Charge Transfer in Collisions of S^4+ with H.

NASA Astrophysics Data System (ADS)

Stancil, P. C.; Turner, A. R.; Cooper, D. L.; Schultz, D. R.; Rakovic, M. J.; Fritsch, W.; Zygelman, B.

2001-05-01

Charge transfer processes due to collisions of ground state S^4+ ions with atomic hydrogen were investigated for energies between 1 meV/u and 10 MeV/u using the quantum-mechanical molecular-orbital close-coupling (MOCC), atomic-orbital close-coupling, classical trajectory Monte Carlo (CTMC), and continuum distorted wave methods. The MOCC calculations utilized ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained with the spin-coupled valence-bond approach. A number of variants of the CTMC approach were explored, including different momentum and radial distributions for the initial state, as well as effective charge and quantum-defect models to determine the corresponding quantum state after capture into final partially-stripped S^3+ excited classical states. Hydrogen target isotope effects were explored and rate coefficients for temperatures between 100 and 10^6 K will be presented

Oxidative coupling of sp 2 and sp 3 carbon-hydrogen bonds to construct dihydrobenzofurans.

PubMed

Shi, Jiang-Ling; Wang, Ding; Zhang, Xi-Sha; Li, Xiao-Lei; Chen, Yu-Qin; Li, Yu-Xue; Shi, Zhang-Jie

2017-08-10

Metal-catalyzed cross-couplings provide powerful, concise, and accurate methods to construct carbon-carbon bonds from organohalides and organometallic reagents. Recent developments extended cross-couplings to reactions where one of the two partners connects with an aryl or alkyl carbon-hydrogen bond. From an economic and environmental point of view, oxidative couplings between two carbon-hydrogen bonds would be ideal. Oxidative coupling between phenyl and "inert" alkyl carbon-hydrogen bonds still awaits realization. It is very difficult to develop successful strategies for oxidative coupling of two carbon-hydrogen bonds owning different chemical properties. This article provides a solution to this challenge in a convenient preparation of dihydrobenzofurans from substituted phenyl alkyl ethers. For the phenyl carbon-hydrogen bond activation, our choice falls on the carboxylic acid fragment to form the palladacycle as a key intermediate. Through careful manipulation of an additional ligand, the second "inert" alkyl carbon-hydrogen bond activation takes place to facilitate the formation of structurally diversified dihydrobenzofurans.Cross-dehydrogenative coupling is finding increasing application in synthesis, but coupling two chemically distinct sites remains a challenge. Here, the authors report an oxidative coupling between sp 2 and sp 3 carbons by sequentially activating the more active aryl site followed by the alkyl position.

Ab initio study of charge transfer in B2+ low-energy collisions with atomic hydrogen

NASA Astrophysics Data System (ADS)

Turner, A. R.; Cooper, D. L.; Wang, J. G.; Stancil, P. C.

2003-07-01

Charge transfer processes due to collisions of ground state B2+(2s 2S) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with the existing experiments shows our results to be in good agreement. When E<80 eV/u, the differences between the current total MOCC cross sections with and without rotational coupling are small (<3%). Rotational coupling becomes more important with increasing energy: for collision energies E>400 eV/u, inclusion of rotational coupling increases the total cross section by 50% 80%, improving the agreement between the current calculations and experiments. For state-selective cross sections, rotational coupling induces mixing between different symmetries; however, its effect, especially at low collision energies, is not as important as had been suggested in previous work.

Charge transfer of O3+ ions with atomic hydrogen

NASA Astrophysics Data System (ADS)

Wang, J. G.; Stancil, P. C.; Turner, A. R.; Cooper, D. L.

2003-01-01

Charge transfer processes due to collisions of ground state O3+(2s22p 2P) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational coupling matrix elements obtained with the spin-coupled valence-bond approach. Total and state-selective cross sections and rate coefficients are presented. Comparison with existing experimental and theoretical data shows our results to be in better agreement with the measurements than the previous calculations, although problems with some of the state-selective measurements are noted. Our calculations demonstrate that rotational coupling is not important for the total cross section, but for state-selective cross sections, its relevance increases with energy. For the ratios of triplet to singlet cross sections, significant departures from a statistical value are found, generally in harmony with experiment.

Effect of silane/hydrogen ratio on microcrystalline silicon thin films by remote inductively coupled plasma

NASA Astrophysics Data System (ADS)

Guo, Y. N.; Wei, D. Y.; Xiao, S. Q.; Huang, S. Y.; Zhou, H. P.; Xu, S.

2013-05-01

Hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared by remote low frequency inductively coupled plasma (ICP) chemical vapor deposition system, and the effect of silane/hydrogen ratio on the microstructure and electrical properties of μc-Si:H films was systematically investigated. As silane/hydrogen ratio increases, the crystalline volume fraction Fc decreases and the ratio of the intensity of (220) peak to that of (111) peak drops as silane flow rate is increased. The FTIR result indicates that the μc-Si:H films prepared by remote ICP have a high optical response with a low hydrogen content, which is in favor of reducing light-induced degradation effect. Furthermore, the processing window of the phase transition region for remote ICP is much wider than that for typical ICP. The photosensitivity of μc-Si:H films can exceed 100 at the transition region and this ensures the possibility of the fabrication of microcrystalline silicon thin film solar cells with a open-circuit voltage of about 700 mV.

Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

PubMed

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

NASA Astrophysics Data System (ADS)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

Dedicated nuclear facilities for electrolytic hydrogen production

NASA Technical Reports Server (NTRS)

Foh, S. E.; Escher, W. J. D.; Donakowski, T. D.

1979-01-01

An advanced technology, fully dedicated nuclear-electrolytic hydrogen production facility is presented. This plant will produce hydrogen and oxygen only and no electrical power will be generated for off-plant use. The conceptual design was based on hydrogen production to fill a pipeline at 1000 psi and a 3000 MW nuclear base, and the base-line facility nuclear-to-shaftpower and shaftpower-to-electricity subsystems, the water treatment subsystem, electricity-to-hydrogen subsystem, hydrogen compression, efficiency, and hydrogen production cost are discussed. The final conceptual design integrates a 3000 MWth high-temperature gas-cooled reactor operating at 980 C helium reactor-out temperature, direct dc electricity generation via acyclic generators, and high-current density, high-pressure electrolyzers based on the solid polymer electrolyte approach. All subsystems are close-coupled and optimally interfaced and pipeline hydrogen is produced at 1000 psi. Hydrogen costs were about half of the conventional nuclear electrolysis process.

Anharmonicity in a double hydrogen transfer reaction studied in a single porphycene molecule on a Cu(110) surface.

PubMed

Liu, S; Baugh, D; Motobayashi, K; Zhao, X; Levchenko, S V; Gawinkowski, S; Waluk, J; Grill, L; Persson, M; Kumagai, T

2018-05-07

Anharmonicity plays a crucial role in hydrogen transfer reactions in hydrogen-bonding systems, which leads to a peculiar spectral line shape of the hydrogen stretching mode as well as highly complex intra/intermolecular vibrational energy relaxation. Single-molecule study with a well-defined model is necessary to elucidate a fundamental mechanism. Recent low-temperature scanning tunnelling microscopy (STM) experiments revealed that the cis↔cis tautomerization in a single porphycene molecule on Cu(110) at 5 K can be induced by vibrational excitation via an inelastic electron tunnelling process and the N-H(D) stretching mode couples with the tautomerization coordinate [Kumagai et al. Phys. Rev. Lett. 2013, 111, 246101]. Here we discuss a pronounced anharmonicity of the N-H stretching mode observed in the STM action spectra and the conductance spectra. Density functional theory calculations find a strong intermode coupling of the N-H stretching with an in-plane bending mode within porphycene on Cu(110).

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Numerical studies from quantum to macroscopic scales of carbon nanoparticules in hydrogen plasma

NASA Astrophysics Data System (ADS)

Lombardi, Guillaume; Ngandjong, Alain; Mezei, Zsolt; Mougenot, Jonathan; Michau, Armelle; Hassouni, Khaled; Seydou, Mahamadou; Maurel, François

2016-09-01

Dusty plasmas take part in large scientific domains from Universe Science to nanomaterial synthesis processes. They are often generated by growth from molecular precursor. This growth leads to the formation of larger clusters which induce solid germs nucleation. Particle formed are described by an aerosol dynamic taking into account coagulation, molecular deposition and transport processes. These processes are controlled by the elementary particle. So there is a strong coupling between particle dynamics and plasma discharge equilibrium. This study is focused on the development of a multiscale physic and numeric model of hydrogen plasmas and carbon particles around three essential coupled axes to describe the various physical phenomena: (i) Macro/mesoscopic fluid modeling describing in an auto-coherent way, characteristics of the plasma, molecular clusters and aerosol behavior; (ii) the classic molecular dynamics offering a description to the scale molecular of the chains of chemical reactions and the phenomena of aggregation; (iii) the quantum chemistry to establish the activation barriers of the different processes driving the nanopoarticule formation.

Aqueous heterogeneity at the air/water interface revealed by 2D-HD-SFG spectroscopy.

PubMed

Hsieh, Cho-Shuen; Okuno, Masanari; Hunger, Johannes; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2014-07-28

Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface--whereas in bulk water the coupling is homogeneous. For strongly hydrogen-bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near-surface region. For weakly hydrogen-bonded OH groups that absorb around 3500 cm(-1), which are assigned to the outermost, yet hydrogen-bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen-bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemically engineering the metal-semiconductor interface for room-temperature transfer hydrogenation of nitroarenes with formic acid.

PubMed

Li, Xin-Hao; Cai, Yi-Yu; Gong, Ling-Hong; Fu, Wei; Wang, Kai-Xue; Bao, Hong-Liang; Wei, Xiao; Chen, Jie-Sheng

2014-12-08

A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensional fuel pin model validation by prediction of hydrogen distribution in cladding and comparison with experiment

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

Aly, A.; Avramova, Maria; Ivanov, Kostadin

To correctly describe and predict this hydrogen distribution there is a need for multi-physics coupling to provide accurate three-dimensional azimuthal, radial, and axial temperature distributions in the cladding. Coupled high-fidelity reactor-physics codes with a sub-channel code as well as with a computational fluid dynamics (CFD) tool have been used to calculate detailed temperature distributions. These high-fidelity coupled neutronics/thermal-hydraulics code systems are coupled further with the fuel-performance BISON code with a kernel (module) for hydrogen. Both hydrogen migration and precipitation/dissolution are included in the model. Results from this multi-physics analysis is validated utilizing calculations of hydrogen distribution using models informed bymore » data from hydrogen experiments and PIE data.« less

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

An integrated MEMS infrastructure for fuel processing: hydrogen generation and separation for portable power generation

NASA Astrophysics Data System (ADS)

Varady, M. J.; McLeod, L.; Meacham, J. M.; Degertekin, F. L.; Fedorov, A. G.

2007-09-01

Portable fuel cells are an enabling technology for high efficiency and ultra-high density distributed power generation, which is essential for many terrestrial and aerospace applications. A key element of fuel cell power sources is the fuel processor, which should have the capability to efficiently reform liquid fuels and produce high purity hydrogen that is consumed by the fuel cells. To this end, we are reporting on the development of two novel MEMS hydrogen generators with improved functionality achieved through an innovative process organization and system integration approach that exploits the advantages of transport and catalysis on the micro/nano scale. One fuel processor design utilizes transient, reverse-flow operation of an autothermal MEMS microreactor with an intimately integrated, micromachined ultrasonic fuel atomizer and a Pd/Ag membrane for in situ hydrogen separation from the product stream. The other design features a simpler, more compact planar structure with the atomized fuel ejected directly onto the catalyst layer, which is coupled to an integrated hydrogen selective membrane.

Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.

PubMed

Elsaesser, Thomas

2009-09-15

Hydrogen bonding plays a key role in the structural, physical, and chemical properties of liquids such as water and in macromolecular structures such as proteins. Vibrational spectroscopy is an important tool for understanding hydrogen bonding because it provides a way to observe local molecular geometries and their interaction with the environment. Linear vibrational spectroscopy has mapped characteristic changes of vibrational spectra and the occurrence of new bands that form upon hydrogen bonding. However, linear vibrational spectroscopy gives very limited insight into ultrafast dynamics of the underlying molecular interactions, such as the motions of hydrogen-bonded groups, energy dissipation and delocalization, and the fluctuations within hydrogen-bonded structures that occur in the ultrafast time domain. Nonlinear vibrational spectroscopy with its femtosecond time resolution can discern these dynamic processes in real time and has emerged as an important tool for unraveling molecular dynamics and for quantifying interactions that govern the vibrational and structural dynamics of hydrogen bonds. This Account reviews recent progress originating from third-order nonlinear methods of coherent multidimensional vibrational spectroscopy. Ultrafast dynamics of intermolecular hydrogen bonds are addressed for a number of prototype systems: hydrogen-bonded carboxylic acid dimers in an aprotic liquid environment, the disordered fluctuating hydrogen-bond network of liquid water, and DNA oligomers interacting with water. Cyclic carboxylic acid dimers display a rich scheme of vibrational couplings, resulting in OH stretching absorption bands with highly complex spectral envelopes. Two-dimensional spectroscopy of acetic acid dimers in a nonpolar liquid environment demonstrates that multiple Fermi resonances of the OH stretching mode with overtones and combination tones of fingerprint vibrations dominate both the 2D and linear absorption spectra. The coupling of the OH stretching mode with low-frequency hydrogen-bonding modes leads to additional progressions and coherent low-frequency hydrogen-bond motions in the subpicosecond time domain. In water, the 2D spectra reveal ultrafast spectral diffusion on a sub-100 fs time scale caused by the ultrafast structural fluctuations of the strongly coupled hydrogen-bond network. Librational motions play a key role for the ultrafast loss of structural memory. Spectral diffusion rates are enhanced by resonant transfer of OH stretching quanta between water molecules, typically occurring on a 100 fs time scale. In DNA oligomers, femtosecond nonlinear vibrational spectroscopy resolves NH and OH stretching bands in the highly congested infrared spectra of these molecules, which contain alternating adenine-thymine pairs. Studies at different levels of hydration reveal the spectral signatures of water molecules directly interacting with the phosphate groups of DNA and of a second water species forming a fluctuating environment around the DNA oligomers. We expect that the application of 2D infrared spectroscopy in an extended spectral range will reveal the intrinsic coupling between water and specific functional units of DNA.

Measurements of energy distribution and thrust for microwave plasma coupling of electrical energy to hydrogen for propulsion

NASA Technical Reports Server (NTRS)

Morin, T.; Chapman, R.; Filpus, J.; Hawley, M.; Kerber, R.; Asmussen, J.; Nakanishi, S.

1982-01-01

A microwave plasma system for transfer of electrical energy to hydrogen flowing through the system has potential application for coupling energy to a flowing gas in the electrothermal propulsion concept. Experimental systems have been designed and built for determination of the energy inputs and outputs and thrust for the microwave coupling of energy to hydrogen. Results for experiments with pressure in the range 100 microns-6 torr, hydrogen flow rate up to 1000 micronmoles/s, and total absorbed power to 700 w are presented.

Atmospheric Hydrogen Scavenging: from Enzymes to Ecosystems

PubMed Central

Constant, Philippe; Hards, Kiel; Morales, Sergio E.; Oakeshott, John G.; Russell, Robyn J.; Taylor, Matthew C.; Berney, Michael; Conrad, Ralf; Cook, Gregory M.

2014-01-01

We have known for 40 years that soils can consume the trace amounts of molecular hydrogen (H2) found in the Earth's atmosphere. This process is predicted to be the most significant term in the global hydrogen cycle. However, the organisms and enzymes responsible for this process were only recently identified. Pure culture experiments demonstrated that several species of Actinobacteria, including streptomycetes and mycobacteria, can couple the oxidation of atmospheric H2 to the reduction of ambient O2. A combination of genetic, biochemical, and phenotypic studies suggest that these organisms primarily use this fuel source to sustain electron input into the respiratory chain during energy starvation. This process is mediated by a specialized enzyme, the group 5 [NiFe]-hydrogenase, which is unusual for its high affinity, oxygen insensitivity, and thermostability. Atmospheric hydrogen scavenging is a particularly dependable mode of energy generation, given both the ubiquity of the substrate and the stress tolerance of its catalyst. This minireview summarizes the recent progress in understanding how and why certain organisms scavenge atmospheric H2. In addition, it provides insight into the wider significance of hydrogen scavenging in global H2 cycling and soil microbial ecology. PMID:25501483

Review of the methods to form hydrogen peroxide in electrical discharge plasma with liquid water

NASA Astrophysics Data System (ADS)

Locke, Bruce R.; Shih, Kai-Yuan

2011-06-01

This paper presents a review of the literature dealing with the formation of hydrogen peroxide from plasma processes. Energy yields for hydrogen peroxide generation by plasma from water span approximately three orders of magnitude from 4 × 10-2 to 80 g kWh-1. A wide range of plasma processes from rf to pulsed, ac, and dc discharges directly in the liquid phase have similar energy yields and may thus be limited by radical quenching processes at the plasma-liquid interface. Reactor modification using discharges in bubbles and discharges over the liquid phase can provide modest improvements in energy yield over direct discharge in the liquid, but the interpretation is complicated by additional chemical reactions of gas phase components such as ozone and nitrogen oxides. The highest efficiency plasma process utilizes liquid water droplets that may enhance efficiency by sequestering hydrogen peroxide in the liquid and by suppressing decomposition reactions by radicals from the gas and at the interface. Kinetic simulations of water vapor reported in the literature suggest that plasma generation of hydrogen peroxide should approach 45% of the thermodynamics limit, and this fact coupled with experimental studies demonstrating improvements with the presence of the condensed liquid phase suggest that further improvements in energy yield may be possible. Plasma generation of hydrogen peroxide directly from water compares favorably with a number of other methods including electron beam, ultrasound, electrochemical and photochemical methods, and other chemical processes.

Evaluation of biological hydrogen sulfide oxidation coupled with two-stage upflow filtration for groundwater treatment.

PubMed

Levine, Audrey D; Raymer, Blake J; Jahn, Johna

2004-01-01

Hydrogen sulfide in groundwater can be oxidized by aerobic bacteria to form elemental sulfur and biomass. While this treatment approach is effective for conversion of hydrogen sulfide, it is important to have adequate control of the biomass exiting the biological treatment system to prevent release of elemental sulfur into the distribution system. Pilot scale tests were conducted on a Florida groundwater to evaluate the use of two-stage upflow filtration downstream of biological sulfur oxidation. The combined biological and filtration process was capable of excellent removal of hydrogen sulfide and associated turbidity. Additional benefits of this treatment approach include elimination of odor generation, reduction of chlorine demand, and improved stability of the finished water.

DWPF Simulant CPC Studies For SB8

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

Newell, J. D.

2013-09-25

Prior to processing a Sludge Batch (SB) in the Defense Waste Processing Facility (DWPF), flowsheet studies using simulants are performed. Typically, the flowsheet studies are conducted based on projected composition(s). The results from the flowsheet testing are used to 1) guide decisions during sludge batch preparation, 2) serve as a preliminary evaluation of potential processing issues, and 3) provide a basis to support the Shielded Cells qualification runs performed at the Savannah River National Laboratory (SRNL). SB8 was initially projected to be a combination of the Tank 40 heel (Sludge Batch 7b), Tank 13, Tank 12, and the Tank 51more » heel. In order to accelerate preparation of SB8, the decision was made to delay the oxalate-rich material from Tank 12 to a future sludge batch. SB8 simulant studies without Tank 12 were reported in a separate report.1 The data presented in this report will be useful when processing future sludge batches containing Tank 12. The wash endpoint target for SB8 was set at a significantly higher sodium concentration to allow acceptable glass compositions at the targeted waste loading. Four non-coupled tests were conducted using simulant representing Tank 40 at 110-146% of the Koopman Minimum Acid requirement. Hydrogen was generated during high acid stoichiometry (146% acid) SRAT testing up to 31% of the DWPF hydrogen limit. SME hydrogen generation reached 48% of of the DWPF limit for the high acid run. Two non-coupled tests were conducted using simulant representing Tank 51 at 110-146% of the Koopman Minimum Acid requirement. Hydrogen was generated during high acid stoichiometry SRAT testing up to 16% of the DWPF limit. SME hydrogen generation reached 49% of the DWPF limit for hydrogen in the SME for the high acid run. Simulant processing was successful using previously established antifoam addition strategy. Foaming during formic acid addition was not observed in any of the runs. Nitrite was destroyed in all runs and no N2O was detected during SME processing. Mercury behavior was consistent with that seen in previous SRAT runs. Mercury was stripped below the DWPF limit on 0.8 wt% for all runs. Rheology yield stress fell within or below the design basis of 1-5 Pa. The low acid Tank 40 run (106% acid stoichiometry) had the highest yield stress at 3.78 Pa.« less

Biohythane production from marine macroalgae Sargassum sp. coupling dark fermentation and anaerobic digestion.

PubMed

Costa, José C; Oliveira, João V; Pereira, Maria A; Alves, Maria M; Abreu, Angela A

2015-08-01

Potential biohythane production from Sargassum sp. was evaluated in a two stage process. In the first stage, hydrogen dark fermentation was performed by Caldicellulosiruptor saccharolyticus. Sargassum sp. concentrations (VS) of 2.5, 4.9 and 7.4gL(-1) and initial inoculum concentrations (CDW) of 0.04 and 0.09gL(-1) of C. saccharolyticus were used in substrate/inoculum ratios ranging from 28 to 123. The end products from hydrogen production process were subsequently used for biogas production. The highest hydrogen and methane production yields, 91.3±3.3Lkg(-1) and 541±10Lkg(-1), respectively, were achieved with 2.5gL(-1) of Sargassum sp. (VS) and 0.09gL(-1)of inoculum (CDW). The biogas produced contained 14-20% of hydrogen. Potential energy production from Sargassum sp. in two stage process was estimated in 242GJha(-1)yr(-1). A maximum energy supply of 600EJyr(-1) could be obtained from the ocean potential area for macroalgae production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

Highly efficient and autocatalytic H2₂ dissociation for CO₂ reduction into formic acid with zinc.

PubMed

Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

2014-03-28

Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH(-) complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal.

Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

PubMed Central

Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

2014-01-01

Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH− complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal. PMID:24675820

Status of SAFT silver hydrogen cell development

NASA Technical Reports Server (NTRS)

Goualard, B. J.

1983-01-01

Nickel-hydrogen cells appear to be an improvement over the nickel-cadmium in applications requiring longer lifetime and reduced weight. An even more efficient couple, the silver-hydrogen couple, is also considered. After a theoretical study first performed by the Battelle Institute of Geneva under ESA (European Space Agency) contract, SAFT has undertaken more detailed analyses of the silver-hydrogen degradation mechanisms. ESA and the French Department of Defense contracted with SAFT for a full-development program of the silver-hydrogen technology.

Isolation of high quality graphene from Ru by solution phase intercalation

NASA Astrophysics Data System (ADS)

Koren, E.; Sutter, E.; Bliznakov, S.; Ivars-Barcelo, F.; Sutter, P.

2013-09-01

We introduce a method for isolating graphene grown on epitaxial Ru(0001)/α-Al2O3. The strong graphene/Ru(0001) coupling is weakened by electrochemically driven intercalation of hydrogen underpotentially deposited in aqueous KOH solution, which allows the penetration of water molecules at the graphene/Ru(0001) interface. Following these electrochemically driven processes, the graphene can be isolated by electrochemical hydrogen evolution and transferred to arbitrary supports. Raman and transport measurements demonstrate the high quality of the transferred graphene. Our results show that intercalation, typically carried out in vacuum, can be extended to solution environments for graphene processing under ambient conditions.

Coal liquefaction process utilizing coal/CO.sub.2 slurry feedstream

DOEpatents

Comolli, Alfred G.; McLean, Joseph B.

1989-01-01

A coal hydrogenation and liquefaction process in which particulate coal feed is pressurized to an intermediate pressure of at least 500 psig and slurried with CO.sub.2 liquid to provide a flowable coal/CO.sub.2 slurry feedstream, which is further pressurized to at least 1000 psig and fed into a catalytic reactor. The coal particle size is 50-375 mesh (U.S. Sieve Series) and provides 50-80 W % coal in the coal/CO.sub.2 slurry feedstream. Catalytic reaction conditions are maintained at 650.degree.-850.degree. F. temperature, 1000-4000 psig hydrogen partial pressure and coal feed rate of 10-100 lb coal/hr ft.sup.3 reactor volume to produce hydrocarbon gas and liquid products. The hydrogen and CO.sub.2 are recovered from the reactor effluent gaseous fraction, hydrogen is recycled to the catalytic reactor, and CO.sub.2 is liquefied and recycled to the coal slurrying step. If desired, two catalytic reaction stages close coupled together in series relation can be used. The process advantageously minimizes the recycle and processing of excess hydrocarbon liquid previously needed for slurrying the coal feed to the reactor(s).

Inductively and capacitively coupled plasmas at interface: A comparative study towards highly efficient amorphous-crystalline Si solar cells

NASA Astrophysics Data System (ADS)

Guo, Yingnan; Ong, Thiam Min Brian; Levchenko, I.; Xu, Shuyan

2018-01-01

A comparative study on the application of two quite different plasma-based techniques to the preparation of amorphous/crystalline silicon (a-Si:H/c-Si) interfaces for solar cells is presented. The interfaces were fabricated and processed by hydrogen plasma treatment using the conventional plasma-enhanced chemical vacuum deposition (PECVD) and inductively coupled plasma chemical vapour deposition (ICP-CVD) methods The influence of processing temperature, radio-frequency power, treatment duration and other parameters on interface properties and degree of surface passivation were studied. It was found that passivation could be improved by post-deposition treatment using both ICP-CVD and PECVD, but PECVD treatment is more efficient for the improvement on passivation quality, whereas the minority carrier lifetime increased from 1.65 × 10-4 to 2.25 × 10-4 and 3.35 × 10-4 s after the hydrogen plasma treatment by ICP-CVD and PECVD, respectively. In addition to the improvement of carrier lifetimes at low temperatures, low RF powers and short processing times, both techniques are efficient in band gap adjustment at sophisticated interfaces.

NMR scalar couplings across Watson–Crick base pair hydrogen bonds in DNA observed by transverse relaxation-optimized spectroscopy

PubMed Central

Pervushin, Konstantin; Ono, Akira; Fernández, César; Szyperski, Thomas; Kainosho, Masatsune; Wüthrich, Kurt

1998-01-01

This paper describes the NMR observation of 15N—15N and 1H—15N scalar couplings across the hydrogen bonds in Watson–Crick base pairs in a DNA duplex, hJNN and hJHN. These couplings represent new parameters of interest for both structural studies of DNA and theoretical investigations into the nature of the hydrogen bonds. Two dimensional [15N,1H]-transverse relaxation-optimized spectroscopy (TROSY) with a 15N-labeled 14-mer DNA duplex was used to measure hJNN, which is in the range 6–7 Hz, and the two-dimensional hJNN-correlation-[15N,1H]-TROSY experiment was used to correlate the chemical shifts of pairs of hydrogen bond-related 15N spins and to observe, for the first time, hJHN scalar couplings, with values in the range 2–3.6 Hz. TROSY-based studies of scalar couplings across hydrogen bonds should be applicable for large molecular sizes, including protein-bound nucleic acids. PMID:9826668

Electrochemical Coupling of Biomass-Derived Acids: New C8 Platforms for Renewable Polymers and Fuels.

PubMed

Wu, Linglin; Mascal, Mark; Farmer, Thomas J; Arnaud, Sacha Pérocheau; Wong Chang, Maria-Angelica

2017-01-10

Electrolysis of biomass-derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C 6 for biofuels and renewable materials production. Kolbe coupling of biomass-derived levulinic acid is used to obtain 2,7-octanedione, a new platform molecule only two low process-intensity steps removed from raw biomass. Hydrogenation to 2,7-octanediol provides a chiral secondary diol largely unknown to polymer chemistry, whereas intramolecular aldol condensation followed by hydrogenation yields branched cycloalkanes suitable for use as high-octane, cellulosic gasoline. Analogous electrolysis of an itaconic acid-derived methylsuccinic monoester yields a chiral 2,5-dimethyladipic acid diester, another underutilized monomer owing to lack of availability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave plasma generation of hydrogen atoms for rocket propulsion

NASA Technical Reports Server (NTRS)

Chapman, R.; Filpus, J.; Morin, T.; Snellenberger, R.; Asmussen, J.; Hawley, M.; Kerber, R.

1981-01-01

A flow microwave plasma reaction system is used to study the conversion of hydrogen to hydrogen atoms as a function of pressure, power density, cavity tuning, cavity mode, and time in the plasma zone. Hydrogen atom concentration is measured down-stream from the plasma by NOCl titration. Extensive modeling of the plasma and recombination zones is performed with the plasma zone treated as a backmix reaction system and the recombination zone treated as a plug flow. The thermodynamics and kinetics of the recombination process are examined in detail to provide an understanding of the conversion of recombination energy to gas kinetic energy. It is found that cavity tuning, discharge stability, and optimum power coupling are critically dependent on the system pressure, but nearly independent of the flow rate.

Thermochemical nonequilibrium in atomic hydrogen at elevated temperatures

NASA Technical Reports Server (NTRS)

Scott, R. K.

1972-01-01

A numerical study of the nonequilibrium flow of atomic hydrogen in a cascade arc was performed to obtain insight into the physics of the hydrogen cascade arc. A rigorous mathematical model of the flow problem was formulated, incorporating the important nonequilibrium transport phenomena and atomic processes which occur in atomic hydrogen. Realistic boundary conditions, including consideration of the wall electrostatic sheath phenomenon, were included in the model. The governing equations of the asymptotic region of the cascade arc were obtained by writing conservation of mass and energy equations for the electron subgas, an energy conservation equation for heavy particles and an equation of state. Finite-difference operators for variable grid spacing were applied to the governing equations and the resulting system of strongly coupled, stiff equations were solved numerically by the Newton-Raphson method.

Coupling Glucose Dehydrogenation with CO2 Hydrogenation by Hydrogen Transfer in Aqueous Media at Room Temperature.

PubMed

Ding, Guodong; Su, Ji; Zhang, Cheng; Tang, Kan; Yang, Lisha; Lin, Hongfei

2018-05-08

Conversion of carbon dioxide into value-added chemicals and fuels provides a direct solution to reduce excessive CO2 in the atmosphere. Herein, a novel catalytic reaction system is presented by coupling the dehydrogenation of glucose with the hydrogenation of a CO2 derived salt, ammonium carbonate, in the ethanol-water mixture. For the first time, the hydrogenation of CO2 into formate by glucose has been achieved under ambient conditions. Under the optimal reaction conditions, the highest yield of formate reached ~ 46 %. We find that the apparent pH value in the ethanol-water mixture plays a central role in determining the performance of the hydrogen transfer reaction. Based on the 13C NMR and ESI-MS results, a possible pathway of the coupled glucose dehydrogenation and CO2 hydrogenation reactions was proposed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a Reactor Model for Chemical Conversion of Lunar Regolith

NASA Technical Reports Server (NTRS)

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

2009-01-01

Lunar regolith will be used for a variety of purposes such as oxygen and propellant production and manufacture of various materials. The design and development of chemical conversion reactors for processing lunar regolith will require an understanding of the coupling among the chemical, mass and energy transport processes occurring at the length and time scales of the overall reactor with those occurring at the corresponding scales of the regolith particles. To this end, a coupled transport model is developed using, as an example, the reduction of ilmenite-containing regolith by a continuous flow of hydrogen in a flow-through reactor. The ilmenite conversion occurs on the surface and within the regolith particles. As the ilmenite reduction proceeds, the hydrogen in the reactor is consumed, and this, in turn, affects the conversion rate of the ilmenite in the particles. Several important quantities are identified as a result of the analysis. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the time for hydrogen to diffuse into the pores of the regolith particles and the chemical reaction time. The paper investigates the relationships between these quantities and their impact on the regolith conversion. Application of the model to various chemical reactor types, such as fluidized-bed, packed-bed, and rotary-bed configurations, are discussed.

Development of a Reactor Model for Chemical Conversion of Lunar Regolith

NASA Technical Reports Server (NTRS)

Hedge, uday; Balasubramaniam, R.; Gokoglu, S.

2007-01-01

Lunar regolith will be used for a variety of purposes such as oxygen and propellant production and manufacture of various materials. The design and development of chemical conversion reactors for processing lunar regolith will require an understanding of the coupling among the chemical, mass and energy transport processes occurring at the length and time scales of the overall reactor with those occurring at the corresponding scales of the regolith particles. To this end, a coupled transport model is developed using, as an example, the reduction of ilmenite-containing regolith by a continuous flow of hydrogen in a flow-through reactor. The ilmenite conversion occurs on the surface and within the regolith particles. As the ilmenite reduction proceeds, the hydrogen in the reactor is consumed, and this, in turn, affects the conversion rate of the ilmenite in the particles. Several important quantities are identified as a result of the analysis. Reactor scale parameters include the void fraction (i.e., the fraction of the reactor volume not occupied by the regolith particles) and the residence time of hydrogen in the reactor. Particle scale quantities include the time for hydrogen to diffuse into the pores of the regolith particles and the chemical reaction time. The paper investigates the relationships between these quantities and their impact on the regolith conversion. Application of the model to various chemical reactor types, such as fluidized-bed, packed-bed, and rotary-bed configurations, are discussed.

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

Filamentous carbon particles for cleaning oil spills and method of production

DOEpatents

Muradov, Nazim

2010-04-06

A compact hydrogen generator is coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. The hydrogen generator can be conveniently integrated with high temperature fuel cells to produce an efficient and self-contained source of electrical power.

The Use of Spontaneous Raman Scattering for Hydrogen Leak Detection

NASA Technical Reports Server (NTRS)

Degroot, Wim A.

1994-01-01

A fiber optic probe has been built and demonstrated that utilizes back scattered spontaneous Raman spectroscopy to detect and identify gaseous species. The small probe, coupled to the laser and data acquisition equipment with optical fibers, has applications in gaseous leak detection and process monitoring. The probe design and data acquisition system are described. Raman scattering theory has been reviewed and the results of intensity calculations of hydrogen and nitrogen Raman scattering are given. Because the device is in its developmental stage, only preliminary experimental results are presented here. Intensity scans across the rotational-vibrational Raman lines of nitrogen and hydrogen are presented. Nitrogen at a partial pressure of 0.077 MPa was detected. Hydrogen at a partial pressure of 2 kPa approached the lower limit of detectability with the present apparatus. Potential instrument improvements that would allow more sensitive and rapid hydrogen detection are identified.

An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol.

PubMed

Yue, Hairong; Ma, Xinbin; Gong, Jinlong

2014-05-20

Ethanol is an attractive end product and a versatile feedstock because a widespread market exists for its commercial use as a fuel additive or a potential substitute for gasoline. Currently, ethanol is produced primarily by fermentation of biomass-derived sugars, particularly those containing six carbons, but coproducts 5-carbon sugars and lignin remain unusable. Another major process for commercial production of ethanol is hydration of ethylene over solid acidic catalysts, yet not sustainable considering the depletion of fossil fuels. Catalytic conversion of synthetic gas (CO + H2) could produce ethanol in large quantities. However, the direct catalytic conversion of synthetic gas to ethanol remains challenging, and no commercial process exists as of today although the research has been ongoing for the past 90 years, since such the process suffers from low yield and poor selectivity due to slow kinetics of the initial C-C bond formation and fast chain growth of the C2 intermediates. This Account describes recent developments in an alternative approach for the synthesis of ethanol via synthetic gas. This process is an integrated technology consisting of the coupling of CO with methanol to form dimethyl oxalate and the subsequent hydrogenation to yield ethanol. The byproduct of the second step (methanol) can be separated and used in circulation as the feedstock for the coupling step. The coupling reaction of carbon monoxide for producing dimethyl oxalate takes place under moderate reaction conditions with high selectivity (∼95%), which ideally leads to a self-closing, nonwaste, catalytic cycling process. This Account also summarizes the progress on the development of copper-based catalysts for the hydrogenation reaction with remarkable efficiencies and stability. The unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) species are responsible for the activity of the catalyst with high yield of ethanol (∼91%). The understanding of nature of valence states of Cu could also guide the rational design of Cu-based catalysts for other similar reactions, particularly for hydrogenation catalytic systems. In addition, by regulating the reaction condition and the surface structure of the catalysts, the products in the hydrogenation steps, such as ethanol, methyl glycolate, and ethylene glycol, could be tuned efficiently. This synthetic approach enables a more sustainable ethanol, methyl glycolate, and ethylene glycol synthesis in industry and greatly reduces the dependence on petroleum resources and the emission of the greenhouse gas.

Temperature peaking at beginning of breakdown in 2.45 GHz pulsed off-resonance electron cyclotron resonance ion source hydrogen plasma

NASA Astrophysics Data System (ADS)

Cortázar, O. D.; Megía-Macías, A.; Vizcaíno-de-Julián, A.

2012-10-01

An experimental study of temperature and density evolution during breakdown in off-resonance ECR hydrogen plasma is presented. Under square 2.45 GHz microwave excitation pulses with a frequency of 50 Hz and relative high microwave power, unexpected transient temperature peaks that reach 18 eV during 20 μs are reported at very beginning of plasma breakdown. Decays of such peaks reach final stable temperatures of 5 eV at flat top microwave excitation pulse. Evidence of interplay between incoming power and duty cycle giving different kind of plasma parameters evolutions engaged to microwave coupling times is observed. Under relative high power conditions where short microwave coupling times are recorded, high temperature peaks are measured. However, for lower incoming powers and longer coupling times, temperature evolves gradually to a higher final temperature without peaking. On the other hand, the early instant where temperature peaks are observed also suggest a possible connection with preglow processes during breakdown in ECRIS plasmas.

ON-SITE APPLICABILITY OF HYDROGEN PEROXIDE PRODUCING MICROBIAL ELECTROCHEMICAL CELLS COUPLED WITH UV IN WASTEWATER DISINFECTION STUDY

EPA Science Inventory

There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals when coupled w...

The hydrogen tunneling splitting in malonaldehyde: A full-dimensional time-independent quantum mechanical method

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

Wu, Feng; Ren, Yinghui; Bian, Wensheng, E-mail: bian@iccas.ac.cn

The accurate time-independent quantum dynamics calculations on the ground-state tunneling splitting of malonaldehyde in full dimensionality are reported for the first time. This is achieved with an efficient method developed by us. In our method, the basis functions are customized for the hydrogen transfer process which has the effect of greatly reducing the size of the final Hamiltonian matrix, and the Lanczos method and parallel strategy are used to further overcome the memory and central processing unit time bottlenecks. The obtained ground-state tunneling splitting of 24.5 cm{sup −1} is in excellent agreement with the benchmark value of 23.8 cm{sup −1}more » computed with the full-dimensional, multi-configurational time-dependent Hartree approach on the same potential energy surface, and we estimate that our reported value has an uncertainty of less than 0.5 cm{sup −1}. Moreover, the role of various vibrational modes strongly coupled to the hydrogen transfer process is revealed.« less

Thermal modeling of nickel-hydrogen battery cells operating under transient orbital conditions

NASA Technical Reports Server (NTRS)

Schrage, Dean S.

1991-01-01

An analytical study of the thermal operating characteristics of nickel-hydrogen battery cells is presented. Combined finite-element and finite-difference techniques are employed to arrive at a computationally efficient composite thermal model representing a series-cell arrangement operating in conjunction with a radiately coupled baseplate and coldplate thermal bus. An aggressive, low-mass design approach indicates that thermal considerations can and should direct the design of the thermal bus arrangement. Special consideration is given to the potential for mixed conductive and convective processes across the hydrogen gap. Results of a compressible flow model are presented and indicate the transfer process is suitably represented by molecular conduction. A high-fidelity thermal model of the cell stack (and related components) indicates the presence of axial and radial temperature gradients. A detailed model of the thermal bus reveals the thermal interaction of individual cells and is imperative for assessing the intercell temperature gradients.

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

PubMed

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

2016-12-20

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

Apparatus and methods for storing and releasing hydrogen

DOEpatents

Heung, Leung K.

2001-01-01

A rechargeable device that stores and discharges hydrogen is described. The device stores hydrogen in a solid form and supplies hydrogen as a gas when needed. The solid storage medium may be metal hydride in a ground particle form that avoids the need for compaction or other treatment. Dividers partition a container into separate chambers, each provided with a matrix, formed from an appropriate material like a thermally-conductive aluminum foam, which forms a number of cells. For proper chamber size, the ratio of chamber length to container diameter should be between about 0.5 and 2. Metal hydride particles (or other hydrogen storage medium) may be placed within the cells, which help prevent excessive particle settling. The container is provided with a hydrogen transfer port through which hydrogen gas passes upon either discharging from or charging of the metal hydride particles. A filter may be placed within the port to allow hydrogen to flow but prevent particles from escaping. A heat transferring surface is formed by, for instance, a channel that is thermally coupled with the aluminum foam. Fluid flows through the channel to deliver or remove heat during the respective hydrogen discharging or charging processes.

Apparatus and methods for storing and releasing hydrogen

DOEpatents

Heung, Leung K.

2000-01-01

A rechargeable device that stores and discharges hydrogen is described. The device stores hydrogen in a solid form and supplies hydrogen as a gas when needed. The solid storage medium may be metal hydride in a ground particle form that avoids the need for compaction or other treatment. Dividers partition a container into separate chambers, each provided with a matrix, formed from an appropriate material like a thermally-conductive aluminum foam, which forms a number of cells. For proper chamber size, the ratio of chamber length to container diameter should be between about 0.5 and 2. Metal hydride particles (or other hydrogen storage medium) may be placed within the cells, which help prevent excessive particle settling. The container is provided with a hydrogen transfer port through which hydrogen gas passes upon either discharging from or charging of the metal hydride particles. A filter may be placed within the port to allow hydrogen to flow but prevent particles from escaping. A heat transferring surface is formed by, for instance, a channel that is thermally coupled with the aluminum foam. Fluid flows through the channel to deliver or remove heat during the respective hydrogen discharging or charging processes.

Electron capture in collisions of N^+ with H and H^+ with N

NASA Astrophysics Data System (ADS)

Lin, C. Y.; Stancil, P. C.; Gu, J. P.; Buenker, R. J.; Kimura, M.

2004-05-01

Charge transfer processes due to collisions of N^+ with atomic hydrogen and H^+ with atomic nitrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potential curves and nonadiabatic radial and rotational coupling matrix elements obtained with the multireference single- and double-excitation configuration interaction approach. Total and state-selective cross sections for the energy range 0.1-500 eV/u will be presented and compared with existing experimental and theoretical data.

Palladium-catalyzed Heck-type cross-couplings of unactivated alkyl iodides.

PubMed

McMahon, Caitlin M; Alexanian, Erik J

2014-06-02

A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C-C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base- or nucleophile-sensitive functionality. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous hydrogen and ethanol production from cascade utilization of mono-substrate in integrated dark and photo-fermentative reactor.

PubMed

Liu, Bing-Feng; Xie, Guo-Jun; Wang, Rui-Qing; Xing, De-Feng; Ding, Jie; Zhou, Xu; Ren, Hong-Yu; Ma, Chao; Ren, Nan-Qi

2015-01-01

Integrating hydrogen-producing bacteria with complementary capabilities, dark-fermentative bacteria (DFB) and photo-fermentative bacteria (PFB), is a promising way to completely recover bioenergy from waste biomass. However, the current coupled models always suffer from complicated pretreatment of the effluent from dark-fermentation or imbalance between dark and photo-fermentation, respectively. In this work, an integrated dark and photo-fermentative reactor (IDPFR) was developed to completely convert an organic substrate into bioenergy. In the IDPFR, Ethanoligenens harbinese B49 and Rhodopseudomonas faecalis RLD-53 were separated by a membrane into dark and photo chambers, while the acetate produced by E. harbinese B49 in the dark chamber could freely pass through the membrane into the photo chamber and serve as a carbon source for R. faecalis RLD-53. The hydrogen yield increased with increasing working volume of the photo chamber, and reached 3.38 mol H2/mol glucose at the dark-to-photo chamber ratio of 1:4. Hydrogen production by the IDPFR was also significantly affected by phosphate buffer concentration, glucose concentration, and ratio of dark-photo bacteria. The maximum hydrogen yield (4.96 mol H2/mol glucose) was obtained at a phosphate buffer concentration of 20 mmol/L, a glucose concentration of 8 g/L, and a ratio of dark to photo bacteria of 1:20. As the glucose and acetate were used up by E. harbinese B49 and R. faecalis RLD-53, ethanol produced by E. harbinese B49 was the sole end-product in the effluent from the IDPFR, and the ethanol concentration was 36.53 mmol/L with an ethanol yield of 0.82 mol ethanol/mol glucose. The results indicated that the IDPFR not only circumvented complex pretreatments on the effluent in the two-stage process, but also overcame the imbalance of growth and metabolic rate between DFB and PFB in the co-culture process, and effectively enhanced cooperation between E. harbinense B49 and R. faecalis RLD-53. Moreover, simultaneous hydrogen and ethanol production were achieved by coupling E. harbinese B49 and R. faecalis RLD-53 in the IDPFR. According to stoichiometry, the hydrogen and ethanol production efficiencies were 82.67% and 82.19%, respectively. Therefore, IDPFR was an effective strategy for coupling DFB and PFB to fulfill efficient energy recovery from waste biomass.

DWPF SIMULANT CPC STUDIES FOR SB7B

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

Koopman, D.

2011-11-01

Lab-scale DWPF simulations of Sludge Batch 7b (SB7b) processing were performed. Testing was performed at the Savannah River National Laboratory - Aiken County Technology Laboratory (SRNL-ACTL). The primary goal of the simulations was to define a likely operating window for acid stoichiometry for the DWPF Sludge Receipt and Adjustment Tank (SRAT). In addition, the testing established conditions for the SRNL Shielded Cells qualification simulation of SB7b-Tank 40 blend, supported validation of the current glass redox model, and validated the coupled process flowsheet at the nominal acid stoichiometry. An acid window of 105-140% by the Koopman minimum acid (KMA) equation (107-142%more » DWPF Hsu equation) worked for the sludge-only flowsheet. Nitrite was present in the SRAT product for the 105% KMA run at 366 mg/kg, while SME cycle hydrogen reached 94% of the DWPF Slurry Mix Evaporator (SME) cycle limit in the 140% KMA run. The window was determined for sludge with added caustic (0.28M additional base, or roughly 12,000 gallons 50% NaOH to 820,000 gallons waste slurry). A suitable processing window appears to be 107-130% DWPF acid equation for sludge-only processing allowing some conservatism for the mapping of lab-scale simulant data to full-scale real waste processing including potentially non-conservative noble metal and mercury concentrations. This window should be usable with or without the addition of up to 7,000 gallons of caustic to the batch. The window could potentially be wider if caustic is not added to SB7b. It is recommended that DWPF begin processing SB7b at 115% stoichiometry using the current DWPF equation. The factor could be increased if necessary, but changes should be made with caution and in small increments. DWPF should not concentrate past 48 wt.% total solids in the SME cycle if moderate hydrogen generation is occurring simultaneously. The coupled flowsheet simulation made more hydrogen in the SRAT and SME cycles than the sludge-only run with the same acid stoichiometric factor. The slow acid addition in MCU seemed to alter the reactions that consumed the small excess acid present such that hydrogen generation was promoted relative to sludge-only processing. The coupled test reached higher wt.% total solids, and this likely contributed to the SME cycle hydrogen limit being exceeded at 110% KMA. It is clear from the trends in the SME processing GC data, however, that the frit slurry formic acid contributed to driving the hydrogen generation rate above the SME cycle limit. Hydrogen generation rates after the second frit addition generally exceeded those after the first frit addition. SRAT formate loss increased with increasing acid stoichiometry (15% to 35%). A substantial nitrate gain which was observed to have occurred after acid addition (and nitrite destruction) was reversed to a net nitrate loss in runs with higher acid stoichiometry (nitrate in SRAT product less than sum of sludge nitrate and added nitric acid). Increased ammonium ion formation was also indicated in the runs with nitrate loss. Oxalate loss on the order 20% was indicated in three of the four acid stoichiometry runs and in the coupled flowsheet run. The minimum acid stoichiometry run had no indicated loss. The losses were of the same order as the official analytical uncertainty of the oxalate concentration measurement, but were not randomly distributed about zero loss, so some actual loss was likely occurring. Based on the entire set of SB7b test data, it is recommended that DWPF avoid concentrating additional sludge solids in single SRAT batches to limit the concentrations of noble metals to SB7a processing levels (on a grams noble metal per SRAT batch basis). It is also recommended that DWPF drop the formic acid addition that accompanies the process frit 418 additions, since SME cycle data showed considerable catalytic activity for hydrogen generation from this additional acid (about 5% increase in stoichiometry occurred from the frit formic acid). Frit 418 also does not appear to need formic acid addition to prevent gel formation in the frit slurry. Simulant processing was successful using 100 ppm of 747 antifoam added prior to nitric acid instead of 200 ppm. This is a potential area for DWPF to cut antifoam usage in any future test program. An additional 100 ppm was added before formic acid addition. Foaming during formic acid addition was not observed. No build-up of oily or waxy material was observed in the off-gas equipment. Lab-scale mercury stripping behavior was similar to SB6 and SB7a. More mercury was unaccounted for as the acid stoichiometry increased.« less

Behind the Mpemba paradox

PubMed Central

Sun, Chang Qing

2015-01-01

Mpemba paradox results from hydrogen-bond anomalous relaxation. Heating stretches the O:H nonbond and shortens the H‒O bond via Coulomb coupling; cooling reverses this process to emit heat at a rate depending on its initial storage. Skin ultra-low mass density raises the thermal diffusivity and favors outward heat flow from the liquid. PMID:27227000

Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts.

PubMed

Hong, Do-Young; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2010-02-21

Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

Heating-Rate-Coupled Model for Hydrogen Reduction of JSC-1A

NASA Technical Reports Server (NTRS)

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

2010-01-01

A previously developed and validated model for hydrogen reduction of JSC-1A for a constant reaction-bed temperature is extended to account for reaction during the bed heat-up period. A quasisteady approximation is used wherein an expression is derived for a single average temperature of reaction during the heat-up process by employing an Arrhenius expression for regolith conversion. Subsequently, the regolith conversion during the heat-up period is obtained by using this representative temperature. Accounting for the reaction during heat-up provides a better estimate of the reaction time needed at the desired regolith-bed operating temperature. Implications for the efficiency of the process, as measured by the energy required per unit mass of oxygen produced, are also indicated.

Understanding oscillatory phenomena in molecular hydrogen generation via sodium borohydride hydrolysis.

PubMed

Budroni, M A; Biosa, E; Garroni, S; Mulas, G R C; Marchettini, N; Culeddu, N; Rustici, M

2013-11-14

The hydrolysis of borohydride salts represents one of the most promising processes for the generation of high purity molecular hydrogen under mild conditions. In this work we show that the sodium borohydride hydrolysis exhibits a fingerprinting periodic oscillatory transient in the hydrogen flow over a wide range of experimental conditions. We disproved the possibility that flow oscillations are driven by supersaturation phenomena of gaseous bubbles in the reactive mixture or by a nonlinear thermal feedback according to a thermokinetic model. Our experimental results indicate that the NaBH4 hydrolysis is a spontaneous inorganic oscillator, in which the hydrogen flow oscillations are coupled to an "oscillophor" in the reactive solution. The discovery of this original oscillator paves the way for a new class of chemical oscillators, with fundamental implications not only for testing the general theory on oscillations, but also with a view to chemical control of borohydride systems used as a source of hydrogen based green fuel.

Particles of spilled oil-absorbing carbon in contact with water

DOEpatents

Muradov, Nazim [Melbourne, FL

2011-03-29

Hydrogen generator coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. Carbon particles with surface filaments having a hydrophobic property of oil film absorption, compositions of matter containing those particles, and a system for using the carbon particles for cleaning oil spills.

Examining student heuristic usage in a hydrogen bonding assessment.

PubMed

Miller, Kathryn; Kim, Thomas

2017-09-01

This study investigates the role of representational competence in student responses to an assessment of hydrogen bonding. The assessment couples the use of a multiple-select item ("Choose all that apply") with an open-ended item to allow for an examination of students' cognitive processes as they relate to the assignment of hydrogen bonding within a structural representation. Response patterns from the multiple-select item implicate heuristic usage as a contributing factor to students' incorrect responses. The use of heuristics is further supported by the students' corresponding responses to the open-ended assessment item. Taken together, these data suggest that poor representational competence may contribute to students' previously observed inability to correctly navigate the concept of hydrogen bonding. © 2017 by The International Union of Biochemistry and Molecular Biology, 45(5):411-416, 2017. © 2017 The International Union of Biochemistry and Molecular Biology.

Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1989-01-01

The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

A H2-evolving photocathode based on direct sensitization of MoS3 with an organic photovoltaic cell

PubMed Central

Bourgeteau, Tiphaine; Tondelier, Denis; Geffroy, Bernard; Brisse, Romain; Laberty-Robert, Christel; Campidelli, Stéphane; de Bettignies, Rémi; Artero, Vincent; Palacin, Serge; Jousselme, Bruno

2013-01-01

An organic solar cell based on a poly-3-hexylthiophene (P3HT): phenyl-C61-butyric acid (PCBM) bulk hetero-junction was directly coupled with molybdenum sulfide resulting in the design of a new type of photocathode for the production of hydrogen. Both the light-harvesting system and the catalyst were deposited by low-cost solution-processed methods, i.e. spin coating and spray coating respectively. Spray-coated MoS3 films are catalytically active in strongly acidic aqueous solutions with the best efficiencies for thicknesses of 40 to 90 nm. The photocathodes display photocurrents higher than reference samples, without catalyst or without coupling with a solar cell. Analysis by gas chromatography confirms the light-induced hydrogen evolution. The addition of titanium dioxide in the MoS3 film enhances electron transport and collection within thick films and therefore the performance of the photocathode. PMID:24404434

Strong vibronic coupling effects in polarized IR spectra of the hydrogen bond in N-methylthioacetamide crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Śmiszek-Lindert, Wioleta; Stadnicka, Katarzyna

2007-06-01

This paper presents the investigation results of the polarized IR spectra of the hydrogen bond in crystals of N-methylthioacetamide. The spectral studies were preceded by the determination of the crystal X-ray structure. The spectra were measured at 283 K and at 77 K by a transmission method, using polarized light. Theoretical analysis of the results concerned the linear dichroic effects, the H/D isotopic and temperature effects, observed in the solid-state IR spectra of the hydrogen and of the deuterium bond at the frequency ranges of the νN-H and the νN-D bands, respectively. The main spectral properties of the crystals can be interpreted satisfactorily in terms of the simple quantitative theory of the IR spectra of the hydrogen bond, i.e., the " strong-coupling" theory on the basis of the hydrogen bond centrosymmetric dimer model. The spectra revealed that the strongest vibrational exciton coupling involved the closely spaced hydrogen bonds, each belonging to a different chain of associated N-methylthioacetamide molecules. The crystal spectral properties, along with an abnormal H/D isotopic effect in the spectra, were found to be strongly influenced by vibronic coupling mechanisms in these dimers. These mechanisms were considered as responsible for the activation in IR of the totally symmetric proton stretching vibrations in the dimers. On analyzing the spectra of isotopically diluted crystalline samples of N-methylthioacetamide, it was proved that a non-random distribution of the protons and deuterons took place in the hydrogen bond lattices. In an individual hydrogen-bonded chain in the crystals distribution of the hydrogen isotope atoms H and D was fully random. The H/D isotopic " self-organization" mechanism, of a vibronic nature, involved a pair of hydrogen bonds from a unit cell, where each hydrogen bond belonged to a different chain of the associated molecules.

Optimization studies of bio-hydrogen production in a coupled microbial electrolysis-dye sensitized solar cell system.

