical Reports Server (NTRS)

Decampli, W. M.; Cameron, A. G. W.; Bodenheimer, P.; Black, D. C.

1978-01-01

If ortho- and para-hydrogen achieve a thermal ratio on dynamical time scales in a molecular hydrogen cloud, then the specific heat is high enough in the temperature range 35-70 K to possibly induce hydrodynamic collapse. The ortho-para ratio in many interstellar cloud fragments is expected to meet this condition. The same may have been true for the primitive solar nebula. Detailed hydrodynamic and hydrostatic calculations are presented that show the effects of the assumed ortho-para ratio on the evolution of Jupiter during its protoplanetary phase. Some possible consequences of a thermalized ortho-para ratio in the atmospheres of the giant planets are also discussed.

Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

DOEpatents

Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

DOEpatents

Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Synthesis and catalytic activity of the metastable phase of gold phosphide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernando, Deshani; Nigro, Toni A.E.; Dyer, I.D.

Recently, transition metal phosphides have found new applications as catalysts for the hydrogen evolution reaction that has generated an impetus to synthesize these materials at the nanoscale. In this work, Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous. Gold nanorods were used as morphological templates with the aim of controlling the shape and size of the resulting gold phosphide particles. We demonstrate that the surface capping ligand of the gold nanoparticle precursors can influence the purity and extent to which the gold phosphide phase will form. Gold nanorods functionalized withmore » 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanorods are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Graphical abstract: Au{sub 2}P{sub 3} was synthesized utilizing the high temperature decomposition of tri-n-octylphosphine as a source of elemental phosphorous and gold nanoparticles as reactants. We demonstrate that the surface capping ligand of the gold nanoparticle precursors influence the purity and extent to which the Au{sub 2}P{sub 3} phase will form. Gold nanorods functionalized with 1-dodecanethiol undergo digestive ripening to produce discrete spherical particles that exhibit reduced reactivity towards phosphorous, resulting in low yields of the gold phosphide. In contrast, gold phosphide was obtained as a phase pure product when cetyltrimethylammonium bromide functionalized gold nanoparticles are used instead. The Au{sub 2}P{sub 3} nanoparticles exhibited higher activity than polycrystalline gold towards the hydrogen evolution reaction. - Highlights: • The surface chemistry of gold affects the synthetic yields of Au{sub 2}P{sub 3}. • Imaging of Au{sub 2}P{sub 3} with transmission electron microscopy results in decomposition. • Au{sub 2}P{sub 3} nanoparticles exhibit activity towards the hydrogen evolution reaction.« less

Hydrogen Peroxide - Material Compatibility Studied by Microcalorimetry

NASA Technical Reports Server (NTRS)

Homung, Steven D.; Davis, Dennis D.; Baker, David; Popp, Christopher G.

2003-01-01

Environmental and toxicity concerns with current hypergolic propellants have led to a renewed interest in propellant grade hydrogen peroxide (HP) for propellant applications. Storability and stability has always been an issue with HP. Contamination or contact of HP with metallic surfaces may cause decomposition, which can result in the evolution of heat and gas leading to increased pressure or thermal hazards. The NASA Johnson Space Center White Sands Test Facility has developed a technique to monitor the decompositions of hydrogen peroxide at temperatures ranging from 25 to 60 C. Using isothermal microcalorimetry we have measured decomposition rates at the picomole/s/g level showing the catalytic effects of materials of construction. In this paper we will present the results of testing with Class 1 and 2 materials in 90 percent hydrogen peroxide.

Early evolution without a tree of life

PubMed Central

2011-01-01

Life is a chemical reaction. Three major transitions in early evolution are considered without recourse to a tree of life. The origin of prokaryotes required a steady supply of energy and electrons, probably in the form of molecular hydrogen stemming from serpentinization. Microbial genome evolution is not a treelike process because of lateral gene transfer and the endosymbiotic origins of organelles. The lack of true intermediates in the prokaryote-to-eukaryote transition has a bioenergetic cause. This article was reviewed by Dan Graur, W. Ford Doolittle, Eugene V. Koonin and Christophe Malaterre. PMID:21714942

Metastable Metal Hydrides for Hydrogen Storage

DOE PAGES

Graetz, Jason

2012-01-01

The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. Onmore » the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.« less

Beyond ICARA II: Implementing Refugee-Related Development Assistance.

ERIC Educational Resources Information Center

Gorman, Robert F.

