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Sample records for dynamic hydrogen electrode

  1. A Simple Hydrogen Electrode

    Science.gov (United States)

    Eggen, Per-Odd

    2009-01-01

    This article describes the construction of an inexpensive, robust, and simple hydrogen electrode, as well as the use of this electrode to measure "standard" potentials. In the experiment described here the students can measure the reduction potentials of metal-metal ion pairs directly, without using a secondary reference electrode. Measurements…

  2. A Simple Hydrogen Electrode

    Science.gov (United States)

    Eggen, Per-Odd

    2009-01-01

    This article describes the construction of an inexpensive, robust, and simple hydrogen electrode, as well as the use of this electrode to measure "standard" potentials. In the experiment described here the students can measure the reduction potentials of metal-metal ion pairs directly, without using a secondary reference electrode. Measurements…

  3. The oxidation of tyrosine and tryptophan studied by a molecular dynamics normal hydrogen electrode.

    Science.gov (United States)

    Costanzo, Francesca; Sulpizi, Marialore; Della Valle, Raffaele Guido; Sprik, Michiel

    2011-06-28

    The thermochemical constants for the oxidation of tyrosine and tryptophan through proton coupled electron transfer in aqueous solution have been computed applying a recently developed density functional theory (DFT) based molecular dynamics method for reversible elimination of protons and electrons. This method enables us to estimate the solvation free energy of a proton (H(+)) in a periodic model system from the free energy for the deprotonation of an aqueous hydronium ion (H(3)O(+)). Using the computed solvation free energy of H(+) as reference, the deprotonation and oxidation free energies of an aqueous species can be converted to pK(a) and normal hydrogen electrode (NHE) potentials. This conversion requires certain thermochemical corrections which were first presented in a similar study of the oxidation of hydrobenzoquinone [J. Cheng, M. Sulpizi, and M. Sprik, J. Chem. Phys. 131, 154504 (2009)]. Taking a different view of the thermodynamic status of the hydronium ion, these thermochemical corrections are revised in the present work. The key difference with the previous scheme is that the hydronium is now treated as an intermediate in the transfer of the proton from solution to the gas-phase. The accuracy of the method is assessed by a detailed comparison of the computed pK(a), NHE potentials and dehydrogenation free energies to experiment. As a further application of the technique, we have analyzed the role of the solvent in the oxidation of tyrosine by the tryptophan radical. The free energy change computed for this hydrogen atom transfer reaction is very similar to the gas-phase value, in agreement with experiment. The molecular dynamics results however, show that the minimal solvent effect on the reaction free energy is accompanied by a significant reorganization of the solvent.

  4. A novel three-electrode solid electrolyte hydrogen gas sensor

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Min; Yang, Chunling; Zhang, Yan [Harbin Insitute of Technology, Harbin (China). School of Computer Science and Technology; Jia, Zheng [Harbin Insitute of Technology, Harbin (China). School of Chemical Engineering and Technology

    2013-07-01

    A three-electrode solid electrolyte hydrogen gas sensor is explored in this paper. The sensor utilized phosphotungstic acid as the electrolyte material and adopted platinum, nickel and tungsten as the three-electrode materials respectively. In real applications, platinum was used as the measuring electrode, nickel was used as the adjusting electrode and tungsten was used as the reference electrode. In order to compare the performance of the new sensor with that of the traditional two-electrode sensor, the hydrogen concentrations were adjusted so as to detect the output of the two-electrode sensor and the three-electrode sensor. The dynamic range between the measuring electrode and the reference electrode is about 0.65V and the highest detectable limit is 12% for the three-electrode solid hydrogen gas sensor. While the dynamic range is about 0.25V and and the highest detectable limit is 1% for the two-electrode solid electrolyte gas sensor. The results demonstrate that the three-electrode solid hydrogen gas sensor has a higher resolution and detectable limit than the two-electrode sensor. abstract environment.

  5. Determining Potentials of Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode from Density-Functional-Theory-Based Molecular Dynamics

    Science.gov (United States)

    Le, Jiabo; Iannuzzi, Marcella; Cuesta, Angel; Cheng, Jun

    2017-07-01

    We develop a computationally efficient scheme to determine the potentials of zero charge (PZC) of metal-water interfaces with respect to the standard hydrogen electrode. We calculate the PZC of Pt(111), Au(111), Pd(111) and Ag(111) at a good accuracy using this scheme. Moreover, we find that the interface dipole potentials are almost entirely caused by charge transfer from water to the surfaces, the magnitude of which depends on the bonding strength between water and the metals, while water orientation hardly contributes at the PZC conditions.

  6. Electrochemical hydrogenation of thiophene on SPE electrodes

    Science.gov (United States)

    Huang, Haiyan; Yuan, Penghui; Yu, Ying; Chung, Keng H.

    2017-01-01

    Electrochemical reduction desulfurization is a promising technology for petroleum refining which is environmental friendly, low cost and able to achieve a high degree of automation. Electrochemical hydrogenation of thiophene was performed in a three-electrode system which SPE electrode was the working electrode. The electrochemical desulfurization was studied by cyclic voltammetry and bulk electrolysis with coulometry (BEC) techniques. The results of cyclic voltammetry showed that the electrochemical hydrogenation reduction reaction occurred at -0.4V. The BEC results showed that the currents generated from thiophene hydrogenation reactions increased with temperature. According to Arrhenius equation, activation energy of thiophene electrolysis was calculated and lower activation energy value indicated it was diffusion controlled reaction. From the products of electrolytic reactions, the mechanisms of electrochemical hydrogenation of thiophene were proposed, consisting of two pathways: openingring followed by hydrogenation, and hydrogenation followed by ring opening.

  7. Lightweight Electrode For Nickel/Hydrogen Cell

    Science.gov (United States)

    Britton, Doris L.

    1994-01-01

    Improved substrate for nickel electrode increases specific energy of nickel/hydrogen cell. Consists of 50 percent by weight nickel fiber, 35 percent nickel powder, and 15 percent cobalt powder. Porosity and thickness of nickel electrodes affect specific energy, initial performance, and cycle life of cell. Substrate easily manufactured with much larger porosities than those of heavy-sintered state-of-art nickel substrate.

  8. Electrochemical storage of hydrogen on carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Jurewicz, K.; Frackowiak, E. [ICTE, Poznan University of Technology (Poland); Gautier, S.; Beguin, F. [CRMD, CNRS Universite, 45 - Orleans (France)

    2000-07-01

    Amount of hydrogen reversibly stored on an activated carbon electrode using electro-decomposition of 6 mol.l{sup -1} KOH aqueous solution has been investigated and compared data obtained under a high pressure of dihydrogen (70 bars) at 273 K. In the electrochemical method, 1.5 wt% of hydrogen was released from carbon during the oxidation process, with a well-defined plateau at ca. - 0.5 V vs Hg/HgO. Relatively smaller values were obtained for the sorption ability under a high pressure of gas. This means that the formation of nascent hydrogen during water reduction favours its easy penetration in the carbon nano-structure, even at ambient pressure and temperature. Our results show that not only carbon nano-tubes should be considered for hydrogen reservoir and that low cost materials such as activated carbons could be convenient in appropriate conditions.

  9. Composite Metal-hydrogen Electrodes for Metal-Hydrogen Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Ruckman, M W; Wiesmann, H; Strongin, M; Young, K; Fetcenko, M

    1997-04-01

    The purpose of this project is to develop and conduct a feasibility study of metallic thin films (multilayered and alloy composition) produced by advanced sputtering techniques for use as anodes in Ni-metal hydrogen batteries. The anodes could be incorporated in thin film solid state Ni-metal hydrogen batteries that would be deposited as distinct anode, electrolyte and cathode layers in thin film devices. The materials could also be incorporated in secondary consumer batteries (i.e. type AF(4/3 or 4/5)) which use electrodes in the form of tapes. The project was based on pioneering studies of hydrogen uptake by ultra-thin Pd-capped metal-hydrogen ratios exceeding and fast hydrogen charging and Nb films, these studies suggested that materials with those of commercially available metal hydride materials discharging kinetics could be produced. The project initially concentrated on gas phase and electrochemical studies of Pd-capped niobium films in laboratory-scale NiMH cells. This extended the pioneering work to the wet electrochemical environment of NiMH batteries and exploited advanced synchrotron radiation techniques not available during the earlier work to conduct in-situ studies of such materials during hydrogen charging and discharging. Although batteries with fast charging kinetics and hydrogen-metal ratios approaching unity could be fabricated, it was found that oxidation, cracking and corrosion in aqueous solutions made pure Nb films-and multiiayers poor candidates for battery application. The project emphasis shifted to alloy films based on known elemental materials used for NiMH batteries. Although commercial NiMH anode materials contain many metals, it was found that 0.24 µm thick sputtered Zr-Ni films cycled at least 50 times with charging efficiencies exceeding 95% and [H]/[M] ratios of 0.7-1.0. Multilayered or thicker Zr-Ni films could be candidates for a thin film NiMH battery that may have practical applications as an integrated power source for

  10. Enhanced DNA sequencing performance through edge-hydrogenation of graphene electrodes

    CERN Document Server

    He, Yuhui; Grigoriev, Anton; Ahuja, Rajeev; Long, Shibing; Huo, ZongLiang; Liu, Ming

    2010-01-01

    We propose using graphene electrodes with hydrogenated edges for solid-state nanopore-based DNA sequencing, and perform molecular dynamics simulations in conjunction with electronic transport calculations to explore the potential merits of this idea. The results of our investigation show that, compared to the unhydrogenated system, edge-hydrogenated graphene electrodes facilitate the temporary formation of H-bonds with suitable atomic sites in the translocating DNA molecule. As a consequence, the average conductivity is drastically raised by about 3 orders of magnitude while exhibiting significantly reduced statistical variance. We have furthermore investigated how these results are affected when the distance between opposing electrodes is varied and have identified two regimes: for narrow electrode separation, the mere hindrance due to the presence of protruding hydrogen atoms in the nanopore is deemed more important, while for wider electrode separation, the formation of H-bonds becomes the dominant effect....

  11. A method for making a hydrogen electrode

    Energy Technology Data Exchange (ETDEWEB)

    Ikeyama, M.; Ivaki, T.; Yanagikhara, N.

    1983-09-08

    A metallic grid is pressed to the surface of a foam metallic plate which contains powders of a compound which adsorb H2. The electrode is processed at the powder caking temperature. The electrode has a long service life.

  12. Crystal structure and some dynamic performances of Ti0.25V0.34Dy0.01Cr0.1Ni0.3 hydrogen storage electrode

    Institute of Scientific and Technical Information of China (English)

    Yu Qing Qiao; Min Shou Zhao; Qiu Ming Zhang; Jing Zhai

    2011-01-01

    Crystal structure and some dynamic performances of Ti0.25V0.34Dy0.01Cr0.1Ni0.3 hydrogen storage electrode alloy have been investigated by XRD,FESEM-EDS,TEM and EIS measurements.The result shows that the alloy is mainly composed of V-based solid solution phase with body-centered-cubic structure and mono-crystal Ni3Ti phase with hexagonal structure(Space grope: P63/mmc),and it was first observed as TiNi-based secondary phase.The higher charge transfer resistance,higher apparent activation energy and lower hydrogen diffusion coefficient are reasons for the poor electrochemical activity of the dehydriding kinetics of Ti-V-Cr-Ni hydride alloy.

  13. Hydrogen Adsorption on Pt, Rh and Pt-Rh Electrodes

    Institute of Scientific and Technical Information of China (English)

    贾梦秋; A.M.Meretskyi

    2005-01-01

    The hydrogen adsorption on Pt-Rh alloys in sulfuric acid aqueous solutions was studied by the method of cathode pulses. Hydrogen adsorption on the electrode with all ratio of alloy components (ωRh = 0-100%) is well described by the Temkin logarithmic isotherm. The surface coverage by adsorbed hydrogen at the same potential is decreased with increasing content of rhodium in the system. A linear dependence of adsorption peak potential on the alloy compositions in the case of weakly bonded adsorbed hydrogen is established. Hydrogen adsorption heat as a function of surface coverage for Pt-Rh-electrodes was obtained. The shape of the current-potential curve and position of the weakly bonded hydrogen adsorption on the potential scale are all related to alloy compositions, thus can serve as the basis for the determination surface composition of allovs.

  14. Hydrogen storage alloy electrode; Suiso kyuzo gokin denkyoku

    Energy Technology Data Exchange (ETDEWEB)

    Kato, H.; Shirakawa, R. [The Furukawa Battery Co. Ltd., Fukushima (Japan)

    1997-12-16

    In a previous method of manufacturing of a hydrogen storage alloy electrode incorporated in t nickel-hydrogen battery as an negative electrode, the binding strength among the alloy powder is not so strong and is pulverized and falls off during charge and discharge processes and also it has a problem of lowering of the collecting ability and mechanical strength of the electrode when a large amount of a binder is used in order to prevent the falling off. This invention aims to present a hydrogen storage alloy electrode useful as an negative electrode of a nickel-hydrogen battery which prevents the falling off of the hydrogen storage alloy powder during charge and discharge processes and shows excellent charge and discharge cycle life characteristics for a long period. In this invention, the hydrogen storage alloy powder is bound with a silane coupling agent, more preferably, with a silane coupling agent and a water repellent or/and thickner. A fluorine-containing silane coupling agent is preferred as the silane coupling agent. 6 tabs.

  15. Photoinduced hydrogen-bonding dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Xu, Jinmei

    2016-09-01

    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water.

  16. The electrochemical Peltier heat of the standard hydrogen electrode reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fang Zheng [Chemistry and Chemical Engineering College, Central South University, Changsha 410083 (China)], E-mail: zfang@csu.edu.cn; Wang Shaofen [School of Chemistry and Environmental Engineering, Changsha University of Science and Technology, Changsha 410077 (China); Zhang Zhenghua [Chemistry and Chemical Engineering College, Central South University, Changsha 410083 (China); Qiu Guanzhou [School of Minerals Processing and Bioengineering, Central South University, Changsha 410083 (China)

    2008-07-10

    A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on {phi}{sub 0}* = 0 and {delta}S{sub 0}* = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN){sub 6}{sup 3-}/Fe(CN){sub 6}{sup 4-} system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied.

  17. Development of Hydrogen Electrodes for Alkaline Water Electrolysis

    DEFF Research Database (Denmark)

    Kjartansdóttir, Cecilía Kristín

    will be needed. Producing hydrogen via water electrolysis using surplus, low cost, power from renewables offers the possibility of increased production capacity and load management with no greenhouse emissions. Hydrogen is a valuable energy carrier, which is able to contribute to various forms of energy, such as......, production of electricity via fuel cells, fuel for internal combustion engines or gas turbines, or as a raw material for the production of synthetic fuels via Sabatier or Fischer - Tropsch process. In some situations it may be suitable to simply inject hydrogen into the existing natural gas based...... infrastructure. Alkaline water electrolysis (AWE) is the current standard (stat of the art) for industrial large-scale water electrolysis systems. One of the main criteria for industrial AWE is efficient and durable electrodes. The aim of the present PhD study was to develop electrode materials for hydrogen...

  18. Simulation of electrocatalytic hydrogen production by a bioinspired catalyst anchored to a pyrite electrode.

    Science.gov (United States)

    Zipoli, Federico; Car, Roberto; Cohen, Morrel H; Selloni, Annabella

    2010-06-30

    The possibility of using the active site, the [FeFe](H) cluster, of the bacterial di-iron hydrogenases as a catalyst for hydrogen production from water by electro- or photocatalysis is of current scientific and technological interest. We present here a theoretical study of hydrogen production by a modified [FeFe](H) cluster stably linked to a pyrite electrode immersed in acidified water. We employed state-of-the-art electronic-structure and first-principles molecular-dynamics methods. We found that a stable sulfur link of the cluster to the surface analogous to that linking the cluster to its enzyme environment cannot be made. However, we have discovered a modification of the cluster which does form a stable, tridentate link to the surface. The pyrite electrode readily produces hydrogen from acidified water when functionalized with the modified cluster, which remains stable throughout the hydrogen production cycle.

  19. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Science.gov (United States)

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

    2017-02-28

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

  20. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

  1. Dynamic behavior of ion-selective electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Pungor, E.; Linder, E.; Toth, K.

    1988-01-01

    This book provides a survey of the different techniques employed to study time-dependent processes of ion-selective electrodes. The fundamentals, the impedance field, the polarization field, and the activity step methods are treated in depth with emphasis on the information content of the results provided by the different techniques relevant to the dynamic characteristics of ion-selective electrodes. Within the activity step methods the different theoretical models derived to describe the potential-time function of ion-selective electrodes are critically discussed.

  2. Catalytic hydrogen evolution by polyaminoacids using mercury electrode

    Directory of Open Access Journals (Sweden)

    Marko Živanovič

    2010-12-01

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

  3. Hydrogenation of chalcones using hydrogen permeating through a Pd and palladized Pd electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, M., E-mail: mcgutier@unse.edu.a [INQUINOA - CONICET, Instituto de Ciencias Quimicas, Facultad de Agronomia Agroindustrias, Universidad Nacional de Santiago del Estero, Avda, Belgrano (S) 1912, 4200, Santiago del Estero (Argentina); Nazareno, M.A. [INQUINOA - CONICET, Instituto de Ciencias Quimicas, Facultad de Agronomia Agroindustrias, Universidad Nacional de Santiago del Estero, Avda, Belgrano (S) 1912, 4200, Santiago del Estero (Argentina); Sosa, V. [Departamento de Quimica Organica, Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Agencia postal 4, Casilla 61, 5000, Cordoba (Argentina); Lopez de Mishima, B.A., E-mail: bmishima@unse.edu.a [INQUINOA - CONICET, Instituto de Ciencias Quimicas, Facultad de Agronomia Agroindustrias, Universidad Nacional de Santiago del Estero, Avda, Belgrano (S) 1912, 4200, Santiago del Estero (Argentina); Mishima, H.T. [INQUINOA - CONICET, Instituto de Ciencias Quimicas, Facultad de Agronomia Agroindustrias, Universidad Nacional de Santiago del Estero, Avda, Belgrano (S) 1912, 4200, Santiago del Estero (Argentina)

    2010-08-01

    The hydrogenation of benzalacetone and benzalacetophenone was carried out using atomic hydrogen permeating through a palladium membrane. A two-compartment cell separated by a Pd sheet or a palladized Pd (Pd/Pd black) sheet electrode was employed. The reduction products were identified by (GC) gas chromatography, UV-vis absorption spectroscopy and NMR spectroscopy. The carbon-carbon double bond was hydrogenated and the benzylacetone and benzylacetophenone were obtained as products using palladium catalyst. The current efficiency for hydrogenation reaction increases when the current density for water electrolysis decreases and depends on the initial chalcone concentration. It is over 90% at the concentration of 10 mmol L{sup -1}. The hydrogen absorption and diffusion into and through a palladium membrane electrode has been studied by using an electrochemical impedance spectroscopy method. The impedance results would indicate that the hydrogen permeated through the membrane is consumed by the chalcone during the hydrogenation process keeping as the permeable boundary condition in the outer side of the Pd membrane the hydrogen activity almost zero. The hydrogen entering the metal through an adsorbed state and the rate of hydrogen absorption is diffusion-controlled.

  4. High hydrogen production rate of microbial electrolysis cell (MEC) with reduced electrode spacing.

    Science.gov (United States)

    Cheng, Shaoan; Logan, Bruce E

    2011-02-01

    Practical applications of microbial electrolysis cells (MECs) require high hydrogen production rates and a compact reactor. These goals can be achieved by reducing electrode spacing but high surface area anodes are needed. The brush anode MEC with electrode spacing of 2 cm had a higher hydrogen production rate and energy efficiency than an MEC with a flat cathode and a 1-cm electrode spacing. The maximum hydrogen production rate with a 2 cm electrode spacing was 17.8 m(3)/m(3)d at an applied voltage of E(ap)=1 V. Reducing electrode spacing increased hydrogen production rates at the lower applied voltages, but not at the higher (>0.6 V) applied voltages. These results demonstrate that reducing electrode spacing can increase hydrogen production rate, but that the closest electrode spacing do not necessarily produce the highest possible hydrogen production rates.

  5. The effects of platinum on nickel electrodes in the nickel hydrogen cell

    Science.gov (United States)

    Zimmerman, Albert H.

    1991-01-01

    Interactions of platinum and platinum compounds with the nickel electrode that are possible in the nickel hydrogen cell, where both the nickel electrode and a platinum catalyst hydrogen electrode are in intimate contact with the alkaline electrolyte, are examined. Additionally, a mechanism of nickel cobalt oxyhydroxide formation in NiH2 cells is presented.

  6. Fabrication of a three-electrode battery using hydrogen-storage materials

    Science.gov (United States)

    Roh, Chi-Woo; Seo, Jung-Yong; Moon, Hyung-Seok; Park, Hyun-Young; Nam, Na-Yun; Cho, Sung Min; Yoo, Pil J.; Chung, Chan-Hwa

    2015-04-01

    In this study, an energy storage device using a three-electrode battery is fabricated. The charging process takes place during electrolysis of the alkaline electrolyte where hydrogen is stored at the palladium bifunctional electrode. Upon discharging, power is generated by operating the alkaline fuel cell using hydrogen which is accumulated in the palladium hydride bifunctional electrode during the charging process. The bifunctional palladium electrode is prepared by electrodeposition using a hydrogen bubble template followed by a galvanic displacement reaction of platinum in order to functionalize the electrode to work not only as a hydrogen storage material but also as an anode in a fuel cell. This bifunctional electrode has a sufficiently high surface area and the platinum catalyst populates at the surface of electrode to operate the fuel cell. The charging and discharging performance of the three-electrode battery are characterized. In addition, the cycle stability is investigated.

  7. Dynamics of hydrogen in hydrogenated amorphous silicon

    Indian Academy of Sciences (India)

    Ranber Singh; S Prakash

    2003-07-01

    The problem of hydrogen diffusion in hydrogenated amorphous silicon (a-Si:H) is studied semiclassically. It is found that the local hydrogen concentration fluctuations-induced extra potential wells, if intense enough, lead to the localized electronic states in a-Si:H. These localized states are metastable. The trapping of electrons and holes in these states leads to the electrical degradation of the material. These states also act as recombination centers for photo-generated carriers (electrons and holes) which in turn may excite a hydrogen atom from a nearby Si–H bond and breaks the weak (strained) Si–Si bond thereby apparently enhancing the hydrogen diffusion and increasing the light-induced dangling bonds.

  8. Hydrogen bond dynamics in bulk alcohols

    NARCIS (Netherlands)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S.

    2015-01-01

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics-quantum mechanical simulation have established many intriguing features of hydrogen

  9. Phase Transformation Dynamics in Porous Battery Electrodes

    CERN Document Server

    Ferguson, Todd R

    2014-01-01

    Porous electrodes composed of multiphase active materials are widely used in Li-ion batteries, but their dynamics are poorly understood. Two-phase models are largely empirical, and no models exist for three or more phases. Using a modified porous electrode theory based on non-equilibrium thermodynamics, we show that experimental phase behavior can be accurately predicted from free energy models, without artificially placing phase boundaries or fitting the open circuit voltage. First, we simulate lithium intercalation in porous iron phosphate, a popular two-phase cathode, and show that the zero-current voltage gap, sloping voltage plateau and under-estimated exchange currents all result from size-dependent nucleation and mosaic instability. Next, we simulate porous graphite, the standard anode with three stable phases, and reproduce experimentally observed fronts of color-changing phase transformations. These results provide a framework for physics-based design and control for electrochemical systems with comp...

  10. Preparation and evaluation of cobalt-nickel electrodes for hydrogen production by electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Fakeeha, A.H.; El Aleem, F.A. [King Saud Univ., Riyadh (Saudi Arabia). Dept. of Chemical Engineering

    2002-07-01

    Hydrogen can be produced by splitting water into hydrogen and oxygen through electrolysis. Different metals and combinations of metals have been screened in order to improve electrolysis. In addition, studies have been conducted to improve the methods of preparing electrodes that give lower potential. A cobalt-nickel electrode was used in this study for hydrogen production. The electro-kinetic parameters for such electrodes and its equivalent circuit were discussed. The combined nickel-cobalt electrode prepared by electro-codeposition exhibited significant catalytic activity towards hydrogen evolution from alkaline medium. The best performance was obtained for Ni-Co electrode in KoH solution at 70 degrees C. The electro-chemical impedance measurements and analysis resulted in an equivalent circuit of the present electrode in which a complex phase element was used to account for the complex rough surface of the electrode. The roughness factor of Ni-Co electrode is 31.9 at 70 degrees C. This is in good comparison with similar values of hydrogen evolution electrodes. 17 refs., 5 tabs., 10 figs.

  11. Hydrogen application dynamics and networks

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, E. [Air Liquide Large Industries, Champigny-sur-Marne (France)

    2010-12-30

    The Chemical Industry consumes large volumes of hydrogen as raw material for the manufacture of numerous products (e.g. polyamides and polyurethanes account for 60% of hydrogen demand). The hydrogen demand was in the recent past and will continue to be driven by the polyurethane family. China will host about 60% of new hydrogen needs over the period 2010-2015 becoming the first hydrogen market next year and reaching 25% of market share by 2015 (vs. only 4% in 2001). Air Liquide supplies large volumes of Hydrogen (and other Industrial Gases) to customers by on-site plants and through pipeline networks which offer significant benefits such as higher safety, reliability and flexibility of supply. Thanks to its long term strategy and heavy investment in large units and pipeline networks, Air Liquide is the Industrial Gas leader in most of the world class Petrochemical basins (Rotterdam, Antwerp, US Gulf Coast, Yosu, Caojing,..) (orig.)

  12. Characterization of All Solid State Hydrogen Ion Selective Electrode Based on PVC-SR Hybrid Membranes

    Directory of Open Access Journals (Sweden)

    Yoon-Bo Shim

    2003-06-01

    Full Text Available Hydrogen ion selective membranes formulated with 3140 RTV silicone rubber (SR in PVC were studied to extend the life time of solid state ion sensors through improved membrane adhesion. All solid state hydrogen ion selective electrodes were prepared by incorporation of tridodecyl amine (TDDA as an ionophore, potassium tetrakis[3.5-bis(p-chlorophenylborate (KTpClPB as a lipophilic additive, bis(2-ethylhexyladipate (DOA as a plasticizer. Their linear dynamic range was pH 2.0-11.0 and showed the near Nernstian slope of 55.1±0.2 mV/pH (r=0.999. The ifluences from alkali and alkaline earth metal ions were studied for the response of the final ISE membrane composition. Impedance spectroscopic data showed that the resistance was increased by increasing SR content in PVC. Brewster Angle Microscopy (BAM image showed clear differences according to the SR compositions in PVC. Life time of the all solid state membrane electrode was extended to about 2 months by preparing the membrane with PVC and SR. The standard reference material from NIST (2181 HEPES Free acid and 2182 NaHEPESate was tested for the ISE and it gave good result.

  13. Hydrogen bond dynamics in bulk alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands)

    2015-06-07

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics–quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid—alcohols—has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

  14. Coulometric determination of dissolved hydrogen with a multielectrolytic modified carbon felt electrode-based sensor

    Institute of Scientific and Technical Information of China (English)

    Hiroaki Matsuura; Yosuke Yamawaki; Kosuke Sasaki; Shunichi Uchiyama

    2013-01-01

    A multielectrolytic modified carbon electrode (MEMCE) was fabricated by the electrolytic-oxidation/reduction processes.First,the functional groups containing nitrogen atoms such as amino group were introduced by the electrode oxidation of carbon felt electrode in an ammonium carbamate aqueous solution,and next,this electrode was electroreduced in sulfuric acid.The redox waves between hydrogen ion and hydrogen molecule at highly positive potential range appeared in the cyclic voltammogram obtained by MEMCE.A coulometric cell using MEMCE with a catalytic activity of electrooxidation of hydrogen molecule was constructed and was used for the measurement of dissolved hydrogen.The typical current vs.time curve was obtained by the repetitive measurement of the dissolved hydrogen.These curves indicated that the measurement of dissolved hydrogen was finished completely in a very short time (ca.10sec).A linear relationship was obtained between the electrical charge needed for the electrooxidation process of hydrogen molecule and dissolved hydrogen concentration.This indicates that the developed coulometfic method can be used for the determination of the dissolved hydrogen concentration.

  15. Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

    Energy Technology Data Exchange (ETDEWEB)

    Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

    2006-07-01

    Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

  16. Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

    Directory of Open Access Journals (Sweden)

    Boris Dyatkin

    2015-12-01

    Full Text Available This study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Unlike hydrogenated pores, aminated pores do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.

  17. Effect of preparation method of metal hydride electrode on efficiency of hydrogen electrosorption process

    Energy Technology Data Exchange (ETDEWEB)

    Giza, Krystyna [Czestochowa University of Technology (Poland). Faculty of Production Engineering and Materials Technology; Drulis, Henryk [Trzebiatowski Institute of Low Temperatures and Structure Research PAS, Wroclaw (Poland)

    2016-02-15

    The preparation of negative electrodes for nickel-metal hydride batteries using LaNi{sub 4.3}Co{sub 0.4}Al{sub 0.3} alloy is presented. The constant current discharge technique is employed to determine the discharge capacity, the exchange current density and the hydrogen diffusion coefficient of the studied electrodes. The electrochemical performance of metal hydride electrode is strongly affected by preparation conditions. The results are compared and the advantages and disadvantages of preparation methods of the electrodes are also discussed.

  18. Standard hydrogen electrode and potential of zero charge in density functional calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Björketun, Mårten; Skúlason, Egill

    2011-01-01

    Methods to explicitly account for half-cell electrode potentials have recently appeared within the framework of density functional theory. The potential of the electrode relative to the standard hydrogen electrode is typically determined by subtracting the experimental value of the absolute......) the calculated work function strongly depends on the structure of the water film covering the metal surface. In this paper, we first identify the most accurate experimental reference for the ASHEP by revisiting up-to-date literature, and validate the choice of electron reference level in single-electrode density...

  19. PHOTOCHARGEABLE BEHAVIOR OF HYDROGEN STORAGE ALLOY ELECTRODE MODIFIED WITH TiO_2 NANOPARTICLES

    Institute of Scientific and Technical Information of China (English)

    王改田; 涂江平; 张博; 张文魁; 吴建波; 黄辉

    2004-01-01

    Photochargeable behavior of hydrogen storage alloy electrode modified with TiO_2 nanoparticles(MH/TiO_2) was investigated by measuring its photocharge-discharge characteristics. The results showed the MH/TiO_2 electrode could store light energy photoelectrochemically when it was illuminated. The potential of the MH/TiO_2 electrode could be charged to 0.843 V.The discharge time of the MH/TiO_2 electrode increased with increasing the illuminating time, The mechanism of photochargeable behavior of the MH/T...

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

    Institute of Scientific and Technical Information of China (English)

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

    2005-01-01

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

  1. Long Life Nickel Electrodes for Nickel-Hydrogen Cells: Fiber Substrates Nickel Electrodes

    Science.gov (United States)

    Rogers, Howard H.

    2000-01-01

    Samples of nickel fiber mat electrodes were investigated over a wide range of fiber diameters, electrode thickness, porosity and active material loading levels. Thickness' were 0.040, 0.060 and 0.080 inches for the plaque: fiber diameters were primarily 2, 4, and 8 micron and porosity was 85, 90, and 95%. Capacities of 3.5 in. diameter electrodes were determined in the flooded condition with both 26 and 31% potassium hydroxide solution. These capacity tests indicated that the highest capacities per unit weight were obtained at the 90% porosity level with a 4 micron diameter fiber plaque. It appeared that the thinner electrodes had somewhat better performance, consistent with sintered electrode history. Limited testing with two-positive-electrode boiler plate cells was also carried out. Considerable difficulty with constructing the cells was encountered with short circuits the major problem. Nevertheless, four cells were tested. The cell with 95% porosity electrodes failed during conditioning cycling due to high voltage during charge. Discharge showed that this cell had lost nearly all of its capacity. The other three cells after 20 conditioning cycles showed capacities consistent with the flooded capacities of the electrodes. Positive electrodes made from fiber substrates may well show a weight advantage of standard sintered electrodes, but need considerably more work to prove this statement. A major problem to be investigated is the lower strength of the substrate compared to standard sintered electrodes. Problems with welding of leads were significant and implications that the electrodes would expand more than sintered electrodes need to be investigated. Loading levels were lower than had been expected based on sintered electrode experiences and the lower loading led to lower capacity values. However, lower loading causes less expansion and contraction during cycling so that stress on the substrate is reduced.

  2. Hydrogen ion-selective poly(vinyl chloride) membrane electrode based on a calix[4]arene.

    Science.gov (United States)

    Kuruoğlu, Demet; Canel, Esin; Memon, Shahabuddin; Yilmaz, Mustafa; Kiliç, Esma

    2003-02-01

    A hydrogen ion-selective poly(vinyl chloride) membrane electrode was constructed using 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetracyanomethoxycalix[4]arene as a neutral carrier. The electrode showed an apparent Nernstian response in the 2-11.5 pH range with a slope of 54.0 +/- 0.2 mV/pH at 20 +/- degrees C. This electrode showed a rapid response of the emf to changes in the pH, high ion selectivity with respect to lithium, sodium and potassium, and characteristics similar to those reported for the conventional pH glass membrane electrode. It can be used as a potentiometric indicator electrode in hydrofluoric acid solutions. The effects of iodide, thiocyanate, perchlorate and bromide on the characteristics of the electrode were also considered.