PubMed

Ajayi, Folusho Francis; Kim, Kyoung-Yeol; Chae, Kyu-Jung; Choi, Mi-Jin; Chang, In Seop; Kim, In S

2010-03-01

Bio-hydrogen production in light-assisted microbial electrolysis cell (MEC) with a dye sensitized solar cell (DSSC) was optimized by connecting multiple MECs to a single dye (N719) sensitized solar cell (V(OC) approx. 0.7 V). Hydrogen production occurred simultaneously in all the connected MECs when the solar cell was irradiated with light. The amount of hydrogen produced in each MEC depends on the activity of the microbial catalyst on their anode. Substrate (acetate) to hydrogen conversion efficiencies ranging from 42% to 65% were obtained from the reactors during the experiment. A moderate light intensity of 430 W m(-2) was sufficient for hydrogen production in the coupled MEC-DSSC. A higher light intensity of 915 W m(-2), as well as an increase in substrate concentration, did not show any improvement in the current density due to limitation caused by the rate of microbial oxidation on the anode. A significant reduction in the surface area of the connected DSSC only showed a slight effect on current density in the coupled MEC-DSSC system when irradiated with light.

Simulation and optimization of pressure swing adsorption systmes using reduced-order modeling

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

Agarwal, A.; Biegler, L.; Zitney, S.

2009-01-01

Over the past three decades, pressure swing adsorption (PSA) processes have been widely used as energyefficient gas separation techniques, especially for high purity hydrogen purification from refinery gases. Models for PSA processes are multiple instances of partial differential equations (PDEs) in time and space with periodic boundary conditions that link the processing steps together. The solution of this coupled stiff PDE system is governed by steep fronts moving with time. As a result, the optimization of such systems represents a significant computational challenge to current differential algebraic equation (DAE) optimization techniques and nonlinear programming algorithms. Model reduction is one approachmore » to generate cost-efficient low-order models which can be used as surrogate models in the optimization problems. This study develops a reducedorder model (ROM) based on proper orthogonal decomposition (POD), which is a low-dimensional approximation to a dynamic PDE-based model. The proposed method leads to a DAE system of significantly lower order, thus replacing the one obtained from spatial discretization and making the optimization problem computationally efficient. The method has been applied to the dynamic coupled PDE-based model of a twobed four-step PSA process for separation of hydrogen from methane. Separate ROMs have been developed for each operating step with different POD modes for each of them. A significant reduction in the order of the number of states has been achieved. The reduced-order model has been successfully used to maximize hydrogen recovery by manipulating operating pressures, step times and feed and regeneration velocities, while meeting product purity and tight bounds on these parameters. Current results indicate the proposed ROM methodology as a promising surrogate modeling technique for cost-effective optimization purposes.« less

Effects of Inductively Coupled Plasma Hydrogen on Long-Wavelength Infrared HgCdTe Photodiodes

NASA Astrophysics Data System (ADS)

Boieriu, P.; Buurma, C.; Bommena, R.; Blissett, C.; Grein, C.; Sivananthan, S.

2013-12-01

Bulk passivation of semiconductors with hydrogen continues to be investigated for its potential to improve device performance. In this work, hydrogen-only inductively coupled plasma (ICP) was used to incorporate hydrogen into long-wavelength infrared HgCdTe photodiodes grown by molecular-beam epitaxy. Fully fabricated devices exposed to ICP showed statistically significant increases in zero-bias impedance values, improved uniformity, and decreased dark currents. HgCdTe photodiodes on Si substrates passivated with amorphous ZnS exhibited reductions in shunt currents, whereas devices on CdZnTe substrates passivated with polycrystalline CdTe exhibited reduced surface leakage, suggesting that hydrogen passivates defects in bulk HgCdTe and in CdTe.

Coupled jump rotational dynamics in aqueous nitrate solutions.

PubMed

Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

2016-12-21

A nitrate ion (NO 3 - ) with its trigonal planar geometry and charges distributed among nitrogen and oxygen atoms can couple to the extensive hydrogen bond network of water to give rise to unique dynamical characteristics. We carry out detailed atomistic simulations and theoretical analyses to investigate these aspects and report certain interesting findings. We find that the nitrate ions in aqueous potassium nitrate solution exhibit large amplitude rotational jump motions that are coupled to the hydrogen bond rearrangement dynamics of the surrounding water molecules. The jump motion of nitrate ions bears certain similarities to the Laage-Hynes mechanism of rotational jump motions of tagged water molecules in neat liquid water. We perform a detailed atomic-level investigation of hydrogen bond rearrangement dynamics of water in aqueous KNO 3 solution to unearth two distinct mechanisms of hydrogen bond exchange that are instrumental to promote these jump motions of nitrate ions. As observed in an earlier study by Xie et al., in the first mechanism, after breaking a hydrogen bond with nitrate ion, water forms a new hydrogen bond with a water molecule, whereas the second mechanism involves just a switching of hydrogen bond between the two oxygen atoms of the same nitrate ion (W. J. Xie et al., J. Chem. Phys. 143, 224504 (2015)). The magnitude as well as nature of the reorientational jump of nitrate ion for the two mechanisms is different. In the first mechanism, nitrate ion predominantly undergoes out-of-plane rotation, while in the second mechanism, in-plane reorientation of NO 3 - is favourable. These have been deduced by computing the torque on the nitrate ion during the hydrogen bond switching event. We have defined and computed the time correlation function for coupled reorientational jump of nitrate and water and obtained the associated relaxation time which is also different for the two mechanisms. These results provide insight into the relation between the coupled reorientational jump dynamics of solute and solvent molecules.

On the mode-coupling treatment of collective density fluctuations for quantum liquids: para-hydrogen and normal liquid helium.

PubMed

Kletenik-Edelman, Orly; Reichman, David R; Rabani, Eran

2011-01-28

A novel quantum mode coupling theory combined with a kinetic approach is developed for the description of collective density fluctuations in quantum liquids characterized by Boltzmann statistics. Three mode-coupling approximations are presented and applied to study the dynamic response of para-hydrogen near the triple point and normal liquid helium above the λ-transition. The theory is compared with experimental results and to the exact imaginary time data generated by path integral Monte Carlo simulations. While for liquid para-hydrogen the combination of kinetic and quantum mode-coupling theory provides semi-quantitative results for both short and long time dynamics, it fails for normal liquid helium. A discussion of this failure based on the ideal gas limit is presented.

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

Theoretical study of photoacidity of HCN: the effect of complexation with water.

PubMed

Muchová, Eva; Spirko, Vladimir; Hobza, Pavel; Nachtigallová, Dana

2006-11-14

The character of the hydrogen bonding and the excited state proton transfer (ESPT) in the model system HCN...H(2)O is investigated. The PES of the two lowest excited states of the H(2)O...HCN complex was calculated using the CASPT2 method. The nonadiabatic coupling of the two states of the (pi-->pi*) and (pi-->sigma*) character is responsible for the excited state proton/hydrogen transfer. Compared to the ground state, the barrier for this process is significantly smaller. An increased number of water molecules in the complex with cyclic hydrogen-bonded network causes a large blue shift of the state of the (pi-->sigma*) character. The question of the dissociation of the complex in its excited state is also addressed.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

PubMed

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Analysis of Ni-HYDRIDE Thin Film after Surface Plasmon Generation by Laser Technique

NASA Astrophysics Data System (ADS)

Violante, V.; Castagna, E.; Sibilia, C.; Paoloni, S.; Sarto, F.

2005-12-01

A nickel hydride thin film was studied by the attenuated total reflection method. The differences in behavior between a "black" film, and a pure nickel film "blank," are shown. The black nickel hydride film has been obtained by a short electrolysis with 1 M Li2SO4 electrolyte in light water, A shift in the minimum of the observed reflected light occurs, together with a change in the minimum shape (i.e. its half-height width increases). These two phenomenon are due to the change in the electronic band structure of the metal induced by electrons added to the lattice by hydrogen. The change of the electronic structure, revealed by the laser coupling conditions, leads us to consider that a hydride phase was created. Both the blank (not hydrogenated) and black (hydrogenated) specimens were taken under He-Ne laser beam at the reflectance minimum angle for about three hours. A SIMS analysis was also implemented to reveal differences in the isotopic composition of Cu, as marker element between the blank and black films, in order to study the coupled effect of electrolysis and plasmon-polariton excitation on LENR processes in condensed matter.

Hydrophilic Association in a Dilute Glutamine Solution Persists Independent of Increasing Temperature.

PubMed

Rhys, Natasha H; Soper, Alan K; Dougan, Lorna

2015-12-24

Recent studies suggest that hydrophilic interactions play an important role in controlling self-assembly in biological processes. To explore the effect of temperature on this interaction, we extend our previous work on the glutamine-water system at 24 °C (at a mole ratio of 1 glutamine to 269 water molecules) and present additional neutron diffraction data, at the same concentration, at 37 and 60 °C, using hydrogen/deuterium substitution on the water and glutamine, coupled with further extensive empirical potential structure refinement computer simulations. Taking all the possible hydrophilic couplings between glutamine molecules into account, we find that nearly one-fifth of the glutamines in solution are linked by hydrogen bonds at any one time. This number contrasts strongly with the ∼3-4% fraction found in the same simulation with random packing and no hydrogen bonds. Within the uncertainties imposed by dilute solution statistics, we find no temperature dependence in these values. The clusters are highly transitory, forming and disappearing rapidly as the simulations proceed. Hydrophobic association of the alkyl groups on glutamine without concomitant hydrophilic association of the charged head and side-chain groups is only weakly observed.

High liquid fuel yielding biofuel processes and a roadmap for the future transportation

NASA Astrophysics Data System (ADS)

Singh, Navneet R.

In a fossil-fuel deprived world when crude oil will be scarce and transportation need cannot be met with electricity and transportation liquid fuel must be produced, biomass derived liquid fuels can be a natural replacement. However, the carbon efficiency of the currently known biomass to liquid fuel conversion processes ranges from 35-40%, yielding 90 ethanol gallon equivalents (ege) per ton of biomass. This coupled with the fact that the efficiency at which solar energy is captured by biomass (<1%) is significantly lower than H 2 (10-27%) and electricity (20-42%), implies that sufficient land area is not available to meet the need for the entire transportation sector. To counter this dilemma, a number of processes have been proposed in this work: a hybrid hydrogen-carbon (H2CAR) process based on biomass gasification followed by the Fischer-Tropsch process such that 100% carbon efficiency is achieved yielding 330 ege/ton biomass using hydrogen derived from a carbon-free energy. The hydrogen requirement for the H2CAR process is 0.33 kg/liter of diesel. To decrease the hydrogen requirement associated with the H2CAR process, a hydrogen bio-oil (H2Bioil) process based on biomass fast-hydropyrolysis/hydrodeoxygenation is proposed which can achieve liquid fuel yield of 215 ege/ton consuming 0.11 kg hydrogen per liter of oil. Due to the lower hydrogen consumption of the H2Bioil process, synergistically integrated transition pathways are feasible where hot syngas derived from coal gasification (H2Bioil-C) or a natural gas reformer (H 2Bioil-NG) is used to supply the hydrogen and process heat for the biomass fast-hydropyrolysis/hydrodeoxygenation. Another off-shoot of the H2Bioil process is the H2Bioil-B process, where hydrogen required for the hydropyrolysis is obtained from gasification of a fraction of the biomass. H2Bioil-B achieves the highest liquid fuel yield (126-146 ege/ton of biomass) reported in the literature for any self-contained conversion of biomass to biofuel. Finally, an integration of the H2Bioil process with the H2CAR process is suggested which can achieve 100% carbon efficiency (330 ege/ton of biomass) at the expense of 0.24 kg hydrogen/liter of oil. A sun-to-fuel efficiency analysis shows that extracting CO2 from air and converting it to liquid fuel is at least two times more efficient than growing dedicated fuel crops and converting them to liquid fuel even for the highest biomass growth rates feasible by algae. This implies that liquid fuel should preferably be produced from sustainably available waste (SAW) biomass first and if the SAW biomass is unable to meet the demand for liquid fuel, then, CO2 should be extracted from air and converted to liquid fuel, rather than growing biomass. Furthermore, based on the Sun-to-Wheels recovery for different transportation pathways, synergistic and complementary use of electricity, hydrogen and biomass, all derived from solar energy, is presented in an energy efficient roadmap to successfully propel the entire future transportation sector.

Mixed ionic and electronic conducting membranes for hydrogen generation and separation

NASA Astrophysics Data System (ADS)

Cui, Hengdong

Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process conditions of interest. Over 10 mumol·cm-2·s-1 (micromoles per square cm per second) of area specific hydrogen flux has been achieved employing a membrane of this material with thickness of 0.2 mm. This flux is several orders of magnitude higher than the hydrogen generation rates reported using other MIEC materials under similar operating conditions.

Hydrogen Transport and Rationalization of Porosity Formation during Welding of Titanium Alloys

NASA Astrophysics Data System (ADS)

Huang, Jianglin; Warnken, Nils; Gebelin, Jean-Christophe; Strangwood, Martin; Reed, Roger C.

2012-02-01

The transport of hydrogen during fusion welding of the titanium alloy Ti-6Al4V is analyzed. A coupled thermodynamic/kinetic treatment is proposed for the mass transport within and around the weld pool. The modeling indicates that hydrogen accumulates in the weld pool as a consequence of the thermodynamic driving forces that arise; a region of hydrogen depletion exists in cooler, surrounding regions in the heat-affected zone and beyond. Coupling with a hydrogen diffusion-controlled bubble growth model is used to simulate bubble growth in the melt and, thus, to make predictions of the hydrogen concentration barrier needed for pore formation. The effects of surface tension of liquid metal and the radius of preexisting microbubble size on the barrier are discussed. The work provides insights into the mechanism of porosity formation in titanium alloys.

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

Coupling of exothermic and endothermic hydrogen storage materials

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

Brooks, Kriston P.; Bowden, Mark E.; Karkamkar, Abhijeet J.

2016-08-01

Chemical hydrogen storage (CHS) materials are a high-storage-density alternative to the gaseous compressed hydrogen currently used to provide hydrogen for fuel cell vehicles. One of the challenges of CHS materials is addressing the thermodynamic and kinetic barriers required to break the chemical bonds and release the hydrogen. Coupling CHS reactions that are endothermic and exothermic during the dehydrogenation can improve the system on-board energy efficiency and thermal control, making such materials viable. Acceptable coupling between reactions requires both thermodynamic and kinetics considerations. Models were developed to predict the reaction enthalpy and rate required to achieve high conversions for both reactionsmore » based on experimental measurements. These modeling results show that the efficiency of coupling of an exothermic and endothermic reaction is more sensitive the magnitude of the ratio of the exothermic and endothermic enthalpies than the ratio of the rates of the two steps. The modeling shows further that a slower rate of the endothermic step is desirable to permit sufficient heating of the reactor by the exothermic step. We look at two examples of a sequential and parallel reaction scheme and provide some of the first insight into the required temperature range to maximize the H2 release from 1,2-BN cyclohexane and indoline.« less

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer Processes

DTIC Science & Technology

devices and photoelectrochemical cells. Theoretical methodology for simulating the nonadiabatic dynamics of photoinduced PCET reactions in solution has...tuning and control of the ultrafast dynamics is crucial for designing renewable and sustainable energy sources, such as artificial photosynthesis...describes the solute with a multiconfigurational method in a bath of explicit solvent molecules. The transferring hydrogen nucleus is represented as a

Strong coupling effects in the polarized IR spectra of the chain hydrogen bond systems in imidazole crystals: H/D isotopic ?self-organization? effects in the IR spectra of isotopically diluted imidazole single crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Michta, Anna

2004-11-01

This paper presents the investigation results of the polarized IR spectra of H1245 imidazole crystals and of D1H245, D1245 and H1D245 imidazole deuterium derivative crystals. The spectra were measured using polarized light at the room temperature and at 77 K by a transmission method, for two different crystalline faces. Theoretical analysis of the results concerned linear dichroic effects, H/D isotopic and temperature effects, observed in the spectra of the hydrogen and of the deuterium bonds in imidazole crystals, at the frequency ranges of νN-H and νN-D bands. The basic crystal spectral properties can be satisfactorily interpreted in a quantitative way for a hydrogen bond linear dimer model. Such a model explains not only a two-branch structure of the νN-H and νN-D bands in crystalline spectra, but also some essential linear dichroic effects in the band frequency ranges, for isotopically diluted crystals. Model calculations, performed within the limits of the strong-coupling model, allowed for quantitative interpretation and for understanding of the basic properties of the hydrogen bond IR spectra of imidazole crystals, H/D isotopic, temperature and dichroic effects included. The results allowed verification of theoretical models proposed recently for the imidazole crystal spectra generation mechanisms. In the scope of our studies, the mechanism of H/D isotopic self-organization processes, taking place in the crystal hydrogen bond lattices, was also recognized. It was proved that for isotopically diluted crystalline samples of imidazole, a non-random distribution of protons and deuterons exclusively occurs in some restricted fragments (domains) of open chains of the hydrogen-bonded molecules. Nevertheless, these co-operative interactions between the hydrogen bonds do not concern adjacent fragments of neighboring hydrogen bond chains in the lattice. Analysis of the isotopic self-organization effects in the spectra of imidazole crystals delivered crucial arguments for understanding of the nature of the hydrogen bond spectra generation mechanisms.

Optimizing investments in coupled offshore wind -electrolytic hydrogen storage systems in Denmark

NASA Astrophysics Data System (ADS)

Hou, Peng; Enevoldsen, Peter; Eichman, Joshua; Hu, Weihao; Jacobson, Mark Z.; Chen, Zhe

2017-08-01

In response to electricity markets with growing levels of wind energy production and varying electricity prices, this research examines incentives for investments in integrated renewable energy power systems. A strategy for using optimization methods for a power system consisting of wind turbines, electrolyzers, and hydrogen fuel cells is explored. This research reveals the investment potential of coupling offshore wind farms with different hydrogen systems. The benefits in terms of a return on investment are demonstrated with data from the Danish electricity markets. This research also investigates the tradeoffs between selling the hydrogen directly to customers or using it as a storage medium to re-generate electricity at a time when it is more valuable. This research finds that the most beneficial configuration is to produce hydrogen at a time that complements the wind farm and sell the hydrogen directly to end users.

Optimizing investments in coupled offshore wind-electrolytic hydrogen storage systems in Denmark

DOE PAGES

Hou, Peng; Enevoldsen, Peter; Eichman, Joshua; ...

2017-05-25

In response to electricity markets with growing levels of wind energy production and varying electricity prices, this research examines incentives for investments in integrated renewable energy power systems. A strategy for using optimization methods for a power system consisting of wind turbines, electrolyzers, and hydrogen fuel cells is explored. This research reveals the investment potential of coupling offshore wind farms with different hydrogen systems. The benefits in terms of a return on investment are demonstrated with data from the Danish electricity markets. This research also investigates the tradeoffs between selling the hydrogen directly to customers or using it as amore » storage medium to re-generate electricity at a time when it is more valuable. Finally, this research finds that the most beneficial configuration is to produce hydrogen at a time that complements the wind farm and sell the hydrogen directly to end users.« less

' Self-organization' processes in proton and deuteron mixtures in open-chain hydrogen bond systems: polarization IR spectra of 4-mercaptopyridine crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Tyl, Aleksandra; Jones, Peter G.

2002-01-01

This paper is devoted to IR spectroscopic studies in polarized light of 4-mercaptopyridine (4-MPD) hydrogen-bonded crystals. These studies were preceded by determination of the 4-mercaptopyridine X-ray structure. Polarization spectra of 4-mercaptopyridine crystals were measured in the frequency ranges of νN-H and νN-D bands at room temperature, and also at the temperature of liquid nitrogen, for the two different crystalline faces: ' bc' and ' ac'. When investigating ' residual' νN-H band shapes for crystals that were diluted by deuterium, strong dichroic effects in the spectra were still observed, providing evidence for the existence in the hydrogen bond chains of domains containing exclusively protons or deuterons. This phenomenon proves the existence of a new kind of H/D isotopic effects in open chain hydrogen bond systems, namely ' self-organization' effects. Such effects, however, were not observed for other open chain hydrogen bond systems, e.g. alcohol crystals. Solid-state spectra of 4-mercaptopyridine were quantitatively interpreted, along with the strong polarization and the isotopic effects, when based on the ' strong-coupling' theory for linearly arranged hydrogen bond dimers.

Alkyne–Aldehyde Reductive C–C Coupling through Ruthenium-Catalyzed Transfer Hydrogenation: Direct Regio- and Stereoselective Carbonyl Vinylation to Form Trisubstituted Allylic Alcohols in the Absence of Premetallated Reagents

PubMed Central

Leung, Joyce C.; Patman, Ryan L.; Sam, Brannon

2011-01-01

Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C–C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C–H oxidative addition in advance of the C–C coupling, and demonstrate that the C–C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

Charge transfer between O6+ and atomic hydrogen

NASA Astrophysics Data System (ADS)

Wu, Y.; Stancil, P. C.; Liebermann, H. P.; Buenker, R. J.; Schultz, D. R.; Hui, Y.

2011-05-01

The charge exchange process has been found to play a dominant role in the production of X-rays and/or EUV photons observed in cometary and planetary atmospheres and from the heliosphere. Charge transfer cross sections, especially state-selective cross sections, are necessary parameters in simulations of X-ray emission. In the present work, charge transfer due to collisions of ground state O6+(1s2 1 S) with atomic hydrogen has been investigated theoretically using the quantum-mechanical molecular-orbital close-coupling method (QMOCC). The multi-reference single- and double-excitation configuration interaction approach (MRDCI) has been applied to compute the adiabatic potential and nonadiabatic couplings, and the atomic basis sets used have been optimized with the method proposed previously to obtain precise potential data. Total and state-selective cross sections are calculated for energies between 10 meV/u and 10 keV/u. The QMOCC results are compared to available experimental and theoretical data as well as to new atomic-orbital close-coupling (AOCC) and classical trajectory Monte Carlo (CTMC) calculations. A recommended set of cross sections, based on the MOCC, AOCC, and CTMC calculations, is deduced which should aid in X-ray modeling studies.

Hybrid bio-photo-electro-chemical cells for solar water splitting

PubMed Central

Pinhassi, Roy I.; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-01-01

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm−2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel. PMID:27550091

Hybrid bio-photo-electro-chemical cells for solar water splitting.

PubMed

Pinhassi, Roy I; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-08-23

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm(-2). Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel.

Hydrogen Generation Via Fuel Reforming

NASA Astrophysics Data System (ADS)

Krebs, John F.

2003-07-01

Reforming is the conversion of a hydrocarbon based fuel to a gas mixture that contains hydrogen. The H2 that is produced by reforming can then be used to produce electricity via fuel cells. The realization of H2-based power generation, via reforming, is facilitated by the existence of the liquid fuel and natural gas distribution infrastructures. Coupling these same infrastructures with more portable reforming technology facilitates the realization of fuel cell powered vehicles. The reformer is the first component in a fuel processor. Contaminants in the H2-enriched product stream, such as carbon monoxide (CO) and hydrogen sulfide (H2S), can significantly degrade the performance of current polymer electrolyte membrane fuel cells (PEMFC's). Removal of such contaminants requires extensive processing of the H2-rich product stream prior to utilization by the fuel cell to generate electricity. The remaining components of the fuel processor remove the contaminants in the H2 product stream. For transportation applications the entire fuel processing system must be as small and lightweight as possible to achieve desirable performance requirements. Current efforts at Argonne National Laboratory are focused on catalyst development and reactor engineering of the autothermal processing train for transportation applications.

Mechanism of conformational coupling in SecA: Key role of hydrogen-bonding networks and water interactions.

PubMed

Milenkovic, Stefan; Bondar, Ana-Nicoleta

2016-02-01

SecA uses the energy yielded by the binding and hydrolysis of adenosine triphosphate (ATP) to push secretory pre-proteins across the plasma membrane in bacteria. Hydrolysis of ATP occurs at the nucleotide-binding site, which contains the conserved carboxylate groups of the DEAD-box helicases. Although crystal structures provide valuable snapshots of SecA along its reaction cycle, the mechanism that ensures conformational coupling between the nucleotide-binding site and the other domains of SecA remains unclear. The observation that SecA contains numerous hydrogen-bonding groups raises important questions about the role of hydrogen-bonding networks and hydrogen-bond dynamics in long-distance conformational couplings. To address these questions, we explored the molecular dynamics of SecA from three different organisms, with and without bound nucleotide, in water. By computing two-dimensional hydrogen-bonding maps we identify networks of hydrogen bonds that connect the nucleotide-binding site to remote regions of the protein, and sites in the protein that respond to specific perturbations. We find that the nucleotide-binding site of ADP-bound SecA has a preferred geometry whereby the first two carboxylates of the DEAD motif bridge via hydrogen-bonding water. Simulations of a mutant with perturbed ATP hydrolysis highlight the water-bridged geometry as a key structural element of the reaction path. Copyright © 2015. Published by Elsevier B.V.

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.

Enantio-Relay Catalysis Constructs Chiral Biaryl Alcohols over Cascade Suzuki Cross-Coupling-Asymmetric Transfer Hydrogenation

NASA Astrophysics Data System (ADS)

Zhang, Dacheng; Gao, Xiaoshuang; Cheng, Tanyu; Liu, Guohua

2014-05-01

The construction of chiral biaryl alcohols using enantio-relay catalysis is a particularly attractive synthetic method in organic synthesis. However, overcoming the intrinsic incompatibility of distinct organometallic complexes and the reaction conditions used are significant challenges in asymmetric catalysis. To overcome these barriers, we have taken advantage of an enantio-relay catalysis strategy and a combined dual-immobilization approach. We report the use of an imidazolium-based organopalladium-functionalized organic-inorganic hybrid silica and ethylene-coated chiral organoruthenium-functionalized magnetic nanoparticles to catalyze a cascade Suzuki cross-coupling-asymmetric transfer hydrogenation reaction to prepare chiral biaryl alcohols in a two-step, one-pot process. As expected, the site-isolated active species, salient imidazolium phase-transfer character and high ethylene-coated hydrophobicity can synergistically boost the catalytic performance. Furthermore, enantio-relay catalysis has the potential to efficiently prepare a variety of chiral biaryl alcohols. Our synthetic strategy is a general method that shows the potential of developing enantio-relay catalysis towards environmentally benign and sustainable organic synthesis.

Wave-packet continuum-discretization approach to ion-atom collisions including rearrangement: Application to differential ionization in proton-hydrogen scattering

NASA Astrophysics Data System (ADS)

Abdurakhmanov, I. B.; Bailey, J. J.; Kadyrov, A. S.; Bray, I.

2018-03-01

In this work, we develop a wave-packet continuum-discretization approach to ion-atom collisions that includes rearrangement processes. The total scattering wave function is expanded using a two-center basis built from wave-packet pseudostates. The exact three-body Schrödinger equation is converted into coupled-channel differential equations for time-dependent expansion coefficients. In the asymptotic region these time-dependent coefficients represent transition amplitudes for all processes including elastic scattering, excitation, ionization, and electron capture. The wave-packet continuum-discretization approach is ideal for differential ionization studies as it allows one to generate pseudostates with arbitrary energies and distribution. The approach is used to calculate the double differential cross section for ionization in proton collisions with atomic hydrogen. Overall good agreement with experiment is obtained for all considered cases.

Investigation of the RF efficiency of inductively coupled hydrogen plasmas at 1 MHz

NASA Astrophysics Data System (ADS)

Rauner, D.; Mattei, S.; Briefi, S.; Fantz, U.; Hatayama, A.; Lettry, J.; Nishida, K.; Tran, M. Q.

2017-08-01

The power requirements of RF heated sources for negative hydrogen ions in fusion are substantial, which poses strong demands on the generators and components of the RF circuit. Consequently, an increase of the RF coupling efficiency would be highly beneficial. Fundamental investigations of the RF efficiency in inductively coupled hydrogen and deuterium discharges in cylindrical symmetry are conducted at the lab experiment CHARLIE. The experiment is equipped with several diagnostics including optical emission spectroscopy and a movable floating double probe to monitor the plasma parameters. The presented investigations are performed in hydrogen at a varying pressure between 0.3 and 10 Pa, utilizing a conventional helical ICP coil driven at a frequency of 1 MHz and a fixed power of 520 W for plasma generation. The coupling efficiency is strongly affected by the variation in pressure, reaching up to 85 % between 1 and 3 Pa while dropping down to only 50 % at 0.3 Pa, which is the relevant operating pressure for negative hydrogen ion sources for fusion. Due to the lower power coupling, also the measured electron density at 0.3 Pa is only 5 . 1016 m-3, while it reaches up to 2.5 . 1017 m-3 with increasing coupling efficiency. In order to gain information on the spatially resolved aspects of RF coupling and plasma heating which are not diagnostically accessible, first simulations of the discharge by an electromagnetic Particle-In-Cell Monte Carlo collision method have been conducted and are compared to the measurement data. At 1 Pa, the simulated data corresponds well to the results of both axially resolved probe measurements and radially resolved emission profiles obtained via OES. Thereby, information regarding the radial distribution of the electron density and mean energy is provided, revealing a radial distribution of the electron density which is well described by a Bessel profile.

Thermal decay of rhodopsin: role of hydrogen bonds in thermal isomerization of 11-cis retinal in the binding site and hydrolysis of protonated Schiff base.

PubMed

Liu, Jian; Liu, Monica Yun; Nguyen, Jennifer B; Bhagat, Aditi; Mooney, Victoria; Yan, Elsa C Y

2009-07-01

Although thermal stability of the G protein-coupled receptor rhodopsin is directly related to its extremely low dark noise level and has recently generated considerable interest, the chemistry behind the thermal decay process of rhodopsin has remained unclear. Using UV-vis spectroscopy and HPLC analysis, we have demonstrated that the thermal decay of rhodopsin involves both hydrolysis of the protonated Schiff base and thermal isomerization of 11-cis to all-trans retinal. Examining the unfolding of rhodopsin by circular dichroism spectroscopy and measuring the rate of thermal isomerization of 11-cis retinal in solution, we conclude that the observed thermal isomerization of 11-cis to all-trans retinal happens when 11-cis retinal is in the binding pocket of rhodopsin. Furthermore, we demonstrate that solvent deuterium isotope effects are involved in the thermal decay process by decreasing the rates of thermal isomerization and hydrolysis, suggesting that the rate-determining step of these processes involves breaking hydrogen bonds. These results provide insight into understanding the critical role of an extensive hydrogen-bonding network on stabilizing the inactive state of rhodopsin and contribute to our current understanding of the low dark noise level of rhodopsin, which enables this specialized protein to function as an extremely sensitive biological light detector. Because similar hydrogen-bonding networks have also been suggested by structural analysis of two other GPCRs, beta1 and beta2 adrenergic receptors, our results could reveal a general role of hydrogen bonds in facilitating GPCR function.

Influence of Pb 2+ ions in the H 2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

NASA Astrophysics Data System (ADS)

Expósito, E.; Sánchez-Sánchez, C. M.; Solla-Gullón, J.; Montiel, V.

The influence of Pb 2+ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H 2 oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H 2 oxidation using a HDE catalyzed with platinum when Pb 2+ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb 2+ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption-oxidation-desorption process of lead on the platinum surface. Due to the low solubility of Pb 2+ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption-oxidation processes cause the oscillatory phenomenon.

High performance of a cobalt–nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives

PubMed Central

Zhou, Peng; Jiang, Liang; Wang, Fan; Deng, Kejian; Lv, Kangle; Zhang, Zehui

2017-01-01

Replacement of precious noble metal catalysts with low-cost, non-noble heterogeneous catalysts for chemoselective reduction and reductive coupling of nitro compounds holds tremendous promise for the clean synthesis of nitrogen-containing chemicals. We report a robust cobalt–nitrogen/carbon (Co–Nx/C-800-AT) catalyst for the reduction and reductive coupling of nitro compounds into amines and their derivates. The Co–Nx/C-800-AT catalyst was prepared by the pyrolysis of cobalt phthalocyanine–silica colloid composites and the subsequent removal of silica template and cobalt nanoparticles. The Co–Nx/C-800-AT catalyst showed extremely high activity, chemoselectivity, and stability toward the reduction of nitro compounds with H2, affording full conversion and >97% selectivity in water after 1.5 hours at 110°C and under a H2 pressure of 3.5 bar for all cases. The hydrogenation of nitrobenzene over the Co–Nx/C-800-AT catalyst can even be smoothly performed under very mild conditions (40°C and a H2 pressure of 1 bar) with an aniline yield of 98.7%. Moreover, the Co–Nx/C-800-AT catalyst has high activity toward the transfer hydrogenation of nitrobenzene into aniline and the reductive coupling of nitrobenzene into other derivates with high yields. These processes were carried out in an environmentally friendly manner without base and ligands. PMID:28232954

Performance of wave function and density functional methods for water hydrogen bond spin-spin coupling constants.

PubMed

García de la Vega, J M; Omar, S; San Fabián, J

2017-04-01

Spin-spin coupling constants in water monomer and dimer have been calculated using several wave function and density functional-based methods. CCSD, MCSCF, and SOPPA wave functions methods yield similar results, specially when an additive approach is used with the MCSCF. Several functionals have been used to analyze their performance with the Jacob's ladder and a set of functionals with different HF exchange were tested. Functionals with large HF exchange appropriately predict 1 J O H , 2 J H H and 2h J O O couplings, while 1h J O H is better calculated with functionals that include a reduced fraction of HF exchange. Accurate functionals for 1 J O H and 2 J H H have been tested in a tetramer water model. The hydrogen bond effects on these intramolecular couplings are additive when they are calculated by SOPPA(CCSD) wave function and DFT methods. Graphical Abstract Evaluation of the additive effect of the hydrogen bond on spin-spin coupling constants of water using WF and DFT methods.

Dynamic Cooperation of Hydrogen Binding and π Stacking in ssDNA Adsorption on Graphene Oxide.

PubMed

Xu, Zhen; Lei, Xiaoling; Tu, Yusong; Tan, Zhi-Jie; Song, Bo; Fang, Haiping

2017-09-21

Functional nanoscale structures consisting of a DNA molecule coupled to graphene or graphene oxide (GO) have great potential for applications in biosensors, biomedicine, nanotechnology, and materials science. Extensive studies using the most sophisticated experimental techniques and theoretical methods have still not clarified the dynamic process of single-stranded DNA (ssDNA) adsorbed on GO surfaces. Based on a molecular dynamics simulation, this work shows that an ssDNA segment could be stably adsorbed on a GO surface through hydrogen bonding and π-π stacking interactions, with preferential binding to the oxidized rather than to the unoxidized region of the GO surface. The adsorption process shows a dynamic cooperation adsorption behavior; the ssDNA segment first captures the oxidized groups of the GO surface by hydrogen bonding interaction, and then the configuration relaxes to maximize the π-π stacking interactions between the aromatic rings of the nucleobases and those of the GO surface. We attributed this behavior to the faster forming hydrogen bonding interaction compared to π-π stacking; the π-π stacking interaction needs more relaxation time to regulate the configuration of the ssDNA segment to fit the aromatic rings on the GO surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions.

PubMed

Zhang, Yagang; Zimmerman, Steven C

2012-01-01

The facile coupling of azobenzene dyes to the quadruply hydrogen-bonding modules 2,7-diamido-1,8-naphthyridine (DAN) and 7-deazaguanine urea (DeUG) is described. The coupling of azobenzene dye 2 to mono-amido DAN units 4, 7, and 9 was effected by classic 4-(dimethylamino)pyridine (DMAP)-catalyzed peptide synthesis with N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride (EDC) as activating agent, affording the respective amide products 5, 8, and 10 in 60-71% yield. The amide linkage was formed through either the aliphatic or aromatic ester group of 2, allowing both the flexibility and absorption maximum to be tuned. Azobenzene dye 1 was coupled to the DeUG unit 11 by Steglich esterification to afford the product amide 12 in 35% yield. Alternatively, azobenzene dye 16 underwent a room-temperature copper-catalyzed azide-alkyne Huisgen cycloaddition with DeUG alkyne 17 to give triazole 18 in 71% yield. Azobenzene coupled DAN modules 5, 8, and 10 are bright orange-red in color, and azobenzene coupled DeUG modules 12 and 18 are orange-yellow in color. Azobenzene coupled DAN and DeUG modules were successfully used as colorimetric indicators for specific DAN-DeUG and DAN-UPy (2-ureido-4(1H)-pyrimidone) quadruply hydrogen-bonding interactions.

Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions

PubMed Central

Zhang, Yagang

2012-01-01

Summary The facile coupling of azobenzene dyes to the quadruply hydrogen-bonding modules 2,7-diamido-1,8-naphthyridine (DAN) and 7-deazaguanine urea (DeUG) is described. The coupling of azobenzene dye 2 to mono-amido DAN units 4, 7, and 9 was effected by classic 4-(dimethylamino)pyridine (DMAP)-catalyzed peptide synthesis with N-(3-dimethylaminopropyl)-N’-ethyl carbodiimide hydrochloride (EDC) as activating agent, affording the respective amide products 5, 8, and 10 in 60–71% yield. The amide linkage was formed through either the aliphatic or aromatic ester group of 2, allowing both the flexibility and absorption maximum to be tuned. Azobenzene dye 1 was coupled to the DeUG unit 11 by Steglich esterification to afford the product amide 12 in 35% yield. Alternatively, azobenzene dye 16 underwent a room-temperature copper-catalyzed azide–alkyne Huisgen cycloaddition with DeUG alkyne 17 to give triazole 18 in 71% yield. Azobenzene coupled DAN modules 5, 8, and 10 are bright orange–red in color, and azobenzene coupled DeUG modules 12 and 18 are orange–yellow in color. Azobenzene coupled DAN and DeUG modules were successfully used as colorimetric indicators for specific DAN–DeUG and DAN–UPy (2-ureido-4(1H)-pyrimidone) quadruply hydrogen-bonding interactions. PMID:22509220

Electron capture and excitation processes in H+-H collisions in dense quantum plasmas

NASA Astrophysics Data System (ADS)

Jakimovski, D.; Markovska, N.; Janev, R. K.

2016-10-01

Electron capture and excitation processes in proton-hydrogen atom collisions taking place in dense quantum plasmas are studied by employing the two-centre atomic orbital close-coupling (TC-AOCC) method. The Debye-Hückel cosine (DHC) potential is used to describe the plasma screening effects on the Coulomb interaction between charged particles. The properties of a hydrogen atom with DHC potential are investigated as a function of the screening strength of the potential. It is found that the decrease in binding energy of nl levels with increasing screening strength is considerably faster than in the case of the Debye-Hückel (DH) screening potential, appropriate for description of charged particle interactions in weakly coupled classical plasmas. This results in a reduction in the number of bound states in the DHC potential with respect to that in the DH potential for the same plasma screening strength, and is reflected in the dynamics of excitation and electron capture processes for the two screened potentials. The TC-AOCC cross sections for total and state-selective electron capture and excitation cross sections with the DHC potential are calculated for a number of representative screening strengths in the 1-300 keV energy range and compared with those for the DH and pure Coulomb potential. The total capture cross sections for a selected number of screening strengths are compared with the available results from classical trajectory Monte Carlo calculations.

The coupling between the ionosphere and the protonosphere and its implications on the long term variations of ionospheric electron content

NASA Technical Reports Server (NTRS)

Waldman, H.

1971-01-01

The long-term variations in the daytime exchange flux are estimated with the use of model hydrogen concentrations based on the inverse relationship between the abundance of neutral hydrogen and the neutral temperature in the thermosphere. The results are found to be compatible with the observed long-term behavior of the ionospheric electron content at a midlatitude location, as revealed by Faraday observations using geostationary satellites. The basic processes occurring in the ionosphere are reviewed, with emphasis on the concepts of limiting velocity and limiting flux. An approach to the problem of numerical simulation of the ionosphere is also presented and discussed.

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

PubMed

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

2017-08-10

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

Coupling of Solar Energy to Hydrogen Peroxide Production in the Cyanobacterium Anacystis nidulans

PubMed Central

Roncel, Mercedes; Navarro, José A.; De la Rosa, Miguel A.

1989-01-01

Hydrogen peroxide production by blue-green algae (cyanobacteria) under photoautotrophic conditions is of great interest as a model system for the bioconversion of solar energy. Our experimental system was based on the photosynthetic reduction of molecular oxygen with electrons from water by Anacystis nidulans 1402-1 as the biophotocatalyst and methyl viologen as a redox intermediate. It has been demonstrated that the metabolic conditions of the algae in their different growth stages strongly influence the capacity for hydrogen peroxide photoproduction, and so the initial formation rate and net peroxide yield became maximum in the mid-log phase of growth. The overall process can be optimized in the presence of certain metabolic inhibitors such as iodoacetamide and p-hydroxymercuribenzoate, as well as by permeabilization of the cellular membrane after drastic temperature changes and by immobilization of the cells in inert supports such as agar and alginate. PMID:16347855

Benchmarking of Improved DPAC Transient Deflagration Analysis Code

DOE PAGES

Laurinat, James E.; Hensel, Steve J.

2017-09-27

The deflagration pressure analysis code (DPAC) has been upgraded for use in modeling hydrogen deflagration transients. The upgraded code is benchmarked using data from vented hydrogen deflagration tests conducted at the HYDRO-SC Test Facility at the University of Pisa. DPAC originally was written to calculate peak pressures for deflagrations in radioactive waste storage tanks and process facilities at the Savannah River Site. Upgrades include the addition of a laminar flame speed correlation for hydrogen deflagrations and a mechanistic model for turbulent flame propagation, incorporation of inertial effects during venting, and inclusion of the effect of water vapor condensation on vesselmore » walls. In addition, DPAC has been coupled with chemical equilibrium with applications (CEA), a NASA combustion chemistry code. The deflagration tests are modeled as end-to-end deflagrations. As a result, the improved DPAC code successfully predicts both the peak pressures during the deflagration tests and the times at which the pressure peaks.« less

Production and characterization of pure cryogenic inertial fusion targets

NASA Astrophysics Data System (ADS)

Boyd, B. A.; Kamerman, G. W.

An experimental cryogenic inertial fusion target generator and two optical techniques for automated target inspection are described. The generator produces 100 microns diameter solid hydrogen spheres at a rate compatible with fueling requirements of conceptual inertial fusion power plants. A jet of liquified hydrogen is disrupted into droplets by an ultrasonically excited nozzle. The droplets solidify into microspheres while falling through a chamber maintained below the hydrogen triple point pressure. Stable operation of the generator has been demonstrated for up to three hours. The optical inspection techniques are computer aided photomicrography and coarse diffraction pattern analysis (CDPA). The photomicrography system uses a conventional microscope coupled to a computer by a solid state camera and digital image memory. The computer enhances the stored image and performs feature extraction to determine pellet parameters. The CDPA technique uses Fourier transform optics and a special detector array to perform optical processing of a target image.

Benchmarking of Improved DPAC Transient Deflagration Analysis Code

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

Laurinat, James E.; Hensel, Steve J.

The deflagration pressure analysis code (DPAC) has been upgraded for use in modeling hydrogen deflagration transients. The upgraded code is benchmarked using data from vented hydrogen deflagration tests conducted at the HYDRO-SC Test Facility at the University of Pisa. DPAC originally was written to calculate peak pressures for deflagrations in radioactive waste storage tanks and process facilities at the Savannah River Site. Upgrades include the addition of a laminar flame speed correlation for hydrogen deflagrations and a mechanistic model for turbulent flame propagation, incorporation of inertial effects during venting, and inclusion of the effect of water vapor condensation on vesselmore » walls. In addition, DPAC has been coupled with chemical equilibrium with applications (CEA), a NASA combustion chemistry code. The deflagration tests are modeled as end-to-end deflagrations. As a result, the improved DPAC code successfully predicts both the peak pressures during the deflagration tests and the times at which the pressure peaks.« less

Removal of pharmaceuticals from wastewater by biological processes, hydrodynamic cavitation and UV treatment.

PubMed

Zupanc, Mojca; Kosjek, Tina; Petkovšek, Martin; Dular, Matevž; Kompare, Boris; Širok, Brane; Blažeka, Željko; Heath, Ester

2013-07-01

To augment the removal of pharmaceuticals different conventional and alternative wastewater treatment processes and their combinations were investigated. We tested the efficiency of (1) two distinct laboratory scale biological processes: suspended activated sludge and attached-growth biomass, (2) a combined hydrodynamic cavitation-hydrogen peroxide process and (3) UV treatment. Five pharmaceuticals were chosen including ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac, and an active metabolite of the lipid regulating agent clofibric acid. Biological treatment efficiency was evaluated using lab-scale suspended activated sludge and moving bed biofilm flow-through reactors, which were operated under identical conditions in respect to hydraulic retention time, working volume, concentration of added pharmaceuticals and synthetic wastewater composition. The suspended activated sludge process showed poor and inconsistent removal of clofibric acid, carbamazepine and diclofenac, while ibuprofen, naproxen and ketoprofen yielded over 74% removal. Moving bed biofilm reactors were filled with two different types of carriers i.e. Kaldnes K1 and Mutag BioChip™ and resulted in higher removal efficiencies for ibuprofen and diclofenac. Augmentation and consistency in the removal of diclofenac were observed in reactors using Mutag BioChip™ carriers (85%±10%) compared to reactors using Kaldnes carriers and suspended activated sludge (74%±22% and 48%±19%, respectively). To enhance the removal of pharmaceuticals hydrodynamic cavitation with hydrogen peroxide process was evaluated and optimal conditions for removal were established regarding the duration of cavitation, amount of added hydrogen peroxide and initial pressure, all of which influence the efficiency of the process. Optimal parameters resulted in removal efficiencies between 3-70%. Coupling the attached-growth biomass biological treatment, hydrodynamic cavitation/hydrogen peroxide process and UV treatment resulted in removal efficiencies of >90% for clofibric acid and >98% for carbamazepine and diclofenac, while the remaining compounds were reduced to levels below the LOD. For ibuprofen, naproxen, ketoprofen and diclofenac the highest contribution to overall removal was attributed to biological treatment, for clofibric acid UV treatment was the most efficient, while for carbamazepine hydrodynamic cavitation/hydrogen peroxide process and UV treatment were equally efficient. Copyright © 2012 Elsevier B.V. All rights reserved.

Failure analysis of fractured capscrews in centrifugal coolant compressor

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

Witherell, C.E.

1985-03-25

This study was made to determine the cause of failure of capscrews that retain a baffle plate in a Freon 11 centrifugal compressor manufactured by the Trane Company. The affected unit is installed in Building 490 at LLNL. The capscrews failed through hydrogen embrittlement. The source for hydrogen appears to have been corrosion. In a dissimilar metal couple of aluminum and uncoated high strength, highly-stressed steel, corrosive environments would generate hydrogen at the the steel side of the couple and embrittle it. There is no evidence that the manufacturer took precautions to prevent such an occurrence.

Coupling mechanism between wear and oxidation processes of 304 stainless steel in hydrogen peroxide environments.

PubMed

Dong, Conglin; Yuan, Chengqing; Bai, Xiuqin; Li, Jian; Qin, Honglin; Yan, Xinping

2017-05-24

Stainless steel is widely used in strongly oxidizing hydrogen peroxide (H 2 O 2 ) environments. It is crucial to study its wear behaviour and failure mode. The tribological properties and oxidation of 304 stainless steel were investigated using a MMW-1 tribo-tester with a three-electrode setup in H 2 O 2 solutions with different concentrations. Corrosion current densities (CCDs), coefficients of frictions (COFs), wear mass losses, wear surface topographies, and metal oxide films were analysed and compared. The results show that the wear process and oxidation process interacted significantly with each other. Increasing the concentration of H 2 O 2 or the oxidation time was useful to form a layer of integrated, homogeneous, compact and thick metal oxide film. The dense metal oxide films with higher mechanical strengths improved the wear process and also reduced the oxidation reaction. The wear process removed the metal oxide films to increase the oxidation reaction. Theoretical data is provided for the rational design and application of friction pairs in oxidation corrosion conditions.

Dissimilatory Fe(III) and Mn(IV) reduction.

PubMed Central

Lovley, D R

1991-01-01

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process. PMID:1886521

Vibrational dynamics of hydrogen-bonded complexes in solutions studied with ultrafast infrared pump-probe spectroscopy.

PubMed

Banno, Motohiro; Ohta, Kaoru; Yamaguchi, Sayuri; Hirai, Satori; Tominaga, Keisuke

2009-09-15

In aqueous solution, the basis of all living processes, hydrogen bonding exerts a powerful effect on chemical reactivity. The vibrational energy relaxation (VER) process in hydrogen-bonded complexes in solution is sensitive to the microscopic environment around the oscillator and to the geometrical configuration of the hydrogen-bonded complexes. In this Account, we describe the use of time-resolved infrared (IR) pump-probe spectroscopy to study the vibrational dynamics of (i) the carbonyl CO stretching modes in protic solvents and (ii) the OH stretching modes of phenol and carboxylic acid. In these cases, the carbonyl group acts as a hydrogen-bond acceptor, whereas the hydroxyl group acts as a hydrogen-bond donor. These vibrational modes have different properties depending on their respective chemical bonds, suggesting that hydrogen bonding may have different mechanisms and effects on the VER of the CO and OH modes than previously understood. The IR pump-probe signals of the CO stretching mode of 9-fluorenone and methyl acetate in alcohol, as well as that of acetic acid in water, include several components with different time constants. Quantum chemical calculations indicate that the dynamical components are the result of various hydrogen-bonded complexes that form between solute and solvent molecules. The acceleration of the VER is due to the increasing vibrational density of states caused by the formation of hydrogen bonds. The vibrational dynamics of the OH stretching mode in hydrogen-bonded complexes were studied in several systems. For phenol-base complexes, the decay time constant of the pump-probe signal decreases as the band peak of the IR absorption spectrum shifts to lower wavenumbers (the result of changing the proton acceptor). For phenol oligomers, the decay time constant of the pump-probe signal decreases as the probe wavenumber decreases. These observations show that the VER time strongly correlates with the strength of hydrogen bonding. This acceleration may be due to increased coupling between the OH stretching mode and the accepting mode of the VER, because the low-frequency shift caused by hydrogen bond formation is very large. Unlike phenol oligomers, however, the pump-probe signals of phenol-base complexes did not exhibit probe frequency dependence. For these complexes, rapid interconversion between different conformations causes rapid fluctuations in the vibrational frequency of the OH stretching modes, and these fluctuations level the VER times of different conformations. For the benzoic acid dimer, a quantum beat at a frequency of around 100 cm(-1) is superimposed on the pump-probe signal. This result indicates the presence of strong anharmonic coupling between the intramolecular OH stretching and the intermolecular stretching modes. From a two-dimensional plot of the OH stretching wavenumber and the low-frequency wavenumber, the wavenumber of the low-frequency mode is found to increase monotonically as the probe wavenumber is shifted toward lower wavenumbers. Our results represent a quantitative determination of the acceleration of VER by the formation of hydrogen bonds. Our studies merit further evaluation and raise fundamental questions about the current theory of vibrational dynamics in the condensed phase.

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.

Validation of a reduced-order jet model for subsonic and underexpanded hydrogen jets

DOE PAGES

Li, Xuefang; Hecht, Ethan S.; Christopher, David M.

2016-01-01

Much effort has been made to model hydrogen releases from leaks during potential failures of hydrogen storage systems. A reduced-order jet model can be used to quickly characterize these flows, with low computational cost. Notional nozzle models are often used to avoid modeling the complex shock structures produced by the underexpanded jets by determining an “effective” source to produce the observed downstream trends. In our work, the mean hydrogen concentration fields were measured in a series of subsonic and underexpanded jets using a planar laser Rayleigh scattering system. Furthermore, we compared the experimental data to a reduced order jet modelmore » for subsonic flows and a notional nozzle model coupled to the jet model for underexpanded jets. The values of some key model parameters were determined by comparisons with the experimental data. Finally, the coupled model was also validated against hydrogen concentrations measurements for 100 and 200 bar hydrogen jets with the predictions agreeing well with data in the literature.« less

SSH2S: Hydrogen storage in complex hydrides for an auxiliary power unit based on high temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Baricco, Marcello; Bang, Mads; Fichtner, Maximilian; Hauback, Bjorn; Linder, Marc; Luetto, Carlo; Moretto, Pietro; Sgroi, Mauro

2017-02-01

The main objective of the SSH2S (Fuel Cell Coupled Solid State Hydrogen Storage Tank) project was to develop a solid state hydrogen storage tank based on complex hydrides and to fully integrate it with a High Temperature Proton Exchange Membrane (HT-PEM) fuel cell stack. A mixed lithium amide/magnesium hydride system was used as the main storage material for the tank, due to its high gravimetric storage capacity and relatively low hydrogen desorption temperature. The mixed lithium amide/magnesium hydride system was coupled with a standard intermetallic compound to take advantage of its capability to release hydrogen at ambient temperature and to ensure a fast start-up of the system. The hydrogen storage tank was designed to feed a 1 kW HT-PEM stack for 2 h to be used for an Auxiliary Power Unit (APU). A full thermal integration was possible thanks to the high operation temperature of the fuel cell and to the relative low temperature (170 °C) for hydrogen release from the mixed lithium amide/magnesium hydride system.

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

PubMed Central

Miller, David C.; Tarantino, Kyle T.; Knowles, Robert R.

2016-01-01

Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter we aim to highlight the origins, development and evolution of PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups. PMID:27573270

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

Li, Xuefang; Hecht, Ethan S.; Christopher, David M.

Much effort has been made to model hydrogen releases from leaks during potential failures of hydrogen storage systems. A reduced-order jet model can be used to quickly characterize these flows, with low computational cost. Notional nozzle models are often used to avoid modeling the complex shock structures produced by the underexpanded jets by determining an “effective” source to produce the observed downstream trends. In our work, the mean hydrogen concentration fields were measured in a series of subsonic and underexpanded jets using a planar laser Rayleigh scattering system. Furthermore, we compared the experimental data to a reduced order jet modelmore » for subsonic flows and a notional nozzle model coupled to the jet model for underexpanded jets. The values of some key model parameters were determined by comparisons with the experimental data. Finally, the coupled model was also validated against hydrogen concentrations measurements for 100 and 200 bar hydrogen jets with the predictions agreeing well with data in the literature.« less

Coupled laboratory experiments and numerical models for generating ice-depth profiles of steady-state hydrogen peroxide concentrations on radiolytically processed icy worlds.

NASA Astrophysics Data System (ADS)

Hand, K. P.; Carlson, R. W.

2007-12-01

The presence of hydrogen peroxide and condensed phase molecular oxygen on the surface of Europa is now well established [1,2] and laboratory experiments have repeatedly demonstrated the viability of various radiolytic processes for explaining the observations [see e.g. 3, 4]. To date, however, both the Europa observations and the laboratory work have been limited to only the upper few, or few tens of microns, of ice. The spectrum of charged particles incident on the surface of Europa penetrates deeper, and deposits energy over a much greater range, than any laboratory experiment has aimed to replicate [5, 6]. Here we present results from laboratory work on hydrogen peroxide production using energetic electrons (4 keV - 16 keV) and couple these results with a numerical model for the integrated steady-state density of hydrogen peroxide as a function of depth into the ice. Production rates and steady-state peroxide levels for a range of initial electron energies are used to generate functions for the number of peroxide molecules produced per initial electron as it penetrates through the ice. We examined the electron energy spectrum from 0.01 MeV to 10 MeV and accounted for electrons incident to the surface over the solid angle from cosine(theta) = 0.3-1.0, where theta is the angle from the normal to the surface. We found that, accounting for production and destruction as a function of energy deposition, steady-state hydrogen peroxide concentrations resulting from electron radiolysis likely increases by a factor of a few to an order of magnitude at a depth of a few hundred microns. In other words, the 0.13 percent by number abundance of peroxide observed by NIMS [1] may be a low-end value; at depth the peroxide concentration could increase to a few percent by number relative to water. [1] Carlson et al. 1999. [2] Spencer and Calvin, 2002. [3] Moore and Hudson, 2000. [4] Loeffler et al., 2006. [5] Cooper et al., 2001 [6] Paranicas et al., 2001.

Non-thermal hydrogen plasma processing effectively increases the antibacterial activity of graphene oxide

NASA Astrophysics Data System (ADS)

Ke, Zhigang; Ma, Yulong; Zhu, Zhongjie; Zhao, Hongwei; Wang, Qi; Huang, Qing

2018-01-01

Graphene-based materials (GMs) are promising antibacterial agents which provide an alternative route to treat pathogenic bacteria with resistance to conventional antibiotics. To further improve their antibacterial activity, many methods have been developed to functionalize the GMs with chemicals. However, the application of additional chemicals may pose potential risks to the environment and human being. Herein, a radio-frequency-driven inductively coupled non-thermal hydrogen plasma was used to treat and reduce graphene oxide (GO) without using any other chemicals, and we found that the plasma-reduced GO (prGO) is with significantly higher bactericidal activity against Escherichia coli. The mechanism of the increased antibacterial activity of prGO is due to that plasma processing breaks down the GO sheets into smaller layers with more rough surface defects, which can thus induce more destructive membrane damages to the bacteria. This work sets another good example, showing that plasma processing is a green and low-cost alternative for GM modification for biomedical applications.