1986-01-01

Reviews the evolution of the Second International Conference on Assistance to Refugees in Africa, which advanced discussions on the connection between refugees and the development process. Discusses potential roles of the World Bank and the World Food Program in providing technical assistance to refugee-related development projects. (Author/GC)

Electron Irradiation of Kuiper Belt Surface Ices: Ternary N2-CH4-CO Mixtures as a Case Study

NASA Astrophysics Data System (ADS)

Kim, Y. S.; Kaiser, R. I.

2012-10-01

The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH4) and carbon monoxide (CO) doped nitrogen (N2) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N2-CH4 and CO-CH4 systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH2N2), and its radical fragment (HCN2); oxygen-bearing products were of acetaldehyde (CH3CHO), formyl radical (HCO), and formaldehyde (H2CO). As in the pure ices, the methyl radical (CH3) and ethane (C2H6) were also detected, as were carbon dioxide (CO2) and the azide radical (N3). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

NASA Astrophysics Data System (ADS)

Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

2016-10-01

An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study.

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

PubMed Central

Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

2017-01-01

Molybdenum sulfides are very attractive noble-metal free electrocatalysts for the hydrogen evolution reaction (HER) from water. Atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx) which displays significantly higher HER activity compared to its crystalline counterpart. Here we show that HER–active a-MoSx, prepared either as nanoparticles or as films, is a molecular–based coordination polymer consisting of discrete [Mo3S13]2– building blocks. Of the three terminal disulfide (S22–) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimisation of this HER electrocatalyst as an alternative to platinum. PMID:26974410

Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

PubMed

Liu, Mengjia; Li, Jinghong

2016-01-27

The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations.

Solar Photoelectrochemical Energy Conversion using Earth-Abundant Nanomaterials

NASA Astrophysics Data System (ADS)

Lukowski, Mark A.

Although the vast majority of energy consumed worldwide is derived from fossil fuels, the growing interest in making cleaner alternative energies more economically viable has motivated recent research efforts aimed to improve photovoltaic, wind, and biomass power generation. Clean power generation also requires clean burning fuels, such as H2 and O2, so that energy can still be provided on demand at all times, despite the intermittent nature inherent to solar or wind power. My research has focused on the rational approach to synthesizing earth-abundant nanomaterials with applications in the generation of clean alternative fuels and understanding the structure-property relationships which directly influence their performance. Herein, we describe the development of low-cost, earth-abundant layered metal chalcogenides as high-performance electrocatalysts for hydrogen evolution, and hematite photoanodes for photoelectrochemical oxygen evolution. This work has revealed a particularly interesting concept where catalytic performance can be enhanced by controlling the phase behavior of the material and taking advantage of previously unexploited properties to overcome the challenges traditionally limiting the performance of these layered materials for hydrogen evolution catalysis.

Improved water electrolysis using magnetic heating of FeC-Ni core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Niether, Christiane; Faure, Stéphane; Bordet, Alexis; Deseure, Jonathan; Chatenet, Marian; Carrey, Julian; Chaudret, Bruno; Rouet, Alain

2018-06-01

Water electrolysis enables the storage of renewable electricity via the chemical bonds of hydrogen. However, proton-exchange-membrane electrolysers are impeded by the high cost and low availability of their noble-metal electrocatalysts, whereas alkaline electrolysers operate at a low power density. Here, we demonstrate that electrocatalytic reactions relevant for water splitting can be improved by employing magnetic heating of noble-metal-free catalysts. Using nickel-coated iron carbide nanoparticles, which are prone to magnetic heating under high-frequency alternating magnetic fields, the overpotential (at 20 mA cm-2) required for oxygen evolution in an alkaline water-electrolysis flow-cell was decreased by 200 mV and that for hydrogen evolution was decreased by 100 mV. This enhancement of oxygen-evolution kinetics is equivalent to a rise of the cell temperature to 200 °C, but in practice it increased by 5 °C only. This work suggests that, in the future, water splitting near the equilibrium voltage could be possible at room temperature, which is currently beyond reach in the classic approach to water electrolysis.

Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

PubMed Central

Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

2016-01-01

An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study. PMID:27703212

Molybdenum and tungsten nanostructures and methods for making and using same

DOEpatents

Kotaro, Sasaki; Chen, Wei-Fu; Muckerman, James T; Adzic, Radoslav R

2015-01-06

The present invention provides molybdenum and tungsten nanostructures, for example, nanosheets and nanoparticles, and methods of making and using same, including using such nanostructures as catlysts for hydrogen evolution reactions.

Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions.