  3. Single electrode dynamic clamp with StdpC.

    Science.gov (United States)

    Samu, David; Marra, Vincenzo; Kemenes, Ildiko; Crossley, Michael; Kemenes, György; Staras, Kevin; Nowotny, Thomas

    2012-10-15

    Dynamic clamp is a powerful approach for electrophysiological investigations allowing researchers to introduce artificial electrical components into target neurons to simulate ionic conductances, chemical or electrotonic inputs or connections to other cells. Due to the rapidly changing and potentially large current injections during dynamic clamp, problematic voltage artifacts appear on the electrode used to inject dynamic clamp currents into a target neuron. Dynamic clamp experiments, therefore, typically use two separate electrodes in the same cell, one for recording membrane potential and one for injecting currents. The requirement for two independent electrodes has been a limiting factor for the use of dynamic clamp in applications where dual recordings of this kind are difficult or impossible to achieve. The recent development of an active electrode compensation (AEC) method has overcome some of these prior limitations, permitting artifact-free dynamic clamp experimentation with a single electrode. Here we describe an AEC method for the free dynamic clamp software StdpC. The AEC component of StdpC is the first such system implemented for the use of non-expert users and comes with a set of semi-automated configuration and calibration procedures that facilitate its use. We briefly introduce the AEC method and its implementation in StdpC and then validate it with an electronic model cell and in two different biological preparations.

  4. Engineered Three-Dimensional Electrodes by HVOF Process for Hydrogen Production

    Science.gov (United States)

    Aghasibeig, Maniya; Moreau, Christian; Dolatabadi, Ali; Wuthrich, Rolf

    2016-12-01

    High velocity oxy-fuel process was used to prepare nickel electrode coatings for hydrogen production by alkaline water electrolysis. To further increase the active surface area of the electrodes, pyramidal fin arrays with two different sizes were deposited on the top surface of the electrodes using mesh screen masks. The surface microstructure, topology and roughness of the coatings were studied using scanning electron microscope, optical microscopy and confocal laser scanning microscopy. Steady-state polarization curves were used to evaluate the electrocatalytic activity of the electrodes. The performance of the electrodes coated using mesh outperformed the electrode deposited without using mesh. In addition, the electrode that was coated using the coarse mesh was characterized with the highest activity with the exchange current density and overpotential values of 9.3 × 10-3 A/cm2 and -306 mV, respectively. Formation of different roughness levels due to the combination of normal and off-normal impact of the coating particles on the surface of the fins was identified as the main factor for the increased activity of this electrode toward the hydrogen evolution reaction.

  5. Hydrogen peroxide biosensor based on electrodeposition of zinc oxide nanoflowers onto carbon nanotubes film electrode

    Institute of Scientific and Technical Information of China (English)

    Hui Ping Bai; Xu Xiao Lu; Guang Ming Yang; Yun Hui Yang

    2008-01-01

    A new amperometric biosensor for hydrogen peroxide was developed based on adsorption of horseradish peroxidase at the glassy carbon electrode modified with zinc oxide nanoflowers produced by electrodeposition onto multi-walled carbon nanotubes (MWNTs) firm. The morphology of the MWNTs/nano-ZnO electrode has been investigated by scanning electron microscopy (SEM), and the electrochemical performance of the electrode has also been studied by amperometric method. The resulting electrode offered an excellent detection for hydrogen peroxide at -0.11 V with a linear response range of 9.9 × 10(-7) to 2.9 × 10(-3) mol/L with a correlation coefficient of 0.991, and response time <5 s. The biosensor displays rapid response and expanded linear response range, and excellent stability.

  6. Flight Weight Design Nickel-Hydrogen Cells Using Lightweight Nickel Fiber Electrodes

    Science.gov (United States)

    Britton, Doris L.; Willis, Bob; Pickett, David F.

    2003-01-01

    The goal of this program is to develop a lightweight nickel electrode for advanced aerospace nickel-hydrogen cells and batteries with improved specific energy and specific volume. The lightweight nickel electrode will improve the specific energy of a nickel-hydrogen cell by >50%. These near-term advanced batteries will reduce power system mass and volume, while decreasing the cost, thus increasing mission capabilities and enabling small spacecraft missions. This development also offers a cost savings over the traditional sinter development methods for fabrication. The technology has been transferred to Eagle-Picher, a major aerospace battery manufacturer, who has scaled up the process developed at NASA GRC and fabricated electrodes for incorporation into flight-weight nickel-hydrogen cells.

  7. Development of a Micro-Fiber Nickel Electrode for Nickel-Hydrogen Cell

    Science.gov (United States)

    Britton, Doris L.

    1996-01-01

    The development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (NiH2) program at the NASA Lewis Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a more efficient and lighter weight electrode for the nickel-hydrogen fuel cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active materials. Initial tests include activation and capacity measurements at different discharge levels followed by half-cell cycle testing at 80 percent depth-of-discharge in a low Earth orbit regime. The electrodes that pass the initial tests are life cycle tested in a boiler plate nickel-hydrogen cell before flightweight designs are built and tested.

  8. Electrochemical characterisation of solid oxide cell electrodes for hydrogen production

    DEFF Research Database (Denmark)

    Bernuy-Lopez, Carlos; Knibbe, Ruth; He, Zeming;

    2011-01-01

    ) in a one-atmosphere set-up. For the oxygen electrode, nano-structured La0.75Sr0.25MnO3 (LSM25) is impregnated into a LSM25/yttria stabilised zirconia (YSZ) composite, whereas for the steam electrode, nano-structured Ni and Ce0.8Gd0.2O2−δ (CGO) is impregnated into a Sr0.94Ti0.9Nb0.10O3−δ (STN) backbone...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-10-27

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

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

    Science.gov (United States)

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

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

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

    Science.gov (United States)

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

    2014-05-01

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

  12. Modeling the Hydrogen Bond within Molecular Dynamics

    Science.gov (United States)

    Lykos, Peter

    2004-01-01

    The structure of a hydrogen bond is elucidated within the framework of molecular dynamics based on the model of Rahman and Stillinger (R-S) liquid water treatment. Thus, undergraduates are exposed to the powerful but simple use of classical mechanics to solid objects from a molecular viewpoint.

  13. Fuel Cell Electrodes for Hydrogen-Air Fuel Cell Assemblies.

    Science.gov (United States)

    The report describes the design and evaluation of a hydrogen-air fuel cell module for use in a portable hydrid fuel cell -battery system. The fuel ... cell module consists of a stack of 20 single assemblies. Each assembly contains 2 electrically independent cells with a common electrolyte compartment

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

    Science.gov (United States)

    Zheng, Jingjing

    2017-08-01

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

  15. The hydrogen evolution reaction on single crystal gold electrode

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-01-15

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

  16. The effect of hydrogen on the morphology of n-type silicon electrodes under electrochemical conditions

    DEFF Research Database (Denmark)

    Goldar, A.; Roser, S.J.; Caruana, D.

    2001-01-01

    We study the electrochemical roughening of a silicon electrode surface during the hydrogen evolution reaction in a fluoride electrolyte using neutron reflection. We demonstrate that as the roughening process modifies the morphology of the silicon surface we can follow the changes by observing...

  17. Flexible Graphene Electrodes for Prolonged Dynamic ECG Monitoring

    Directory of Open Access Journals (Sweden)

    Cunguang Lou

    2016-11-01

    Full Text Available This paper describes the development of a graphene-based dry flexible electrocardiography (ECG electrode and a portable wireless ECG measurement system. First, graphene films on polyethylene terephthalate (PET substrates and graphene paper were used to construct the ECG electrode. Then, a graphene textile was synthesized for the fabrication of a wearable ECG monitoring system. The structure and the electrical properties of the graphene electrodes were evaluated using Raman spectroscopy, scanning electron microscopy (SEM, and alternating current impedance spectroscopy. ECG signals were then collected from healthy subjects using the developed graphene electrode and portable measurement system. The results show that the graphene electrode was able to acquire the typical characteristics and features of human ECG signals with a high signal-to-noise (SNR ratio in different states of motion. A week-long continuous wearability test showed no degradation in the ECG signal quality over time. The graphene-based flexible electrode demonstrates comfortability, good biocompatibility, and high electrophysiological detection sensitivity. The graphene electrode also combines the potential for use in long-term wearable dynamic cardiac activity monitoring systems with convenience and comfort for use in home health care of elderly and high-risk adults.

  18. Formation and Oxidation of Hydrogen Molybdenum Bronze on platinum electrode in sulfuric acid solution

    Institute of Scientific and Technical Information of China (English)

    Jin LU; Jun Hua DU; Wei Shan Li; Jia Mo FU

    2004-01-01

    Hydrogen molybdenum bronze (HxMoO3) can be electrodeposited on platinum and oxidized in two steps to the hydrogen molybdenum bronze with less amount of hydrogen HyMoO3 (yelectrode is cycled from -0.2 to 1.3V (vs. SCE) in 0.05 mol/L Na2MoO4 + 0.5 mol/L H2SO4 solution. During the formation of HxMoO3, the electrochemical reduction of molybdate existing in the form of polymolydate is reversible and is about a five-electron transfer reaction.

  19. Turning cellulose waste into electricity: hydrogen conversion by a hydrogenase electrode.

    Directory of Open Access Journals (Sweden)

    Sergey M Abramov

    Full Text Available Hydrogen-producing thermophilic cellulolytic microorganisms were isolated from cow faeces. Rates of cellulose hydrolysis and hydrogen formation were 0.2 mM L(-1 h(-1 and 1 mM L(-1 h(-1, respectively. An enzymatic fuel cell (EFC with a hydrogenase anode was used to oxidise hydrogen produced in a microbial bioreactor. The hydrogenase electrode was exposed for 38 days (912 h to a thermophilic fermentation medium. The hydrogenase activity remaining after continuous operation under load was 73% of the initial value.

  20. Manganese dioxide graphite composite electrodes: application to the electroanalysis of hydrogen peroxide, ascorbic acid and nitrite.

    Science.gov (United States)

    Langley, Cathryn E; Sljukić, Biljana; Banks, Craig E; Compton, Richard G

    2007-02-01

    The modification of carbon powder with manganese dioxide using a wet impregnation procedure with electrochemical characterisation of the modified powder is described. The process involves saturation of the carbon powder with manganese(II) nitrate followed by thermal treatment at ca. 773 K leading to formation of manganese(IV) oxide on the surface of the carbon powder. The construction of composite electrodes based on manganese dioxide modified carbon powder and epoxy resin is also described, including optimisation of the percentage of the modified carbon powder. Composite electrodes showed attractive performances for electroanalytical applications, proving to be suitable for the electrochemical detection of hydrogen peroxide, ascorbic acid and nitrite ions with limits of detection comparable to the detection limits achieved by other analytical techniques. The results obtained for detection of these analytes, together with composite electrodes flexible design and low cost offers potential application of composite electrodes in biosensors.

  1. The application of hydrogen-palladium electrode for potentiometric acid-base determinations in tetrahydrofuran

    Directory of Open Access Journals (Sweden)

    Jokić Anja B.

    2013-01-01

    Full Text Available The application of the hydrogen-palladium electrode (H2/Pd as the indicator electrode for the determination of relative acidity scale (Es, mV of tetrahydrofuran (THF and the potentiometric titrations of acids in this solvent was investigated. The relative acidity scale tetrahydrofuran was determined from the difference half-neutralization potentials of perchloric acid and tetrabutylammonium hydroxide (TBAH, which were measured by using both H2/Pd-SCE and glass-SCE electrode pairs. The experimentally obtained value of Es scale THF with a H2/Pd-SCE electrode pair was 1155 mV, and those obtained with glass-SCE electrode pair 880 mV. By using a H2/Pd indicator electrode, the individual acids (benzoic acid, palmitic acid, maleic acid, acetyl acetone, α-naphthol and two component acid mixtures (benzoic acid + α-naphthol, palmitic acid + α-naphthol, maleic acid + α-naphthol and maleic acid + ftalic acid were titrated with a standard solution of TBAH. In addition, sodium methylate and potassium hydroxide proved to be very suitable titrating agents for titrating of the individual acids and the acids in mixtures, respectively. The relative error of the determination of acids in mixture was less than 3%. The results are in agreement with those obtained by a conventional glass electrode. The advantages of H2/Pd electrode over a glass electrode in potentiometric acid-base determinations in tetrahydrofuran lie in the following: this electrode gives wider relative acidity scale THF, higher the potential jumps at the titration end-point and relatively fast response time; furthermore, it is very durable, simple to prepare and can be used in the titrations of small volumes. [Projekat Ministarstva nauke Republike Srbije, br.172051

  2. Electrocoagulation of palm oil mill effluent as wastewater treatment and hydrogen production using electrode aluminum.

    Science.gov (United States)

    Nasution, M Ansori; Yaakob, Z; Ali, Ehsan; Tasirin, S M; Abdullah, S R S

    2011-01-01

    Palm oil mill effluent (POME) is highly polluting wastewater generated from the palm oil milling process. Palm oil mill effluent was used as an electrolyte without any additive or pretreatment to perform electrocoagulation (EC) using electricity (direct current) ranging from 2 to 4 volts in the presence of aluminum electrodes with a reactor volume of 20 L. The production of hydrogen gas, removal of chemical oxygen demand (COD), and turbidity as a result of electrocoagulation of POME were determined. The results show that EC can reduce the COD and turbidity of POME by 57 and 62%, respectively, in addition to the 42% hydrogen production. Hydrogen production was also helpful to remove the lighter suspended solids toward the surface. The production of Al(OH)XHO at the aluminum electrode (anode) was responsible for the flocculation-coagulation process of suspended solids followed by sedimentation under gravity. The production of hydrogen gas from POME during EC was also compared with hydrogen gas production by electrolysis of tap water at pH 4 and tap water without pH adjustment under the same conditions. The main advantage of this study is to produce hydrogen gas while treating POME with EC to reduce COD and turbidity effectively.

  3. Hydrogen oxidation on gold electrode in perchloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Sustersic, M.G.; Almeida, N.V.; Von Mengershausen, A.E. [Facultad de Ingenieria y Ciencias Economico Sociales, Universidad Nacional de San Luis, 25 de Mayo N 384, 5730 Villa Mercedes, San Luis (Argentina)

    2010-06-15

    The aim of this research is to study the interface gold/perchloric acid solution in presence of hydrogen. The reactive is generated by H{sup +} ion reduction and by saturating the electrolyte with the gaseous H{sub 2}. No evidence of H{sub 2} dissociative adsorption is found. In special conditions, a strongly adsorbed layer is formed from the atoms diffusing from inside of the metal. The mass transport occurs in three ways: the diffusion of H atoms inwards, the diffusion of H atoms back to the surface and the dissolved H{sub 2} diffusion from the bulk electrolyte to the surface. When dissolved H{sub 2} reacts, the reaction is kinetically controlled when the H{sub 2} partial pressure is high, and it is diffusionally controlled when the reactive partial pressure is low. Above 0.7 V, (measured vs. RHE), the (100) plane surface reconstruction lifts, and the rate determining step is the H diffusion towards inside of the metal, and the current suddenly falls. The Hydrogen redox reaction on gold shows reversibility with respect to the potential when the reactives are the H diffusing outwards of the metal and the H{sup +} ion present in the electrolyte. However, the absolute current values of oxidation and reduction are different because the reactive sources are different. (author)

  4. Progress in the Development of Lightweight Nickel Electrode for Nickel-Hydrogen Cell

    Science.gov (United States)

    Britton, Doris L.

    1999-01-01

    Development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (Ni-H2) program at the NASA Glenn Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a lighter weight electrode for the nickel-hydrogen cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active material. Initial tests include activation and capacity measurements at five different discharge levels, C/2, 1.0 C, 1.37 C, 2.0 C, and 2.74 C. The electrodes are life cycle tested using a half-cell configuration at 40 and 80% depths-of-discharge (DOD) in a low-Earth-orbit regime. The electrodes that pass the initial tests are life cycle-tested in a boiler plate nickel-hydrogen cell before flight weight design are built and tested.

  5. Preparation and evaluation of Ni-Zn electrode for electrolytic hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Fakeeha, A.H.; Abdel-Aleem, F.A. [King Saud Univ., Riyadh (Saudi Arabia). College of Engineering Dept. of Chemical Engineering

    2001-06-01

    An important role in enhancing the economical and technical usage of water electrolysis process is the reduction of the over potential of hydrogen evolution reaction. For this study, the authors electroplated pure Nickel and co-deposited Nickel-Zinc with different loading, to prepare two groups of electrodes. A figure illustrated the over-potential for hydrogen evolution reaction of the prepared electrodes in 1 M KOH solution at 25 Celsius as function of current density. The Nickel-Zinc electrodes gave lower over-potential, as indicated by the Tafel slopes obtained. It was also revealed that as the amount of co-deposited material increased, the over-potential was reduced, within the experimental range. The equivalent circuit for the composite electrode was developed and the roughness factor was calculated from experimental data of alternating current impedance. The explanation for the superiority of the Zinc-Nickel electrode might reside in the high value obtained for the roughness factor. 17 refs., 3 tabs., 6 figs.

  6. The effect of biasing the plasma electrode on hydrogen ion formations in a multicusp ion source

    Energy Technology Data Exchange (ETDEWEB)

    Ego, Hiroyasu; Iwashita, Yoshihisa (Kyoto Univ., Uji (Japan). Inst. for Chemical Research); Takekoshi, Hidekuni

    1992-03-01

    The plasma electrode covered with magnetic cusp fields acting as a magnetic filter was installed in a multicusp ion source. The formation processes of the negative and positive hydrogen ions in this source have been investigated when an electrostatic positive bias is applied to the plasma electrode with respect to the anode chamber. The dominant H[sup -] volume-production process is the recombinational attachment rather than the dissociative attachment when the bias voltage is more than +3V. This recombinational attachment improves the H[sup +] ratio in the extracted positive beam, keeping its current value. (author) 52 refs.

  7. Enhanced hydrogen production of PbTe-PbS/TNAs electrodes modified with ordered mesoporous carbon.

    Science.gov (United States)

    Gao, Shiyuan; Wang, Bin; Liu, Zhongqing

    2017-10-15

    PbTe-PbS/TiO2 nanotube arrays (PbTe-PbS/TNAs) were synthesized by the successive ionic layer adsorption and reaction (SILAR) followed by linear sweep voltammetry (LSV). Using Nafion as a binder, ordered mesoporous carbon was cast on these materials to generate the modified electrodes OMC/PbTe-PbS/TNAs. It was demonstrated that the electrode modification with OMC could enhance the charge transfer between the electrode surface and the electrolyte solution, improve the energy band bending of the electrode/electrolyte interface, increase the active electrochemical surface area of the electrode, and reduce the overpotential of the electrode reactions. Under ambient conditions, the short circuit current density (37.84mAcm(-)(2)) and the active electrochemical surface area (29mFcm(-)(2)) of the OMC/PbTe-PbS/TNAs electrode were 27.49% and 36.79% higher than that of PbTe-PbS/TNAs (29.68mAcm(-)(2) and 21.2mFcm(-)(2)), respectively. A particularly important feature of the OMC modification is that the hot electron extraction capability of the PbTe-PbS/TNAs electrode remained in the new system to provide rapid enhancement of short circuit current density upon increasing temperature. The OMC/PbTe-PbS/TNAs electrode registered a hydrogen generation rate of 11mLcm(2)h(-)(1), with an energy efficiency of 98.79% and a heat efficiency of 43.03% under cell voltage of 1.0V at 55°C. Copyright © 2017 Elsevier Inc. All rights reserved.

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

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

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

    Institute of Scientific and Technical Information of China (English)

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

    2015-01-01

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

  10. Theoretical Research Program on Bio-inspired Inorganic Hydrogen Generating Catalysts and Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Selloni, Annabella; Car, Roberto; Cohen, Morrel H.

    2014-04-17

    In this project, we have successfully designed and characterized a promising biomimetic catalyst/electrode complex, [FeFe]P/FeS2 for producing hydrogen from water. It is comprised of earth-abundant materials and, with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant. The theoretical techniques we have developed and the experience we have gained are broadly applicable for the design and analysis of biomimetic electrochemically active catalysts.

  11. Comparison of lead dioxide and cerium dioxide as mediators for carbon paste electrodes in flow injection-amperometric detection of hydrogen peroxide

    OpenAIRE

    Mihić-Necin, Bojana; Guzsvány, Valéria; Kalcher, Kurt

    2010-01-01

    Carbon paste electrodes (graphite / paraffin oil), bulk-modified with lead dioxide and cerium dioxide, were used as sensors for the amperometric determination of hydrogen peroxide in flow injection analysis. Experimental parameters, such as applied working potential, flow rate of the carrier and injection volume were optimized with a thin-layer flow-through cell. The method was validated with respect to calibration curve, linear dynamic range, detection limit, repeatability and...

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

    Science.gov (United States)

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

    2016-05-11

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

  13. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  14. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-01-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g−1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles. PMID:27270184

  15. Composite metal-hydrogen electrodes for metal-hydrogen batteries. Final report, October 1, 1993--April 15, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Ruckman, M.W.; Strongin, M.; Weismann, H. [and others

    1997-04-01

    The purpose of this project is to develop and conduct a feasibility study of metallic thin films (multilayered and alloy composition) produced by advanced sputtering techniques for use as anodes in Ni-metal hydrogen batteries that would be deposited as distinct anode, electrolyte and cathode layers in thin film devices. The materials could also be incorporated in secondary consumer batteries (i.e. type AF(4/3 or 4/5)) which use electrodes in the form of tapes. The project was based on pioneering studies of hydrogen uptake by ultra-thin Pd-capped Nb films, these studies suggested that materials with metal-hydrogen ratios exceeding those of commercially available metal hydride materials and fast hydrogen charging and discharging kinetics could be produced. The project initially concentrated on gas phase and electrochemical studies of Pd-capped niobium films in laboratory-scale NiMH cells. This extended the pioneering work to the wet electrochemical environment of NiMH batteries and exploited advanced synchrotron radiation techniques not available during the earlier work to conduct in-situ studies of such materials during hydrogen charging and discharging. Although batteries with fast charging kinetics and hydrogen-metal ratios approaching unity could be fabricated, it was found that oxidation, cracking and corrosion in aqueous solutions made pure Nb films and multilayers poor candidates for battery application. The project emphasis shifted to alloy films based on known elemental materials used for NiMH batteries. Although commercial NiMH anode materials contain many metals, it was found that 0.24 {mu}m thick sputtered Zr-Ni films cycled at least 50 times with charging efficiencies exceeding 95% and [H]/[M] ratios of 0.7-1.0. Multilayered or thicker Zr-Ni films could be candidates for a thin film NiMH battery that may have practical applications as an integrated power source for modern electronic devices.

  16. Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

    Directory of Open Access Journals (Sweden)

    Georgios D. Papakonstantinou

    2011-01-01

    Full Text Available The core subject of the present paper represents the interrelated spillover (effusion phenomena both of the primary oxide and the H-adatoms, their theory and practice, causes, appearances and consequences, and evidences of existence, their specific properties, and their alterpolar equilibria and kinetic behavior, structural, and resulting catalytic, and double layer charging features. The aim is to introduce electron conductive and d-d interactive individual and composite (mixed valence hypo-d-oxide compounds, of increased altervalent capacity, or their suboxides (Magnéli phases, as the interactive catalytic supports and therefrom provide (i the strong metal-support interaction (SMSI catalytic effect and (ii dynamic spillover interactive transfer of primary oxides (M-OH and free effusional H-adatoms for further electrode reactions and thereby advance the overall electrocatalytic activity. Since hypo-d-oxides feature the exchange membrane properties, the higher the altervalent capacity, the higher the spillover effect. In fact, altervalent hypo-d-oxides impose spontaneous dissociative adsorption of water molecules and then spontaneously pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic and/or its hydrated state (Pt/W(OH6, responsible for Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3⇔ Pt/W(OH6 and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. Such nanostructured-type electrocatalysts, even of mixed-valence hypo-d-oxide structures (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron conductivity, and nonexchanged initial pure monobronze spillover and catalytic properties. Such a unique electrocatalytic system, as the

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

    Science.gov (United States)

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

    2014-02-01

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

  18. Manufacturing Method of a hydrogen storage electrode. Suiso kyuzo denkyoku no seizo hoho

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, T. (, Hyogo (Japan)); Ishikawa, H.; Miyamura, H.; Kuriyama, N. (, Osaka (Japan)); Takagi, J. (Toyoda Automatic Loom Works, Ltd., Aichi (Japan))

    1990-11-14

    This invention provides a manufacturing method of a hydrogen storage electrode with excellent high discharging ability. In other words, a surface of hydrogen storage alloy powder is porous coated consisting of copper or nickel which is made into a microcapsule; group of this capsule is mix/kneaded with a PTFE powder and the mass is filled in a porous metal or placing between a metal mesh and is then molded under heat and pressure. Amount of coating of copper or nickel is 5-30 weight% of the microcapsule. Amount of PTFE powder is 5-7 weight% of said mixture. Temperature is 300-340 {degrees}C and the pressure is 200-400 kg/cm {sup 2}. According to this invention, the rapid dischargeability of a large square cell consisting of a nickel-hydrogen storage alloy secondary cell is significantly improved. 2 figs.

  19. DEGRADATION BEHAVIORS OF NEW TYPE TiV-BASED HYDROGEN STORAGE ELECTRODE ALLOYS

    Institute of Scientific and Technical Information of China (English)

    X.Z. Sun; Y.F. Zhu; Y. Lin; R. Li; M.X. Gao; H.G. Pan

    2006-01-01

    The degradation behaviors of the TiV-based multiphase hydrogen storage alloy Ti0.8Zr0.2V3.2Mn0.64-Cr0.96Ni1.2 during electrochemical cycling in alkaline electrolyte have been studied by XRD, SEM,EIS and AES measurements. XRD analysis indicates that the alloy consists of a C14-type Laves phase and a V-based solid solution. The lattice parameters of both phases are increased after discharged with cycling, which indicates that more irreversible hydrogen remains not discharged in the alloy. It should be responsible for the decrease of discharge capacity. SEM micrographs show that after 10 electrochemical cycles, a large number of cracks can be observed in the alloy, existing mainly in the V-based solid solution phase. Moreover, after 30 cycles, the alloy particles are obviously pulverized due to the larger expansion and shrinkage of cell volumes during hydrogen absorption and desorption, which induces the fast degradation of the TiV-based hydrogen storage alloys. EIS and AES measurements indicate that some passive oxide film has been formed on the surface of alloy electrode, which has higher charge-transfer resistance, lower hydrogen diffusivity, and less electro-catalytic activity. Therefore it can be concluded that the pulverization and oxidation of the alloy are the main factors responsible for the fast degradation of the TiV-based hydrogen storage alloys.

  20. INTERACTIVE SUPPORTED ELECTROCATALYSTS AND SPILLOVER EFFECT IN ELECTROCATALYSIS FOR HYDROGEN AND OXYGEN ELECTRODE REACTIONS

    Directory of Open Access Journals (Sweden)

    NEDELJKO V. KRSTAJIĆ

    2008-07-01

    Full Text Available The aim of the present paper has been to introduce the electron conductive and d-d-interactive individual and composite hypo-d-oxides of the increased altervalent capacity, or their suboxides (Magneli phases, as catalytic supports and therefrom provide: (i The Strong Metal-Support Interaction (SMSI effect, and (ii the Dynamic spillover interactive transfer of primary oxides (M-OH for further electrode reactions, and thereby advance the overall electrocatalytic activity. The d-band has been pointed out as the bonding, adsorptive and catalytic orbital. In the same context, the phenomenon and significance of the d-d-correlations both in heterogeneous catalysis and electrocatalysis are displayed and inferred. Since hypo-d-oxides feature the exchange membrane properties, the higher the altervalent capacity, the higher the spillover effect. Potentiodynamic experiments have shown that the reversible peak of the primary oxide growth on Pt, Ru and Au supported upon hypo-d-oxides and suboxides becomes distinctly increased in the charge capacity and shifts to remarkably more negative potential values, so that it starts even within the range of H-adatoms desorption, while its reduction extends until and merge with the UPD of hydrogen atoms. With wet tungstenia doped titania supported Pt catalyst in membrane cells these peaks dramatically increase in their charge capacity and reversibly become shrunk with a decreased moisture content in the feeding inert gas mixture, and vice versa. Such distinct potentiodynamic scans, in conjunction with some broaden complementary kinetic electrocatalytic improvements rising from the same hypo-d-oxide and/or suboxide interactive support effects, have been proved to be the best and comparable experimental evidence for the spillover effect of primary oxides.

  1. Electrochemical Peltier heat for the adsorption and desorption of hydrogen on a platinized platinum electrode in sulfuric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Shibata, Shigeo; Sumino, M.P.

    1985-01-01

    The electrochemical Peltier heat for the surface hydrogen process at a pt-Pt electrode in 0.5 M H/sub 2/SO/sub 4/ solution was measured under controlled-potential and controlled-current polarizations using a thick film thermistor electrode. The observed Peltier heat is related to the entropy change of the reversible hydrogen process. In the hydrogen potential region, four stepwise heat changes were observed. These heat changes correspond to the adsorptions of four hydrogen species with different adsorption strengths, respectively. The most weakly bonded hydrogen species Hsub(w) exhibited the largest Peltier heat. This is possibly due to the strong interaction of Hsub(w) with the water molecules of the solvent. Peltier effects for the other three adsorption species are explained in terms of the nature of the adsorption sites where hydrogen atoms adsorb with a different mobility or vibrational movement, resulting in a different entropy. (orig.).

  2. Electrochemical detection of hydrogen peroxide at a waxed graphite electrode modified with platinum-decorated carbon nanotubes

    Institute of Scientific and Technical Information of China (English)

    SHI Qiao-cui; ZENG Wen-fang; ZHU Yunu

    2009-01-01

    Platinum-decorated carbon nanotubes (CNT-Pt) were produced by the chemical reduction method. A novel modified electrode was fabricated by intercalated CNT-Pt in the surface of waxed graphite, which provided excellent electro-catalytic activity and selectivity for both oxidation and reduction of hydrogen peroxide. The current response of the modified electrode for hydrogen peroxide was very rapid and the detection limits in amperometry are 2.5×10-6 mol/L at reduction potential and 4.8×10-6 mol/L at oxidation potential. It was desmonstrated that the electrode with high electro-activity was a suitable basic electrode for preparing enzyme electrode.

  3. Catalase-Based Modified Graphite Electrode for Hydrogen Peroxide Detection in Different Beverages.

    Science.gov (United States)

    Fusco, Giovanni; Bollella, Paolo; Mazzei, Franco; Favero, Gabriele; Antiochia, Riccarda; Tortolini, Cristina

    2016-01-01

    A catalase-based (NAF/MWCNTs) nanocomposite film modified glassy carbon electrode for hydrogen peroxide (H2O2) detection was developed. The developed biosensor was characterized in terms of its bioelectrochemical properties. Cyclic voltammetry (CV) technique was employed to study the redox features of the enzyme in the absence and in the presence of nanomaterials dispersed in Nafion® polymeric solution. The electron transfer coefficient, α, and the electron transfer rate constant, ks , were found to be 0.42 and 1.71 s(-1), at pH 7.0, respectively. Subsequently, the same modification steps were applied to mesoporous graphite screen-printed electrodes. Also, these electrodes were characterized in terms of their main electrochemical and kinetic parameters. The biosensor performances improved considerably after modification with nanomaterials. Moreover, the association of Nafion with carbon nanotubes retained the biological activity of the redox protein. The enzyme electrode response was linear in the range 2.5-1150 μmol L(-1), with LOD of 0.83 μmol L(-1). From the experimental data, we can assess the possibility of using the modified biosensor as a useful tool for H2O2 determination in packaged beverages.

  4. Catalase-Based Modified Graphite Electrode for Hydrogen Peroxide Detection in Different Beverages

    Directory of Open Access Journals (Sweden)

    Giovanni Fusco

    2016-01-01

    Full Text Available A catalase-based (NAF/MWCNTs nanocomposite film modified glassy carbon electrode for hydrogen peroxide (H2O2 detection was developed. The developed biosensor was characterized in terms of its bioelectrochemical properties. Cyclic voltammetry (CV technique was employed to study the redox features of the enzyme in the absence and in the presence of nanomaterials dispersed in Nafion® polymeric solution. The electron transfer coefficient, α, and the electron transfer rate constant, ks, were found to be 0.42 and 1.71 s−1, at pH 7.0, respectively. Subsequently, the same modification steps were applied to mesoporous graphite screen-printed electrodes. Also, these electrodes were characterized in terms of their main electrochemical and kinetic parameters. The biosensor performances improved considerably after modification with nanomaterials. Moreover, the association of Nafion with carbon nanotubes retained the biological activity of the redox protein. The enzyme electrode response was linear in the range 2.5–1150 μmol L−1, with LOD of 0.83 μmol L−1. From the experimental data, we can assess the possibility of using the modified biosensor as a useful tool for H2O2 determination in packaged beverages.

  5. Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sophia, J.; Muralidharan, G., E-mail: muraligru@gmail.com

    2015-10-15

    In this paper, fabrication of glassy carbon electrode (GCE) modified with nano copper particles is discussed. The modified electrode has been tested for the non-enzymatic electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}). The copper nanoparticles (Cu NPs) were prepared employing a simple chemical reduction method. The presence of Cu NPs was confirmed through UV–visible (UV–vis) absorption spectroscopy and X-ray diffraction (XRD) analysis. The size and morphology of the particles were investigated using transmission electron microscopy (TEM). The electrochemical properties of the fabricated sensor were studied via cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical sensor displayed excellent performance features towards H{sub 2}O{sub 2} detection exhibiting wide linear range, low detection limit, swift response time, good reproducibility and stability.