LARGE-SCALE HYDROGEN PRODUCTION FROM NUCLEAR ENERGY USING HIGH TEMPERATURE ELECTROLYSIS

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

James E. O'Brien

2010-08-01

Hydrogen can be produced from water splitting with relatively high efficiency using high-temperature electrolysis. This technology makes use of solid-oxide cells, running in the electrolysis mode to produce hydrogen from steam, while consuming electricity and high-temperature process heat. When coupled to an advanced high temperature nuclear reactor, the overall thermal-to-hydrogen efficiency for high-temperature electrolysis can be as high as 50%, which is about double the overall efficiency of conventional low-temperature electrolysis. Current large-scale hydrogen production is based almost exclusively on steam reforming of methane, a method that consumes a precious fossil fuel while emitting carbon dioxide to the atmosphere. Demandmore » for hydrogen is increasing rapidly for refining of increasingly low-grade petroleum resources, such as the Athabasca oil sands and for ammonia-based fertilizer production. Large quantities of hydrogen are also required for carbon-efficient conversion of biomass to liquid fuels. With supplemental nuclear hydrogen, almost all of the carbon in the biomass can be converted to liquid fuels in a nearly carbon-neutral fashion. Ultimately, hydrogen may be employed as a direct transportation fuel in a “hydrogen economy.” The large quantity of hydrogen that would be required for this concept should be produced without consuming fossil fuels or emitting greenhouse gases. An overview of the high-temperature electrolysis technology will be presented, including basic theory, modeling, and experimental activities. Modeling activities include both computational fluid dynamics and large-scale systems analysis. We have also demonstrated high-temperature electrolysis in our laboratory at the 15 kW scale, achieving a hydrogen production rate in excess of 5500 L/hr.« less

Hydrogen adsorption on two catalysts for the ortho- to parahydrogen conversion: Cr-doped silica and ferric oxide gel.

PubMed

Hartl, Monika; Gillis, Robert Chad; Daemen, Luke; Olds, Daniel P; Page, Katherine; Carlson, Stefan; Cheng, Yongqiang; Hügle, Thomas; Iverson, Erik B; Ramirez-Cuesta, A J; Lee, Yongjoong; Muhrer, Günter

2016-06-29

Molecular hydrogen exists in two spin-rotation coupled states: parahydrogen and orthohydrogen. Due to the variation of energy with rotational level, the occupation of ortho- and parahydrogen states is temperature dependent, with parahydrogen being the dominant species at low temperatures. The equilibrium at 20 K (99.8% parahydrogen) can be reached by natural conversion only after a lengthy process. With the use of a suitable catalyst, this process can be shortened significantly. Two types of commercial catalysts currently being used for ortho- to parahydrogen conversion are: iron(iii) oxide (Fe2O3, IONEX®), and chromium(ii) oxide doped silica catalyst (CrO·SiO2, OXISORB®). We investigate the interaction of ortho- and parahydrogen with the surfaces of these ortho-para conversion catalysts using neutron vibrational spectroscopy. The catalytic surfaces have been characterized using X-ray absorption fine structure (XAFS) and X-ray/neutron pair distribution function measurements.

Quantum entanglement and quantum information in biological systems (DNA)

NASA Astrophysics Data System (ADS)

Hubač, Ivan; Švec, Miloslav; Wilson, Stephen

2017-12-01

Recent studies of DNA show that the hydrogen bonds between given base pairs can be treated as diabatic systems with spin-orbit coupling. For solid state systems strong diabaticity and spin-orbit coupling the possibility of forming Majorana fermions has been discussed. We analyze the hydrogen bonds in the base pairs in DNA from this perspective. Our analysis is based on a quasiparticle supersymmetric transformation which couples electronic and vibrational motion and includes normal coordinates and the corresponding momenta. We define qubits formed by Majorana fermions in the hydrogen bonds and also discuss the entangled states in base pairs. Quantum information and quantum entropy are introduced. In addition to the well-known classical information connected with the DNA base pairs, we also consider quantum information and show that the classical and quantum information are closely connected.

Reply to comment "On the hydrogen escape: Comment to variability of the hydrogen in the Martian upper atmosphere as simulated by a 3D atmosphere-exosphere coupling by J.-Y. Chaufray et al." by V. Krasnopolsky, Icarus, 281, 262

NASA Astrophysics Data System (ADS)

Chaufray, J.-Y.; Gonzalez-Galindo, F.; Forget, F.; Lopez-Valverde, M.; Leblanc, F.; Modolo, R.; Hess, S.

2018-02-01

Krasnopolsky (2017) makes a careful review of our recent results about the Martian hydrogen content of the Martian upper atmosphere (Chaufray et al., 2015). We comment here on his two major points. First, he suggests that the non-thermal escape of H2, and particularly collisions with hot oxygen, not taken into account in our general circulation model (GCM), should modify our reported H2 and H density profiles. This is an important issue; we acknowledge that future effective coupling of our GCM with comprehensive models of the Martian solar wind interaction, ideally after being validated with the latest plasma observations of H2+, would allow for better estimations of the relative importance of the H2 non-thermal and thermal escape processes. For the time being we need assumptions in the GCM, with proper and regular updates. According to a recent and detailed study of the anisotropic elastic and inelastic collision cross sections between O and H2 (Gacesa et al., 2012), the escape rates used by Krasnopolsky (2010) for this process might be overestimated. We therefore do not include non thermal escape of H2 in the model. And secondly, in response to Krasnopolsky's comment on the H escape variability with the solar cycle, we revised our calculations and found a small bug in the computation of the Jeans effusion velocity. Our revised computed H escape rates are included here. They have a small impact on our key conclusions: similar seasonal variations, a reduced variation with the solar cycle but still larger than Krasnopolsky (2017), and again a hydrogen scape systematically lower than the diffusion-limited flux. This bug does not affect the latest Mars Climate Database v5.2.

Suicide Inhibition of Cytochrome P450 Enzymes by Cyclopropylamines via a Ring-opening Mechanism: Proton-Coupled Electron Transfer Makes a Difference

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqian; Li, Xiao-Xi; Liu, Yufang; Wang, Yong

2017-01-01

N-benzyl-N-cyclopropylamine (BCA) has been attracting great interests for decades for its partial suicide inactivation role to cytochrome P450 (P450) via a ring-opening mechanism besides acting as a role of normal substrates. Understanding the mechanism of such partial inactivation is vital to the clinical drug design. Thus, density functional theoretical (DFT) calculations were carried out on such P450-catalyzed reactions, not only on the metabolic pathway, but on the ring-opening inactivation one. Our theoretical results demonstrated that, in the metabolic pathway, besides the normal carbinolamine, an unexpected enamine was formed via the dual hydrogen abstraction (DHA) process, in which the competition between rotation of the H-abstracted substrate radical and the rotation of hydroxyl group of the protonated Cpd II moiety plays a significant role in product branch; In the inactivation pathway, the well-noted single electron transfer (SET) mechanism-involved process was invalidated for its high energy barrier, a proton-coupled electron transfer (PCET(ET)) mechanism plays a role. Our results are consistent with other related theoretical works on heteroatom-hydrogen (X-H, X = O, N) activation and revealed new features. The revealed mechanisms will play a positive role in relative drug design.

Two-Centre Convergent Close-Coupling Approach to Ion-Atom Collisions: Current Progress

NASA Astrophysics Data System (ADS)

Kadyrov, Alisher; Abdurakhmanov, Ilkhom; Bailey, Jackson; Bray, Igor

2016-09-01

There are two versions of the convergent close-coupling (CCC) approach to ion-atom collisions: quantum-mechanical (QM-CCC) and semi-classical (SC-CCC). Recently, both implementations have been extended to include electron-transfer channels. The SC-CCC approach has been applied to study the excitation and the electron-capture processes in proton-hydrogen collisions. The integral alignment parameter A20 for polarization of Lyman- α emission and the cross sections for excitation and electron-capture into the lowest excited states have been calculated for a wide range of the proton impact energies. It has been established that for convergence of the results a very wide range of impact parameters (typically, 0-50 a.u.) is required due to extremely long tails of transition probabilities for transitions into the 2 p states at high energies. The QM-CCC approach allowed to obtain an accurate solution of proton-hydrogen scattering problem including all underlying processes, namely, direct scattering and ionisation, and electron capture into bound and continuum states of the projectile. In this presentation we give a general overview of current progress in applications of the two-centre CCC approach to ion-atom and atom-atom collisions. The work is supported by the Australian Research Council.

Selective catalytic two-step process for ethylene glycol from carbon monoxide

PubMed Central

Dong, Kaiwu; Elangovan, Saravanakumar; Sang, Rui; Spannenberg, Anke; Jackstell, Ralf; Junge, Kathrin; Li, Yuehui; Beller, Matthias

2016-01-01

Upgrading C1 chemicals (for example, CO, CO/H2, MeOH and CO2) with C–C bond formation is essential for the synthesis of bulk chemicals. In general, these industrially important processes (for example, Fischer Tropsch) proceed at drastic reaction conditions (>250 °C; high pressure) and suffer from low selectivity, which makes high capital investment necessary and requires additional purifications. Here, a different strategy for the preparation of ethylene glycol (EG) via initial oxidative coupling and subsequent reduction is presented. Separating coupling and reduction steps allows for a completely selective formation of EG (99%) from CO. This two-step catalytic procedure makes use of a Pd-catalysed oxycarbonylation of amines to oxamides at room temperature (RT) and subsequent Ru- or Fe-catalysed hydrogenation to EG. Notably, in the first step the required amines can be efficiently reused. The presented stepwise oxamide-mediated coupling provides the basis for a new strategy for selective upgrading of C1 chemicals. PMID:27377550

A full-dimensional potential energy surface and quantum dynamics of inelastic collision process for H2-HF

NASA Astrophysics Data System (ADS)

Yang, Dongzheng; Huang, Jing; Zuo, Junxiang; Hu, Xixi; Xie, Daiqian

2018-05-01

A full-dimensional ab initio potential energy surface for the H2-HF van der Waals complex was constructed by employing the coupled-cluster singles and doubles with noniterative inclusion of connected triples with augmented correlation-consistent polarised valence quadruple-zeta basis set plus bond functions. Using the improved coupled-states approximation including the nearest neighbor Coriolis couplings, we calculated the state-to-state scattering dynamics for pure rotational and ro-vibrational energy transfer processes. For pure rotational energy transfer, our results showed a different dynamical behavior for para-H2 and ortho-H2 in collision with hydrogen fluoride (HF), which is consistent with the previous study. Interestingly, some strong resonant peaks were presented in the cross sections for ro-vibrational energy transfer. In addition, the calculated vibrational-resolved rate constant is in agreement with the experimental results reported by Bott et al. These dynamics data can be further applied to the numerical simulation of HF chemical lasers.

Inelastic Transitions in Slow Collisions of Anti-Hydrogen with Hydrogen Atoms

NASA Astrophysics Data System (ADS)

Harrison, Robert; Krstic, Predrag

2007-06-01

We calculate excited adiabatic states and nonadiabatic coupling matrix elements of a quasimolecular system containing hydrogen and anti-hydrogen atoms, for a range of internuclear distances from 0.2 to 20 Bohrs. High accuracy is achieved by exact diagonalization of the molecular Hamiltionian in a large Gaussian basis. Nonadiabatic dynamics was calculated by solving MOCC equations. Positronium states are included in the consideration.

Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

PubMed

Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

2017-07-06

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Ab initio characterization of coupling strength for all types of dangling-bond pairs on the hydrogen-terminated Si(100)-2 × 1 surface

NASA Astrophysics Data System (ADS)

Shaterzadeh-Yazdi, Zahra; Sanders, Barry C.; DiLabio, Gino A.

2018-04-01

Recent work has suggested that coupled silicon dangling bonds sharing an excess electron may serve as building blocks for quantum-cellular-automata cells and quantum computing schemes when constructed on hydrogen-terminated silicon surfaces. In this work, we employ ab initio density-functional theory to examine the details associated with the coupling between two dangling bonds sharing one excess electron and arranged in various configurations on models of phosphorous-doped hydrogen-terminated silicon (100) surfaces. Our results show that the coupling strength depends strongly on the relative orientation of the dangling bonds on the surface and on the separation between them. The orientation of dangling bonds is determined by the anisotropy of the silicon (100) surface, so this feature of the surface is a significant contributing factor to variations in the strength of coupling between dangling bonds. The results demonstrate that simple models for approximating tunneling, such as the Wentzel-Kramer-Brillouin method, which do not incorporate the details of surface structure, are incapable of providing reasonable estimates of tunneling rates between dangling bonds. The results provide guidance to efforts related to the development of dangling-bond based computing elements.

Selective sp3 C–H alkylation via polarity-match-based cross-coupling

PubMed Central

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-01-01

The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

Selective sp3 C-H alkylation via polarity-match-based cross-coupling

NASA Astrophysics Data System (ADS)

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-07-01

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander; Hammes-Schiffer, Sharon

2015-11-17

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approachmore » in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (applications to molecular electrocatalysts).« less

Rotational and translational dynamics and their relation to hydrogen bond lifetimes in an ionic liquid by means of NMR relaxation time experiments and molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Strate, Anne; Neumann, Jan; Overbeck, Viviane; Bonsa, Anne-Marie; Michalik, Dirk; Paschek, Dietmar; Ludwig, Ralf

2018-05-01

We report a concerted theoretical and experimental effort to determine the reorientational dynamics as well as hydrogen bond lifetimes for the doubly ionic hydrogen bond +OH⋯O- in the ionic liquid (2-hydroxyethyl)trimethylammonium bis(trifluoromethylsulfonyl)imide [Ch][NTf2] by using a combination of NMR relaxation time experiments, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. Due to fast proton exchange, the determination of rotational correlation times is challenging. For molecular liquids, 17O-enhanced proton relaxation time experiments have been used to determine the rotational correlation times for the OH vectors in water or alcohols. As an alternative to those expensive isotopic substitution experiments, we employed a recently introduced approach which is providing access to the rotational dynamics from a single NMR deuteron quadrupolar relaxation time experiment. Here, the deuteron quadrupole coupling constants (DQCCs) are obtained from a relation between the DQCC and the δ1H proton chemical shifts determined from a set of DFT calculated clusters in combination with experimentally determined proton chemical shifts. The NMR-obtained rotational correlation times were compared to those obtained from MD simulations and then related to viscosities for testing the applicability of popular hydrodynamic models. In addition, hydrogen bond lifetimes were derived, using hydrogen bond population correlation functions computed from MD simulations. Here, two different time domains were observed: The short-time contributions to the hydrogen lifetimes and the reorientational correlation times have roughly the same size and are located in the picosecond range, whereas the long-time contributions decay with relaxation times in the nanosecond regime and are related to rather slow diffusion processes. The computed average hydrogen bond lifetime is dominated by the long-time process, highlighting the importance and longevity of hydrogen-bonded ion pairs in these ionic liquids.

Raman investigation of ro-vibrational modes of interstitial H2 in Si

NASA Astrophysics Data System (ADS)

Koch, S. G.; Lavrov, E. V.; Weber, J.

2012-08-01

A Raman scattering study of ro-vibrational transitions Q(J) of the interstitial H2 in Si is presented. It is shown that the Q(2) mode of para hydrogen is coupled to the TAX phonon of Si. The mode appears in the spectra at temperatures above 200 K. The results presented also suggest that the Q(3) transition of ortho hydrogen is resonantly coupled to the OΓ phonon.

Direct Coupling of Thermo- and Photocatalysis for Conversion of CO2 -H2 O into Fuels.

PubMed

Zhang, Li; Kong, Guoguo; Meng, Yaping; Tian, Jinshu; Zhang, Lijie; Wan, Shaolong; Lin, Jingdong; Wang, Yong

2017-12-08

Photocatalytic CO 2 reduction into renewable hydrocarbon solar fuels is considered as a promising strategy to simultaneously address global energy and environmental issues. This study focused on the direct coupling of photocatalytic water splitting and thermocatalytic hydrogenation of CO 2 in the conversion of CO 2 -H 2 O into fuels. Specifically, it was found that direct coupling of thermo- and photocatalysis over Au-Ru/TiO 2 leads to activity 15 times higher (T=358 K; ca. 99 % CH 4 selectivity) in the conversion of CO 2 -H 2 O into fuels than that of photocatalytic water splitting. This is ascribed to the promoting effect of thermocatalytic hydrogenation of CO 2 by hydrogen atoms generated in situ by photocatalytic water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical Biomolecular Dynamics: Picosecond Hydrogen Bonding Regulates Microsecond Conformational Transitions.

PubMed

Buchenberg, Sebastian; Schaudinnus, Norbert; Stock, Gerhard

2015-03-10

Biomolecules exhibit structural dynamics on a number of time scales, including picosecond (ps) motions of a few atoms, nanosecond (ns) local conformational transitions, and microsecond (μs) global conformational rearrangements. Despite this substantial separation of time scales, fast and slow degrees of freedom appear to be coupled in a nonlinear manner; for example, there is theoretical and experimental evidence that fast structural fluctuations are required for slow functional motion to happen. To elucidate a microscopic mechanism of this multiscale behavior, Aib peptide is adopted as a simple model system. Combining extensive molecular dynamics simulations with principal component analysis techniques, a hierarchy of (at least) three tiers of the molecule's free energy landscape is discovered. They correspond to chiral left- to right-handed transitions of the entire peptide that happen on a μs time scale, conformational transitions of individual residues that take about 1 ns, and the opening and closing of structure-stabilizing hydrogen bonds that occur within tens of ps and are triggered by sub-ps structural fluctuations. Providing a simple mechanism of hierarchical dynamics, fast hydrogen bond dynamics is found to be a prerequisite for the ns local conformational transitions, which in turn are a prerequisite for the slow global conformational rearrangement of the peptide. As a consequence of the hierarchical coupling, the various processes exhibit a similar temperature behavior which may be interpreted as a dynamic transition.

Electron, proton and hydrogen-atom transfers in photosynthetic water oxidation.

PubMed Central

Tommos, Cecilia

2002-01-01

When photosynthetic organisms developed so that they could use water as an electron source to reduce carbon dioxide, the stage was set for efficient proliferation. Algae and plants spread globally and provided the foundation for our atmosphere and for O(2)-based chemistry in biological systems. Light-driven water oxidation is catalysed by photosystem II, the active site of which contains a redox-active tyrosine denoted Y(Z), a tetramanganese cluster, calcium and chloride. In 1995, Gerald Babcock and co-workers presented the hypothesis that photosynthetic water oxidation occurs as a metallo-radical catalysed process. In this model, the oxidized tyrosine radical is generated by coupled proton/electron transfer and re-reduced by abstracting hydrogen atoms from substrate water or hydroxide-ligated to the manganese cluster. The proposed function of Y(Z) requires proton transfer from the tyrosine site upon oxidation. The oxidation mechanism of Y(Z) in an inhibited and O(2)-evolving photosystem II is discussed. Domino-deprotonation from Y(Z) to the bulk solution is shown to be consistent with a variety of data obtained on metal-depleted samples. Experimental data that suggest that the oxidation of Y(Z) in O(2)-evolving samples is coupled to proton transfer in a hydrogen-bonding network are described. Finally, a dielectric-dependent model for the proton release that is associated with the catalytic cycle of photosystem II is discussed. PMID:12437877

Application of low temperature plasmas for restoration/conservation of archaeological objects

NASA Astrophysics Data System (ADS)

Krčma, F.; Blahová, L.; Fojtíková, P.; Graham, W. G.; Grossmannová, H.; Hlochová, L.; Horák, J.; Janová, D.; Kelsey, C. P.; Kozáková, Z.; Mazánková, V.; Procházka, M.; Přikryl, R.; Řádková, L.; Sázavská, V.; Vašíček, M.; Veverková, R.; Zmrzlý, M.

2014-12-01

The low-temperature low-pressure hydrogen based plasmas were used to study the influence of processes and discharge conditions on corrosion removal. The capacitive coupled RF discharge in the continuous or pulsed regime was used at operating pressure of 100-200 Pa. Plasma treatment was monitored by optical emission spectroscopy. To be able to study influence of various process parameters, the model corroded samples with and without sandy incrustation were prepared. The SEM-EDX analyzes were carried out to verify corrosion removal efficiency. Experimental conditions were optimized for the selected most frequent materials of original metallic archaeological objects (iron, bronze, copper, and brass). Chlorides removal is based on hydrogen ion reactions while oxides are removed mainly by neutral species interactions. A special focus was kept for the samples temperature because it was necessary to avoid any metallographic changes in the material structure. The application of higher power pulsed regime with low duty cycle seems be the best treatment regime. The low pressure hydrogen plasma is not applicable for objects with a very broken structure or for nonmetallic objects due to the non-uniform heat stress. Due to this fact, the new developed plasmas generated in liquids were applied on selected original archaeological glass materials.

The setup of an extraction system coupled to a hydrogen isotopes distillation column

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

Zamfirache, M.; Bornea, A.; Stefanescu, I.

2008-07-15

Among the most difficult problems of cryogenic distillation one stands apart: the extraction of the heavy fraction. By an optimal design of the cycle scheme, this problem could be avoided. A 'worst case scenario' is usually occurring when the extracted fraction consists of one prevalent isotope such as hydrogen and small amounts of the other two hydrogen isotopes (deuterium and/or tritium). This situation is further complicated by two parameters of the distillation column: the extraction flow rate and the hold-up. The present work proposes the conceptual design of an extraction system associated to the cryogenic distillation column used in hydrogenmore » separation processes. During this process, the heavy fraction (DT, T{sub 2}) is separated, its concentration being the highest at the bottom of the distillation column. From this place the extraction of the gaseous phase can now begin. Being filled with adsorbent, the extraction system is used to temporarily store the heavy fraction. Also the extraction system provides samples for the gas Chromatograph. The research work is focused on the existent pilot plant for tritium and deuterium separation from our institute to validate the experiments carried out until now. (authors)« less

Deep levels due to hydrogen in ZnO single crystals

NASA Astrophysics Data System (ADS)

Parmar, Narendra; Weber, Marc; Lynn, Kelvin

2009-05-01

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

The nature of hydrogen-bonding interactions in nonsteroidal anti-inflammatory drugs revealed by polarized IR spectroscopy

NASA Astrophysics Data System (ADS)

Hachuła, Barbara

2018-01-01

The influence of hydrogen-bonding interactions in the solid phase on the IR spectroscopic pattern of the νOsbnd H band of nonsteroidal anti-inflammatory drugs (NSAIDs) was studied experimentally by IR spectroscopy with the use of polarized light at two temperatures (293 K and 77 K) and in isotopic dilution. The neat and deuterated crystals of (S)-naproxen ((S)-NPX), (R)-flurbiprofen ((R)-FBP), (RS)-flurbiprofen ((RS)-FBP) and (RS)-ketoprofen ((RS)-KTP) were obtained by melt crystallization between the two squeezed CaF2 plates. The vibrational spectra of selected α-aryl propionic acid derivatives (2APAs) reflected the characteristics of their hydrogen-bond networks, i.e., 2APAs were characterized by the chain ((S)-NPX, (R)-FBP) and by dimeric ((RS)-FBP, (RS)-KTP) arrangement of hydrogen bonds in the crystal lattice. Spectroscopic results showed that the interchain (through-space) exciton coupling, between two laterally-spaced hydrogen bonds, dominates in the crystals of four NSAIDs. The same exciton coupled hydrogen bonds were also responsible for the H/D isotopic recognition mechanism in the crystalline spectra of deuterated 2APAs. The presented spectral results may help to predict the hydrogen bond motifs in the crystalline NSAIDs, which structures are not yet known, based on their IR spectra of hydrogen bond in the crystals.

Nanomaterials driven energy, environmental and biomedical research

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

Sharma, Prakash C.; Srinivasan, Sesha S.; Wilson, Jeremiah F.

We have developed state-of-the-art nanomaterials such as nanofibers, nanotubes, nanoparticles, nanocatalysts and nanostructures for clean energy, environmental and biomedical research. Energy can neither be created nor be destroyed, but it can be converted from one form to another. Based on this principle, chemical energy such as hydrogen has been produced from water electrolysis at a much lower voltage using RuO{sub 2} nanoparticles on the Si wafer substrate. Once the hydrogen is produced from the clean sources such as solar energy and water, it has to be stored by physisorption or chemisorption processes on to the solid state systems. For themore » successful physical adsorption of hydrogen molecule, we have developed novel polyaniline nanostructures via chemical templating and electrospinning routes. Chemical or complex hydrides involving nano MgH{sub 2} and transition metal nanocatalysts have been synthesized to tailor both the thermodynamics and kinetics of hydrogen (chemi) sorption respectively. Utilization of solar energy (UV-Vis) and a coupling of novel semiconductor oxide nanoparticles have been recently demonstrated with enhancement in photo-oxidation and/or photo-reduction processes for the water/air detoxification and sustainable liquid fuel production respectively. Magnetic nanoparticles such as ZnFe{sub 2}O{sub 4} have been synthesized and optimized for biomedical applications such as targeted drug delivery and tumor diagnostic sensing (MRI)« less

Charge exchange cross sections in slow collisions of Si3+ with Hydrogen atom

NASA Astrophysics Data System (ADS)

Joseph, Dwayne; Quashie, Edwin; Saha, Bidhan

2011-05-01

In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. Work supported by NSF CREST project (grant #0630370).

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

San Fabián, J.; Omar, S.; García de la Vega, J. M., E-mail: garcia.delavega@uam.es

The effect of a fraction of Hartree-Fock exchange on the calculated spin-spin coupling constants involving fluorine through a hydrogen bond is analyzed in detail. Coupling constants calculated using wavefunction methods are revisited in order to get high-level calculations using the same basis set. Accurate MCSCF results are obtained using an additive approach. These constants and their contributions are used as a reference for density functional calculations. Within the density functional theory, the Hartree-Fock exchange functional is split in short- and long-range using a modified version of the Coulomb-attenuating method with the SLYP functional as well as with the original B3LYP.more » Results support the difficulties for calculating hydrogen bond coupling constants using density functional methods when fluorine nuclei are involved. Coupling constants are very sensitive to the Hartree-Fock exchange and it seems that, contrary to other properties, it is important to include this exchange for short-range interactions. Best functionals are tested in two different groups of complexes: those related with anionic clusters of type [F(HF){sub n}]{sup −} and those formed by difluoroacetylene and either one or two hydrogen fluoride molecules.« less

Vibrationally-resolved Charge Transfer of O^3+ Ions with Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Wang, J. G.; Stancil, P. C.; Turner, A. R.; Cooper, D. L.

2003-05-01

Charge transfer processes due to collisions of ground state O^3+ ions with H2 are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained with the spin-coupled valence-bond approach. Vibrationally-resolved cross sections for energies between 0.1 eV/u and 2 keV/u using the infinite order sudden approximation (IOSA), vibrational sudden approximation (VSA), and electronic approximation (EA), but including Frank-Condon factors (the centroid approximation) will be presented. Comparison with existing experimental data for total cross sections shows best agreement with IOSA and discrepancies for VSA and EA. Triplet-singlet cross section ratios obtained with IOSA are found generally to be in harmony with experiment. JGW and PCS acknowledge support from NASA grant 11453.

On-site applicability of hydrogen peroxide producing microbial electrochemical cells (MECs) coupled with UV in wastewater disinfection study

EPA Science Inventory

Background: There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals wh...

Anaerobic Formate and Hydrogen Metabolism.

PubMed

Sawers, R Gary; Blokesch, Melanie; Böck, August

2004-12-01

During fermentative growth, Escherichia coli degrades carbohydrates via the glycolytic route into two pyruvate molecules. Pyruvate can be reduced to lactate or nonoxidatively cleaved by pyruvate formate lyase into acetyl-coenzyme A (acetyl-CoA) and formate. Acetyl-CoA can be utilized for energy conservation in the phosphotransacetylase (PTA) and acetate kinase (ACK) reaction sequence or can serve as an acceptor for reducing equivalents gathered during pyruvate formation, through the action of alcohol dehydrogenase (AdhE). Formic acid is strongly acidic and has a redox potential of -420 mV under standard conditions and therefore can be classified as a high-energy compound. Its disproportionation into CO2 and molecular hydrogen (Em,7 -420 mV) via the formate hydrogenlyase (FHL) system is therefore of high selective value. The FHL reaction involves the participation of at least seven proteins, most of which are metalloenzymes, with requirements for iron, molybdenum, nickel, or selenium. Complex auxiliary systems incorporate these metals. Reutilization of the hydrogen evolved required the evolution of H2 oxidation systems, which couple the oxidation process to an appropriate energy-conserving terminal reductase. E. coli has two hydrogen-oxidizing enzyme systems. Finally, fermentation is the "last resort" of energy metabolism, since it gives the minimal energy yield when compared with respiratory processes. Consequently, fermentation is used only when external electron acceptors are absent. This has necessitated the establishment of regulatory cascades, which ensure that the metabolic capability is appropriately adjusted to the physiological condition. Here we review the genetics, biochemistry, and regulation of hydrogen metabolism and its hydrogenase maturation system.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Perspective on recent developments on sulfur-containing agents and hydrogen sulfide signaling.

PubMed

Jacob, Claus; Anwar, Awais; Burkholz, Torsten

2008-10-01

The last couple of years have witnessed the coming together of several initially unconnected lines of investigation which now link natural sulfur products to hydrogen sulfide release and wide ranging cardiovascular protection. It has become apparent that sulfur compounds contained within garlic, onions, mushrooms and various edible beans and fruits may be transformed chemically or enzymatically in the human body with subsequent formation of hydrogen sulfide. The latter has emerged during the last decade from a shadowy existence as toxic gas to be recognized as the third gaseous transmitter besides nitric oxide ( (.)NO) and carbon monoxide (CO). Hydrogen sulfide is formed endogenously in the human body by enzymes such as cystathionine beta-synthase (CBS) in the brain and cystathionine gamma-lyase (CSE) in liver, vascular and non-vascular smooth muscle. Although its exact chemical and biochemical modes of action are still not fully understood, levels of hydrogen sulfide in the brain and vasculature have unambiguously been associated with human health and disease. Not surprisingly, agents releasing hydrogen sulfide, as well as inhibitors of hydrogen sulfide synthesis (CBS and CSE inhibitors) have been investigated. Apart from linking our daily diet to a healthy brain and cardiovasculature, these findings may also provide new leads for drug design. Future studies will therefore need to focus on how such compounds are formed and transformed in the relevant plants, how food processing affects their chemical constitution, and how they release hydrogen sulfide (or control its levels) in the human body. Such multidisciplinary research should ultimately answer the all-important question if a hearty diet is also good for the heart.

Catalytically Enhanced Hydrogen Sorption in Mg-MgH2 by Coupling Vanadium-Based Catalyst and Carbon Nanotubes

PubMed Central

Kadri, Atikah; Jia, Yi; Chen, Zhigang; Yao, Xiangdong

2015-01-01

Mg (MgH2)-based composites, using carbon nanotubes (CNTs) and pre-synthesized vanadium-based complex (VCat) as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of 6.50 wt. % of hydrogen per minute and 6.50 wt. % of hydrogen release in 10 min at 200 °C and 300 °C, respectively. The temperature programmed desorption (TPD) results reveal that coupling VCat and CNTs reduces both peak and onset temperatures by more than 60 °C and 114 °C, respectively. In addition, the presence of both VCat and CNTs reduces the enthalpy and entropy of desorption of about 7 kJ/mol H2 and 11 J/mol H2·K, respectively, as compared to those of the commercial MgH2, which ascribe to the decrease of desorption temperature. From the study of the effect of CNTs milling time, it is shown that partially destroyed CNTs (shorter milling time) are better to enhance the hydrogen sorption performance.

An experimental study of ammonia borane based hydrogen storage systems

NASA Astrophysics Data System (ADS)

Deshpande, Kedaresh A.

2011-12-01

Hydrogen is a promising fuel for the future, capable of meeting the demands of energy storage and low pollutant emission. Chemical hydrides are potential candidates for chemical hydrogen storage, especially for automobile applications. Ammonia borane (AB) is a chemical hydride being investigated widely for its potential to realize the hydrogen economy. In this work, the yield of hydrogen obtained during neat AB thermolysis was quantified using two reactor systems. First, an oil bath heated glass reactor system was used with AB batches of 0.13 gram (+/- 0.001 gram). The rates of hydrogen generation were measured. Based on these experimental data, an electrically heated steel reactor system was designed and constructed to handle up to 2 grams of AB per batch. A majority of components were made of stainless-steel. The system consisted of an AB reservoir and feeder, a heated reactor, a gas processing unit and a system control and monitoring unit. An electronic data acquisition system was used to record experimental data. The performance of the steel reactor system was evaluated experimentally through batch reactions of 30 minutes each, for reaction temperatures in the range from 373 K to 430 K. The experimental data showed exothermic decomposition of AB accompanied by rapid generation of hydrogen during the initial period of the reaction. 90% of the hydrogen was generated during the initial 120 seconds after addition of AB to the reactor. At 430 K, the reaction produced 12 wt.% of hydrogen. The heat diffusion in the reactor system and the process of exothermic decomposition of AB were coupled in a two-dimensional model. Neat AB thermolysis was modeled as a global first order reactions based on Arrhenius theory. The values of equation constants were derived from curve fit of experimental data. The pre-exponential constant and the activation energy were estimated to be 4 s-1 (+/- 0.4 s-1) and 13000 J mol -1 s-1 (+/- 1050 J mol-1 s -1) respectively. The model was solved in COMSOL Multiphysics. The model was capable of simulating the transient response of the system and captured the observed trends such as the decrease in reactor temperature upon addition of AB and exothermic decomposition.

Electro Decomposition of Ammonia into Hydrogen for Fuel Cell Use

DTIC Science & Technology

2012-01-01

electrolyte for the experiments reflects the average amount of urea observed in human urine , 20 g/L/day. Figure 5 shows the flow dia- gram of a single cell...to improve the current density of the urea electrolysis process and to reduce the onset potential of the urea oxidation. The synthesis of layered...the new developments in the synthesis of nickel nanosheets can be coupled with the ammonia and urea electrolysis technology. This work concludes

The tropolone-isobutylamine complex: a hydrogen-bonded troponoid without dominant π-π interactions.

PubMed

Vealey, Zachary N; Mercado, Brandon Q; Vaccaro, Patrick H

2016-10-01

Tropolone long has served as a model system for unraveling the ubiquitous phenomena of proton transfer and hydrogen bonding. This molecule, which juxtaposes ketonic, hydroxylic, and aromatic functionalities in a framework of minimal complexity, also has provided a versatile platform for investigating the synergism among competing intermolecular forces, including those generated by hydrogen bonding and aryl coupling. Small members of the troponoid family typically produce crystals that are stabilized strongly by pervasive π-π, C-H...π, or ion-π interactions. The organic salt (TrOH·iBA) formed by a facile proton-transfer reaction between tropolone (TrOH) and isobutylamine (iBA), namely isobutylammonium 7-oxocyclohepta-1,3,5-trien-1-olate, C 4 H 12 N + ·C 7 H 5 O 2 - , has been investigated by X-ray crystallography, with complementary quantum-chemical and statistical-database analyses serving to elucidate the nature of attendant intermolecular interactions and their synergistic effects upon lattice-packing phenomena. The crystal structure deduced from low-temperature diffraction measurements displays extensive hydrogen-bonding networks, yet shows little evidence of the aryl forces (viz. π-π, C-H...π, and ion-π interactions) that typically dominate this class of compounds. Density functional calculations performed with and without the imposition of periodic boundary conditions (the latter entailing isolated subunits) documented the specificity and directionality of noncovalent interactions occurring between the proton-donating and proton-accepting sites of TrOH and iBA, as well as the absence of aromatic coupling mediated by the seven-membered ring of TrOH. A statistical comparison of the structural parameters extracted for key hydrogen-bond linkages to those reported for 44 previously known crystals that support similar binding motifs revealed TrOH·iBA to possess the shortest donor-acceptor distances of any troponoid-based complex, combined with unambiguous signatures of enhanced proton-delocalization processes that putatively stabilize the corresponding crystalline lattice and facilitate its surprisingly rapid formation under ambient conditions.

Development of a Microwave Regenerative Sorbent-Based Hydrogen Purifier

NASA Technical Reports Server (NTRS)

Wheeler, Richard R., Jr.; Dewberry, Ross H.; McCurry, Bryan D.; Abney, Morgan B.; Greenwood, Zachary W.

2016-01-01

This paper describes the design and fabrication of a Microwave Regenerative Sorbent-based Hydrogen Purifier (MRSHP). This unique microwave powered technology was developed for the purification of a hydrogen stream produced by the Plasma Pyrolysis Assembly (PPA). The PPA is a hydrogen recovery (from methane) post processor for NASA's Sabatier-based carbon dioxide reduction process. Embodied in the Carbon dioxide Reduction Assembly (CRA), currently aboard the International Space Station (ISS), the Sabatier reaction employs hydrogen to catalytically recover oxygen, in the form of water, from respiratory carbon dioxide produced by the crew. This same approach is base-lined for future service in the Air Revitalization system on extended missions into deep space where resupply is not practical. Accordingly, manned exploration to Mars may only become feasible with further closure of the air loop as afforded by the greater hydrogen recovery permitted by the PPA with subsequent hydrogen purification. By utilizing the well-known high sorbate loading capacity of molecular sieve 13x, coupled with microwave dielectric heating phenomenon, MRSHP technology is employed as a regenerative filter for a contaminated hydrogen gas stream. By design, freshly regenerated molecular sieve 13x contained in the MRSHP will remove contaminants from the effluent of a 1-CM scale PPA for several hours prior to breakthrough. By reversing flow and pulling a relative vacuum the MRSHP prototype then uses 2.45 GHz microwave power, applied through a novel coaxial antenna array, to rapidly heat the sorbent bed and drive off the contaminants in a short duration vacuum/thermal contaminant desorption step. Finally, following rapid cooling via room temperature cold plates, the MRSHP is again ready to serve as a hydrogen filter.

Numerical modeling of gas mixing and bio-chemical transformations during underground hydrogen storage within the project H2STORE

NASA Astrophysics Data System (ADS)

Hagemann, B.; Feldmann, F.; Panfilov, M.; Ganzer, L.

2015-12-01

The change from fossil to renewable energy sources is demanding an increasing amount of storage capacities for electrical energy. A promising technological solution is the storage of hydrogen in the subsurface. Hydrogen can be produced by electrolysis using excessive electrical energy and subsequently converted back into electricity by fuel cells or engine generators. The development of this technology starts with adding small amounts of hydrogen to the high pressure natural gas grid and continues with the creation of pure underground hydrogen storages. The feasibility of hydrogen storage in depleted gas reservoirs is investigated in the lighthouse project H2STORE financed by the German Ministry for Education and Research. The joint research project has project members from the University of Jena, the Clausthal University of Technology, the GFZ Potsdam and the French National Center for Scientic Research in Nancy. The six sub projects are based on laboratory experiments, numerical simulations and analytical work which cover the investigation of mineralogical, geochemical, physio-chemical, sedimentological, microbiological and gas mixing processes in reservoir and cap rocks. The focus in this presentation is on the numerical modeling of underground hydrogen storage. A mathematical model was developed which describes the involved coupled hydrodynamic and microbiological effects. Thereby, the bio-chemical reaction rates depend on the kinetics of microbial growth which is induced by the injection of hydrogen. The model has been numerically implemented on the basis of the open source code DuMuX. A field case study based on a real German gas reservoir was performed to investigate the mixing of hydrogen with residual gases and to discover the consequences of bio-chemical reactions.

Cell Structure Evolution of Aluminum Foams Under Reduced Pressure Foaming

NASA Astrophysics Data System (ADS)

Cao, Zhuokun; Yu, Yang; Li, Min; Luo, Hongjie

2016-09-01

Ti-H particles are used to increase the gas content in aluminum melts for reduced pressure foaming. This paper reports on the RPF process of AlCa alloy by adding TiH2, but in smaller amounts compared to traditional process. TiH2 is completely decomposed by stirring the melt, following which reduced pressure is applied. TiH2 is not added as the blowing agent; instead, it is added for increasing the H2 concentration in the liquid AlCa melt. It is shown that pressure change induces further release of hydrogen from Ti phase. It is also found that foam collapse is caused by the fast bubble coalescing during pressure reducing procedure, and the instability of liquid film is related to the significant increase in critical thickness of film rupture. A combination of lower amounts of TiH2, coupled with reduced pressure, is another way of increasing hydrogen content in the liquid aluminum. A key benefit of this process is that it provides time to transfer the molten metal to a mold and then apply the reduced pressure to produce net shape foam parts.

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.

The nature of hydrogen-bonding interactions in nonsteroidal anti-inflammatory drugs revealed by polarized IR spectroscopy.

PubMed

Hachuła, Barbara

2018-01-05

The influence of hydrogen-bonding interactions in the solid phase on the IR spectroscopic pattern of the ν OH band of nonsteroidal anti-inflammatory drugs (NSAIDs) was studied experimentally by IR spectroscopy with the use of polarized light at two temperatures (293K and 77K) and in isotopic dilution. The neat and deuterated crystals of (S)-naproxen ((S)-NPX), (R)-flurbiprofen ((R)-FBP), (RS)-flurbiprofen ((RS)-FBP) and (RS)-ketoprofen ((RS)-KTP) were obtained by melt crystallization between the two squeezed CaF 2 plates. The vibrational spectra of selected α-aryl propionic acid derivatives (2APAs) reflected the characteristics of their hydrogen-bond networks, i.e., 2APAs were characterized by the chain ((S)-NPX, (R)-FBP) and by dimeric ((RS)-FBP, (RS)-KTP) arrangement of hydrogen bonds in the crystal lattice. Spectroscopic results showed that the interchain (through-space) exciton coupling, between two laterally-spaced hydrogen bonds, dominates in the crystals of four NSAIDs. The same exciton coupled hydrogen bonds were also responsible for the H/D isotopic recognition mechanism in the crystalline spectra of deuterated 2APAs. The presented spectral results may help to predict the hydrogen bond motifs in the crystalline NSAIDs, which structures are not yet known, based on their IR spectra of hydrogen bond in the crystals. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron capture in collisions of Si3+ ions with atomic hydrogen from low to intermediate energies

NASA Astrophysics Data System (ADS)

Liu, C. H.; Liu, L.; Wang, J. G.

2014-07-01

The electron capture process for the Si3+(3s) + H(1s) collisions is investigated by the quantum-mechanical molecular orbital close-coupling (MOCC) method and by the two-center atomic orbital close-coupling (AOCC) method in the energy range of 10-5-10 keV/u and 0.8-200 keV/u, respectively. Total and state-selective cross sections are presented and compared with the available theoretical and experimental results. The present MOCC and AOCC results agree well with the experimental measurements, but show some discrepancy with the calculations of Wang et al. [Phys. Rev. A 74, 052709 (2006), 10.1103/PhysRevA.74.052709] at E > 40 eV/u because of the inclusion of rotational couplings, which play important roles in the electron capture process. At lower energies, the present results are about three to five times smaller than those of Wang et al. due to the difference in the molecular data at large internuclear distances. The energy behaviors of the electron capture cross sections are discussed on the basis of identified reaction mechanisms.

Charge-exchange coupling between pickup ions across the heliopause and its effect on energetic neutral hydrogen flux

DOE PAGES

Zirnstein, Eric J.; Heerikhuisen, J.; Zank, G. P.; ...

2014-02-24

Pickup ions (PUIs) appear to play an integral role in the multi-component nature of the plasma in the interaction between the solar wind (SW) and local interstellar medium (LISM). Three-dimensional (3D) MHD simulations with a kinetic treatment for neutrals and PUIs are currently still not viable. In light of recent energetic neutral atom (ENA) observations by the Interstellar Boundary EXplorer, the purpose of this paper is to illustrate the complex coupling between PUIs across the heliopause (HP) as facilitated by ENAs using estimates of PUI properties extracted from a 3D MHD simulation of the SW-LISM interaction with kinetic neutrals. First,more » we improve upon the multi-component treatment of the inner heliosheath (IHS) plasma from Zank et al. by including the extinction of PUIs through charge-exchange. We find a significant amount of energy is transferred away from hot, termination shock-processed PUIs into a colder, "freshly injected" PUI population. Second, we extend the multi-component approach to estimate ENA flux from the outer heliosheath (OHS), formed from charge-exchange between interstellar hydrogen atoms and energetic PUIs. These PUIs are formed from ENAs in the IHS that crossed the HP and experienced charge-exchange. Lastly, our estimates, based on plasma-neutral simulations of the SW-LISM interaction and a post-processing analysis of ENAs and PUIs, suggest the majority of flux visible at 1 AU from the front of the heliosphere, between ~0.02 and 10 keV, originates from OHS PUIs, indicating strong coupling between the IHS and OHS plasmas through charge-exchange.« less

Hydrogenation thermodynamics of melt-spun magnesium rich Mg-Ni nanocrystalline alloys with the addition of multiwalled carbon nanotubes and TiF3

NASA Astrophysics Data System (ADS)

Hou, Xiaojiang; Hu, Rui; Zhang, Tiebang; Kou, Hongchao; Li, Jinshan

2016-02-01

Based on the complexity of hydrogen absorption/desorption process and from the perspective of overall control, the as-cast Mg-10wt%Ni (Mg10Ni) alloy has been successively optimized by melt-spinning and surface catalyzed to realize the internal refinement as well as surface modification. The isothermal hydrogenation behavior of modified Mg-rich alloys has been investigated in this work. The results indicate that melt-spun Mg10Ni catalyzed by multiwalled carbon nanotubes (MWCNTs) coupling with TiF3 possesses superior activation properties and can absorb 6.23 wt% at 250 °C under 2.5 MPa. It is worth mentioning that the hydrogenation capacities of Mg10Ni-MWCNTs-TiF3 are 5.93 wt% and 5.99 wt% within the initial 1 min and 5 min, respectively. Meanwhile, the catalytic effect of MWCNTs and TiF3 has been discussed. The improved activation performance as well as the thermodynamics properties of Mg10Ni catalyzed by MWCNTs and TiF3 is attributed to the synergistic effect on dissociation of H2 molecules, diffusion of H-atoms and heterogeneous nucleation of hydrides.

Mechanistic Insights into Photocatalyzed Hydrogen Desorption from Palladium Surfaces Assisted by Localized Surface Plasmon Resonances.

PubMed

Spata, Vincent A; Carter, Emily A

2018-04-24

Nanoparticles synthesized from plasmonic metals can absorb low-energy light, producing an oscillation/excitation of their valence electron density that can be utilized in chemical conversions. For example, heterogeneous photocatalysis can be achieved within heterometallic antenna-reactor complexes (HMARCs), by coupling a reactive center at which a chemical reaction occurs to a plasmonic nanoparticle that acts as a light-absorbing antenna. For example, HMARCs composed of aluminum antennae and palladium (Pd) reactive centers have been demonstrated recently to catalyze selective hydrogenation of acetylene to ethylene. Here, we explore within a theoretical framework the rate-limiting step of hydrogen photodesorption from a Pd surface-crucial to achieving partial rather than full hydrogenation of acetylene-to understand the mechanism behind the photodesorption process within the HMARC assembly. To properly describe electronic excited states of the metal-molecule system, we employ embedded complete active space self-consistent field and n-electron valence state perturbation theory to second order within density functional embedding theory. The results of these calculations reveal that the photodesorption mechanism does not create a frequently invoked transient negative ion species but instead enhances population of available excited-state, low-barrier pathways that exhibit negligible charge-transfer character.

Low temperature synthesis of silicon quantum dots with plasma chemistry control in dual frequency non-thermal plasmas.

PubMed

Sahu, Bibhuti Bhusan; Yin, Yongyi; Han, Jeon Geon; Shiratani, Masaharu

2016-06-21

The advanced materials process by non-thermal plasmas with a high plasma density allows the synthesis of small-to-big sized Si quantum dots by combining low-temperature deposition with superior crystalline quality in the background of an amorphous hydrogenated silicon nitride matrix. Here, we make quantum dot thin films in a reactive mixture of ammonia/silane/hydrogen utilizing dual-frequency capacitively coupled plasmas with high atomic hydrogen and nitrogen radical densities. Systematic data analysis using different film and plasma characterization tools reveals that the quantum dots with different sizes exhibit size dependent film properties, which are sensitively dependent on plasma characteristics. These films exhibit intense photoluminescence in the visible range with violet to orange colors and with narrow to broad widths (∼0.3-0.9 eV). The observed luminescence behavior can come from the quantum confinement effect, quasi-direct band-to-band recombination, and variation of atomic hydrogen and nitrogen radicals in the film growth network. The high luminescence yields in the visible range of the spectrum and size-tunable low-temperature synthesis with plasma and radical control make these quantum dot films good candidates for light emitting applications.

Microstructure and Tribological Properties of AlCoCrFeNiTi0.5 High-Entropy Alloy in Hydrogen Peroxide Solution

NASA Astrophysics Data System (ADS)

Yu, Y.; Liu, W. M.; Zhang, T. B.; Li, J. S.; Wang, J.; Kou, H. C.; Li, J.

2014-01-01

Microstructure and tribological properties of an AlCoCrFeNiTi0.5 high-entropy alloy in high-concentration hydrogen peroxide solution were investigated in this work. The results show that the sigma phase precipitates and the content of bcc2 decrease during the annealing process. Meanwhile, the complex construction of the interdendrite region changes into simple isolated-island shape, and much more spherical precipitates are formed. Those changes of microstructure during the annealing process lead to the increase of hardness of this alloy. In the testing conditions, the AlCoCrFeNiTi0.5 alloy shows smoother worn surfaces and steadier coefficient of friction curves than does the 1Cr18Ni9Ti stainless steel, and SiC ceramic preserves better wear resistance than ZrO2 ceramic. After annealing, the wear resistance of the AlCoCrFeNiTi0.5 alloy increases coupled with SiC counterface but decreases with ZrO2 counterface.

Methods and apparatus for the on-site production of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Buschmann, Wayne E. (Inventor); James, Patrick I. (Inventor)

2010-01-01

Methods, apparatus, and applications for the on-site production of hydrogen peroxide are described. An embodiment of the apparatus comprises at least one anolyte chamber coupled to at least one anode, at least one catholyte chamber, wherein the at least one catholyte chamber is coupled to at least one cathode, at least one anode membrane and at least one cathode membrane, wherein the anode membrane is adjacent to the at least one anode, wherein the cathode membrane is adjacent to the at least one cathode, at least one central chamber disposed between the at least one anolyte chamber and the at least one catholyte chamber. Hydrogen peroxide is produced by reduction of an oxygen-containing gas at the cathode.

Non-aqueous electrolytes for isotachophoresis of weak bases and its application to the comprehensive preconcentration of the 20 proteinogenic amino acids in column-coupling ITP/CE-MS.

PubMed

Kler, Pablo A; Huhn, Carolin

2014-11-01

Isotachophoresis (ITP) has long been used alone but also as a preconcentration technique for capillary electrophoresis (CE). Unfortunately, up to now, its application is restricted to relatively strong acids and bases as either the degree of (de)protonation is too low or the water dissociation is too high, evoking zone electrophoresis. With the comprehensive ITP analysis of all 20 proteinogenic amino acids as model analytes, we, here, show that non-aqueous ITP using dimethylsulfoxide as a solvent solves this ITP shortcoming. Dimethylsulfoxide changes the pH regime of analytes and electrolytes but, more importantly, strongly reduces the proton mobility by prohibiting hydrogen bonds and thus, the so-called Zundel-Eigen-Zundel electrical conduction mechanism of flipping hydrogen bonds. The effects are demonstrated in an electrolyte system with taurine or H(+) as terminator, and imidazole as leader together with strong acids such as oxalic and even trifluoroacetic acid as counterions, both impossible to use in aqueous solution. Mass spectrometric as well as capacitively coupled contactless conductivity detection (C(4)D) are used to follow the ITP processes. To demonstrate the preconcentration capabilities of ITP in a two-dimensional set-up, we, here, also demonstrate that our non-aqueous ITP method can be combined with capillary electrophoresis-mass spectrometry in a column-coupling system using a hybrid approach of capillaries coupled to a microfluidic interface. For this, C(4)D was optimized for on-chip detection with the electrodes aligned on top of a thin glass lid of the microfluidic chip.

A Review of Hydrogen Production by Photosynthetic Organisms Using Whole-Cell and Cell-Free Systems.

PubMed

Martin, Baker A; Frymier, Paul D

2017-10-01

Molecular hydrogen is a promising currency in the future energy economy due to the uncertain availability of finite fossil fuel resources and environmental effects from their combustion. It also has important uses in the production of fertilizers and platform chemicals as well as in upgrading conventional fuels. Conventional methods for producing molecular hydrogen from natural gas produce carbon dioxide and use a finite resource as feedstock. However, these issues can be overcome by using light energy from the Sun combined with microorganisms and their molecular machinery capable of photosynthesis. In the presence of light, the proteins involved in photosynthesis coupled with appropriate catalysts in higher plants, algae, and cyanobacteria can produce molecular hydrogen, and optimization via genetic modifications and biomolecular engineering further improves production rates. In this review, we will discuss techniques that have been utilized to improve rates of hydrogen production in biological systems based on the protein machinery of photosynthesis coupled with appropriate catalysts. We will also suggest areas for improvement and future directions for work in the field.

Titania Composites with 2 D Transition Metal Carbides as Photocatalysts for Hydrogen Production under Visible-Light Irradiation

DOE PAGES

Wang, Hui; Peng, Rui; Hood, Zachary D.; ...

2016-05-24

In the MXenes family of two-dimensional transition-metal carbides there were successful demonstrations of co-catalysts with rutile TiO 2 for visible-light-induced solar hydrogen production from water splitting. The physicochemical properties of Ti 3C 2T x MXene coupled with TiO 2 were investigated by a variety of characterization techniques. The effect of the Ti 3C 2T x loading on the photocatalytic performance of the TiO 2/Ti 3C 2T x composites was elucidated. Moreover, with an optimized Ti 3C 2T x content of 5 wt %, the TiO 2/Ti 3C 2T x composite shows a 400 % enhancement in the photocatalytic hydrogen evolutionmore » reaction compared with that of pure rutile TiO 2. We also expanded our exploration to other MXenes (Nb 2CT x and Ti 2CT x) as co-catalysts coupled with TiO 2, and these materials also exhibited enhanced hydrogen production. These results manifest the generality of MXenes as effective co-catalysts for solar hydrogen production.« less

Titania Composites with 2 D Transition Metal Carbides as Photocatalysts for Hydrogen Production under Visible-Light Irradiation.

PubMed

Wang, Hui; Peng, Rui; Hood, Zachary D; Naguib, Michael; Adhikari, Shiba P; Wu, Zili

2016-06-22

MXenes, a family of two-dimensional transition-metal carbides, were successfully demonstrated as co-catalysts with rutile TiO2 for visible-light-induced solar hydrogen production from water splitting. The physicochemical properties of Ti3 C2 Tx MXene coupled with TiO2 were investigated by a variety of characterization techniques. The effect of the Ti3 C2 Tx loading on the photocatalytic performance of the TiO2 /Ti3 C2 Tx composites was elucidated. With an optimized Ti3 C2 Tx content of 5 wt %, the TiO2 /Ti3 C2 Tx composite shows a 400 % enhancement in the photocatalytic hydrogen evolution reaction compared with that of pure rutile TiO2 . We also expanded our exploration to other MXenes (Nb2 CTx and Ti2 CTx ) as co-catalysts coupled with TiO2 , and these materials also exhibited enhanced hydrogen production. These results manifest the generality of MXenes as effective co-catalysts for solar hydrogen production. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of curcumin and ursolic acid on the mitochondrial coupling efficiency and hydrogen peroxide emission of intact skeletal myoblasts.