PubMed

Gao, Wei; Gou, Wangyan; Zhou, Xuemei; Ho, Johnny C; Ma, Yuanyuan; Qu, Yongquan

2018-01-17

The interface between electrolytes and electrocatalysts would largely determine their corresponding activity and stability. Herein, modulating the surface characteristics of NiMo nanoparticles by various adsorbed amines gives the tunability on their interfacial properties and subsequently improves their catalytic performance for hydrogen evolution reaction (HER) in alkaline solutions. Diamines can significantly improve their HER activity by decreasing the charge-transfer resistance and modulating the electronic structures of interfacial active sites. Importantly, among various amines, ethylenediamine facilitates the HER activity of NiMo with a remarkable decrease of 268 mV in the overpotential to reach 10 mA cm -2 as compared with that of the unmodified NiMo in 1.0 M KOH. This method provides a novel strategy of regulating the interfacial properties to strengthen the catalytic performance of electrocatalysts.

Biodegradability engineering of biodegradable Mg alloys: Tailoring the electrochemical properties and microstructure of constituent phases

PubMed Central

Cha, Pil-Ryung; Han, Hyung-Seop; Yang, Gui-Fu; Kim, Yu-Chan; Hong, Ki-Ha; Lee, Seung-Cheol; Jung, Jae-Young; Ahn, Jae-Pyeong; Kim, Young-Yul; Cho, Sung-Youn; Byun, Ji Young; Lee, Kang-Sik; Yang, Seok-Jo; Seok, Hyun-Kwang

2013-01-01

Crystalline Mg-based alloys with a distinct reduction in hydrogen evolution were prepared through both electrochemical and microstructural engineering of the constituent phases. The addition of Zn to Mg-Ca alloy modified the corrosion potentials of two constituent phases (Mg + Mg2Ca), which prevented the formation of a galvanic circuit and achieved a comparable corrosion rate to high purity Mg. Furthermore, effective grain refinement induced by the extrusion allowed the achievement of much lower corrosion rate than high purity Mg. Animal studies confirmed the large reduction in hydrogen evolution and revealed good tissue compatibility with increased bone deposition around the newly developed Mg alloy implants. Thus, high strength Mg-Ca-Zn alloys with medically acceptable corrosion rate were developed and showed great potential for use in a new generation of biodegradable implants. PMID:23917705

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

NASA Astrophysics Data System (ADS)

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

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.

Properties of galaxies reproduced by a hydrodynamic simulation

NASA Astrophysics Data System (ADS)

Vogelsberger, M.; Genel, S.; Springel, V.; Torrey, P.; Sijacki, D.; Xu, D.; Snyder, G.; Bird, S.; Nelson, D.; Hernquist, L.

2014-05-01

Previous simulations of the growth of cosmic structures have broadly reproduced the `cosmic web' of galaxies that we see in the Universe, but failed to create a mixed population of elliptical and spiral galaxies, because of numerical inaccuracies and incomplete physical models. Moreover, they were unable to track the small-scale evolution of gas and stars to the present epoch within a representative portion of the Universe. Here we report a simulation that starts 12 million years after the Big Bang, and traces 13 billion years of cosmic evolution with 12 billion resolution elements in a cube of 106.5 megaparsecs a side. It yields a reasonable population of ellipticals and spirals, reproduces the observed distribution of galaxies in clusters and characteristics of hydrogen on large scales, and at the same time matches the `metal' and hydrogen content of galaxies on small scales.

Phase-controlled synthesis of polymorphic tungsten diphosphide with hybridization of monoclinic and orthorhombic phases as a novel electrocatalyst for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Pi, Mingyu; Wu, Tianli; Guo, Weimeng; Wang, Xiaodeng; Zhang, Dingke; Wang, Shuxia; Chen, Shijian

2017-05-01

The design and development of high-efficiency and non-noble-metal hydrogen evolution reaction (HER) electrocatalysts for future clean and renewable energy system has excited significant research interests over the recent years. In this communication, the polymorphic tungsten diphosphide (p-WP2) nanoparticles with mixed monoclinic (α-) and orthorhombic (β-) phases are synthesized by phase-controlled phosphidation route via vacuum capsulation and explored as a novel efficient electrocatalyst towards HER. The p-WP2 catalyst delivers superior performance with excellent stability under both acidic and alkaline conditions over its single phases of α-WP2 and β-WP2. This finding demonstrates that a highly efficient hybrid electrocatalyst can be achieved via precise composition controlling and may open up exciting opportunities for their practical applications toward energy conversion.