  6. Hydrogen oxidation kinetics on model Pd/C electrodes: Electrochemical impedance spectroscopy and rotating disk electrode study

    Energy Technology Data Exchange (ETDEWEB)

    Pronkin, Sergey N., E-mail: sergey.pronkin@unistra.f [Laboratory of Materials, Surfaces and Catalytic Processes, UMR 7515 of CNRS-UdS-ECPM, 25 rue Becquerel, 67087 Strasbourg (France); Bonnefont, Antoine [Institut de Chimie de Strasbourg, UMR 7177, CNRS-Universite de Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg (France); Ruvinskiy, Pavel S.; Savinova, Elena R. [Laboratory of Materials, Surfaces and Catalytic Processes, UMR 7515 of CNRS-UdS-ECPM, 25 rue Becquerel, 67087 Strasbourg (France)

    2010-03-30

    This work reports on the kinetics of the hydrogen oxidation reaction (HOR) on model Pd nanoparticles supported on a low surface area carbon substrate. Two Pd/C samples, with the average particle size 2.6 and 4.0 nm were used. The structure of the catalysts was characterized with the ex situ (electron microscopy) and in situ (electrochemical) methods. We utilized the electrochemical impedance spectroscopy (EIS) and the rotating disk electrode (RDE) voltammetry to study the kinetics of the HOR on Pd/C. The relevance of these techniques for elucidating the kinetics and the mechanism of the HOR on Pd/C was explored. The experimental results suggest that the catalytic activity of Pd in the HOR is more than 2 orders of magnitude lower than that of Pt, and does not depend on the particle size in the range from 2.6 to 4.0 nm. Computational modeling of the experimental steady-state (RDE) and non-steady-state (EIS) data shows that the reaction kinetics can be adequately described within Heyrovsky-Volmer mechanism, with the rate constants upsilon{sub 0H} = (8.8 +- 1.5) x 10{sup -10} mol cm{sup -2} s{sup -1} and upsilon{sub 0V} = (1.0 +- 0.3) x 10{sup -8} mol cm{sup -2} s{sup -1}. The model suggests that underpotentially deposited hydrogen H{sub UPD} is unlikely to be the active intermediate H{sub ad} of the HOR. It is concluded that the surface coverage of H{sub ad} deviates from that of H{sub UPD} with increasing overpotential, and the lateral interactions within H{sub ad} adlayer are weak.

  7. A solid-contact pH-selective electrode based on tridodecylamine as hydrogen neutral ionophore

    Science.gov (United States)

    Zhang, Jianxin; Guo, Yixuan; Li, Shangjin; Xu, Hui

    2016-10-01

    The solid-state pH electrode has the potential possibility to be used in many extreme situations with satisfactory accuracy and low cost. But its performance is affected by the solid electrolyte, preparation process, and the structure of the sensitive membrane, etc. In this work, the relationships between these factors and the characteristic of the prepared electrode were verified by controlling the preparation conditions with a variety of electrochemical methods. Firstly, the solid electrolyte poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) was electrochemically deposited on the screen-printed carbon electrode (SPCE) substrate by a potentiostatic method in an aqueous solution containing 0.01 M 3,4-ethylenedioxythiophene (EDOT) and 0.1 M polystyrene sulfonic (PSS) acid as the supporting electrolyte. The PEDOT films were then characterized by cyclic voltammetry (CV) in the 0.1 M NaNO3 aqueous solution in order to obtain the optimized polymerization potential and charges where the PEDOT film would have a higher redox capacitance. Finally, the pH electrode was prepared by coating the SPCE/PEDOT(PSS) with a plasticized polyvinyl chloride (PVC) membrane containing tridodecylamine as hydrogen ionophore manually, and experiments were carried out to study the effect of the usage of PVC per square millimeter on the response time and stability of the electrode to optimize the PVC film thickness. The potentiometric response of the pH electrode was studied in the buffer solutions with pH ranging from 5.00 to 10.81 by the open-circuit potential (OCP) method. Experimental results show that the sensitivity of the electrode is  -55.7  ±  0.5 mV pH-1 (r 2  >  0.9980) at room temperature (24  ±  1 °C) with pH ranging from 2.00-10.50, approximating to the theoretical nernstian slope (-59.16 mV pH-1),and the response time was less than 10 s. Moreover, it has low impedance, high accuracy and potential stability as well as some

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

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

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

  9. A microbial fluidized electrode electrolysis cell (MFEEC) for enhanced hydrogen production

    KAUST Repository

    Liu, Jia

    2014-12-01

    A microbial fluidized electrode electrolysis cell (MFEEC) was used to enhance hydrogen gas production from dissolved organic matter. Flowable granular activated carbon (GAC) particles were used to provide additional surface area for growth of exoelectrogenic bacteria. The use of this exoelectrogenic biofilm on the GAC particles with fluidization produced higher current densities and hydrogen gas recoveries than controls (no recirculation or no GAC), due to intermittent contact of the capacitive particles with the anode. The total cumulative charge of 1688C m-2 with the MFEEC reactor (a recirculation flow rate of 19 mL min-1) was 20% higher than that of the control reactor (no GAC). The highest hydrogen gas yield of 0.82 ± 0.01 mol-H2/mol-acetate (17 mL min-1) was 39% higher than that obtained without recirculation (0.59 ± 0.01 mol-H 2/mol-acetate), and 116% higher than that of the control (no GAC, without recirculation). These results show that flowable GAC particles provide a useful approach for enhancing hydrogen gas production in bioelectrochemical systems. © 2014 Elsevier B.V. All rights reserved.

  10. A microbial fluidized electrode electrolysis cell (MFEEC) for enhanced hydrogen production

    Science.gov (United States)

    Liu, Jia; Zhang, Fang; He, Weihua; Yang, Wulin; Feng, Yujie; Logan, Bruce E.

    2014-12-01

    A microbial fluidized electrode electrolysis cell (MFEEC) was used to enhance hydrogen gas production from dissolved organic matter. Flowable granular activated carbon (GAC) particles were used to provide additional surface area for growth of exoelectrogenic bacteria. The use of this exoelectrogenic biofilm on the GAC particles with fluidization produced higher current densities and hydrogen gas recoveries than controls (no recirculation or no GAC), due to intermittent contact of the capacitive particles with the anode. The total cumulative charge of 1688C m-2 with the MFEEC reactor (a recirculation flow rate of 19 mL min-1) was 20% higher than that of the control reactor (no GAC). The highest hydrogen gas yield of 0.82 ± 0.01 mol-H2/mol-acetate (17 mL min-1) was 39% higher than that obtained without recirculation (0.59 ± 0.01 mol-H2/mol-acetate), and 116% higher than that of the control (no GAC, without recirculation). These results show that flowable GAC particles provide a useful approach for enhancing hydrogen gas production in bioelectrochemical systems.

  11. Amperometric Biosensor for Hydrogen Peroxide Based on Electrodeposited Sub-micrometer Gold Modified Glassy Carbon Electrode

    Institute of Scientific and Technical Information of China (English)

    WANG,Shu-Qing(王树青); CHEN,Jun(陈峻); LIN,Xiang-Qin(林祥钦)

    2004-01-01

    A new type of hydrogen peroxide amperometric biosensor was fabricated based on electrochemically deposited sub-micrometer Au particles(sm-Au)on a glassy carbon electrode(GCE).Electrochemical deposition condition was optimized for obtaining uniformly distributed sub-micrometer sized Au array on the electrode surface.The hydrogen peroxide sensor was fabricated by adsorbing phenothiazine methylene blue(MB)molecules on the surface of sm-Au and covering a cross-linked horseradish peroxidase(HRP)layer,labeled as HRP/MB/sm-Au/GCE.The characteristics of this biosensor were evaluated with respect to applied potential and pH.The amperometric response of the sensor was linear to the H2O2 concentration over a wide range of 9.9×10-6-1.11×10-2 mol/L.A detection limit(s/n=3)of 3.0×10-6 mol/L H2O2 was estimated for a sampled chronoamperometric detection at 1.5 min after potential step of 200 to-400 mV vs.SCE.The immobilized MB molecules shuttled electrons at(=0.77 and an apparent electron transfer rate constant of =0.053 s-1.Interference of ascorbic acid,dopamine and uric acid was investigated.This sensor has very good stability and reproducibility for long-term use.

  12. Measurements and modelling of hydrogen dynamics in tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Johannes [Max-Planck-Institut fuer Plasmaphysik, Boltzmannstr. 2, D-85748 Garching (Germany); Technische Universitaet Muenchen, James-Franck-Str. 1, D-85748 Garching (Germany); Schwarz-Selinger, Thomas; Schmid, Klaus; Toussaint, Udo von; Jacob, Wolfgang [Max-Planck-Institut fuer Plasmaphysik, Boltzmannstr. 2, D-85748 Garching (Germany)

    2015-05-01

    Although hydrogen retention in defect free tungsten is low it can be significantly altered by plasma wetting. Thus understanding the interaction and dynamics of hydrogen in tungsten becomes an important issue. Present understanding distinguishes between solute and trapped hydrogen inventory. The solute hydrogen is located in the tetrahedral interstitial sites of bbc tungsten and can diffuse rapidly due to the low activation energy of 0.2-0.4 eV. The trapped hydrogen inventory resides at defects like vacancies, grain boundaries or dislocations, with de-trapping energies between 0.8-2.0 eV and is therefore less mobile. Common ex-situ experiments only allow the investigation of hydrogen retained in traps, while the solute is out of experimental reach due to its fast out-gassing at ambient temperatures. In this study the dynamics of the solute hydrogen in tungsten is measured in-situ for the first time. Diffusion/trapping simulations reveal that for low temperature e.g. 200 K, the solute hydrogen dominates the total inventory and its out-gassing after implantation is slowed down to the timescale of hours. Therefore in-situ hydrogen implantation and nuclear reaction analysis of tungsten samples are conducted at temperatures down to 140 K investigating experimentally the dynamics of solute hydrogen.

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

    Institute of Scientific and Technical Information of China (English)

    黄令; 杨防祖; 孙世刚; 许书楷; 周绍民

    2003-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1991-10-01

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

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

    Science.gov (United States)

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

    2017-09-19

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

  16. Electrodeposition of Silver Nanoparticles on MWCNT Film Electrodes for Hydrogen Peroxide Sensing

    Institute of Scientific and Technical Information of China (English)

    DING,Yan-Feng; JIN,Guan-Ping; YIN,Jun-Guang

    2007-01-01

    Silver (Ag) nanoparticles were directly electrodeposited on multi-walled carbon nanotubes (MWCNT) in AgNO3/LiNO3 containing EDTA (ethylenediaminetetraacetic acid). The structure and nature of the resulting Ag/MWNT composite were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and the distribution shape of Ag nanoparticles was found to be dependent on the presence of EDTA. The modified electrode showed excellent electrocatalytic activity to redox reaction of hydrogen peroxide and the mechanism of hydrogen peroxide was partly reversible procession with oxidation and reduction peaks at 0.77 and -0.83 V, respectively. The oxidation and reduction peak currents were linearly related to hydrogen peroxide concentration in the range of 1×10-6-3×10-4 and 1×10-8-7×10-4 mol·L-1 with correlation coefficients of 0.996 and 0.986, and 3s-detection limit of 9 × 10-7 and 7 × 10-9 mol·L-1.

  17. Preparation of Pt/polypyrrole-para toluene sulfonate hydrogen peroxide sensitive electrode for the utilizing as a biosensor.

    Science.gov (United States)

    Çete, Servet; Bal, Özgür

    2013-12-01

    A film electrode with electropolymerization of pyrrole (Py) and para-toluene sulfonate (pTS) as a anionic dopant is prepared and its sensitivity to hydrogen peroxide is investigated. The polypyrrole is deposited on a 0.5 cm(2) Pt plate an electrochemically prepared pTS ion-doped polypyrrole film by scanning the electrode potential between - 0.8 and + 0.8 V at a scan rate of 20 mV/s. The electrode's sensitivity to hydrogen peroxide is investigated at room temperature using 0.1 M phosphate buffer at pH 7.5. The working potential is found as a 0.3 V. The concentrations of pyrrole and pTS are 50mM M and 25 mM. Polypyrrole was coated on the electrode surface within 10 cycles. İmmobilization of glucose oxidase carried out on Pt/polypyrrole-para toluene sulfonate (Pt/PPy-pTS) film by cross-linking with glutaraldehyde. The morphology of electrodes was characterized by SEM and AFM. Moreover, contact angle measurements were made with 1 μL water of polymer film and enzyme electrode. It has shown that enzyme electrode is very sensitive against to glucose.

  18. A Hydrogen Peroxide Biosensor Combined HRP Doped Polypyrrole with Ferrocene Modified Sol-gel Derived Composite Carbon Electrode

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel amperometric biosensor for the detection of hydrogen peroxide is described.The biosensor was constructed by electrodepositing HRP/PPy membrane on the surface of ferrocenecarboxylic acid mediated sol-gel derived composite carbon electrode. The biosensor gives response to hydrogen peroxide in a few seconds with detection limit of 5×l0-7 mol · L-1(based on signal: noise=3). Linear range is up to 0.2 mmol · L-1.

  19. A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rau, M.S.; Gennero de Chialvo, M.R. [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina); Chialvo, A.C., E-mail: achialvo@fiq.unl.edu.a [Programa de Electroquimica Aplicada e Ingenieria Electroquimica (PRELINE), Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Santiago del Estero 2829, 3000 Santa Fe (Argentina)

    2010-07-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H{sub 2}SO{sub 4} solution at different rotation rates ({omega}). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on {omega}{sup 1/2}. On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.

  20. Surface Modification of AB2. and AB5 Hydrogen Storage Alloy Electrodes by the Hot-Charging Treatment

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The effect of the hot-charging treatment on the performance ofAB2 and AB5 hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking o.f the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB5 type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.

  1. Fabrication of platinum coated nanoporous gold film electrode: A nanostructured ultra low-platinum loading electrocatalyst for hydrogen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kiani, Abolfazl; Hatami, Somayeh [Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan (Iran)

    2010-06-15

    The electrolytic hydrogen evolution reaction (HER) on platinum coated nanoporous gold film (PtNPGF) electrode is demonstrated. The deposition of platinum occurred as a spontaneous redox process in which a copper layer, obtained by underpotential deposition, was oxidized by platinum ions, which were reduced and simultaneously deposited. The present method could provide a very low Pt-loading electrode and the results demonstrated that ultra thin Pt coating effected efficiently and behaved as the nanostructured Pt for electrocatalytic hydrogen evolution reaction. The loading of Pt was calculated as 4.2 x 10{sup -3} {mu}g cm{sup -2} for PtNPGF electrode. The current density at -0.4 V and -0.8 V vs. Ag/AgCl was as high as 0.66 A {mu}g{sup -1} Pt and 3 A {mu}g{sup -1} Pt, respectively and the j{sub 0} was evaluated as 0.03 mA cm{sup -2} or 8 mA {mu}g{sup -1} Pt. The results indicated that increasing electrode area had no catalytic effect, but the nanostructure nature of as-fabricated electrode and submonolayer deposition of copper resulted in electrocatalytic activity for PtNPGF electrode. (author)

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

    Science.gov (United States)

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

    2011-09-01

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

  3. Dynamics of hydrogen dissociation on stepped platinum

    NARCIS (Netherlands)

    Groot, I. M. N.; Schouten, K. J. P.; Kleyn, A. W.; Juurlink, L. B. F.

    2008-01-01

    We have studied the reactivity of hydrogen on the Pt(211) stepped surface using supersonic molecular beam techniques. We observe an energy dependence that is indicative of indirect adsorption below 9 kJ mol(-1) and direct adsorption between 0 and 37 kJ mol(-1). Comparison of our results to

  4. NQR application to the study of hydrogen dynamics in hydrogen-bonded molecular dimers

    Science.gov (United States)

    Asaji, Tetsuo

    2016-12-01

    The temperature dependences of 1H NMR as well as 35Cl NQR spin-lattice relaxation times T 1 were investigated in order to study the hydrogen transfer dynamics in carboxylic acid dimers in 3,5-dichloro- and 2,6-dichlorobenzoic acids. The asymmetry energy A/ k B and the activation energy V/ k B for the hydrogen transfer were estimated to be 240 K and 900 K, and 840 K and 2500 K, respectively, for these compounds. In spite of a large asymmetric potential the quantum nature of hydrogen transfer is recognized in the slope of the temperature dependence of T 1 on the low-temperature side of the T 1 minimum. The NQR T 1 measurements was revealed to be a good probe for the hydrogen transfer dynamics.

  5. Millisecond dynamics of thermal expansion of mechanically controllable break junction electrodes studied in the tunneling regime

    Science.gov (United States)

    Kolesnychenko, O. Yu.; Toonen, A. J.; Shklyarevskii, O. I.; van Kempen, H.

    2001-10-01

    The thermal expansion dynamics of W, Pt-Ir, and Au mechanically controllable break junction electrodes was studied in the millisecond range. By measuring a transient tunnel current as a function of time, we found that, at low temperatures, the electrode elongation Δs˜t1/2 due to the large values of thermal diffusivity of metals. The magnitude of Δs varies in direct proportion to the power P dissipated in the electrodes.

  6. Thermo-Gas Dynamics of Hydrogen Combustion and Explosion

    CERN Document Server

    Gelfand, Boris E; Medvedev, Sergey P; Khomik, Sergey V

    2012-01-01

    The potential of hydrogen as an important future energy source has generated fresh interest in the study of hydrogenous gas mixtures. Indeed, both its high caloricity and reactivity are unique properties, the latter underscoring safety considerations when handling such mixtures.   The present monograph is devoted to the various aspects of hydrogen combustion and explosion processes. In addition to theoretical and phenomenological considerations, this work also collates the results of many experiments from less well known sources. The text reviews the literature in this respect, thereby providing valuable information about the thermo-gas-dynamical parameters of combustion processes for selected experimental settings in a range of scientific and industrial applications.

  7. Atomistic simulation of hydrogen dynamics near dislocations in vanadium hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Hiroshi, E-mail: h.ogawa@aist.go.jp

    2015-10-05

    Highlights: • Hydrogen–dislocation interaction was simulated by molecular dynamics method. • Different distribution of H atoms were observed at edge and screw dislocation. • Planner distribution of hydrogen may be caused by partialized edge dislocation. • Hydrogen diffusivity was reduced in both edge and screw dislocation models. • Pipe diffusion was observed for edge dislocation but not for screw dislocation. - Abstract: Kinetics of interstitial hydrogen atoms near dislocation cores were analyzed by atomistic simulation. Classical molecular dynamics method was applied to model structures of edge and screw dislocations in α-phase vanadium hydride. Simulation showed that hydrogen atoms aggregate near dislocation cores. The spatial distribution of hydrogen has a planner shape at edge dislocation due to dislocation partialization, and a cylindrical shape at screw dislocation. Simulated self-diffusion coefficients of hydrogen atoms in dislocation models were a half- to one-order lower than that of dislocation-free model. Arrhenius plot of self-diffusivity showed slightly different activation energies for edge and screw dislocations. Directional dependency of hydrogen diffusion near dislocation showed high and low diffusivity along edge and screw dislocation lines, respectively, hence so called ‘pipe diffusion’ possibly occur at edge dislocation but does not at screw dislocation.

  8. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: excitation dynamics and ion flux asymmetry

    Science.gov (United States)

    Bruneau, B.; Diomede, P.; Economou, D. J.; Longo, S.; Gans, T.; O'Connell, D.; Greb, A.; Johnson, E.; Booth, J.-P.

    2016-08-01

    Parallel plate capacitively coupled plasmas in hydrogen at relatively high pressure (~1 Torr) are excited with tailored voltage waveforms containing up to five frequencies. Predictions of a hybrid model combining a particle-in-cell simulation with Monte Carlo collisions and a fluid model are compared to phase resolved optical emission spectroscopy measurements, yielding information on the dynamics of the excitation rate in these discharges. When the discharge is excited with amplitude asymmetric waveforms, the discharge becomes electrically asymmetric, with different ion energies at each of the two electrodes. Unexpectedly, large differences in the \\text{H}2+ fluxes to each of the two electrodes are caused by the different \\text{H}3+ energies. When the discharge is excited with slope asymmetric waveforms, only weak electrical asymmetry of the discharge is observed. In this case, electron power absorption due to fast sheath expansion at one electrode is balanced by electron power absorption at the opposite electrode due to a strong electric field reversal.

  9. Bio-hydrogen: immobilization of enzymes on electrodes modified by clayey nano-particles; Biohydrogene: immobilisation d'enzymes sur des electrodes modifiees par des nanoparticules argileuses

    Energy Technology Data Exchange (ETDEWEB)

    Lojou, E.; Giudici-Orticoni, M.T.; Bianco, P. [Centre National de la Recherche Scientifique (CNRS), Lab. de Bioenergetique et Ingenierie des Proteines, 13 - Marseille (France)

    2006-07-01

    In this work, has been studied the immobilization of enzymes inside micro-films constituted of clayey nano-particles and layer by layer nano-assembling of clayey nano-particles and enzyme. Natural clays have very great specific surface areas, very strong ions exchange capacities and a swelling lamellar structure particularly well adapted to the non denaturing adsorption of proteins and charged enzymes. In this study, the enzymes have been extracted of sulfate-reducing bacteria. The immobilization of this system in clayey films has been studied by micro-gravimetry/electrochemistry coupling and the catalytic activity towards the production and the consumption of hydrogen quantified. At first, the clay is deposited in layer of thickness of the micron on the gold or graphite electrode. When the hydrogenase is immobilized in the clayey film, the electro-enzymatic oxidation of hydrogen occurs inside the clayey structure. An electrode able to measure either the hydrogen consumption or its production on a wide pH range as thus been prepared, by co-immobilization of hydrogenase and of MV{sup 2+} in montmorillonite films. The catalytic efficiencies obtained by immobilization in the clayey matrix of the two physiological partners, cytochrome c3 and hydrogenase, are strongly improved. Then, this process has been still improved, and three cytochrome c3/clay bilayers have been superposed without loss of the enzymatic activity. (O.M.)

  10. Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

    Directory of Open Access Journals (Sweden)

    Jakšić Jelena M.

    2012-01-01

    Full Text Available Altervalent hypo-d-oxides of transition metal series impose spontaneous dissociative adsorption of water molecules and pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic, and/or its hydrated state (Pt/W(OH6 responsible for the primary oxide (Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3 Pt/W(OH6, and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. As the consequence, the new striking and unpredictable prospects both in law and medium temperature proton exchange membrane fuell cell (L&MT PEMFC and water electrolysis (WE have been opened by the interactive supported individual (Pt, Pd, Ni or prevailing hyper-d-electronic nanostructured intermetallic phase clusters (WPt3, NbPt3, HfPd3, ZrNi3, grafted upon and within high altervalent capacity hypo-d-oxides (WO3, Nb2O5, Ta2O5, TiO2 and their proper mixed valence compounds, to create a novel type of alterpolar interchangeable composite electrocatalysts for hydrogen and oxygen electrode reactions. Whereas in aqueous media Pt (Pt/C features either chemisorbed catalytic surface properties of H-adatoms (Pt-H, or surface oxide (Pt=O, missing any effusion of other interacting species, new generation and selection of composite and interactive strong metal-support interaction (SMSI electrocatalysts in condensed wet state primarily characterizes interchangeable extremely fast reversible spillover of either H-adatoms, or the primary oxides (Pt-OH, Au-OH, or the invertible bronze type behavior of these significant interactive electrocatalytic ingredients. Such nanostructured type electrocatalysts, even of mixed hypo-d-oxide structure (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron

  11. A Hydrogen Peroxide Sensor Prepared by Electropolymerization of Pyrrole Based on Screen-Printed Carbon Paste Electrodes

    OpenAIRE

    Hui Xu; You Wang; Guang Li

    2007-01-01

    A disposable amperometric biosensor for commercial use to detect hydrogen peroxide has been developed. The sensor is based on screen-printed carbon paste electrodes modified by electropolymerization of pyrrole with horseradish peroxidase (HRP) entrapped. The facture techniques of fabricating the enzyme electrodes are suitable for mass production and quality control. The biosensor shows a linear amperometric response to H2O2 from 0.1 to 2.0 mM, with a sensitivity of 33.24 µA mM-1 cm-2. Differe...

  12. Capturing the transient species at the electrode-electrolyte interface by in situ dynamic molecular imaging.

    Science.gov (United States)

    Yu, Jiachao; Zhou, Yufan; Hua, Xin; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-09-21

    In situ time-resolved identification of interfacial transient reaction species were captured using imaging mass spectrometry, leading to the discovery of more complex elementary electrode reactions and providing an unprecedented understanding of the reaction mechanism on the electrode surface and solid-electrolyte interface using dynamic molecular imaging.

  13. Adsorption and hydrogenation of simple alkenes at Pt-group metal electrodes studied by DEMS: influence of the crystal orientation

    Science.gov (United States)

    Müller, Ulrich; Schmiemann, Udo; Dülberg, Andreas; Baltruschat, Helmut

    1995-07-01

    The adsorption of ethene and cyclohexene on mono-and polycrystalline Pt and on polycrystalline Pd electrodes was studied using differential electrochemical mass spectrometry (DEMS). Both molecules are partially hydrated to an oxygen containing species upon adsorption on Pt. In the case of ethene, this species dissociated to methane and adsorbed CO at negative potentials. Another part of the adsorbed ethene can be cathodically desorbed as ethane and butane. The ratio of the various species formed strongly depends on crystal orientation and adsorption potential. Contrary to heterogenous gas phase hydrogenation (and also contrary to some earlier reports on electrochemical hydrogenation), the rate of the Faradaic hydrogenation reaction is also strongly dependent on the crystallographic orientation, being faster on Pt(110) or roughened surfaces. During hydrogenation, H/D exchange occurs to an appreciable degree, suggesting the participation of adsorbed intermediates.

  14. Car-Parrinello simulation of hydrogen bond dynamics in sodium hydrogen bissulfate.

    Science.gov (United States)

    Pirc, Gordana; Stare, Jernej; Mavri, Janez

    2010-06-14

    We studied proton dynamics of a short hydrogen bond of the crystalline sodium hydrogen bissulfate, a hydrogen-bonded ferroelectric system. Our approach was based on the established Car-Parrinello molecular dynamics (CPMD) methodology, followed by an a posteriori quantization of the OH stretching motion. The latter approach is based on snapshot structures taken from CPMD trajectory, calculation of proton potentials, and solving of the vibrational Schrodinger equation for each of the snapshot potentials. The so obtained contour of the OH stretching band has the center of gravity at about 1540 cm(-1) and a half width of about 700 cm(-1), which is in qualitative agreement with the experimental infrared spectrum. The corresponding values for the deuterated form are 1092 and 600 cm(-1), respectively. The hydrogen probability densities obtained by solving the vibrational Schrodinger equation allow for the evaluation of potential of mean force along the proton transfer coordinate. We demonstrate that for the present system the free energy profile is of the single-well type and features a broad and shallow minimum near the center of the hydrogen bond, allowing for frequent and barrierless proton (or deuteron) jumps. All the calculated time-averaged geometric parameters were in reasonable agreement with the experimental neutron diffraction data. As the present methodology for quantization of proton motion is applicable to a variety of hydrogen-bonded systems, it is promising for potential use in computational enzymology.

  15. The hydrogen-bond collective dynamics in liquid methanol

    Science.gov (United States)

    Bellissima, Stefano; de Panfilis, Simone; Bafile, Ubaldo; Cunsolo, Alessandro; González, Miguel Angel; Guarini, Eleonora; Formisano, Ferdinando

    2016-12-01

    The relatively simple molecular structure of hydrogen-bonded (HB) systems is often belied by their exceptionally complex thermodynamic and microscopic behaviour. For this reason, after a thorough experimental, computational and theoretical scrutiny, the dynamics of molecules in HB systems still eludes a comprehensive understanding. Aiming at shedding some insight into this topic, we jointly used neutron Brillouin scattering and molecular dynamics simulations to probe the dynamics of a prototypical hydrogen-bonded alcohol, liquid methanol. The comparison with the most thoroughly investigated HB system, liquid water, pinpoints common behaviours of their THz microscopic dynamics, thereby providing additional information on the role of HB dynamics in these two systems. This study demonstrates that the dynamic behaviour of methanol is much richer than what so far known, and prompts us to establish striking analogies with the features of liquid and supercooled water. In particular, based on the strong differences between the structural properties of the two systems, our results suggest that the assignment of some dynamical properties to the tetrahedral character of water structure should be questioned. We finally highlight the similarities between the characteristic decay times of the time correlation function, as obtained from our data and the mean lifetime of hydrogen bond known in literature.

  16. Mechanistic Switching by Hydronium Ion Activity for Hydrogen Evolution and Oxidation over Polycrystalline Platinum Disk and Platinum/Carbon Electrodes

    KAUST Repository

    Shinagawa, Tatsuya

    2014-07-22

    Fundamental electrochemical reactions, namely the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), are re-evaluated under various pH conditions over polycrystalline Pt disk electrodes and Pt/C electrodes to investigate the overpotential and Tafel relations. Kinetic trends are observed and can be classified into three pH regions: acidic (1-5), neutral (5-9), and alkaline (9-13). Under neutral conditions, in which H2O becomes the primary reactant, substantial overpotential, which is not affected by pH and the supporting electrolyte type, is required for electrocatalysis in both directions. This ion independence, including pH, suggests that HER/HOR performance under neutral conditions solely reflects the intrinsic electrocatalytic activity of Pt in the rate determining steps, which involve electron transfer with water molecules. A global picture of the HER/HOR, resulting from mechanistic switching accompanied by change in pH, is detailed.

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

    Science.gov (United States)

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

    2017-03-01

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

  18. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction.

    Science.gov (United States)

    Rowley-Neale, Samuel J; Brownson, Dale A C; Smith, Graham C; Sawtell, David A G; Kelly, Peter J; Banks, Craig E

    2015-11-21

    We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.

  19. Dynamic Simulation and Optimization of Nuclear Hydrogen Production Systems

    Energy Technology Data Exchange (ETDEWEB)

    Paul I. Barton; Mujid S. Kaximi; Georgios Bollas; Patricio Ramirez Munoz

    2009-07-31

    This project is part of a research effort to design a hydrogen plant and its interface with a nuclear reactor. This project developed a dynamic modeling, simulation and optimization environment for nuclear hydrogen production systems. A hybrid discrete/continuous model captures both the continuous dynamics of the nuclear plant, the hydrogen plant, and their interface, along with discrete events such as major upsets. This hybrid model makes us of accurate thermodynamic sub-models for the description of phase and reaction equilibria in the thermochemical reactor. Use of the detailed thermodynamic models will allow researchers to examine the process in detail and have confidence in the accurary of the property package they use.

  20. Dynamics of Hydrogen Elimination from Unsaturated Hydrocarbons

    Science.gov (United States)

    Cromwell, Evan Francis

    State-of-the-art laser and molecular beam techniques are used to study the dynamics of H_2 elimination from 1,4-cyclohexadiene and ethylene. Information on the transition state configurations and the dynamics of the dissociation processes for these reactions is reported. A brief introduction to these studies is presented in Chapter I. An ultrahigh-brightness laser system, developed to study the spectroscopy and dynamics of molecules and clusters from the vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) to the near infra-red spectral regions is described in Chapter II. The laser utilizes pulse amplification of a single-mode ring dye laser, frequency doubling, and four-wave mixing in a pulsed jet. Pulse energies of > 120mJ in the visible, >35mJ in the uv, >15mJ in the infra-red and > 10^{11} photons/pulse in the VUV-XUV have been obtained. The bandwidth of the laser has been measured to be 91MHz in the visible and 210MHz in the XUV. In Chapter III a comprehensive study of the dynamics of H_2 elimination from 1,4- and 1,3-cyclohexadiene is reported. Rotational and vibrational quantum state distributions as well as translation energy distributions for the H_2 product are measured. State specific detection of H_2 is accomplished with a transform limited vuv-xuv laser system via (1 + 1) REMPI. Rate constants for the H_2 elimination and 1,4 to 1,3 isomerization reactions are derived. A (v, J) correlation for H _2 with {bf v}| {bf J} primarily is observed from anisotropy in the Doppler profiles. A clear picture of the transition state configuration of 1,4-cyclohexadiene is provided from the information obtained. A study of the dynamics of H_2 elimination from ethylene is presented in the last Chapter. A complete H_2 product energy distribution is obtained. The distribution of energy in H_2 product from the dissociation of 1,1-d_2 ethylene is also presented. Two separate H_2 elimination channels are observed, a 1,1 elimination and a 1,2 elimination, in the

  1. Nonlinear dynamics of capacitive charging and desalination by porous electrodes

    NARCIS (Netherlands)

    Biesheuvel, P.M.; Bazant, M.Z.

    2010-01-01

    The rapid and efficient exchange of ions between porous electrodes and aqueous solutions is important in many applications, such as electrical energy storage by supercapacitors, water desalination and purification by capacitive deionization, and capacitive extraction of renewable energy from a salin

  2. Hydrogen.

    Science.gov (United States)

    Bockris, John O'M

    2011-11-30

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

  3. Pt、Rh及Pt-Rh合金电极上氢的吸附%Hydrogen Adsorption on Pt, Rh and Pt-Rh Electrodes

    Institute of Scientific and Technical Information of China (English)

    贾梦秋; A.M.Meretskyi

    2005-01-01

    The hydrogen adsorption on Pt-Rh alloys in sulfuric acid aqueous solutions was studied by the method of cathode pulses. Hydrogen adsorption on the electrode with all ratio of alloy components (wRh = 0-100%) is well described by the Temkin logarithmic isotherm. The surface coverage by adsorbed hydrogen at the same potential is decreased with increasing content of rhodium in the system. A linear dependence of adsorption peak potential on the alloy compositions in the case of weakly bonded adsorbed hydrogen is established. Hydrogen adsorption heat as a function of surface coverage for Pt-Rh-electrodes was obtained. The shape of the current-potential curve and position of the weakly bonded hydrogen adsorption on the potential scale are all related to alloy compositions, thus can serve as the basis for the determination surface composition of alloys.

  4. Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

    Science.gov (United States)

    Bates, Michael

    Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline

  5. Nonlinear Dynamics of Capacitive Charging and Desalination by Porous Electrodes

    CERN Document Server

    Biesheuvel, P M

    2009-01-01

    The rapid and efficient exchange of ions between porous electrodes and aqueous solutions is important in many applications, such as electrical energy storage by super-capacitors, water desalination and purification by capacitive deionization (or desalination), and capacitive extraction of renewable energy from a salinity difference. Here, we present a unified mean-field theory for capacitive charging and desalination by ideally polarizable porous electrodes (without Faradaic reactions or specific adsorption of ions) in the limit of thin double layers (compared to typical pore dimensions). We illustrate the theory in the case of a dilute, symmetric, binary electrolyte using the Gouy-Chapman-Stern (GCS) model of the double layer, for which simple formulae are available for salt adsorption and capacitive charging of the diffuse part of the double layer. We solve the full GCS mean-field theory numerically for realistic parameters in capacitive deionization, and we derive reduced models for two limiting regimes wi...