PubMed

Tueller, Daniel J; Harley, Jackson S; Hancock, Chad R

2017-10-21

Curcumin may improve blood glucose management, but the mechanism is not fully established. We demonstrated that curcumin (40 μM) reduced the mitochondrial coupling efficiency (percentage of oxygen consumption coupled to ATP synthesis) of intact skeletal muscle cells. A 30-minute pretreatment with curcumin reduced mitochondrial coupling efficiency by 17.0 ± 0.4% relative to vehicle (p < 0.008). Curcumin pretreatment also decreased the rate of hydrogen peroxide emission by 43 ± 13% compared to vehicle (p < 0.05). Analysis of cell respiration in the presence of curcumin revealed a 40 ± 4% increase in the rate of oxygen consumption upon curcumin administration (p < 0.05 compared to vehicle). No difference in mitochondrial coupling efficiency was observed between vehicle- and curcumin-pretreated cells after permeabilization of cell membranes (p > 0.7). The interaction between curcumin and ursolic acid, another natural compound that may improve blood glucose management, was also examined. Pretreatment with ursolic acid (0.12 μM) increased the mitochondrial coupling efficiency of intact cells by 4.1 ± 1.1% relative to vehicle (p < 0.008) and attenuated the effect of curcumin when the two compounds were used in combination. The observed changes to mitochondrial coupling efficiency and hydrogen peroxide emission were consistent with the established effects of curcumin on blood glucose control. Our findings also show that changes to mitochondrial coupling efficiency after curcumin pretreatment may go undetected unless cells are assessed in the intact condition. Copyright © 2017 Elsevier Inc. All rights reserved.

Conformational transitions of uracil transporter UraA from Escherichia coli: a molecular simulation study.

PubMed

Yang, Liu; Yang, Lianjuan; Yu, Hui; Liu, Lu; Zhao, Xi; Huang, Xuri

2017-10-26

The Escherichia coli uracil/H + symporter UraA, known as the representative nucleobase/cation symporter 2(NCS2) protein, gets involved in several crucial physiological processes for most living organisms on Earth, such as the uptake of nucleobases and transport of vitamin C. Some experiments proposed a working model to explain proton-coupling and uracil transporting process of UraA on the basis of the crystal structure of NCS2 protein, but the details of conformational changes remained unknown. Thus, in order to make clear conformational changes caused by the protonation and deprotonation process of some conserved proton-coupled residues, the molecular dynamics simulation was used to study the conformation of UraA complexes in different protonation states. The results demonstrated that the protonation of residue Glu241 and Glu290 resulted in the whole conformational transition from the inward-open to the outward-open state. It can be concluded that Glu290 was crucial in a network of hydrogen-bonds in the middle of the core domain involving another essential residue, mainly including tyr288 in TM8, Tyr342, Ser338 in TM12, and the network of hydrogen-bonds was the key to maintain the stability of conformation. Protonation of Glu290 affects the stability of network of H-bond and changed the domains TM3 TM10 TM12. Thus, Glu290 may play a vital role as a 'proton trigger' that affects spatial structural of amino and residues near substrate binding side leading to an outward-open conformation transition.

l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

PubMed Central

Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

2009-01-01

Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

Spheroidization of silica powders by radio frequency inductively coupled plasma with Ar-H2 and Ar-N2 as the sheath gases at atmospheric pressure

NASA Astrophysics Data System (ADS)

Li, Lin; Ni, Guo-hua; Guo, Qi-jia; Lin, Qi-fu; Zhao, Peng; Cheng, Jun-li

2017-09-01

Amorphous spherical silica powders were prepared by inductively coupled thermal plasma treatment at a radio frequency of 36.2 MHz. The effects of the added content of hydrogen and nitrogen into argon (serving as the sheath gas), as well as the carrier gas flow rate, on the spheroidization rate of silica powders, were investigated. The prepared silica powders before and after plasma treatment were examined by scanning electron microscopy, X-ray diffraction, and laser granulometric analysis. Results indicated that the average size of the silica particles increased, and the transformation of crystals into the amorphous state occurred after plasma treatment. Discharge image processing was employed to analyze the effect of the plasma temperature field on the spheroidization rate. The spheroidization rate of the silica powder increased with the increase of the hydrogen content in the sheath gas. On the other hand, the spheroidization rate of the silica power first increased and then decreased with the increase of the nitrogen content in the sheath gas. Moreover, the amorphous content increased with the increase of the spheroidization rate of the silica powder.

Efficient and Selective Electrochemical and Photoelectrochemical Reduction of 5-Hydroxymethylfurfural to 2,5-Bis(hydroxymethyl)furan using Water as the Hydrogen Source

DOE PAGES

Roylance, John J.; Kim, Tae Woo; Choi, Kyoung-Shin

2016-02-17

Reductive biomass conversion has been conventionally conducted using H 2 gas under high-temperature and-pressure conditions. Here, efficient electrochemical reduction of 5-hydroxymethylfurfural (HMF), a key intermediate for biomass conversion, to 2,5-bis(hydroxymethyl)furan (BHMF), an important monomer for industrial processes, was demonstrated using Ag catalytic electrodes. This process uses water as the hydrogen source under ambient conditions and eliminates the need to generate and consume H 2 for hydrogenation, providing a practical and efficient route for BHMF production. By systematic investigation of HMF reduction on the Ag electrode surface, BHMF production was achieved with the Faradaic efficiency and selectivity nearing 100%, and plausiblemore » reduction mechanisms were also elucidated. Furthermore, construction of a photoelectrochemical cell (PEC) composed of an n-type BiVO 4 semiconductor anode, which uses photogenerated holes for water oxidation, and a catalytic Ag cathode, which uses photoexcited electrons from BiVO 4 for the reduction of HMF to BHMF, was demonstrated to utilize solar energy to significantly decrease the external voltage necessary for HMF reduction. This shows the possibility of coupling electrochemical HMF reduction and solar energy conversion, which can provide more efficient and environmentally benign routes for reductive biomass conversion.« less

Detection of hydrogen peroxide based on long-path absorption spectroscopy using a CW EC-QCL

NASA Astrophysics Data System (ADS)

Sanchez, N. P.; Yu, Y.; Dong, L.; Griffin, R.; Tittel, F. K.

2016-02-01

A sensor system based on a CW EC-QCL (mode-hop-free range 1225-1285 cm-1) coupled with long-path absorption spectroscopy was developed for the monitoring of gas-phase hydrogen peroxide (H2O2) using an interference-free absorption line located at 1234.055 cm-1. Wavelength modulation spectroscopy (WMS) with second harmonic detection was implemented for data processing. Optimum levels of pressure and modulation amplitude of the sensor system led to a minimum detection limit (MDL) of 25 ppb using an integration time of 280 sec. The selected absorption line for H2O2, which exhibits no interference from H2O, makes this sensor system suitable for sensitive and selective monitoring of H2O2 levels in decontamination and sterilization processes based on Vapor Phase Hydrogen Peroxide (VPHP) units, in which a mixture of H2O and H2O2 is generated. Furthermore, continuous realtime monitoring of H2O2 concentrations in industrial facilities employing this species can be achieved with this sensing system in order to evaluate average permissible exposure levels (PELs) and potential exceedances of guidelines established by the US Occupational Safety and Health Administration for H2O2.

Unravelling biocomplexity of electroactive biofilms for producing hydrogen from biomass

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

Lewis, Alex J.; Campa, Maria F.; Hazen, Terry C.

Nature recruits various types of microbes to transform its waste products into reusable building blocks. In order to develop engineered systems to enable humans to generate useful products from complex sources such as biomass, a better understanding of the synergy between microbial species is necessary. Here we investigate a bioelectrochemical system for conversion of a complex biomass-derived pyrolysis stream into hydrogen via microbial electrolysis. Interaction between the exoelectrogens and fermentative organisms is key in this process. Comparing bioelectroconversion of a switchgrass-derived bio-oil aqueous phase (BOAP) with a model exoelectrogenic substrate, acetic acid, we demonstrate that fermentative breakdown of BOAP tomore » acetate is the limiting step in the syntophic conversion process. The anode microbial community displayed simultaneous conversion of sugar derivatives, phenolic compounds, carboxylic acids, etc. present in BOAP, but at differing rates through division of labor and syntrophic exchange. Maximum removal for BOAP reached 43 mg COD/h vs. 59 mg COD/h for pure acetic acid. Furthermore, maximum hydrogen production for BOAP reached 11 L/L-d vs. 35 L/L-day for pure acetic acid. Coulombic efficiency for both substrates was >80%. Unpoising of the anode haulted exoelectrogenesis and allowed fermentative processes to proceed resulting in acetic acid accumulation at the rate of 8.4 mg/h. Coupled to the simultaneous conversion of compounds present within BOAP, these results support the division of labor and syntrophic interactions suggested here. The hydrogen productivity is the highest achieved to date for a biomass-derived stream. The exoelectrogenic rates achieved signify that commercial feasibility can be achieved if fermentative rates can be improved.« less

Unravelling biocomplexity of electroactive biofilms for producing hydrogen from biomass

DOE PAGES

Lewis, Alex J.; Campa, Maria F.; Hazen, Terry C.; ...

2017-07-11

Nature recruits various types of microbes to transform its waste products into reusable building blocks. In order to develop engineered systems to enable humans to generate useful products from complex sources such as biomass, a better understanding of the synergy between microbial species is necessary. Here we investigate a bioelectrochemical system for conversion of a complex biomass-derived pyrolysis stream into hydrogen via microbial electrolysis. Interaction between the exoelectrogens and fermentative organisms is key in this process. Comparing bioelectroconversion of a switchgrass-derived bio-oil aqueous phase (BOAP) with a model exoelectrogenic substrate, acetic acid, we demonstrate that fermentative breakdown of BOAP tomore » acetate is the limiting step in the syntophic conversion process. The anode microbial community displayed simultaneous conversion of sugar derivatives, phenolic compounds, carboxylic acids, etc. present in BOAP, but at differing rates through division of labor and syntrophic exchange. Maximum removal for BOAP reached 43 mg COD/h vs. 59 mg COD/h for pure acetic acid. Furthermore, maximum hydrogen production for BOAP reached 11 L/L-d vs. 35 L/L-day for pure acetic acid. Coulombic efficiency for both substrates was >80%. Unpoising of the anode haulted exoelectrogenesis and allowed fermentative processes to proceed resulting in acetic acid accumulation at the rate of 8.4 mg/h. Coupled to the simultaneous conversion of compounds present within BOAP, these results support the division of labor and syntrophic interactions suggested here. The hydrogen productivity is the highest achieved to date for a biomass-derived stream. The exoelectrogenic rates achieved signify that commercial feasibility can be achieved if fermentative rates can be improved.« less

H/D isotopic recognition and temperature effects in IR spectra of hydrogen-bonded cyclic dimers in crystals: 3-Methylcinnamic acid and 4-phenylbutyric acid

NASA Astrophysics Data System (ADS)

Hachuła, Barbara; Jabłońska-Czapla, Magdalena; Flakus, Henryk T.; Nowak, Maria; Kusz, Joachim

2015-01-01

In the present work, the experimental and theoretical study of the nature of the inter-hydrogen bond interactions in two different carboxylic acids, 3-methylcinnamic acid (3MCA) and 4-phenylbutyric acid (4PBA), were reported. The polarized IR spectra of 3MCA and 4PBA crystals were recorded at the frequency ranges of the νOsbnd H and νOsbnd D bands. The spectral properties of 3MCA and 4PBA interpreted with the aid of the calculations based on the "strong-coupling" model. The differences in the spectral properties of the two different dimeric systems in the crystals provide a valuable information about the existence of a direct relationship between the crystal spectral properties in IR and the electronic structure of the molecular systems. In 3MCA crystals strong vibrational exciton interactions favor a "tail-to-head" (TH)-type Davydov coupling widespread via the π-electrons, whereas in 4PBA crystals a weak "through-space" (SS) exciton coupling is responsible for a "side-to-side"-type coupling. The relative contribution of each individual exciton coupling mechanism in IR spectra generation strongly depends on temperature and molecular electronic structure. The H/D isotopic recognition effect, depending on a non-random distribution of protons and deuterons in the crystal hydrogen bridges, was also analyzed.

H/D isotopic recognition and temperature effects in IR spectra of hydrogen-bonded cyclic dimers in crystals: 3-methylcinnamic acid and 4-phenylbutyric acid.

PubMed

Hachuła, Barbara; Jabłońska-Czapla, Magdalena; Flakus, Henryk T; Nowak, Maria; Kusz, Joachim

2015-01-05

In the present work, the experimental and theoretical study of the nature of the inter-hydrogen bond interactions in two different carboxylic acids, 3-methylcinnamic acid (3MCA) and 4-phenylbutyric acid (4PBA), were reported. The polarized IR spectra of 3MCA and 4PBA crystals were recorded at the frequency ranges of the νO-H and νO-D bands. The spectral properties of 3MCA and 4PBA interpreted with the aid of the calculations based on the "strong-coupling" model. The differences in the spectral properties of the two different dimeric systems in the crystals provide a valuable information about the existence of a direct relationship between the crystal spectral properties in IR and the electronic structure of the molecular systems. In 3MCA crystals strong vibrational exciton interactions favor a "tail-to-head" (TH)-type Davydov coupling widespread via the π-electrons, whereas in 4PBA crystals a weak "through-space" (SS) exciton coupling is responsible for a "side-to-side"-type coupling. The relative contribution of each individual exciton coupling mechanism in IR spectra generation strongly depends on temperature and molecular electronic structure. The H/D isotopic recognition effect, depending on a non-random distribution of protons and deuterons in the crystal hydrogen bridges, was also analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanistic modeling of sulfur-deprived photosynthesis and hydrogen production in suspensions of Chlamydomonas reinhardtii

PubMed Central

Williams, C R; Bees, MA

2014-01-01

The ability of unicellular green algal species such as Chlamydomonas reinhardtii to produce hydrogen gas via iron-hydrogenase is well known. However, the oxygen-sensitive hydrogenase is closely linked to the photosynthetic chain in such a way that hydrogen and oxygen production need to be separated temporally for sustained photo-production. Under illumination, sulfur-deprivation has been shown to accommodate the production of hydrogen gas by partially-deactivating O2 evolution activity, leading to anaerobiosis in a sealed culture. As these facets are coupled, and the system complex, mathematical approaches potentially are of significant value since they may reveal improved or even optimal schemes for maximizing hydrogen production. Here, a mechanistic model of the system is constructed from consideration of the essential pathways and processes. The role of sulfur in photosynthesis (via PSII) and the storage and catabolism of endogenous substrate, and thus growth and decay of culture density, are explicitly modeled in order to describe and explore the complex interactions that lead to H2 production during sulfur-deprivation. As far as possible, functional forms and parameter values are determined or estimated from experimental data. The model is compared with published experimental studies and, encouragingly, qualitative agreement for trends in hydrogen yield and initiation time are found. It is then employed to probe optimal external sulfur and illumination conditions for hydrogen production, which are found to differ depending on whether a maximum yield of gas or initial production rate is required. The model constitutes a powerful theoretical tool for investigating novel sulfur cycling regimes that may ultimately be used to improve the commercial viability of hydrogen gas production from microorganisms. Biotechnol. Bioeng. 2014;111: 320–335. © 2013 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. PMID:24026984

Mechanistic modeling of sulfur-deprived photosynthesis and hydrogen production in suspensions of Chlamydomonas reinhardtii.

PubMed

Williams, C R; Bees, M A

2014-02-01

The ability of unicellular green algal species such as Chlamydomonas reinhardtii to produce hydrogen gas via iron-hydrogenase is well known. However, the oxygen-sensitive hydrogenase is closely linked to the photosynthetic chain in such a way that hydrogen and oxygen production need to be separated temporally for sustained photo-production. Under illumination, sulfur-deprivation has been shown to accommodate the production of hydrogen gas by partially-deactivating O2 evolution activity, leading to anaerobiosis in a sealed culture. As these facets are coupled, and the system complex, mathematical approaches potentially are of significant value since they may reveal improved or even optimal schemes for maximizing hydrogen production. Here, a mechanistic model of the system is constructed from consideration of the essential pathways and processes. The role of sulfur in photosynthesis (via PSII) and the storage and catabolism of endogenous substrate, and thus growth and decay of culture density, are explicitly modeled in order to describe and explore the complex interactions that lead to H2 production during sulfur-deprivation. As far as possible, functional forms and parameter values are determined or estimated from experimental data. The model is compared with published experimental studies and, encouragingly, qualitative agreement for trends in hydrogen yield and initiation time are found. It is then employed to probe optimal external sulfur and illumination conditions for hydrogen production, which are found to differ depending on whether a maximum yield of gas or initial production rate is required. The model constitutes a powerful theoretical tool for investigating novel sulfur cycling regimes that may ultimately be used to improve the commercial viability of hydrogen gas production from microorganisms. © 2013 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

Structural Analogues of Selfotel.

PubMed

Dziuganowska, Zofia A; Ślepokura, Katarzyna; Volle, Jean-Noël; Virieux, David; Pirat, Jean-Luc; Kafarski, Paweł

2016-06-17

A small library of phosphonopiperidylcarboxylic acids, analogues of NMDA antagonist selfotel (CGS 19755), was synthesized. First, the series of aromatic esters was obtained via a palladium-catalyzed cross-coupling reaction (Hirao coupling) of dialkyl phosphites with bromopyridinecarboxylates, followed by their hydrolysis. Then, hydrogenation of the resulting phosphonopyridylcarboxylic acids over PtO2 yielded the desired phosphonopiperidylcarboxylic acids. NMR studies indicated that the hydrogenation reaction proceeds predominantly by cis addition. Several compounds were obtained as monocrystal structures. Preliminary biological studies performed on cultures of neurons suggest that the obtained compounds possess promising activity toward NMDA receptors.

Investigations of interhydrogen bond dynamical coupling effects in the polarized IR spectra of acetanilide crystals.

PubMed

Flakus, Henryk T; Michta, Anna

2010-02-04

This Article presents the investigation results of the polarized IR spectra of the hydrogen bond in acetanilide (ACN) crystals measured in the frequency range of the proton and deuteron stretching vibration bands, nu(N-H) and nu(N-D). The basic spectral properties of the crystals were interpreted quantitatively in terms of the "strong-coupling" theory. The model of the centrosymmetric dimer of hydrogen bonds postulated by us facilitated the explanation of the well-developed, two-branch structure of the nu(N-H) and nu(N-D) bands as well as the isotopic dilution effects in the spectra. On the basis of the linear dichroic and temperature effects in the polarized IR spectra of ACN crystals, the H/D isotopic "self-organization" effects were revealed. A nonrandom distribution of hydrogen isotope atoms (H or D) in the lattice was deduced from the spectra of isotopically diluted ACN crystals. It was also determined that identical hydrogen isotope atoms occupy both hydrogen bonds in the dimeric systems, where each hydrogen bond belongs to a different chain. A more complex fine structure pattern of nu(N-H) and nu(N-D) bands in ACN spectra in comparison with the spectra of other secondary amides (e.g., N-methylacetamide) can be explained in terms of the "relaxation" theory of the IR spectra of hydrogen-bonded systems.

Absolute atomic hydrogen densities in a radio frequency discharge measured by two-photon laser induced fluorescence imaging

NASA Astrophysics Data System (ADS)

Chérigier, L.; Czarnetzki, U.; Luggenhölscher, D.; Schulz-von der Gathen, V.; Döbele, H. F.

1999-01-01

Absolute atomic hydrogen densities were measured in the gaseous electronics conference reference cell parallel plate reactor by Doppler-free two-photon absorption laser induced fluorescence spectroscopy (TALIF) at λ=205 nm. The capacitively coupled radio frequency discharge was operated at 13.56 MHz in pure hydrogen under various input power and pressure conditions. The Doppler-free excitation technique with an unfocused laser beam together with imaging the fluorescence radiation by an intensified charge coupled device camera allows instantaneous spatial resolution along the radial direction. Absolute density calibration is obtained with the aid of a flow tube reactor and titration with NO2. The influence of spatial intensity inhomogenities along the laser beam and subsequent fluorescence are corrected by TALIF in xenon. A full mapping of the absolute density distribution between the electrodes was obtained. The detection limit for atomic hydrogen amounts to about 2×1018 m-3. The dissociation degree is of the order of a few percent.

Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study

NASA Astrophysics Data System (ADS)

Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.

2017-09-01

Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

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

Wang, Hui; Peng, Rui; Hood, Zachary D.

In the MXenes family of two-dimensional transition-metal carbides there were successful demonstrations of co-catalysts with rutile TiO 2 for visible-light-induced solar hydrogen production from water splitting. The physicochemical properties of Ti 3C 2T x MXene coupled with TiO 2 were investigated by a variety of characterization techniques. The effect of the Ti 3C 2T x loading on the photocatalytic performance of the TiO 2/Ti 3C 2T x composites was elucidated. Moreover, with an optimized Ti 3C 2T x content of 5 wt %, the TiO 2/Ti 3C 2T x composite shows a 400 % enhancement in the photocatalytic hydrogen evolutionmore » reaction compared with that of pure rutile TiO 2. We also expanded our exploration to other MXenes (Nb 2CT x and Ti 2CT x) as co-catalysts coupled with TiO 2, and these materials also exhibited enhanced hydrogen production. These results manifest the generality of MXenes as effective co-catalysts for solar hydrogen production.« less

Nuclear Thermal Rocket Element Environmental Simulator (NTREES) Upgrade Activities

NASA Technical Reports Server (NTRS)

Emrich, William

2013-01-01

A key technology element in Nuclear Thermal Propulsion is the development of fuel materials and components which can withstand extremely high temperatures while being exposed to flowing hydrogen. NTREES provides a cost effective method for rapidly screening of candidate fuel components with regard to their viability for use in NTR systems. The NTREES is designed to mimic the conditions (minus the radiation) to which nuclear rocket fuel elements and other components would be subjected to during reactor operation. The NTREES consists of a water cooled ASME code stamped pressure vessel and its associated control hardware and instrumentation coupled with inductive heaters to simulate the heat provided by the fission process. The NTREES has been designed to safely allow hydrogen gas to be injected into internal flow passages of an inductively heated test article mounted in the chamber.

Travelling wave resonators fabricated with low-loss hydrogenated amorphous silicon

NASA Astrophysics Data System (ADS)

Lipka, Timo; Amthor, Julia; Trieu, Hoc Khiem; Müller, Jörg

2013-05-01

Low-loss hydrogenated amorphous silicon is employed for the fabrication of various planar integrated travelling wave resonators. Microring, racetrack, and disk resonators of different dimensions were fabricated with CMOS-compatible processes and systematically investigated. The key properties of notch filter ring resonators as extinction ratio, Q-factor, free spectral range, and the group refractive index were determined for resonators of varying radius, thereby achieving critically coupled photonic systems with high extinction ratios of about 20 dB for both polarizations. Racetrack resonators that are arranged in add/drop configuration and high quality factor microdisk resonators were optically characterized, with the microdisks exhibiting Q-factors of greater than 100000. Four-channel add/drop wavelength-division multiplexing filters that are based on cascaded racetrack resonators are studied. The design, the fabrication, and the optical characterization are presented.

Carrier-envelope phase dependence of the directional fragmentation and hydrogen migration in toluene in few-cycle laser fields.

PubMed

Li, Hui; Kling, Nora G; Förg, Benjamin; Stierle, Johannes; Kessel, Alexander; Trushin, Sergei A; Kling, Matthias F; Kaziannis, Spyros

2016-07-01

The dissociative ionization of toluene initiated by a few-cycle laser pulse as a function of the carrier envelope phase (CEP) is investigated using single-shot velocity map imaging. Several ionic fragments, CH3 (+), H2 (+), and H3 (+), originating from multiply charged toluene ions present a CEP-dependent directional emission. The formation of H2 (+) and H3 (+) involves breaking C-H bonds and forming new bonds between the hydrogen atoms within the transient structure of the multiply charged precursor. We observe appreciable intensity-dependent CEP-offsets. The experimental data are interpreted with a mechanism that involves laser-induced coupling of vibrational states, which has been found to play a role in the CEP-control of molecular processes in hydrocarbon molecules, and appears to be of general importance for such complex molecules.

Solar fuels via artificial photosynthesis.

PubMed

Gust, Devens; Moore, Thomas A; Moore, Ana L

2009-12-21

Because sunlight is diffuse and intermittent, substantial use of solar energy to meet humanity's needs will probably require energy storage in dense, transportable media via chemical bonds. Practical, cost effective technologies for conversion of sunlight directly into useful fuels do not currently exist, and will require new basic science. Photosynthesis provides a blueprint for solar energy storage in fuels. Indeed, all of the fossil-fuel-based energy consumed today derives from sunlight harvested by photosynthetic organisms. Artificial photosynthesis research applies the fundamental scientific principles of the natural process to the design of solar energy conversion systems. These constructs use different materials, and researchers tune them to produce energy efficiently and in forms useful to humans. Fuel production via natural or artificial photosynthesis requires three main components. First, antenna/reaction center complexes absorb sunlight and convert the excitation energy to electrochemical energy (redox equivalents). Then, a water oxidation complex uses this redox potential to catalyze conversion of water to hydrogen ions, electrons stored as reducing equivalents, and oxygen. A second catalytic system uses the reducing equivalents to make fuels such as carbohydrates, lipids, or hydrogen gas. In this Account, we review a few general approaches to artificial photosynthetic fuel production that may be useful for eventually overcoming the energy problem. A variety of research groups have prepared artificial reaction center molecules. These systems contain a chromophore, such as a porphyrin, covalently linked to one or more electron acceptors, such as fullerenes or quinones, and secondary electron donors. Following the excitation of the chromophore, photoinduced electron transfer generates a primary charge-separated state. Electron transfer chains spatially separate the redox equivalents and reduce electronic coupling, slowing recombination of the charge-separated state to the point that catalysts can use the stored energy for fuel production. Antenna systems, employing a variety of chromophores that absorb light throughout the visible spectrum, have been coupled to artificial reaction centers and have incorporated control and photoprotective processes borrowed from photosynthesis. Thus far, researchers have not discovered practical solar-driven catalysts for water oxidation and fuel production that are robust and use earth-abundant elements, but they have developed artificial systems that use sunlight to produce fuel in the laboratory. For example, artificial reaction centers, where electrons are injected from a dye molecule into the conduction band of nanoparticulate titanium dioxide on a transparent electrode, coupled to catalysts, such as platinum or hydrogenase enzymes, can produce hydrogen gas. Oxidizing equivalents from such reaction centers can be coupled to iridium oxide nanoparticles, which can oxidize water. This system uses sunlight to split water to oxygen and hydrogen fuel, but efficiencies are low and an external electrical potential is required. Although attempts at artificial photosynthesis fall short of the efficiencies necessary for practical application, they illustrate that solar fuel production inspired by natural photosynthesis is achievable in the laboratory. More research will be needed to identify the most promising artificial photosynthetic systems and realize their potential.

Anaerobic gaseous biofuel production using microalgal biomass - A review.

PubMed

Wirth, Roland; Lakatos, Gergely; Böjti, Tamás; Maróti, Gergely; Bagi, Zoltán; Rákhely, Gábor; Kovács, Kornél L

2018-05-24

Most photosynthetic organisms store and convert solar energy in an aerobic process and produce biomass for various uses. Utilization of biomass for the production of renewable energy carriers employs anaerobic conditions. This review focuses on microalgal biomass and its use for biological hydrogen and methane production. Microalgae offer several advantages compared to terrestrial plants. Strategies to maintain anaerobic environment for biohydrogen production are summarized. Efficient biogas production via anaerobic digestion is significantly affected by the biomass composition, pretreatment strategies and the parameters of the digestion process. Coupled biohydrogen and biogas production increases the efficiency and sustainability of renewable energy production. Copyright © 2018. Published by Elsevier Ltd.

Electron- and positron-molecule scattering: development of the molecular convergent close-coupling method

NASA Astrophysics Data System (ADS)

Zammit, Mark C.; Fursa, Dmitry V.; Savage, Jeremy S.; Bray, Igor

2017-06-01

Starting from first principles, this tutorial describes the development of the adiabatic-nuclei convergent close-coupling (CCC) method and its application to electron and (single-centre) positron scattering from diatomic molecules. We give full details of the single-centre expansion CCC method, namely the formulation of the molecular target structure; solving the momentum-space coupled-channel Lippmann-Schwinger equation; deriving adiabatic-nuclei cross sections and calculating V-matrix elements. Selected results are presented for electron and positron scattering from molecular hydrogen H2 and electron scattering from the vibrationally excited molecular hydrogen ion {{{H}}}2+ and its isotopologues (D2 +, {{{T}}}2+, HD+, HT+ and TD+). Convergence in both the close-coupling (target state) and projectile partial-wave expansions of fixed-nuclei electron- and positron-molecule scattering calculations is demonstrated over a broad energy-range and discussed in detail. In general, the CCC results are in good agreement with experiments.

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.

Ordered ground states of metallic hydrogen and deuterium

NASA Technical Reports Server (NTRS)

Ashcroft, N. W.

1981-01-01

The physical attributes of some of the more physically distinct ordered states of metallic hydrogen and metallic deuterium at T = 0 and nearby are discussed. The likelihood of superconductivity in both is considered with respect to the usual coupling via the density fluctuations of the ions.

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

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

Abu-Omar, Mahdi

2017-01-06

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

Boosting dark fermentation with co-cultures of extreme thermophiles for biohythane production from garden waste.

PubMed

Abreu, Angela A; Tavares, Fábio; Alves, Maria Madalena; Pereira, Maria Alcina

2016-11-01

Proof of principle of biohythane and potential energy production from garden waste (GW) is demonstrated in this study in a two-step process coupling dark fermentation and anaerobic digestion. The synergistic effect of using co-cultures of extreme thermophiles to intensify biohydrogen dark fermentation is demonstrated using xylose, cellobiose and GW. Co-culture of Caldicellulosiruptor saccharolyticus and Thermotoga maritima showed higher hydrogen production yields from xylose (2.7±0.1molmol(-1) total sugar) and cellobiose (4.8±0.3molmol(-1) total sugar) compared to individual cultures. Co-culture of extreme thermophiles C. saccharolyticus and Caldicellulosiruptor bescii increased synergistically the hydrogen production yield from GW (98.3±6.9Lkg(-1) (VS)) compared to individual cultures and co-culture of T. maritima and C. saccharolyticus. The biochemical methane potential of the fermentation end-products was 322±10Lkg(-1) (CODt). Biohythane, a biogas enriched with 15% hydrogen could be obtained from GW, yielding a potential energy generation of 22.2MJkg(-1) (VS). Copyright © 2016 Elsevier Ltd. All rights reserved.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

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

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab

A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with amore » multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.« less

Electron impact excitation of the n = 2 to n = 3 transition in atomic hydrogen near threshold

NASA Astrophysics Data System (ADS)

Hata, J.; Morgan, L. A.; McDowell, M. R. C.

1980-06-01

Close-coupling calculations of electron impact excitation of the n = 2 to n = 3 transition of atomic hydrogen at energies below the n = 4 threshold are presented. The algebraic variational close-coupling code of Morgan (1980) with an eighteen-state basis was used to obtain cross sections at eight impact energies from 2.04 to 2.45 eV, and calculations in a six-state close-coupling model were compared with the six-state calculations of Burke et al. (1967). The six-state values are found to be in satisfactory agreement with the exception of the singlet contribution to the 2s-3s transition. Near the n = 3 threshold the cross section obtained in the full calculation is found to be almost a factor of 2 lower than that predicted by Johnson (1972), thus explaining in part the discrepancy between Johnson's results and experiments on hydrogen plasmas. Estimates of rate coefficients based on the cross sections and assuming a Maxwellian velocity distribution, however, are shown to remain in disagreement with experiment.

Impact of Salt Waste Processing Facility Streams on the Nitric-Glycolic Flowsheet in the Chemical Processing Cell

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

Martino, C.

An evaluation of the previous Chemical Processing Cell (CPC) testing was performed to determine whether the planned concurrent operation, or “coupled” operations, of the Defense Waste Processing Facility (DWPF) with the Salt Waste Processing Facility (SWPF) has been adequately covered. Tests with the nitricglycolic acid flowsheet, which were both coupled and uncoupled with salt waste streams, included several tests that required extended boiling times. This report provides the evaluation of previous testing and the testing recommendation requested by Savannah River Remediation. The focus of the evaluation was impact on flammability in CPC vessels (i.e., hydrogen generation rate, SWPF solvent components,more » antifoam degradation products) and processing impacts (i.e., acid window, melter feed target, rheological properties, antifoam requirements, and chemical composition).« less

Theoretical understanding on the v(1)-SO4(2-) band perturbed by the formation of magnesium sulfate ion pairs.

PubMed

Zhang, Hao; Zhang, Yun-Hong; Wang, Feng

2009-02-01

The factors determining the spectroscopic characteristics of the v(1)-SO4(2-) band of the MgSO4 ion pairs are discussed via ab initio calculation, including coupling effect, hydrogen bonding effect, and direct contact effect of Mg2+ with SO4(2-). With the calculation of the heavy water hydrated contact ion pairs (CIP), the overlap between the librations of water and the v(1)-SO4(2-) band can be separated, and thus the coupling effect is abstracted, and this coupling effect leads to a blue shift for the v(1)-SO4(2-) band of 5.6 cm(-1) in the monodentate CIP and 3.6 cm(-1) in the bidentate CIP. The hydrogen bonding between each water molecule without relation to Mg2+ and the sulfate ion makes the v(1)-SO4(2-) band blue shift of 3.7 cm(-1). When the outer-sphere water around Mg2+ are hydrogen bonded between SO4(2-) and Mg2+, it will make the largest disturbance to the v(1)-SO4(2-) band. Moreover, the inner-sphere water can affect the v(1)-SO4(2-) band conjunct with the direct contact of Mg2+ with SO4(2-), showing a blue shift of 14.4 cm(-1) in the solvent-shared ion pair, 22.6 cm(-1) in the monodentate CIP, 4.3 cm(-1) in the bidentate CIP, and 21.4 cm(-1) in the tridentate CIP. At last, the Raman spectral evolution in the efflorescence production process is tried to be rationalized. The shoulder at 995 cm(-1) is attributed to the monodentate CIP with 2-3 outer-sphere water molecules, whereas the new peak at 1021 cm(-1) at high concentration is assigned to the formation of aqueous triple ion.

Kinetic and spectroscopic studies of the [palladium(Ar-bian)]-catalyzed semi-hydrogenation of 4-octyne.

PubMed

Kluwer, Alexander M; Koblenz, Tehila S; Jonischkeit, Thorsten; Woelk, Klaus; Elsevier, Cornelis J

2005-11-09

The kinetics of the stereoselective semi-hydrogenation of 4-octyne in THF by the highly active catalyst [Pd{(m,m'-(CF(3))(2)C(6)H(3))-bian}(ma)] (2) (bian = bis(imino)acenaphthene; ma = maleic anhydride) has been investigated. The rate law under hydrogen-rich conditions is described by r = k[4-octyne](0.65)[Pd][H(2)], showing first order in palladium and dihydrogen and a broken order in substrate. Parahydrogen studies have shown that a pairwise transfer of hydrogen atoms occurs in the rate-limiting step. In agreement with recent theoretical results, the proposed mechanism consists of the consecutive steps: alkyne coordination, heterolytic dihydrogen activation (hydrogenolysis of one Pd-N bond), subsequent hydro-palladation of the alkyne, followed by addition of N-H to palladium, reductive coupling of vinyl and hydride and, finally, substitution of the product alkene by the alkyne substrate. Under hydrogen-limiting conditions, side reactions occur, that is, formation of catalytically inactive palladacycles by oxidative alkyne coupling. Furthermore, it has been shown that (Z)-oct-4-ene is the primary reaction product, from which the minor product (E)-oct-4-ene is formed by an H(2)-assisted, palladium-catalyzed isomerization reaction.

Cold weather hydrogen generation system and method of operation

DOEpatents

Dreier, Ken Wayne; Kowalski, Michael Thomas; Porter, Stephen Charles; Chow, Oscar Ken; Borland, Nicholas Paul; Goyette, Stephen Arthur

2010-12-14

A system for providing hydrogen gas is provided. The system includes a hydrogen generator that produces gas from water. One or more heat generation devices are arranged to provide heating of the enclosure during different modes of operation to prevent freezing of components. A plurality of temperature sensors are arranged and coupled to a controller to selectively activate a heat source if the temperature of the component is less than a predetermined temperature.

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozian, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The essentially nonoscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Numerical Simulations of High-Speed Chemically Reacting Flow

NASA Technical Reports Server (NTRS)

Ton, V. T.; Karagozin, A. R.; Marble, F. E.; Osher, S. J.; Engquist, B. E.

1994-01-01

The Essentially NonOscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Solution-Based Synthesis of Crystalline Silicon from Liquid Silane through Laser and Chemical Annealing

DOE PAGES

Iyer, Ganjigunte R. S.; Hobbie, Erik K.; Guruvenket, Srinivasan; ...

2012-05-23

We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si 6H 12). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Lastly, our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient post-processing tomore » produce crystalline silicon thin films.« less

Force on an electric/magnetic dipole and classical approach to spin-orbit coupling in hydrogen-like atoms

NASA Astrophysics Data System (ADS)

Kholmetskii, A. L.; Missevitch, O. V.; Yarman, T.

2017-09-01

We carry out the classical analysis of spin-orbit coupling in hydrogen-like atoms, using the modern expressions for the force and energy of an electric/magnetic dipole in an electromagnetic field. We disclose a novel physical meaning of this effect and show that for a laboratory observer the energy of spin-orbit interaction is represented solely by the mechanical energy of the spinning electron (considered as a gyroscope) due to the Thomas precession of its spin. Concurrently we disclose some errors in the old and new publications on this subject.

Rovibrational states of interstitial H2 in Si

NASA Astrophysics Data System (ADS)

Koch, S.; Lavrov, E. V.; Weber, J.

2011-06-01

Rovibrational Q(J) transitions of the interstitial H2 molecule in Si have been investigated by Raman scattering in the temperature range 90-388 K. In accordance with an earlier suggestion [M. Hiller, E. V. Lavrov, and J. Weber, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.235214 74, 235214 (2006)], it is shown that the Q(2) transition of para hydrogen couples to the TAX phonon of Si and appears in the Raman spectra at temperatures above 200 K. The results presented also indicate that the rotational J=3 state of ortho hydrogen is resonantly coupled to the OΓ phonon.

Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II

DOE PAGES

Huynh, Mioy T.; Mora, S. Jimena; Villalba, Matias; ...

2017-05-09

Nature employs a TyrZ-His pair as a redox relay that couples proton transfer to the redox process between P680 and the water oxidizing catalyst in photosystem II. Artificial redox relays composed of different benzimidazole–phenol dyads (benzimidazole models His and phenol models Tyr) with substituents designed to simulate the hydrogen bond network surrounding the TyrZ-His pair have been prepared. Furthermore, when the benzimidazole substituents are strong proton acceptors such as primary or tertiary amines, theory predicts that a concerted two proton transfer process associated with the electrochemical oxidation of the phenol will take place. Furthermore, theory predicts a decrease in themore » redox potential of the phenol by ~300 mV and a small kinetic isotope effect (KIE). Indeed, electrochemical, spectroelectrochemical, and KIE experimental data are consistent with these predictions. Our results were obtained by using theory to guide the rational design of artificial systems and have implications for managing proton activity to optimize efficiency at energy conversion sites involving water oxidation and reduction.« less

Hydrogen in the Methanol Production Process

ERIC Educational Resources Information Center

Kralj, Anita Kovac; Glavic, Peter

2006-01-01

Hydrogen is a very important industrial gas in chemical processes. It is very volatile; therefore, it can escape from the process units and its mass balance is not always correct. In many industrial processes where hydrogen is reacted, kinetics are often related to hydrogen pressure. The right thermodynamic properties of hydrogen can be found for…

Long-Range Vibrational Dynamics Are Directed by Watson-Crick Base Pairing in Duplex DNA.

PubMed

Hithell, Gordon; Shaw, Daniel J; Donaldson, Paul M; Greetham, Gregory M; Towrie, Michael; Burley, Glenn A; Parker, Anthony W; Hunt, Neil T

2016-05-05

Ultrafast two-dimensional infrared (2D-IR) spectroscopy of a 15-mer A-T DNA duplex in solution has revealed structure-dependent vibrational coupling and energy transfer processes linking bases with the sugar-phosphate backbone. Duplex melting induces significant changes in the positions of off-diagonal peaks linking carbonyl and ring-stretching vibrational modes of the adenine and thymine bases with vibrations of the phosphate group and phosphodiester linkage. These indicate that Watson-Crick hydrogen bonding and helix formation lead to a unique vibrational coupling arrangement of base vibrational modes with those of the phosphate unit. On the basis of observations from time-resolved 2D-IR data, we conclude that rapid energy transfer processes occur between base and backbone, mediated by additional modes located on the deoxyribose moiety within the same nucleotide. These relaxation dynamics are insensitive to duplex melting, showing that efficient intramolecular energy relaxation to the solvent via the phosphate groups is the key to excess energy dissipation in both single- and double-stranded DNA.

Laser beam coupling with capillary discharge plasma for laser wakefield acceleration applications

NASA Astrophysics Data System (ADS)

Bagdasarov, G. A.; Sasorov, P. V.; Gasilov, V. A.; Boldarev, A. S.; Olkhovskaya, O. G.; Benedetti, C.; Bulanov, S. S.; Gonsalves, A.; Mao, H.-S.; Schroeder, C. B.; van Tilborg, J.; Esarey, E.; Leemans, W. P.; Levato, T.; Margarone, D.; Korn, G.

2017-08-01

One of the most robust methods, demonstrated to date, of accelerating electron beams by laser-plasma sources is the utilization of plasma channels generated by the capillary discharges. Although the spatial structure of the installation is simple in principle, there may be some important effects caused by the open ends of the capillary, by the supplying channels etc., which require a detailed 3D modeling of the processes. In the present work, such simulations are performed using the code MARPLE. First, the process of capillary filling with cold hydrogen before the discharge is fired, through the side supply channels is simulated. Second, the simulation of the capillary discharge is performed with the goal to obtain a time-dependent spatial distribution of the electron density near the open ends of the capillary as well as inside the capillary. Finally, to evaluate the effectiveness of the beam coupling with the channeling plasma wave guide and of the electron acceleration, modeling of the laser-plasma interaction was performed with the code INF&RNO.

Coupling of a 2.5 kW steam reformer with a 1 kW el PEM fuel cell

NASA Astrophysics Data System (ADS)

Mathiak, J.; Heinzel, A.; Roes, J.; Kalk, Th.; Kraus, H.; Brandt, H.

The University of Duisburg-Essen has developed a compact multi-fuel steam reformer suitable for natural gas, propane and butane. This steam reformer was combined with a polymer electrolyte membrane fuel cell (PEM FC) and a system test of the process chain was performed. The fuel processor comprises a prereformer step, a primary reformer, water gas shift reactors, a steam generator, internal heat exchangers in order to achieve an optimised heat integration and an external burner for heat supply as well as a preferential oxidation step (PROX) as CO purification. The fuel processor is designed to deliver a thermal hydrogen power output from 500 W to 2.5 kW. The PEM fuel cell stack provides about 1 kW electrical power. In the following paper experimental results of measurements of the single components PEM fuel cell and fuel processor as well as results of the coupling of both to form a process chain are presented.

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

NASA Astrophysics Data System (ADS)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

New Catalyst Reduces Wasted Carbon in Biofuel Process, Lowers Cost

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

Researchers at NREL recently developed a catalyst formulation that incorporates more hydrogen into the DME-to-high-octane gasoline process, resulting in a higher yield to gasoline-range products. Further, the researchers developed a secondary process that efficiently couples a portion of the gasoline-range product to yield jet/diesel fuels. The modified catalyst doubles the conversion rate of DME, which can be produced from biomass, to the high-octane gasoline product and significantly decreases the formation of wasted byproducts. For the distillate-range product, 80% of the mixture is in line with ASTM standards for use as a jet fuel blendstock. The increased productivity of high-octane gasolinemore » and the development of a value-added distillate blendstock process further improve the economic viability toward commercially implementing this renewable fuels process.« less

The GA sulfur-iodine water-splitting process - A status report

NASA Astrophysics Data System (ADS)

Besenbruch, G. E.; Chiger, H. D.; McCorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

Synergistic efficiency of the desilication of brackish underground water in Saudi Arabia by coupling γ-radiation and Fenton process: Membrane scaling prevention in reverse osmosis process

NASA Astrophysics Data System (ADS)

Aljohani, Mohammed S.

2017-12-01

One of the main water resources in arid Saudi Arabia is underground water. However, this brackish water has high silica content which can cause a recalcitrant deposit on the membrane in the reverse osmosis units during its desalination. In this study, we examined the synergistic efficiency of the removal of silica from the Buwaib water sample, when combining two advanced oxidation processes, γ-irradiation and the Fenton process, using hydrogen peroxide and zero valent metal iron as source of Fe3+. This latter adsorbs effectively on silica and co-precipitate. The influence of absorbed dose, iron dosage and pH effect were investigated. This preliminary study showed that these attractive and effective hybrid processes are very efficient in removing silica.

The GA sulfur-iodine water-splitting process - A status report

NASA Technical Reports Server (NTRS)

Besenbruch, G. E.; Chiger, H. D.; Mccorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

1981-01-01

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

Hydrogen underground storage in siliciclastic reservoirs - intention and topics of the H2STORE project

NASA Astrophysics Data System (ADS)

Pudlo, Dieter; Ganzer, Leonhard; Henkel, Steven; Liebscher, Axel; Kühn, Michael; De Lucia, Marco; Panfilov, Michel; Pilz, Peter; Reitenbach, Viktor; Albrecht, Daniel; Würdemann, Hilke; Gaupp, Reinhard

2013-04-01

The transfer of energy supply from nuclear and CO2-emitting power generation to renewable energy production sources is strongly reliant to the potential of storing high capacities of energy in a safe and reliable way in time spans of several months. One conceivable option can be the storage of hydrogen and (related) synthetic natural gas (SNG) production in appropriate underground structures, like salt caverns and pore space reservoirs. Successful storage of hydrogen in the form of town gas in salt caverns has been proven in several demonstration projects and can be considered as state of the art technology. However, salt structures have only limited importance for hydrogen storage due to only small cavern volumes and the limited occurrence of salt deposits suitable for flushing of cavern constructions. Thus, regarding potential high-volume storage sites, siliciclastic deposits like saline aquifers and depleted gas reservoirs are of increasing interest. Motivated by a project call and sponsored by the German government the H2STORE ("Hydrogen to Store") collaborative project will investigate the feasibility and the requirements for pore space storage of hydrogen. Thereby depleted gas reservoirs are a major concern of this study. This type of geological structure is chosen because of their well investigated geological settings and proved sealing capacities, which already enable a present (and future) use as natural (and synthetic) reservoir gas storages. Nonetheless hydrogen and hydrocarbon in porous media exhibit major differences in physico-chemical behaviour, essentially due to the high diffusivity and reactivity of hydrogen. The biotic and abiotic reactions of hydrogen with rocks and fluids will be necessary observed in siliciclastic sediments which consist of numerous inorganic and organic compounds and comprise original formation fluids. These features strongly control petrophysical behaviour (e.g. porosity, permeability) and therefore fluid (hydrogen) migration. To reveal the relevance of these interactions and their impact on petrophysics and fluid mechanics in H2STORE six subprojects are included, which are devoted to various aspects of hydrogen storage in pore space reservoirs. The analytical and (laboratory) experimental studies will be based on rock and fluid samples issued from different reservoir sandstone and cap rock mudstone types originated from different depths all over Germany. Thereby data on sedimentological, geochemical, mineralogical, hydrochemical, petrophysical and microbiological rock composition will be gained. These studies will be completed with conceptual mathematical and numerical modelling of dynamic reservoir processes, including basin/facies burial evolution, mineralogical alteration, hydro-/geochemical reactions and gas mixing processes coupled with population dynamics of methanogenic microorganisms and dynamic displacement instability effects. The estimation of the hydrogen impact on reservoir behaviour of different rock types at depths will enable an evaluation of the feasibility of "Eco-/Green" methane and synthetic natural gas (SNG) generation by hydrogen reaction with CO2. The verification/falsification of specific processes will also enhance predictions on the operational reliability, the ecological tolerance, and the economic efficiency of future energy storing plants. These aspects are main motivations for any industrial investors and the public acceptance of such new technologies within the framework of an overall power supply by renewable energy production.

Numerical study of shock-wave/boundary layer interactions in premixed hydrogen-air hypersonic flows

NASA Technical Reports Server (NTRS)

Yungster, Shaye

1991-01-01

A computational study of shock wave/boundary layer interactions involving premixed combustible gases, and the resulting combustion processes is presented. The analysis is carried out using a new fully implicit, total variation diminishing (TVD) code developed for solving the fully coupled Reynolds-averaged Navier-Stokes equations and species continuity equations in an efficient manner. To accelerate the convergence of the basic iterative procedure, this code is combined with vector extrapolation methods. The chemical nonequilibrium processes are simulated by means of a finite-rate chemistry model for hydrogen-air combustion. Several validation test cases are presented and the results compared with experimental data or with other computational results. The code is then applied to study shock wave/boundary layer interactions in a ram accelerator configuration. Results indicate a new combustion mechanism in which a shock wave induces combustion in the boundary layer, which then propagates outwards and downstream. At higher Mach numbers, spontaneous ignition in part of the boundary layer is observed, which eventually extends along the entire boundary layer at still higher values of the Mach number.

The role of impurities on the process of growing potassium hydrogen phthalate crystals from solution; A quantitative approach

NASA Astrophysics Data System (ADS)

Hottenhuis, M. H. J.; Lucasius, C. B.

1988-09-01

Quantitative information about the influence of impurities on the crystal growth process of potassium hydrogen phthalate from its aqueous solution was obtained at two levels: microscopic and macroscopic. At the microscopic level, detailed in situ observations of spiral steps at the (010) face were performed. The velocity of these steps was measured, as well in a "clean" as in a contaminated solution, where the influence of a number of different impurities was investigated. This resulted in a measure of effectiveness of step retardation for each of these impurities. From the same microscopic observations it was observed how these effectiveness factors were influenced by the supersaturation σ, the saturation temperature Ts of the solution and the concentration cimp of the impurity that w as used. At the macroscopic level, ICP (inductively coupled plasma) measurements were carried out in order to determine the distribution coefficient of the same impurities. In these measurements again the influence of the impurity concentration and the supersaturation on the distribution coefficient kD was determined.

Mechanism of nuclear spin initiated para-H2 to ortho-H2 conversion.

PubMed

Buntkowsky, G; Walaszek, B; Adamczyk, A; Xu, Y; Limbach, H-H; Chaudret, B

2006-04-28

In this paper a quantitative explanation for a diamagnetic ortho/para H2 conversion is given. The description is based on the quantum-mechanical density matrix formalism originally developed by Alexander and Binsch for studies of exchange processes in NMR spectra. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a three spin system, the reactions of the hydrogen gas with the catalysts are treated as a phenomenological rate process, described by a rate constant. Numerical calculations reveal that for nearly all possible geometrical arrangements of the three spin system an efficient spin conversion is obtained. Only in the chemically improbable case of a linear group H-X-H no spin conversion is obtained. The efficiency of the spin conversion depends strongly on the lifetime of the H-X-H complex and on the presence of exchange interactions between the two hydrogens. Even moderate exchange couplings cause a quench of the spin conversion. Thus a sufficiently strong binding of the dihydrogen to the S spin is necessary to render the quenching by the exchange interaction ineffective.

Numerical study of shock-wave/boundary layer interactions in premixed hydrogen-air hypersonic flows

NASA Technical Reports Server (NTRS)

Yungster, Shaye

1990-01-01

A computational study of shock wave/boundary layer interactions involving premixed combustible gases, and the resulting combustion processes is presented. The analysis is carried out using a new fully implicit, total variation diminishing (TVD) code developed for solving the fully coupled Reynolds-averaged Navier-Stokes equations and species continuity equations in an efficient manner. To accelerate the convergence of the basic iterative procedure, this code is combined with vector extrapolation methods. The chemical nonequilibrium processes are simulated by means of a finite-rate chemistry model for hydrogen-air combustion. Several validation test cases are presented and the results compared with experimental data or with other computational results. The code is then applied to study shock wave/boundary layer interactions in a ram accelerator configuration. Results indicate a new combustion mechanism in which a shock wave induces combustion in the boundary layer, which then propagates outwards and downstream. At higher Mach numbers, spontaneous ignition in part of the boundary layer is observed, which eventually extends along the entire boundary layer at still higher values of the Mach number.

New look at the Badger-Bauer rule: Correlations of spectroscopic IR and NMR parameters with hydrogen bond energy and geometry. FHF complexes

NASA Astrophysics Data System (ADS)

Tupikina, E. Yu.; Denisov, G. S.; Melikova, S. M.; Kucherov, S. Yu.; Tolstoy, P. M.

2018-07-01

In this work correlation dependencies between hydrogen bond energy ΔE for complexes with Fsbnd H⋯F hydrogen bond and their spectroscopic characteristics of the IR and NMR spectra are presented. We considered 26 complexes in a wide hydrogen bond energy range 0.2-47 kcal/mol. For each complex we calculated complexation energy (MP2/6-311++G(d,p)), IR spectroscopic parameters (FH stretching frequency ν, FH stretching frequency in local mode approximation νLM at MP2/6-311++G(d,p) level) and NMR parameters (chemical shift of hydrogen δH and fluorine nuclei δF, Nuclear Independent Chemical Shielding and spin-spin coupling constants 1JFH, 1hJH...F, 2hJFF at B3LYP/pcSseg-2 level). It was shown that changes of parameters upon complexation, i.e. changes of the stretching frequency in local mode approximation ΔνLM, change of the proton chemical shift ΔδH and change of the absolute value of spin-spin coupling constant 1JFH could be used for estimation of corresponding hydrogen bond strength. Furthermore, we build correlation dependencies between abovementioned spectroscopic characteristics and geometric ones, such as the asymmetry of bridging proton position q1 = 0.5·(rFH - rH…F).

Characterization of the water of crystallization in CsMnCl3.2H2O (2D2O) by Raman scattering

NASA Astrophysics Data System (ADS)

Jia, Weiyi; Strauss, E.; Yen, W. M.; Xia, Kehui; Zhao, Minguang

1989-06-01

Raman spectra of CsMnCl3.2H2O (2D2O) (CMC) were measured at low temperatures. The spectra demonstrated features which are related to the chain and layered structures of the compound. The vibration characteristics of the water of crystallization were investigated in detail, allowing us to derive the spatial orientation of the water molecules and the direction of their hydrogen bonds. Strong Raman scattering from the OH stretching mode in the (zz) configuration indicates the existence of hydrogen bonds linking the layers along the z axis. Various combination frequencies of the water vibrations were observed; for example, the OH (OD) stretching mode is seen to couple to vibrations of oxygen and chlorine atoms. These combination modes play an important role in quenching 4T1-->6A1 electronic transition of Mn2+ ions through multiphonon nonradiative processes.

Palladium-tin catalysts for the direct synthesis of H 2O 2 with high selectivity

DOE PAGES

Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

2016-02-25

The direct synthesis of hydrogen peroxide (H 2O 2 ) from H 2 and O 2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H 2O 2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriatemore » second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H 2O 2 production that do not contain gold.« less

Solvent screening for a hard-to-dissolve molecular crystal.

PubMed

Maiti, A; Pagoria, P F; Gash, A E; Han, T Y; Orme, C A; Gee, R H; Fried, L E

2008-09-01

Materials with a high-degree of inter- and intra-molecular hydrogen bonding generally have limited solubility in conventional organic solvents. This presents a problem for the dissolution, manipulation and purification of these materials. Using a state-of-the-art density-functional-theory based quantum chemical solvation model we systematically evaluated solvents for a known hydrogen-bonded molecular crystal. This, coupled with direct solubility measurements, uncovered a class of ionic liquids involving fluoride anions that possess more than two orders of magnitude higher solvation power as compared with the best conventional solvents. The crystal structure of one such ionic liquid, determined by X-ray diffraction spectroscopy, indicates that F- ions are stabilized through H-bonded chains with water. The presence of coordinating water in such ionic liquids seems to facilitate the dissolution process by keeping the chemical activity of the F- ions in check.