Mesoporous Phosphorus-Doped g-C3N4 Nanostructured Flowers with Superior Photocatalytic Hydrogen Evolution Performance.

PubMed

Zhu, Yun-Pei; Ren, Tie-Zhen; Yuan, Zhong-Yong

2015-08-05

Graphitic carbon nitride (g-C3N4) has been deemed a promising heterogeneous metal-free catalyst for a wide range of applications, such as solar energy utilization toward water splitting, and its photocatalytic performance is reasonably adjustable through tailoring its texture and its electronic and optical properties. Here phosphorus-doped graphitic carbon nitride nanostructured flowers of in-plane mesopores are synthesized by a co-condensation method in the absence of any templates. The interesting structures, together with the phosphorus doping, can promote light trapping, mass transfer, and charge separation, enabling it to perform as a more impressive catalyst than its pristine carbon nitride counterpart for catalytic hydrogen evolution under visible light irradiation. The catalyst has low cost, is environmentally friendly, and represents a potential candidate in photoelectrochemistry.

Enhanced hydrogen evolution performance of ultra thin nanoslice/nanopetal structured XS{sub 2} (X = W, Mo): From experiment to theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Honglin; Tang, Zheng; Zhu, Ziqiang

2016-07-14

The production of H{sub 2} through water splitting to make the reaction process economical and friendly has attracted a lot attention. In this work, we synthesized the novel well-defined nanostructured WS{sub 2}/MoS{sub 2} composite for using as the electrocatalyst of hydrogen evolution. The final obtained nanoslice/nanopetal nanostructured WS{sub 2}/MoS{sub 2} composite possessed massive active sites that originated from its well-defined hierarchical structure with densely stacked MoS{sub 2} nanopetals. The synthesized composite exhibited significantly enhanced hydrogen evolution reaction (HER) activity and clearly superior to the pristine MoS{sub 2}/WS{sub 2}. With the purpose to give a theoretical explanation of the corresponding enhancementmore » mechanism, the first-principles investigation based on the density functional theory was further employed to survey the electronic properties of different structures. Charge density difference and Bader charge analyses revealed that electrons could directional transfer from WS{sub 2} to MoS{sub 2} and provided an “electron-rich” environment, which was beneficial to the improvement of HER efficiency. These analytical methods will necessarily offer new angles to explain the enhancement mechanism of HER processes regarding the interaction between WS{sub 2} and MoS{sub 2}, which can accurately elucidate the reason why composite structure exhibits a better HER performance based on the experimental results.« less

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

PubMed

Chen, Ziliang; Wu, Renbing; Liu, Yang; Ha, Yuan; Guo, Yanhui; Sun, Dalin; Liu, Miao; Fang, Fang

2018-06-10

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm -2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H 2 SO 4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced electrocatalytic activity of MoS(x) on TCNQ-treated electrode for hydrogen evolution reaction.

PubMed

Chang, Yung-Huang; Nikam, Revannath D; Lin, Cheng-Te; Huang, Jing-Kai; Tseng, Chien-Chih; Hsu, Chang-Lung; Cheng, Chia-Chin; Su, Ching-Yuan; Li, Lain-Jong; Chua, Daniel H C

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 Mo(5+) 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.

Chemistry in dynamically evolving clouds

NASA Technical Reports Server (NTRS)

Tarafdar, S. P.; Prasad, S. S.; Huntress, W. T., Jr.; Villere, K. R.; Black, D. C.

1985-01-01

A unified model of chemical and dynamical evolution of isolated, initially diffuse and quiescent interstellar clouds is presented. The model uses a semiempirically derived dependence of the observed cloud temperatures on the visual extinction and density. Even low-mass, low-density, diffuse clouds can collapse in this model, because the inward pressure gradient force assists gravitational contraction. In contrast, previous isothermal collapse models required the low-mass diffuse clouds to be unrealistically cold before gravitational contraction could start. Theoretically predicted dependences of the column densities of various atoms and molecules, such as C and CO, on visual extinction in diffuse clouds are in accord with observations. Similarly, the predicted dependences of the fractional abundances of various chemical species (e.g., CO, H2CO, HCN, HCO(+)) on the total hydrogen density in the core of the dense clouds also agree with observations reported to date in the literature. Compared with previous models of interstellar chemistry, the present model has the potential to explain the wide spectrum of chemical and physical properties of both diffuse and dense clouds with a common formalism employing only a few simple initial conditions.