  6. Evaluation of Tafel-Volmer kinetic parameters for the hydrogen oxidation reaction on Pt(1 1 0) electrodes

    Science.gov (United States)

    Mann, R. F.; Thurgood, C. P.

    2011-05-01

    Modelling of PEM fuel cells has long been an active research area to improve understanding of cell and stack operation, facilitate design improvements and support simulation studies. The prediction of activation polarization in most PEM models has concentrated on the cathode losses since anode losses are commonly much smaller and tend to be ignored. Further development of the anode activation polarization term is being undertaken to broaden the application and usefulness of PEM models in general. Published work on the kinetics of the hydrogen oxidation reaction (HOR) using Pt(h k l) electrodes in dilute H2SO4 has been recently reassessed and published. Correlations for diffusion-free exchange current densities were developed and empirical predictive equations for the anode activation polarization were proposed for the experimental conditions of the previously published work: Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) electrodes, pH2 of 1 atm, and temperatures of 1, 30 and 60 °C. It was concluded that the HOR on Pt(1 1 0) electrodes followed a Tafel-Volmer reaction sequence. The aim of the present paper is to generalize these Tafel-Volmer correlations, apply them to published data for Pt(1 1 0) electrodes and further develop the modelling of anode activation polarization over the range of operating conditions found in PEMFC operation.

  7. A Study of Gas Diffusion Electrodes for the Coupled Reaction of Water Electrolysis and Electrocatalytic Benzene Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    HuangHaiyan; YuYing; WangJing

    2005-01-01

    Gas diffusion electrodes are applied to the coupled reaction of water electrolysis and electrocatalytic benzene hydrogenation. The effects of the preparation conditions of electrodes, electrolyte acidity, the concentration of benzene and water vapor, and the flow rate of N2 are investigated by evaluating the efficiency of the current. Furthermore, the optimal operational conditions have been ascertained. The results of our experiment show that gas diffusion electrodes have good performance when the content of PTFE is 10% (wt) and that of Nation is 0.75mg/cm2. The optimal operational conditions are as follows: The temperature of electrolysis is 70℃, acidity 0.5tool/L, the concentration of benzene 26%,the concentration of vapor 10%, the flow rate of N2 80mL/min-240mL/min. The efficiency of the current can reach 35% under optimal operational conditions. Then, a conclusion can be drawn that gas diffusion electrodes can improve the rate of the coupled reaction effectively.

  8. Overview of studies on hydrogen storage electrode alloys%贮氢电极合金研究概况

    Institute of Scientific and Technical Information of China (English)

    王国元; 潘洪革; 陈长聘

    2001-01-01

    Compared with other batteries, Ni-MH batteries had excellent electrochemical react mechanism, high peak power and nonpoisonous to environments. MH electrode provideed very important opportunities for material engineering and material optimization. The influences of electrochemical corrosion, element substitution, phase structure etc. of AB5,AB2,A2B(Mg-based), Ti-based multi-elements electrode materials and V-based solid solution electrode alloys on their electrochemical properties were summarized. And the main directions of studies on hydrogen storage electrode alloys were reviewed.%与其它电池系统相比,MH-Ni电池具有优良的电化学反应机理,高的峰值功率,对环境无害。MH电极材料为工程化和材料优化研究提供了很多机会。概述了AB5、AB2、A2B(Mg基)、Ti基多元合金及V基固溶体合金的电极材料的电化学腐蚀、元素替代、相结构等对其电化学性能的影响,并指出了目前贮氢电极的主要研究方向。

  9. Dynamical localization: Hydrogen atoms in magnetic and microwave fields

    Energy Technology Data Exchange (ETDEWEB)

    Benvenuto, F.; Casati, G. [Dipartimento di Fisica dellUniversita, Via Castelnuovo 7, 22100 Como (Italy); Shepelyansky, D.L. [Laboratoire de Physique Quantique, UMR C5626 du CNRS, Universite Paul Sabatier, 31062, Toulouse (France)

    1997-03-01

    We show that dynamical localization for excited hydrogen atoms in magnetic and microwave fields takes place at quite low microwave frequency ({omega}n{sup 3}{lt}1). Estimates of the localization length are given for different parameter regimes, showing that the quantum delocalization border drops significantly as compared to the case of zero magnetic field. This opens up broad possibilities for laboratory investigations. {copyright} {ital 1997} {ital The American Physical Society}

  10. Removal of a hydrogenated amorphous carbon film from the tip of a micropipette electrode using direct current corona discharge.

    Science.gov (United States)

    Kakuta, Naoto; Okuyama, Naoki; Yamada, Yukio

    2010-02-01

    Micropipette electrodes are fabricated by coating glass micropipettes first with metal and then with hydrogenated amorphous carbon (a-C:H) as an electrical insulator. Furthermore, at the tip of the micropipette electrode, the deposited a-C:H film needs to be removed to expose the metal-coated surface and hollow for the purposes of electrical measurement and injection. This paper describes a convenient and reliable method for removing the a-C:H film using direct current corona discharge in atmospheric air. The initial film removal occurred at an applied voltage of 1.5-2.0 kV, accompanied by an abrupt increase in the discharge current. The discharge current then became stable at a microampere level in the glow corona mode, and the removed area gradually extended.

  11. High-performance hydrogen production and oxidation electrodes with hydrogenase supported on metallic single-wall carbon nanotube networks.

    Science.gov (United States)

    Svedružić, Draženka; Blackburn, Jeffrey L; Tenent, Robert C; Rocha, John-David R; Vinzant, Todd B; Heben, Michael J; King, Paul W

    2011-03-30

    We studied the electrocatalytic activity of an [FeFe]-hydrogenase from Clostridium acetobutylicum (CaH2ase) immobilized on single-wall carbon nanotube (SWNT) networks. SWNT networks were prepared on carbon cloth by ultrasonic spraying of suspensions with predetermined ratios of metallic and semiconducting nanotubes. Current densities for both proton reduction and hydrogen oxidation electrocatalytic activities were at least 1 order of magnitude higher when hydrogenase was immobilized onto SWNT networks with high metallic tube (m-SWNT) content in comparison to hydrogenase supported on networks with low metallic tube content or when SWNTs were absent. We conclude that the increase in electrocatalytic activities in the presence of SWNTs was mainly due to the m-SWNT fraction and can be attributed to (i) substantial increases in the active electrode surface area, and (ii) improved electronic coupling between CaH2ase redox-active sites and the electrode surface.

  12. Electrode modified with a composite film of ZnO nanorods and Ag nanoparticles as a sensor for hydrogen peroxide.

    Science.gov (United States)

    Lin, Chia-Yu; Lai, Yi-Hsuan; Balamurugan, A; Vittal, R; Lin, Chii-Wann; Ho, Kuo-Chuan

    2010-06-30

    A conducting fluorine-doped tin oxide (FTO) electrode, first modified with zinc oxide nanorods (ZnONRs) and subsequently attached with photosynthesized silver nanoparticles (AgNPs), designated as AgNPs/ZnONRs/FTO electrode, was used as an amperometric sensor for the determination of hydrogen peroxide. The first layer (ZnONRs) was obtained by chemical bath deposition (CBD), and was utilized simultaneously as the catalyst for the photoreduction of Ag ions under UV irradiation and as the matrix for the immobilization of AgNPs. The aspect ratio of ZnONRs to be deposited was optimized by controlling the number of their CBDs to render enough surface area for Ag deposition, and the amount of AgNPs to be attached was controlled by adjusting the UV-irradiation time. The immobilized AgNPs showed excellent electrocatalytic response to the reduction of hydrogen peroxide. The resultant amperometric sensor showed 10-fold enhanced sensitivity for the detection of H(2)O(2), compared to that without AgNPs, i.e., only with a layer of ZnONRs. Amperometric determination of H(2)O(2) at -0.55 V gave a limit of detection of 0.9 microM (S/N=3) and a sensitivity of 152.1 mA M(-1) cm(-2) up to 0.983 mM, with a response time (steady-state, t(95)) of 30-40 s. The selectivity of the sensor was investigated against ascorbic acid (AA) and uric acid (UA). Energy dispersive X-ray (EDX) analysis, transmission electron microscopic (TEM) image, X-ray diffraction (XRD) patterns, cyclic voltammetry (CV), and scanning electron microscopic (SEM) images were utilized to characterize the modified electrode. Sensing properties of the modified electrode were studied both by CV and amperometric analysis.

  13. Fabrication of Carbon-Platinum Interdigitated Array Electrodes and Their Application for Investigating Homogeneous Hydrogen Evolution Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fei; Divan, Ralu; Parkinson, Bruce A.

    2015-06-29

    Carbon interdigitated array (IDA) electrodes have been applied to study the homogeneous hydrogen evolution electrocatalyst [Ni(PPh2NBn2)2]2+ (where PPh2NBn2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane). The existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. The currents on IDA electrodes for an EC’ (electron transfer reaction followed by a catalytic reaction) mechanism are derived from the number of redox cycles and the contribution of non-catalytic currents. The catalytic reaction rate constant was then extracted from the IDA current equations. Applying the IDA current and kinetic equations to the electrochemical response of the [Ni(PPh2NBn2)2]2+ catalyst yielded a rate constant of 0.10 s-1 for the hydrogen evolution reaction that agrees with the literature value. The quantitative analysis of IDA cyclic voltammetry can be used as a simple and straightforward method for determining rate constants in other catalytic systems. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE. Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

  14. A hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on natural nano-structure attapulgite modified glassy carbon electrode.

    Science.gov (United States)

    Chen, Huihui; Zhang, Zhe; Cai, Dongqing; Zhang, Shengyi; Zhang, Bailin; Tang, Jilin; Wu, Zhengyan

    2011-10-30

    A novel strategy to fabricate hydrogen peroxide (H(2)O(2)) sensor was developed by electrodepositing Ag nanoparticles (NPs) on a glassy carbon electrode modified with natural nano-structure attapulgite (ATP). The result of electrochemical experiments showed that such constructed sensor had a favorable catalytic ability to reduce H(2)O(2). The good catalytic activity of the sensor was ascribed to the ATP that facilitated the formation and homogenous distribution of small Ag NPs. The resulted sensor achieved 95% of the steady-state current within 2s and had a 2.4 μM detection limit of H(2)O(2).

  15. DNA-Templated Silver Nanoclusters Formation at Gold Electrode Surface and Its Application to Hydrogen Peroxide Detection

    Institute of Scientific and Technical Information of China (English)

    许媛媛; 陈阳阳; 杨娜娜; 孙丽洲; 李根喜

    2012-01-01

    In this work, we have prepared Ag nanoclusters (Ag NCs) at gold electrode surface by using thiol-modified oligodeoxynucleotide consisting of eighteen cytosine deoxyribonucleotides (polyC18) as template and NaBH4 as reducing agent. Experimental results show that Ag nanoclusters (Ag NCs) can be formed around the template polyC18, while the formation can be characterized with electrochemical method. Further studies reveal that the fab- ricated Ag NCs may display high catalytic activity for the reduction of hydrogen peroxide (H2O2), which can be further used for the detection of H20〉

  16. Supported noble metals on hydrogen-treated TiO2 nanotube arrays as highly ordered electrodes for fuel cells.

    Science.gov (United States)

    Zhang, Changkun; Yu, Hongmei; Li, Yongkun; Gao, Yuan; Zhao, Yun; Song, Wei; Shao, Zhigang; Yi, Baolian

    2013-04-01

    Hydrogen-treated TiO2 nanotube (H-TNT) arrays serve as highly ordered nanostructured electrode supports, which are able to significantly improve the electrochemical performance and durability of fuel cells. The electrical conductivity of H-TNTs increases by approximately one order of magnitude in comparison to air-treated TNTs. The increase in the number of oxygen vacancies and hydroxyl groups on the H-TNTs help to anchor a greater number of Pt atoms during Pt electrodeposition. The H-TNTs are pretreated by using a successive ion adsorption and reaction (SIAR) method that enhances the loading and dispersion of Pt catalysts when electrodeposited. In the SIAR method a Pd activator can be used to provide uniform nucleation sites for Pt and leads to increased Pt loading on the H-TNTs. Furthermore, fabricated Pt nanoparticles with a diameter of 3.4 nm are located uniformly around the pretreated H-TNT support. The as-prepared and highly ordered electrodes exhibit excellent stability during accelerated durability tests, particularly for the H-TNT-loaded Pt catalysts that have been annealed in ultrahigh purity H2 for a second time. There is minimal decrease in the electrochemical surface area of the as-prepared electrode after 1000 cycles compared to a 68 % decrease for the commercial JM 20 % Pt/C electrode after 800 cycles. X-ray photoelectron spectroscopy shows that after the H-TNT-loaded Pt catalysts are annealed in H2 for the second time, the strong metal-support interaction between the H-TNTs and the Pt catalysts enhances the electrochemical stability of the electrodes. Fuel-cell testing shows that the power density reaches a maximum of 500 mWcm(-2) when this highly ordered electrode is used as the anode. When used as the cathode in a fuel cell with extra-low Pt loading, the new electrode generates a specific power density of 2.68 kWg(Pt) (-1) . It is indicated that H-TNT arrays, which have highly ordered nanostructures, could be used as ordered electrode supports

  17. Development of a Hydrogen Peroxide Sensor Based on Screen-Printed Electrodes Modified with Inkjet-Printed Prussian Blue Nanoparticles

    Directory of Open Access Journals (Sweden)

    Stefano Cinti

    2014-08-01

    Full Text Available A sensor for the simple and sensitive measurement of hydrogen peroxide has been developed which is based on screen printed electrodes (SPEs modified with Prussian blue nanoparticles (PBNPs deposited using piezoelectric inkjet printing. PBNP-modified SPEs were characterized using physical and electrochemical techniques to optimize the PBNP layer thickness and electroanalytical conditions for optimum measurement of hydrogen peroxide. Sensor optimization resulted in a limit of detection of 2 × 10−7 M, a linear range from 0 to 4.5 mM and a sensitivity of 762 μA∙mM–1∙cm–2 which was achieved using 20 layers of printed PBNPs. Sensors also demonstrated excellent reproducibility (<5% rsd.

  18. Hydrogen Oxidation on Gas Diffusion Electrodes for Phosphoric Acid Fuel Cells in the Presence of Carbon Monoxide and Oxygen

    DEFF Research Database (Denmark)

    Gang, Xiao; Li, Qingfeng; Hjuler, Hans Aage

    1995-01-01

    Hydrogen oxidation has been studied on a carbon-supported platinum gas diffusion electrode in a phosphoric acidelectrolyte in the presence of carbon monoxide and oxygen in the feed gas. The poisoning effect of carbon monoxide presentin the feed gas was measured in the temperature range from 80...... to 150°C. It was found that throughout the temperaturerange, the potential loss due to the CO poisoning can be reduced to a great extent by the injection of small amounts ofgaseous oxygen into the hydrogen gas containing carbon monoxide. By adding 5 volume percent (v/o) oxygen, an almost......CO-free performance can be obtained for carbon monoxide concentrations up to 0.5 v/o CO at 130°C, 0.2 v/o CO at 100°C,and 0.1 v/o CO at 80°C, respectively....

  19. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective...... of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  20. Hydrogen

    Directory of Open Access Journals (Sweden)

    John O’M. Bockris

    2011-11-01

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

  1. CATALYTIC AND ELECTROCATALYTIC ACTIVITY OF Pt-Ru/C ELECTRODE FOR HYDROGEN OXIDATION IN ALKALINE

    Directory of Open Access Journals (Sweden)

    D. LABOU

    2008-07-01

    Full Text Available The kinetics of the oxidation of H2 on PtRu/C gas-diffusion electrode was studied by interfacing the electrode with aqueous electrolytes at different pH values. The conducting electrolytes were KOH and HClO4 aqueous solutions with different concentrations. It is shown that the nature of the aqueous electrolyte plays the role of an active catalyst support for the PtRu/C electrode which drastically affects its catalytic properties. During the aforementioned interaction, termed electrochemical metal support interaction (EMSI, the electrochemical potential of the electrons at the catalyst Fermi level is equalised with the electrochemical potential of the solvated electron in the aqueous electrolyte. The electrochemical experiments carried out at various pH values showed that the electrochemical promotion catalysis (EPOC is more intense when the catalyst-electrode is interfaced with electrolytes with high pH values where the OH– ionic conduction prevails. It was concluded that similar to the solid state electrochemical systems EPOC proceeds through the formation of a polar adsorbed promoting layer of , electrochemically supplied by the OH- species, at the three phase boundaries of the gas exposed gas diffusion catalyst-electrode surface.

  2. Evaluation of Biofuel Cells with Hemoglobin as Cathodic Electrocatalysts for Hydrogen Peroxide Reduction on Bare Indium-Tin-Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Yusuke Ayato

    2013-12-01

    Full Text Available A biofuel cell (BFC cathode has been developed based on direct electron transfer (DET of hemoglobin (Hb molecules with an indium-tin-oxide (ITO electrode and their electrocatalysis for reduction of hydrogen peroxide (H2O2. In this study, the ITO-coated glass plates or porous glasses were prepared by using a chemical vapor deposition (CVD method and examined the electrochemical characteristics of the formed ITO in pH 7.4 of phosphate buffered saline (PBS solutions containing and not containing Hb. In half-cell measurements, the reduction current of H2O2 due to the electrocatalytic activity of Hb increased with decreasing electrode potential from around 0.1 V versus Ag|AgCl|KCl(satd. in the PBS solution. The practical open-circuit voltage (OCV on BFCs utilizing H2O2 reduction at the Hb-ITO cathode with a hydrogen (H2 oxidation anode at a platinum (Pt electrode was expected to be at least 0.74 V from the theoretical H2 oxidation potential of −0.64 V versus Ag|AgCl|KCl(satd. in pH 7.4. The assembled single cell using the ITO-coated glass plate showed the OCV of 0.72 V and the maximum power density of 3.1 µW cm−2. The maximum power per single cell was recorded at 21.5 µW by using the ITO-coated porous glass.

  3. Dynamics of hydrogen-like atom bounded by maximal acceleration

    CERN Document Server

    Friedman, Yaakov

    2012-01-01

    The existence of a maximal acceleration for massive objects was conjectured by Caianiello 30 years ago based on the Heisenberg uncertainty relations. Many consequences of this hypothesis have been studied, but until now, there has been no evidence that boundedness of the acceleration may lead to quantum behavior. In previous research, we predicted the existence of a universal maximal acceleration and developed a new dynamics for which all admissible solutions have an acceleration bounded by the maximal one. Based on W. K\\"{u}ndig's experiment, as reanalyzed by Kholmetskii et al, we estimated its value to be of the order $10^{19}m/s^2$. We present here a solution of our dynamical equation for a classical hydrogen-like atom and show that this dynamics leads to some aspects of quantum behavior. We show that the position of an electron in a hydrogen-like atom can be described only probabilistically. We also show that in this model, the notion of "center of mass" must be modified. This modification supports the no...

  4. Hydrogen adsorption on hydrogen storage alloy surface and electrochemical performances of the M1Ni{sub 4.0}Co{sub 0.6}Al{sub 0.4} alloy electrodes before and after surface treatment

    Energy Technology Data Exchange (ETDEWEB)

    Chen, W.X.; Xu, Z.D. [Zhejiang Univ., Hangzhou (China). Dept. of Chemistry; Tu, J.P. [Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering; Li, H.Y.; Chen, S.; Bao, S.N. [Zhejiang Univ., Hangzhou (China). Dept. of Physics; Yuan, J. [Zhejiang Univ., Hangzhou (China). State Key Lab. of Si Material Science

    2001-07-01

    The surfaces of the hydrogen storage alloy powders (MlNi{sub 4.0}Co{sub 0.6}Al{sub 0.4}) before and after surface treating were analyzed by X-ray photoelectron spectroscopy (XPS), electron probe micro-analysis (EPMA), inductively coupled plasma spectroscopy (ICP). It was found that a Ni-rich surface layer was produced and the specific surface area was augmented by the surface treatment with a hot 6 MKOH or 6 MKOH+0.02 MKBH{sub 4} solution due to the preferential dissolution of Al and the etching of the hot alkaline solution. The effect of the surface treatments on the hydrogen adsorption on the alloy surface was for the first time evaluated by means of the thermal desorption spectroscopy (TDS). It was found that the surface treatments enhanced the hydrogen adsorption on the alloy surfaces and produced new adsorption states. The untreated alloy had only one hydrogen adsorption peak at about 400 K. There were two hydrogen adsorption states at about 540 and 630 K on the surface of the alloy treated with 6 MKOH. In the case of the alloy treated with 6 MKOH+0.02 MKBH{sub 4} three hydrogen adsorption peaks were observed at about 390, 540 and 630 K, respectively. The results of electrochemical measurements showed that the treated alloy electrodes exhibited higher exchange current density for the hydrogen electrode reaction than the untreated hydrogen alloy. After the surface treatment, the hydrogen adsorption enhancement on the treated alloy surface facilitated the hydrogen electrode reaction process on the alloy electrodes and results in good activation and low polarization resistance. (author)

  5. Optimization of hydrogen vehicle refueling via dynamic simulation

    DEFF Research Database (Denmark)

    Rothuizen, Erasmus Damgaard; Mérida, W.; Rokni, Masoud

    2013-01-01

    A dynamic model has been developed to analyze and optimize the thermodynamics and design of hydrogen refueling stations. The model is based on Dymola software and incorporates discrete components. Two refueling station designs were simulated and compared. The modeling results indicate that pressure...... loss in the vehicle's storage system is one of the main factors determining the mass flow and peak cooling requirements of the refueling process. The design of the refueling station does not influence the refueling of the vehicle when the requirements of the technical information report J2601 from...

  6. Dynamic impedance model of the skin-electrode interface for transcutaneous electrical stimulation.

    Directory of Open Access Journals (Sweden)

    José Luis Vargas Luna

    Full Text Available Transcutaneous electrical stimulation can depolarize nerve or muscle cells applying impulses through electrodes attached on the skin. For these applications, the electrode-skin impedance is an important factor which influences effectiveness. Various models describe the interface using constant or current-depending resistive-capacitive equivalent circuit. Here, we develop a dynamic impedance model valid for a wide range stimulation intensities. The model considers electroporation and charge-dependent effects to describe the impedance variation, which allows to describe high-charge pulses. The parameters were adjusted based on rectangular, biphasic stimulation pulses generated by a stimulator, providing optionally current or voltage-controlled impulses, and applied through electrodes of different sizes. Both control methods deliver a different electrical field to the tissue, which is constant throughout the impulse duration for current-controlled mode or have a very current peak for voltage-controlled. The results show a predominant dependence in the current intensity in the case of both stimulation techniques that allows to keep a simple model. A verification simulation using the proposed dynamic model shows coefficient of determination of around 0.99 in both stimulation types. The presented method for fitting electrode-skin impedance can be simple extended to other stimulation waveforms and electrode configuration. Therefore, it can be embedded in optimization algorithms for designing electrical stimulation applications even for pulses with high charges and high current spikes.

  7. Hydrogen diffusion in La{sub 1.5}Nd{sub 0.5}MgNi{sub 9} alloy electrodes of the Ni/MH battery

    Energy Technology Data Exchange (ETDEWEB)

    Volodin, A.A. [Institute of Problems of Chemical Physics of RAS, Chernogolovka (Russian Federation); Denys, R.V. [Institute for Energy Technology, P.O. Box 40, Kjeller NO2027 (Norway); Tsirlina, G.A. [Department of Electrochemistry, Moscow State University, Moscow (Russian Federation); Tarasov, B.P. [Institute of Problems of Chemical Physics of RAS, Chernogolovka (Russian Federation); Fichtner, M. [Institute of Nanotechnology, Karlsruhe Institute of Technology, Karlsruhe (Germany); Yartys, V.A., E-mail: volodymyr.yartys@ife.no [Institute for Energy Technology, P.O. Box 40, Kjeller NO2027 (Norway)

    2015-10-05

    Highlights: • Hydrogen diffusion in the La{sub 1.5}Nd{sub 0.5}MgNi{sub 9} alloy electrode was studied. • Various techniques of low amplitude potentiostatic data treatment were used. • D{sub H} demonstrates a maximum (2 × 10{sup −11} cm{sup 2}/s) at 85% of discharge of the electrode. • Maximum is associated with a conversion of β-hydride into a solid α-solution. • Optimization of material and electrode will allow high discharge rates. - Abstract: Hydrogen diffusion in the La{sub 1.5}Nd{sub 0.5}MgNi{sub 9} battery electrode material has been studied using low amplitude potentiostatic experiments. Complex diffusion behavior is examined in frames of electroanalytical models proposed for the lithium intercalation materials. Hydrogen diffusion coefficient D{sub H} changes with hydrogen content in the metal hydride anode electrode and has a maximum of ca. 2 × 10{sup −11} cm{sup 2}/s at ca. 85% of discharge. Such a behavior differs from the trends known for the transport in lithium battery materials, but qualitatively agrees with the data for the highly concentrated β-PdH{sub x}.

  8. Effect of N,C-ITO on Composite N,C-Ti/N,C-ITO/ITO Electrode Used for Photoelectrochemical Degradation of Aqueous Pollutant with Simultaneous Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Kee-Rong Wu

    2012-01-01

    Full Text Available This study reports the effect of N,C-ITO (indium tin oxide layer on composite N,C-TiO2/N,C-ITO/ITO (Ti/TO electrode used for efficient photoelectrocatalytic (PEC degradation of aqueous pollutant with simultaneous hydrogen production. The structural properties of the composite Ti/TO electrode that determined by X-ray diffraction and Raman scattering, show primarily the crystallized anatase TiO2 phase and distinct diffraction patterns of polycrystalline In2O3 phase. Under solar light illumination, the composite Ti/TO electrode yields simultaneously a hydrogen production rate of 12.0 μmol cm−2 h−1 and degradation rate constant of  cm−2 h−1 in organic pollutant. It implies that the overlaid N,C-TiO2 layer enhances not only the photocurrent response of the composite Ti/TO electrode at entire applied potentials, but also the flat band potential; a shift of about 0.1 V toward cathode, which is desperately beneficial in the PEC process. In light of the X-ray photoelectron spectroscopy findings, these results are attributable partly to the synergetic effect of N,C-codoping into the TiO2 and ITO lattices on their band gap narrowing and photosensitizing as well. Thus, the Ti/TO electrode can potentially serve an efficient PEC electrode for simultaneous pollutant degradation and hydrogen production.

  9. 碱性电解水析氢电极的研究进展%Research progress in hydrogen electrode materials for alkaline water electrolysis

    Institute of Scientific and Technical Information of China (English)

    张开悦; 刘伟华; 陈晖; 张博; 刘建国; 严川伟

    2015-01-01

    电解水制氢将成为未来绿色制氢工业的核心技术。研究新型阴极材料以有效降低阴极过电位,对降低电解水能耗和设备成本、提高生产稳定性和安全性,具有十分重要的现实意义。本文主要对碱性水溶液电解制氢工业的析氢阴极材料进行综述。围绕电极结晶结构设计和尺寸结构设计两个主要的电极发展方向,重点介绍了3类基于电沉积制备技术的Ni基电极材料:合金析氢电极、复合析氢电极、多孔析氢电极。分析了当前析氢电极在实验研发与工业应用中存在的问题。指出采用电沉积法,制备催化活性更高且适用于工业电解环境的多元复合电极材料将是今后析氢电极发展的趋势。%Water electrolysis will become the core technology of environmental production for hydrogen industry in the future. It is very important to study new cathode materials for reducing the cathode overpotential. Because it not only can reduce energy consumption and the cost of water electrolysis,but also can enhance the stability and safety of production. This paper mainly discusses the research status of hydrogen electrode materials for alkaline water electrolysis. Based on the major improvement of catalytic activity for hydrogen evolution reaction,this paper mainly focuses on the electrodepositing preparation method for three kinds of nickel-based electrodes,which are alloy hydrogen evolution electrode,composite hydrogen evolution electrode,and porous hydrogen evolution electrode. The existing problems on hydrogen evolution electrode in experimental research and industrial application are analyzed. In the end,it is pointed out that the more catalytic activity and more stable electrochemical performance of multivariate composite electrodes based on electrodepositing preparation will be the future of hydrogen electrode development.

  10. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether): Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    WU RongLiang; JI Qing; KONG Bin; YANG XiaoZhen

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether) (PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution func-tions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain, and there still exists a significant amount (10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentra-tion as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer, which leads to inefficient con-tacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds, but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry (DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME, which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition, at the concentration of 86%, each ether oxygen atom bonded with water is assigned 1.56 water molecules on average, and 'free' water molecules emerge at the concentration of around 54%.

  11. Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ~27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and ’free’ water molecules emerge at the concentration of around 54%.

  12. Electrochemical determination of hydrogen peroxide using Rhodobacter capsulatus cytochrome c peroxidase at a gold electrode

    NARCIS (Netherlands)

    De Wael, K.; Buschop, H.; Heering, H.A.; De Smet, L.; Van Beeumen, J.; Devreese, B.; Adriaens, A.

    2007-01-01

    We describe the redox behaviour of horse heart cytochrome c (HHC) and Rhodobacter capsulatus cytochrome c peroxidase (RcCCP) at a gold electrode modified with 4,4′-bipyridyl. RcCCP shows no additional oxidation or reduction peaks compared to the electrochemistry of only HHC, which indicates that it

  13. Equilibration dynamics and conductivity of warm dense hydrogen

    Science.gov (United States)

    Zastrau, U.; Sperling, P.; Becker, A.; Bornath, T.; Bredow, R.; Döppner, T.; Dziarzhytski, S.; Fennel, T.; Fletcher, L. B.; Förster, E.; Fortmann, C.; Glenzer, S. H.; Göde, S.; Gregori, G.; Harmand, M.; Hilbert, V.; Holst, B.; Laarmann, T.; Lee, H. J.; Ma, T.; Mithen, J. P.; Mitzner, R.; Murphy, C. D.; Nakatsutsumi, M.; Neumayer, P.; Przystawik, A.; Roling, S.; Schulz, M.; Siemer, B.; Skruszewicz, S.; Tiggesbäumker, J.; Toleikis, S.; Tschentscher, T.; White, T.; Wöstmann, M.; Zacharias, H.; Redmer, R.

    2014-07-01

    We investigate subpicosecond dynamics of warm dense hydrogen at the XUV free-electron laser facility (FLASH) at DESY (Hamburg). Ultrafast impulsive electron heating is initiated by a ≤300-fs short x-ray burst of 92-eV photon energy. A second pulse probes the sample via x-ray scattering at jitter-free variable time delay. We show that the initial molecular structure dissociates within (0.9±0.2) ps, allowing us to infer the energy transfer rate between electrons and ions. We evaluate Saha and Thomas-Fermi ionization models in radiation hydrodynamics simulations, predicting plasma parameters that are subsequently used to calculate the static structure factor. A conductivity model for partially ionized plasma is validated by two-temperature density-functional theory coupled to molecular dynamic simulations and agrees with the experimental data. Our results provide important insights and the needed experimental data on transport properties of dense plasmas.

  14. Nuclear quantum effect on intramolecular hydrogen bond of hydrogen maleate anion: An ab initio path integral molecular dynamics study

    Science.gov (United States)

    Kawashima, Yukio; Tachikawa, Masanori

    2013-05-01

    Ab initio path integral molecular dynamics simulation was performed to understand the nuclear quantum effect on the hydrogen bond of hydrogen malonate anion. Static calculation predicted the proton transfer barrier as 0.12 kcal/mol. Conventional ab initio molecular dynamics simulation at 300 K found proton distribution with a double peak on the proton transfer coordinate. Inclusion of thermal effect alone elongates the hydrogen bond length, which increases the barrier height. Inclusion of nuclear quantum effect washes out this barrier, and distributes a single broad peak in the center. H/D isotope effect on the proton transfer is also discussed.

  15. Effect Of Dynamic Characteristics of Power Supplies on Aerosol Composition While Welding With Coated Electrodes

    Science.gov (United States)

    Il'yaschenko, D. P.; Chinakhov, D. A.; Sadikov, I. D.

    2016-08-01

    In the context of a significant increase in production output and use of welding technologies in the manufacturing of engineering products the problem of hygienic characteristics of working conditions in arc fusion welding is becoming increasingly important. The work represents how the dynamic characteristics of a power supply affect the transfer of alloying elements from a coated electrode into a base metal, a slag phase and a solid component of welding fumes. Short-circuit current limiting in inverters reduces overheating of electrode metal drops by 15%; welding fumes quantitative component - to 38%; manganese - to 30%; thermal radiation intensity - by 37%.

  16. Hydrogen storage alloys rapidly solidified by the melt-spinning method and their characteristics as metal hydride electrodes. [LaNiAl; LaNiCoAl

    Energy Technology Data Exchange (ETDEWEB)

    Mishima, R. (Mitsubishi Kasei Corp., Research Center, Yokohama (Japan)); Miyamura, H. (Government Industrial Research Inst., Osaka (Japan)); Sakai, T. (Government Industrial Research Inst., Osaka (Japan)); Kuriyama, N. (Government Industrial Research Inst., Osaka (Japan)); Ishikawa, H. (Government Industrial Research Inst., Osaka (Japan)); Uehara, I. (Government Industrial Research Inst., Osaka (Japan))

    1993-02-23

    Rapidly solidified LaNi[sub 5]-based hydrogen storage alloys were prepared by a melt-spinning method. The prepared melt-spun alloy ribbon had very fine crystal grain of below 10 [mu]m. The hydrogen absorption behavior and electrode properties of the alloys were greatly improved. Heat treatment at 400 C which did not cause enlargement of the grain further improved these properties. (orig.)