Carrier-envelope phase dependence of the directional fragmentation and hydrogen migration in toluene in few-cycle laser fields

PubMed Central

Li, Hui; Kling, Nora G.; Förg, Benjamin; Stierle, Johannes; Kessel, Alexander; Trushin, Sergei A.; Kling, Matthias F.; Kaziannis, Spyros

2016-01-01

The dissociative ionization of toluene initiated by a few-cycle laser pulse as a function of the carrier envelope phase (CEP) is investigated using single-shot velocity map imaging. Several ionic fragments, CH3+, H2+, and H3+, originating from multiply charged toluene ions present a CEP-dependent directional emission. The formation of H2+ and H3+ involves breaking C-H bonds and forming new bonds between the hydrogen atoms within the transient structure of the multiply charged precursor. We observe appreciable intensity-dependent CEP-offsets. The experimental data are interpreted with a mechanism that involves laser-induced coupling of vibrational states, which has been found to play a role in the CEP-control of molecular processes in hydrocarbon molecules, and appears to be of general importance for such complex molecules. PMID:26958589

Alternative RF coupling configurations for H{sup −} ion sources

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

Briefi, S.; Fantz, U.; AG Experimentelle Plasmaphysik, Universität Augsburg, 86135 Augsburg

2015-04-08

RF heated sources for negative hydrogen ions both for fusion and accelerators require very high RF powers in order to achieve the required H{sup −} current what poses high demands on the RF generators and the RF circuit. Therefore it is highly desirable to improve the RF efficiency of the sources. This could be achieved by applying different RF coupling concepts than the currently used inductive coupling via a helical antenna, namely Helicon coupling or coupling via a planar ICP antenna enhanced with ferrites. In order to investigate the feasibility of these concepts, two small laboratory experiments have been setmore » up. The PlanICE experiment, where the enhanced inductive coupling is going to be investigated, is currently under assembly. At the CHARLIE experiment systematic measurements concerning Helicon coupling in hydrogen and deuterium are carried out. The investigations show that a prominent feature of Helicon discharges occurs: the so-called low-field peak. This is a local improvement of the coupling efficiency at a magnetic field strength of a few mT which results in an increased electron density and dissociation degree. The full Helicon mode has not been achieved yet due to the limited available RF power and magnetic field strength but it might be sufficient for the application of the coupling concept to ion sources to operate the discharge in the low-field-peak region.« less

Alternative RF coupling configurations for H- ion sources

NASA Astrophysics Data System (ADS)

Briefi, S.; Gutmann, P.; Fantz, U.

2015-04-01

RF heated sources for negative hydrogen ions both for fusion and accelerators require very high RF powers in order to achieve the required H- current what poses high demands on the RF generators and the RF circuit. Therefore it is highly desirable to improve the RF efficiency of the sources. This could be achieved by applying different RF coupling concepts than the currently used inductive coupling via a helical antenna, namely Helicon coupling or coupling via a planar ICP antenna enhanced with ferrites. In order to investigate the feasibility of these concepts, two small laboratory experiments have been set up. The PlanICE experiment, where the enhanced inductive coupling is going to be investigated, is currently under assembly. At the CHARLIE experiment systematic measurements concerning Helicon coupling in hydrogen and deuterium are carried out. The investigations show that a prominent feature of Helicon discharges occurs: the so-called low-field peak. This is a local improvement of the coupling efficiency at a magnetic field strength of a few mT which results in an increased electron density and dissociation degree. The full Helicon mode has not been achieved yet due to the limited available RF power and magnetic field strength but it might be sufficient for the application of the coupling concept to ion sources to operate the discharge in the low-field-peak region.

Catalytic Carbonyl Allylation, Propargylation and Vinylation from the Alcohol or Aldehyde Oxidation Level via C-C Bond Forming Hydrogenation and Transfer Hydrogenation: A Departure from Preformed Organometallic Reagents**

PubMed Central

Bower, John F.; Kim, In Su; Patman, Ryan L.; Krische, Michael J.

2009-01-01

Classical protocols for carbonyl allylation, propargylation and vinylation typically rely upon the use of preformed allyl metal, allenyl metal and vinyl metal reagents, respectively, mandating stoichiometric generation of metallic byproducts. Through transfer hydrogenative C-C coupling, carbonyl addition may be achieved from the aldehyde or alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Here, we review transfer hydrogenative methods for carbonyl addition, which encompass the first cataltyic protocols enabling direct C–H functionalization of alcohols. PMID:19040235

Imaging hydrogen flames by two-photon, laser-induced fluorescence

NASA Technical Reports Server (NTRS)

Miles, R.; Lempert, W.; Kumar, V.; Diskin, G.

1991-01-01

A nonintrusive multicomponent imaging system is developed which can image hydrogen, hot oxygen, and air simultaneously. An Ar-F excimer laser is injection-locked to cover the Q1 two-photon transition in molecular hydrogen which allows the observation of both hot oxygen and cold hydrogen. Rayleigh scattering from the water molecules occurs at the same frequency as the illuminating laser allowing analysis of the air density. Images of ignited and nonignited hydrogen jets are recorded with a high-sensitivity gated video camera. The images permit the analysis of turbulent hydrogen-core jet, the combustion zone, and the surrounding air, and two-dimensional spatial correlations can be made to study the turbulent structure and couplings between different regions of the flow field. The method is of interest to the study of practical combustion systems which employ hydrogen-air diffusion flames.

LETTER TO THE EDITOR: Iteratively-coupled propagating exterior complex scaling method for electron hydrogen collisions

NASA Astrophysics Data System (ADS)

Bartlett, Philip L.; Stelbovics, Andris T.; Bray, Igor

2004-02-01

A newly-derived iterative coupling procedure for the propagating exterior complex scaling (PECS) method is used to efficiently calculate the electron-impact wavefunctions for atomic hydrogen. An overview of this method is given along with methods for extracting scattering cross sections. Differential scattering cross sections at 30 eV are presented for the electron-impact excitation to the n = 1, 2, 3 and 4 final states, for both PECS and convergent close coupling (CCC), which are in excellent agreement with each other and with experiment. PECS results are presented at 27.2 eV and 30 eV for symmetric and asymmetric energy-sharing triple differential cross sections, which are in excellent agreement with CCC and exterior complex scaling calculations, and with experimental data. At these intermediate energies, the efficiency of the PECS method with iterative coupling has allowed highly accurate partial-wave solutions of the full Schrödinger equation, for L les 50 and a large number of coupled angular momentum states, to be obtained with minimal computing resources.

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and exposure to dust containing the two metal sulfides may present a health burden.

The Mg2+-containing Water Cluster of Mammalian Cytochrome c Oxidase Collects Four Pumping Proton Equivalents in Each Catalytic Cycle*

PubMed Central

Yano, Naomine; Muramoto, Kazumasa; Shimada, Atsuhiro; Takemura, Shuhei; Baba, Junpei; Fujisawa, Hidenori; Mochizuki, Masao; Shinzawa-Itoh, Kyoko; Yamashita, Eiki; Tsukihara, Tomitake; Yoshikawa, Shinya

2016-01-01

Bovine heart cytochrome c oxidase (CcO) pumps four proton equivalents per catalytic cycle through the H-pathway, a proton-conducting pathway, which includes a hydrogen bond network and a water channel operating in tandem. Protons are transferred by H3O+ through the water channel from the N-side into the hydrogen bond network, where they are pumped to the P-side by electrostatic repulsion between protons and net positive charges created at heme a as a result of electron donation to O2 bound to heme a3. To block backward proton movement, the water channel remains closed after O2 binding until the sequential four-proton pumping process is complete. Thus, the hydrogen bond network must collect four proton equivalents before O2 binding. However, a region with the capacity to accept four proton equivalents was not discernable in the x-ray structures of the hydrogen bond network. The present x-ray structures of oxidized/reduced bovine CcO are improved from 1.8/1.9 to 1.5/1.6 Å resolution, increasing the structural information by 1.7/1.6 times and revealing that a large water cluster, which includes a Mg2+ ion, is linked to the H-pathway. The cluster contains enough proton acceptor groups to retain four proton equivalents. The redox-coupled x-ray structural changes in Glu198, which bridges the Mg2+ and CuA (the initial electron acceptor from cytochrome c) sites, suggest that the CuA-Glu198-Mg2+ system drives redox-coupled transfer of protons pooled in the water cluster to the H-pathway. Thus, these x-ray structures indicate that the Mg2+-containing water cluster is the crucial structural element providing the effective proton pumping in bovine CcO. PMID:27605664

The Mg2+-containing Water Cluster of Mammalian Cytochrome c Oxidase Collects Four Pumping Proton Equivalents in Each Catalytic Cycle.

PubMed

Yano, Naomine; Muramoto, Kazumasa; Shimada, Atsuhiro; Takemura, Shuhei; Baba, Junpei; Fujisawa, Hidenori; Mochizuki, Masao; Shinzawa-Itoh, Kyoko; Yamashita, Eiki; Tsukihara, Tomitake; Yoshikawa, Shinya

2016-11-11

Bovine heart cytochrome c oxidase (CcO) pumps four proton equivalents per catalytic cycle through the H-pathway, a proton-conducting pathway, which includes a hydrogen bond network and a water channel operating in tandem. Protons are transferred by H 3 O + through the water channel from the N-side into the hydrogen bond network, where they are pumped to the P-side by electrostatic repulsion between protons and net positive charges created at heme a as a result of electron donation to O 2 bound to heme a 3 To block backward proton movement, the water channel remains closed after O 2 binding until the sequential four-proton pumping process is complete. Thus, the hydrogen bond network must collect four proton equivalents before O 2 binding. However, a region with the capacity to accept four proton equivalents was not discernable in the x-ray structures of the hydrogen bond network. The present x-ray structures of oxidized/reduced bovine CcO are improved from 1.8/1.9 to 1.5/1.6 Å resolution, increasing the structural information by 1.7/1.6 times and revealing that a large water cluster, which includes a Mg 2+ ion, is linked to the H-pathway. The cluster contains enough proton acceptor groups to retain four proton equivalents. The redox-coupled x-ray structural changes in Glu 198 , which bridges the Mg 2+ and Cu A (the initial electron acceptor from cytochrome c) sites, suggest that the Cu A -Glu 198 -Mg 2+ system drives redox-coupled transfer of protons pooled in the water cluster to the H-pathway. Thus, these x-ray structures indicate that the Mg 2+ -containing water cluster is the crucial structural element providing the effective proton pumping in bovine CcO. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Learning about Regiochemistry from a Hydrogen-Atom Abstraction Reaction in Water

ERIC Educational Resources Information Center

Sears-Dundes, Christopher; Huon, Yoeup; Hotz, Richard P.; Pinhas, Allan R.

2011-01-01

An experiment has been developed in which the hydrogen-atom abstraction and the coupling of propionitrile, using Fenton's reagent, are investigated. Students learn about the regiochemistry of radical formation, the stereochemistry of product formation, and the interpretation of GC-MS data, in a safe reaction that can be easily completed in one…

p-Dimethylaminobenzamide as an ICT dual fluorescent neutral receptor for anions under proton coupled electron transfer sensing mechanism

NASA Astrophysics Data System (ADS)

Wu, Fang-Ying; Jiang, Yun-Bao

2002-04-01

The intramolecular charge transfer (ICT) dual fluorescence of p-dimethylaminobenzamide (DMABA) in acetonitrile was found to show highly sensitive response to HSO 4- over several other anions such as H 2PO 4-,AcO - and ClO 4-. In the presence of bisulfate anion the dual fluorescence intensity ratio and the total intensity of DMABA decreased while the dual emission band positions remained unchanged. Absorption titration indicated that a 1:1 hydrogen bonding complex was formed between bisulfate anion and DMABA, which gave a binding constant of 2.02×10 4 mol-1 l that is two orders of magnitude higher than those for other anions. The obvious isotopic effect observed in the fluorescence quenching [ K SV( HSO4-)/K SV( DSO4-)=1.63 ] suggests that the hydrogen atom moving is an important reaction coordinate. It was assumed that the dual fluorescence response was due to proton coupled electron transfer mediated by hydrogen bonds within the 1:1 HSO 4--DMABA hydrogen-bonding complex.

Non-equilibrium hydrogen ionization in 2D simulations of the solar atmosphere

NASA Astrophysics Data System (ADS)

Leenaarts, J.; Carlsson, M.; Hansteen, V.; Rutten, R. J.

2007-10-01

Context: The ionization of hydrogen in the solar chromosphere and transition region does not obey LTE or instantaneous statistical equilibrium because the timescale is long compared with important hydrodynamical timescales, especially of magneto-acoustic shocks. Since the pressure, temperature, and electron density depend sensitively on hydrogen ionization, numerical simulation of the solar atmosphere requires non-equilibrium treatment of all pertinent hydrogen transitions. The same holds for any diagnostic application employing hydrogen lines. Aims: To demonstrate the importance and to quantify the effects of non-equilibrium hydrogen ionization, both on the dynamical structure of the solar atmosphere and on hydrogen line formation, in particular Hα. Methods: We implement an algorithm to compute non-equilibrium hydrogen ionization and its coupling into the MHD equations within an existing radiation MHD code, and perform a two-dimensional simulation of the solar atmosphere from the convection zone to the corona. Results: Analysis of the simulation results and comparison to a companion simulation assuming LTE shows that: a) non-equilibrium computation delivers much smaller variations of the chromospheric hydrogen ionization than for LTE. The ionization is smaller within shocks but subsequently remains high in the cool intershock phases. As a result, the chromospheric temperature variations are much larger than for LTE because in non-equilibrium, hydrogen ionization is a less effective internal energy buffer. The actual shock temperatures are therefore higher and the intershock temperatures lower. b) The chromospheric populations of the hydrogen n = 2 level, which governs the opacity of Hα, are coupled to the ion populations. They are set by the high temperature in shocks and subsequently remain high in the cool intershock phases. c) The temperature structure and the hydrogen level populations differ much between the chromosphere above photospheric magnetic elements and above quiet internetwork. d) The hydrogen n = 2 population and column density are persistently high in dynamic fibrils, suggesting that these obtain their visibility from being optically thick in Hα also at low temperature. Movie and Appendix A are only available in electronic form at http://www.aanda.org

A nonequilibrium model for a moderate pressure hydrogen microwave discharge plasma

NASA Technical Reports Server (NTRS)

Scott, Carl D.

1993-01-01

This document describes a simple nonequilibrium energy exchange and chemical reaction model to be used in a computational fluid dynamics calculation for a hydrogen plasma excited by microwaves. The model takes into account the exchange between the electrons and excited states of molecular and atomic hydrogen. Specifically, electron-translation, electron-vibration, translation-vibration, ionization, and dissociation are included. The model assumes three temperatures, translational/rotational, vibrational, and electron, each describing a Boltzmann distribution for its respective energy mode. The energy from the microwave source is coupled to the energy equation via a source term that depends on an effective electric field which must be calculated outside the present model. This electric field must be found by coupling the results of the fluid dynamics and kinetics solution with a solution to Maxwell's equations that includes the effects of the plasma permittivity. The solution to Maxwell's equations is not within the scope of this present paper.

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.

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.

Electron– and positron–molecule scattering: development of the molecular convergent close-coupling method

DOE PAGES

Zammit, Mark C.; Fursa, Dmitry V.; Savage, Jeremy S.; ...

2017-05-22

Starting from first principles, this tutorial describes the development of the adiabatic-nuclei convergent close-coupling (CCC) method and its application to electron and (single-centre) positron scattering from diatomic molecules. In this paper, we give full details of the single-centre expansion CCC method, namely the formulation of the molecular target structure; solving the momentum-space coupled-channel Lippmann-Schwinger equation; deriving adiabatic-nuclei cross sections and calculatingmore » $V$-matrix elements. Selected results are presented for electron and positron scattering from molecular hydrogen H$$_2$$ and electron scattering from the vibrationally excited molecular hydrogen ion H$$_2^+$$ and its isotopologues (D$$_2^+$$, T$$_2^+$$, HD$^+$, HT$^+$ and TD$^+$). Finally, convergence in both the close-coupling (target state) and projectile partial-wave expansions of fixed-nuclei electron- and positron-molecule scattering calculations is demonstrated over a broad energy-range and discussed in detail. In general the CCC results are in good agreement with experiments.« less

Protonation-state-Coupled Conformational Dynamics in Reaction Mechanisms of Channel and Pump Rhodopsins

DOE PAGES

Bondar, Ana-Nicoleta; Smith, Jeremy C.

2017-07-25

Channel and pump rhodopsins use energy from light absorbed by a covalently bound retinal chromophore to transport ions across membranes of microbial cells. Ion transfer steps, including proton transfer, can couple to changes in protein conformational dynamics and water positions. Although general principles of how microbial rhodopsins function are largely understood, key issues pertaining to reaction mechanisms remain unclear. Here, we compare the protonation-coupled dynamics of pump and channelrhodopsins, highlighting the roles that water dynamics, protein electrostatics and protein flexibility can have in ion transport mechanisms. We discuss observations supporting important functional roles of inter- and intra-helical carboxylate/hydroxyl hydrogen-bonding motifs.more » Specifically, we use the proton pump bacteriorhodopsin, the sodium pump KR2, channelrhodopsins and Anabaena sensory rhodopsin. We outline the usefulness of theoretic biophysics approaches to the study of retinal proteins, challenges in studying the hydrogen-bond dynamics of rhodopsin active sites, and implications for conformational coupling in membrane transporters.« less

Protonation-state-Coupled Conformational Dynamics in Reaction Mechanisms of Channel and Pump Rhodopsins

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

Bondar, Ana-Nicoleta; Smith, Jeremy C.

Channel and pump rhodopsins use energy from light absorbed by a covalently bound retinal chromophore to transport ions across membranes of microbial cells. Ion transfer steps, including proton transfer, can couple to changes in protein conformational dynamics and water positions. Although general principles of how microbial rhodopsins function are largely understood, key issues pertaining to reaction mechanisms remain unclear. Here, we compare the protonation-coupled dynamics of pump and channelrhodopsins, highlighting the roles that water dynamics, protein electrostatics and protein flexibility can have in ion transport mechanisms. We discuss observations supporting important functional roles of inter- and intra-helical carboxylate/hydroxyl hydrogen-bonding motifs.more » Specifically, we use the proton pump bacteriorhodopsin, the sodium pump KR2, channelrhodopsins and Anabaena sensory rhodopsin. We outline the usefulness of theoretic biophysics approaches to the study of retinal proteins, challenges in studying the hydrogen-bond dynamics of rhodopsin active sites, and implications for conformational coupling in membrane transporters.« less

From Artificial Atoms to Nanocrystal Molecules: Preparation and Properties of More Complex Nanostructures

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

Choi, Charina L; Alivisatos, A Paul

2009-10-20

Quantum dots, which have found widespread use in fields such as biomedicine, photovoltaics, and electronics, are often called artificial atoms due to their size-dependent physical properties. Here this analogy is extended to consider artificial nanocrystal molecules, formed from well-defined groupings of plasmonically or electronically coupled single nanocrystals. Just as a hydrogen molecule has properties distinct from two uncoupled hydrogen atoms, a key feature of nanocrystal molecules is that they exhibit properties altered from those of the component nanoparticles due to coupling. The nature of the coupling between nanocrystal atoms and its response to vibrations and deformations of the nanocrystal moleculemore » bonds are of particular interest. We discuss synthetic approaches, predicted and observed physical properties, and prospects and challenges toward this new class of materials.« less

Three computational mise-en-scènes of red- and blue-shifted hydrogen bonding motifs: Concept of negative intramolecular coupling-What else?

NASA Astrophysics Data System (ADS)

Kryachko, Eugene S.

This work is a kind of attempt to rethink some problems which are related to the blue-shifted "hydrogen bonds" and which have been left in the past decade as not yet fully resolved. The impetus for such rethink is originated from the three computational mise-en-scènes on red- and blue-shifted hydrogen bonding motifs, which are aimed to be thoroughly studied in this work, thus resolving the above problems.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

PubMed

Badalyan, Artavazd; Stahl, Shannon S

2016-07-21

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1–2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2′-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2′-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

NASA Astrophysics Data System (ADS)

Badalyan, Artavazd; Stahl, Shannon S.

2016-07-01

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Investigation of Helicon discharges as RF coupling concept of negative hydrogen ion sources

NASA Astrophysics Data System (ADS)

Briefi, S.; Fantz, U.

2013-02-01

The ITER reference source for H- and D- requires a high RF input power (up to 90 kW per driver). To reduce the demands on the RF circuit, it is highly desirable to reduce the power consumption while retaining the values of the relevant plasma parameters namely the positive ion density and the atomic hydrogen density. Helicon plasmas are a promising alternative RF coupling concept but they are typically generated in long thin discharge tubes using rare gases and an RF frequency of 13.56 MHz. Hence the applicability to the ITER reference source geometry, frequency and the utilization of hydrogen/deuterium has to be proved. In this paper the strategy of the approach for using Helicon discharges for ITER reference source parameters is introduced and the first promising measurements which were carried out at a small laboratory experiment are presented. With increasing RF power a mode transition to the Helicon regime was observed for argon and argon/hydrogen mixtures. In pure hydrogen/deuterium the mode transition could not yet be achieved as the available RF power is too low. In deuterium a special feature of Helicon discharges, the socalled low field peak, could be observed at a moderate B-field of 3 mT.

A simple model for molecular hydrogen chemistry coupled to radiation hydrodynamics

NASA Astrophysics Data System (ADS)

Nickerson, Sarah; Teyssier, Romain; Rosdahl, Joakim

2018-06-01

We introduce non-equilibrium molecular hydrogen chemistry into the radiation-hydrodynamics code RAMSES-RT. This is an adaptive mesh refinement grid code with radiation hydrodynamics that couples the thermal chemistry of hydrogen and helium to moment-based radiative transfer with the Eddington tensor closure model. The H2 physics that we include are formation on dust grains, gas phase formation, formation by three-body collisions, collisional destruction, photodissociation, photoionisation, cosmic ray ionisation and self-shielding. In particular, we implement the first model for H2 self-shielding that is tied locally to moment-based radiative transfer by enhancing photo-destruction. This self-shielding from Lyman-Werner line overlap is critical to H2 formation and gas cooling. We can now track the non-equilibrium evolution of molecular, atomic, and ionised hydrogen species with their corresponding dissociating and ionising photon groups. Over a series of tests we show that our model works well compared to specialised photodissociation region codes. We successfully reproduce the transition depth between molecular and atomic hydrogen, molecular cooling of the gas, and a realistic Strömgren sphere embedded in a molecular medium. In this paper we focus on test cases to demonstrate the validity of our model on small scales. Our ultimate goal is to implement this in large-scale galactic simulations.

Process design and economic analysis of the zinc selenide thermochemical hydrogen cycle

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

Otsuki, H.H.; Krikorian, O.H.

1978-09-06

A detailed preliminary design for a hydrogen production plant has been developed based on an improved version of the ZnSe thermochemical cycle for decomposing water. In the latest version of the cycle, ZnCl/sub 2/ is converted directly to ZnO through high temperature steam hydrolysis. This eliminates the need for first converting ZnCl/sub 2/ to ZnSO/sub 4/ and also slightly reduces the overall heat requirement. Moreover, it broadens the temperature range over which prime heat is required and improves the coupling of the cycle with a nuclear reactor heat source. The ZnSe cycle is driven by a very-high-temperature nuclear reactor (VHTR)more » proposed by Westinghouse that provides a high-temperature (1283 K) helium working gas for process heat and power. The plant is sized to produce 27.3 Mg H/sub 2//h (60,000 lb H/sub 2//h) and requires specially designed equipment to perform the critical reaction steps in the cycle. We have developed conceptual designs for several of the important process steps to make cost estimates, and have obtained a cycle efficiency of about 40% and a hydrogen production cost of about $14/GJ. We believe that the cost is high because input data on reaction rates and equipment lifetimes have been conservatively estimated and the cycle parameters have not been optimized. Nonetheless, this initial analysis serves an important function in delineating areas in the cycle where additional research is needed to increase efficiency and reduce costs in a more advanced version of the cycle.« less

Methods and systems for the production of hydrogen

DOEpatents

Oh, Chang H [Idaho Falls, ID; Kim, Eung S [Ammon, ID; Sherman, Steven R [Augusta, GA

2012-03-13

Methods and systems are disclosed for the production of hydrogen and the use of high-temperature heat sources in energy conversion. In one embodiment, a primary loop may include a nuclear reactor utilizing a molten salt or helium as a coolant. The nuclear reactor may provide heat energy to a power generation loop for production of electrical energy. For example, a supercritical carbon dioxide fluid may be heated by the nuclear reactor via the molten salt and then expanded in a turbine to drive a generator. An intermediate heat exchange loop may also be thermally coupled with the primary loop and provide heat energy to one or more hydrogen production facilities. A portion of the hydrogen produced by the hydrogen production facility may be diverted to a combustor to elevate the temperature of water being split into hydrogen and oxygen by the hydrogen production facility.

High capacity hydrogen storage materials: attributes for automotive applications and techniques for materials discovery.

PubMed

Yang, Jun; Sudik, Andrea; Wolverton, Christopher; Siegel, Donald J

2010-02-01

Widespread adoption of hydrogen as a vehicular fuel depends critically upon the ability to store hydrogen on-board at high volumetric and gravimetric densities, as well as on the ability to extract/insert it at sufficiently rapid rates. As current storage methods based on physical means--high-pressure gas or (cryogenic) liquefaction--are unlikely to satisfy targets for performance and cost, a global research effort focusing on the development of chemical means for storing hydrogen in condensed phases has recently emerged. At present, no known material exhibits a combination of properties that would enable high-volume automotive applications. Thus new materials with improved performance, or new approaches to the synthesis and/or processing of existing materials, are highly desirable. In this critical review we provide a practical introduction to the field of hydrogen storage materials research, with an emphasis on (i) the properties necessary for a viable storage material, (ii) the computational and experimental techniques commonly employed in determining these attributes, and (iii) the classes of materials being pursued as candidate storage compounds. Starting from the general requirements of a fuel cell vehicle, we summarize how these requirements translate into desired characteristics for the hydrogen storage material. Key amongst these are: (a) high gravimetric and volumetric hydrogen density, (b) thermodynamics that allow for reversible hydrogen uptake/release under near-ambient conditions, and (c) fast reaction kinetics. To further illustrate these attributes, the four major classes of candidate storage materials--conventional metal hydrides, chemical hydrides, complex hydrides, and sorbent systems--are introduced and their respective performance and prospects for improvement in each of these areas is discussed. Finally, we review the most valuable experimental and computational techniques for determining these attributes, highlighting how an approach that couples computational modeling with experiments can significantly accelerate the discovery of novel storage materials (155 references).

Electron capture in collisions of N+ with H and H+ with N

NASA Astrophysics Data System (ADS)

Lin, C. Y.; Stancil, P. C.; Gu, J. P.; Buenker, R. J.; Kimura, M.

2005-06-01

Charge-transfer processes due to collisions of N+ with atomic hydrogen and H+ with atomic nitrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial and rotational couplings obtained with the multireference single- and double-excitation configuration interaction approach. Total and state-selective cross sections for the energy range 0.1meV/u-1keV/u are presented and compared with existing experimental and theoretical data. A large number of low-energy resonances are obtained for exoergic channels and near thresholds of endoergic channels. Rate coefficients are also obtained and comparison to previous calculations suggests nonadiabatic effects dominate for temperatures greater than 20 000 K, but that the spin-orbit interaction plays a major role for lower temperatures.

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE PAGES

d'Entremont, A.; Corgnale, C.; Sulic, M.; ...

2017-08-31

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

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

d'Entremont, A.; Corgnale, C.; Sulic, M.

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

DOE PAGES

Parkison, Adam J.; Nelson, Andrew Thomas

2016-01-11

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

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

Parkison, Adam J.; Nelson, Andrew Thomas

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Dynamics and couplings of N-H stretching excitations of guanosine-cytidine base pairs in solution.

PubMed

Yang, Ming; Szyc, Łukasz; Röttger, Katharina; Fidder, Henk; Nibbering, Erik T J; Elsaesser, Thomas; Temps, Friedrich

2011-05-12

N-H stretching vibrations of hydrogen-bonded guanosine-cytidine (G·C) base pairs in chloroform solution are studied with linear and ultrafast nonlinear infrared (IR) spectroscopy. Assignment of the IR-active bands in the linear spectrum is made possible by combining structural information on the hydrogen bonds in G·C base pairs with literature results of density functional theory calculations, and empirical relations connecting frequency shifts and intensity of the IR-active vibrations. A local mode representation of N-H stretching vibrations is adopted, consisting of ν(G)(NH(2))(f) and ν(C)(NH(2))(f) modes for free NH groups of G and C, and of ν(G)(NH(2))(b), ν(G)(NH), and ν(C)(NH(2))(b) modes associated with N-H stretching motions of hydrogen-bonded NH groups. The couplings and relaxation dynamics of the N-H stretching excitations are studied with femtosecond mid-infrared two-dimensional (2D) and pump-probe spectroscopy. The N-H stretching vibrations of the free NH groups of G and C have an average population lifetime of 2.4 ps. Besides a vibrational population lifetime shortening to subpicosecond values observed for the hydrogen-bonded N-H stretching vibrations, the 2D spectra reveal vibrational excitation transfer from the ν(G)(NH(2))(b) mode to the ν(G)(NH) and/or ν(C)(NH(2))(b) modes. The underlying intermode vibrational couplings are on the order of 10 cm(-1).

Study of Catalyst Variation Effect in Glycerol Conversion Process to Hydrogen Gas by Steam Reforming

NASA Astrophysics Data System (ADS)

Widayat; Hartono, R.; Elizabeth, E.; Annisa, A. N.

2018-04-01

Along with the economic development, needs of energy being increase too. Hydrogen as alternative energy has many usages. Besides that, hydrogen is one source of energy that is a clean fuel, but process production of hydrogen from natural gas as a raw material has been used for a long time. Therefore, there is need new invention to produce hydrogen from the others raw material. Glycerol, a byproduct of biodiesel production, is a compound which can be used as a raw material for hydrogen production. By using glycerol as a raw material of hydrogen production, we can get added value of glycerol as well as an energy source solution. The process production of hydrogen by steam reforming is a thermochemical process with efficiency 70%. This process needs contribution of catalyst to improve its efficiency and selectivity of the process. In this study will be examined the effect variation of catalyst for glycerol conversion process to hydrogen by steam reforming. The method for catalyst preparation was variation of catalyst impregnation composition, catalyst calcined with difference concentration of hydrochloric acid and calcined with difference hydrochloric acid ratio. After that, all of catalyst which have been prepared, used for steam reforming process for hydrogen production from glycerol as a raw material. From the study, the highest yield of hydrogen gas showed in the process production by natural zeolite catalyst with 1:15 Hydrochloric acid ratio was 42.28%. Hydrogen yield for 2M calcined natural zeolite catalyst was 38.37%, for ZSM-5 catalyst was 15.83%, for 0.5M calcined natural zeolite was 13.09% and for ultrasonic natural zeolite was 11.43%. The lowest yield of hydrogen gas showed in catalyst 2Zn/ZSM-5 with 11.22%. This result showed that hydrogen yield product was affected by catalyst variation because of the catalyst has difference characteristic and difference catalytic activity after the catalyst preparation process.

Study of Hydrogen Production Method using Latent Heat of Liquefied Natural Gas

NASA Astrophysics Data System (ADS)

Ogawa, Masaru; Seki, Tatsuyoshi; Honda, Hiroshi; Nakamura, Motomu; Takatani, Yoshiaki

In recent years, Fuel Cell Electrical Vehicle is expected to improve urban environment. Particularly a hydrogen fuel type FCEV expected for urban use, because its excellent characters such as short startup time, high responsibility and zero emission. On the other hand, as far as hydrogen production is concerned, large amount of CO2 is exhausted into the atmosphere by the process of LNG reforming. In our research, we studied the utilization of LNG latent heat for hydrogen gas production process as well as liquefied hydrogen process. Furthermore, CO2---Capturing as liquid state or solid state from hydrogen gas production process by LNG is also studied. Results of research shows that LNG latent heat is very effect to cool hydrogen gas for conventional hydrogen liquefied process. However, the LNG latent heat is not available for LNG reforming process. If we want to use LNG latent heat for this process, we have to develop new hydrogen gas produce process. In this new method, both hydrogen and CO2 is cooled by LNG directly, and CO2 is removed from the reforming gas. In order to make this method practical, we should develop a new type heat-exchanger to prevent solid CO2 from interfering the performance of it.

Solvent induced temperature dependencies of NMR parameters of hydrogen bonded anionic clusters

NASA Astrophysics Data System (ADS)

Golubev, Nikolai S.; Shenderovich, Ilja G.; Tolstoy, Peter M.; Shchepkin, Dmitry N.

2004-07-01

The solvent induced temperature dependence of NMR parameters (proton and fluorine chemical shifts, the two-bond scalar spin coupling constant across the hydrogen bridge, 2hJFF) for dihydrogen trifluoride anion, (FH) 2F -, in a polar aprotic solvent, CDF 3/CDF 2Cl, is reported and discussed. The results are interpreted in terms of a simple electrostatic model, accounting a decrease of electrostatic repulsion of two negatively charged fluorine atoms on placing into a dielectric medium. The conclusion is drawn that polar medium causes some contraction of hydrogen bonds in ionic clusters combined with a decrease of hydrogen bond asymmetry.

Feasibility demonstration for hydrogen chloride detection using a chemisorption technique and a quartz crystal microbalance

NASA Technical Reports Server (NTRS)

Jex, D. W.; Workman, G. L.

1975-01-01

A method of measuring concentrations of hydrogen chloride between 1 part per billion and 10 parts per million at standard temperature and pressure is presented. The feasibility of a low-cost device incorporating a chemisorption technique coupled with a quartz crystal microbalance was demonstrated in the field at the Viking B launch using a Titan-Centaur vehicle from Kennedy Space Center on August 20, 1975. Hydrogen chloride is a product of solid rocket combustion. The concentration level of hydrogen chloride for this particular launch was measured as approximately 0.2 parts per million at 4 km from the launch site.

Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer

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

Esboui, Mounir, E-mail: mounir.esboui@fst.rnu.tn; Technical and Vocational Training Corporation, Hail College of Technology, P.O. Box 1960, Hail 81441

The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH{sub 3}){sub 2} complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH{sub 3}){sub 2} cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocationmore » analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A″({sup 1}πσ{sup ∗}) and A′({sup 1}nσ{sup ∗}) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A′({sup 1}ππ{sup ∗}) and A″({sup 1}nπ{sup ∗}) potential energy surfaces. For the unconstrained complex, potential energy profiles show two {sup 1}ππ{sup ∗}-{sup 1}πσ{sup ∗} conical intersections along enol → keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.« less

High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

NASA Astrophysics Data System (ADS)

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

2018-05-01

Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

Excitation and charge transfer in low-energy hydrogen atom collisions with neutral oxygen

NASA Astrophysics Data System (ADS)

Barklem, P. S.

2018-02-01

Excitation and charge transfer in low-energy O+H collisions is studied; it is a problem of importance for modelling stellar spectra and obtaining accurate oxygen abundances in late-type stars including the Sun. The collisions have been studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals (LCAO) model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multichannel Landau-Zener model. The method has been extended to include configurations involving excited states of hydrogen using an estimate for the two-electron transition coupling, but this extension was found to not lead to any remarkably high rates. Rate coefficients are calculated for temperatures in the range 1000-20 000 K, and charge transfer and (de)excitation processes involving the first excited S-states, 4s.5So and 4s.3So, are found to have the highest rates. Data are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/vizbin/qcat?J/A+A/610/A57. The data are also available at http://https://github.com/barklem/public-data

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

Gas phase reaction of nitric acid with hydroxyl radical without and with water. A theoretical investigation.

PubMed

Gonzalez, Javier; Anglada, Josep M

2010-09-02

The gas phase reaction between nitric acid and hydroxyl radical, without and with a single water molecule, has been investigated theoretically using the DFT-B3LYP, MP2, QCISD, and CCSD(T) theoretical approaches with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction without water begins with the formation of a prereactive hydrogen-bonded complex and has several elementary reactions processes. They include proton coupled electron transfer, hydrogen atom transfer, and proton transfer mechanisms, and our kinetic study shows a quite good agreement of the behavior of the rate constant with respect to the temperature and to the pressure with the experimental results from the literature. The addition of a single water molecule results in a much more complex potential energy surface although the different elementary reactions found have the same electronic features that the naked reaction. Two transition states are stabilized by the effect of a hydrogen bond interaction originated by the water molecule, and in the prereactive hydrogen bond region there is a geometrical rearrangement necessary to prepare the HO and HNO(3) moieties to react to each other. This step contributes the reaction to be slower than the reaction without water and explains the experimental finding, pointing out that there is no dependence for the HNO(3) + HO reaction on water vapor.

Synchronous microbial vanadium (V) reduction and denitrification in groundwater using hydrogen as the sole electron donor.

PubMed

Jiang, Yufeng; Zhang, Baogang; He, Chao; Shi, Jiaxin; Borthwick, Alistair G L; Huang, Xueyang

2018-05-21

Groundwater co-contaminated by vanadium (V) (V(V)) and nitrate requires efficient remediation to prevent adverse environmental impacts. However, little is known about simultaneous bio-reductions of V(V) and nitrate supported by gaseous electron donors in aquifers. This study is among the first to examine microbial V(V) reduction and denitrification with hydrogen as the sole electron donor. V(V) removal efficiency of 91.0 ± 3.2% was achieved in test bioreactors within 7 d, with synchronous, complete removal of nitrate. V(V) was reduced to V(IV), which precipitated naturally under near-neutral conditions, and nitrate tended to be converted to nitrogen, both of which processes helped to purify the groundwater. Volatile fatty acids (VFAs) were produced from hydrogen oxidation. High-throughput 16S rRNA gene sequencing and metagenomic analyses revealed the evolutionary behavior of microbial communities and functional genes. The genera Dechloromonas and Hydrogenophaga promoted bio-reductions of V(V) and nitrate directly coupled to hydrogen oxidation. Enriched Geobacter and denitrifiers also indicated synergistic mechanism, with VFAs acting as organic carbon sources for heterotrophically functional bacteria while reducing V(V) and nitrate. These findings are likely to be useful in revealing biogeochemical fates of V(V) and nitrate in aquifer and developing technology for removing them simultaneously from groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Carbon sequestration in soybean crop soils: the role of hydrogen-coupled CO2 fixation

NASA Astrophysics Data System (ADS)

Graham, A.; Layzell, D. B.; Scott, N. A.; Cen, Y.; Kyser, T. K.

2011-12-01

Conversion of native vegetation to agricultural land in order to support the world's growing population is a key factor contributing to global climate change. However, the extent to which agricultural activities contribute to greenhouse gas emissions compared to carbon storage is difficult to ascertain, especially for legume crops, such as soybeans. Soybean establishment often leads to an increase in N2O emissions because N-fixation leads to increased soil available N during decomposition of the low C:N legume biomass. However, soybean establishment may also reduce net greenhouse gas emissions by increasing soil fertility, plant growth, and soil carbon storage. The mechanism behind increased carbon storage, however, remains unclear. One explanation points to hydrogen coupled CO2 fixation; the process by which nitrogen fixation releases H2 into the soil system, thereby promoting chemoautotrophic carbon fixation by soil microbes. We used 13CO2 as a tracer to track the amount and fate of carbon fixed by hydrogen coupled CO2 fixation during one-year field and laboratory incubations. The objectives of the research are to 1) quantify rates of 13CO2 fixation in soil collected from a field used for long-term soybean production 2) examine the impact of H2 gas concentration on rates of 13CO2 fixation, and 3) measure changes in δ13C signature over time in 3 soil fractions: microbial biomass, light fraction, and acid stable fraction. If this newly-fixed carbon is incorporated into the acid-stable soil C fraction, it has a good chance of contributing to long-term soil C sequestration under soybean production. Soil was collected in the field both adjacent to root nodules (nodule soil) and >3cm away (root soil) and labelled with 13CO2 (1% v/v) in the presence and absence of H2 gas. After a two week labelling period, δ13C signatures already revealed differences in the four treatments of bulk soil: -17.1 for root, -17.6 for nodule, -14.2 for root + H2, and -6.1 for nodule + H2. Labelled soil was then placed in nylon mesh bags and buried in the field at a depth of 15cm in a soybean field at the Central Experiment Farm in Ottawa, Ontario. Samples will be removed at intervals of 1,2,3,6,9,12, and 15 months, and the δ13C of three soil fractions will be examined to reveal changes in carbon storage over time. Our results will provide insights into the fate of carbon fixed during hydrogen coupled CO2 fixation, and demonstrate whether this CO2 fixation can contribute to the long-term greenhouse gas balance of soybean production systems.

Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

PubMed

Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

2018-02-14

Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

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

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

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

Casey, Charles P

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis Charles P. Casey, Principal Investigator Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin 53706 Phone 608-262-0584 FAX: 608-262-7144 Email: casey@chem.wisc.edu http://www.chem.wisc.edu/main/people/faculty/casey.html Executive Summary. Our goal was to learn the intimate mechanistic details of reactions involved in homogeneous catalysis and to use the insight we gain to develop new and improved catalysts. Our work centered on the hydrogenation of polar functional groups such as aldehydes and ketones and on hydroformylation. Specifically, we concentrated on catalysts capable of simultaneously transferring hydride from a metal center and a proton frommore » an acidic oxygen or nitrogen center to an aldehyde or ketone. An economical iron based catalyst was developed and patented. Better understanding of fundamental organometallic reactions and catalytic processes enabled design of energy and material efficient chemical processes. Our work contributed to the development of catalysts for the selective and mild hydrogenation of ketones and aldehydes; this will provide a modern green alternative to reductions by LiAlH4 and NaBH4, which require extensive work-up procedures and produce waste streams. (C5R4OH)Ru(CO)2H Hydrogenation Catalysts. Youval Shvo described a remarkable catalytic system in which the key intermediate (C5R4OH)Ru(CO)2H (1) has an electronically coupled acidic OH unit and a hydridic RuH unit. Our efforts centered on understanding and improving upon this important catalyst for reduction of aldehydes and ketones. Our mechanistic studies established that the reduction of aldehydes by 1 to produce alcohols and a diruthenium bridging hydride species occurs much more rapidly than regeneration of the ruthenium hydride from the diruthenium bridging hydride species. Our mechanistic studies require simultaneous transfer of hydride from ruthenium to the aldehyde carbon and of a proton from the CpOH unit to the aldehyde oxygen and support reduction of the aldehyde without its prior coordination to ruthenium. Another important step in the catalysis is the regeneration of 1 from reaction of H2 with the stable diruthenium bridging hydride complex 2. Studies of the microscopic reverse of this process (hydrogen evolution from 1 which occurs at 80°C) in the presence of alcohol (the product of aldehyde hydrogenation) have shown that a dihydrogen complex is formed reversibly at a rate much faster than hydrogen evolution. Kinetic and theoretical studies in collaboration with Professor Qiang Cui of Wisconsin indicated an important role for alcohol in mediating transfer of hydrogen to ruthenium. One key to developing more active catalysts was to destabilize the bridging hydride intermediate 2 to prevent its formation or to speed its conversion to a reactive monohydride 1 by reaction with H2. We found several successful ways to destabilize the bridging hydride and to obtain more active catalysts. Most recently, we discovered related iron catalysts for hydrogenation that do not form dimers; the cost advantage of iron catalysts is spectacular. Iron Catalysts. In an exciting development, we found that a related iron complex is also a very active ketone hydrogenation catalyst. This hydrogenation catalyst shows high chemoselectivity for aldehydes, ketones, and imines and isolated C=C, CºC, C-X, -NO2, epoxides, and ester functions are unaffected by the hydrogenation conditions. Mechanistic studies have established a reversible hydrogen transfer step followed by rapid dihydrogen activation. The same iron complex also catalyzes transfer hydrogenation of ketones.« less

Method for low temperature catalytic production of hydrogen

DOEpatents

Mahajan, Devinder

2003-07-22

The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

Apparatus for Pumping a Fluid

NASA Technical Reports Server (NTRS)

van Boeyen, Roger W. (Inventor); Reeh, Jonathan A. (Inventor); Kesmez, Mehmet (Inventor); Heselmeyer, Eric A. (Inventor); Parkey, Jeffrey S. (Inventor)

2016-01-01

An electrochemically actuated pump and an electrochemical actuator for use with a pump. The pump includes one of various stroke volume multiplier configurations with the pressure of a pumping fluid assisting actuation of a driving fluid bellows. The electrochemical actuator has at least one electrode fluidically coupled to the driving fluid chamber of the first pump housing and at least one electrode fluidically coupled to the driving fluid chamber of the second pump housing. Accordingly, the electrochemical actuator selectively pressurizes hydrogen gas within a driving fluid chamber. The actuator may include a membrane electrode assembly including an ion exchange membrane with first and second catalyzed electrodes in contact with opposing sides of the membrane, and first and second hydrogen gas chambers in fluid communication with the first and second electrodes, respectively. A controller may reverse the polarity of a voltage source electrically coupled to the current collectors.

Sequence-dependent nucleosome sliding in rotation-coupled and uncoupled modes revealed by molecular simulations

PubMed Central

Tan, Cheng; Takada, Shoji

2017-01-01

While nucleosome positioning on eukaryotic genome play important roles for genetic regulation, molecular mechanisms of nucleosome positioning and sliding along DNA are not well understood. Here we investigated thermally-activated spontaneous nucleosome sliding mechanisms developing and applying a coarse-grained molecular simulation method that incorporates both long-range electrostatic and short-range hydrogen-bond interactions between histone octamer and DNA. The simulations revealed two distinct sliding modes depending on the nucleosomal DNA sequence. A uniform DNA sequence showed frequent sliding with one base pair step in a rotation-coupled manner, akin to screw-like motions. On the contrary, a strong positioning sequence, the so-called 601 sequence, exhibits rare, abrupt transitions of five and ten base pair steps without rotation. Moreover, we evaluated the importance of hydrogen bond interactions on the sliding mode, finding that strong and weak bonds favor respectively the rotation-coupled and -uncoupled sliding movements. PMID:29194442

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

Zammit, Mark C.; Fursa, Dmitry V.; Savage, Jeremy S.

Starting from first principles, this tutorial describes the development of the adiabatic-nuclei convergent close-coupling (CCC) method and its application to electron and (single-centre) positron scattering from diatomic molecules. In this paper, we give full details of the single-centre expansion CCC method, namely the formulation of the molecular target structure; solving the momentum-space coupled-channel Lippmann-Schwinger equation; deriving adiabatic-nuclei cross sections and calculatingmore » $V$-matrix elements. Selected results are presented for electron and positron scattering from molecular hydrogen H$$_2$$ and electron scattering from the vibrationally excited molecular hydrogen ion H$$_2^+$$ and its isotopologues (D$$_2^+$$, T$$_2^+$$, HD$^+$, HT$^+$ and TD$^+$). Finally, convergence in both the close-coupling (target state) and projectile partial-wave expansions of fixed-nuclei electron- and positron-molecule scattering calculations is demonstrated over a broad energy-range and discussed in detail. In general the CCC results are in good agreement with experiments.« less

Influence of hydrogen effusion from hydrogenated silicon nitride layers on the regeneration of boron-oxygen related defects in crystalline silicon

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

Wilking, S., E-mail: Svenja.Wilking@uni-konstanz.de; Ebert, S.; Herguth, A.

The degradation effect boron doped and oxygen-rich crystalline silicon materials suffer from under illumination can be neutralized in hydrogenated silicon by the application of a regeneration process consisting of a combination of slightly elevated temperature and carrier injection. In this paper, the influence of variations in short high temperature steps on the kinetics of the regeneration process is investigated. It is found that hotter and longer firing steps allowing an effective hydrogenation from a hydrogen-rich silicon nitride passivation layer result in an acceleration of the regeneration process. Additionally, a fast cool down from high temperature to around 550 °C seems tomore » be crucial for a fast regeneration process. It is suggested that high cooling rates suppress hydrogen effusion from the silicon bulk in a temperature range where the hydrogenated passivation layer cannot release hydrogen in considerable amounts. Thus, the hydrogen content of the silicon bulk after the complete high temperature step can be increased resulting in a faster regeneration process. Hence, the data presented here back up the theory that the regeneration process might be a hydrogen passivation of boron-oxygen related defects.« less

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series

NASA Astrophysics Data System (ADS)

Mattioda, A. L.; Bauschlicher, C. W.; Ricca, A.; Bregman, J.; Hudgins, D. M.; Allamandola, L. J.

2017-06-01

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CHoop) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CHoop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400 cm-1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515 cm-1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600 cm-1) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds.

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2011 CFR

2011-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... Compliance Requirements § 63.2465 What requirements must I meet for process vents that emit hydrogen halide... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

Process for exchanging hydrogen isotopes between gaseous hydrogen and water

DOEpatents

Hindin, Saul G.; Roberts, George W.

1980-08-12

A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

Bio-hydrogen production from tempeh and tofu processing wastes via fermentation process using microbial consortium: A mini-review

NASA Astrophysics Data System (ADS)

Rengga, Wara Dyah Pita; Wati, Diyah Saras; Siregar, Riska Yuliana; Wulandari, Ajeng Riswanti; Lestari, Adela Ayu; Chafidz, Achmad

2017-03-01

One of alternative energies that can replace fossil fuels is hydrogen. Hydrogen can be used to generate electricity and to power combustion engines for transportation. Bio-hydrogen produced from tempeh and tofu processing waste can be considered as a renewable energy. Bio-hydrogen produced from tempeh and tofu processing waste is beneficial because the waste of soybean straw and tofu processing waste is plentiful, cheap, renewable and biodegradable. Specification of tempeh and tofu processing waste were soybean straw and sludge of tofu processing. They contain carbohydrates (cellulose, hemicellulose, and lignin) and methane. This paper reviews the optimal condition to produce bio-hydrogen from tempeh and tofu processing waste. The production of bio-hydrogen used microbial consortium which were enriched from cracked cereals and mainly dominated by Clostridium butyricum and Clostridium roseum. The production process of bio-hydrogen from tempeh and tofu processing waste used acid pre-treatment with acid catalyzed hydrolysis to cleave the bond of hemicellulose and cellulose chains contained in biomass. The optimal production of bio-hydrogen has a yield of 6-6.8 mL/g at 35-60 °C, pH 5.5-7 in hydraulic retention time (HRT) less than 16 h. The production used a continuous system in an anaerobic digester. This condition can be used as a reference for the future research.

Autothermal hydrogen storage and delivery systems

DOEpatents

Pez, Guido Peter [Allentown, PA; Cooper, Alan Charles [Macungie, PA; Scott, Aaron Raymond [Allentown, PA

2011-08-23

Processes are provided for the storage and release of hydrogen by means of dehydrogenation of hydrogen carrier compositions where at least part of the heat of dehydrogenation is provided by a hydrogen-reversible selective oxidation of the carrier. Autothermal generation of hydrogen is achieved wherein sufficient heat is provided to sustain the at least partial endothermic dehydrogenation of the carrier at reaction temperature. The at least partially dehydrogenated and at least partially selectively oxidized liquid carrier is regenerated in a catalytic hydrogenation process where apart from an incidental employment of process heat, gaseous hydrogen is the primary source of reversibly contained hydrogen and the necessary reaction energy.

Numerical study of heating and evaporation processes of quartz particles in RF inductively coupled plasma

NASA Astrophysics Data System (ADS)

Grishin, Yu M.; Miao, Long

2017-05-01

Numerical simulations of heat and evaporation processes of quartz particles in Ar radio frequency inductively coupled plasma (ICP) are investigated. The quartz particles are supplied by the carrier gas into the ICP within gas-cooling. It is shown that with the increase of amplitude of discharge current above critical value there is a toroidal vortex in the ICP torch at the first coil. The conditions for the formation of vortex and the parameters of the vortex tube have been evaluated and determined. The influence of vortex, discharge current, coil numbers and feed rate of carrier gas on the evaporation efficiency of quartz particles have been demonstrated. It was found that the optimal discharge current is close to the critical value when the quartz particles with initial sizes up to 130 μm can be fully vaporized in the ICP torch with thermal power of 10kW. The heat and evaporation processes of quartz particles in the ICP torch have significant importance for the study of one-step plasma chemical reaction method directly producing silicon from silicide (SiO2) in the argon-hydrogen plasma.

Remediation of water contaminated with diesel oil using a coupled process: Biological degradation followed by heterogeneous Fenton-like oxidation.

PubMed

Chen, Yuan; Lin, Jiajiang; Chen, Zuliang

2017-09-01

The treatment of a synthetically prepared wastewater containing diesel oil has been investigated using combined treatment schemes based on the biological treatment followed by an advanced oxidation process. 78% of diesel oil was degraded by Acinetobacter venetianus in 96 h, while the removal efficiency of chemical oxygen demand (COD) in the aqueous phase was only 56.8%, indicating that degraded metabolites existed in solution. To solve this problem, a Fenton-like system consisting of nanoscale zero-valent iron (nZVI) and hydrogen peroxide was used for further oxidation of the metabolites after biodegradation. Results showed that the total COD removal increased from 56.8% to 89% under the optimal condition. In addition, effects of initial pH (2.0-9.0), ZVI dosage (0-2.0 g L-1), hydrogen peroxide (H 2 O 2 ) dosage concentration (0-15 mmol L-1) and temperature (298-308 K) on the treatment efficiency of the combined process were studied. Scanning electron microscopy (SEM) demonstrated that changes to the surface of nZVI occurred. GC-MS revealed that the degraded metabolites were mineralized practically by nZVI/H 2 O 2 system. The results points towards the potential of Fenton-like oxidation as a short post-treatment after a biological process for the treatment of organic pollutants in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

H2S-mediated thermal and photochemical methane activation.

PubMed

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric V

2013-12-02

Sustainable, low-temperature methods for natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) mixed with methane, deemed altogether as sub-quality or "sour" gas. We propose a unique method of activation to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3 , and an energy carrier such as H2. For this purpose, we investigated the H2S-mediated methane activation to form a reactive CH3SH species by means of direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4 + H2S complex resulted in a barrierless relaxation by a conical intersection to form a ground-state CH3SH + H2 complex. The resulting CH3SH could further be coupled over acidic catalysts to form higher hydrocarbons, and the resulting H2 used as a fuel. This process is very different from conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced control over the conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the current industrial steam methane reforming (SMR). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin-Spin Coupling Constants

NASA Astrophysics Data System (ADS)

Sanchez, Marina; Provasi, Patricio F.; Aucar, Gustavo A.; Sauer, Stephan P. A.

Locally dense basis sets (

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.

Studies of the use of heat from high temperature nuclear sources for hydrogen production processes

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

Future uses of hydrogen and hydrogen production processes that can meet the demand for hydrogen in the coming decades were considered. To do this, a projection was made of the market for hydrogen through the year 2000. Four hydrogen production processes were selected, from among water electrolysis, fossil based and thermochemical water decomposition systems, and evaluated, using a consistent set of ground rules, in terms of relative performance, economics, resource requirements, and technology status.

Biofuels from microalgae.

PubMed

Li, Yanqun; Horsman, Mark; Wu, Nan; Lan, Christopher Q; Dubois-Calero, Nathalie

2008-01-01

Microalgae are a diverse group of prokaryotic and eukaryotic photosynthetic microorganisms that grow rapidly due to their simple structure. They can potentially be employed for the production of biofuels in an economically effective and environmentally sustainable manner. Microalgae have been investigated for the production of a number of different biofuels including biodiesel, bio-oil, bio-syngas, and bio-hydrogen. The production of these biofuels can be coupled with flue gas CO2 mitigation, wastewater treatment, and the production of high-value chemicals. Microalgal farming can also be carried out with seawater using marine microalgal species as the producers. Developments in microalgal cultivation and downstream processing (e.g., harvesting, drying, and thermochemical processing) are expected to further enhance the cost-effectiveness of the biofuel from microalgae strategy.

Characterization of hydrogen responsive nanoporous palladium films synthesized via a spontaneous galvanic displacement reaction.