Zepto-molar electrochemical detection of Brucella genome based on gold nanoribbons covered by gold nanoblooms

NASA Astrophysics Data System (ADS)

Rahi, Amid; Sattarahmady, Naghmeh; Heli, Hossein

2015-12-01

Gold nanoribbons covered by gold nanoblooms were sonoelectrodeposited on a polycrystalline gold surface at -1800 mV (vs. AgCl) with the assistance of ultrasound and co-occurrence of the hydrogen evolution reaction. The nanostructure, as a transducer, was utilized to immobilize a Brucella-specific probe and fabrication of a genosensor, and the process of immobilization and hybridization was detected by electrochemical methods, using methylene blue as a redox marker. The proposed method for detection of the complementary sequence, sequences with base-mismatched (one-, two- and three-base mismatches), and the sequence of non-complementary sequence was assayed. The fabricated genosensor was evaluated for the assay of the bacteria in the cultured and human samples without polymerase chain reactions (PCR). The genosensor could detect the complementary sequence with a calibration sensitivity of 0.40 μA dm3 mol-1, a linear concentration range of 10 zmol dm-3 to 10 pmol dm-3, and a detection limit of 1.71 zmol dm-3.

Numerical Simulation of Hydrogen Assisted Cracking in Supermartensitic Stainless Steel Welds

DTIC Science & Technology

2005-01-27

Arc efficiency dependent on welding process (for GTAW it is in the range of 0.45 - 0 .7 5)TrDw2] 0 ,,or Fraction of hydrogen concentration at the...8 Figure 2-4: Region of y-, 6- and a-phase in the iron- chromium ...improve corrosion resistance and mechanical properties of this steel[sPM3 7 ][SPM 47] Since chromium with a content in the range of 11 to 14 wt.-% and

A photo-assisted microbial electrolysis cell for the exclusive biohydrogen production using a MoS2-coated p-type copper oxide

NASA Astrophysics Data System (ADS)

Jeon, Yongwon; Kim, Jun Hyun; Koo, Kyoungmin; Kim, Sunghyun

2018-01-01

A microbial electrolysis cell (MEC) has been regarded as an emerging new technology for the biohydrogen production from various organic substances, even from wastewater. One major problem is, however, that methane dominates produced gases in a long-term operation. Here we report that a photo-assisted MEC (PAMEC) is an efficient way to produce hydrogen with a p-type semiconductor cathode. When Cu2O coated with MoS2 as cocatalyst (MoS2/Cu2O) is employed, only hydrogen with essentially no methane and carbon dioxide was produced from acetate at -0.8 V bias under visible light illumination at a rate of 2.72 m3H2 m-3d-1. No appreciable performance degradation is observed over 50 days of operation. At lower bias voltage, methane and carbon dioxide begins to be produced. Energy efficiency based on input electricity and hydrogen yield are 225% and 3.4, respectively. This excellent feature of PAMEC is attributed to p-type semiconductor characteristics of Cu2O and proton reduction activity of MoS2. Electrons generated from acetate oxidation at the anode are photoexcited to the conduction band at the Cu2O acquiring enough reduction potential to reduce protons. The concept of PAMEC can be extended to wastewater treatment for the hydrogen production.

A study of the red-shift of a neutral donor bound exciton in GaN nanorods by hydrogenation

NASA Astrophysics Data System (ADS)

Park, Byung-Guon; Lee, Sang-Tae; Reddeppa, Maddaka; Kim, Moon-Deock; Oh, Jae-Eung; Lee, Sang-Kwon

2017-09-01

In this paper we account for the physics behind the exciton peak shift in GaN nanorods (NRs) due to hydrogenation. GaN NRs were selectively grown on a patterned Ti/Si(111) substrate using plasma-assisted molecular beam epitaxy, and the effect of hydrogenation on their optical properties was investigated in detail using low-temperature photoluminescence measurements. Due to hydrogenation, the emissions corresponding to the donor-acceptor pair and yellow luminescence in GaN NRs were strongly suppressed, while the emission corresponding to the neutral to donor bound exciton (D0X) exhibited red-shift. Thermal annealing of hydrogenated GaN NRs demonstrated the recovery of the D0X and deep level emission. To determine the nature of the D0X peak shift due to hydrogenation, comparative studies were carried out on various diameters of GaN NRs, which can be controlled by different growth conditions and wet-etching times. Our experimental results reveal that the D0X shift depends on the diameter of the GaN NRs after hydrogenation. The results clearly demonstrate that the hydrogenation leads to band bending of GaN NRs as compensated by hydrogen ions, which causes a red-shift in the D0X emission.