  17. Network dynamics of cultured hippocampal neurons in a multi-electrode array

    Science.gov (United States)

    Taguchi, Takahisa; Kudoh, Suguru N.

    2005-02-01

    The neurons in dissociation culture autonomously re-organized their functional neuronal networks, after the process for elongating neurites and establishing synaptic connections. The spatio-temporal patterns of activity in the networks might be a reflection of functional neuron assemblies. The functional connections were dynamically modified by synaptic potentiation and the process may be required for reorganization of the functional group of neurons. Such neuron assemblies are critical for information processing in brain. To visualize the functional connections between neurons, we have analyzed the autonomous activity of synaptically induced action potentials in the living neuronal networks on a multi-electrode array, using "connection map analysis" that we developed for this purpose. Moreover, we designed aan original wide area covering electrode array and succeeded in recording spontaneous action potentials from wider area than commercial multi electrode arrays.

  18. Characteristics of multi-component MI-based hydrogen storage alloys and their hydride electrodes

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A series of multi-component MI-based hydrogen storage alloys with a cobalt atomic ratio of 0.40-0.75 w ere prepared. The electrochemical properties under different charge-discharge conditions and PCT characteristics measured by electrochemical method were investigated. The addition of other alloying elements for partial substitution of Co lowers the hydrogen equilibrium pressure and discharge capacity, but improves the cycling stability and makes the alloys keep nearly the same rate discharge capability and high-temperature discharge capability as those of the compared alloy.The reasons were discussed.

  19. Amperometric detection of hydrogen peroxide at nano-nickel oxide/thionine and celestine blue nanocomposite-modified glassy carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Noorbakhsh, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 426, Sanandaj (Iran, Islamic Republic of)], E-mail: absalimi@uok.ac.ir

    2009-11-01

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with nickel oxide (NiOx) nanoparticles and water-soluble dyes. By immersing the GC/NiOx modified electrode into thionine (TH) or celestine blue (CB) solutions for a short period of time (5-120 s), a thin film of the proposed molecules was immobilized onto the electrode surface. The modified electrodes showed stable and a well-defined redox couples at a wide pH range (2-12), with surface confined characteristics. In comparison to usual methods for the immobilization of dye molecules, such as electropolymerization or adsorption on the surface of preanodized electrodes, the electrochemical reversibility and stability of these modified electrodes have been improved. The surface coverage and heterogeneous electron transfer rate constants (k{sub s}) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 x 10{sup -10} mol cm{sup -2}, 6.12 s{sup -1}, 5.9 x 10{sup -10} mol cm{sup -2} and 6.58 s{sup -1}, respectively. The results clearly show the high loading ability of the NiOx nanoparticles and great facilitation of the electron transfer between the immobilized TH, CB and NiOx nanoparticles. The modified electrodes show excellent electrocatalytic activity toward hydrogen peroxide reduction at a reduced overpotential. The catalytic rate constants for hydrogen peroxide reduction at GC/NiOx/CB and GC/NiOx/TH were 7.96 ({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1} and 5.5 ({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1}, respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 {mu}M, 4.14 nA {mu}M{sup -1} nA {mu}M{sup -1} and 5 {mu}M to 20 mM, and 0.36 {mu}M, 7.62 nA {mu}M{sup -1}, and 1 {mu}M to 10 mM for the GC/NiOx/TH and GC/NiOx/CB modified electrodes, respectively. Compared to other modified electrodes, these modified electrodes have many advantages, such as remarkable catalytic activity, good

  20. Hydrogen bond dynamics in alcohols studied by 2D IR spectroscopy

    NARCIS (Netherlands)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L C; Pshenichnikov, Maxim S.

    2015-01-01

    Ultrafast hydrogen-bond dynamics in alcohols are studied by 2D IR spectroscopy and combined molecular dynamics—quantum mechanical simulations on the OH stretching mode. Fast memory loss in *100 fs are attributed to intact hydrogen-bond fluctuations. Stable (at the experimental timescale) hydrogen bo

  1. A Thorax Simulator for Complex Dynamic Bioimpedance Measurements With Textile Electrodes.

    Science.gov (United States)

    Ulbrich, Mark; Muhlsteff, Jens; Teichmann, Daniel; Leonhardt, Steffen; Walter, Marian

    2015-06-01

    Bioimpedance measurements on the human thorax are suitable for assessment of body composition or hemodynamic parameters, such as stroke volume; they are non-invasive, easy in application and inexpensive. When targeting personal healthcare scenarios, the technology can be integrated into textiles to increase ease, comfort and coverage of measurements. Bioimpedance is generally measured using two electrodes injecting low alternating currents (0.5-10 mA) and two additional electrodes to measure the corresponding voltage drop. The impedance is measured either spectroscopically (bioimpedance spectroscopy, BIS) between 5 kHz and 1 MHz or continuously at a fixed frequency around 100 kHz (impedance cardiography, ICG). A thorax simulator is being developed for testing and calibration of bioimpedance devices and other new developments. For the first time, it is possible to mimic the complete time-variant properties of the thorax during an impedance measurement. This includes the dynamic real part and dynamic imaginary part of the impedance with a peak-to-peak value of 0.2 Ω and an adjustable base impedance (24.6 Ω ≥ Z0 ≥ 51.6 Ω). Another novelty is adjustable complex electrode-skin contact impedances for up to 8 electrodes to evaluate bioimpedance devices in combination with textile electrodes. In addition, an electrocardiographic signal is provided for cardiographic measurements which is used in ICG devices. This provides the possibility to generate physiologic impedance changes, and in combination with an ECG, all parameters of interest such as stroke volume (SV), pre-ejection period (PEP) or extracellular resistance (Re) can be simulated. The speed of all dynamic signals can be altered. The simulator was successfully tested with commercially available BIS and ICG devices and the preset signals are measured with high correlation (r = 0.996).

  2. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    Science.gov (United States)

    Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2014-11-01

    The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  3. Hydrogen-incorporated TiS2 ultrathin nanosheets with ultrahigh conductivity for stamp-transferrable electrodes.

    Science.gov (United States)

    Lin, Chenwen; Zhu, Xiaojiao; Feng, Jun; Wu, Changzheng; Hu, Shuanglin; Peng, Jing; Guo, Yuqiao; Peng, Lele; Zhao, Jiyin; Huang, Jianliu; Yang, Jinlong; Xie, Yi

    2013-04-03

    As a conceptually new class of two-dimensional (2D) materials, the ultrathin nanosheets as inorganic graphene analogues (IGAs) play an increasingly vital role in the new-generation electronics. However, the relatively low electrical conductivity of inorganic ultrathin nanosheets in current stage significantly hampered their conducting electrode applications in constructing nanodevices. We developed the unprecedentedly high electrical conductivity in inorganic ultrathin nanosheets. The hydric titanium disulfide (HTS) ultrathin nanosheets, as a new IGAs, exhibit the exclusively high electrical conductivity of 6.76 × 10(4) S/m at room temperature, which is superior to indium tin oxide (1.9 × 10(4) S/m), recording the best value in the solution assembled 2D thin films of both graphene (5.5 × 10(4) S/m) and inorganic graphene analogues (5.0 × 10(2) S/m). The modified hydrogen on S-Ti-S layers contributes additional electrons to the TiS2 layered frameworks, rendering the controllable electrical conductivity as well as the electron concentrations. Together with synergic advantages of the excellent mechanical flexibility, high stability, and stamp-transferrable properties, the HTS thin films show promising capability for being the next generation conducting electrode material in the nanodevice fields.

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

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  5. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    KAUST Repository

    Li, Yang

    2014-11-07

    © 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  6. Fabrication of Metal Nanoparticle-Modified Screen Printed Carbon Electrodes for the Evaluation of Hydrogen Peroxide Content in Teeth Whitening Strips

    Science.gov (United States)

    Popa, Adriana; Abenojar, Eric C.; Vianna, Adam; Buenviaje, Czarina Y. A.; Yang, Jiahua; Pascual, Cherrie B.; Samia, Anna Cristina S.

    2015-01-01

    A laboratory experiment in which students synthesize Ag, Au, and Pt nanoparticles (NPs) and use them to modify screen printed carbon electrodes for the electroanalysis of the hydrogen peroxide content in commercially available teeth whitening strips is described. This experiment is designed for two 3-h laboratory periods and can be adapted for…

  7. Oxygen and hydrogen peroxide reduction catalyses in neutral aqueous media using copper ion loaded glassy carbon electrode electrolyzed in ammonium carbamate solution

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Hiroaki; Yamazaki, Haruhito [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan); Wang, Xiuyun [School of Chemical Engineering, University of Science and Technology Liaoning, Anshan, Liaoning, 114051 (China); Uchiyama, Shunichi [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan)], E-mail: uchiyama@sit.ac.jp

    2009-01-30

    An aminated glassy carbon electrode (AGCE) can be obtained by the electrode oxidation of glassy carbon electrode in ammonium carbamate solution. In the cyclic voltammetric experiments, the electrode reduction of the dissolved oxygen began from -0.15 V vs. Ag/AgCl in neutral aqueous media when the aminated glassy carbon electrode was used as a working electrode although it began from -0.40 V vs. Ag/AgCl when a polished GCE was used. The nitrogen containing groups introduced by the electrode oxidation of carbamic acid must be related with the acceleration of the electron transfer rate of oxygen. Moreover, the new reduction wave of the dissolved oxygen appeared at +0.15 V vs. Ag/AgCl when copper (II) ion was coordinated to AGCE surface. This reduction potential of oxygen coincided with that of copper (II) ion and this fact suggests that the coordinated copper ion to the aminated carbon surface works as a redox mediator of oxygen. The reduction product of oxygen was monitored by rotating platinum ring - aminated glassy carbon disk electrode, and it was found that most of oxygen was reduced to water in a potential range negative than -0.4 V vs. Ag/AgCl. By using AGCE, it was recognized that the catalytic reduction of hydrogen peroxide was also taken place as well as oxygen reduction.

  8. Quantum dynamics of hydrogen atoms on graphene. II. Sticking

    Energy Technology Data Exchange (ETDEWEB)

    Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Jackson, Bret [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany); Martinazzo, Rocco, E-mail: rocco.martinazzo@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Richerche, v. Golgi 19, 20133 Milano (Italy)

    2015-09-28

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  9. Wave packet molecular dynamics simulations of warm dense hydrogen

    CERN Document Server

    Knaup, M; Toepffer, C; Zwicknagel, G

    2003-01-01

    Recent shock-wave experiments with deuterium in a regime where a plasma phase-transition has been predicted and their theoretical interpretation are the matter of a controversial discussion. In this paper, we apply 'wave packet molecular dynamics' (WPMD) simulations to investigate warm dense hydrogen. The WPMD method was originally used by Heller for a description of the scattering of composite particles such as simple atoms and molecules; later it was applied to Coulomb systems by Klakow et al. In the present version of our model the protons are treated as classical point-particles, whereas the electrons are represented by a completely anti-symmetrized Slater sum of periodic Gaussian wave packets. We present recent results for the equation of state of hydrogen at constant temperature T = 300 K and of deuterium at constant Hugoniot E - E sub 0 + 1/2(1/n - 1/n sub 0)(p + p sub 0) = 0, and compare them with the experiments and several theoretical approaches.

  10. Imaging Dynamic Collision and Oxidation of Single Silver Nanoparticles at the Electrode/Solution Interface.

    Science.gov (United States)

    Hao, Rui; Fan, Yunshan; Zhang, Bo

    2017-09-06

    The electrochemical interface is an ultrathin interfacial region between the electrode surface and the electrolyte solution and is often characterized by numerous dynamic processes, such as solvation and desolvation, heterogeneous electron transfer, molecular adsorption and desorption, diffusion, and surface rearrangement. Many of these processes are driven and modulated by the presence of a large interfacial potential gradient. The study and better understanding of the electrochemical interface is important for designing better electrochemical systems where their applications may include batteries, fuel cells, electrocatalytic water splitting, corrosion protection, and electroplating. This, however, has proved to be a challenging analytical task due to the ultracompact and dynamic evolving nature of the electrochemical interface. Here, we describe the use of an electrochemical nanocell to image the dynamic collision and oxidation process of single silver nanoparticles at the surface of a platinum nanoelectrode. A nanocell is prepared by depositing a platinum nanoparticle at the tip of a quartz nanopipette forming a bipolar nanoelectrode. The compact size of the nanocell confines the motion of the silver nanoparticle in a 1-D space. The highly dynamic process of nanoparticle collision and oxidation is imaged by single-particle fluorescence microscopy. Our results demonstrate that silver nanoparticle collision and oxidation is highly dynamic and likely controlled by a strong electrostatic effect at the electrode/solution interface. We believe that the use of a platinum nanocell and single molecule/nanoparticle fluorescence microscopy can be extended to other systems to yield highly dynamic information about the electrochemical interface.

  11. Ionic liquid modified carbon paste electrode and investigation of its electrocatalytic activity to hydrogen peroxide

    Indian Academy of Sciences (India)

    Erhan Canbay; Hayati Türkmen; Erol Akyilmaz

    2014-05-01

    This paper reports on the preparation and advantages of novel amperometric biosensors in the presence of hydrophobic ionic liquid (IL), 1-methyl-3-butylimidazolium bromide ([MBIB]). Carbon paste bio-sensor has been constructed by entrapping horseradish peroxidase in graphite and IL mixed with paraffin oil as a binder. The resulting IL/graphite material brings new capabilities for electrochemical devices by combining the advantages of ILs composite electrodes. Amounts of H2O2 were amperometrically detected by monitoring current values at reduction potential (–0.15 V) of K3Fe(CN)6. Decrease in biosensor responses were linearly related to H2O2 concentrations between 10 and 100 M with 2 s response time. Limit of detection of the biosensor were calculated to be 3.98 M for H2O2. In the optimization studies of the biosensor some parameters such as optimum pH, optimum temperature, enzyme amount, interference effects of some substances on the biosensor response, reproducibility and storage stability were carried out. The promising results are ascribed to the use of an ionic liquid, which forms an excellent charge-transfer bridge and wide electrochemical windows in the bulk of carbon paste electrode.

  12. Hydrogen bioelectrooxidation on gold nanoparticle-based electrodes modified by Aquifex aeolicus hydrogenase: Application to hydrogen/oxygen enzymatic biofuel cells.

    Science.gov (United States)

    Monsalve, Karen; Roger, Magali; Gutierrez-Sanchez, Cristina; Ilbert, Marianne; Nitsche, Serge; Byrne-Kodjabachian, Deborah; Marchi, Valérie; Lojou, Elisabeth

    2015-12-01

    For the first time, gold nanoparticle-based electrodes have been used as platforms for efficient immobilization of the [NiFe] hydrogenase from the hyperthermophilic bacterium Aquifex aeolicus. AuNPs were characterized by electronic microscopy, dynamic light scattering and UV-Vis spectroscopy. Two sizes around 20.0±5.3 nm and 37.2±4.3 nm nm were synthesized. After thiol-based functionalization, the AuNPs were proved to allow direct H2 oxidation over a large range of temperatures. A high current density up to 1.85±0.15 mA·cm(-2) was reached at the smallest AuNPs, which is 170 times higher than the one recorded at the bare gold electrode. The catalytic current was especially studied as a function of the AuNP size and amount, and procedure for deposition. A synergetic effect between the AuNP porous deposit and the increase surface area was shown. Compared to previously used nanomaterials such as carbon nanofibers, the covalent grafting of the enzyme on the thiol-modified gold nanoparticles was shown to enhance the stability of the hydrogenase. This bioanode was finally coupled to a biocathode where BOD from Myrothecium verrucaria was immobilized on AuNP-based film. The performance of the so-mounted H2/O2 biofuel cell was evaluated, and a power density of 0.25 mW·cm(-2) was recorded.

  13. Quantum molecular dynamics simulations of hydrogen production and solar cells

    Science.gov (United States)

    Mou, Weiwei

    The global energy crisis presents two major challenges for scientists around the world: Producing cleaner energy which is sustainable for the environment; And improving the efficiency of energy production as well as consumption. It is crucial and yet elusive to understand the atomistic mechanisms and electronic properties, which are needed in order to tackle those challenges. Quantum molecular dynamics simulations and nonadiabatic quantum molecular dynamics are two of the dominant methods used to address the atomistic and electronic properties in various energy studies. This dissertation is an ensemble of three studies in energy research: (1) Hydrogen production from the reaction of aluminum clusters with water to provide a renewable energy cycle; (2) The photo-excited charge transfer and recombination at a quaterthiophene/zinc oxide interface to improve the power conversion efficiency of hybrid poly(3-hexylthiophene) (P3HT) /ZnO solar cells; and (3) the charge transfer at a rubrene/C60 interface to understand why phenyl groups in rubrene improve the performance of rubrene/C60 solar cells.

  14. High capacity hydrogen storage alloy negative electrodes for use in nickel–metal hydride batteries

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Hiroshi, E-mail: inoue-h@chem.osakafu-u.ac.jp; Kotani, Norihiro; Chiku, Masanobu; Higuchi, Eiji

    2015-10-05

    Highlights: • Rare earth-free TiV{sub 2.1−x}Cr{sub x}Ni{sub 0.3} (x = 0.4–1.0) alloys were prepared by arc-melting. • All alloys were composed of two phases, bcc phase and TiNi-based phase. • The higher Cr content, the lower discharge capacity, the higher cycle durability. • The lower charge-transfer resistance led to the higher HRD. • The TiV{sub 1.6}Cr{sub 0.5}Ni{sub 0.3} alloy electrode had the highest HRD. - Abstract: Rare earth-free V-based TiV{sub 2.1−x}Cr{sub x}Ni{sub 0.3} (x = 0.4–1.0) alloys were prepared by arc-melting. All alloys were composed of two phases, the primary phase in which the V and Cr constituents were mainly distributed and the secondary phase in which the Ti and Ni constituents were mainly distributed. When the Cr content was increased, the maximum discharge capacity was decreased, but charge–discharge cycle durability was improved. The lower the charge-transfer resistance and the higher the specific discharge current at which the positive shift of potential at degree of discharge of 50% stagnates, the higher the HRD. In the present study, the TiV{sub 1.6}Cr{sub 0.5}Ni{sub 0.3} alloy electrode had the highest HRD.

  15. Fabrication of gallium hexacyanoferrate modified carbon ionic liquid paste electrode for sensitive determination of hydrogen peroxide and glucose

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Behzad, E-mail: haghighi@iasbs.ac.ir; Khosravi, Mehdi; Barati, Ali

    2014-07-01

    Gallium hexacyanoferrate (GaHCFe) and graphite powder were homogeneously dispersed into n-dodecylpyridinium hexafluorophosphate and paraffin to fabricate GaHCFe modified carbon ionic liquid paste electrode (CILPE). Mixture experimental design was employed to optimize the fabrication of GaHCFe modified CILPE (GaHCFe-CILPE). A pair of well-defined redox peaks due to the redox reaction of GaHCFe through one-electron process was observed for the fabricated electrode. The fabricated GaHCFe-CILPE exhibited good electrocatalytic activity towards reduction and oxidation of H{sub 2}O{sub 2}. The observed sensitivities for the electrocatalytic oxidation and reduction of H{sub 2}O{sub 2} at the operating potentials of + 0.8 and − 0.2 V were about 13.8 and 18.3 mA M{sup −1}, respectively. The detection limit (S/N = 3) for H{sub 2}O{sub 2} was about 1 μM. Additionally, glucose oxidase (GOx) was immobilized on GaHCFe-CILPE using two methodology, entrapment into Nafion matrix and cross-linking with glutaraldehyde and bovine serum albumin, in order to fabricate glucose biosensor. Linear dynamic rage, sensitivity and detection limit for glucose obtained by the biosensor fabricated using cross-linking methodology were 0.1–6 mM, 0.87 mA M{sup −1} and 30 μM, respectively and better than those obtained (0.2–6 mM, 0.12 mA M{sup −1} and 50 μM) for the biosensor fabricated using entrapment methodology. - Highlights: • Gallium hexacyanoferrate modified carbon ionic liquid paste electrode was fabricated. • Mixture experimental design was used to optimize electrode fabrication. • Response trace plot was used to show the effect of electrode materials on response. • The sensor exhibited electrocatalytic activity towards H{sub 2}O{sub 2} reduction and oxidation. • Glucose biosensor was fabricated by immobilization of glucose oxidase on sensor.

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

    Directory of Open Access Journals (Sweden)

    A. Survila

    2011-01-01

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

  17. A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy

    Directory of Open Access Journals (Sweden)

    Sun Qian

    2011-02-01

    Full Text Available Hydrogen partial pressure is an important parameter to calculate hydrogen concentration levels in molten aluminum alloy. A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy is studied. Dynamic and rapid measurement is realized through changing the volume of the vacuum chamber and calculating the pressure difference ΔP between the theoretical and measured pressures in the vacuum chamber. Positive ΔP indicates hydrogen transmits from melt to vacuum chamber and negative ΔP means the reverse. When ΔP is equal to zero, hydrogen transmitted from both sides reached a state of dynamical equilibrium and the pressure in the vacuum chamber is equal to the hydrogen partial pressure in the molten aluminum alloy. Compared with other existing measuring methods, the new method can significantly shorten the testing time and reduce measuring cost.

  18. Microsensor measurements of hydrogen gas dynamics in cyanobacterial microbial mats.

    Science.gov (United States)

    Nielsen, Michael; Revsbech, Niels P; Kühl, Michael

    2015-01-01

    We used a novel amperometric microsensor for measuring hydrogen gas production and consumption at high spatio-temporal resolution in cyanobacterial biofilms and mats dominated by non-heterocystous filamentous cyanobacteria (Microcoleus chtonoplastes and Oscillatoria sp.). The new microsensor is based on the use of an organic electrolyte and a stable internal reference system and can be equipped with a chemical sulfide trap in the measuring tip; it exhibits very stable and sulfide-insensitive measuring signals and a high sensitivity (1.5-5 pA per μmol L(-1) H2). Hydrogen gas measurements were done in combination with microsensor measurements of scalar irradiance, O2, pH, and H2S and showed a pronounced H2 accumulation (of up to 8-10% H2 saturation) within the upper mm of cyanobacterial mats after onset of darkness and O2 depletion. The peak concentration of H2 increased with the irradiance level prior to darkening. After an initial build-up over the first 1-2 h in darkness, H2 was depleted over several hours due to efflux to the overlaying water, and due to biogeochemical processes in the uppermost oxic layers and the anoxic layers of the mats. Depletion could be prevented by addition of molybdate pointing to sulfate reduction as a major sink for H2. Immediately after onset of illumination, a short burst of presumably photo-produced H2 due to direct biophotolysis was observed in the illuminated but anoxic mat layers. As soon as O2 from photosynthesis started to accumulate, the H2 was consumed rapidly and production ceased. Our data give detailed insights into the microscale distribution and dynamics of H2 in cyanobacterial biofilms and mats, and further support that cyanobacterial H2 production can play a significant role in fueling anaerobic processes like e.g., sulfate reduction or anoxygenic photosynthesis in microbial mats.

  19. Microsensor Measurements of Hydrogen Gas Dynamics in Cyanobacterial Microbial Mats

    Directory of Open Access Journals (Sweden)

    Michael eNielsen

    2015-07-01

    Full Text Available We used a novel amperometric microsensor for measuring hydrogen gas production and consumption at high spatio-temporal resolution in cyanobacterial biofilms and mats dominated by non-heterocystous filamentous cyanobacteria (Microcoleus chtonoplastes and Oscillatoria spp.. The new microsensor is based on the use of an organic electrolyte and a stable internal reference system and can be equipped with a chemical sulfide trap in the measuring tip; it exhibits very stable and sulfide-insensitive measuring signals and a high sensitivity (1.5-5 pA per µmol L-1 H2. Hydrogen gas measurements were done in combination with microsensor measurements of scalar irradiance, O2, pH, and H2S and showed a pronounced H2 accumulation (of up to 8-10% H2 saturation within the upper mm of cyanobacterial mats after onset of darkness and O2 depletion. The peak concentration of H2 increased with the irradiance level prior to darkening. After an initial build-up over the first 1-2 hours in darkness, H2 was depleted over several hours due to efflux to the overlaying water, and due to biogeochemical processes in the uppermost oxic layers and the anoxic layers of the mats. Depletion could be prevented by addition of molybdate pointing to sulfate reduction as a major sink for H2. Immediately after onset of illumination, a short burst of presumably photo-produced H2 due to direct photobiolysis was observed in the illuminated but anoxic mat layers. As soon as O2 from photosynthesis started to accumulate, the H2 was consumed rapidly and production ceased. Our data give detailed insights into the microscale distribution and dynamics of H2 in cyanobacterial biofilms and mats, and further support that cyanobacterial H2 production can play a significant role in fueling anaerobic processes like e.g. sulfate reduction or anoxygenic photosynthesis in microbial mats.

  20. A hydrogen peroxide sensor based on a horseradish peroxidase/polyaniline/carboxy-functionalized multiwalled carbon nanotube modified gold electrode

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Mu-Yi, E-mail: huamy@mail.cgu.edu.t [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Lin, Yu-Chen [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Tsai, Rung-Ywan [Electronics and Optoelectronics Research Laboratories, Industrial Technology Research Institute, 195, Sec. 4, Chung Hsing Rd., Hsinchu 31040, Taiwan (China); Chen, Hsiao-Chien; Liu, Yin-Chih [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China)

    2011-10-30

    We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 x 10{sup -3} S cm{sup -1}, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H{sub 2}O{sub 2}) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H{sub 2}O{sub 2} and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H{sub 2}O{sub 2} concentrations (86 {mu}M-10 mM). This sensor exhibited good sensitivity (194.9 {mu}A mM{sup -1} cm{sup -2}), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of -0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H{sub 2}O{sub 2} with high performance and excellent stability.

  1. Contact and Support Considerations in the Hydrogen Evolution Reaction Activity of Petaled MoS2 Electrodes.

    Science.gov (United States)

    Finn, Shane T; Macdonald, Janet E

    2016-09-28

    Petaled MoS2 electrodes grown hydrothermally from Mo foils are found to have an 800 nm, intermediate, MoSxOy layer. Similar petaled MoS2 films without this intermediate layer are grown on Au. X-ray photoelectron and Raman spectroscopies and transmission electron microscopy indicate the resulting petaled multilayer MoS2 films are frayed and exhibit single-layer, 1T-MoS2 behavior at the edges. We compare the electrocatalytic hydrogen evolution reaction activity via linear sweep voltammetry with Tafel analysis as well as the impedance properties of the electrodes. We find that petaled MoS2/Au and petaled MoS2/Mo exhibit comparable overpotential to 10 mA cm(-2) at -279 vs -242 mV, respectively, and similar Tafel slopes of ∼68 mV/decade indicating a similar rate-determining step. The exchange current normalized to the geometric area of petaled MoS2/Au (0.000921 mA cm(-2)) is 3 times smaller than that of petaled MoS2/Mo (0.00290 mA cm(-2)), and is attributed to the lower petal density on the Au support. However, Au supports increase the turnover frequency per active site of petaled MoS2 to 0.48 H2 Mo(-1) s(-1) from 0.25 H2 Mo(-1) s(-1) on Mo supports. Both petaled MoS2 films have nearly ohmic contacts to their supports with uncompensated resistivity Ru of <2.5 Ω·cm(2).

  2. Reference Electrodes in Metal Corrosion

    Directory of Open Access Journals (Sweden)

    S. Szabó

    2010-01-01

    Full Text Available With especial regard to hydrogen electrode, the theoretical fundamentals of electrode potential, the most important reference electrodes and the electrode potential measurement have been discussed. In the case of the hydrogen electrode, it have been emphasised that there is no equilibrium between the hydrogen molecule (H2 and the hydrogen (H+, hydronium (H3O+ ion in the absence of a suitable catalyst. Taking into account the practical aspects as well, the theorectical basis of working of hydrogen, copper-copper sulphate, mercury-mercurous halide, silver-silver halide, metal-metal oxide, metal-metal sulphate and “Thalamid” electrodes, has been discussed.

  3. Effects of hydrogen-bond environment on single particle and pair dynamics in liquid water

    Indian Academy of Sciences (India)

    Amalendu Chandra; Snehasis Chowdhuri

    2001-10-01

    We have performed molecular dynamics simulations of liquid water at 298 and 258 K to investigate the effects of hydrogen-bond environment on various single-particle and pair dynamical properties of water molecules at ambient and supercooled conditions. The water molecules are modelled by the extended simple point charge (SPC/E) model. We first calculate the distribution of hydrogen-bond environment in liquid water at both temperatures and then investigate how the selfdiffusion and orientational relaxation of a single water molecule and also the relative diffusion and relaxation of the hydrogen-bond of a water pair depend on the nature of the hydrogen-bond environment of the tagged molecules. We find that the various dynamical quantities depend significantly on the hydrogen-bond environment, especially at the supercooled temperature. The present study provides a molecular-level insight into the dynamics of liquid water under ambient and supercooled conditions.

  4. Direct and mediated electrochemistry of peroxidase and its electrocatalysis on a variety of screen-printed carbon electrodes: amperometric hydrogen peroxide and phenols biosensor.

    Science.gov (United States)

    Chekin, Fereshteh; Gorton, Lo; Tapsobea, Issa

    2015-01-01

    This study compares the behaviour of direct and mediated electrochemistry of horseradish peroxidase (HRP) immobilised on screen-printed carbon electrodes (SPCEs), screen-printed carbon electrodes modified with carboxyl-functionalised multi-wall carbon nanotubes (MWCNT-SPCEs) and screen-printed carbon electrodes modified with carboxyl-functionalised single-wall carbon nanotubes (SWCNT-SPCEs). The techniques of cyclic voltammetry and amperometry in the flow mode were used to characterise the properties of the HRP immobilised on screen-printed electrodes. From measurements of the mediated and mediatorless currents of hydrogen peroxide reduction at the HRP-modified electrodes, it was concluded that the fraction of enzyme molecules in direct electron transfer (DET) contact with the electrode varies substantially for the different electrodes. It was observed that the screen-printed carbon electrodes modified with carbon nanotubes (MWCNT-SPCEs and SWCNT-SPCEs) demonstrated a substantially higher percentage (≈100 %) of HRP molecules in DET contact than the screen-printed carbon electrodes (≈60 %). The HRP-modified electrodes were used for determination of hydrogen peroxide in mediatorless mode. The SWCNT-SPCE gave the lowest detection limit (0.40 ± 0.09 μM) followed by MWCNT-SPCE (0.48 ± 0.07 μM) and SPCE (0.98 ± 0.2 μM). These modified electrodes were additionally developed for amperometric determination of phenolic compounds. It was found that the SWCNT-SPCE gave a detection limit for catechol of 110.2 ± 3.6 nM, dopamine of 640.2 ± 9.2 nM, octopamine of 3341 ± 15 nM, pyrogallol of 50.10 ± 2.9 nM and 3,4-dihydroxy-L-phenylalanine of 980.7 ± 8.7 nM using 50 μM H2O2 in the flow carrier.

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

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

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

  6. Fast and stable redox reactions of MnO₂/CNT hybrid electrodes for dynamically stretchable pseudocapacitors.

    Science.gov (United States)

    Gu, Taoli; Wei, Bingqing

    2015-07-21

    Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics.

  7. Self-Sterilized Flexible Single-Electrode Triboelectric Nanogenerator for Energy Harvesting and Dynamic Force Sensing.

    Science.gov (United States)

    Guo, Huijuan; Li, Tao; Cao, Xiaotao; Xiong, Jin; Jie, Yang; Willander, Magnus; Cao, Xia; Wang, Ning; Wang, Zhong Lin

    2017-01-24

    Triboelectric nanogenerators (TENGs) offer great opportunities to deploy advanced wearable electronics that integrate a power generator and smart sensor, which eliminates the associated cost and sustainability concerns. Here, an embodiment of such integrated platforms has been presented in a graphene oxide (GO) based single-electrode TENG (S-TENG). The as-designed multifunctional device could not only harvest tiny bits of mechanical energy from ambient movements with a high power density of 3.13 W·m(-2) but also enable detecting dynamic force with an excellent sensitivity of about 388 μA·MPa(-1). Because of the two-dimensional nanostructure and excellent surface properties, the GO-based S-TENG shows sensitive force detection and sound antimicrobial activity in comparison with conventional poly(tetrafluoroethylene) (PTFE) electrodes. This technology offers great applicability prospects in portable/wearable electronics, micro/nanoelectromechanical devices, and self-powered sensors.

  8. Molecular dynamics simulation of the deposition process of hydrogenated diamond-like carbon (DLC) films

    Institute of Scientific and Technical Information of China (English)

    ZHANG YuJun; DONG GuangNeng; MAO JunHong; XIE YouBai

    2008-01-01

    The deposition process of hydrogenated diamond-like carbon (DLC) film greatly affects its frictional properties. In this study, CH3 radicals are selected as source species to deposit hydrogenated DLC films for molecular dynamics simulation. The growth and structural properties of hydrogenated DLC films are investigated and elucidated in detail. By comparison and statistical analysis, the authors find that the ratio of carbon to hydrogen in the films generally shows a monotonously increasing trend with the increase of impact energy. Carbon atoms are more reactive during deposition and more liable to bond with substrate atoms than hydrogen atoms. In addition, there exists a peak value of the number of hydrogen atoms deposited in hydrogenated DLC films. The trends of the variation are opposite on the two sides of this peak point, and itbecomes stable when impact energy is greater than 80 eV. The average relative density also indicates a rising trend along with the increment of impact energy, while it does not reach the saturation value until impact energy comes to 50 eV. The hydrogen content in source species is a key factor to determine the hydrogen content in hydrogenated DLC films. When the hydrogen content in source species is high, the hydrogen content in hydrogenated DLC films is accordingly high.