PubMed

Patton, J F; Lavrik, N V; Joy, D C; Hunter, S R; Datskos, P G; Smith, D B; Sepaniak, M J

2012-11-23

A model is presented regarding the mechanistic properties associated with the interaction of hydrogen with nanoporous palladium (np-Pd) films prepared using a spontaneous galvanic displacement reaction (SGDR), which involves PdCl(2) reduction by atomic Ag. Characterization of these films shows both chemical and morphological factors, which influence the performance characteristics of np-Pd microcantilever (MC) nanomechanical sensing devices. Raman spectroscopy, uniquely complemented with MC response profiles, is used to explore the chemical influence of palladium oxide (PdO). These combined techniques support a reaction mechanism that provides for rapid response to H(2) and recovery in the presence of O(2). Post-SGDR processing via reduction of PdCl(2)(s) in a H(2) environment results in a segregated nanoparticle three-dimensional matrix dispersed in a silver layer. The porous nature of the reduced material is shown by high resolution scanning electron microscopy. Extended grain boundaries, typical of these materials, result in a greater surface area conducive to fast sorption/desorption of hydrogen, encouraged by the presence of PdO. X-ray diffraction and inductively coupled plasma-optical emission spectroscopy are employed to study changes in morphology and chemistry occurring in these nanoporous films under different processing conditions. The unique nature of chemical/morphological effects, as demonstrated by the above characterization methods, provides evidence in support of observed nanomechanical response/recovery profiles offering insight for catalysis, H(2) storage and improved sensing applications.

Adsorption and dissociation of molecular hydrogen on the (0001) surface of double hexagonal close packed americium

NASA Astrophysics Data System (ADS)

Dholabhai, P. P.; Ray, A. K.

2009-01-01

Hydrogen molecule adsorption on the (0001) surface of double hexagonal packed americium has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals method (FP-L/APW+lo). Weak molecular hydrogen adsorptions were observed. Adsorption energies were optimized with respect to the distance of the adsorbates from the surface for three approach positions at three adsorption sites, namely t1 (one-fold top), b2 (two-fold bridge), and h3 (three-fold hollow) sites. Adsorption energies were computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at the fully relativistic level (with spin-orbit coupling SOC). The most stable configuration corresponds to a horizontal adsorption with the molecular approach being perpendicular to a lattice vector. The surface coverage is equivalent to one-fourth of a monolayer (ML), with the adsorption energies at the NSOC and SOC theoretical levels being 0.0997 eV and 0.1022 eV, respectively. The respective distance of the hydrogen molecule from the surface and hydrogen-hydrogen distance was found to be 2.645 Å and 0.789 Å, respectively. The work functions decreased and the net magnetic moments remained almost unchanged in all cases compared with the corresponding quantities of bare dhcp Am (0001) surface. The adsorbate-substrate interactions have been analyzed in detail using the partial charges inside the muffin-tin spheres, difference charge density distributions, and the local density of states. The effects of adsorption on the Am 5f electron localization-delocalization characteristics have been discussed. Reaction barrier for the dissociation of hydrogen molecule has been presented.

Muonium in Stishovite: Implications for the Possible Existence of Neutral Atomic Hydrogen in the Earth's Deep Mantle

PubMed Central

Funamori, Nobumasa; Kojima, Kenji M.; Wakabayashi, Daisuke; Sato, Tomoko; Taniguchi, Takashi; Nishiyama, Norimasa; Irifune, Tetsuo; Tomono, Dai; Matsuzaki, Teiichiro; Miyazaki, Masanori; Hiraishi, Masatoshi; Koda, Akihiro; Kadono, Ryosuke

2015-01-01

Hydrogen in the Earth's deep interior has been thought to exist as a hydroxyl group in high-pressure minerals. We present Muon Spin Rotation experiments on SiO2 stishovite, which is an archetypal high-pressure mineral. Positive muon (which can be considered as a light isotope of proton) implanted in stishovite was found to capture electron to form muonium (corresponding to neutral hydrogen). The hyperfine-coupling parameter and the relaxation rate of spin polarization of muonium in stishovite were measured to be very large, suggesting that muonium is squeezed in small and anisotropic interstitial voids without binding to silicon or oxygen. These results imply that hydrogen may also exist in the form of neutral atomic hydrogen in the deep mantle. PMID:25675890

On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2016-11-01

Equations of state for hydrogen bonding fluids are typically described by two energy scales. A short range highly directional hydrogen bonding energy scale as well as a reference energy scale which accounts for dispersion and orientationally averaged multi-pole attractions. These energy scales are always treated independently. In recent years, extensive first principles quantum mechanics calculations on small water clusters have shown that both hydrogen bond and reference energy scales depend on the number of incident hydrogen bonds of the water molecule. In this work, we propose a new methodology to couple the reference energy scale to the degree of hydrogen bonding in the fluid. We demonstrate the utility of the new approach by showing that it gives improved predictions of water-hydrocarbon mutual solubilities.

Muonium in Stishovite: Implications for the Possible Existence of Neutral Atomic Hydrogen in the Earth's Deep Mantle

NASA Astrophysics Data System (ADS)

Funamori, Nobumasa; Kojima, Kenji M.; Wakabayashi, Daisuke; Sato, Tomoko; Taniguchi, Takashi; Nishiyama, Norimasa; Irifune, Tetsuo; Tomono, Dai; Matsuzaki, Teiichiro; Miyazaki, Masanori; Hiraishi, Masatoshi; Koda, Akihiro; Kadono, Ryosuke

2015-02-01

Hydrogen in the Earth's deep interior has been thought to exist as a hydroxyl group in high-pressure minerals. We present Muon Spin Rotation experiments on SiO2 stishovite, which is an archetypal high-pressure mineral. Positive muon (which can be considered as a light isotope of proton) implanted in stishovite was found to capture electron to form muonium (corresponding to neutral hydrogen). The hyperfine-coupling parameter and the relaxation rate of spin polarization of muonium in stishovite were measured to be very large, suggesting that muonium is squeezed in small and anisotropic interstitial voids without binding to silicon or oxygen. These results imply that hydrogen may also exist in the form of neutral atomic hydrogen in the deep mantle.

Fluctuating hydrogen-bond networks govern anomalous electron transfer kinetics in a blue copper protein.

PubMed

Kretchmer, Joshua S; Boekelheide, Nicholas; Warren, Jeffrey J; Winkler, Jay R; Gray, Harry B; Miller, Thomas F

2018-06-12

We combine experimental and computational methods to address the anomalous kinetics of long-range electron transfer (ET) in mutants of Pseudomonas aeruginosa azurin. ET rates and driving forces for wild type (WT) and three N47X mutants (X = L, S, and D) of Ru(2,2'-bipyridine) 2 (imidazole)(His83) azurin are reported. An enhanced ET rate for the N47L mutant suggests either an increase of the donor-acceptor (DA) electronic coupling or a decrease in the reorganization energy for the reaction. The underlying atomistic features are investigated using a recently developed nonadiabatic molecular dynamics method to simulate ET in each of the azurin mutants, revealing unexpected aspects of DA electronic coupling. In particular, WT azurin and all studied mutants exhibit more DA compression during ET (>2 Å) than previously recognized. Moreover, it is found that DA compression involves an extended network of hydrogen bonds, the fluctuations of which gate the ET reaction, such that DA compression is facilitated by transiently rupturing hydrogen bonds. It is found that the N47L mutant intrinsically disrupts this hydrogen-bond network, enabling particularly facile DA compression. This work, which reveals the surprisingly fluctional nature of ET in azurin, suggests that hydrogen-bond networks can modulate the efficiency of long-range biological ET. Copyright © 2018 the Author(s). Published by PNAS.

Apparatus and process for separating hydrogen isotopes

DOEpatents

Heung, Leung K; Sessions, Henry T; Xiao, Xin

2013-06-25

The apparatus and process for separating hydrogen isotopes is provided using dual columns, each column having an opposite hydrogen isotopic effect such that when a hydrogen isotope mixture feedstock is cycled between the two respective columns, two different hydrogen isotopes are separated from the feedstock.

Thermochemical water decomposition. [hydrogen separation for energy applications

NASA Technical Reports Server (NTRS)

Funk, J. E.

1977-01-01

At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

Modeling complex dispersed energy and clean water systems for the United States/Mexico border

NASA Astrophysics Data System (ADS)

Herrera, Hugo Francisco Lopez

As world population grows, and its technology evolves, the demand for electricity inexorably increases. Until now most of this electricity has been produced via fossil fuels, non-renewable energy resources that are irreversibly deteriorating our environment. On the economical aspect it does not get any better. Let's not forget market rules, the higher the demand and lower the offer, the higher the price we will have to pay. Oil is an excellent example. Some countries try to solve this situation with Pharaohnic projects, i.e. investing absurd amounts of money in 'green electricity' building monstrous dams to power equally monstrous hydroelectric power plants. The only problem with this is that it is not green at all---it does have an enormous environmental impact---it is extremely complicated and expensive to implement. It is important to point out, that this research project does not try to solve world's thirst for electricity. It is rather aimed to help solve this problematic at a much lower scale---it should be considered as an extremely small step in the right direction. It focuses on satisfying the local electricity needs with renewable, non-contaminating and locally available resources. More concisely, this project focuses on the attainment and use of hydrogen as an alternate energy source in El Paso/Juarez region. Clean technology is nowadays available to produce hydrogen and oxygen, i.e. the photoelectrolysis process. Photovoltaic cells coupled with electrolytic devices can be used to produce hydrogen and oxygen in a sustainable manner. In this research, simulation models of hybrid systems were designed and developed. They were capable to compare, predict and evaluate different options for hydrogen generation. On the other hand, with the produced hydrogen from the electrolysis process it was possible to generate electricity through fuel cells. The main objectives of the proposed research were to define how to use the resources for the attainment of hydrogen and distribution of it in El Paso/Juarez region. More precisely, the goals were the conversion of brines and waste-waters to hydrogen via electrolysis, and the generation of electricity through fuel cells. Thereafter, the specific objectives were to (1) design a simulation model for hydrogen generation, (2) design and simulate a model of photovoltaic (PV) array capable to generate the required energy for the process, (3) simulate fuel cells in order to be used as electricity power supply in remote houses, and (4) simulate a complete remote house hybrid system. The results of this research gave us information about the feasibility of high-volume hydrogen generation with the diverse resources of the region. On the other hand, this research has shown the alternatives of local energy generation, and efficiency of a remote house hybrid system located in El Paso/Juarez area. Experiences obtained from this research will also provide information for future investigations in the field of alternate energy sources, in order to get a clean environment through sustainable development.

The mechanism of proton conduction in phosphoric acid

NASA Astrophysics Data System (ADS)

Vilčiauskas, Linas; Tuckerman, Mark E.; Bester, Gabriel; Paddison, Stephen J.; Kreuer, Klaus-Dieter

2012-06-01

Neat liquid phosphoric acid (H3PO4) has the highest intrinsic proton conductivity of any known substance and is a useful model for understanding proton transport in other phosphate-based systems in biology and clean energy technologies. Here, we present an ab initio molecular dynamics study that reveals, for the first time, the microscopic mechanism of this high proton conductivity. Anomalously fast proton transport in hydrogen-bonded systems involves a structural diffusion mechanism in which intramolecular proton transfer is driven by specific hydrogen bond rearrangements in the surrounding environment. Aqueous media transport excess charge defects through local hydrogen bond rearrangements that drive individual proton transfer reactions. In contrast, strong, polarizable hydrogen bonds in phosphoric acid produce coupled proton motion and a pronounced protic dielectric response of the medium, leading to the formation of extended, polarized hydrogen-bonded chains. The interplay between these chains and a frustrated hydrogen-bond network gives rise to the high proton conductivity.

Iron-rich clay minerals on Mars - Potential sources or sinks for hydrogen and indicators of hydrogen loss over time

NASA Technical Reports Server (NTRS)

Burt, D. M.

1989-01-01

Although direct evidence is lacking, indirect evidence suggests that iron-rich clay minerals or poorly-ordered chemical equivalents are widespread on the Martian surface. Such clays can act as sources or sinks for hydrogen ('hydrogen sponges'). Ferrous clays can lose hydrogen and ferric clays gain it by the coupled substitution Fe(3+)O(Fe(2+)OH)-1, equivalent to minus atomic H. This 'oxy-clay' substitution involves only proton and electron migration through the crystal structure, and therefore occurs nondestructively and reversibly, at relatively low temperatures. The reversible, low-temperature nature of this reaction contrasts with the irreversible nature of destructive dehydroxylation (H2O loss) suffered by clays heated to high temperatures. In theory, metastable ferric oxy-clays formed by dehydrogenation of ferrous clays over geologic time could, if exposed to water vapor, extract the hydrogen from it, releasing oxygen.

Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

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

Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina

2013-01-01

It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principlesmore » total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.« less

Efficiency and cost advantages of an advanced-technology nuclear electrolytic hydrogen-energy production facility

NASA Technical Reports Server (NTRS)

Donakowski, T. D.; Escher, W. J. D.; Gregory, D. P.

1977-01-01

The concept of an advanced-technology (viz., 1985 technology) nuclear-electrolytic water electrolysis facility was assessed for hydrogen production cost and efficiency expectations. The facility integrates (1) a high-temperature gas-cooled nuclear reactor (HTGR) operating a binary work cycle, (2) direct-current (d-c) electricity generation via acyclic generators, and (3) high-current-density, high-pressure electrolyzers using a solid polymer electrolyte (SPE). All subsystems are close-coupled and optimally interfaced for hydrogen production alone (i.e., without separate production of electrical power). Pipeline-pressure hydrogen and oxygen are produced at 6900 kPa (1000 psi). We found that this advanced facility would produce hydrogen at costs that were approximately half those associated with contemporary-technology nuclear electrolysis: $5.36 versus $10.86/million Btu, respectively. The nuclear-heat-to-hydrogen-energy conversion efficiency for the advanced system was estimated as 43%, versus 25% for the contemporary system.

Role of a Water Network around the Mn4CaO5 Cluster in Photosynthetic Water Oxidation: A Fourier Transform Infrared Spectroscopy and Quantum Mechanics/Molecular Mechanics Calculation Study.

PubMed

Nakamura, Shin; Ota, Kai; Shibuya, Yuichi; Noguchi, Takumi

2016-01-26

Photosynthetic water oxidation takes place at the Mn4CaO5 cluster in photosystem II. Around the Mn4CaO5 cluster, a hydrogen bond network is formed by several water molecules, including four water ligands. To clarify the role of this water network in the mechanism of water oxidation, we investigated the effects of the removal of Ca(2+) and substitution with metal ions on the vibrations of water molecules coupled to the Mn4CaO5 cluster by means of Fourier transform infrared (FTIR) difference spectroscopy and quantum mechanics/molecular mechanics (QM/MM) calculations. The OH stretching vibrations of nine water molecules forming a network between D1-D61 and YZ were calculated using the QM/MM method. On the the calculated normal modes, a broad positive feature at 3200-2500 cm(-1) in an S2-minus-S1 FTIR spectrum was attributed to the vibrations of strongly hydrogen-bonded OH bonds of water involving the vibrations of water ligands to a Mn ion and the in-phase coupled vibration of a water network connected to YZ, while bands in the 3700-3500 cm(-1) region were assigned to the coupled vibrations of weakly hydrogen-bonded OH bonds of water. All the water bands were lost upon Ca(2+) depletion and Ba(2+) substitution, which inhibit the S2 → S3 transition, indicating that a solid water network was broken by these treatments. By contrast, Sr(2+) substitution slightly altered the water bands around 3600 cm(-1), reflecting minor modification in water interactions, consistent with the retention of water oxidation activity with a decreased efficiency. These results suggest that the water network around the Mn4CaO5 cluster plays an essential role in the water oxidation mechanism particularly in a concerted process of proton transfer and water insertion during the S2 → S3 transition.

Electronic structure and electron-phonon coupling in TiH$$_2$$

DOE PAGES

Shanavas, Kavungal Veedu; Lindsay, Lucas R.; Parker, David S.

2016-06-15

Calculations using first principles methods and strong coupling theory are carried out to understand the electronic structure and superconductivity in cubic and tetragonal TiHmore » $$_2$$. A large electronic density of states at the Fermi level in the cubic phase arises from Ti-$$t_{2g}$$ states and leads to a structural instability against tetragonal distortion at low temperatures. However, constraining the in-plane lattice constants diminishes the energy gain associated with the tetragonal distortion, allowing the cubic phase to be stable at low temperatures. Furthermore, calculated phonon dispersions show decoupled acoustic and optic modes arising from Ti and H vibrations, respectively and frequencies of optic modes to be rather high. The cubic phase has a large electron-phonon coupling parameter $$\\lambda$$ and critical temperature of several K. Contribution of the hydrogen sublattice to $$\\lambda$$ is found to be small in this material, which we understand from strong coupling theory to be due to the small H-$s$ DOS at the Fermi level and high energy of hydrogen modes at the tetrahedral sites.« less

CO-CO coupling on Cu facets: Coverage, strain and field effects

DOE PAGES

Sandberg, Robert B.; Montoya, Joseph H.; Chan, Karen; ...

2016-08-21

We present a DFT study on the effect of coverage, strain, and electric field on CO-CO coupling energetics on Cu (100), (111), and (211). Our calculations indicate that CO-CO coupling is facile on all three facets in the presence of a cation-induced electric field in the Helmholtz plane, with the lowest barrier on Cu(100). The CO dimerization pathway is therefore expected to play a role in C 2 formation at potentials negative of the Cu potential of zero charge, corresponding to CO 2/CO reduction conditions at high pH. Both increased *CO coverage and tensile strain further improve C-C coupling energeticsmore » on Cu (111) and (211). Since CO dimerization is facile on all 3 Cu facets, subsequent surface hydrogenation steps may also play an important role in determining the overall activity towards C 2 products. Adsorption of *CO, *H, and *OH on the 3 facets were investigated with a Pourbaix analysis. Here, the (211) facet has the largest propensity to co-adsorb *CO and *H, which would favor surface hydrogenation following CO dimerization.« less

Bound and resonance states of the dipolar anion of hydrogen cyanide: Competition between threshold effects and rotation in an open quantum system

DOE PAGES

Fossez, K.; Michel, N.; Nazarewicz, W.; ...

2015-01-12

In this paper, bound and resonance states of the dipole-bound anion of hydrogen cyanide HCN – are studied using a nonadiabatic pseudopotential method and the Berggren expansion technique involving bound states, decaying resonant states, and nonresonant scattering continuum. We devise an algorithm to identify the resonant states in the complex energy plane. To characterize spatial distributions of electronic wave functions, we introduce the body-fixed density and use it to assign families of resonant states into collective rotational bands. We find that the nonadiabatic coupling of electronic motion to molecular rotation results in a transition from the strong-coupling to weak-coupling regime.more » In the strong-coupling limit, the electron moving in a subthreshold, spatially extended halo state follows the rotational motion of the molecule. Above the ionization threshold, the electron's motion in a resonance state becomes largely decoupled from molecular rotation. Finally, the widths of resonance-band members depend primarily on the electron orbital angular momentum.« less

Coal liquefaction process

DOEpatents

Karr, Jr., Clarence

1977-04-19

An improved coal liquefaction process is provided which enables conversion of a coal-oil slurry to a synthetic crude refinable to produce larger yields of gasoline and diesel oil. The process is characterized by a two-step operation applied to the slurry prior to catalytic desulfurization and hydrogenation in which the slurry undergoes partial hydrogenation to crack and hydrogenate asphaltenes and the partially hydrogenated slurry is filtered to remove minerals prior to subsequent catalytic hydrogenation.

Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

DOEpatents

Cortes-Concepcion, Jose A.; Anton, Donald L.

2016-04-26

A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

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.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

PubMed

De, Sudipta; Saha, Basudeb; Luque, Rafael

2015-02-01

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Watching hydrogen-bond dynamics in a β-turn by transient two-dimensional infrared spectroscopy

NASA Astrophysics Data System (ADS)

Kolano, Christoph; Helbing, Jan; Kozinski, Mariusz; Sander, Wolfram; Hamm, Peter

2006-11-01

X-ray crystallography and nuclear magnetic resonance measurements provide us with atomically resolved structures of an ever-growing number of biomolecules. These static structural snapshots are important to our understanding of biomolecular function, but real biomolecules are dynamic entities that often exploit conformational changes and transient molecular interactions to perform their tasks. Nuclear magnetic resonance methods can follow such structural changes, but only on millisecond timescales under non-equilibrium conditions. Time-resolved X-ray crystallography has recently been used to monitor the photodissociation of CO from myoglobin on a subnanosecond timescale, yet remains challenging to apply more widely. In contrast, two-dimensional infrared spectroscopy, which maps vibrational coupling between molecular groups and hence their relative positions and orientations, is now routinely used to study equilibrium processes on picosecond timescales. Here we show that the extension of this method into the non-equilibrium regime allows us to observe in real time in a short peptide the weakening of an intramolecular hydrogen bond and concomitant opening of a β-turn. We find that the rate of this process is two orders of magnitude faster than the `folding speed limit' established for contact formation between protein side chains.

Development of compact fuel processor for 2 kW class residential PEMFCs

NASA Astrophysics Data System (ADS)

Seo, Yu Taek; Seo, Dong Joo; Jeong, Jin Hyeok; Yoon, Wang Lai

Korea Institute of Energy Research (KIER) has been developing a novel fuel processing system to provide hydrogen rich gas to residential polymer electrolyte membrane fuel cells (PEMFCs) cogeneration system. For the effective design of a compact hydrogen production system, the unit processes of steam reforming, high and low temperature water gas shift, steam generator and internal heat exchangers are thermally and physically integrated into a packaged hardware system. Several prototypes are under development and the prototype I fuel processor showed thermal efficiency of 73% as a HHV basis with methane conversion of 81%. Recently tested prototype II has been shown the improved performance of thermal efficiency of 76% with methane conversion of 83%. In both prototypes, two-stage PrOx reactors reduce CO concentration less than 10 ppm, which is the prerequisite CO limit condition of product gas for the PEMFCs stack. After confirming the initial performance of prototype I fuel processor, it is coupled with PEMFC single cell to test the durability and demonstrated that the fuel processor is operated for 3 days successfully without any failure of fuel cell voltage. Prototype II fuel processor also showed stable performance during the durability test.

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.

DFT Study on Nitrite Reduction Mechanism in Copper-Containing Nitrite Reductase.

PubMed

Lintuluoto, Masami; Lintuluoto, Juha M

2016-01-12

Dissimilatory reduction of nitrite by copper-containing nitrite reductase (CuNiR) is an important step in the geobiochemical nitrogen cycle. The proposed mechanisms for the reduction of nitrite by CuNiRs include intramolecular electron and proton transfers, and these two events are understood to couple. Proton-coupled electron transfer is one of the key processes in enzyme reactions. We investigated the geometric structure of bound nitrite and the mechanism of nitrite reduction on CuNiR using density functional theory calculations. Also, the proton transfer pathway, the key residues, and their roles in the reaction mechanism were clarified in this study. In our results, the reduction of T2 Cu site promotes the proton transfer, and the hydrogen bond network around the binding site has an important role not only to stabilize the nitrite binding but also to promote the proton transfer to nitrite.

H2S mediated thermal and photochemical methane activation

PubMed Central

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric

2013-01-01

Sustainable, low temperature methods of natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) in mixture with methane, CH4, altogether deemed as sub-quality or “sour” gas. We propose a unique method for activating this “sour” gas to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier, such as H2. For this purpose, we computationally investigated H2S mediated methane activation to form a reactive CH3SH species via direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex results in a barrier-less relaxation via a conical intersection to form a ground state CH3SH+H2 complex. The resulting CH3SH can further be heterogeneously coupled over acidic catalysts to form higher hydrocarbons while the H2 can be used as a fuel. This process is very different from a conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced controllability over the process conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the currently industrially used methane steam reforming (SMR). PMID:24150813

Quantum nature of protons in water probed by scanning tunneling microscopy and spectroscopy

NASA Astrophysics Data System (ADS)

Guo, Jing; Lü, Jing-Tao; Feng, Yexin; Chen, Ji; Peng, Jinbo; Lin, Zeren; Meng, Xiangzhi; Wang, Zhichang; Li, Xin-Zheng; Wang, En-Ge; Jiang, Ying; Jing-Tao Lü Team; Xin-Zheng Li Team

The complexity of hydrogen-bonding interaction largely arises from the quantum nature of light hydrogen nuclei, which has remained elusive for decades. Here we report the direct assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy (IETS) based on a low-temperature scanning tunneling microscope (STM). The IETS signals are resonantly enhanced by gating the frontier orbitals of water via a chlorine-terminated STM tip, such that the hydrogen-bonding strength can be determined with unprecedentedly high accuracy from the redshift in the O-H stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when the hydrogen bond is strongly coupled to the polar atomic sites of the surface.

Dispersion measurement by the single introduction method coupled with the back-sorption procedure: A chemisorption and TPD study of the different chemisorbed hydrogen species

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

Ragaini, V.; Giannantonio, R.; Magni, P.

1994-03-01

The Single Introduction (S.I.) method for the measurement by hydrogen chemisorption of metal dispersion in supported metal catalysts has been tested on two commercial 5% Pd/Al[sub 2]O[sub 3] catalysts. The S.I. results are compared with those obtained by the classical method of determining the adsorption isotherm (i.e., the multiple introduction method) and by O[sub 2]/H[sub 2] titration. As in Part I of this work, both chemisorption and thermal desorption have been used to find the best experimental conditions for the [open quotes]Back-Sorption[close quotes] procedure. It is shown that [alpha]- and [beta]-palladium hydrides can be decomposed by outgassing the samples formore » less than 5 min at 305 K and 10[sup [minus]6] Torr and that 30 min pumping at the same temperature and pressure is sufficient to eliminate from the catalyst surface the weakly adsorbed hydrogen as well. It has also been verified that chemisorption of hydrogen on these catalysts at room temperature is complete at pressures lower than those required for the [alpha] [yields] [beta] phase transition, so that it is possible to perform dispersion measurements by means of a simple S.I. of hydrogen coupled with Back-Sorption below 15 Torr at 305 K. Temperature-programmed desorption of hydrogen on one of the samples outlines the need to discriminate among the different adsorbed species for a more detailed characterization of supported metal catalysts. 44 refs., 10 figs., 2 tabs.« less

Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water.

PubMed

Smith, Richard L; Buckwalter, Seanne P; Repert, Deborah A; Miller, Daniel N

2005-05-01

Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water

USGS Publications Warehouse

Smith, R.L.; Buckwalter, S.P.; Repert, D.A.; Miller, D.N.

2005-01-01

Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

Hydrogen ion microlithography

DOEpatents

Tsuo, Y. Simon; Deb, Satyen K.

1990-01-01

Disclosed is a hydrogen ion microlithography process for use in microelectronic fabrication and semiconductor device processing. The process comprises the steps of providing a single layer of either an amorphous silicon or hydrogenated amorphous silicon material. A pattern is recorded in a selected layer of amorphous silicon or hydrogenated amorphous silicon materials by preferentially implanting hydrogen ions therein so as to permit the selected layer to serve as a mask-resist wafer suitable for subsequent development and device fabrication. The layer is developed to provide a surface pattern therein adaptable for subsequent use in microelectronic fabrication and semiconductor device processing.

Synthesis of pyridine-fused perylene imides with an amidine moiety for hydrogen bonding.

PubMed

Ito, Satoru; Hiroto, Satoru; Shinokubo, Hiroshi

2013-06-21

Pyridine-fused perylene tetracarboxylic acid bisimides (PBIs) were synthesized via Suzuki-Miyaura coupling and acid condensation. The fused PBIs with electron-donating substituents exhibited an intramolecular charge transfer interaction. One of the N-alkyl substituents was selectively removed with BBr3 to create an amidine guest binding site. A hydrogen bonding interaction with pentafluorobenzoic acid changed the absorption spectra and enhanced fluorescence.

Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

DOE PAGES

Luo, Weifang; Cowgill, Donald F.

2015-07-22

Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H 2 + PdD and D 2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H 2/atm cm 2 s is found for H 2 + PdD atmore » 298 K, 1.4 times higher than that for D 2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

Electron- and positron-impact atomic scattering calculations using propagating exterior complex scaling

NASA Astrophysics Data System (ADS)

Bartlett, P. L.; Stelbovics, A. T.; Rescigno, T. N.; McCurdy, C. W.

2007-11-01

Calculations are reported for four-body electron-helium collisions and positron-hydrogen collisions, in the S-wave model, using the time-independent propagating exterior complex scaling (PECS) method. The PECS S-wave calculations for three-body processes in electron-helium collisions compare favourably with previous convergent close-coupling (CCC) and time-dependent exterior complex scaling (ECS) calculations, and exhibit smooth cross section profiles. The PECS four-body double-excitation cross sections are significantly different from CCC calculations and highlight the need for an accurate representation of the resonant helium final-state wave functions when undertaking these calculations. Results are also presented for positron-hydrogen collisions in an S-wave model using an electron-positron potential of V12 = - (8 + (r1 - r2)2)-1/2. This model is representative of the full problem, and the results demonstrate that ECS-based methods can accurately calculate scattering, ionization and positronium formation cross sections in this three-body rearrangement collision.

Microbial electrohydrogenesis linked to dark fermentation as integrated application for enhanced biohydrogen production: A review on process characteristics, experiences and lessons.

PubMed

Bakonyi, Péter; Kumar, Gopalakrishnan; Koók, László; Tóth, Gábor; Rózsenberszki, Tamás; Bélafi-Bakó, Katalin; Nemestóthy, Nándor

2018-03-01

Microbial electrohydrogenesis cells (MECs) are devices that have attracted significant attention from the scientific community to generate hydrogen gas electrochemically with the aid of exoelectrogen microorganisms. It has been demonstrated that MECs are capable to deal with the residual organic materials present in effluents generated along with dark fermentative hydrogen bioproduction (DF). Consequently, MECs stand as attractive post-treatment units to enhance the global H 2 yield as a part of a two-stage, integrated application (DF-MEC). In this review article, it is aimed (i) to assess results communicated in the relevant literature on cascade DF-MEC systems, (ii) describe the characteristics of each steps involved and (iii) discuss the experiences as well as the lessons in order to facilitate knowledge transfer and help the interested readers with the construction of more efficient coupled set-ups, leading eventually to the improvement of overall biohydrogen evolution performances. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lichenysin, a cyclooctapeptide occurring in Chinese liquor jiannanchun reduced the headspace concentration of phenolic off-flavors via hydrogen-bond interactions.

PubMed

Zhang, Rong; Wu, Qun; Xu, Yan

2014-08-20

Nonvolatile compounds play important roles in the quality of alcoholic beverages. In our previous work, a type of cyclooctapeptide lichenysin was newly identified in Chinese strong-aroma type liquor. In this work, it was found that lichenysin could selectively affect aroma volatility in strong-aroma type (Jiannanchun) liquor. Interaction of lichenysin and volatile phenolic compounds (off-odors in strong-aroma type liquor) was characterized using headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS). HS-SPME results indicated that lichenysin very efficiently suppressed the volatility of phenolic compounds by 36-48% (P < 0.05). Thermodynamic analysis showed that the binding process was mainly mediated by hydrogen bonding. Furthermore, the mixture of lichenysin and 4-ethylguaiacol revealed intermolecular cross peaks between the aH (Val) of lichenysin and the 1H of 4-ethylguaiacol, by using nuclear Overhauser effect spectroscopy. This study will help to further understand the interaction mechanisms between flavor and nonvolatile matrix components in Chinese liquors.

The High-Resolution Structure of Activated Opsin Reveals a Conserved Solvent Network in the Transmembrane Region Essential for Activation.

PubMed

Blankenship, Elise; Vahedi-Faridi, Ardeschir; Lodowski, David T

2015-12-01

Rhodopsin, a light-activated G protein coupled receptor (GPCR), has been the subject of numerous biochemical and structural investigations, serving as a model receptor for GPCRs and their activation. We present the 2.3-Å resolution structure of native source rhodopsin stabilized in a conformation competent for G protein binding. An extensive water-mediated hydrogen bond network linking the chromophore binding site to the site of G protein binding is observed, providing connections to conserved motifs essential for GPCR activation. Comparison of this extensive solvent-mediated hydrogen-bonding network with the positions of ordered solvent in earlier crystallographic structures of rhodopsin photointermediates reveals both static structural and dynamic functional water-protein interactions present during the activation process. When considered along with observations that solvent occupies similar positions in the structures of other GPCRs, these analyses strongly support an integral role for this dynamic ordered water network in both rhodopsin and GPCR activation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evidence for photosensitised hydrogen production from water in the absence of precious metals, redox-mediators and co-catalysts.

PubMed

Salzl, S; Ertl, M; Knör, G

2017-03-22

The water-soluble zinc porphyrin complex Zn(TPPS) 4- with TPPS = tetrakis-(4-sulfonatophenyl)porphyrin surprisingly was found to produce significant amounts of hydrogen from aqueous sulfite or amine solutions under visible-light exposure without requiring any other components such as electron relays or additional proton reduction catalysts. Although the production rates and total amounts of chemically stored fuel obtained under these conditions are still much too low to be relevant for practical applications, the background of this unprecedented observation was further studied in its own right. Since the central metal zinc is unlikely to be involved in proton-coupled electron transfer steps upon long-wavelength irradiation and the process does not seem to be much affected by variations of the electron donor added, the mechanism of photocatalytic H 2 release is suggested to involve previously neglected redox features of the in situ generated hydroporphyrin ligand system in aqueous solution.

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2014 CFR

2014-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2013 CFR

2013-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2012 CFR

2012-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas

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

Not Available

1986-02-01

To make the coal-to-hydrogen route economically attractive, improvements are being sought in each step of the process: coal gasification, water-carbon monoxide shift reaction, and hydrogen separation. This report addresses the use of membranes in the hydrogen separation step. The separation of hydrogen from synthesis gas is a major cost element in the manufacture of hydrogen from coal. Separation by membranes is an attractive, new, and still largely unexplored approach to the problem. Membrane processes are inherently simple and efficient and often have lower capital and operating costs than conventional processes. In this report current ad future trends in hydrogen productionmore » and use are first summarized. Methods of producing hydrogen from coal are then discussed, with particular emphasis on the Texaco entrained flow gasifier and on current methods of separating hydrogen from this gas stream. The potential for membrane separations in the process is then examined. In particular, the use of membranes for H{sub 2}/CO{sub 2}, H{sub 2}/CO, and H{sub 2}/N{sub 2} separations is discussed. 43 refs., 14 figs., 6 tabs.« less

Concept study of a hydrogen containment process during nuclear thermal engine ground testing

NASA Astrophysics Data System (ADS)

Wang, Ten-See; Stewart, Eric T.; Canabal, Francisco

A new hydrogen containment process was proposed for ground testing of a nuclear thermal engine. It utilizes two thermophysical steps to contain the hydrogen exhaust. First, the decomposition of hydrogen through oxygen-rich combustion at higher temperature; second, the recombination of remaining hydrogen with radicals at low temperature. This is achieved with two unit operations: an oxygen-rich burner and a tubular heat exchanger. A computational fluid dynamics methodology was used to analyze the entire process on a three-dimensional domain. The computed flammability at the exit of the heat exchanger was less than the lower flammability limit, confirming the hydrogen containment capability of the proposed process.

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

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

Hou, Peng; Enevoldsen, Peter; Eichman, Joshua

In response to electricity markets with growing levels of wind energy production and varying electricity prices, this research examines incentives for investments in integrated renewable energy power systems. A strategy for using optimization methods for a power system consisting of wind turbines, electrolyzers, and hydrogen fuel cells is explored. This research reveals the investment potential of coupling offshore wind farms with different hydrogen systems. The benefits in terms of a return on investment are demonstrated with data from the Danish electricity markets. This research also investigates the tradeoffs between selling the hydrogen directly to customers or using it as amore » storage medium to re-generate electricity at a time when it is more valuable. Finally, this research finds that the most beneficial configuration is to produce hydrogen at a time that complements the wind farm and sell the hydrogen directly to end users.« less

Ammonia-hydrogen bromide and ammonia-hydrogen iodide complexes: anion photoelectron and ab initio studies.

PubMed

Eustis, S N; Whiteside, A; Wang, D; Gutowski, M; Bowen, K H

2010-01-28

The ammonia-hydrogen bromide and ammonia-hydrogen iodide, anionic heterodimers were studied by anion photoelectron spectroscopy. In complementary studies, these anions and their neutral counterparts were also investigated via ab initio theory at the coupled cluster level. In both systems, neutral NH(3)...HX dimers were predicted to be linear, hydrogen-bonded complexes, whereas their anionic dimers were found to be proton-transferred species of the form, (NH(4)(+)X(-))(-). Both experimentally measured and theoretically predicted vertical detachment energies (VDE) are in excellent agreement for both systems, with values for (NH(4)(+)Br(-))(-) being 0.65 and 0.67 eV, respectively, and values for (NH(4)(+)I(-))(-) being 0.77 and 0.81 eV, respectively. These systems are discussed in terms of our previous study of (NH(4)(+)Cl(-))(-).

Process for hydrogenating coal and coal solvents

DOEpatents

Tarrer, Arthur R.; Shridharani, Ketan G.

1983-01-01

A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260.degree. C. to 315.degree. C. in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent. Optimally, the reaction temperature is 275.degree. C. Alternately, the reaction can be conducted in a hydrogen atmosphere at 350.degree. C.

The Effects of Hydrogen-Like Impurity and Temperature on State Energies and Transition Frequency of Strong-Coupling Bound Polaron in an Asymmetric Gaussian Potential Quantum Well

NASA Astrophysics Data System (ADS)

Xiao, Jing-lin

2018-02-01

In the present work, we study the ground state energy, the first excited state energy and the transition frequency (TF) between the two states of the strong-coupling impurity bound polaron in an asymmetric Gaussian potential quantum well (AGPQW) by using the variational method of the Pekar type. By employing quantum statistics theory, the temperature effect on the state energies (SEs) and the TF are also calculated with a hydrogen-like impurity at the coordinate origin of the AGPQW. According to the obtained results, we found that the SEs and the TF are increasing functions of the temperature, whereas they are decreasing ones of the Coulombic impurity potential.

Nonlinear vibrational excitations in molecular crystals molecular mechanics calculations

NASA Astrophysics Data System (ADS)

Pumilia, P.; Abbate, S.; Baldini, G.; Ferro, D. R.; Tubino, R.

1992-03-01

The coupling constant for vibrational solitons χ has been examined in a molecular mechanics model for acetanilide (ACN) molecular crystal. According to A.C. Scott, solitons can form and propagate in solid acetanilide over a threshold energy value. This can be regarded as a structural model for the spines of hydrogen bond chains stabilizing the α helical structure of proteins. A one dimensional hydrogen bond chain of ACN has been built, for which we have found that, even though experimental parameters are correctly predicted, the excessive rigidity of the isolated chain prevents the formation of a localized distortion around the excitation. Yet, C=O coupling value with softer lattice modes could be rather high, allowing self-trapping to take place.

Palladium- and nickel-catalyzed Kumada cross-coupling reactions of gem-difluoroalkenes and monofluoroalkenes with Grignard reagents.

PubMed

Dai, Wenpeng; Xiao, Juan; Jin, Guanyi; Wu, Jingjing; Cao, Song

2014-11-07

A novel Kumada-Tamao-Corriu cross-coupling reaction of gem-di- or monofluoroalkenes with Grignard reagents, with or without β-hydrogen atoms, in the presence of a catalytic amount of palladium- or nickel-based catalysts has been developed. The reaction is performed under mild conditions (room temperature or reflux in diethyl ether for 1-2 h) and leads to di-cross- or mono-cross-coupled products in good to high yields.

Hyperspherical Symmetry of Hydrogenic Orbitals and Recoupling Coefficients among Alternative Bases

NASA Astrophysics Data System (ADS)

Aquilanti, Vincenzo; Cavalli, Simonetta; Coletti, Cecilia

1998-04-01

Fock's representation of momentum space hydrogenic orbitals in terms of harmonics on the hypersphere S3 of a four-dimensional space is extended to classify alternative bases. These orbitals are of interest for Sturmian expansions of use in atomic and molecular structure calculations and for the description of atoms in fields. Because of the correspondence between the S3 manifold and the SU\\(2\\) group, new sum rules are established which are of relevance for the connection, not only among hydrogen atom orbitals in different bases, but also among the usual vector coupling coefficients and rotation matrix elements.

Rotational relaxation of molecular hydrogen at moderate temperatures

NASA Technical Reports Server (NTRS)

Sharma, S. P.

1994-01-01

Using a coupled rotation-vibration-dissociation model the rotational relaxation times for molecular hydrogen as a function of final temperature (500-5000 K), in a hypothetical scenario of sudden compression, are computed. The theoretical model is based on a master equation solver. The bound-bound and bound-free transition rates have been computed using a quasiclassical trajectory method. A review of the available experimental data on the rotational relaxation of hydrogen is presented, with a critical overview of the method of measurements and data reduction, including the sources of errors. These experimental data are then compared with the computed results.

Solar hydrogen production: renewable hydrogen production by dry fuel reforming

NASA Astrophysics Data System (ADS)

Bakos, Jamie; Miyamoto, Henry K.

2006-09-01

SHEC LABS - Solar Hydrogen Energy Corporation constructed a pilot-plant to demonstrate a Dry Fuel Reforming (DFR) system that is heated primarily by sunlight focusing-mirrors. The pilot-plant consists of: 1) a solar mirror array and solar concentrator and shutter system; and 2) two thermo-catalytic reactors to convert Methane, Carbon Dioxide, and Water into Hydrogen. Results from the pilot study show that solar Hydrogen generation is feasible and cost-competitive with traditional Hydrogen production. More than 95% of Hydrogen commercially produced today is by the Steam Methane Reformation (SMR) of natural gas, a process that liberates Carbon Dioxide to the atmosphere. The SMR process provides a net energy loss of 30 to 35% when converting from Methane to Hydrogen. Solar Hydrogen production provides a 14% net energy gain when converting Methane into Hydrogen since the energy used to drive the process is from the sun. The environmental benefits of generating Hydrogen using renewable energy include significant greenhouse gas and criteria air contaminant reductions.

Utilization of Low-Pressure Plasma to Inactivate Bacterial Spores on Stainless Steel Screws

PubMed Central

Stapelmann, Katharina; Fiebrandt, Marcel; Raguse, Marina; Awakowicz, Peter; Reitz, Günther

2013-01-01

Abstract A special focus area of planetary protection is the monitoring, control, and reduction of microbial contaminations that are detected on spacecraft components and hardware during and after assembly. In this study, wild-type spores of Bacillus pumilus SAFR-032 (a persistent spacecraft assembly facility isolate) and the laboratory model organism B. subtilis 168 were used to study the effects of low-pressure plasma, with hydrogen alone and in combination with oxygen and evaporated hydrogen peroxide as a process gas, on spore survival, which was determined by a colony formation assay. Spores of B. pumilus SAFR-032 and B. subtilis 168 were deposited with an aseptic technique onto the surface of stainless steel screws to simulate a spore-contaminated spacecraft hardware component, and were subsequently exposed to different plasmas and hydrogen peroxide conditions in a very high frequency capacitively coupled plasma reactor (VHF-CCP) to reduce the spore burden. Spores of the spacecraft isolate B. pumilus SAFR-032 were significantly more resistant to plasma treatment than spores of B. subtilis 168. The use of low-pressure plasma with an additional treatment of evaporated hydrogen peroxide also led to an enhanced spore inactivation that surpassed either single treatment when applied alone, which indicates the potential application of this method as a fast and suitable way to reduce spore-contaminated spacecraft hardware components for planetary protection purposes. Key Words: Bacillus spores—Contamination—Spacecraft hardware—Plasma sterilization—Planetary protection. Astrobiology 13, 597–606. PMID:23768085

Ecophysiological adaptations of anaerobic bacteria to low pH. [Sarcina ventriculi; Lactobacillus helveticus

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

Goodwin, S.D.

1986-01-01

The ecological and physiological adaptations of anaerobic bacteria to low pH were investigated in field and laboratory studies. Determinations of hydrogen kinetic parameters demonstrated that overall hydrogen metabolism was inhibited in acid ecosystems. In particular, hydrogen metabolism became progressively uncoupled at low pH. This uncoupling resulted in a slowing of carbon flow during anaerobic digestion and the accumulation of intermediary metabolites. The addition of carbon electron donors to acid bog sediments resulted in the accumulation of hydrogen and a slowing of the overall rates of anaerobic digestion. As an adaptation to low pH, anaerobic bacterial populations shifted from production ofmore » acid intermediary metabolites (e.g. acetate and lactate) to the production of neutral intermediary metabolites (e.g. ethanol). This shift was observed both in situ and in pure cultures of hydrolytic strains isolated from bog sediments. Detailed physiological studies of Sarcina ventriculi showed an adaptation to growth at low pH by mechanisms which allowed the continued production of ethanol from glucose and the maintenance of a proton motive force at low cytoplasmic pH values. Further physiological studies Lactobacillus helveticus showed that the accumulation of acidic end-product (lactic acid) strongly influenced cellular electrochemical parameters. Based on the results of computer simulations and laboratory studies of the physiology of the organism in the presence of organic acids, a new model for the passive coupling of energy conservation to the efflux of lactic acid in an electroneutral process is proposed.« less

Hydrogen ion microlithography

DOEpatents

Tsuo, Y.S.; Deb, S.K.

1990-10-02

Disclosed is a hydrogen ion microlithography process for use in microelectronic fabrication and semiconductor device processing. The process comprises the steps of providing a single layer of either an amorphous silicon or hydrogenated amorphous silicon material. A pattern is recorded in a selected layer of amorphous silicon or hydrogenated amorphous silicon materials by preferentially implanting hydrogen ions therein so as to permit the selected layer to serve as a mask-resist wafer suitable for subsequent development and device fabrication. The layer is developed to provide a surface pattern therein adaptable for subsequent use in microelectronic fabrication and semiconductor device processing. 6 figs.

Process, including membrane separation, for separating hydrogen from hydrocarbons

DOEpatents

Baker, Richard W.; Lokhandwala, Kaaeid A.; He, Zhenjie; Pinnau, Ingo

2001-01-01

Processes for providing improved methane removal and hydrogen reuse in reactors, particularly in refineries and petrochemical plants. The improved methane removal is achieved by selective purging, by passing gases in the reactor recycle loop across membranes selective in favor of methane over hydrogen, and capable of exhibiting a methane/hydrogen selectivity of at least about 2.5 under the process conditions.

Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences.

PubMed

Gorgas, Nikolaus; Kirchner, Karl

2018-06-19

Sustainable processes that utilize nontoxic, readily available, and inexpensive starting materials for organic synthesis constitute a major objective in modern chemical research. In this context, it is highly important to perform reactions under catalytic conditions and to replace precious metal catalysts by earth-abundant nonprecious metal catalysts. In particular, iron and manganese are promising candidates, as these are among the most abundant metals in the earth's crust, are inexpensive, and exhibit a low environmental impact. As far as chemical processes are concerned, hydrogenations and acceptorless alcohol dehydrogenation (AAD), sometimes in conjunction with hydrogen autotransfer reactions, are becoming important areas of research. While the first is a very important synthetic process representing a highly atom-efficient and clean methodology, AAD is an oxidant-free, environmentally benign reaction where carbonyl compounds together with dihydrogen as a valuable product and/or reactant (autotransfer) and water are formed. Carbonyl compounds, typically generated in situ, can be converted into other useful organic materials such as amines, imines, or heterocycles. In 2016 several groups, including ours, discovered for the first time the potential of hydride biscarbonyl Mn(I) complexes bearing strongly bound PNP pincer ligands or related tridentate ligands as highly effective and versatile catalysts for hydrogenation, transfer hydrogenation, and dehydrogenation reactions. These complexes are isoelectronic analogues of the respective hydride monocarbonyl Fe(II) PNP compounds and display similar reactivities but also quite divergent behavior depending on the coligands. Moreover, manganese compounds show improved long-term stability and high robustness toward harsh reaction conditions. In light of these recent achievements, this Account contrasts Mn(I) and Fe(II) PNP pincer catalysts, highlighting specific features that are connected to particular structural and electronic properties. It also addresses opportunities and restrictions in their catalytic applications. Apart from classical hydrogenations, it also covers the most recent developments of these catalysts for AAD resulting in the synthesis of complex organic molecules such as heterocycles via multicomponent reactions. The ambivalent hydrogen-based redox chemistry provides access to a variety of synthetically valuable reductive and oxidative coupling reactions. Hence, these catalysts cover a broad scope of catalytic applications and exhibit activities and productivities that are becoming competitive with those of well-established precious metal catalysts. The knowledge about the nature and characteristics of active Mn(I)- and Fe(II)-based systems paves the way for conceptually and mechanistically well-founded research, which might lead to further developments and the discovery of novel catalysts extending the current scope and limitations of reactivity. It underlines that base metal catalysts are beginning to challenge precious metal catalysts and contributes to the further advancement of waste-free sustainable base metal catalysis.

Turnstiles and bifurcators: the disequilibrium converting engines that put metabolism on the road.

PubMed

Branscomb, Elbert; Russell, Michael J

2013-02-01

The Submarine Hydrothermal Alkaline Spring Theory for the emergence of life holds that it is the ordered delivery of hydrogen and methane in alkaline hydrothermal solutions at a spontaneously precipitated inorganic osmotic and catalytic membrane to the carbon dioxide and other electron acceptors in the earliest acidulous cool ocean that, through these gradients, drove life into being. That such interactions between hydrothermal fuels and potential oxidants have so far not been accomplished in the lab is because some steps along the necessary metabolic pathways are endergonic and must therefore be driven by being coupled to thermodynamically larger exergonic processes. But coupling of this kind is far from automatic and it is not enough to merely sum the ΔGs of two supposedly coupled reactions and show their combined thermodynamic viability. An exergonic reaction will not drive an endergonic one unless 'forced' to do so by being tied to it mechanistically via an organized "engine" of "Free Energy Conversion" (FEC). Here we discuss the thermodynamics of FEC and advance proposals regarding the nature and roles of the FEC devices that could, in principle, have arisen spontaneously in the alkaline hydrothermal context and have forced the onset of a protometabolism. The key challenge is to divine what these initial engines of life were in physicochemical terms and as part of that, what structures provided the first "turnstile-like" mechanisms needed to couple the partner processes in free energy conversion; in particular to couple the dissipation of geochemically given gradients to, say, the reduction of CO(2) to formate and the generation of a pyrophosphate disequilibrium. This article is part of a Special Issue entitled: The evolutionary aspects of bioenergetic systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Coupling thermoelectricity and electrocatalysis for hydrogen production via PbTesbnd PbS/TiO2 heterojunction

NASA Astrophysics Data System (ADS)

Liu, Zhongqing; Cao, Xiaohao; Wang, Bin; Xia, Min; Lin, Sidney; Guo, Zhanhu; Zhang, Xiaoming; Gao, Shiyuan

2017-02-01

PbTesbnd PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTesbnd PbS/TiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTesbnd PbS/TNAs, the two electrode system in which PbTesbnd PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 °C and 1.0 V bath voltage, the system registers 6.1 mL cm-2 h-1 rate of hydrogen generation, consuming electric power of 26.2 kW h kg-1 H2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling.

Applications of statistical and atomic physics to the spectral line broadening and stock markets

NASA Astrophysics Data System (ADS)

Volodko, Dmitriy

The purpose of this investigation is the application of time correlation function methodology on the theoretical research of the shift of hydrogen and hydrogen-like spectral lines due to electrons and ions interaction with the spectral line emitters-dipole ionic-electronic shift (DIES) and the describing a behavior of stock-market in terms of a simple physical model simulation which obeys Levy statistical distribution---the same as that of the real stock-market index. Using Generalized Theory of Stark broadening of electrons in plasma we discovered a new source of the shift of hydrogen and hydrogen-like spectral lines that we called a dipole ionic-electronic shift (DIES). This shift results from the indirect coupling of electron and ion microfields in plasmas which is facilitated by the radiating atom/ion. We have shown that the DIES, unlike all previously known shifts, is highly nonlinear and has a different sign for different ranges of plasma parameters. The most favorable conditions for observing the DIES correspond to plasmas of high densities, but of relatively low temperature. For the Balmer-alpha line of hydrogen with the most favorable observational conditions Ne > 1018 cm-3, T < 2 eV, the DIES has been already confirmed experimentally. Based on the study of the time correlations and of the probability distribution of fluctuations in the stock market, we developed a relatively simple physical model, which simulates the Dow Jones Industrials index and makes short-term (a couple of days) predictions of its trend.

Enhanced coproduction of hydrogen and methane from cornstalks by a three-stage anaerobic fermentation process integrated with alkaline hydrolysis.

PubMed

Cheng, Xi-Yu; Liu, Chun-Zhao

2012-01-01

A three-stage anaerobic fermentation process including H(2) fermentation I, H(2) fermentation II, methane fermentation was developed for the coproduction of hydrogen and methane from cornstalks. Hydrogen production from cornstalks using direct microbial conversion by Clostridium thermocellum 7072 was markedly enhanced in the two-stage thermophilic hydrogen fermentation process integrated with alkaline treatment. The highest total hydrogen yield from cornstalks in the two-stage fermentation process reached 74.4 mL/g-cornstalk. The hydrogen fermentation effluents and alkaline hydrolyzate were further used for methane fermentation by anaerobic granular sludge, and the total methane yield reached 205.8 mL/g-cornstalk. The total energy recovery in the three-stage anaerobic fermentation process integrated with alkaline hydrolysis reached 70.0%. Copyright © 2011 Elsevier Ltd. All rights reserved.

Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons

DOEpatents

Baker, Richard W.; Lokhandwala, Kaaeid A.; He, Zhenjie; Pinnau, Ingo

2001-01-01

An improved process for separating hydrogen from hydrocarbons. The process includes a pressure swing adsorption step, a compression/cooling step and a membrane separation step. The membrane step relies on achieving a methane/hydrogen selectivity of at least about 2.5 under the conditions of the process.

Nickel nanoparticles-embedded N-doped carbon nanotubes as a biocompatible electrocatalyst in a water splitting-biosynthetic hybrid system for CO2 conversion.

PubMed

Li, Zhongjian; Li, Gang; Chen, Xinlu; Xia, Zheng; Yao, Jiani; Yang, Bin; Lei, Lecheng; Hou, Yang

2018-05-29

CO2 reduction has drawn increasing attention due to the concern of global warming. Water splitting-biosynthetic hybrid systems are novel and efficient approaches for CO2 conversion. Intimate coupling of electrocatalysts and biosynthesis requires the catalysts possess both high catalytic performance and excellent biocompatibility, which is a bottleneck of developing such catalysts. Here, a novel Ni nanoparticles-embedded N-doped carbon nanotubes (Ni@N-C) complex was synthesized as a hydrogen evolution reaction electrocatalyst and was coupled with a hydrogen-oxidizing autotroph, Cupriavidus necator H16, to convert CO2 to poly-β-hydroxybutyrate. In the Ni@N-C, the Ni nanoparticles were encapsulated in N-C nanotubes, which prevented bacteria from direct contact with Ni and inhibited Ni2+ leaching. As a result, Ni@N-C exhibited excellent biocompatibility and stability. This work demonstrates electrocatalysts and biosynthesis can be intimately coupled via rational catalyst design. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced Hydrogen Liquefaction Process

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

Schwartz, Joseph; Kromer, Brian; Neu, Ben

2011-09-28

The project identified and quantified ways to reduce the cost of hydrogen liquefaction, and reduce the cost of hydrogen distribution. The goal was to reduce the power consumption by 20% and then to reduce the capital cost. Optimizing the process, improving process equipment, and improving ortho-para conversion significantly reduced the power consumption of liquefaction, but by less than 20%. Because the efficiency improvement was less than the target, the program was stopped before the capital cost was addressed. These efficiency improvements could provide a benefit to the public to improve the design of future hydrogen liquefiers. The project increased themore » understanding of hydrogen liquefaction by modeling different processes and thoroughly examining ortho-para separation and conversion. The process modeling provided a benefit to the public because the project incorporated para hydrogen into the process modeling software, so liquefaction processes can be modeled more accurately than using only normal hydrogen. Adding catalyst to the first heat exchanger, a simple method to reduce liquefaction power, was identified, analyzed, and quantified. The demonstrated performance of ortho-para separation is sufficient for at least one identified process concept to show reduced power cost when compared to hydrogen liquefaction processes using conventional ortho-para conversion. The impact of improved ortho-para conversion can be significant because ortho para conversion uses about 20-25% of the total liquefaction power, but performance improvement is necessary to realize a substantial benefit. Most of the energy used in liquefaction is for gas compression. Improvements in hydrogen compression will have a significant impact on overall liquefier efficiency. Improvements to turbines, heat exchangers, and other process equipment will have less impact.« less

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series.

PubMed

Mattioda, A L; Bauschlicher, C W; Ricca, A; Bregman, J; Hudgins, D M; Allamandola, L J

2017-06-15

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CH oop ) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CH oop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400cm -1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515cm -1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600cm -1 ) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds. Published by Elsevier B.V.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

2016-11-01

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

SnO2, IrO2, Ta2O5, Bi2O3, and TiO2 nanoparticle anodes: electrochemical oxidation coupled with the cathodic reduction of water to yield molecular H2

NASA Astrophysics Data System (ADS)

Choi, Jina; Qu, Yan; Hoffmann, Michael R.

2012-08-01

In recent years, the search for environmentally friendly alternative energy sources with reduced carbon footprints has increased. The coupling of photovoltaic power sources with advanced electrolysis systems for hydrogen production via water splitting using organic contaminants as sacrificial electron donors has been considered to a be viable alternative. In this report, we demonstrated the feasibility of a scaled-up rooftop prototype of the proposed hybrid photovoltaic-electrolysis system, which utilizes semiconductor nanoparticles coated on to metal substrates as electrodes for the generation of hydrogen coupled with the oxidation of wastewater. Application of an anodic bias of >2.0 V to bismuth-doped TiO2 (BiO x -TiO2) on Ti metal anodes with a sequential under-coatings of nanoparticulate SnO2, IrO2, Ta2O5, and Bi2O3 results in the electrochemical degradation of a variety of organic chemical contaminants in water (i.e., rhodamine B (Rh.B), methylene blue (MB), salicylic acid, triclosan, and phenol) and actual wastewater from a chemical manufacturing plant, while at the same time, molecular hydrogen is produced at stainless steel (SS) cathodes. The kinetics of the anodic substrates oxidation is investigated as a function of the cell current ( I cell), substrate concentration, and background electrolyte composition (e.g., NaCl, Na2SO4, or seawater). Average current efficiencies were found to be in the range of 4-22 %, while the cathodic current and energy efficiencies for hydrogen production were found to be in the range of 50-70 % and 20-40 %, respectively.

Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas. Task 1, Literature survey

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

Not Available

1986-02-01

To make the coal-to-hydrogen route economically attractive, improvements are being sought in each step of the process: coal gasification, water-carbon monoxide shift reaction, and hydrogen separation. This report addresses the use of membranes in the hydrogen separation step. The separation of hydrogen from synthesis gas is a major cost element in the manufacture of hydrogen from coal. Separation by membranes is an attractive, new, and still largely unexplored approach to the problem. Membrane processes are inherently simple and efficient and often have lower capital and operating costs than conventional processes. In this report current ad future trends in hydrogen productionmore » and use are first summarized. Methods of producing hydrogen from coal are then discussed, with particular emphasis on the Texaco entrained flow gasifier and on current methods of separating hydrogen from this gas stream. The potential for membrane separations in the process is then examined. In particular, the use of membranes for H{sub 2}/CO{sub 2}, H{sub 2}/CO, and H{sub 2}/N{sub 2} separations is discussed. 43 refs., 14 figs., 6 tabs.« less

Weak Long-Range Correlated Motions in a Surface Patch of Ubiquitin Involved in Molecular Recognition

PubMed Central

2011-01-01

Long-range correlated motions in proteins are candidate mechanisms for processes that require information transfer across protein structures, such as allostery and signal transduction. However, the observation of backbone correlations between distant residues has remained elusive, and only local correlations have been revealed using residual dipolar couplings measured by NMR spectroscopy. In this work, we experimentally identified and characterized collective motions spanning four β-strands separated by up to 15 Å in ubiquitin. The observed correlations link molecular recognition sites and result from concerted conformational changes that are in part mediated by the hydrogen-bonding network. PMID:21634390

Cooperative rearrangements leading to long range order in monolayers of supramolecular polymers.

PubMed

Vonau, F; Aubel, D; Bouteiller, L; Reiter, G; Simon, L

2007-08-24

Using scanning tunneling microscopy (STM), we followed the self-organization process of a supramolecular polymer monolayer deposited on a gold surface. During the growth of ordered domains from small to large scales, the molecule-molecule interactions were found to overrule the coupling to the substrate, causing a reorientation of the monolayer. The flexibility at the molecular level, due to reversible hydrogen bonds, was directly visualized by STM. The supramolecules were able to slide and insert between neighboring molecules, allowing the annihilation of domain boundaries and improving long range order. Large domains were found to cross monoatomic steps on the substrate without perturbation of their order.

On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon Chemistry

NASA Astrophysics Data System (ADS)

Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

2014-07-01

The chemical processing of ethylene ices (C2H4) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

NASA Technical Reports Server (NTRS)

Shanabarger, Mickey R.

1993-01-01

The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

Coupling of the coronal helium abundance to the solar wind

NASA Technical Reports Server (NTRS)

Hansteen, Viggo H.; Leer, Egil; Holzer, Thomas E.

1994-01-01

Models of the transition region-corona-solar wind system are investigated in order to find the coronal helium abundance and to study the role played by coronal helium in controlling the solar wind proton flux. The thermal force on alpha-particles in the transition region sets the flow of helium into the corona. The frictional coupling between alpha-particles and protons and/or the electric polarization field determines the proton flux in the solar wind as well as the fate of the coronal helium content. The models are constructed by solving the time-dependent population and momentum equations for all species of hydrogen and helium in an atmosphere with a given temperature profile. Several temperature profiles are considered in order to very the roles of frictional coupling and electric polarization field in the solar wind, and the thermal force in the transition region. Steady-state solutions are found for coronae with a hydrogen flux at 1 AU of 1.0 x 10(exp 9)/cm(exp 2)/sec or larger. For coronae with lower hydrogen fluxes, the helium flux into the corona is larger than the flux 'pulled out' by the solar wind protons, and solutions with increasing coronal helium content are found. The timescale for forming a helium-filled corona, that may allow for a steady outflow, is long compared to the mixing time for the corona.

Modeling the CH Stretch Vibrational Spectroscopy of M(+)[Cyclohexane] (M = Li, Na, and K) Ions.

PubMed

Sibert, Edwin L; Tabor, Daniel P; Lisy, James M

2015-10-15

The CH stretch vibrations of M(+)[cyclohexane][Ar] (M = Li, Na, and K) cluster ions were theoretically modeled. Results were compared to the corresponding infrared photodissociation spectra of Patwari and Lisy [ J. Chem. Phys A 2007 , 111 , 7585 ]. The experimental spectra feature a substantial spread in CH stretch vibration frequencies due to the alkali metal cation binding to select hydrogens of cyclohexane. This spread was observed to increase with decreasing metal ion size. Exploring the potential energy landscape revealed the presence of three conformers whose energy minima lie within ∼1 kcal of each other. It was determined that in all conformers the metal ion interacts with three hydrogen atoms; these hydrogen atoms can be either equatorial or axial. The corresponding spectra for these conformers were obtained with a theoretical model Hamiltonian [ J. Chem. Phys. 2013 , 138 , 064308 ] that consists of local mode CH stretches bilinearly coupled to each other and Fermi coupled to lower frequency modes. Frequencies and coupling parameters were obtained from electronic structure calculations that were subsequently scaled on the basis of previous studies. Theoretical spectra of a single low energy conformer were found to match well with the experimental spectra. The relative frequency shifts with changing metal ion size were accurately modeled with parameters generated by using ωB97X-D/6-311++(2d,p) calculations.

C-C cross-coupling of primary and secondary benzylic alcohols using supported gold-based bimetallic catalysts.

PubMed

Liu, Xiang; Ding, Ran-Sheng; He, Lin; Liu, Yong-Mei; Cao, Yong; He, He-Yong; Fan, Kang-Nian

2013-04-01

Clean alcohol-alcohol cross-coupling: A clean and efficient one-pot direct C-C cross-coupling of equimolar amounts of primary and secondary alcohols by a facile hydrogen autotransfer pathway is achieved over a robust and easily recovered hydrotalcite-supported Au-Pd bimetallic catalyst system. A variety of primary and secondary alcohols have been selectively converted into the corresponding β-alkylated ketones in good yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2013-07-23

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

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.

Mapping the force field of a hydrogen-bonded assembly

NASA Astrophysics Data System (ADS)

Sweetman, A. M.; Jarvis, S. P.; Sang, Hongqian; Lekkas, I.; Rahe, P.; Wang, Yu; Wang, Jianbo; Champness, N. R.; Kantorovich, L.; Moriarty, P.

2014-05-01

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated. Here we use dynamic force microscopy (DFM) to quantitatively map the tip-sample force field for naphthalene tetracarboxylic diimide molecules hydrogen-bonded in two-dimensional assemblies. A comparison of experimental images and force spectra with their simulated counterparts shows that intermolecular contrast arises from repulsive tip-sample interactions whose interpretation can be aided via an examination of charge density depletion across the molecular system. Interpreting DFM images of hydrogen-bonded systems therefore necessitates detailed consideration of the coupled tip-molecule system: analyses based on intermolecular charge density in the absence of the tip fail to capture the essential physical chemistry underpinning the imaging mechanism.

Theoretical investigation of the effect of hydrogen addition on the formation and properties of soliton in direct current argon plasma

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

Saikia, P., E-mail: partha.008@gmail.com; Goswami, K. S.; Saikia, B. K.

2014-03-15

In this study the effect of hydrogen addition on the formation and properties of soliton in direct-current (DC) argon plasma is theoretically investigated. By coupling fluid equations with Poisons equation for such multi-component plasma, the Mach number and amplitude of the soliton are determined following pseudo potential method. Addition of hydrogen in argon discharge leads to the decrease of electron, Ar{sup +} ion density while a reverse trend was observed for ArH{sup +} and hydrogen like ions. It was found that presence of hydrogen like ions in argon plasma affects the formation of soliton with its amplitude significantly decreases asmore » concentration of hydrogen increases. On the other hand, increase in ion to electron temperature ratios of the lighter ions in the discharge also has a significant influence on the amplitude and formation of soliton. The inverse relation between solitons width and amplitude is found to be consistent for the entire range of study.« less

HYFIRE II: fusion/high-temperature electrolysis conceptual-design study. Annual report

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

Fillo, J.A.

1983-08-01

As in the previous HYFIRE design study, the current study focuses on coupling a Tokamak fusion reactor with a high-temperature blanket to a High-Temperature Electrolyzer (HTE) process to produce hydrogen and oxygen. Scaling of the STARFIRE reactor to allow a blanket power to 6000 MW(th) is also assumed. The primary difference between the two studies is the maximum inlet steam temperature to the electrolyzer. This temperature is decreased from approx. 1300/sup 0/ to approx. 1150/sup 0/C, which is closer to the maximum projected temperature of the Westinghouse fuel cell design. The process flow conditions change but the basic design philosophymore » and approaches to process design remain the same as before. Westinghouse assisted in the study in the areas of systems design integration, plasma engineering, balance-of-plant design, and electrolyzer technology.« less

Electrochemical Visualization of Intracellular Hydrogen Peroxide at Single Cells.

PubMed

He, Ruiqin; Tang, Huifen; Jiang, Dechen; Chen, Hong-yuan

2016-02-16

In this Letter, the electrochemical visualization of hydrogen peroxide inside one cell was achieved first using a comprehensive Au-luminol-microelectrode and electrochemiluminescence. The capillary with a tip opening of 1-2 μm was filled with the mixture of chitosan and luminol, which was coated with the thin layers of polyvinyl chloride/nitrophenyloctyl ether (PVC/NPOE) and gold as the microelectrode. Upon contact with the aqueous hydrogen peroxide, hydrogen peroxide and luminol in contact with the gold layer were oxidized under the positive potential resulting in luminescence for the imaging. Due to the small diameter of the electrode, the microelectrode tip was inserted into one cell and the bright luminescence observed at the tip confirmed the visualization of intracellular hydrogen peroxide. The further coupling of oxidase on the electrode surface could open the field in the electrochemical imaging of intracellular biomolecules at single cells, which benefited the single cell electrochemical detection.

Ab initio studies of hydrogen adatoms on bilayer graphene

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Ukpong, A. M.; Chetty, N.

2012-05-01

We present a comparative density functional study of the adsorption of hydrogen on bilayer graphene. Six different exchange-correlation functionals are employed to explore the possible configurations of hydrogen adsorption at 50% coverage. Using the four variants of the nonlocal van der Waals density functional, we identify three distinct competing configurations that retain the coupled bilayer structure at 0 K. One of the configurations undergoes a spontaneous transformation from hexagonal to tetrahedral structure, under hydrogenation, with heat of formation ranging between -0.03 eV (vdW-DF) and -0.37 eV (vdW-DFC09x). This configuration has a finite band gap of around 3 eV, whereas all other competing configurations are either semimetallic or metallic. We also find two unique low-energy competing configurations of decoupled bilayer graphene, and therefore suggest the possibility of graphene exfoliation by hydrogen intercalation.

Surface properties of hydrogenated nanodiamonds: a chemical investigation.

PubMed

Girard, H A; Petit, T; Perruchas, S; Gacoin, T; Gesset, C; Arnault, J C; Bergonzo, P

2011-06-28

Hydrogen terminations (C-H) confer to diamond layers specific surface properties such as a negative electron affinity and a superficial conductive layer, opening the way to specific functionalization routes. For example, efficient covalent bonding of diazonium salts or of alkene moieties can be performed on hydrogenated diamond thin films, owing to electronic exchanges at the interface. Here, we report on the chemical reactivity of fully hydrogenated High Pressure High Temperature (HPHT) nanodiamonds (H-NDs) towards such grafting, with respect to the reactivity of as-received NDs. Chemical characterizations such as FTIR, XPS analysis and Zeta potential measurements reveal a clear selectivity of such couplings on H-NDs, suggesting that C-H related surface properties remain dominant even on particles at the nanoscale. These results on hydrogenated NDs open up the route to a broad range of new functionalizations for innovative NDs applications development. This journal is © the Owner Societies 2011

Probing hydrogen positions in hydrous compounds: information from parametric neutron powder diffraction studies.

PubMed

Ting, Valeska P; Henry, Paul F; Schmidtmann, Marc; Wilson, Chick C; Weller, Mark T

2012-05-21

We demonstrate the extent to which modern detector technology, coupled with a high flux constant wavelength neutron source, can be used to obtain high quality diffraction data from short data collections, allowing the refinement of the full structures (including hydrogen positions) of hydrous compounds from in situ neutron powder diffraction measurements. The in situ thermodiffractometry and controlled humidity studies reported here reveal that important information on the reorientations of structural water molecules with changing conditions can be easily extracted, providing insight into the effects of hydrogen bonding on bulk physical properties. Using crystalline BaCl2·2H2O as an example system, we analyse the structural changes in the compound and its dehydration intermediates with changing temperature and humidity levels to demonstrate the quality of the dynamic structural information on the hydrogen atoms and associated hydrogen bonding that can be obtained without resorting to sample deuteration.

The photobiological production of hydrogen: potential efficiency and effectiveness as a renewable fuel.

PubMed

Prince, Roger C; Kheshgi, Haroon S

2005-01-01

Photosynthetic microorganisms can produce hydrogen when illuminated, and there has been considerable interest in developing this to a commercially viable process. Its appealing aspects include the fact that the hydrogen would come from water, and that the process might be more energetically efficient than growing, harvesting, and processing crops. We review current knowledge about photobiological hydrogen production, and identify and discuss some of the areas where scientific and technical breakthroughs are essential for commercialization. First we describe the underlying biochemistry of the process, and identify some opportunities for improving photobiological hydrogen production at the molecular level. Then we address the fundamental quantum efficiency of the various processes that have been suggested, technological issues surrounding large-scale growth of hydrogen-producing microorganisms, and the scale and efficiency on which this would have to be practiced to make a significant contribution to current energy use.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Process Research of Polycrystalline Silicon Material (PROPSM)

NASA Technical Reports Server (NTRS)

Culik, J. S.

1984-01-01

A passivation process (hydrogenation) that will improve the power generation of solar cells fabricated from presently produced, large grain, cast polycrystalline silicon (Semix), a potentially low cost material are developed. The first objective is to verify the operation of a DC plasma hydrogenation system and to investigate the effect of hydrogen on the electrical performance of a variety of polycrystalline silicon solar cells. The second objective is to parameterize and optimize a hydrogenation process for cast polycrystalline silicon, and will include a process sensitivity analysis. The sample preparation for the first phase is outlined. The hydrogenation system is described, and some early results that were obtained using the hydrogenation system without a plasma are summarized. Light beam induced current (LBIC) measurements of minicell samples, and their correlation to dark current voltage characteristics, are discussed.

Effect of the Lateral Exospheric Transport on the Horizontal Hydrogen Distribution Near the Exobase of Mars

NASA Astrophysics Data System (ADS)

Chaufray, J.-Y.; Yelle, R. V.; Gonzalez-Galindo, F.; Forget, F.; Lopez-Valverde, M.; Leblanc, F.; Modolo, R.

2018-03-01

We simulate the hydrogen density near the exobase of Mars, using the 3-D Martian Global Circulation Model of Laboratoire de Météorologie Dynamique, coupled to an exospheric ballistic model to compute the downward ballistic flux. The simulated hydrogen distribution near the exobase obtained at two different seasons—Ls = 180° and Ls = 270°—is close to Zero Net Ballistic Flux equilibrium. In other words, the hydrogen density near the exobase adjusts to have a balance between the local upward ballistic and the downward ballistic flux due to a short lateral migration time in the exosphere compared to the vertical diffusion time. This equilibrium leads to a hydrogen density n near the exobase directly controlled by the exospheric temperature T by the relation nT5/2 = constant. This relation could be used to extend 1-D hydrogen exospheric model of Mars used to derive the hydrogen density and escape flux at Mars from Lyman-α observations to 3-D model based on observed or modeled exospheric temperature near the exobase, without increasing the number of free parameters.

Two-stage coal liquefaction without gas-phase hydrogen

DOEpatents

Stephens, H.P.

1986-06-05

A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

Multidisciplinary approaches to solar hydrogen

PubMed Central

Bren, Kara L.

2015-01-01

This review summarizes three different approaches to engineering systems for the solar-driven evolution of hydrogen fuel from water: molecular, nanomaterials and biomolecular. Molecular systems have the advantage of being highly amenable to modification and detailed study and have provided great insight into photophysics, electron transfer and catalytic mechanism. However, they tend to display poor stability. Systems based on nanomaterials are more robust but also are more difficult to synthesize in a controlled manner and to modify and study in detail. Biomolecular systems share many properties with molecular systems and have the advantage of displaying inherently high efficiencies for light absorption, electron–hole separation and catalysis. However, biological systems must be engineered to couple modules that capture and convert solar photons to modules that produce hydrogen fuel. Furthermore, biological systems are prone to degradation when employed in vitro. Advances that use combinations of these three tactics also are described. Multidisciplinary approaches to this problem allow scientists to take advantage of the best features of biological, molecular and nanomaterials systems provided that the components can be coupled for efficient function. PMID:26052425

Electronic state and optical response in a hydrogen-bonded molecular conductor

NASA Astrophysics Data System (ADS)

Naka, Makoto; Ishihara, Sumio

2018-06-01

Motivated by recent experimental studies of hydrogen-bonded molecular conductors κ -X 3(Cat-EDT-TTF) 2[X =H , D], interplays of protons and correlated electrons, and their effects on magnetic, dielectric, and optical properties, are studied theoretically. We introduce a model Hamiltonian for κ -X 3(Cat-EDT-TTF) 2, in which molecular dimers are connected by hydrogen bonds. Ground-state phase diagram and optical conductivity spectra are examined by using the mean-field approximation and the exact diagonalization method in finite-size cluster. Three types of the competing electronic and protonic phases, charge density wave phase, polar charge-ordered phase, and antiferromagnetic dimer-Mott insulating phase are found. Observed softening of the interdimer excitation due to the electron-proton coupling implies reduction of the effective electron-electron repulsion, i.e., "Hubbard U ," due to the quantum proton motion. Contrastingly, the intradimer charge excitation is hardened due to the proton-electron coupling. Implications of the theoretical calculations to the recent experimental results in κ -X 3(Cat-EDT-TTF) 2 are discussed.

Biferrocene-Based Diphosphine Ligands: Synthesis and Application of Walphos Analogues in Asymmetric Hydrogenations

PubMed Central

2013-01-01

A total of four biferrocene-based Walphos-type ligands have been synthesized, structurally characterized, and tested in the rhodium-, ruthenium- and iridium-catalyzed hydrogenation of alkenes and ketones. Negishi coupling conditions allowed the biferrocene backbone of these diphosphine ligands to be built up diastereoselectively from the two nonidentical and nonracemic ferrocene fragments (R)-1-(N,N-dimethylamino)ethylferrocene and (SFc)-2-bromoiodoferrocene. The molecular structures of (SFc)-2-bromoiodoferrocene, the coupling product, two ligands, and the two complexes ([PdCl2(L)] and [RuCl(p-cymene)(L)]PF6) were determined by X-ray diffraction. The structural features of complexes and the catalysis results obtained with the newly synthesized biferrocene-based ligands were compared with those of the corresponding Walphos ligands. PMID:23457421

Inelastic collisions of positrons with one-valence-electron targets

NASA Technical Reports Server (NTRS)

Abdel-Raouf, Mohamed Assad

1990-01-01

The total elastic and positronium formation cross sections of the inelastic collisions between positrons and various one-valence-electron atoms, (namely hydrogen, lithium, sodium, potassium and rubidium), and one-valence-electron ions, (namely hydrogen-like, lithium-like and alkaline-earth positive ions) are determined using an elaborate modified coupled-static approximation. Special attention is devoted to the behavior of the Ps cross sections at the energy regions lying above the Ps formation thresholds.

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.

Collisionless Coupling between Explosive Debris Plasma and Magnetized Ambient Plasma

NASA Astrophysics Data System (ADS)

Bondarenko, Anton

2016-10-01

The explosive expansion of a dense debris plasma cloud into relatively tenuous, magnetized, ambient plasma characterizes a wide variety of astrophysical and space phenomena, including supernova remnants, interplanetary coronal mass ejections, and ionospheric explosions. In these rarified environments, collective electromagnetic processes rather than Coulomb collisions typically mediate the transfer of momentum and energy from the debris plasma to the ambient plasma. In an effort to better understand the detailed physics of collisionless coupling mechanisms in a reproducible laboratory setting, the present research jointly utilizes the Large Plasma Device (LAPD) and the Phoenix laser facility at UCLA to study the super-Alfvénic, quasi-perpendicular expansion of laser-produced carbon (C) and hydrogen (H) debris plasma through preformed, magnetized helium (He) ambient plasma via a variety of diagnostics, including emission spectroscopy, wavelength-filtered imaging, and magnetic field induction probes. Large Doppler shifts detected in a He II ion spectral line directly indicate initial ambient ion acceleration transverse to both the debris plasma flow and the background magnetic field, indicative of a fundamental process known as Larmor coupling. Characterization of the laser-produced debris plasma via a radiation-hydrodynamics code permits an explicit calculation of the laminar electric field in the framework of a ``hybrid'' model (kinetic ions, charge-neutralizing massless fluid electrons), thus allowing for a simulation of the initial response of a distribution of He II test ions. A synthetic Doppler-shifted spectrum constructed from the simulated velocity distribution of the accelerated test ions excellently reproduces the spectroscopic measurements, confirming the role of Larmor coupling in the debris-ambient interaction.

Method of production of pure hydrogen near room temperature from aluminum-based hydride materials

DOEpatents

Pecharsky, Vitalij K.; Balema, Viktor P.

2004-08-10

The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.

A multiphase interfacial model for the dissolution of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary calculations to demonstrate the application and value of the model.

Effect of the oxidation front penetration on in-clad hydrogen migration

NASA Astrophysics Data System (ADS)

Feria, F.; Herranz, L. E.

2018-03-01

In LWR fuel claddings the embrittlement due to hydrogen precipitates (i.e., hydrides) is a degrading mechanism that concerns in nuclear safety, particularly in dry storage. A relevant factor is the radial distribution of the hydrogen absorbed, especially the hydride rim formed. Thus, a reliable assessment of fuel performance should account for hydrogen migration. Based on the current state of modelling of hydrogen dynamics in the cladding, a 1D radial model has been derived and coupled with the FRAPCON code. The model includes the effect of the oxidation front progression on in-clad hydrogen migration, based on experimental observations found (i.e., dissolution/diffusion/re-precipitation of the hydrogen in the matrix ahead of the oxidation front). A remarkable quantitative impact of this new contribution has been shown by analyzing the hydrogen profile across the cladding of several high burnup fuel scenarios (>60 GW d/tU); other potential contributions like thermodiffusion and diffusion in the hydride phase hardly make any difference. Comparisons against PIE measurements allow concluding that the model accuracy notably increases when the effect of the oxidation front is accounted for in the hydride rim formation. In spite of the promising results, further validation would be needed.

Modeling Issues and Results for Hydrogen Isotopes in NIF Materials

NASA Astrophysics Data System (ADS)

Grossman, Arthur A.; Doerner, R. P.; Luckhardt, S. C.; Seraydarian, R.; Sze, D.; Burnham, A.

1998-11-01

The TMAP4 (G. Longhurst, et al. INEL 1992) model of hydrogen isotope transport in solid materials includes a particle diffusion calculation with Fick's Law modified for Soret Effect (Thermal Diffusion or Thermomigration), coupled to heat transport calculations which are needed because of the strong temperature dependence of diffusivity. These TMAP4 calculations applied to NIF show that high temperatures approaching the melting point and strong thermal gradients of 10^6 K/cm are reached in the first micron of wall material during the SXR pulse. These strong thermal gradients can drive hydrogen isotope migration up or down the thermal gradient depending on the sign of the heat of transport (Soret coefficient) which depends on whether the material dissolves hydrogen endothermically or exothermically. Two candidates for NIF wall material-boron carbide and stainless steel are compared. Boron carbide dissolves hydrogen exothermically so it may drive Soret migration down the thermal gradient deeper into the material, although the thermal gradient is not as large and hydrogen is not as mobile as in stainless steel. Stainless steel dissolves hydrogen endothermically, with a negative Soret coefficient which can drive hydrogen up the thermal gradient and out of the wall.

Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

NASA Astrophysics Data System (ADS)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.

Electrochemical supramolecular recognition of hemin-carbon composites

NASA Astrophysics Data System (ADS)

Le, Hien Thi Ngoc; Jeong, Hae Kyung

2018-04-01

Hemin-graphite oxide-carbon nanotube (hemin-GO-CNT) and hemin-thermally reduced graphite oxide-carbon nanotube (hemin-TRGO-CNT) composites are synthesized and investigated for the electrochemical supramolecular recognition by electron transfer between biomolecules (dopamine and hydrogen peroxide) and the composite electrodes. Redox reaction mechanisms of two composites with dopamine and hydrogen peroxide are explained in detail by using cyclic voltammetry and differential pulse voltammetry. Hemin-TRGO-CNT displays higher electrochemical detection for dopamine and hydrogen peroxide than that of hemin-GO-CNT, exhibiting enhancement of the electron transfer due to the effective immobilization of redox couple of hemin (Fe2+/Fe3+) on the TRGO-CNT surface.

Impact of Oxidative Dissolution on Black Shale Fracturing: Implication for Shale Fracturing Treatment Design

NASA Astrophysics Data System (ADS)

You, L.; Chen, Q.; Kang, Y.; Cheng, Q.; Sheng, J.

2017-12-01

Black shales contain a large amount of environment-sensitive compositions, e.g., clay minerals, carbonate, siderite, pyrite, and organic matter. There have been numerous studies on the black shales compositional and pore structure changes caused by oxic environments. However, most of the studies did not focus on their ability to facilitate shale fracturing. To test the redox-sensitive aspects of shale fracturing and its potentially favorable effects on hydraulic fracturing in shale gas reservoirs, the induced microfractures of Longmaxi black shales exposed to deionized water, hydrochloric acid, and hydrogen peroxide at room-temperature for 240 hours were imaged by scanning electron microscopy (SEM) and CT-scanning in this paper. Mineral composition, acoustic emission, swelling, and zeta potential of the untreated and oxidative treatment shale samples were also recorded to decipher the coupled physical and chemical effects of oxidizing environments on shale fracturing processes. Results show that pervasive microfractures (Fig.1) with apertures ranging from tens of nanometers to tens of microns formed in response to oxidative dissolution by hydrogen peroxide, whereas no new microfracture was observed after the exposure to deionized water and hydrochloric acid. The trajectory of these oxidation-induced microfractures was controlled by the distribution of phyllosilicate framework and flaky or stringy organic matter in shale. The experiments reported in this paper indicate that black shales present the least resistance to crack initiation and subcritical slow propagation in hydrogen peroxide, a process we refer to as oxidation-sensitive fracturing, which are closely related to the expansive stress of clay minerals, dissolution of redox-sensitive compositions, destruction of phyllosilicate framework, and the much lower zeta potential of hydrogen peroxide solution-shale system. It could mean that the injection of fracturing water with strong oxidizing aqueous solution may play an important role in improving hydraulic fracturing of shale formation by reducing the energy requirements for crack growth. However, additional work is needed to the selection of highly-effective, economical, and environmentally friendly oxidants.

Modeling the hydrothermal circulation and the hydrogen production at the Rainbow site with Cast3M

NASA Astrophysics Data System (ADS)

Perez, F.; Mügler, C.; Charlou, J.; Jean-baptiste, P.

2012-12-01

On the Mid-Atlantic Ridge, the Rainbow venting site is described as an ultramafic-hosted active hydrothermal site and releases high fluxes of methane and hydrogen [1, 2]. This behavior has first been interpreted as the result of serpentinization processes. But geochemical reactions involving olivine and plagioclase assemblages, and leading to chlorite, tremolite, talc and magnetite assemblages, could contribute to the observed characteristics of the exiting fluid [2]. The predominance of one of these geochemical reactions or their coexistence strongly depend on the hydrothermal fluid circulation. We developed and validated a 2D/3D numerical model using a Finite Volume method to simulate heat driven fluid flows in the framework of the Cast3M code [3, 4]. We also developed a numerical model for hydrogen production and transport that is based on experimental studies of the serpentinization processes [5-6]. This geochemical model takes into account the exothermic and water-consuming behavior of the serpentinization reaction and it can be coupled to our thermo-hydrogeological model. Our simulations provide temperatures, mass fluxes and venting surface areas very close to those estimated in-situ [7]. We showed that a single-path model [8] was necessary to simulate high values such as the in-situ measured temperatures and estimated water mass fluxes of the Rainbow site [7]. This single-path model will be used to model the production and transport of hydrogen at the Rainbow hydrothermal site. References [1]Charlou et al. (2010) AGU Monograph series. [2]Seyfried et al. (2011) Geochim. Cosmochim. Acta 75, 1574-1593. [3]http://www-cast3m.cea.fr. [4]Martin & Fyfe (1970) Chem. Geol. 6, 185-202. [5] Marcaillou et al. (2011) Earth and Planet. Sci. Lett. 303, 281-290. [6]Malvoisin et al. (2012) JGR, 117, B01104. [7]Perez et al. (2012) submited to Computational Geosciences. [8]Lowell & Germanovich (2004) AGU, Washington DC, USA.

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.

Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

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

Ravi Kumar, Venkatraman; Rajkumar, Nagappan; Umapathy, Siva, E-mail: umapathy@ipc.iisc.ernet.in

2015-01-14

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-π{sup 1}*; S{sub 1} state) and the shorter (1π-π{sup 1}*; S{sub 2} state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bondmore » weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S{sub 2} state relative to the ground state. Raman excitation profiles of PQ (400–1800 cm{sup −1}) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C{sub 2ν} symmetry constraint on the S{sub 2} state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling.« less

Study of hydrogen bond polarized IR spectra of cinnamic acid crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Jabłońska, Magdalena

2004-11-01

This paper presents the results of investigation of the polarized IR spectra of cinnamic acid and of its deuterium derivative crystals. The spectra were measured by a transmission method, using polarized light, at the room temperature and at 77 K, for two different crystalline faces. Theoretical analysis of the results concerned linear dichroic effects, H/D isotopic and temperature effects, observed in the spectra of the hydrogen and of the deuterium bonds in cinnamic acid crystals, at the frequency ranges of the νO-H and the νO-D bands. The basic crystal spectral properties could be satisfactorily interpreted in a quantitative way for a centrosymmetric cyclic hydrogen bond dimer model. Such a model explains not only a two-branch structure of the νO-H and νO-D bands in crystalline spectra, but also some essential linear dichroic effects in the band frequency ranges, measured for isotopically diluted crystals. Model calculations, performed within the limits of the 'strong-coupling' model, allowed for quantitative interpretation and for understanding of the basic properties of the hydrogen bond IR spectra of cinnamic acid crystals, H/D isotopic, temperature and dichroic effects included. In the scope of our studies the mechanism of H/D isotopic 'self-organization' processes, taking place in the crystal hydrogen bond lattices, was also recognized. It was proved that for isotopically diluted crystalline samples of cinnamic acid, a non-random distribution of protons and deuterons occurs exclusively in the hydrogen bond dimers. Nevertheless, these co-operative interactions between the hydrogen bonds do not involve the adjacent hydrogen bond dimers in each unit cell. The two-branch fine structure pattern of the νO-H and νO-D bands was ascribed to the vibronic mechanism of vibrational dipole selection rule breaking in centrosymmetric hydrogen bond dimers. The observed in the spectra very high intensity of the forbidden transition sub-band in the analyzed νO-H and νO-D bands is a manifestation of an extremely effective symmetry rule breaking mechanism. It correlates with a relatively large excess electron charge on the cinnamic aid dimer carboxyl groups. This effect is a result of a partial withdrawal of the electron charge, from the conjugated π-bond systems of the styryl substituents, by the carboxyl groups. This statement has been supported by ab initio calculations.

Hydrogen Plasma Processing of Iron Ore

NASA Astrophysics Data System (ADS)

Sabat, Kali Charan; Murphy, Anthony B.

2017-06-01

Iron is currently produced by carbothermic reduction of oxide ores. This is a multiple-stage process that requires large-scale equipment and high capital investment, and produces large amounts of CO2. An alternative to carbothermic reduction is reduction using a hydrogen plasma, which comprises vibrationally excited molecular, atomic, and ionic states of hydrogen, all of which can reduce iron oxides, even at low temperatures. Besides the thermodynamic and kinetic advantages of a hydrogen plasma, the byproduct of the reaction is water, which does not pose any environmental problems. A review of the theory and practice of iron ore reduction using a hydrogen plasma is presented. The thermodynamic and kinetic aspects are considered, with molecular, atomic and ionic hydrogen considered separately. The importance of vibrationally excited hydrogen molecules in overcoming the activation energy barriers, and in transferring energy to the iron oxide, is emphasized. Both thermal and nonthermal plasmas are considered. The thermophysical properties of hydrogen and argon-hydrogen plasmas are discussed, and their influence on the constriction and flow in the of arc plasmas is considered. The published R&D on hydrogen plasma reduction of iron oxide is reviewed, with both the reduction of molten iron ore and in-flight reduction of iron ore particles being considered. Finally, the technical and economic feasibility of the process are discussed. It is shown that hydrogen plasma processing requires less energy than carbothermic reduction, mainly because pelletization, sintering, and cokemaking are not required. Moreover, the formation of the greenhouse gas CO2 as a byproduct is avoided. In-flight reduction has the potential for a throughput at least equivalent to the blast furnace process. It is concluded that hydrogen plasma reduction of iron ore is a potentially attractive alternative to standard methods.

Process for manufacture of thick film hydrogen sensors

DOEpatents

Perdieu, Louisa H.

2000-09-09

A thick film process for producing hydrogen sensors capable of sensing down to a one percent concentration of hydrogen in carrier gasses such as argon, nitrogen, and air. The sensor is also suitable to detect hydrogen gas while immersed in transformer oil. The sensor includes a palladium resistance network thick film printed on a substrate, a portion of which network is coated with a protective hydrogen barrier. The process utilizes a sequence of printing of the requisite materials on a non-conductive substrate with firing temperatures at each step which are less than or equal to the temperature at the previous step.

Hydrogen bonding and spin density distribution in the QB semiquinone of bacterial reaction centers and comparison with the QA site

PubMed Central

Martin, Erik; Samoilova, Rimma I.; Narasimhulu, Kupala V.; Lin, Tzu-Jen; O’Malley, Patrick J.; Wraight, Colin A.; Dikanov, Sergei A.

2011-01-01

In the photosynthetic reaction center from Rhodobacter sphaeroides, the primary (QA) and secondary (QB) electron acceptors are both ubiquinone-10, but with very different properties and functions. To investigate the protein environment that imparts these functional differences, we have applied X-band HYSCORE, a 2D pulsed EPR technique, to characterize the exchangeable protons around the semiquinone (SQ) in the QA and QB sites, using samples of 15N-labeled reaction centers, with the native high spin Fe2+ exchanged for diamagnetic Zn2+, prepared in 1H2O and 2H2O solvent. The powder HYSCORE method is first validated against the orientation-selected Q-band ENDOR study of the QA SQ by Flores et al. (Biophys. J. 2007, 92, 671–682), with good agreement for two exchangeable protons with anisotropic hyperfine tensor components, T, both in the range 4.6–5.4 MHz. HYSCORE was then applied to the QB SQ where we found proton lines corresponding to T~5.2, 3.7 MHz and T~1.9 MHz. Density functional-based quantum mechanics/molecular mechanics (QM/MM) calculations, employing a model of the QB site, were used to assign the observed couplings to specific hydrogen bonding interactions with the QB SQ. These calculations allow us to assign the T=5.2 MHz proton to the His-L190 NδH…O4 (carbonyl) hydrogen bonding interaction. The T =3.7 MHz spectral feature most likely results from hydrogen bonding interactions of O1 (carbonyl) with both Gly-L225 peptide NH and Ser-L223 hydroxyl OH, which possess calculated couplings very close to this value. The smaller 1.9 MHz coupling is assigned to a weakly bound peptide NH proton of Ile-L224. The calculations performed with this structural model of the QB site show less asymmetric distribution of unpaired spin density over the SQ than seen for the QA site, consistent with available experimental data for 13C and 17O carbonyl hyperfine couplings. The implications of these interactions for QB function and comparisons with the QA site are discussed. PMID:21417328

Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Alkyl Grignard Reagents and Identification of Selective Anti-Breast Cancer Agents**

PubMed Central

Osborne, Charlotte A.; Moore, Curtis E.; Morrissette, Naomi S.; Jarvo, Elizabeth R.

2014-01-01

β-Hydrogen-containing alkyl Grignard reagents were used in a stereospecific nickel-catalyzed cross-coupling reaction to form sp3–sp3 carbon–carbon bonds. Aryl Grignard reagents were also utilized to synthesize 1,1-diarylalkanes. Several compounds synthesized by this method exhibited selective inhibition of proliferation of MCF-7 breast cancer cells. PMID:24478275

Syntrophomonas wolfei Uses an NADH-Dependent, Ferredoxin-Independent [FeFe]-Hydrogenase To Reoxidize NADH

PubMed Central

Losey, Nathaniel A.; Mus, Florence; Peters, John W.; Le, Huynh M.

2017-01-01

ABSTRACT Syntrophomonas wolfei syntrophically oxidizes short-chain fatty acids (four to eight carbons in length) when grown in coculture with a hydrogen- and/or formate-using methanogen. The oxidation of 3-hydroxybutyryl-coenzyme A (CoA), formed during butyrate metabolism, results in the production of NADH. The enzyme systems involved in NADH reoxidation in S. wolfei are not well understood. The genome of S. wolfei contains a multimeric [FeFe]-hydrogenase that may be a mechanism for NADH reoxidation. The S. wolfei genes for the multimeric [FeFe]-hydrogenase (hyd1ABC; SWOL_RS05165, SWOL_RS05170, SWOL_RS05175) and [FeFe]-hydrogenase maturation proteins (SWOL_RS05180, SWOL_RS05190, SWOL_RS01625) were coexpressed in Escherichia coli, and the recombinant Hyd1ABC was purified and characterized. The purified recombinant Hyd1ABC was a heterotrimer with an αβγ configuration and a molecular mass of 115 kDa. Hyd1ABC contained 29.2 ± 1.49 mol of Fe and 0.7 mol of flavin mononucleotide (FMN) per mole enzyme. The purified, recombinant Hyd1ABC reduced NAD+ and oxidized NADH without the presence of ferredoxin. The HydB subunit of the S. wolfei multimeric [FeFe]-hydrogenase lacks two iron-sulfur centers that are present in known confurcating NADH- and ferredoxin-dependent [FeFe]-hydrogenases. Hyd1ABC is a NADH-dependent hydrogenase that produces hydrogen from NADH without the need of reduced ferredoxin, which differs from confurcating [FeFe]-hydrogenases. Hyd1ABC provides a mechanism by which S. wolfei can reoxidize NADH produced during syntrophic butyrate oxidation when low hydrogen partial pressures are maintained by a hydrogen-consuming microorganism. IMPORTANCE Our work provides mechanistic understanding of the obligate metabolic coupling that occurs between hydrogen-producing fatty and aromatic acid-degrading microorganisms and their hydrogen-consuming partners in the process called syntrophy (feeding together). The multimeric [FeFe]-hydrogenase used NADH without the involvement of reduced ferredoxin. The multimeric [FeFe]-hydrogenase would produce hydrogen from NADH only when hydrogen concentrations were low. Hydrogen production from NADH by Syntrophomonas wolfei would likely cease before any detectable amount of cell growth occurred. Thus, continual hydrogen production requires the presence of a hydrogen-consuming partner to keep hydrogen concentrations low and explains, in part, the obligate requirement that S. wolfei has for a hydrogen-consuming partner organism during growth on butyrate. We have successfully expressed genes encoding a multimeric [FeFe]-hydrogenase in E. coli, demonstrating that such an approach can be advantageous to characterize complex redox proteins from difficult-to-culture microorganisms. PMID:28802265

Adsorption process to recover hydrogen from feed gas mixtures having low hydrogen concentration

DOEpatents

Golden, Timothy Christopher; Weist, Jr., Edward Landis; Hufton, Jeffrey Raymond; Novosat, Paul Anthony

2010-04-13

A process for selectively separating hydrogen from at least one more strongly adsorbable component in a plurality of adsorption beds to produce a hydrogen-rich product gas from a low hydrogen concentration feed with a high recovery rate. Each of the plurality of adsorption beds subjected to a repetitive cycle. The process comprises an adsorption step for producing the hydrogen-rich product from a feed gas mixture comprising 5% to 50% hydrogen, at least two pressure equalization by void space gas withdrawal steps, a provide purge step resulting in a first pressure decrease, a blowdown step resulting in a second pressure decrease, a purge step, at least two pressure equalization by void space gas introduction steps, and a repressurization step. The second pressure decrease is at least 2 times greater than the first pressure decrease.

Hydrogen production from coal using a nuclear heat source

NASA Technical Reports Server (NTRS)

Quade, R. N.

1976-01-01

A strong candidate for hydrogen production in the intermediate time frame of 1985 to 1995 is a coal-based process using a high-temperature gas-cooled reactor (HTGR) as a heat source. Expected process efficiencies in the range of 60 to 70% are considerably higher than all other hydrogen production processes except steam reforming of a natural gas. The process involves the preparation of a coal liquid, hydrogasification of that liquid, and steam reforming of the resulting gaseous or light liquid product. A study showing process efficiency and cost of hydrogen vs nuclear reactor core outlet temperature has been completed, and shows diminishing returns at process temperatures above about 1500 F. A possible scenario combining the relatively abundant and low-cost Western coal deposits with the Gulf Coast hydrogen users is presented which provides high-energy density transportation utilizing coal liquids and uranium.

On-Chip Photonic Circuits for Atom-Light Interaction in Quantum Information and Integrated Optical Spectrometer for Astrophotonics

NASA Astrophysics Data System (ADS)

Meng, Yang

Photonic circuits are becoming very promising in many different applications, such as optical amplification, optical switching and wavelength division multiplexing optical networks, lab-on-chip in bioengineering, atom-light interaction in quantum information processing, wavelength selecting and filtering in astronomy, etc. Thanks to major developments in the nanofabrication technology, smaller but more powerful photonic circuits can be made to realize more complex applications. Here we propose two on-chip photonic circuits: one is for atom-light interaction in quantum information, and the other is for an optical spectrometer in astronomy. Part I. The atom-light interaction can be used for a number of quantum based application, such as quantum information processing and atomic sensing. These significant applications make atom-light interaction a strong candidate for next-generation quantum computers and ultraprecise magnetic or navigation sensors. People have proposed various types of atom-photon interaction, and enhancing the interaction by using a small mode area has also been demonstrated in several platforms such as a hollow-core fiber, a hollow-core waveguide, a tapered fiber, and a nanowaveguide. In our work, we propose a nanowaveguide platform for collective atom-light interaction through the evanescent optical field coupling. We have demonstrated a centimeter-long silicon nitride nanowaveguide that has a sub-micrometer mode area and high fiber-to-waveguide coupling efficiencies for near-infrared wavelengths, working as evanescent field atom trapping/probing of an ensemble of 87Rb atoms. Inverse tapers are made at both ends of the waveguide that adiabatically transfer the weakly guided fiber-coupled mode to a strongly guided mode with an evanescent field for a better fiber-waveguide coupling efficiency. The coupling efficiency improves from around 2% to around 80% for both wavelengths. Trapping atoms by nanowaveguide modes is challenging because the small mode area generates high heat flux at the waveguide in an ultra-high vacuum. This platform has good thermal conductance and could transfer high enough optical powers to trap atoms in an ultra-high vacuum compared to a standalone photonic crystal waveguide with no substrate or an evanescent field coupled with a nanofiber. We have experimentally measured the optical absorption of thermal 87Rb atoms through the guided waveguide mode. We have also demonstrated an atom-chip mirror MOT with the same dimension of the platform that can be transferred to the proximity of the surface by magnetic field controls. Part II. In astronomical applications, wavelength analysis is very important especially for the wavelength selecting and filtering. Here we focus on the wavelength range from 1microm to 1.7microm. There are many valuable applications that make this near infrared wavelength range so important. For example, the Lyman-alpha line of hydrogen is one of the very important emission lines of hydrogen for understanding the origin and creation of the universe. Since the universe has expanded for more than 10 billion years after the big bang, the Lyman-alpha line of hydrogen has redshifted from 121.5nm to the 1microm-to-1.7microm wavelength range according to Hubble's Law. In addition, analysis of this wavelength range can also help us understand many other cosmic phenomena such as quasars, Gamma-ray bursts, etc. Therefore, a good spectrometer is needed to achieve this. Here we present an echelle grating which is based on an on-chip spectrometer that covers the near infrared wavelength range from 1.45um to 1.7um. To begin with, we use optical waveguides as the input and output channels. We have successfully achieved a reliable fabrication process to make the on-chip echelle-grating spectrometer. We have also achieved high fiber-waveguide coupling efficiency (94% per facet at 1550nm) and low propagation loss (-0.975dB/cm at 1550nm) for the input and output waveguides. In addition, we have characterized the bending loss of the waveguide. Finally, we have successfully measured the output spectrum of the echelle grating we designed and found it to be in good agreement with our simulation.

Direct Aldehyde C-H Arylation and Alkylation via the Combination of Nickel, Hydrogen Atom Transfer, and Photoredox Catalysis.

PubMed

Zhang, Xiaheng; MacMillan, David W C

2017-08-23

A mechanism that enables direct aldehyde C-H functionalization has been achieved via the synergistic merger of photoredox, nickel, and hydrogen atom transfer catalysis. This mild, operationally simple protocol transforms a wide variety of commercially available aldehydes, along with aryl or alkyl bromides, into the corresponding ketones in excellent yield. This C-H abstraction coupling technology has been successfully applied to the expedient synthesis of the medicinal agent haloperidol.

Hydrogen-Exchange Mass Spectrometry for the Study of Intrinsic Disorder in Proteins

PubMed Central

Balasubramaniam, Deepa; Komives, Elizabeth A.

2012-01-01

Amide hydrogen/deuterium exchange detected by mass spectrometry (HXMS) is seeing wider use for the identification of intrinsically disordered parts of proteins. In this review, we discuss examples of how discovery of intrinsically disordered regions and their removal can aid in structure determination, biopharmaceutical quality control, the characterization of how posttranslational modifications affect weak structuring of disordered regions, the study of coupled folding and binding, and the characterization of amyloid formation. PMID:23099262

In vitro hydrogen production--using energy from the sun.

PubMed

Krassen, Henning; Ott, Sascha; Heberle, Joachim

2011-01-07

Using solar energy to produce molecular hydrogen is a promising way to supply the civilization with clean energy. Nature provides the key components to collect solar energy as well as to reduce protons, scientists have developed mimics of these enzymatic centers and also found new ways to catalyze the same reactions. This perspective article surveys the different components and in particular the various coupling possibilities of a light sensitizer and catalyst. Pros and cons are discussed.

Neutron-scattering spectrum of cesium hydrogen dinitrate

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

Roziere, J.; Berney, C.V.

1976-03-17

The neutron-scattering spectrum of cesium hydrogen dinitrate was obtained in order to complete previously reported structural chemical studies obtained by x-ray diffraction and infrared-Raman spectra. The proton position was of particular interest. Satellite peak intensities suggested proton coupling to motions of the NO/sub 3//sup -/ groups, and therefore not located at the center of the distorted tetrahedron formed by four of the oxygen groups. The precise position of the proton was not established. (DDA)

Complete solution of electronic excitation and ionization in electron-hydrogen molecule scattering

DOE PAGES

Zammit, Mark C.; Savage, Jeremy S.; Fursa, Dmitry V.; ...

2016-06-08

The convergent close-coupling method has been used to solve the electron-hydrogen molecule scattering problem in the fixed-nuclei approximation. Excellent agreement with experiment is found for the grand total, elastic, electronic-excitation, and total ionization cross sections from the very low to the very high energies. This shows that for the electronic degrees of freedom the method provides a complete treatment of electron scattering on molecules as it does for atoms.

Flash hydrogenation of coal

DOEpatents

Manowitz, Bernard; Steinberg, Meyer; Sheehan, Thomas V.; Winsche, Warren E.; Raseman, Chad J.

1976-01-01

A process for the hydrogenation of coal comprising the contacting of powdered coal with hydrogen in a rotating fluidized bed reactor. A rotating fluidized bed reactor suitable for use in this process is also disclosed. The coal residence time in the reactor is limited to less than 5 seconds while the hydrogen contact time is not in excess of 0.2 seconds.

Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals.

PubMed

Tan, Ting; Yang, Xueliang; Krauter, Caroline M; Ju, Yiguang; Carter, Emily A

2015-06-18

The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest.

Ab Initio Calculations of Anharmonic Vibrational Spectroscopy for Hydrogen Fluoride (HF)n (n=3,4) and Mixed Hydrogen Fluoride/Water (HF)n(H20)n (n=1,2,4) Clusters

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Gerber, R. Benny; Kwak, Dochan (Technical Monitor)

2001-01-01

Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n with n=3,4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n=1,2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field (CC-VSCF) method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the MP2 potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Gerber, R. Benny

2002-01-01

Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

Analysis of the control structures for an integrated ethanol processor for proton exchange membrane fuel cell systems

NASA Astrophysics Data System (ADS)

Biset, S.; Nieto Deglioumini, L.; Basualdo, M.; Garcia, V. M.; Serra, M.

The aim of this work is to investigate which would be a good preliminary plantwide control structure for the process of Hydrogen production from bioethanol to be used in a proton exchange membrane (PEM) accounting only steady-state information. The objective is to keep the process under optimal operation point, that is doing energy integration to achieve the maximum efficiency. Ethanol, produced from renewable feedstocks, feeds a fuel processor investigated for steam reforming, followed by high- and low-temperature shift reactors and preferential oxidation, which are coupled to a polymeric fuel cell. Applying steady-state simulation techniques and using thermodynamic models the performance of the complete system with two different control structures have been evaluated for the most typical perturbations. A sensitivity analysis for the key process variables together with the rigorous operability requirements for the fuel cell are taking into account for defining acceptable plantwide control structure. This is the first work showing an alternative control structure applied to this kind of process.

Comparative study of inelastic squared form factors of the vibronic states of B 1Σu+ , C 1Πu , and E F 1Σg+ for molecular hydrogen: Inelastic x-ray and electron scattering

NASA Astrophysics Data System (ADS)

Xu, Long-Quan; Kang, Xu; Peng, Yi-Geng; Xu, Xin; Liu, Ya-Wei; Wu, Yong; Yang, Ke; Hiraoka, Nozomu; Tsuei, Ku-Ding; Wang, Jian-Guo; Zhu, Lin-Fan

2018-03-01

A joint experimental and theoretical investigation of the valence-shell excitations of hydrogen has been performed by the high-resolution inelastic x-ray scattering and electron scattering as well as the multireference single- and double-excitation configuration-interaction method. Momentum-transfer-dependent inelastic squared form factors for the vibronic series belonging to the B 1Σu+ ,C 1Πu , and E F 1Σg+ electronic states of molecular hydrogen have been derived from the inelastic x-ray scattering method at an impact photon energy around 10 keV, and the electron energy-loss spectra measured at an incident electron energy of 1500 eV. It is found that both the present and the previous calculations cannot satisfactorily reproduce the inelastic squared form-factor profiles for the higher vibronic transitions of the B 1Σu+ state of molecular hydrogen, which may be due to the electronic-vibrational coupling for the higher vibronic states. For the C 1Πu state and some vibronic excitations of E F 1Σg+ state, the present experimental results are in good agreement with the present and previous calculations, while the slight differences between the inelastic x-ray scattering and electron energy-loss spectroscopy results in the larger squared momentum-transfer region may be attributed to the increasing role of the higher-order Born terms in the electron-scattering process.

Correlating Nitrile IR Frequencies to Local Electrostatics Quantifies Noncovalent Interactions of Peptides and Proteins.

PubMed

Deb, Pranab; Haldar, Tapas; Kashid, Somnath M; Banerjee, Subhrashis; Chakrabarty, Suman; Bagchi, Sayan

2016-05-05

Noncovalent interactions, in particular the hydrogen bonds and nonspecific long-range electrostatic interactions are fundamental to biomolecular functions. A molecular understanding of the local electrostatic environment, consistently for both specific (hydrogen-bonding) and nonspecific electrostatic (local polarity) interactions, is essential for a detailed understanding of these processes. Vibrational Stark Effect (VSE) has proven to be an extremely useful method to measure the local electric field using infrared spectroscopy of carbonyl and nitrile based probes. The nitrile chemical group would be an ideal choice because of its absorption in an infrared spectral window transparent to biomolecules, ease of site-specific incorporation into proteins, and common occurrence as a substituent in various drug molecules. However, the inability of VSE to describe the dependence of IR frequency on electric field for hydrogen-bonded nitriles to date has severely limited nitrile's utility to probe the noncovalent interactions. In this work, using infrared spectroscopy and atomistic molecular dynamics simulations, we have reported for the first time a linear correlation between nitrile frequencies and electric fields in a wide range of hydrogen-bonding environments that may bridge the existing gap between VSE and H-bonding interactions. We have demonstrated the robustness of this field-frequency correlation for both aromatic nitriles and sulfur-based nitriles in a wide range of molecules of varying size and compactness, including small molecules in complex solvation environments, an amino acid, disordered peptides, and structured proteins. This correlation, when coupled to VSE, can be used to quantify noncovalent interactions, specific or nonspecific, in a consistent manner.