  9. A computational fluid dynamics study of hydrogen bubbles in an electrochemical reactor

    Directory of Open Access Journals (Sweden)

    Renata da Silva Cavalcanti

    2005-06-01

    Full Text Available Most electrochemical reactors present reactions with the growth and departure of gas bubbles which influence on the reactor hydrodynamics and this study is usually complex, representing a vast field for research. The present paper had as objective to study a bi-phase (gas-liquid system aiming to foresee the influence of departure of hydrogen bubbles generated on effective electrode surface situated on cathodic semi-cell. Nevertheless, it was idealized that the gas was injected into the semi cell, through the effective electrode surface With this hypothesis, it was possible to study, and numerically analyze, the hydrodynamic behavior of the hydrogen bubbles in the interior of the study domain, applying concepts of computational fluid dynamics by using the computational applicative CFX-4 for the application of the MUSIG ("MUltiple-SIze-Group" model, taking into consideration the phenomena of coalescence and the distribution of the diameter of the bubbles.A maioria dos reatores eletroquímicos apresenta reações com crescimento e desprendimento de bolhas de gás influenciando na hidrodinâmica dos reatores e seu estudo é, geralmente, complexo representando um campo amplo para pesquisas. O presente artigo teve por objetivo estudar um sistema bifásico (gás-líquido visando prever a influência do desprendimento das bolhas de hidrogênio geradas na superfície específica do eletrodo localizada na semicélula catódica. No entanto, foi idealizado que o gás fora injetado no interior da semicélula através da superfície específica do eletrodo. Com esta hipótese, foi possível estudar e analisar numericamente o comportamento hidrodinâmico das bolhas de hidrogênio no interior do domínio de estudo, aplicando-se os conceitos de fluidodinâmica computacional usando o aplicativo computacional CFX-4 para aplicação do modelo MUSIG ("Multiple-size-group" levando em consideração os fenômenos da coalescência e da distribuição do diâmetro das

  10. Cost-effective flow injection amperometric system with metal nanoparticle loaded carbon nanotube modified screen printed carbon electrode for sensitive determination of hydrogen peroxide.

    Science.gov (United States)

    Reanpang, Preeyaporn; Themsirimongkon, Suwaphid; Saipanya, Surin; Chailapakul, Orawon; Jakmunee, Jaroon

    2015-11-01

    Various metal nanoparticles (NPs) decorated on carbon nanotube (CNT) was modified on the home-made screen printed carbon electrode (SPCE) in order to enhances sensitivity of hydrogen peroxide (H2O2) determination. The simple casting method was used for the electrode modification. The monometallic and bimetallic NPs modified electrodes were investigated for their electrochemical properties for H2O2 reduction. The Pd-CNT/SPCE is appropriated to measure the H2O2 reduction at a potential of -0.3 V, then this modified electrode was incorporated with a home-made flow through cell and applied in a simple flow injection amperometry (FI-Amp). Some parameters influencing the resulted modified electrode and the FI-Amp system were studied. The proposed detection system was able to detect H2O2 in the range of 0.1-1.0 mM, with detection limit of 20 µM. Relative standard deviation for 100 replicated injections of 0.6 mM H2O2 was 2.3%. The reproducibility of 6 electrodes preparing in 3 different lots was 8.2%. It was demonstrated for determination of H2O2 in disinfectant, hair colorant and milk samples. Recoveries in the range of 90-109% were observed. The developed system provided high stability, good repeatability, high sample throughput and low reagent consumption.

  11. Dynamics of Single Hydrogen Bubbles at a Platinum Microelectrode.

    Science.gov (United States)

    Yang, Xuegeng; Karnbach, Franziska; Uhlemann, Margitta; Odenbach, Stefan; Eckert, Kerstin

    2015-07-28

    Bubble dynamics, including the formation, growth, and detachment, of single H2 bubbles was studied at a platinum microelectrode during the electrolysis of 1 M H2SO4 electrolyte. The bubbles were visualized through a microscope by a high-speed camera. Electrochemical measurements were conducted in parallel to measure the transient current. The periodic current oscillations, resulting from the periodic formation and detachment of single bubbles, allow the bubble lifetime and size to be predicted from the transient current. A comparison of the bubble volume calculated from the current and from the recorded bubble image shows a gas evolution efficiency increasing continuously with the growth of the bubble until it reaches 100%. Two different substrates, glass and epoxy, were used to embed the Pt wire. While nearly no difference was found with respect to the growth law for the bubble radius, the contact angle differs strongly for the two types of cell. Data provided for the contact point evolution further complete the image of single hydrogen bubble growth. Finally, the velocity field driven by the detached bubble was measured by means of PIV, and the effects of the convection on the subsequent bubble were evaluated.

  12. Hydrogen bond dynamics and vibrational spectral diffusion in aqueous solution of acetone: A first principles molecular dynamics study

    Indian Academy of Sciences (India)

    Bhabani S Mallik; Amalendu Chandra

    2012-01-01

    We present an ab initio molecular dynamics study of vibrational spectral diffusion and hydrogen bond dynamics in aqueous solution of acetone at room temperature. It is found that the frequencies of OD bonds in the acetone hydration shell have a higher stretch frequency than those in the bulk water. Also, on average, the frequencies of hydration shell OD modes are found to increase with increase in the acetone-water hydrogen bond distance. The vibrational spectral diffusion of the hydration shell water molecules reveals three time scales: A short-time relaxation (∼80 fs) corresponding to the dynamics of intact acetone-water hydrogen bonds, a slower relaxation (∼1.3 ps) corresponding to the lifetime of acetone-water hydrogen bonds and another longer time constant (∼12 ps) corresponding to the escape dynamics of water from the solute hydration shell. The present first principles results are compared with those of available experiments and classical simulations.

  13. Hydrogen sensing based on proton and electron transport across and along the interface solid oxide electrolyte-platinum electrode

    Energy Technology Data Exchange (ETDEWEB)

    Sakthivel, M; Weppner, W [Chair for Sensors and Solid State Ionics, Faculty of Engineering, Christian Albrechts University, Kaiserstrasse 2, Kiel D-24143 (Germany)

    2007-12-07

    A new class of low temperature proton-conducting-type hydrogen gas sensor was developed using Dion-Jacobson type layered perovskite oxides. A laminated structure with a junction of charge carriers at the interface between a predominantly ionically and predominately electronically conducting material was prepared by using the multistep-impregnation-reduction method for the deposition of Pt on top of a perovskite oxide. The proton conductivity of the layered perovskite materials was studied between room temperature and 250 deg. C. The sensing characteristic was studied by using H{sub 2} concentrations between 1% and 7%. The optimum operating temperature of the sensor was found to be at 45 deg. C. The formation of the galvanic cell voltage is described in terms of reactions at the interfaces and the surface of the electrodes. The experimental results indicate the motion of electrons within the Pt and of protons within the perovskite oxide along the interface. Hence, modelling the system response upon a change in gas concentrations can be beneficial for understanding the individual processes and optimizing the overall performance. (review article)

  14. REVIEW ARTICLE: Hydrogen sensing based on proton and electron transport across and along the interface solid oxide electrolyte platinum electrode

    Science.gov (United States)

    Sakthivel, M.; Weppner, W.

    2007-12-01

    A new class of low temperature proton-conducting-type hydrogen gas sensor was developed using Dion-Jacobson type layered perovskite oxides. A laminated structure with a junction of charge carriers at the interface between a predominantly ionically and predominately electronically conducting material was prepared by using the multistep-impregnation-reduction method for the deposition of Pt on top of a perovskite oxide. The proton conductivity of the layered perovskite materials was studied between room temperature and 250 °C. The sensing characteristic was studied by using H2 concentrations between 1% and 7%. The optimum operating temperature of the sensor was found to be at 45 °C. The formation of the galvanic cell voltage is described in terms of reactions at the interfaces and the surface of the electrodes. The experimental results indicate the motion of electrons within the Pt and of protons within the perovskite oxide along the interface. Hence, modelling the system response upon a change in gas concentrations can be beneficial for understanding the individual processes and optimizing the overall performance.

  15. Electrochemical properties of LaMO3 (M=Co or Fe) as the negative electrode in a hydrogen battery

    Science.gov (United States)

    Lim, D.-K.; Im, H.-N.; Kim, J.; Song, S.-J.

    2013-01-01

    Undoped orthorthombic LaFeO3 and monoclinic LaCoO3 oxides were selected as an anode material for Ni-H battery due to their high electron conductivity by multivalent transition status of B-site cation. Both groups of oxides were prepared by a conventional solid-state reaction method, and their electrochemical charge/discharge properties were investigated. The electrochemical kinetic properties, exchange current density, and proton diffusivity were also extracted using linear polarization measurement and the potential-step method. X-ray photoelectron spectroscopy (XPS) analysis was used to measure the oxidation state of the transition metal in the specimens. A non-linear least-square fitting deconvoluted the peaks, suggesting that the valence state of Fe and Co in the sample was mainly +3. The hydrogen diffusion rate was also estimated using the potential-step method, giving 5.42×10-16 and 5.72×10-16 cm2 s-1 for LaCoO3 and LaFeO3, respectively which are an order of magnitude larger than that of Sr doped LaFeO3 oxide electrodes.

  16. Glassy carbon electrode modified with a graphene oxide/poly(o-phenylenediamine) composite for the chemical detection of hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Tran, Trung Hieu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749 (Korea, Republic of); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749 (Korea, Republic of)

    2014-11-01

    Conducting poly(o-phenylenediamine) (POPD)/graphene oxide (GO) composites were prepared using a facile and efficient method involving the in-situ polymerization of OPD in the presence of GO in an aqueous medium. Copper sulfate was used as an oxidative initiator for the polymerization of OPD. Scanning electron microscopy and transmission electron microscopy images showed that POPD microfibrils were formed and distributed relatively uniformly with GO sheets in the obtained composites. X-ray diffraction results revealed the highly crystal structure of POPD. This composite exhibited good catalytic activity and stability. These results highlight the potential applications of POPD/GO composites as excellent electrochemical sensors. The composites were used to modify glass carbon electrodes for the chemical detection of hydrogen peroxide in aqueous media. - Highlights: • Graphene oxide/poly(o-phenylenediamine) composites were prepared efficiently. • POPD microfibrils were distributed relatively uniformly with GO sheets. • The composite exhibited good catalytic activity and stability for H{sub 2}O{sub 2} sensing.

  17. New hydrogen titanium phosphate sulfate electrodes for Li-ion and Na-ion batteries

    Science.gov (United States)

    Zhao, Ran; Mieritz, Daniel; Seo, Dong-Kyun; Chan, Candace K.

    2017-03-01

    NASICON-type materials with general formula AxM2(PO4)3 (A = Li or Na, M = Ti, V, and Fe) are promising candidates for Li- and Na-ion batteries due to their open three-dimensional framework structure. Here we report the electrochemical properties of hydrogen titanium phosphate sulfate, H0.4Ti2(PO4)2.4(SO4)0.6 (HTPS), a new mixed polyanion material with NASICON structure. Micron-sized HTPS aggregates with crystallite grain size of ca. 23 nm are synthesized using a sol-gel synthesis in an acidic medium. The properties of the as-synthesized HTPS, ball-milled HTPS, and samples prepared as carbon composites using an in-situ glucose decomposition reaction are investigated. A capacity of 148 mAh g-1 corresponding to insertion of 2 Li+ per formula unit is observed in the ball-milled HTPS over the potential window of 1.5-3.4 V vs. Li/Li+. Lithiation at ca. 2.8 and 2.5 V is determined to occur through filling of the M1 and M2 sites, respectively. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) are used characterize the HTPS before and after cycling. Evaluation of the HTPS in a Na-ion cell is also performed. A discharge capacity of 93 mAh g-1 with sodiation at ca. 2.9 and 2.2 V vs. Na/Na+ is observed.

  18. Estimation of dynamic properties of attractors observed in hollow copper electrode atmospheric pressure arc plasma system

    Indian Academy of Sciences (India)

    S Ghorul; S N Sahasrabudhe; P S S Murthy; A K Das; N Venkatramani

    2002-07-01

    Understanding of the basic nature of arc root fluctuation is still one of the unsolved problems in thermal arc plasma physics. It has direct impact on myriads of thermal plasma applications being implemented at present. Recently, chaotic nature of arc root behavior has been reported through the analysis of voltages, acoustic and optical signals which are generated from a hollow copper electrode arc plasma torch. In this paper we present details of computations involved in the estimation process of various dynamic properties and show how they reflect chaotic behavior of arc root in the system.

  19. Hydrogen production at high Faradaic efficiency by a bio-electrode based on TiO2 adsorption of a new [FeFe]-hydrogenase from Clostridium perfringens.

    Science.gov (United States)

    Morra, Simone; Valetti, Francesca; Sarasso, Veronica; Castrignanò, Silvia; Sadeghi, Sheila J; Gilardi, Gianfranco

    2015-12-01

    The [FeFe]-hydrogenase CpHydA from Clostridium perfringens was immobilized by adsorption on anatase TiO2 electrodes for clean hydrogen production. The immobilized enzyme proved to perform direct electron transfer to and from the electrode surface and catalyses both H2 oxidation (H2 uptake) and H2 production (H2 evolution) with a current density for H2 evolution of about 2 mA cm(-1). The TiO2/CpHydA bioelectrode remained active for several days upon storage and when a reducing potential was set, H2 evolution occurred with a mean Faradaic efficiency of 98%. The high turnover frequency of H2 production and the tight coupling of electron transfer, resulting in a Faradaic efficiency close to 100%, support the exploitation of the novel TiO2/CpHydA stationary electrode as a powerful device for H2 production.

  20. Hydrogen Bonding and Related Properties in Liquid Water: A Car-Parrinello Molecular Dynamics Simulation Study.

    Science.gov (United States)

    Guardia, Elvira; Skarmoutsos, Ioannis; Masia, Marco

    2015-07-23

    The local hydrogen-bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen-bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen-bonding network in liquid water has shown that this network is very labile, and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen-bonding states associated with the formation of four hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen-bonding state. Finally, the dependence of the librational and vibrational modes of water molecules on the local hydrogen-bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low-frequency Raman spectrum of liquid water.

  1. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes.

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-02-06

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs.

  2. Insight into the Role of Surface Wettability in Electrocatalytic Hydrogen Evolution Reactions Using Light-Sensitive Nanotubular TiO2 Supported Pt Electrodes

    Science.gov (United States)

    Meng, Chenhui; Wang, Bing; Gao, Ziyue; Liu, Zhaoyue; Zhang, Qianqian; Zhai, Jin

    2017-01-01

    Surface wettability is of importance for electrochemical reactions. Herein, its role in electrochemical hydrogen evolution reactions is investigated using light-sensitive nanotubular TiO2 supported Pt as hydrogen evolution electrodes (HEEs). The HEEs are fabricated by photocatalytic deposition of Pt particles on TiO2 nanotubes followed by hydrophobization with vaporized octadecyltrimethoxysilane (OTS) molecules. The surface wettability of HEEs is subsequently regulated in situ from hydrophobicity to hydrophilicity by photocatalytic decomposition of OTS molecules using ultraviolet light. It is found that hydrophilic HEEs demonstrate a larger electrochemical active area of Pt and a lower adhesion force to a gas bubble when compared with hydrophobic ones. The former allows more protons to react on the electrode surface at small overpotential so that a larger current is produced. The latter leads to a quick release of hydrogen gas bubbles from the electrode surface at large overpotential, which ensures the contact between catalysts and electrolyte. These two characteristics make hydrophilic HEEs generate a much high current density for HERs. Our results imply that the optimization of surface wettability is of significance for improving the electrocatalytic activity of HEEs. PMID:28165487

  3. An amperometric hydrogen peroxide biosensor based on Co{sub 3}O{sub 4} nanoparticles and multiwalled carbon nanotube modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Kaçar, Ceren; Dalkiran, Berna; Erden, Pınar Esra, E-mail: erdenpe@gmail.com; Kiliç, Esma

    2014-08-30

    Highlights: • Hydrogen peroxide biosensor was constructed by combining the advantageous properties of MWCNTs and Co{sub 3}O{sub 4}. • Incorporating Co{sub 3}O{sub 4} nanoparticles into MWCNTs/gelatin film increased the electron transfer. • Co{sub 3}O{sub 4}/MWCNTs/gelatin/HRP/Nafion/GCE showed strong anti-interference ability. • Hydrogen peroxide was successfully determined in disinfector with an average recovery of 100.78 ± 0.89. - Abstract: In this work a new type of hydrogen peroxide biosensor was fabricated based on the immobilization of horseradish peroxidase (HRP) by cross-linking on a glassy carbon electrode (GCE) modified with Co{sub 3}O{sub 4} nanoparticles, multiwall carbon nanotubes (MWCNTs) and gelatin. The introduction of MWCNTs and Co{sub 3}O{sub 4} nanoparticles not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate, resulting in a high sensitivity of the biosensor. The fabrication process of the sensing surface was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Amperometric detection of hydrogen peroxide was investigated by holding the modified electrode at −0.30 V (vs. Ag/AgCl). The biosensor showed optimum response within 5 s at pH 7.0. The optimized biosensor showed linear response range of 7.4 × 10{sup −7}–1.9 × 10{sup −5} M with a detection limit of 7.4 × 10{sup −7}. The applicability of the purposed biosensor was tested by detecting hydrogen peroxide in disinfector samples. The average recovery was calculated as 100.78 ± 0.89.

  4. Hydrogen bond dynamics in liquid water: Ab initio molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Cheolhee; Kim, Eunae [College of Pharmacy, Chosun University, Gwangju (Korea, Republic of); Yeom, Min Sun [Korea Institute of Science and Technology Information, Daejeon (Korea, Republic of)

    2016-01-15

    The effect of intermolecular interaction on the distribution of the harmonic vibrational frequencies of water molecules was investigated through ab initio molecular dynamics simulations based on the Born-Oppenheimer approach. For single water, the effect of the dynamics of the oxygen atom in single water and the simulation time step on the frequency distribution were examined. The distributions of the OH stretching and HOH bending vibrational frequencies of liquid water were compared to those of single water. The probability distributions of the change in OH bond length and the lifetime of the dangling OH bond were also obtained. The distribution of the frequencies was strongly affected by the long lifetime of the dangling OH bond, resulting in the formation of hydrogen bonds between water molecules.

  5. Hydrogen bonding and related properties in liquid water: a Car-Parrinello molecular dynamics simulation study

    OpenAIRE

    Guàrdia Manuel, Elvira; Skarmoutsos, Ioannis; Masia, Marco

    2015-01-01

    The local hydrogen-bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the ...

  6. Ab initio molecular dynamics simulation of hydrogen fluoride at several thermodynamic states

    DEFF Research Database (Denmark)

    Kreitmeir, M.; Bertagnolli, H.; Mortensen, Jens Jørgen;

    2003-01-01

    Liquid hydrogen fluoride is a simple but interesting system for studies of the influence of hydrogen bonds on physical properties. We have performed ab initio molecular dynamics simulations of HF at several thermodynamic states, where we examine the microscopic structure of the liquid as well...... as its static and dynamic properties. The results obtained show good agreement with well established data, and, moreover, we were able to show significant changes within the structure depending on the system's temperature and density....

  7. Dynamic characteristics of the SMH actuator using hydrogen-absorbing alloys

    Science.gov (United States)

    Kim, Kyong; Pang, D. Y.; Choi, K. H.; Lee, S. C.; Kim, Y. Y.; Kwon, T. K.; Hong, C. U.; Kim, N. G.

    2005-12-01

    The dynamic characteristics of the special metal hydride(SMH) actuator using hydrogen absorbing alloys has been studied through the experiments on the characteristics of the temperature-pressure relation using a Peltier module. The SMH actuator uses the reversible reactions between thermal energy and mechanical energy inside hydrogen-absorbing alloys. It is well known that hydrogen-absorbing alloys can reversely absorb and desorb a large volume of hydrogen gas, more than about 1000 times of their own volume. By using Peltier element, we can actively control the energy conversion through hydrogen-absorbing alloys through hydriding and dehydriding reactions. Heating hydrogen-absorbing alloys using Peltier element will increase the equilibrium pressure of hydrogen gas resulting in the desorption of hydrogen gas by the alloys. Whereas, by cooling the alloys, the equilibrium pressure of hydrogen gas will decrease and hydrogen gas will be absorbed. In the present study, a simple special metal hydride (SMH) actuator, consisting of plated hydrogen-absorbing alloys as a power source, Peltier elements as a heat source, and a cylinder with metal bellows as a mechanical functioning part, has been developed. An electro-less copper plating has been used to improve the thermal conductivity of the hydrogen-absorbing alloys. To study the effects of the electro-less copper plating and the dynamic characteristics of the newly developed SMH actuator, a series of experiments has been performed and analyzed. The experiment demonstrated that the SMH actuator, which contains only 14.5 g of hydrogen-absorbing alloys, was able to easily lift 40 kg of weight with the displacement of 35 mm. The displacement of the cylinder was controlled in the periodic movement. The developed SMH actuator has merits in its small size, light weight, noiseless operation, and compliances similar to those of human bodies. Therefore, the SMH actuator is suitable for uses in medical and rehabilitation applications.

  8. Ab initio molecular dynamics simulation study of successive hydrogenation reactions of carbon monoxide producing methanol

    Science.gov (United States)

    Pham, Thi Nu; Ono, Shota; Ohno, Kaoru

    2016-04-01

    Doing ab initio molecular dynamics simulations, we demonstrate a possibility of hydrogenation of carbon monoxide producing methanol step by step. At first, the hydrogen atom reacts with the carbon monoxide molecule at the excited state forming the formyl radical. Formaldehyde was formed after adding one more hydrogen atom to the system. Finally, absorption of two hydrogen atoms to formaldehyde produces methanol molecule. This study is performed by using the all-electron mixed basis approach based on the time dependent density functional theory within the adiabatic local density approximation for an electronic ground-state configuration and the one-shot GW approximation for an electronic excited state configuration.

  9. Simple electro-assisted immobilization of ciprofloxacin on carbon nanotube modified electrodes: its selective hydrogen peroxide electrocatalysis.

    Science.gov (United States)

    Sornambikai, Sundaram; Kumar, Annamalai Senthil

    2014-09-01

    Ciprofloxacin (Cf) is a synthetic fourth generation fluoroquinolone class antibiotic used for the treatment of gram-positive, gram-negative and mycobacterium species infections. Electrochemical characteristic of the Cf antibiotic on carbon nanotube modified glassy carbon electrode (GCE/CNT) in pH 7 phosphate buffer solution has been investigated. Electrochemically oxidized radical byproduct of the Cf drug, which is formed as intermediate, gets immobilized on the GCE/CNT (GCE/Cf@CNT) and showed stable and well defined surface confined redox peak at -0.220 V versus Ag/AgCl. Control electrochemical experiment with unmodified GCE failed to show any such immobilization and redox features. Physicochemical characterizations of the Cf@CNT by transmission electron microscope, scanning electron microscope, infrared spectroscopy, UV-Vis and gas chromatography coupled mass spectroscopic analyses of Cf@CNT collectively revealed presence of native form of the Cf antibiotic molecule onto the CNT. The interaction between the Cf molecule and the CNT tubes are revealed from the decreased intensity in the Raman spectrum. The GCE/Cf@CNT showed excellent electrocatalytic response to hydrogen peroxide reduction reaction in pH 7 phosphate buffer solution. Amperometric i-t analysis for the detection of H2O2 showed a current linearity plot upto [H2O2] = 200 μM at an applied potential - 0.1 V versus Ag/AgCl with a current sensitivity value 678 μA mM(-1) cm(-2). No interferences were noticed with ascorbic acid, uric acid, cysteine and nitrite. The present study can be highly helpful to understand the interaction between the Cf and H2O2 in physiological systems and for the removal of Cf from the antibiotic polluted water samples especially in the aquaculture and agricultural systems.

  10. First Operating Results of a Dynamic Gas Bearing Turbine in AN Industrial Hydrogen Liquefier

    Science.gov (United States)

    Bischoff, S.; Decker, L.

    2010-04-01

    Hydrogen has been brought into focus of industry and public since fossil fuels are depleting and costs are increasing dramatically. Beside these issues new high-tech processes in the industry are in need for hydrogen at ultra pure quality. To achieve these requirements and for efficient transportation, hydrogen is liquefied in industrial plants. Linde Gas has commissioned a new 5.5 TPD Hydrogen liquefier in Leuna, Germany, which has been engineered and supplied by Linde Kryotechnik. One of the four expansion turbines installed in the liquefaction process is equipped with dynamic gas bearings. Several design features and operational characteristics of this application will be discussed. The presentation will include results of efficiency and operational reliability that have been determined from performance tests. The advantages of the Linde dynamic gas bearing turbine for future use in hydrogen liquefaction plants will be shown.

  11. Structural and dynamical properties of hydrogen fluoride in aqueous solution: an ab initio quantum mechanical charge field molecular dynamics simulation.

    Science.gov (United States)

    Kritayakornupong, Chinapong; Vchirawongkwin, Viwat; Hofer, Thomas S; Rode, Bernd M

    2008-09-25

    The novel ab initio quantum mechanical charge field (QMCF) molecular dynamics simulation at the Hartree-Fock level has been employed to investigate hydration structure and dynamics of hydrogen fluoride in aqueous solution. The average H-F bond length of 0.93 A obtained from the QMCF MD simulation is in good agreement with the experimental data. The HHF...Ow distance of 1.62 A was evaluated for the first hydration shell, and 2.00 A was observed for the FHF...Hw distance. The stability of hydrogen bonding is more pronounced in the hydrogen site of hydrogen fluoride, with a single water molecule in this part of the first hydration shell. A wide range of coordination numbers between 3 and 9 with an average value of 5.6 was obtained for the fluorine site. The force constants of 819.1 and 5.9 N/m were obtained for the HHF-FHF and HHF...Ow interactions, respectively, proving the stability of the nondissociated form of hydrogen fluoride in aqueous solution. The mean residence times of 2.1 and 2.5 ps were determined for ligand exchange processes in the neighborhood of fluorine and hydrogen atoms of hydrogen fluoride, respectively, indicating a weak structure-making effect of hydrogen fluoride in water. The corresponding H-bond lifetimes attribute this effect to the H atom site of HF.

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

    Science.gov (United States)

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

    1981-01-01

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

  13. Development of sensitive amperometric hydrogen peroxide sensor using a CuNPs/MB/MWCNT-C{sub 60}-Cs-IL nanocomposite modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Roushani, Mahmoud, E-mail: mahmoudroushani@yahoo.com; Bakyas, Kobra; Zare Dizajdizi, Behruz

    2016-07-01

    A sensitive hydrogen peroxide (H{sub 2}O{sub 2}) sensor was constructed based on copper nanoparticles/methylene blue/multiwall carbon nanotubes–fullerene–chitosan–ionic liquid (CuNPs/MB/MWCNTs–C{sub 60}–Cs–IL) nanocomposites. The MB/MWCNTs–C{sub 60}–Cs–IL and CuNPs were modified glassy carbon electrode (GCE) by the physical adsorption and electrodeposition of copper nitrate solution, respectively. The physical morphology and chemical composition of the surface of modified electrode was investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The electrochemical properties of CuNPs/MB/MWCNTs–C{sub 60}–Cs–IL/GCE were investigated by cyclic voltammetry (CV) and amperometry techniques and the sensor exhibited remarkably strong electrocatalytic activities toward the reduction of hydrogen peroxide. The peak currents possess a linear relationship with the concentration of H{sub 2}O{sub 2} in the range of 0.2 μM to 2.0 mM, and the detection limit is 55.0 nM (S/N = 3). In addition, the modified electrode was used to determine H{sub 2}O{sub 2} concentration in human blood serum sample with satisfactory results. - Highlights: • CuNPs/MB/MWCNT-C{sub 60}-Cs-IL/GC electrode was constructed by layer-by-layer method. • The catalytic performance of the sensor was studied with the use of amperometric technique. • The constructed sensor showed enhanced electrocatalytic activity toward the reduction of H{sub 2}O{sub 2}. • The CuNPs/MB/MWCNT-C{sub 60}-Cs-IL/GC electrode demonstrated high stability for the detection of H{sub 2}O{sub 2}.

  14. Hydrogen sensor based on Au and YSZ/HgO/Hg electrode for in situ measurement of dissolved H2 in high-temperature and -pressure fluids.

    Science.gov (United States)

    Zhang, R H; Hu, S M; Zhang, X T; Wang, Y

    2008-11-15

    Gold as a hydrogen-sensing electrode for in situ measurement of dissolved H2 in aqueous solutions under extreme conditions is reported. The dissolved H2 sensor, constructed with a Au-based sensing element and coupled with a YSZ/HgO/Hg electrode, is well suited for determining dissolved H2 concentrations of aqueous fluids at elevated temperatures and pressures. The Au electrode is made of Au wire mounted in a quartz bar, which can be pressurized and heated in the high-pressure and -temperature conditions. The Au-YSZ sensor has been tested for its potential response to the concentrations of dissolved H2 in fluids by using a flow-through reactor at high temperatures up to 400 degrees C and pressures to 38 MPa. Good sensitivity and linear response between the hydrogen concentrations in the fluids and the H2 sensor potentials are reported for hydrogen gas in the concentration range of 0.1-0.001 M H2 in aqueous fluids at temperatures up to 340 degrees C and 30 MPa. Nernstian response of the cell potential to dissolved H2 in fluids was determined at 340 degrees C and 30 MPa, described as follows: DeltaE = 0.9444 + 0. 0603 log m H2 The experimental results indicate that the Au-YSZ/HgO/Hg cell can be used to measure the solubility of H2 in aqueous fluid at temperatures and pressures near to the critical state of water. Thus, this type of Au hydrogen sensor could be easily used for in situ measurement of H2 in hydrothermal fluids in a high-pressure vessel, or at midocean ridge, due to its structure of compression resistance.

  15. On the impedance of galvanic cells XXV. The double-layer capacitance of the dropping mercury electrode in 1 M HCl, 7.5 M HCl and 5.2 M HClO4 and the kinetic parameters of the hydrogen electrode reaction as a function of temperature in these solutions

    NARCIS (Netherlands)

    Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1969-01-01

    The impedance of the dropping mercury electrode in aqueous solutions in 1 M HCl, 7.5 M HCl and 5.2 M HClO4, saturated with hydrogen at one atmosphere was measured at temperatures between −39° and +72° both in and outside the potential region where the electrode reaction, e+H+ H2, proceeds. Analysis

  16. Design Principles and Dynamic Front End Reconfiguration for Low Noise EEG Acquisition With Finger Based Dry Electrodes.

    Science.gov (United States)

    Nathan, Viswam; Jafari, Roozbeh

    2015-10-01

    Dry electrodes are a convenient alternative to wet electrodes for electroencephalography (EEG) acquisition systems. Dry electrodes are subject to a higher amount of noise at the electrode scalp interface and these effects can be worsened due to non-ideal design or improper placement on the head. In this work, we investigate a popular dry electrode design based on a number of resistive 'finger' shaped contacts. We conduct experiments comparing designs with varying numbers of fingers using two impedance measurement methods and show that sparser arrangements of fingers are more robust to varying use cases and are more effective at penetrating through hair on the scalp. We then show that these impedance measurement metrics could be used to sort individual fingers within one electrode according to quality of electrical contact. We show that the signals from individual fingers can differ from each other significantly due to differing local effects of impedance and noise, and demonstrate through experimental results that dynamically selecting only a subset of fingers with good contact impedance can improve the overall signal-to-noise ratio of the EEG signal from that electrode.

  17. Hydrogen dynamics in soil organic matter as determined by 13C and 2H labeling experiments

    Science.gov (United States)

    Paul, Alexia; Hatté, Christine; Pastor, Lucie; Thiry, Yves; Siclet, Françoise; Balesdent, Jérôme

    2016-12-01

    Understanding hydrogen dynamics in soil organic matter is important to predict the fate of 3H in terrestrial environments. One way to determine hydrogen fate and to point out processes is to examine the isotopic signature of the element in soil. However, the non-exchangeable hydrogen isotopic signal in soil is complex and depends on the fate of organic compounds and microbial biosyntheses that incorporate water-derived hydrogen. To decipher this complex system and to understand the close link between hydrogen and carbon cycles, we followed labeled hydrogen and labeled carbon throughout near-natural soil incubations. We performed incubation experiments with three labeling conditions: 1 - 13C2H double-labeled molecules in the presence of 1H2O; 2 - 13C-labeled molecules in the presence of 2H2O; 3 - no molecule addition in the presence of 2H2O. The preservation of substrate-derived hydrogen after 1 year of incubation (ca. 5 % in most cases) was lower than the preservation of substrate-derived carbon (30 % in average). We highlighted that 70 % of the C-H bonds are broken during the degradation of the molecule, which permits the exchange with water hydrogen. Added molecules are used more for trophic resources. The isotopic composition of the non-exchangeable hydrogen was mainly driven by the incorporation of water hydrogen during microbial biosynthesis. It is linearly correlated with the amount of carbon that is degraded in the soil. The quantitative incorporation of water hydrogen in bulk material and lipids demonstrates that non-exchangeable hydrogen exists in both organic and mineral-bound forms. The proportion of the latter depends on soil type and minerals. This experiment quantified the processes affecting the isotopic composition of non-exchangeable hydrogen, and the results can be used to predict the fate of tritium in the ecosystem or the water deuterium signature in organic matter.

  18. Dynamics of hydrogen bonds in water and consequences for the unusual behaviour of supercooled water

    Indian Academy of Sciences (India)

    José Teixeira

    2008-10-01

    The dynamics of liquid water is evaluated by the coherent quasi-elastic scattering at two different momentum transfers, in order to discriminate hydrogen bond life-time from molecular dynamics. The results indicate a possible issue for the puzzle of the behaviour of supercooled water.

  19. Hydrogen-bond dynamics in water explored by heterodyne-detected photon echo

    NARCIS (Netherlands)

    Yeremenko, S; Pshenichnikov, MS; Wiersma, DA; Pshenichnikov, Maxim S.