Metabolic interdependencies between phylogenetically novel fermenters and respiratory organisms in an unconfined aquifer

PubMed Central

Wrighton, Kelly C; Castelle, Cindy J; Wilkins, Michael J; Hug, Laura A; Sharon, Itai; Thomas, Brian C; Handley, Kim M; Mullin, Sean W; Nicora, Carrie D; Singh, Andrea; Lipton, Mary S; Long, Philip E; Williams, Kenneth H; Banfield, Jillian F

2014-01-01

Fermentation-based metabolism is an important ecosystem function often associated with environments rich in organic carbon, such as wetlands, sewage sludge and the mammalian gut. The diversity of microorganisms and pathways involved in carbon and hydrogen cycling in sediments and aquifers and the impacts of these processes on other biogeochemical cycles remain poorly understood. Here we used metagenomics and proteomics to characterize microbial communities sampled from an aquifer adjacent to the Colorado River at Rifle, CO, USA, and document interlinked microbial roles in geochemical cycling. The organic carbon content in the aquifer was elevated via acetate amendment of the groundwater occurring over 2 successive years. Samples were collected at three time points, with the objective of extensive genome recovery to enable metabolic reconstruction of the community. Fermentative community members include organisms from a new phylum, Melainabacteria, most closely related to Cyanobacteria, phylogenetically novel members of the Chloroflexi and Bacteroidales, as well as candidate phyla genomes (OD1, BD1-5, SR1, WWE3, ACD58, TM6, PER and OP11). These organisms have the capacity to produce hydrogen, acetate, formate, ethanol, butyrate and lactate, activities supported by proteomic data. The diversity and expression of hydrogenases suggests the importance of hydrogen metabolism in the subsurface. Our proteogenomic data further indicate the consumption of fermentation intermediates by Proteobacteria can be coupled to nitrate, sulfate and iron reduction. Thus, fermentation carried out by previously unknown members of sediment microbial communities may be an important driver of nitrogen, hydrogen, sulfur, carbon and iron cycling. PMID:24621521

Thermodynamic Evaluation of Hydrogen Absorption by Niobium During SRF Fabrication

NASA Astrophysics Data System (ADS)

Ricker, R. E.; Myneni, G. R.

2011-03-01

The properties and performance of the ultra high purity Nb used to fabricate superconducting radio frequency (SRF) particle accelerator cavities have been found to vary with processing conditions. One hypothesis for these variations is that hydrogen, absorbed during processing, is responsible for this behavior. The key assumption behind this hypothesis is that niobium can absorb hydrogen from one or more of the processing environments. This paper reviews work examining the validity of this assumption. It was determined that Nb will spontaneously react with water producing adsorbed atomic hydrogen that is readily absorbed into the metal. The passivating oxide film normally prevents this reaction, but this film is frequently removed during processing and it is attacked by the fluoride ion used in the polishing solutions for SRF cavities. However, during electropolishing that cathodic reduction of hydrogen is transferred to the auxiliary electrode and this should suppress hydrogen absorption.

40 CFR 98.162 - GHGs to report.

Code of Federal Regulations, 2010 CFR

2010-07-01

... GREENHOUSE GAS REPORTING Hydrogen Production § 98.162 GHGs to report. You must report: (a) CO2 process emissions from each hydrogen production process unit. (b) CO2, CH4 and N2O combustion emissions from each hydrogen production process unit. You must calculate and report these combustion emissions under subpart C...

Digestion of Crystalline Silicotitanate (CST)

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

DARREL, WALKER

2004-11-04

Researchers tested methods for chemically dissolving crystalline silicotitanate (CST) as a substitute for mechanical grinding to reduce particle size before vitrification. Testing used the commercially available form of CST, UOP IONSIV(R) IE-911. Reduction of the particle size to a range similar to that of the glass frit used by the Defense Waste Processing Facility (DWPF) could reduce problems with coupling cesium ion exchange to the vitrification process. This study found that IONSIV(R) IE-911 dissolves completely using a combination of acid, hydrogen peroxide, and fluoride ion. Neutralization of the resulting acidic solution precipitates components of the IONSIV(R) IE-911. Digestion requires extremelymore » corrosive conditions. Also, large particles may reform during neutralization, and the initiation and rate of gas generation are unpredictable. Therefore, the method is not recommended as a substitute for mechanical grinding.« less

Sol processing of conjugated carbon nitride powders for thin-film fabrication.

PubMed

Zhang, Jinshui; Zhang, Mingwen; Lin, Lihua; Wang, Xinchen

2015-05-18

The chemical protonation of graphitic carbon nitride (CN) solids with strong oxidizing acids, for example HNO3, is demonstrated as an efficient pathway for the sol processing of a stable CN colloidal suspension, which can be translated into thin films by dip/disperse-coating techniques. The unique features of CN colloids, such as the polymeric matrix and the reversible hydrogen bonding, result in the thin-film electrodes derived from the sol solution exhibiting a high mechanical stability with improved conductivity for charge transport, and thus show a remarkably enhanced photo-electrochemical performance. The polymer system can in principle be broadly tuned by hybridization with desired functionalities, thus paving the way for the application of CN for specific tasks, as exemplified here by coupling with carbon nanotubes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rotationally inelastic cross sections, rates and cooling times for para-H2 +, ortho-D2 + and HD+ in cold helium gas

NASA Astrophysics Data System (ADS)

Vera, Mario Hernández; Schiller, Stephan; Wester, Roland; Gianturco, Francesco Antonio

2017-05-01

In the present work we discuss the dynamical processes guiding the relaxation of the internal rotational energy of three diatomic ions, the para-H2+, the ortho-D2+ and the HD+ in collision with He atoms. The state-changing cross sections and rates for these Molecular Hydrogen Ions (MHIs) are obtained from Close Coupling quantum dynamics calculations and the decay times into their respective ground states are computed by further solving the relevant time-evolution equations. The comparison of the results from the three molecules allows us to obtain a detailed understanding, and a deep insight, on the relative efficiencies of the relaxation processes considered. Contribution to the Topical Issue "Dynamics of Molecular Systems (MOLEC 2016)", edited by Alberto Garcia-Vela, Luis Banares and Maria Luisa Senent.

Survey of hydrogen production and utilization methods. Volume 1: Executive summary

NASA Technical Reports Server (NTRS)

Gregory, D. P.; Pangborn, J. B.; Gillis, J. C.

1975-01-01

The use of hydrogen as a synthetic fuel is considered. Processes for the production of hydrogen are described along with the present and future industrial uses of hydrogen as a fuel and as a chemical feedstock. Novel and unconventional hydrogen-production techniques are evaluated, with emphasis placed on thermochemical and electrolytic processes. Potential uses for hydrogen as a fuel in industrial and residential applications are identified and reviewed in the context of anticipated U.S. energy supplies and demands. A detailed plan for the period from 1975 to 1980 prepared for research on and development of hydrogen as an energy carrier is included.

Charge transfer and ionization in collisions of Si3+ with H from low to high energy

NASA Astrophysics Data System (ADS)

Wang, J. G.; He, B.; Ning, Y.; Liu, C. L.; Yan, J.; Stancil, P. C.; Schultz, D. R.

2006-11-01

Charge transfer processes due to collisions of ground state Si3+(3sS1) ions with atomic hydrogen are investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) and classical-trajectory Monte Carlo (CTMC) methods. The MOCC calculations utilize ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained from Herrero [J. Phys. B 29, 5583 (1996)] which were calculated with a full configuration-interaction method. Total and state-selective single-electron capture cross sections are obtained for collision energies from 0.01eV/u to 1MeV/u . Total and state-selective rate coefficients are also presented for temperatures from 2×103K to 107K . Comparison with existing data reveals that the total CTMC cross sections are in good agreement with the experimental measurements at the higher considered energies and that previous Landau-Zener calculations underestimate the total rate coefficients by a factor of up to two. The CTMC calculations of target ionization are presented for high energies.

Achieving Simultaneous CO2 and H2 S Conversion via a Coupled Solar-Driven Electrochemical Approach on Non-Precious-Metal Catalysts.

PubMed

Ma, Weiguang; Wang, Hong; Yu, Wei; Wang, Xiaomei; Xu, Zhiqiang; Zong, Xu; Li, Can

2018-03-19

Carbon dioxide (CO 2 ) and hydrogen sulfide (H 2 S) are generally concomitant with methane (CH 4 ) in natural gas and traditionally deemed useless or even harmful. Developing strategies that can simultaneously convert both CO 2 and H 2 S into value-added products is attractive; however it has not received enough attention. A solar-driven electrochemical process is demonstrated using graphene-encapsulated zinc oxide catalyst for CO 2 reduction and graphene catalyst for H 2 S oxidation mediated by EDTA-Fe 2+ /EDTA-Fe 3+ redox couples. The as-prepared solar-driven electrochemical system can realize the simultaneous conversion of CO 2 and H 2 S into carbon monoxide and elemental sulfur at near neutral conditions with high stability and selectivity. This conceptually provides an alternative avenue for the purification of natural gas with added economic and environmental benefits. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-08-24

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

Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling.

PubMed

Xu, Jun; Shen, Chao; Zhu, Xiaolei; Zhang, Pengfei; Ajitha, Manjaly J; Huang, Kuo-Wei; An, Zhongfu; Liu, Xiaogang

2016-03-18

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonperturbative Quantum Physics from Low-Order Perturbation Theory.

PubMed

Mera, Héctor; Pedersen, Thomas G; Nikolić, Branislav K

2015-10-02

The Stark effect in hydrogen and the cubic anharmonic oscillator furnish examples of quantum systems where the perturbation results in a certain ionization probability by tunneling processes. Accordingly, the perturbed ground-state energy is shifted and broadened, thus acquiring an imaginary part which is considered to be a paradigm of nonperturbative behavior. Here we demonstrate how the low order coefficients of a divergent perturbation series can be used to obtain excellent approximations to both real and imaginary parts of the perturbed ground state eigenenergy. The key is to use analytic continuation functions with a built-in singularity structure within the complex plane of the coupling constant, which is tailored by means of Bender-Wu dispersion relations. In the examples discussed the analytic continuation functions are Gauss hypergeometric functions, which take as input fourth order perturbation theory and return excellent approximations to the complex perturbed eigenvalue. These functions are Borel consistent and dramatically outperform widely used Padé and Borel-Padé approaches, even for rather large values of the coupling constant.

Cavitand-Based Polyphenols as Highly Reactive Organocatalysts for the Coupling of Carbon Dioxide and Oxiranes.

PubMed

Martínez-Rodríguez, Luis; Otalora Garmilla, Javier; Kleij, Arjan W

2016-04-07

A variety of cavitand-based polyphenols was prepared from cheap and accessible aldehyde and resorcinol/pyrogallol reagents to give the respective resorcin[4]- or pyrogallol[4]arenes. The preorganization of the phenolic units allows intra- and intermolecular hydrogen bond (HB) networks that affect both the reactivity and stability of these HB-donor catalysts. Unexpectedly, we found that the resorcin[4]arenes show cooperative catalysis behavior compared to the parent resorcinol in the catalytic coupling of epoxides and CO2 with a significantly higher turnover. At elevated reaction temperatures, the resorcin[4]arene-based catalyst 3 d displays the best catalytic performance with very high turnover numbers and frequencies, combining increased reactivity and stability compared to pyrogallol, and an ample substrate scope. This type of polyphenol structure thus illustrates the importance of a new, highly competitive organocatalyst design to devise sustainable CO2 conversion processes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of vapor phase hydrogen peroxide sterilization process for spacecraft applications

NASA Technical Reports Server (NTRS)

Rohatgi, N.; Schubert, W.; Knight, J.; Quigley, M.; Forsberg, G.; Ganapathi, G.; Yarbrough, C.; Koukol, R.

2001-01-01

This paper will present test data and discussion on the work we are conducting at JPL to address the following issues: 1) efficacy of sterilization process; 2) diffusion of hydrogen peroxide under sterilization process conditions into hard to reach places; 3) materials and components compatibility with the sterilization process and 4) development of methodology to protect sensitive components from hydrogen peroxide vapor.

Binuclear Phthalocyanines as Model Electrocatalysts for the Reduction of Oxygen.

DTIC Science & Technology

1985-05-01

solution, in which case the final product is Co(II)Pc. Aqueous acid addition (under nitrogen) to Co(I)Pc (in DCB/OH-) yields Co(II)Pc and presumably hydrogen ...little doubt, given the tendency for Co(I) to reduce aqueous acid to hydrogen [101, that hydrogen is produced in this reaction, though it was not proven...reduction occurs in water by a 2-electron process to hydrogen peroxide or a 4-electron process to water. This latter process must be catalysed on a

Hydrogen loss and its improved retention in hydrogen plasma treated a-SiNx:H films: ERDA study with 100 MeV Ag7+ ions

NASA Astrophysics Data System (ADS)

Bommali, R. K.; Ghosh, S.; Khan, S. A.; Srivastava, P.

2018-05-01

Hydrogen loss from a-SiNx:H films under irradiation with 100 MeV Ag7+ ions using elastic recoil detection analysis (ERDA) experiment is reported. The results are explained under the basic assumptions of the molecular recombination model. The ERDA hydrogen concentration profiles are composed of two distinct hydrogen desorption processes, limited by rapid molecular diffusion in the initial stages of irradiation, and as the fluence progresses a slow process limited by diffusion of atomic hydrogen takes over. Which of the aforesaid processes dominates, is determined by the continuously evolving Hydrogen concentration within the films. The first process dominates when the H content is high, and as the H concentration falls below a certain threshold (Hcritical) the irradiation generated H radicals have to diffuse through larger distances before recombining to form H2, thereby significantly bringing down the hydrogen evolution rate. The ERDA measurements were also carried out for films treated with low temperature (300 °C) hydrogen plasma annealing (HPA). The HPA treated films show a clear increase in Hcritical value, thus indicating an improved diffusion of atomic hydrogen, resulting from healing of weak bonds and passivation of dangling bonds. Further, upon HPA films show a significantly higher H concentration relative to the as-deposited films, at advanced fluences. These results indicate the potential of HPA towards improved H retention in a-SiNx:H films. The study distinguishes clearly the presence of two diffusion processes in a-SiNx:H whose diffusion rates differ by an order of magnitude, with atomic hydrogen not being able to diffuse further beyond ∼ 1 nm from the point of its creation.

Realizing controllable graphene nucleation by regulating the competition of hydrogen and oxygen during chemical vapor deposition heating.

PubMed

Zhang, Haoran; Zhang, Yaqian; Zhang, Yanhui; Chen, Zhiying; Sui, Yanping; Ge, Xiaoming; Deng, Rongxuan; Yu, Guanghui; Jin, Zhi; Liu, Xinyu

2016-08-24

Oxygen can passivate Cu surface active sites when graphene nucleates. Thus, the nucleation density is decreased. The CuO/Cu substrate was chosen for graphene domain synthesis in our study. The results indicate that the CuO/Cu substrate is beneficial for large-scale, single-crystal graphene domain synthesis. Graphene grown on the CuO/Cu substrate exhibits fewer nucleation sites than on Cu foils, suggesting that graphene follows an oxygen-dominating growth. Hydrogen treatment via a heating process could weaken the surface oxygen's role in limiting graphene nucleation under the competition of hydrogen and oxygen and could transfer the synthesis of graphene into a hydrogen-dominating growth. However, the competition only exists during the chemical vapor deposition heating process. For non-hydrogen heated samples, oxygen-dominating growth is experienced even though the samples are annealed in hydrogen for a long time after the heating process. With the temperature increases, the role of hydrogen gradually decreases. The balance of hydrogen and oxygen is adjusted by introducing hydrogen gas at a different heating temperatures. The oxygen concentration on the substrate surface is believed to determine the reactions mechanisms based on the secondary ion mass spectrometry test results. This study provides a new method for the controllable synthesis of graphene nucleation during a heating process.

Literature review on pickling inhibitors and cadmium electroplating processes

NASA Technical Reports Server (NTRS)

Elsea, A. R.; Fletcher, E. E.; Groeneveld, T. P.

1969-01-01

Because introduction of hydrogen during bright-cadmium electroplating of high strength steels causes hydrogen-stress cracking, a program was undertaken to evaluate various processes and materials. Report describes effectiveness of inhibitors for reducing hydrogen absorption by steels.

Origins of life systems chemistry

NASA Astrophysics Data System (ADS)

Sutherland, J.

2015-10-01

By reconciling previously conflicting views about the origin of life - in which one or other cellular subsystem emerges first, and then 'invents' the others - a new modus operandi for its study is suggested. Guided by this, a cyanosulfidic protometabolism is uncovered which uses UV light and the stoichiometric reducing power of hydrogen sulfide to convert hydrogen cyanide, and a couple of other prebiotic feedstock molecules which can be derived therefrom, into nucleic acid, peptide and lipid building blocks. Copper plays several key roles in this chemistry, thus, for example, copper(I) catalysed cross coupling and copper(II) driven oxidative crosscoupling reactions generate key feedstock molecules. Geochemical scenarios consistent with this protometabolism are outlined. Finally, the transition of a system from the inanimate to the animate state is considered in the context of there being intermediate stages of partial 'aliveness'.

Evaluation of the Propensity of Niobium to Absorb Hydrogen During Fabrication of Superconducting Radio Frequency Cavities for Particle Accelerators

PubMed Central

Ricker, R. E.; Myneni, G. R.

2010-01-01

During the fabrication of niobium superconducting radio frequency (SRF) particle accelerator cavities procedures are used that chemically or mechanically remove the passivating surface film of niobium pentoxide (Nb2O5). Removal of this film will expose the underlying niobium metal and allow it to react with the processing environment. If these reactions produce hydrogen at sufficient concentrations and rates, then hydrogen will be absorbed and diffuse into the metal. High hydrogen activities could result in supersaturation and the nucleation of hydride phases. If the metal repassivates at the conclusion of the processing step and the passive film blocks hydrogen egress, then the absorbed hydrogen or hydrides could be retained and alter the performance of the metal during subsequent processing steps or in-service. This report examines the feasibility of this hypothesis by first identifying the postulated events, conditions, and reactions and then determining if each is consistent with accepted scientific principles, literature, and data. Established precedent for similar events in other systems was found in the scientific literature and thermodynamic analysis found that the postulated reactions were not only energetically favorable, but produced large driving forces. The hydrogen activity or fugacity required for the reactions to be at equilibrium was determined to indicate the propensity for hydrogen evolution, absorption, and hydride nucleation. The influence of processing conditions and kinetics on the proximity of hydrogen surface coverage to these theoretical values is discussed. This examination found that the hypothesis of hydrogen absorption during SRF processing is consistent with published scientific literature and thermodynamic principles. PMID:27134791

Integrated process and dual-function catalyst for olefin epoxidation

DOEpatents

Zhou, Bing; Rueter, Michael

2003-01-01

The invention discloses a dual-functional catalyst composition and an integrated process for production of olefin epoxides including propylene oxide by catalytic reaction of hydrogen peroxide from hydrogen and oxygen with olefin feeds such as propylene. The epoxides and hydrogen peroxide are preferably produced simultaneously in situ. The dual-functional catalyst comprises noble metal crystallites with dimensions on the nanometer scale (on the order of <1 nm to 10 nm), specially dispersed on titanium silicalite substrate particles. The dual functional catalyst catalyzes both the direct reaction of hydrogen and oxygen to generate hydrogen peroxide intermediate on the noble metal catalyst surface and the reaction of the hydrogen peroxide intermediate with the propylene feed to generate propylene oxide product. Combining both these functions in a single catalyst provides a very efficient integrated process operable below the flammability limits of hydrogen and highly selective for the production of hydrogen peroxide to produce olefin oxides such as propylene oxide without formation of undesired co-products.

Production of hydrogen driven from biomass waste to power Remote areas away from the electric grid utilizing fuel cells and internal combustion engines vehicles

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

Tawfik, Hazem

Recent concerns over the security and reliability of the world’s energy supply has caused a flux towards the research and development of renewable sources. A leading renewable source has been found in the biomass gasification of biological materials derived from organic matters such as wood chips, forest debris, and farm waste that are found in abundance in the USA. Accordingly, there is a very strong interest worldwide in the development of new technologies that provide an in-depth understanding of this economically viable energy source. This work aims to allow the coupling of biomass gasification and fuel cell systems as wellmore » as Internal Combustion Engines (ICE) to produce high-energy efficiency, clean environmental performance and near-zero greenhouse gas emissions. Biomass gasification is a process, which produces synthesis gas (syngas) that contains 19% hydrogen and 20% carbon monoxide from inexpensive organic matter waste. This project main goal is to provide cost effective energy to the public utilizing remote farms’ waste and landfill recycling area.« less

Comparative study of thermochemical processes for hydrogen production from biomass fuels.

PubMed

Biagini, Enrico; Masoni, Lorenzo; Tognotti, Leonardo

2010-08-01

Different thermochemical configurations (gasification, combustion, electrolysis and syngas separation) are studied for producing hydrogen from biomass fuels. The aim is to provide data for the production unit and the following optimization of the "hydrogen chain" (from energy source selection to hydrogen utilization) in the frame of the Italian project "Filiera Idrogeno". The project focuses on a regional scale (Tuscany, Italy), renewable energies and automotive hydrogen. Decentred and small production plants are required to solve the logistic problems of biomass supply and meet the limited hydrogen infrastructures. Different options (gasification with air, oxygen or steam/oxygen mixtures, combustion, electrolysis) and conditions (varying the ratios of biomass and gas input) are studied by developing process models with uniform hypothesis to compare the results. Results obtained in this work concern the operating parameters, process efficiencies, material and energetic needs and are fundamental to optimize the entire hydrogen chain. Copyright 2010 Elsevier Ltd. All rights reserved.

An Approach for Hydrogen Recycling in a Closed-loop Life Support Architecture to Increase Oxygen Recovery Beyond State-of-the-Art

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Miller, Lee; Greenwood, Zachary; Alvarez, Giraldo

2014-01-01

State-of-the-art atmosphere revitalization life support technology on the International Space Station is theoretically capable of recovering 50% of the oxygen from metabolic carbon dioxide via the Carbon Dioxide Reduction Assembly (CRA). When coupled with a Plasma Pyrolysis Assembly (PPA), oxygen recovery increases dramatically, thus drastically reducing the logistical challenges associated with oxygen resupply. The PPA decomposes methane to predominantly form hydrogen and acetylene. Because of the unstable nature of acetylene, a down-stream separation system is required to remove acetylene from the hydrogen stream before it is recycled to the CRA. A new closed-loop architecture that includes a PPA and downstream Hydrogen Purification Assembly (HyPA) is proposed and discussed. Additionally, initial results of separation material testing are reported.

Molecular dynamics studies of electron-ion temperature equilibration in hydrogen plasmas within the coupled-mode regime

DOE PAGES

Benedict, Lorin X.; Surh, Michael P.; Stanton, Liam G.; ...

2017-04-10

Here, we use classical molecular dynamics (MD) to study electron-ion temperature equilibration in two-component plasmas in regimes for which the presence of coupled collective modes has been predicted to substantively reduce the equilibration rate. Guided by previous kinetic theory work, we examine hydrogen plasmas at a density of n = 10 26cm –3, T i = 10 5K, and 10 7 K < Te < 10 9K. The nonequilibrium classical MD simulations are performed with interparticle interactions modeled by quantum statistical potentials (QSPs). Our MD results indicate (i) a large effect from time-varying potential energy, which we quantify by appealingmore » to an adiabatic two-temperature equation of state, and (ii) a notable deviation in the energy equilibration rate when compared to calculations from classical Lenard-Balescu theory including the QSPs. In particular, it is shown that the energy equilibration rates from MD are more similar to those of the theory when coupled modes are neglected. We suggest possible reasons for this surprising result and propose directions of further research along these lines.« less

The (CH2)2O-H2O hydrogen bonded complex. Ab Initio calculations and Fourier transform infrared spectroscopy from neon matrix and a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL.

PubMed

Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebène, B; Alikhani, M E; Georges, R; Moudens, A; Goubet, M; Huet, T R; Pirali, O; Roy, P

2011-03-31

A series of hydrogen bonded complexes involving oxirane and water molecules have been studied. In this paper we report on the vibrational study of the oxirane-water complex (CH(2))(2)O-H(2)O. Neon matrix experiments and ab initio anharmonic vibrational calculations have been performed, providing a consistent set of vibrational frequencies and anharmonic coupling constants. The implementation of a new large flow supersonic jet coupled to the Bruker IFS 125 HR spectrometer at the infrared AILES beamline of the French synchrotron SOLEIL (Jet-AILES) enabled us to record first jet-cooled Fourier transform infrared spectra of oxirane-water complexes at different resolutions down to 0.2 cm(-1). Rovibrational parameters and a lower bound of the predissociation lifetime of 25 ps for the v(OH)(b) = 1 state have been derived from the rovibrational analysis of the ν(OH)(b) band contour recorded at respective rotational temperatures of 12 K (Jet-AILES) and 35 K (LADIR jet).

40 CFR Table 4 to Subpart Ddddd of... - Operating Limits for Boilers and Process Heaters With Hydrogen Chloride Emission Limits

Code of Federal Regulations, 2011 CFR

2011-07-01

... Process Heaters With Hydrogen Chloride Emission Limits 4 Table 4 to Subpart DDDDD of Part 63 Protection of... Heaters With Hydrogen Chloride Emission Limits As stated in § 63.7500, you must comply with the following applicable operating limits: If you demonstrate compliance with applicable hydrogen chloride emission limits...

40 CFR Table 4 to Subpart Ddddd of... - Operating Limits for Boilers and Process Heaters With Hydrogen Chloride Emission Limits

Code of Federal Regulations, 2012 CFR

2012-07-01

... Process Heaters With Hydrogen Chloride Emission Limits 4 Table 4 to Subpart DDDDD of Part 63 Protection of... Heaters With Hydrogen Chloride Emission Limits As stated in § 63.7500, you must comply with the following applicable operating limits: If you demonstrate compliance with applicable hydrogen chloride emission limits...

40 CFR Table 4 to Subpart Ddddd of... - Operating Limits for Boilers and Process Heaters With Hydrogen Chloride Emission Limits

Code of Federal Regulations, 2010 CFR

2010-07-01

... Process Heaters With Hydrogen Chloride Emission Limits 4 Table 4 to Subpart DDDDD of Part 63 Protection of... Heaters With Hydrogen Chloride Emission Limits As stated in § 63.7500, you must comply with the following applicable operating limits: If you demonstrate compliance with applicable hydrogen chloride emission limits...

Hydropyrolysis process

DOEpatents

Ullman, Alan Z.; Silverman, Jacob; Friedman, Joseph

1986-01-01

An improved process for producing a methane-enriched gas wherein a hydrogen-deficient carbonaceous material is treated with a hydrogen-containing pyrolysis gas at an elevated temperature and pressure to produce a product gas mixture including methane, carbon monoxide and hydrogen. The improvement comprises passing the product gas mixture sequentially through a water-gas shift reaction zone and a gas separation zone to provide separate gas streams of methane and of a recycle gas comprising hydrogen, carbon monoxide and methane for recycle to the process. A controlled amount of steam also is provided which when combined with the recycle gas provides a pyrolysis gas for treatment of additional hydrogen-deficient carbonaceous material. The amount of steam used and the conditions within the water-gas shift reaction zone and gas separation zone are controlled to obtain a steady-state composition of pyrolysis gas which will comprise hydrogen as the principal constituent and a minor amount of carbon monoxide, steam and methane so that no external source of hydrogen is needed to supply the hydrogen requirements of the process. In accordance with a particularly preferred embodiment, conditions are controlled such that there also is produced a significant quantity of benzene as a valuable coproduct.

Hydrogen, a potential safeguard for graft-versus-host disease and graft ischemia-reperfusion injury?

PubMed Central

Yuan, Lijuan; Shen, Jianliang

2016-01-01

Post-transplant complications such as graft-versus-host disease and graft ischemia-reperfusion injury are crucial challenges in transplantation. Hydrogen can act as a potential antioxidant, playing a preventive role against post-transplant complications in animal models of multiple organ transplantation. Herein, the authors review the current literature regarding the effects of hydrogen on graft ischemia-reperfusion injury and graft-versus-host disease. Existing data on the effects of hydrogen on ischemia-reperfusion injury related to organ transplantation are specifically reviewed and coupled with further suggestions for future work. The reviewed studies showed that hydrogen (inhaled or dissolved in saline) improved the outcomes of organ transplantation by decreasing oxidative stress and inflammation at both the transplanted organ and the systemic levels. In conclusion, a substantial body of experimental evidence suggests that hydrogen can significantly alleviate transplantation-related ischemia-reperfusion injury and have a therapeutic effect on graft-versus-host disease, mainly via inhibition of inflammatory cytokine secretion and reduction of oxidative stress through several underlying mechanisms. Further animal experiments and preliminary human clinical trials will lay the foundation for hydrogen use as a drug in the clinic. PMID:27652837

Sea water magnesium fuel cell power supply

NASA Astrophysics Data System (ADS)

Hahn, Robert; Mainert, Jan; Glaw, Fabian; Lang, K.-D.

2015-08-01

An environmentally friendly magnesium fuel cell system using seawater electrolyte and atmospheric oxygen was tested under practical considerations for use as maritime power supply. The hydrogen rate and therefore the power density of the system were increased by a factor of two by using hydrogen evolution cathodes with a gas separation membrane instead of submerged cathodes without gas separation. Commercial magnesium AZ31 rolled sheet anodes can be dissolved in seawater for hydrogen production, down to a thickness below 100 μm thickness, resulting in hydrogen generation efficiency of the anode of over 80%. A practical specific energy/energy density of the alloy of more than 1200 Wh/kg/3000 Wh/l was achieved when coupled to a fuel cell with atmospheric air breathing cathode. The performance of several AZ31 alloy anodes was tested as well as the influence of temperature, electrolyte concentration and anode - cathode separation. The excess hydrogen produced by the magnesium hydrogen evolving cell, due to the negative difference effect, is proportional to the cell current in case of the AZ31 alloys, which simplifies system control considerably. Stable long-term operation of the system was demonstrated at low pressures which can be maintained in an open-seawater-submerged hydrogen generator.

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

Hydrogen recovery process

DOEpatents

Baker, Richard W.; Lokhandwala, Kaaeid A.; He, Zhenjie; Pinnau, Ingo

2000-01-01

A treatment process for a hydrogen-containing off-gas stream from a refinery, petrochemical plant or the like. The process includes three separation steps: condensation, membrane separation and hydrocarbon fraction separation. The membrane separation step is characterized in that it is carried out under conditions at which the membrane exhibits a selectivity in favor of methane over hydrogen of at least about 2.5.

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

Wrighton, Kelly C.; Castelle, Cindy; Wilkins, Michael J.

Fermentation-based metabolism is an important ecosystem function often associated with environments rich in organic carbon, such as wetlands, sewage sludge, and the mammalian gut. The diversity of microorganisms and pathways involved in carbon and hydrogen cycling in sediments and aquifers and the impacts of these processes on other biogeochemical cycles remain poorly understood. Here we used metagenomics and proteomics to characterize microbial communities sampled from an aquifer adjacent to the Colorado River at Rifle, Colorado, USA, and document interlinked microbial roles in geochemical cycling. The organic carbon content in the aquifer was elevated via two acetate-based biostimulation treatments. Samples weremore » collected at three time points, with the objective of extensive genome recovery to enable metabolic reconstruction of the community. Fermentative community members include genomes from a new phylum (ACD20), phylogenetically novel members of the Chloroflexi and Bacteroidetes, as well as candidate phyla genomes (OD1, BD1-5, SR1, WWE3, ACD58, TM6, PER, and OP11). These organisms have the capacity to produce hydrogen, acetate, formate, ethanol, butyrate, and lactate, activities supported by proteomic data. The diversity and expression of hydrogenases suggests the importance of hydrogen currency in the subsurface. Our proteogenomic data further indicate the consumption of fermentation intermediates by Proteobacteria can be coupled to nitrate, sulfate, and iron reduction. Thus, fermentation carried out by previously unstudied members of sediment microbial communities may be an important driver of diverse subsurface biogeochemical cycles.« less

Orientation and Order of the Amide Group of Sphingomyelin in Bilayers Determined by Solid-State NMR

PubMed Central

Matsumori, Nobuaki; Yamaguchi, Toshiyuki; Maeta, Yoshiko; Murata, Michio

2015-01-01

Sphingomyelin (SM) and cholesterol (Chol) are considered essential for the formation of lipid rafts; however, the types of molecular interactions involved in this process, such as intermolecular hydrogen bonding, are not well understood. Since, unlike other phospholipids, SM is characterized by the presence of an amide group, it is essential to determine the orientation of the amide and its order in the lipid bilayers to understand the nature of the hydrogen bonds in lipid rafts. For this study, 1′-13C-2-15N-labeled and 2′-13C-2-15N-labeled SMs were prepared, and the rotational-axis direction and order parameters of the SM amide in bilayers were determined based on 13C and 15N chemical-shift anisotropies and intramolecular 13C-15N dipole coupling constants. Results revealed that the amide orientation was minimally affected by Chol, whereas the order was enhanced significantly in its presence. Thus, Chol likely promotes the formation of an intermolecular hydrogen-bond network involving the SM amide without significantly changing its orientation, providing a higher order to the SM amide. To our knowledge, this study offers new insight into the significance of the SM amide orientation with regard to molecular recognition in lipid rafts, and therefore provides a deeper understanding of the mechanism of their formation. PMID:26083921

Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

PubMed

Yin, Li-Chang; Wang, Ping; Kang, Xiang-Dong; Sun, Cheng-Hua; Cheng, Hui-Ming

2007-03-28

Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate.

Cyanobacterial and microcystins dynamics following the application of hydrogen peroxide to waste stabilisation ponds

NASA Astrophysics Data System (ADS)

Barrington, D. J.; Ghadouani, A.; Ivey, G. N.

2013-02-01

Cyanobacteria and cyanotoxins are a risk to human and ecological health, and a hindrance to biological wastewater treatment. This study investigated the use of hydrogen peroxide (H2O2) for the removal of cyanobacteria and cyanotoxins from within waste stabilization ponds (WSPs). The daily dynamics of cyanobacteria and microcystins (a commonly occurring cyanotoxin) were examined following the addition of H2O2 to wastewater within both the laboratory and at the full-scale within a WSP. Hydrogen peroxide treatment at concentrations ≥ 10-4 g H2O2 μg-1 of total phytoplankton chlorophyll a led to the death of cyanobacteria, in turn releasing intracellular microcystins to the dissolved state. In the full-scale trial, dissolved microcystins were then degraded to negligible concentrations by H2O2 and environmental processes within five days. A shift in the phytoplankton assemblage towards beneficial chlorophyta species was also observed within days of H2O2 addition. However, within weeks, the chlorophyta population was significantly reduced by the re-establishment of toxic cyanobacterial species. This re-establishment was likely due to the inflow of cyanobacteria from ponds earlier in the treatment train, suggesting that whilst H2O2 may be a suitable short-term management technique, it must be coupled with control over inflows if it is to improve WSP performance in the longer term.

Low-energy electron scattering from atomic hydrogen. II. Elastic and inelastic scattering

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

James, K.E. Jr.; Childers, J.G.; Khakoo, M.A.

2004-02-01

We present measurements of differential cross sections for elastic electron scattering from atomic hydrogen at 20 eV and 40 eV incident electron energies and ratios of differential cross sections for electron-impact excitation of atomic hydrogen to the n=2, 3, and 4 levels at incident electron energies of 14.6 eV, 15.6 eV, 17.6 eV, 20 eV, 25 eV, and 40 eV with scattering angles ranging from 10 deg. to 130 deg. We compare our results to available experimental measurements and recent convergent close-coupling calculations. Our results resolve significant discrepancies that existed between theory and past experiments.

Defect engineering of two-dimensional WO3 nanosheets for enhanced electrochromism and photoeletrochemical performance

NASA Astrophysics Data System (ADS)

Zhou, Xiaofang; Zheng, Xiaoli; Yan, Bo; Xu, Tao; Xu, Qun

2017-04-01

The capability of introduction of oxygen vacancies in a controlled way has emerged as the heart of modern transition metal oxide semiconductor chemistry. As chemical defects, the oxygen vacancies have been proposed as electron donors, which are prone to increase carrier density and promote charge carrier separation. Herein, we have successfully prepared 2D WO3 ultrathin nanosheets with abundant surface oxygen vacancies by a combination of facile solvothermal reaction and hydrogenation method. The resultant hydrogenated WO3 ultrathin nanosheets exhibit remarkable electrochromism and photocatalytic performances compared with the non-hydrogenated samples, mainly due to their increased oxygen vacancies, narrowed band gap coupled with fast charge transfer and enhanced adsorption of visible light.

Structure and vibrational properties of the dominant O-H center in β-Ga2O3

NASA Astrophysics Data System (ADS)

Weiser, Philip; Stavola, Michael; Fowler, W. Beall; Qin, Ying; Pearton, Stephen

2018-06-01

Hydrogen has a strong influence on the electrical properties of transparent conducting oxides where it can give rise to shallow donors and can passivate deep compensating defects. We have carried out infrared absorption experiments on H- and D-doped β-Ga2O3 that involve temperature- and polarization-dependent effects as well as relative H- and D-concentrations to probe the defect structures that hydrogen can form. The results of analysis of these data, coupled with detailed theoretical calculations, show that the dominant O-H vibrational line observed at 3437 cm-1 for hydrogenated Ga2O3 is due to a relaxed VGa-2H center.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

NASA Astrophysics Data System (ADS)

Matos, Wladiana O.; Menezes, Eveline A.; Gonzalez, Mário H.; Costa, Letícia M.; Trevizan, Lilian C.; Nogueira, Ana Rita A.

2009-06-01

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) micro-vessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 µL. The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe, Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2 4-1 fractional factorial design: 650 W microwave power, 7 min digestion time, 50 µL nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials.

Electron Transport in a Dioxygenase-Ferredoxin Complex: Long Range Charge Coupling between the Rieske and Non-Heme Iron Center

PubMed Central

Jono, Ryota; Shimizu, Kentaro

2016-01-01

Dioxygenase (dOx) utilizes stereospecific oxidation on aromatic molecules; consequently, dOx has potential applications in bioremediation and stereospecific oxidation synthesis. The reactive components of dOx comprise a Rieske structure Cys2[2Fe-2S]His2 and a non-heme reactive oxygen center (ROC). Between the Rieske structure and the ROC, a universally conserved Asp residue appears to bridge the two structures forming a Rieske-Asp-ROC triad, where the Asp is known to be essential for electron transfer processes. The Rieske and ROC share hydrogen bonds with Asp through their His ligands; suggesting an ideal network for electron transfer via the carboxyl side chain of Asp. Associated with the dOx is an itinerant charge carrying protein Ferredoxin (Fdx). Depending on the specific cognate, Fdx may also possess either the Rieske structure or a related structure known as 4-Cys-[2Fe-2S] (4-Cys). In this study, we extensively explore, at different levels of theory, the behavior of the individual components (Rieske and ROC) and their interaction together via the Asp using a variety of density function methods, basis sets, and a method known as Generalized Ionic Fragment Approach (GIFA) that permits setting up spin configurations manually. We also report results on the 4-Cys structure for comparison. The individual optimized structures are compared with observed spectroscopic data from the Rieske, 4-Cys and ROC structures (where information is available). The separate pieces are then combined together into a large Rieske-Asp-ROC (donor/bridge/acceptor) complex to estimate the overall coupling between individual components, based on changes to the partial charges. The results suggest that the partial charges are significantly altered when Asp bridges the Rieske and the ROC; hence, long range coupling through hydrogen bonding effects via the intercalated Asp bridge can drastically affect the partial charge distributions compared to the individual isolated structures. The results are consistent with a proton coupled electron transfer mechanism. PMID:27656882

Repeatable hydrogen generation of 3D microporous nickel membrane using chemical milling

NASA Astrophysics Data System (ADS)

Seo, Keumyoung; Lim, Taekyung; Ju, Sanghyun

2018-05-01

In this study, we investigated a novel method of hydrogen generation through a chemical milling process. In the process of generating hydrogen with a thermochemical water-splitting method using a 3D microporous nickel membrane, the nickel surface is oxidized, leading to a decreased generation of hydrogen gas with time. To regenerate hydrogen from the oxidized catalysts, the oxidized metal surface was easily removed at room temperature, re-exposing a metal surface with abundant oxygen vacancies for continuous hydrogen generation. With this method, ~110 µmol · g‑1 of hydrogen gas was continuously produced per cycle. Since this method enabled us to create a fit state for hydrogen generation without extra heat, light, or electrical energy, it can solve the biggest commercialization challenge: inefficiency because the energy required for hydrogen generation is higher than the energy of the generated hydrogen.

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

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

Ali T-Raissi

The aim of this work was to assess issues of cost, and performance associated with the production and storage of hydrogen via following three feedstocks: sub-quality natural gas (SQNG), ammonia (NH{sub 3}), and water. Three technology areas were considered: (1) Hydrogen production utilizing SQNG resources, (2) Hydrogen storage in ammonia and amine-borane complexes for fuel cell applications, and (3) Hydrogen from solar thermochemical cycles for splitting water. This report summarizes our findings with the following objectives: Technoeconomic analysis of the feasibility of the technology areas 1-3; Evaluation of the hydrogen production cost by technology areas 1; and Feasibility of ammoniamore » and/or amine-borane complexes (technology areas 2) as a means of hydrogen storage on-board fuel cell powered vehicles. For each technology area, we reviewed the open literature with respect to the following criteria: process efficiency, cost, safety, and ease of implementation and impact of the latest materials innovations, if any. We employed various process analysis platforms including FactSage chemical equilibrium software and Aspen Technologies AspenPlus and HYSYS chemical process simulation programs for determining the performance of the prospective hydrogen production processes.« less

Hydrogen storage and phase transformations in Mg-Pd nanoparticles

NASA Astrophysics Data System (ADS)

Callini, E.; Pasquini, L.; Rude, L. H.; Nielsen, T. K.; Jensen, T. R.; Bonetti, E.

2010-10-01

Microstructure refinement and synergic coupling among different phases are currently explored strategies to improve the hydrogen storage properties of traditional materials. In this work, we apply a combination of these methods and synthesize Mg-Pd composite nanoparticles by inert gas condensation of Mg vapors followed by vacuum evaporation of Pd clusters. Irreversible formation of the Mg6Pd intermetallic phase takes place upon vacuum annealing, resulting in Mg/Mg6Pd composite nanoparticles. Their hydrogen storage properties are investigated and connected to the undergoing phase transformations by gas-volumetric techniques and in situ synchrotron radiation powder x-ray diffraction. Mg6Pd transforms reversibly into different Mg-Pd intermetallic compounds upon hydrogen absorption, depending on temperature and pressure. In particular, at 573 K and 1 MPa hydrogen pressure, the metal-hydride transition leads to the formation of Mg3Pd and Mg5Pd2 phases. By increasing the pressure to 5 MPa, the Pd-richer MgPd intermetallic is obtained. Upon hydrogen desorption, the Mg6Pd phase is reversibly recovered. These phase transformations result in a specific hydrogen storage capacity associated with Mg-Pd intermetallics, which attain the maximum value of 3.96 wt % for MgPd and influence both the thermodynamics and kinetics of hydrogen sorption in the composite nanoparticles.

Thermocatalytic process for CO.sub.2-free production of hydrogen and carbon from hydrocarbons

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2011-08-23

A novel process and apparatus are disclosed for sustainable CO.sub.2-free production of hydrogen and carbon by thermocatalytic decomposition (dissociation, pyrolysis, cracking) of hydrocarbon fuels over carbon-based catalysts in the absence of air and/or water. The apparatus and thermocatalytic process improve the activity and stability of carbon catalysts during the thermocatalytic process and produce both high purity hydrogen (at least, 99.0 volume %) and carbon, from any hydrocarbon fuel, including sulfurous fuels. In a preferred embodiment, production of hydrogen and carbon is achieved by both internal and external activation of carbon catalysts. Internal activation of carbon catalyst is accomplished by recycling of hydrogen-depleted gas containing unsaturated and aromatic hydrocarbons back to the reactor. External activation of the catalyst can be achieved via surface gasification with hot combustion gases during catalyst heating. The process and apparatus can be conveniently integrated with any type of fuel cell to generate electricity.

The Effect of Converting to a U.S. Hydrogen Fuel Cell Vehicle Fleet on Emissions and Energy Use

NASA Astrophysics Data System (ADS)

Colella, W. G.; Jacobson, M. Z.; Golden, D. M.

2004-12-01

This study analyzes the potential change in emissions and energy use from replacing fossil-fuel based vehicles with hydrogen fuel cell vehicles. This study examines three different hydrogen production scenarios to determine their resultant emissions and energy usage: hydrogen produced via 1) steam reforming of methane, 2) coal gasification, or 3) wind electrolysis. The atmospheric model simulations require two primary sets of data: the actual emissions associated with hydrogen fuel production and use, and the corresponding reduction in emissions associated with reducing fossil fuel use. The net change in emissions is derived using 1) the U.S. EPA's National Emission Inventory (NEI) that incorporates several hundred categories of on-road vehicles and 2) a Process Chain Analysis (PCA) for the different hydrogen production scenarios. NEI: The quantity of hydrogen-related emission is ultimately a function of the projected hydrogen consumption in on-road vehicles. Data for hydrogen consumption from on-road vehicles was derived from the number of miles driven in each U.S. county based on 1999 NEI data, the average fleet mileage of all on-road vehicles, the average gasoline vehicle efficiency, and the efficiency of advanced 2004 fuel cell vehicles. PCA: PCA involves energy and mass balance calculations around the fuel extraction, production, transport, storage, and delivery processes. PCA was used to examine three different hydrogen production scenarios: In the first scenario, hydrogen is derived from natural gas, which is extracted from gas fields, stored, chemically processed, and transmitted through pipelines to distributed fuel processing units. The fuel processing units, situated in similar locations as gasoline refueling stations, convert natural gas to hydrogen via a combination of steam reforming and fuel oxidation. Purified hydrogen is compressed for use onboard fuel cell vehicles. In the second scenario, hydrogen is derived from coal, which is extracted from mines and chemically processed into a hydrogen rich gas. Hydrogen is transmitted through pipelines to refueling stations. In the third scenario, hydrogen is derived via electrolysis powered by wind-generated electricity that has been transmitted across the country to electrolyzers at distributed hydrogen refueling stations. If hydrogen is produced via the first scenario, total annual U.S. production of carbon dioxide (CO2) could be expected to decrease by approximately 900 million metric tons, or 16 percent of annual U.S. CO2 production from all anthropogenic sources. Under this scenario, compared with the conventional vehicle fleet, a fuel cell vehicle fleet would produce some additional CO2 emissions due to the electric power required for the compression of hydrogen, but less CO2 emissions on the road during vehicle operation. This scenario results in an additional methane leakage of approximately one million metric tons per year, or 4 percent of annual U.S. methane emissions from all anthropogenic sources.

Photosynthetic electron partitioning between [FeFe]-hydrogenase and ferredoxin:NADP+-oxidoreductase (FNR) enzymes in vitro

PubMed Central

Yacoby, Iftach; Pochekailov, Sergii; Toporik, Hila; Ghirardi, Maria L.; King, Paul W.; Zhang, Shuguang

2011-01-01

Photosynthetic water splitting, coupled to hydrogenase-catalyzed hydrogen production, is considered a promising clean, renewable source of energy. It is widely accepted that the oxygen sensitivity of hydrogen production, combined with competition between hydrogenases and NADPH-dependent carbon dioxide fixation are the main limitations for its commercialization. Here we provide evidence that, under the anaerobic conditions that support hydrogen production, there is a significant loss of photosynthetic electrons toward NADPH production in vitro. To elucidate the basis for competition, we bioengineered a ferredoxin-hydrogenase fusion and characterized hydrogen production kinetics in the presence of Fd, ferredoxin:NADP+-oxidoreductase (FNR), and NADP+. Replacing the hydrogenase with a ferredoxin-hydrogenase fusion switched the bias of electron transfer from FNR to hydrogenase and resulted in an increased rate of hydrogen photoproduction. These results suggest a new direction for improvement of biohydrogen production and a means to further resolve the mechanisms that control partitioning of photosynthetic electron transport. PMID:21606330

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Methods for measuring exchangeable protons in glycosaminoglycans.

PubMed

Beecher, Consuelo N; Larive, Cynthia K

2015-01-01

Recent NMR studies of the exchangeable protons of GAGs in aqueous solution, including those of the amide, sulfamate, and hydroxyl moieties, have demonstrated potential for the detection of intramolecular hydrogen bonds, providing insights into secondary structure preferences. GAG amide protons are observable by NMR over wide pH and temperature ranges; however, specific solution conditions are required to reduce the exchange rate of the sulfamate and hydroxyl protons and allow their detection by NMR. Building on the vast body of knowledge on detection of hydrogen bonds in peptides and proteins, a variety of methods can be used to identify hydrogen bonds in GAGs including temperature coefficient measurements, evaluation of chemical shift differences between oligo- and monosaccharides, and relative exchange rates measured through line shape analysis and EXSY spectra. Emerging strategies to allow direct detection of hydrogen bonds through heteronuclear couplings offer promise for the future. Molecular dynamic simulations are important in this effort both to predict and confirm hydrogen bond donors and acceptors.

Design Principles for Nickel/Hydrogen Cells and Batteries

NASA Technical Reports Server (NTRS)

Thaller, Lawrence H.; Manzo, Michelle A.; Gonzalez-Sanabria, Olga D.

1987-01-01

Individual-pressure-vessel (IPV) nickel/hydrogen cells and bipolar batteries developed for use as energy-storage subsystems for satelite applications. Design principles applied draw upon extensive background in separator technology, alkaline-fuel-cell technology and several alkaline-cell technology areas. Principals are rather straightforward applications of capillary-force formalisms, coupled with slowly developing data base resulting from careful post-test analyses. Based on preconceived assumptions relative to how devices work and how to be designed so they display longer cycle lives at deep discharge.

Protonic transport through solitons in hydrogen-bonded systems

NASA Astrophysics Data System (ADS)

Kavitha, L.; Jayanthi, S.; Muniyappan, A.; Gopi, D.

2011-09-01

We offer an alternative route for investigating soliton solutions in hydrogen-bonded (HB) chains. We invoke the modified extended tangent hyperbolic function method coupled with symbolic computation to solve the governing equation of motion for proton dynamics. We investigate the dynamics of proton transfer in HB chains through bell-shaped soliton excitations, which trigger the bio-energy transport in most biological systems. This solitonic mechanism of proton transfer could play functional roles in muscular contraction, enzymatic activity and oxidative phosphorylation.

Biological components and bioelectronic interfaces of water splitting photoelectrodes for solar hydrogen production.

PubMed

Braun, Artur; Boudoire, Florent; Bora, Debajeet K; Faccio, Greta; Hu, Yelin; Kroll, Alexandra; Mun, Bongjin S; Wilson, Samuel T

2015-03-09

Artificial photosynthesis (AP) is inspired by photosynthesis in nature. In AP, solar hydrogen can be produced by water splitting in photoelectrochemical cells (PEC). The necessary photoelectrodes are inorganic semiconductors. Light-harvesting proteins and biocatalysts can be coupled with these photoelectrodes and thus form bioelectronic interfaces. We expand this concept toward PEC devices with vital bio-organic components and interfaces, and their integration into the built environment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

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

Zhou, Li; Maity, Surajit; Abplanalp, Matt

2014-07-20

The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) andmore » n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.« less

Neutron inelastic scattering by amino acids

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

Thaper, C.L.; Sinha, S.K.; Dasannacharya, B.A.

Inelastic neutron scattering experiments on normal, N-deuterated glycine, normal and N-deuterated alanine, L-valine, L-tyrosine and, L-phenylalanine at 100 K, are reported. Coupling of the external modes to different hydrogens is discussed.

Characterization of high-pressure capacitively coupled hydrogen plasmas

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

Nunomura, S.; Kondo, M.

2007-11-01

Capacitively coupled very-high-frequency hydrogen plasmas have been systematically diagnosed in a wide range of a gas pressure from 5 mTorr to 10 Torr. The plasma parameters, ion species, and ion energy distributions (IEDs) are measured using a Langmuir probe, optical emission spectroscopy, and energy filtered mass spectrometer. The measurement results show that the ion species in a hydrogen plasma is determined from ionization channels and subsequent ion-molecule reactions. The ions are dominated by H{sub 2}{sup +} at a less-collisional condition of < or approx. 20 mTorr, whereas those are dominated by H{sub 3}{sup +} at a collisional condition of >more » or approx. 20 mTorr. The IED is determined by both the sheath potential drop and ion-neutral collisions in the plasma sheath. The IED is broadened for a collisional sheath at > or approx. 0.3 Torr and the ion bombardment energy is lowered. For high-pressure discharge operated at {approx_equal}10 Torr, plasmas are characterized by a low electron temperature of {approx_equal}0.8 eV and a low ion bombardment energy of < or approx. 15 eV.« less

Analysis and design of an ultrahigh temperature hydrogen-fueled MHD generator

NASA Technical Reports Server (NTRS)

Moder, Jeffrey P.; Myrabo, Leik N.; Kaminski, Deborah A.

1993-01-01

A coupled gas dynamics/radiative heat transfer analysis of partially ionized hydrogen, in local thermodynamic equilibrium, flowing through an ultrahigh temperature (10,000-20,000 K) magnetohydrodynamic (MHD) generator is performed. Gas dynamics are modeled by a set of quasi-one-dimensional, nonlinear differential equations which account for friction, convective and radiative heat transfer, and the interaction between the ionized gas and applied magnetic field. Radiative heat transfer is modeled using nongray, absorbing-emitting 2D and 3D P-1 approximations which permit an arbitrary variation of the spectral absorption coefficient with frequency. Gas dynamics and radiative heat transfer are coupled through the energy equation and through the temperature- and density-dependent absorption coefficient. The resulting nonlinear elliptic problem is solved by iterative methods. Design of such MHD generators as onboard, open-cycle, electric power supplies for a particular advanced airbreathing propulsion concept produced an efficient and compact 128-MWe generator characterized by an extraction ratio of 35.5 percent, a power density of 10,500 MWe/cu m, and a specific (extracted) energy of 324 MJe/kg of hydrogen. The maximum wall heat flux and total wall heat load were 453 MW/sq m and 62 MW, respectively.

Hydrogen-bonded complexes between dimethyl sulfoxide and monoprotic acids: molecular properties and IR spectroscopy.

PubMed

Belarmino, Márcia K D L; Cruz, Vanessa F; Lima, Nathália B D

2014-11-01

MP2/6-31++G(d,p) and DFT B3LYP/6-31++G(d,p) calculations were performed of the structure, binding energies, and vibrational modes of complexes between dimethyl sulfoxide (DMSO) as a proton acceptor and monoprotic linear acids HX (X = F, Cl, CN) as well as monoprotic carboxylic acids HOOCR (R = -H, -CH3, -C6H5) in 1:1 and 1:2 stoichiometric ratios. The results show that two different structures are possible in the 1:2 ratio: in the first, the DMSO molecule interacts with both acid molecules (leading to a "Y" structure); in the second, the DMSO interacts with only one monoprotic acid. The second structure shows a lower stability per hydrogen bond. The spontaneities of the reactions to form the 1:1 and 1:2 complexes are greatly influenced by the X group of the linear acid. With the exception of HCN, all the reactions are spontaneous. In the 1:2 complexes with Y structure, we observed that the hydrogen atoms of the linear acid are coupled in symmetric and asymmetric modes, while this type of coupling is absent from the other 1:2 complexes.

First-principles study of magnetism, lattice dynamics, and superconductivity in LaFeSiHx

NASA Astrophysics Data System (ADS)

Hung, Linda; Yildirim, Taner

2018-06-01

The structural, electronic, magnetic, and vibrational properties of LaFeSiHx for x between 0 and 1 are investigated using density functional theory calculations. We find that the electronic and magnetic properties are strongly controlled by the hydrogen concentration x in LaFeSiHx. While fully hydrogenated LaFeSiH has a striped antiferromagnetic ground state, the underdoped LaFeSiHx for x ≤0.75 is not magnetic within the virtual crystal approximation or with explicit doping of supercells. The antiferromagnetic configuration breaks the symmetry of Fe d orbitals and increases electron-phonon coupling up to 50 % , especially for modes in the 20-50 meV range that are associated with Fe atomic movement. We find competing nearest and next-nearest-neighbor exchange interactions and significant spin-phonon coupling, qualitatively similar but smaller in magnitude compared those found in LaOFeAs superconductors. Hence, it is likely that the mechanism of superconductivity for LaFeSiHx is, like that of LaOFeAs, also unconventional. We furthermore suggest that LaFeSiHx could be a good proton conductor due to phase stability with a wide range of hydrogen concentrations x <1 .