    2003-01-01

    Results of heterodyne-detected photon echo experiments on the OH stretching mode of water are reported and discussed. Two vibrational dynamical processes with time constants of 130 and 900 fs were identified. The former is attributed to bond breaking dynamics of a single hydrogen bond, the latter to

  20. On the Intramolecular Hydrogen Bond in Solution: Car-Parrinello and Path Integral Molecular Dynamics Perspective.

    Science.gov (United States)

    Dopieralski, Przemyslaw; Perrin, Charles L; Latajka, Zdzislaw

    2011-11-08

    The issue of the symmetry of short, low-barrier hydrogen bonds in solution is addressed here with advanced ab initio simulations of a hydrogen maleate anion in different environments, starting with the isolated anion, going through two crystal structures (sodium and potassium salts), then to an aqueous solution, and finally in the presence of counterions. By Car-Parrinello and path integral molecular dynamics simulations, it is demonstrated that the position of the proton in the intramolecular hydrogen bond of an aqueous hydrogen maleate anion is entirely related to the solvation pattern around the oxygen atoms of the intramolecular hydrogen bond. In particular, this anion has an asymmetric hydrogen bond, with the proton always located on the oxygen atom that is less solvated, owing to the instantaneous solvation environment. Simulations of water solutions of hydrogen maleate ion with two different counterions, K(+) and Na(+), surprisingly show that the intramolecular hydrogen-bond potential in the case of the Na(+) salt is always asymmetric, regardless of the hydrogen bonds to water, whereas for the K(+) salt, the potential for H motion depends on the location of the K(+). It is proposed that repulsion by the larger and more hydrated K(+) is weaker than that by Na(+) and competitive with solvation by water.

  1. [Analysis of dynamic characteristics for fermentative hydrogen-producing bacteria community and hydrogen producing capability in CSTR].

    Science.gov (United States)

    Song, Jia-Xiu; Ren, Nan-Qi; Chen, Ying; An, Dong

    2009-07-15

    The start into the types of fermentation was carried out by pH adjustment from 4.2 to 6.0 in CSTR system. The process of transforming of hydrogen production and dynamic community of bacteria were studied. The results showed that with the organic load maintained at (33 +/- 1) kg/(m3 x d), there was no change in 10 d for the type of fermentation, the amount of hydrogen does not reduce in 8 d. After 15 d, the system was transformed from the ethanol-based type into butyric acid type and water alkalinity was from 250 mg/L to 2450 mg/L. The use of fluorescence in situ hybridization (FISH) system was in response to the 3 groups of micro-organisms. It was found that in the process of transforming, Clostridium cluster XI increases and Clostridium cluster I and II decreases. Enterobacteriaceae always existed with no change. The microbial growth must be considered with hydrogen production capability. The average hydrogen production rate reached to 23.6 mol/(kg x d) with Clostridium cluster I and II dominated in fermentation reactor.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Yu; Li, Xin [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Advanced Water Management Centre, The University of Queensland, QLD 4072 (Australia); Yao, Fubing [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Li, Xiaoming, E-mail: xmli@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Zhao, Jianwei; Xu, Qiuxiang; Zhang, Chang; Zeng, Guangming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

    2016-04-15

    Graphical abstract: Main mechanism of simultaneous bromate and nitrate removal in the RBER. - Highlights: • Cathode of RBER was designed to automatically rotate. • Simultaneous bromate and nitrate removal was achieved by auto-hydrogenotrophic reduction. • The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h. • An electron transfer process and main reaction mechanism in RBER was explored. - Abstract: Simultaneous reduction of bromate and nitrate was investigated using a rotating biofilm-electrode reactor (RBER) with graphite carbon (GC) rods as anode and activated carbon fiber (ACF) bonded with steel ring as cathode. In RBER, the community of denitrifying bacteria immobilized on the cathode surface could completely utilize hydrogen (H{sub 2}) as the electron donor, which was internally produced by the electrolysis of water. The short-term test confirmed that the RBER system could reduce 150–800 μg/L bromate to below 10 μg/L under autotrophic conditions. The reduced bromate was considered to be roughly equivalent to the amount of bromide in effluent, indicating that bromate was completely reduced to bromide without accumulation of by-products. The long-term test (over 120 days) showed that the removal fluxes of bromate and nitrate could be improved by increasing the electric current and decreasing the hydraulic retention time (HRT). But nitrite in effluent was significantly accumulated when the electric current was beyond 10 mA and the HRT was less than 6 h. The maximum bromate reduction rate estimated by the Monod equation was 109.12 μg/L h when the electric current was 10 mA and HRT was 12 h. It was proposed that the electron transfer process in RBER produced H{sub 2} on the surface of the ACF cathode, and the microbial cultures attached closely on the cathode which could completely utilize H{sub 2} as electron donors for reduction of bromate and nitrate.

  3. Reaction dynamics and statistical theory for the growth of hydrogen bonding clusters

    Institute of Scientific and Technical Information of China (English)

    WANG; Haijun; BA; Xinwu(巴信武); ZHAO; Min(赵敏)

    2002-01-01

    The similarities between the formation of hydrogen bonds and polycondensation reactions are stated from the statistical viewpoint, and then taking the hydrogen bonding system of AaDd type as an example, the growing process of hydrogen bonding clusters is investigated in terms of the theory of reaction dynamics and statistical theory for polymeric reactions. The two methods lead to the same conclusions, stating that the statistical theory for polymerization is applicable to the hydrogen bonding systems. Based on this consideration, the explicit relationship between the conversions of proton-donors and proton-acceptors and the Gibbs free energy of the system under study is given. Furthermore, the sol-gel phase transition is predicted to take place in some hydrogen bonding systems, and the corresponding generalized scaling laws describing this kind of phase transition are obtained.

  4. Comparative analysis of the electroactive area of Pt/C PEMFC electrodes in liquid and solid polymer contact by underpotential hydrogen adsorption/desorption

    Energy Technology Data Exchange (ETDEWEB)

    Chaparro, A.M.; Martin, A.J.; Folgado, M.A.; Gallardo, B. [Dep. de Energia, CIEMAT, Avda. Complutense, 22, 28040 Madrid (Spain); Daza, L. [Dep. de Energia, CIEMAT, Avda. Complutense, 22, 28040 Madrid (Spain); Instituto de Catalisis y Petroleoquimica (CSIC), Marie Curie 2, Campus Cantoblanco, 28049 Madrid (Spain)

    2009-06-15

    Because of the different experimental conditions found in literature for the measurement of the electroactive area of Pt/C electrodes of proton exchange membrane fuel cells (PEMFC) by means of underpotential hydrogen adsorption (H{sub UPD}) voltammetry, specially concerning sweep rate and temperature, it was found necessary to perform an analysis of these parameters. With this aim, the electroactive area of PEMFC electrodes has been measured by means of H{sub UPD} voltammetry at different sweep rates and temperatures, in liquid electrolyte and solid polymer contact. Both configurations show that H{sub UPD} adsorption and desorption charges are strongly dependent on sweep rate voltage and temperature. The most common behaviour observed is a maximum in H{sub UPD} desorption charge, typically in the 100-10 mV s{sup -1} sweep rate range, whereas H{sub UPD} adsorption charge shows continuous increase with decreasing sweep rate. The decrease of desorption charge at low sweep rates is attributed to adsorbing species related with carbon support reactivity. These processes are also responsible for the increase in desorption H{sub UPD} charge at low sweep rate. At high sweep rate, both adsorption and desorption H{sub UPD} charges decrease due to limiting diffusion of protons through the microporous electrode. As a consequence, it is found that the closest approximation to the real electroactive area (i.e. the area accessible to protons) corresponds to the maximum in the H{sub UPD} desorption charge in the range of 10-100 mV s{sup -1} sweep rate. The influence of measuring temperature is also tested in the range 25 C-80 C. A dependence of the adsorption and desorption hydrogen charges is found, due to thermodynamic and kinetics factors. We observe that the processes competing with hydrogen adsorption, i.e. generation and adsorption of carbon species are enhanced with temperature, so a low measuring temperature is found as most appropriate. (author)

  5. Charge polarization with large amplitude hydrogen motion of pyrazinyl radical: implication for the diffusion dynamics

    Science.gov (United States)

    Morita, Akihiro; Kato, Shigeki

    2001-11-01

    In this Letter we discuss in the case of pyrazinyl radical the effect of the large amplitude motion on the charge polarization. The extra hydrogen of pyrazinyl radical is nonplanar at the equilibrium geometry, whereas it is delocalized in the vibrational ground state along the wagging direction. The large amplitude motion of the hydrogen triply enhances the effective out-of-plane polarizability of the ground state. This augmented charge polarization could play a considerable role in the diffusion dynamics in solutions.

  6. A dynamic general equilibrium analysis on fostering a hydrogen economy in Korea

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Jeong Hwan [Climate Change Research Dep., Korea Energy Economics Institute, Uiwang-si, Gyeonggi-do (Korea, Republic of); Cho, Gyeong-Lyeob [Korea Economics Research Institute, Yoido-dong, Yeongdungpo-ku, Seoul (Korea, Republic of)

    2010-09-15

    Hydrogen is anticipated to become one of the major alternative energy technologies for a sustainable energy system. This study analyzes the dynamic economic impacts of building a hydrogen economy in Korea employing a dynamic Computable General Equilibrium (CGE) model. As a frontier technology, hydrogen is featured as having a slow diffusion rate due to option value, positive externality, resistance of old technology, and complementary vintages. Without government intervention, hydrogen-derived energy will supply up to 6.5% of final energy demand by 2040. Simulation outcomes show that as price subsidy rates increase by 10%, 20%, and 30%, hydrogen demand will increase by 9.2%, 15.2%, and 37.7%, respectively, of final energy demand by 2040. The output of the transportation sector will increase significantly, while demands for oil and electricity will decline. Demands for coal and LNG will experience little change. Household consumption will decline because of the increase of income taxes. Overall GDP will increase because of the increase in exports and investments. CO{sub 2} emission will decline for medium and high subsidy rate cases, but increase for low subsidy cases. Ultimately, subsidy policy on hydrogen will not be an effective measure for mitigating CO{sub 2} emission in Korea when considering dynamic general equilibrium effects. (author)

  7. Ultrasfast Dynamics in Dense Hydrogen Explored at Flash

    Energy Technology Data Exchange (ETDEWEB)

    Hilbert, V; Zastrau, U; Neumayer, P; Hochhaus, D; Toleikis, S; Harmand, M; Przystawik, A; Tschentscher, T; Glenzer, S H; Doeppner, T; Fortmann, C; White, T; Gregori, G; Gode, S; Tiggesbaumker, J; Skruszewicz, S; Meiwes-Broer, K H; Sperling, P; Redmer, R; Forster, E

    2011-08-01

    The short pulse duration and high intensity of the FLASH (Free-electron LASer in Hamburg) allows us to generate and probe homogeneous warm dense non-equilibrium hydrogen within a single extreme ultraviolet (EUV) light pulse. By analyzing the spectrum of the 13.5 nm Thomson scattered light we determine the plasma temperature and density. We find that classical models of this interaction are in good agreement with our dense plasma conditions. In a FEL-pump FEL-probe experiment droplets of liquid hydrogen and their scattering behavior for different pump-probe setups were observed under 20{sup o} and 90{sup o}. We find that the scattering behavior of the scattered intensity depends on the scattering angle.

  8. Enzyme dynamics and hydrogen tunnelling in a thermophilic alcohol dehydrogenase

    Science.gov (United States)

    Kohen, Amnon; Cannio, Raffaele; Bartolucci, Simonetta; Klinman, Judith P.; Klinman, Judith P.

    1999-06-01

    Biological catalysts (enzymes) speed up reactions by many orders of magnitude using fundamental physical processes to increase chemical reactivity. Hydrogen tunnelling has increasingly been found to contribute to enzyme reactions at room temperature. Tunnelling is the phenomenon by which a particle transfers through a reaction barrier as a result of its wave-like property. In reactions involving small molecules, the relative importance of tunnelling increases as the temperature is reduced. We have now investigated whether hydrogen tunnelling occurs at elevated temperatures in a biological system that functions physiologically under such conditions. Using a thermophilic alcohol dehydrogenase (ADH), we find that hydrogen tunnelling makes a significant contribution at 65°C this is analogous to previous findings with mesophilic ADH at 25°C ( ref. 5). Contrary to predictions for tunnelling through a rigid barrier, the tunnelling with the thermophilic ADH decreases at and below room temperature. These findings provide experimental evidence for a role of thermally excited enzyme fluctuations in modulating enzyme-catalysed bond cleavage.

  9. Water dynamics: relation between hydrogen bond bifurcations, molecular jumps, local density & hydrophobicity.

    Science.gov (United States)

    Titantah, John Tatini; Karttunen, Mikko

    2013-10-21

    Structure and dynamics of water remain a challenge. Resolving the properties of hydrogen bonding lies at the heart of this puzzle. We employ ab initio Molecular Dynamics (AIMD) simulations over a wide temperature range. The total simulation time was ≈ 2 ns. Both bulk water and water in the presence of a small hydrophobic molecule were simulated. We show that large-angle jumps and bond bifurcations are fundamental properties of water dynamics and that they are intimately coupled to both local density and hydrogen bond strength oscillations in scales from about 60 to a few hundred femtoseconds: Local density differences are the driving force for bond bifurcations and the consequent large-angle jumps. The jumps are intimately connected to the recently predicted hydrogen bond energy asymmetry. Our analysis also appears to confirm the existence of the so-called negativity track provided by the lone pairs of electrons on the oxygen atom to enable water rotation.

  10. High loading MnO2 nanowires on graphene paper: facile electrochemical synthesis and use as flexible electrode for tracking hydrogen peroxide secretion in live cells.

    Science.gov (United States)

    Dong, Shuang; Xi, Jiangbo; Wu, Yanan; Liu, Hongwei; Fu, Chaoyang; Liu, Hongfang; Xiao, Fei

    2015-01-01

    Recent progress in flexible and lightweight electrochemical sensor systems requires the development of paper-like electrode materials. Here, we report a facile and green synthesis of a new type of MnO2 nanowires-graphene nanohybrid paper by one-step electrochemical method. This strategy demonstrates a collection of unique features including the effective electrochemical reduction of graphene oxide (GO) paper and the high loading of MnO2 nanowires on electrochemical reduced GO (ERGO) paper. When used as flexible electrode for nonenzymatic detection of hydrogen peroxide (H2O2), MnO2-ERGO paper exhibits high electrocatalytic activity toward the redox of H2O2 as well as excellent stability, selectivity and reproducibility. The amperometric responses are linearly proportional to H2O2 concentration in the range 0.1-45.4 mM, with a detection limit of 10 μM (S/N=3) and detection sensitivity of 59.0 μA cm(-2) mM(-1). These outstanding sensing performances enable the practical application of MnO2-ERGO paper electrode for the real-time tracking H2O2 secretion by live cells macrophages. Therefore, the proposed graphene-based nanohybrid paper electrode with intrinsic flexibility, tailorable shapes and adjustable properties can contribute to the full realization of high-performance flexible electrode material used in point-of-care testing devices and portable instruments for in-vivo clinical diagnostics and on-site environmental monitoring. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Near-uv photon efficiency in a TiO2 electrode - Application to hydrogen production from solar energy

    Science.gov (United States)

    Desplat, J.-L.

    1976-01-01

    An n-type (001) TiO2 electrode irradiated at 365 nm was tested under anodic polarization. A saturation current independent of pH and proportional to light intensity has been observed. Accurate measurements of the incident power lead to a 60 per cent photon efficiency. A photoelectrochemical cell built with such an electrode, operated under solar irradiation without concentration, produced an electrolysis current of 0.7 mA/sq cm without applied voltage.

  12. Discrete kink dynamics in hydrogen-bonded chains: The one-component model

    DEFF Research Database (Denmark)

    Karpan, V. M.; Zolotaryuk, Yaroslav; Christiansen, Peter Leth

    2002-01-01

    We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on-site poten......We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on...

  13. Hydrogen dynamics in Na3AlH6: A combined density functional theory and quasielastic neutron scattering study

    DEFF Research Database (Denmark)

    Voss, Johannes; Shi, Qing; Jacobsen, Hjalte Sylvest

    2007-01-01

    alanate with TiCl3, and here we study hydrogen dynamics in doped and undoped Na3AlH6 using a combination of density functional theory calculations and quasielastic neutron scattering. The hydrogen dynamics is found to be vacancy mediated and dominated by localized jump events, whereas long-range bulk......Understanding the elusive catalytic role of titanium-based additives on the reversible hydrogenation of complex hydrides is an essential step toward developing hydrogen storage materials for the transport sector. Improved bulk diffusion of hydrogen is one of the proposed effects of doping sodium...

  14. Investigation of the Dynamics of a Clamped-Clamped Microbeam Near the Third Mode Using a Partial Electrode

    KAUST Repository

    Masri, Karim M.

    2014-08-17

    We present an investigation of the dynamics of a clamped-clamped microbeam excited electrostatically near its third mode. To maximize the response at the third mode, a partial electrode configuration is utilized. A multi-mode Galerkin method is used to develop a reduced order model (ROM) of the beam. A shooting method to find the periodic motion is utilized to generate frequency response curves. The curves show hardenining behavior and dynamic pull-in. We show that the dynamic amplitude of the partial configuration is higher than that of a full electrode configuration. These results are promising for the use of higher-order modes for mass detection and for ultra sensitive resonant sensors.

  15. Applying dynamic data collection to improve dry electrode system performance for a P300-based brain-computer interface

    Science.gov (United States)

    Clements, J. M.; Sellers, E. W.; Ryan, D. B.; Caves, K.; Collins, L. M.; Throckmorton, C. S.

    2016-12-01

    Objective. Dry electrodes have an advantage over gel-based ‘wet’ electrodes by providing quicker set-up time for electroencephalography recording; however, the potentially poorer contact can result in noisier recordings. We examine the impact that this may have on brain-computer interface communication and potential approaches for mitigation. Approach. We present a performance comparison of wet and dry electrodes for use with the P300 speller system in both healthy participants and participants with communication disabilities (ALS and PLS), and investigate the potential for a data-driven dynamic data collection algorithm to compensate for the lower signal-to-noise ratio (SNR) in dry systems. Main results. Performance results from sixteen healthy participants obtained in the standard static data collection environment demonstrate a substantial loss in accuracy with the dry system. Using a dynamic stopping algorithm, performance may have been improved by collecting more data in the dry system for ten healthy participants and eight participants with communication disabilities; however, the algorithm did not fully compensate for the lower SNR of the dry system. An analysis of the wet and dry system recordings revealed that delta and theta frequency band power (0.1-4 Hz and 4-8 Hz, respectively) are consistently higher in dry system recordings across participants, indicating that transient and drift artifacts may be an issue for dry systems. Significance. Using dry electrodes is desirable for reduced set-up time; however, this study demonstrates that online performance is significantly poorer than for wet electrodes for users with and without disabilities. We test a new application of dynamic stopping algorithms to compensate for poorer SNR. Dynamic stopping improved dry system performance; however, further signal processing efforts are likely necessary for full mitigation.

  16. Effect of hydrogen on dynamic charge transport in amorphous oxide thin film transistors

    Science.gov (United States)

    Kim, Taeho; Nam, Yunyong; Hur, Ji-Hyun; Park, Sang-Hee Ko; Jeon, Sanghun

    2016-08-01

    Hydrogen in zinc oxide based semiconductors functions as a donor or a defect de-activator depending on its concentration, greatly affecting the device characteristics of oxide thin-film transistors (TFTs). Thus, controlling the hydrogen concentration in oxide semiconductors is very important for achieving high mobility and minimizing device instability. In this study, we investigated the charge transport dynamics of the amorphous semiconductor InGaZnO at various hydrogen concentrations as a function of the deposition temperature of the gate insulator. To examine the nature of dynamic charge trapping, we employed short-pulse current-voltage and transient current-time measurements. Among various examined oxide devices, that with a high hydrogen concentration exhibits the best performance characteristics, such as high saturation mobility (10.9 cm2 v-1 s-1), low subthreshold slope (0.12 V/dec), and negligible hysteresis, which stem from low defect densities and negligible transient charge trapping. Our finding indicates that hydrogen atoms effectively passivate the defects in subgap states of the bulk semiconductor, minimizing the mobility degradation and threshold voltage instability. This study indicates that hydrogen plays a useful role in TFTs by improving the device performance and stability.

  17. Dynamical Model of Rocket Propellant Loading with Liquid Hydrogen

    Data.gov (United States)

    National Aeronautics and Space Administration — A dynamical model describing the multi-stage process of rocket propellant loading has been developed. It accounts for both the nominal and faulty regimes of...

  18. The electrical characterization and response to hydrogen of Schottky diodes with a resistive metal electrode-rectifying an oversight in Schottky diode investigation

    Energy Technology Data Exchange (ETDEWEB)

    Dawson, P; Feng, L; Penate-Quesada, L [Centre for Nanostructured Media, School of Maths and Physics, Queen' s University of Belfast, Belfast BT7 1NN (United Kingdom); Hill, G [EPSRC National Centre for III-V Technologies, Mappin Street, University ofSheffield, Sheffield S1 3JD (United Kingdom); Mitra, J, E-mail: P.dawson@qub.ac.uk

    2011-03-30

    Schottky-barrier structures with a resistive metal electrode are examined using the 4-point probe method where the probes are connected to the metal electrode only. The observation of a significant decrease in resistance with increasing temperature (over a range of {approx}100 K) in the diode resistance-temperature (R{sub D}-T) characteristic is considered due to charge carrier confinement to the metal electrode at low temperature (high resistance), with the semiconductor progressively opening up as a parallel current carrying channel (low resistance) with increasing temperature due to increasing thermionic emission across the barrier. A simple model is constructed, based on thermionic emission at quasi-zero bias, that generates good fits to the experimental data. The negative differential resistance (NDR) region in the R{sub D}-T characteristic is a general effect and is demonstrated across a broad temperature range for a variety of Schottky structures grown on Si-, GaAs- and InP-substrates. In addition the NDR effect is harnessed in micro-scaled Pd/n-InP devices for the detection of low levels of hydrogen in an ambient atmosphere of nitrogen.

  19. Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Li Shenfeng; Zhu Xiaoying; Zhang Wei; Xie Guoming [Key Laboratory of Laboratory Medical Diagnostics, Ministry of Education, Department of Laboratory Medicine, Chongqing Medical University, Chongqing 400016 (China); Feng Wenli, E-mail: fengwlcqmu@sina.com [Key Laboratory of Laboratory Medical Diagnostics, Ministry of Education, Department of Laboratory Medicine, Chongqing Medical University, Chongqing 400016 (China)

    2012-01-15

    In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H{sub 2}O{sub 2}), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H{sub 2}O{sub 2} detection. The linear response range of the biosensor to H{sub 2}O{sub 2} concentration was from 5 Multiplication-Sign 10{sup -7} mol L{sup -1} to 1.5 Multiplication-Sign 10{sup -3} mol L{sup -1} with a detection limit of 3.75 Multiplication-Sign 10{sup -8} mol L{sup -1} (based on S/N = 3).

  20. Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO2 films] revealed that MnO2 film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO2 films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO2 films showed that the Fe(III)-doped RuO2-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO2 films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H2O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb10Sn20Ti70, Cu63Ni37 and Cu25Ni75 alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu63Ni37 alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO3- at the Cu-Ni alloy electrode is superior to

  1. Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

    Science.gov (United States)

    Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

    2013-04-07

    Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

  2. Preparation of Al-Mg Alloy Electrodes by Using Powder Metallurgy and Their Application for Hydrogen Production

    Directory of Open Access Journals (Sweden)

    Wen-Nong Hsu

    2014-01-01

    Full Text Available The choice of an electrode is the most critical parameter for water electrolysis. In this study, powder metallurgy is used to prepare aluminum-magnesium (Al-Mg alloy electrodes. In addition to pure Mg and Al electrodes, five Al-Mg alloy electrodes composed of Al-Mg (10 wt%, Al-Mg (25 wt%, Al-Mg (50 wt%, and Al-Mg (75 wt% were prepared. In water electrolysis experiments, the pure Al electrode exhibited optimal electrolytic efficiency. However, the Al-Mg (25 wt% alloy was the most efficient when the anticorrosion effect and materials costs were considered. In this study, an ultrasonic field was applied to the electrolysis cell to improve its efficiency. The results revealed that the current increased by approximately 23.1% when placed in a 30 wt% KOH solution under the ultrasonic field. Electrochemical polarization impedance spectroscopy (EIS was employed to evaluate the effect of the ultrasonic field on the reduction of polarization resistance. The results showed that the concentration impedance in the 30 wt% KOH electrolyte decreased markedly by 44%–51% Ω.

  3. Synthesis and characterization of a Sr0.95Y0.05TiO3-δ-based hydrogen electrode for reversible solid oxide cells

    KAUST Repository

    Ling, Yihan

    2015-01-01

    Reversible solid oxide cells (RSOCs) can generate electricity as solid oxide fuel cells (SOFC) facing a shortage of electricity and can also store the electricity as solid oxide electrolysis cells (SOEC) at the time of excessive electricity. The composite Sr0.95Y0.05TiO3-δ-Sm0.2Ce0.8O1.9 (SYT-SDC) as the hydrogen electrode provides a promising alternative for a conventional Ni/YSZ. The possible charge compensation mechanism of SYT is described as Sr0.95Y0.05Ti0.95-2δ 4+Ti2δ+0.05 3+O3-δ. The Ti3+ is approximately 11.73% in the reduced SYT by XRD Rietveld refinement, electron paramagnetic resonance (EPR) and thermogravimetry (TG) analysis. Voltage-current curves and impedance spectra are measured as a function of applied voltages to characterize the cells. The bulk resistance (Ro) and the electrode polarization resistance (Rp) at open circuit voltages (OCV) at 750 °C are 9.06 Ω cm2 and 10.57 Ω cm2, respectively. The Ro values have a small amount of changes with small slopes both in the SOFC (-0.29 Ω cm2 V-1) and SOEC mode (0.5 Ω cm2 V-1), whereas the Rp values decrease all the time with the increasing voltages at both the SOFC (-2.59 Ω cm2 V-1) and SOEC mode (-9.65 Ω cm2 V-1), indicating that the electrical conductivity and electro-catalytic property of the SYT-based hydrogen electrode can be improved under the SOEC mode. This journal is

  4. A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

    Science.gov (United States)

    Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

    2016-11-01

    Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

  5. Path integral centroid molecular dynamics simulation of para-hydrogen sandwiched by graphene sheets

    Science.gov (United States)

    Minamino, Yuki; Kinugawa, Kenichi

    2016-11-01

    The carbon-hydrogen composite systems of para-hydrogen (p-H2) sandwiched by a couple of graphene sheets have been investigated by means of path integral centroid molecular dynamics simulations at 17 K. It has been shown that sandwiched hydrogen is liquid-like but p-H2 molecules are preferably adsorbed onto the graphene sheets because of attractive graphene-hydrogen interaction. The diffusion coefficient of p-H2 molecules in the direction parallel to the graphene sheets is comparable to that in pure liquid p-H2. There exists a characteristic mode of 140 cm-1 of the p-H2 molecules, attributed to adsorption-binding motion perpendicular to the graphene sheets.

  6. Research of new AB type hydrogen storage materials that can be used as a negative electrode in nickel -metal hydride battery; Recherche de nouveaux composes intermetalliques hydrurables de type AB utilisables comme electrode negative d`accumulateur nickel-hydrure

    Energy Technology Data Exchange (ETDEWEB)

    Jordy, Ch.

    1994-12-15

    The aim of this work is to determine new AB type hydrogen storage materials that can be used as a negative electrode in nickel-metal hydride battery. The main requested solid-gas hydrogenation properties are as follows : a reversible capacity higher than 400 mAh/g and a plateau pressure close to 0, 01 MPa at 25 deg C. Binary intermetallic compounds have been selected according to their high hydrogen capacity. The thermodynamic properties of the hydride have to be adjusted by partial substitution of the A and/or B elements. The selected binary intermetallic rate to the substitution was based on known thermodynamic models and on criteria on hydrogen atom occupation in interstitial sites. The only alloys, which could have interest, are the one which are homogeneous. Amongst them, the compounds Ti(Fe{sub 1-x}) where M=Ni,Co,Mn,Cr, showed a solid-gas capacity higher than 400 mAh/g and a plateau pressure close to 0,01 MPa at 25 deg C. Nevertheless, the electrochemical capacity is extremely low due to the iron corrosion in concentrated KOH. The electrochemical capacities of (Ti{sub 1-x-y} Zr{sub x}M{sub y})Ni compounds for M=V and Si are the most promising in the AB type since a 350 m Ah/g reversible capacity has been measured bY THE CONSTANT POTENTIAL METHOD. We also showed that the partial zirconium substitution made the martensitic transformation temperature higher. (author)

  7. In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode-Electrolyte Interface: a SIMS Approach.

    Science.gov (United States)

    Wang, Zhaoying; Zhang, Yanyan; Liu, Bingwen; Wu, Kui; Thevuthasan, Suntharampillai; Baer, Donald R; Zhu, Zihua; Yu, Xiao-Ying; Wang, Fuyi

    2017-01-03

    The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability, we report the first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.

  8. Nanoporous gold on three-dimensional nickel foam: An efficient hybrid electrode for hydrogen peroxide electroreduction in acid media

    Science.gov (United States)

    Ke, Xi; Xu, Yantong; Yu, Changchun; Zhao, Jie; Cui, Guofeng; Higgins, Drew; Li, Qing; Wu, Gang

    2014-12-01

    A hybrid structure of nanoporous gold (NPG) on three-dimensional (3D) macroporous Ni foam has been synthesized by electrodeposition of Au-Sn alloy film followed by a facile chemical dealloying process under free corrosion conditions. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) are used to characterize the morphology and structure of the NPG/Ni foam hybrids. It is shown that the Ni foam skeletons are uniformly wrapped by the NPG film which is composed of bicontinuous nanostructures consisting of interconnected ligaments and nanopores. Electroreduction of H2O2 on the NPG/Ni foam hybrid electrode in acid media is investigated by linear scan voltammetry, chronoamperometry and electrochemical impedance spectroscopy. It is found that such hierarchical porous electrode displays superior activity, durability and mass transport property for H2O2 electroreduction. These results demonstrate the potential of the NPG/Ni foam hybrid electrodes for the applications in fuel cell technology.

  9. Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations.

    Science.gov (United States)

    Sato, T; Ramirez-Cuesta, A J; Daemen, L; Cheng, Y-Q; Tomiyasu, K; Takagi, S; Orimo, S

    2016-09-27

    Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4](-) was investigated using inelastic neutron scattering viewed from vibrational dynamics. The hydrogen release followed the softening of translational and [AlH4](-) librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

  10. Dynamic optimization and robust explicit model predictive control of hydrogen storage tank

    KAUST Repository

    Panos, C.

    2010-09-01

    We present a general framework for the optimal design and control of a metal-hydride bed under hydrogen desorption operation. The framework features: (i) a detailed two-dimension dynamic process model, (ii) a design and operational dynamic optimization step, and (iii) an explicit/multi-parametric model predictive controller design step. For the controller design, a reduced order approximate model is obtained, based on which nominal and robust multi-parametric controllers are designed. © 2010 Elsevier Ltd.

  11. Capturing the transient species at the electrode-electrolyte interface by in situ dynamic molecular imaging

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jiachao; Zhou, Yufan; Hua, Xin; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-09-01

    The electrochemical interface between the solid electrode and liquid electrolyte has long been studied because of its importance in electrical energy storage, material synthesis, catalysis, and energy conversions.1 However, such interfaces are complex and extremely difficult to observe directly and are poorly under-stood due to lack of true in situ tools.2 Although electrochemical techniques have been widely used to investigate such interfaces, they are based on macroscopic models or current changes that could not provide direct ionic and molecular information of the interfacial structure. Many in situ and ex situ spectroscopy and microscopy techniques have been used to study the solid–liquid (s–l) interface.3,4 In situ TEM in sealed liquid cells has notably become a popular choice to provide structural information of s–l at the atomic level.5,6 However, real-time spatial mapping of the ionic and molecular intermediate species at the dynamic inter-face still remains a key challenge.

  12. Quantum dynamics of hydrogen atoms on graphene. I. System-bath modeling

    Energy Technology Data Exchange (ETDEWEB)

    Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Jackson, Bret [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany); Martinazzo, Rocco, E-mail: rocco.martinazzo@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Richerche, v. Golgi 19, 20133 Milano (Italy)

    2015-09-28

    An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice and is obtained from an empirical force field through inversion of a classical equilibrium correlation function describing the hydrogen motion. By construction, model building easily accommodates improvements coming from the use of higher level electronic structure theory for the system. Further, it is well suited to a determination of the system-environment coupling by means of ab initio molecular dynamics. This paper details the system-bath modeling and shows its application to the quantum dynamics of vibrational relaxation of a chemisorbed hydrogen atom, which is here investigated at T = 0 K with the help of the multi-configuration time-dependent Hartree method. Paper II deals with the sticking dynamics.

  13. Eletrodo de hidrogênio: o que há nos livros didáticos além de E¸ = 0? The hydrogen electrode: what is there in the textbooks beyond E¸ = 0?

    Directory of Open Access Journals (Sweden)

    Wanda de Oliveira

    2009-01-01

    Full Text Available The results of an exercise on electrochemistry for General Chemistry students are presented. The difficulty encountered by students in predicting the shift in the potential of the hydrogen electrode under non-standard conditions prompted a search in textbooks on how the subject is developed. Besides several instances of inconsistencies in defining the standard state, such as including the temperature in the definition, a number of incorrect depictions of the hydrogen electrode were discovered. Of the 28 General Chemistry books, 16 Physical Chemistry books and 24 Internet pages, 30, 20 and 46%, respectively, showed devices that would not work in practice.

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

    Science.gov (United States)

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

    2016-01-01

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

  15. Si-H bond dynamics in hydrogenated amorphous silicon

    Science.gov (United States)

    Scharff, R. Jason; McGrane, Shawn D.

    2007-08-01

    The ultrafast structural dynamics of the Si-H bond in the rigid solvent environment of an amorphous silicon thin film is investigated using two-dimensional infrared four-wave mixing techniques. The two-dimensional infrared (2DIR) vibrational correlation spectrum resolves the homogeneous line shapes ( 4ps waiting times. The Si-H stretching mode anharmonic shift is determined to be 84cm-1 and decreases slightly with vibrational frequency. The 1→2 linewidth increases with vibrational frequency. Frequency dependent vibrational population times measured by transient grating spectroscopy are also reported. The narrow homogeneous line shape, large inhomogeneous broadening, and lack of spectral diffusion reported here present the ideal backdrop for using a 2DIR probe following electronic pumping to measure the transient structural dynamics implicated in the Staebler-Wronski degradation [Appl. Phys. Lett. 31, 292 (1977)] in a-Si:H based solar cells.

  16. Electronic Principles of Hydrogen Incorporation and Dynamics in Metal Hydrides

    Directory of Open Access Journals (Sweden)

    Ljiljana Matović

    2012-08-01

    Full Text Available An approach to various metal hydrides based on electronic principles is presented. The effective medium theory (EMT is used to illustrate fundamental aspects of metal-hydrogen interaction and clarify the most important processes taking place during the interaction. The elaboration is extended using the numerous existing results of experiment and calculations, as well as using some new material. In particular, the absorption/desorption of H in the Mg/MgH2 system is analyzed in detail, and all relevant initial structures and processes explained. Reasons for the high stability and slow sorption in this system are noted, and possible solutions proposed. The role of the transition-metal impurities in MgH2 is briefly discussed, and some interesting phenomena, observed in complex intermetallic compounds, are mentioned. The principle mechanism governing the Li-amide/imide transformation is also discussed. Latterly, some perspectives for the metal-hydrides investigation from the electronic point of view are elucidated.

  17. Numerical simulation of particle dynamics in an orifice-electrode system. Application to counting and sizing by impedance measurement.

    Science.gov (United States)

    Isèbe, Damien; Nérin, Philippe

    2013-04-01

    This paper describes how to numerically tackle the problem of counting and sizing particles by impedance measurement in an orifice-electrode system. The model allows to simulate the particle dynamics submitted to strong hydrodynamic stresses through a microorifice and to compute the voltage pulses generated by the modification of the inner dielectric medium. This approach gives important information about particles size distribution and allows to quantify the role of trajectory and orientation of particles on the size measurement.

  18. On the dynamics of a wind-hydrogen energy system undergoing a suitable operation planning

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Clua, J.G. [National University of La Plata, Buenos Aires (Argentina). Faculty of Engineering. Lab. de Electronica Industrial, Control e Instrumentacion (LEICI)]. E-mail: jose.garciaclua@ing.unlp.edu.ar; Mantz, R.J. [National University of La Plata, Buenos Aires (Argentina). Scientific Research Commission of the Province of Buenos Aires (CICpBA); Battista, H. de [Consejo Nacional de Investigaciones Cientificas y Tecnicas - CONICET, Buenos Aires (Argentina)

    2008-07-01

    Hydrogen production from renewable energy sources represents a potential solution for sustainable development. However, there are still some barriers to a cost-competitive hydrogen economy. Among other open topics, there is a need for suitable controllers being capable of maximizing the wind energy extraction despite the primary resource variability and, at the same time, of accomplishing the electrolyzer specifications. Several operation strategies have been proposed to cope with these objectives. Nevertheless, the design of dynamic controllers to track a given strategy is a problem less treated in literature, though not less important. For the proper design of such controllers it is necessary to study the inherent properties of the system dynamics. In this context, this paper is devoted to investigate the dynamic behaviour of a wind-hydrogen energy system where the wind turbine is coupled to the electrolyzer through an electronic converter. Particular attention is given to the zero dynamics of the system because of their potential limitations to the operation strategy tracking. It is found that the zero dynamics exhibits interesting phenomena such as bifurcation of equilibria, which mainly appears because of the nonlinearity introduced by the aerodynamic torque. (author)

  19. Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations

    Science.gov (United States)

    Yamada, Steven A.; Thompson, Ward H.; Fayer, Michael D.

    2017-06-01

    Many of water's remarkable properties arise from its tendency to form an intricate and robust hydrogen bond network. Understanding the dynamics that govern this network is fundamental to elucidating the behavior of pure water and water in biological and physical systems. In ultrafast nonlinear infrared experiments, the accessible time scales are limited by water's rapid vibrational relaxation (1.8 ps for dilute HOD in H2O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here, hydrogen bonding dynamics in bulk D2O were studied from the perspective of the much longer lived (36.2 ps) CN stretch mode of selenocyanate (SeCN-) using polarization selective pump-probe (PSPP) experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and molecular dynamics simulations. The simulations make use of the empirical frequency mapping approach, applied to SeCN- for the first time. The PSPP experiments and simulations show that the orientational correlation function decays via fast (2.0 ps) restricted angular diffusion (wobbling-in-a-cone) and complete orientational diffusive randomization (4.5 ps). Spectral diffusion, quantified in terms of the frequency-frequency correlation function, occurs on two time scales. The initial 0.6 ps time scale is attributed to small length and angle fluctuations of the hydrogen bonds between water and SeCN-. The second 1.4 ps measured time scale, identical to that for HOD in bulk D2O, reports on the collective reorganization of the water hydrogen bond network around the anion. The experiments and simulations provide details of the anion-water hydrogen bonding and demonstrate that SeCN- is a reliable vibrational probe of the ultrafast spectroscopy of water.

  20. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  1. Measurement of the dynamic response of compressed hydrogen by inelastic X-ray scattering

    Science.gov (United States)

    Falk, K.; Jephcoat, A. P.; Crowley, B. J. B.; Fäustlin, R. R.; Fortmann, C.; Y Khattak, F.; Kleppe, A. K.; Riley, D.; Toleikis, S.; Wark, J.; Wilhelm, H.; Gregori, G.

    2010-08-01

    Measurement of the dynamic properties of hydrogen and helium under extreme pressures is a key to understanding the physics of planetary interiors. The inelastic scattering signal from statically compressed hydrogen inside diamond anvil cells at 2.8 GPa and 6.4 GPa was measured at the Diamond Light Source synchrotron facility in the UK. The first direct measurement of the local field correction to the Coulomb interactions in degenerate plasmas was obtained from spectral shifts in the scattering data and compared to predictions by the Utsumi-Ichimaru theory for degenerate electron liquids.

  2. Fast and stable redox reactions of MnO2/CNT hybrid electrodes for dynamically stretchable pseudocapacitors

    Science.gov (United States)

    Gu, Taoli; Wei, Bingqing

    2015-07-01

    Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics.Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid

  3. Hydrogen atom temperature measured with wavelength-modulated laser absorption spectroscopy in large scale filament arc negative hydrogen ion source

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, H., E-mail: nakano@nifs.ac.jp; Goto, M.; Tsumori, K.; Kisaki, M.; Ikeda, K.; Nagaoka, K.; Osakabe, M.; Takeiri, Y.; Kaneko, O. [National Institute for Fusion Science, 322-6 Oroshi-cho, Toki 5095292 (Japan); Nishiyama, S.; Sasaki, K. [Graduate school of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 0608628 (Japan)

    2015-04-08

    The velocity distribution function of hydrogen atoms is one of the useful parameters to understand particle dynamics from negative hydrogen production to extraction in a negative hydrogen ion source. Hydrogen atom temperature is one of the indicators of the velocity distribution function. To find a feasibility of hydrogen atom temperature measurement in large scale filament arc negative hydrogen ion source for fusion, a model calculation of wavelength-modulated laser absorption spectroscopy of the hydrogen Balmer alpha line was performed. By utilizing a wide range tunable diode laser, we successfully obtained the hydrogen atom temperature of ∼3000 K in the vicinity of the plasma grid electrode. The hydrogen atom temperature increases as well as the arc power, and becomes constant after decreasing with the filling of hydrogen gas pressure.

  4. Dynamics of interstitial hydrogen molecules in crystalline silicon

    Energy Technology Data Exchange (ETDEWEB)

    Estreicher, S.K.; Wells, K. [Department of Physics, Texas Tech University, Lubbock, TX (United States); Fedders, P.A. [Department of Physics, Washington University, St. Louis, MO (United States); Ordejon, Pablo [Institut de Ciencia de Materiales de Barcelona, CSIC, Campus de la UAB, Bellaterra, Barcelona (Spain)

    2001-07-23

    The static and dynamic properties of interstitial H{sub 2}, HD and D{sub 2} molecules in crystalline silicon are obtained from ab initio molecular-dynamics simulations with atomic-like basis sets. The static (T=0) calculations agree with those of most other authors: the centre of mass (CM) of H{sub 2} is at the tetrahedral interstitial (T) site, the molecule is a nearly-free rotator, and the activation energy for diffusion is 0.90 eV. However, these results fail to explain a number of experimental observations, such as why H{sub 2} is infrared (IR) active, why the expected ortho/para splitting is not present, why the symmetry is C{sub 1}, why the piezospectroscopic tensors of H{sub 2} and D{sub 2} are identical or why the exposure to an H/D mix results in a single HD line which is not only at the wrong place but also much weaker than expected. In the present work, we extend the static calculations to include the constant-temperature dynamics for H{sub 2} in Si. At T>0 K, the CM of the molecule no longer remains at the T site. Instead, H{sub 2} 'bounces' off the walls of its tetrahedral cage and exchanges energy with the host crystal. The average position of the CM is away from the T site along <100>. Under uniaxial stress, the CM shifts off that axis and the molecule has C{sub 1} symmetry. The H-H stretch frequency calculated from the Fourier transform of the v-v autocorrelation function is close to the measured one. Since the potential energy experienced by H{sub 2} in Si near the T site is very flat, we argue that H{sub 2} should be a nearly free quantum mechanical rotator. Up to room temperature, only the j=0 and j=1 rotational states are occupied, H{sub 2} resembles a sphere rather than a dumbbell, the symmetry is determined by the position of the CM and HD is equivalent to DH in any symmetry. The rapid motion of the CM implies that an ortho-to-para transition will occur if a large magnetic moment is nearby. Several candidates are proposed. Since

  5. Electroless deposition of Gold-Platinum Core@Shell Nanoparticles on Glassy Carbon Electrode for Non-Enzymatic Hydrogen Peroxide sensing#

    Indian Academy of Sciences (India)

    Gowthaman N S K; Abraham John S

    2016-03-01

    A non-enzymatic hydrogen peroxide sensor was developed using gold@platinum nanoparticlesz (Au@PtNPs) with core@shell structure fabricated on glassy carbon electrode (GCE) by electroless depositionmethod. Initially, gold nanoparticles (AuNPs) were deposited on GCE by reducing HAuCl4 in the presence of NH2OH and the deposited AuNPs on GCE act as the nucleation centre for the deposition of platinum nanoparticles (PtNPs) in the presence of H2PtCl6 and NH2OH. SEM and AFM studies demonstrated that the electrolessdeposition of Pt on Au was isotropic and uniform. Further, Au@PtNP-modified substrates were characterizedby X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray analysis (EDAX) and cyclic voltammetry (CV). XPS showed characteristic binding energies at 71.2 and 74.4 eV for PtNPs and, 83.6 and 87.3 eV forAuNPs indicating the zero-valent nature in both of them. The electrocatalytic activity of Au@PtNP-modifiedelectrode was investigated towards hydrogen peroxide (HP) reduction. The modified electrode exhibited higherelectrocatalytic activity towards HP by not only shifting its reduction potential by 370 mV towards less positivepotential but also by enhancing the reduction current when compared to bare and AuNP-modified GCE. Thepresent method shows better sensitivity compared to the reported methods in literature and the detection limitwas found to be 60 nM.

  6. FT-IR spectroelectrochemical study of the reduction of 1,4-dinitrobenzene on Au electrode: Hydrogen bonding and protonation in proton donor mixed media

    Energy Technology Data Exchange (ETDEWEB)

    Tian Dexiang [Department of Chemistry, Anhui University, 230039, Hefei, Anhui province (China); Jin Baokang, E-mail: bkjinhf@yahoo.com.cn [Department of Chemistry, Anhui University, 230039, Hefei, Anhui province (China)

    2011-10-30

    Highlights: > 1,4-Dinitrobenzene electrochemical reduction on the Au electrode is explored. > Radical anion (PNB{center_dot}{sup -}) is found both in aprotic media and in proton donors mixed media. > The H-bonding forming between PNB{center_dot}{sup -}, PNB{sup 2-} and proton donors in low donors concentration. > The protonation of PNB{sup 2-} occurs in high concentration proton donor mixed media. - Abstract: The electrochemical behavior of 1,4-dinitrobenzene (1,4-PNB) on the Au electrode was investigated by cyclic voltammetry (CV), in situ FT-IR spectroelectrochemistry, cyclic voltabsorptometry (CVA) and derivative cyclic voltabsorptometry (DCVA) techniques. In aprotic media, 1,4-dinitrobenzene is reversibly reduced in two-step one-electron transfer. A series of IR absorption bands at 1056, 1210, 1341, 1356, 1464 and 1549 cm{sup -1}, tracing to PNB; PNB{center_dot}{sup -} and PNB{sup 2-} are observed. In the presence of proton donors mixed media, with increasing concentrations of proton donors, hydrogen-bonding and protonation process are found successively. The values of combining proton donors with per PNB{sup 2-} to form hydrogen-bonding are estimated by using electrochemical parameters. The result of forming aromatic nitroso compound is supported by tracing the change of IR absorption bands at 1149 and 1587 cm{sup -1} at high concentration of proton donors. Based on CVA and DCVA techniques, it is clearly distinguished that the mechanisms of electrochemical reduction of PNB are elaborated in different systems.

  7. Three-dimensional molecular dynamics simulation of hydrogen-enhanced dislocation emission and crack propagation

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A three-dimensional molecular dynamics simulation using the embedded atom method (EAM) potentials shows that for both pure Ni and Ni+H, dislocations are firstly emitted during loading and the crack propagates after enough disloca tions are emitted. In the case of hydrogen embrittlement, local plastic deformat ion is a precondition for crack propagation. For the crack along the (1 11) slip pla ne, one atom fraction in percent of hydrogen can decrease the critical stress in tensity for dislocation emission KIe from 0.42 to 0.36 MPam 1/2, and that for crack propagation KIp from 0.80 to 0.76 MPam1/2. Therefore, hydrogen enhances dislocation emission and crack pro pagation.

  8. Ab Initio Path Integral Molecular Dynamics Simulation of Hydrogen in Silicon

    Science.gov (United States)

    Probert, M. I. J.; Glover, M. J.

    2006-05-01

    We report results of a first-principles theoretical study of an isolated neutral hydrogen atom in crystalline silicon. Spin-polarised density functional theory is used to treat the electrons, and the path-integral molecular dynamics method is used to describe the quantum properties of the nucleus at finite temperature. This is necessary as the hydrogen atom has sufficiently low mass that it exhibits significant nuclear quantum delocalisation and zero-point motion even at room temperature. Unlike post-hoc treatments, such as calculating a static potential energy surface, the path-integral treatment enables such effects to be included "on-the-fly". This is found to be significant, as a coupling is found between the structure of the host silicon lattice and the quantum delocalisation of the hydrogen defect.

  9. Hydrogen and muonium in diamond: A path-integral molecular dynamics simulation

    Science.gov (United States)

    Herrero, Carlos P.; Ramírez, Rafael; Hernández, Eduardo R.

    2006-06-01

    Isolated hydrogen, deuterium, and muonium in diamond have been studied by path-integral molecular dynamics simulations in the canonical ensemble. Finite-temperature properties of these point defects were analyzed in the range from 100 to 800K . Interatomic interactions were modeled by a tight-binding potential fitted to density-functional calculations. The most stable position for these hydrogenic impurities is found at the C-C bond center. Vibrational frequencies have been obtained from a linear-response approach, based on correlations of atom displacements at finite temperatures. The results show a large anharmonic effect in impurity vibrations at the bond center site, which hardens the vibrational modes with respect to a harmonic approximation. Zero-point motion causes an appreciable shift of the defect level in the electronic gap, as a consequence of electron-phonon interaction. This defect level goes down by 70meV when replacing hydrogen by muonium.

  10. Molecular dynamics simulation of temperature profile in partially hydrogenated graphene and graphene with grain boundary.

    Science.gov (United States)

    Lotfi, Erfan; Neek-Amal, M; Elahi, M

    2015-11-01

    Temperature profile in graphene, graphene with grain boundary and vacancy defects and hydrogenated graphene with different percentage of H-atoms are determined using molecular dynamics simulation. We also obtained the temperature profile in a graphene nanoribbon containing two types of grain boundaries with different misorientation angles, θ=21.8° and θ=32.2°. We found that a temperature gap appears in the temperature profile of a graphene nanoribbon with a grain boundary at the middle. Moreover, we found that the temperature profile in the partially hydrogenated graphene varies with the percentage of hydrogens, i.e. the C:H ratio. Our results show that a grain boundary line in the graphene sheet can change the thermal transport through the system which might be useful for controlling thermal flow in nanostructured graphene.

  11. Nitrogen-Doped Nanoporous Carbon Membranes with Co/CoP Janus-Type Nanocrystals as Hydrogen Evolution Electrode in Both Acidic and Alkaline Environments

    KAUST Repository

    Wang, Hong

    2017-03-31

    Self-supported electrocatalysts being generated and employed directly as electrodes for energy conversion has been intensively pursued in the fields of materials chemistry and energy. Herein, we report a synthetic strategy to prepare freestanding hierarchically structured, nitrogen-doped nanoporous graphitic carbon membranes functionalized with Janus-type Co/CoP nanocrystals (termed as HNDCM-Co/CoP), which were successfully applied as a highly efficient, binder-free electrode in the hydrogen evolution reaction (HER). Benefited from multiple structural merits, such as a high degree of graphitization, three-dimensionally interconnected micro/meso/macropores, uniform nitrogen doping, well-dispersed Co/CoP nanocrystals, as well as the confinement effect of the thin carbon layer on the nanocrystals, HNDCM-Co/CoP exhibited superior electrocatalytic activity and long-term operation stability for HER under both acidic and alkaline conditions. As a proof-of-concept of practical usage, a 5.6 cm × 4 cm × 60 μm macroscopic piece of HNDCM-Co/CoP was prepared in our laboratory. Driven by a solar cell, electroreduction of water in alkaline conditions (pH 14) was performed, and H was produced at a rate of 16 mL/min, demonstrating its potential as real-life energy conversion systems.

  12. Sensors for Highly Toxic Gases: Methylamine and Hydrogen Chloride Detection at Low Concentrations in an Ionic Liquid on Pt Screen Printed Electrodes

    Science.gov (United States)

    Murugappan, Krishnan; Silvester, Debbie S.

    2015-01-01

    Commercially available Pt screen printed electrodes (SPEs) have been employed as possible electrode materials for methylamine (MA) and hydrogen chloride (HCl) gas detection. The room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) was used as a solvent and the electrochemical behaviour of both gases was first examined using cyclic voltammetry. The reaction mechanism appears to be the same on Pt SPEs as on Pt microelectrodes. Furthermore, the analytical utility was studied to understand the behaviour of these highly toxic gases at low concentrations on SPEs, with calibration graphs obtained from 10 to 80 ppm. Three different electrochemical techniques were employed: linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV), with no significant differences in the limits of detection (LODs) between the techniques (LODs were between 1.4 to 3.6 ppm for all three techniques for both gases). The LODs achieved on Pt SPEs were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL) limits of the two gases (5 ppm for HCl and 10 ppm for MA), suggesting that Pt SPEs can successfully be combined with RTILs to be used as cheap alternatives for amperometric gas sensing in applications where these toxic gases may be released. PMID:26506358

  13. Sensors for Highly Toxic Gases: Methylamine and Hydrogen Chloride Detection at Low Concentrations in an Ionic Liquid on Pt Screen Printed Electrodes

    Directory of Open Access Journals (Sweden)

    Krishnan Murugappan

    2015-10-01

    Full Text Available Commercially available Pt screen printed electrodes (SPEs have been employed as possible electrode materials for methylamine (MA and hydrogen chloride (HCl gas detection. The room temperature ionic liquid (RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide ([C2mim][NTf2] was used as a solvent and the electrochemical behaviour of both gases was first examined using cyclic voltammetry. The reaction mechanism appears to be the same on Pt SPEs as on Pt microelectrodes. Furthermore, the analytical utility was studied to understand the behaviour of these highly toxic gases at low concentrations on SPEs, with calibration graphs obtained from 10 to 80 ppm. Three different electrochemical techniques were employed: linear sweep voltammetry (LSV, differential pulse voltammetry (DPV and square wave voltammetry (SWV, with no significant differences in the limits of detection (LODs between the techniques (LODs were between 1.4 to 3.6 ppm for all three techniques for both gases. The LODs achieved on Pt SPEs were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL limits of the two gases (5 ppm for HCl and 10 ppm for MA, suggesting that Pt SPEs can successfully be combined with RTILs to be used as cheap alternatives for amperometric gas sensing in applications where these toxic gases may be released.

  14. Rhodium nanoparticle-modified screen-printed graphite electrodes for the determination of hydrogen peroxide in tea extracts in the presence of oxygen.

    Science.gov (United States)

    Gatselou, Vasiliki A; Giokas, Dimothenis L; Vlessidis, Athanasios G; Prodromidis, Mamas I

    2015-03-01

    In this work we describe the fabrication of nanostructured electrocatalytic surfaces based on polyethyleneimine (PEI)-supported rhodium nanoparticles (Rh-NP) over graphite screen-printed electrodes (SPEs) for the determination of hydrogen peroxide in the presence of oxygen. Rh-NP, electrostatically stabilized by citrate anions, were immobilized over graphite SPEs, through coulombic attraction on a thin film of positively charged PEI. The functionalized sensors, polarized at 0.0 V vs. Ag/AgCl/3 M KCl, exhibited a linear response to H2O2 over the concentration range from 5 to 600 μmol L(-1) H2O2 in the presence of oxygen. The 3σ limit of detection was 2 μmol L(-1) H2O2, while the reproducibility of the method at the concentration level of 10 μmol L(-1) H2O2 (n=10) and between different sensors (n=4) was lower than 3 and 5%, respectively. Most importantly, the sensors showed an excellent working and storage stability at ambient conditions and they were successfully applied to the determination of H2O2 produced by autooxidation of polylphenols in tea extracts with ageing. Recovery rates ranged between 97 and 104% suggesting that the as-prepared electrodes can be used for the development of small-scale, low-cost chemical sensors for use in on-site applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Influences of low-Ti substitution for La and Mg on the electrochemical and kinetic characteristics of AB3-type hydrogen storage alloy electrodes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The(La0.67Mg0.33)1-xTixNi2.75Co0.25(x = 0,0.05,0.10,0.15 and 0.20,at%) alloys were synthesized by arc melting and subsequent heat solid-liquid diffusing method.The structure,electrochemical properties and kinetic characteristics of the alloys were investigated systematically.The results showed that all the alloys mainly consisted of the(La,Mg)Ni3,LaNi5 phases,and the lattice parameters and the cell volumes of the(La,Mg)Ni3 and LaNi5 phases decreased with increasing Ti content.The alloy electrodes could be activated to reach their maximum discharge capacity within five cycles.The cycle life after 100 charge/discharge cycles(C100/Cmax) and the high-rate dischargeability at a discharge current density of 1200 mA/g first increased and then decreased.All the results showed that low-Ti content in AB3-type hydrogen storage alloys was beneficial to improvements of the overall electrochemical properties,and the optimum overall electrochemical performance of the alloy electrodes was obtained when x = 0.05.

  16. Polarized potential and electrode materials implication on electro-fermentative di-hydrogen production: Microbial assemblages and hydrogenase gene copy variation.

    Science.gov (United States)

    Arunasri, Kotakonda; Annie Modestra, J; Yeruva, Dileep Kumar; Vamshi Krishna, K; Venkata Mohan, S

    2016-01-01

    This study examined the changes in microbial diversity in response to different electrode materials viz., stainless steel mesh (SS) and graphite plate as anodes in two microbial electrolysis cell (MEC) each poised at 0.2V, 0.4V, 0.6V and 0.8V. Changes in microbiota prior to and after pretreatment along with microbiota enriched in response to various poised potentials with SS and graphite are monitored by 16S rRNA gene based DGGE profiling. Significant shifts in microbial community were noticed at all these experimental conditions. Correspondingly, the level of hydrogenase belonging to genera Bacillus, Pseudomonas, Rhodopseudomonas and Clostridium was studied by quantitative real time PCR (RT-PCR) at various applied potentials. DGGE based 16S rRNA gene profiling revealed enriched members belonging to phylum Firmicutes predominantly present at 0.8V in both MECs contributing to high hydrogen production. This study first time explored the growth behavior of mixed consortia in response to poised potentials and electrode materials.

  17. TiO2-NT electrodes modified with Ag and diamond like carbon (DLC) for hydrogen production by alkaline water electrolysis

    Science.gov (United States)

    Baran, Evrim; Baz, Zeynep; Esen, Ramazan; Yazici Devrim, Birgül

    2017-10-01

    In present work, the two-step anodization technique was applied for synthesis of TiO2 nanotube (NT). Silver and diamond like carbon (DLC) were coated on the surface of as prepared TiO2-NT using chemical reduction method and MW ECR plasma system. The morphology, composition and structure of the electrodes were examined by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results showed that Ag nanoparticles, having size in the range of 48-115 nm, are evenly distributed on the top, inside and outside surface of TiO2-NT and when DLC was coated on the surface of TiO2-NT and TiO2-NT-Ag, the top of nanotubes were partially open and the pore diameter of hexagonal structure decreased from 165 nm to of 38-80 nm. On the other hand, the microhardness test and contact angle measurements revealed that additions of Ag and diamond like carbon have a positive effect on the mechanical properties of TiO2-NT film. The electrocatalytic properties of the electrodes towards the hydrogen evolution reaction (HER) were investigated by the electrochemical measurements recorded in 1 M KOH solution. In addition, long-term durability of electrodes towards HER and the energy consumption of alkaline electrolysis were investigated. The energy requirement showed that while the deposition of silver provides approximately 14.95% savings of the energy consumption, the DLC coating causes increase in energy consumption.

  18. Real-time electrochemical detection of hydrogen peroxide secretion in live cells by Pt nanoparticles decorated graphene-carbon nanotube hybrid paper electrode.

    Science.gov (United States)

    Sun, Yimin; He, Kui; Zhang, Zefen; Zhou, Aijun; Duan, Hongwei

    2015-06-15

    In this work, we develop a new type of flexible and lightweight electrode based on highly dense Pt nanoparticles decorated free-standing graphene-carbon nanotube (CNT) hybrid paper (Pt/graphene-CNT paper), and explore its practical application as flexible electrochemical biosensor for the real-time tracking hydrogen peroxide (H2O2) secretion by live cells. For the fabrication of flexible nanohybrid electrode, the incorporation of CNT in graphene paper not only improves the electrical conductivity and the mechanical strength of graphene paper, but also increases its surface roughness and provides more nucleation sites for metal nanoparticles. Ultrafine Pt nanoparticles are further decorated on graphene-CNT paper by well controlled sputter deposition method, which offers several advantages such as defined particle size and dispersion, high loading density and strong adhesion between the nanoparticles and the substrate. Consequently, the resultant flexible Pt/graphene-CNT paper electrode demonstrates a variety of desirable electrochemical properties including large electrochemical active surface area, excellent electrocatalytic activity, high stability and exceptional flexibility. When used for nonenzymatic detection of H2O2, Pt/graphene-CNT paper exhibits outstanding sensing performance such as high sensitivity, selectivity, stability and reproducibility. The sensitivity is 1.41 µA µM(-1) cm(-2) with a linear range up to 25 µM and a low detection limit of 10 nM (S/N=3), which enables the resultant biosensor for the real-time tracking H2O2 secretion by live cells macrophages.

  19. Characteristics and dynamics of the boundary layer in RF-driven sources for negative hydrogen ions

    Energy Technology Data Exchange (ETDEWEB)

    Wimmer, Christian

    2014-10-16

    The design of the neutral beam injection system of the upcoming ITER fusion device is based on the IPP (Max-Planck-Institut fuer Plasmaphysik, Garching) prototype source for negative hydrogen ions. The latter consists of a driver, in which hydrogen (or deuterium) molecules are dissociated in a large degree in a hydrogen plasma; the plasma expands then towards the plasma grid, on which negative hydrogen ions are formed by conversion of atoms or positive ions by the surface process and are extracted in the following accompanied by the co-extraction of electrons via a three grid system. Electrons are removed out of the extracted beam prior full acceleration using deflection magnets, bending them onto the second grid. The thermal load limits the tolerable amount of co-extracted electrons. A magnetic filter field in the expansion chamber reduces the electron temperature and density, on the one hand in order to minimize the destruction process of negative hydrogen ions by electron collisions and on the other hand in order to reduce the co-extracted electron current density. Caesium is evaporated into the source for an effective production of negative hydrogen ions, lowering the work function of the plasma grid. Due to the high chemical reactivity of caesium, the high vacuum condition in the source and the plasma-wall interaction, complex redistribution processes of Cs take place in the ion source. The boundary layer is the plasma volume between the magnetic filter field and the plasma grid, in which the most important physics of the negative ion source takes place: the production of negative hydrogen ions at the plasma grid, their transport through the plasma and the following extraction. A deeper understanding of the plasma and Cs dynamics in the boundary layer is desirable in order to achieve a stable long-pulse operation as well as to identify possible future improvements. For this reason, the boundary layer of the prototype source has been characterized in this work

  20. Dynamic behavior of surface film on LiCoO{sub 2} thin film electrode

    Energy Technology Data Exchange (ETDEWEB)

    Matsui, Masaki [Material Engineering Div. 3, Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan); Department of Applied Chemistry, Graduate School of Urban Environmental Science, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0397 (Japan); Dokko, Kaoru; Kanamura, Kiyoshi [Department of Applied Chemistry, Graduate School of Urban Environmental Science, Tokyo Metropolitan University, 1-1 Minami-Ohsawa, Hachioji, Tokyo 192-0397 (Japan)

    2008-02-15

    Electrochemical oxidation behavior of non-aqueous electrolytes on LiCoO{sub 2} thin film electrodes were investigated by in situ polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). LiCoO{sub 2} thin film electrode on gold substrate was prepared by rf-sputtering method. In situ PM-FTIR spectra were obtained at various electrode potentials during cyclic voltammetry measurement between 3.5 V vs. Li/Li{sup +} and 4.2 V vs. Li/Li{sup +}. During anodic polarization, oxidation of non-aqueous electrolyte was observed, and oxidized products remained on the electrode at the potential higher than 3.75 V vs. Li/Li{sup +} as a surface film. During cathodic polarization, the stripping of the surface film was observed at the potential lower than 3.9 V vs. Li/Li{sup +}. Depth profile of XPS also showed that more organic surface film remained on charged LiCoO{sub 2} than that on discharged one. AFM images of charged and discharged electrodes showed that some decomposed products deposited on charged electrode and disappeared from the surface of discharged one. These results indicate that the surface film on LiCoO{sub 2} is not so stable. (author)

  1. Dynamic behavior of surface film on LiCoO 2 thin film electrode

    Science.gov (United States)

    Matsui, Masaki; Dokko, Kaoru; Kanamura, Kiyoshi

    Electrochemical oxidation behavior of non-aqueous electrolytes on LiCoO 2 thin film electrodes were investigated by in situ polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). LiCoO 2 thin film electrode on gold substrate was prepared by rf-sputtering method. In situ PM-FTIR spectra were obtained at various electrode potentials during cyclic voltammetry measurement between 3.5 V vs. Li/Li + and 4.2 V vs. Li/Li +. During anodic polarization, oxidation of non-aqueous electrolyte was observed, and oxidized products remained on the electrode at the potential higher than 3.75 V vs. Li/Li + as a surface film. During cathodic polarization, the stripping of the surface film was observed at the potential lower than 3.9 V vs. Li/Li +. Depth profile of XPS also showed that more organic surface film remained on charged LiCoO 2 than that on discharged one. AFM images of charged and discharged electrodes showed that some decomposed products deposited on charged electrode and disappeared from the surface of discharged one. These results indicate that the surface film on LiCoO 2 is not so stable.

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

    Directory of Open Access Journals (Sweden)

    Katsuaki Tanabe

    2016-01-01

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

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

    Science.gov (United States)

    Tanabe, Katsuaki

    2016-01-01

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

  4. "Zwitterionic Proton Sponge" Hydrogen Bonding Investigations on the Basis of Car-Parrinello Molecular Dynamics.

    Science.gov (United States)

    Jezierska, Aneta; Panek, Jarosław J

    2015-06-22

    1,8-Bis(dimethylamino)-4,5-dihydroxynaphthalene has been investigated on the basis of static DFT computations and Car-Parrinello molecular dynamics. The simulations were performed in the gas phase and in the solid state. The studied "zwitterionic proton sponge" possesses two, short intramolecular hydrogen bonds (O-H···O and N-H···N) classified as Low Barrier Hydrogen Bonds (LBHBs); therefore, the system studied is strongly anharmonic. In addition, the compound exists as a "zwitterion" in solution and in the solid state, thus the intramolecular hydrogen bonds belong to the class of charge-assisted interactions. The applied quantum-chemical methods enabled investigations of metric and spectroscopic parameters of the molecule. The time-evolution investigations of the H-bonding showed a strong delocalization of the bridge protons and their high mobility, reflected in the low barriers on the free energy surfaces. Frequent proton transfer phenomena were noticed. The power spectra of atomic velocity were computed to analyze the vibrational features associated with O-H and N-H stretching. A broad absorption was indicated for both hydrogen bridges. For the first time, Car-Parrinello molecular dynamics results are reported for the compound, and they indicate a broad, shallow but not barrierless, potential well for each of the bridge protons.

  5. A Hydrogen Peroxide Sensor Prepared by Electropolymerization of Pyrrole Based on Screen-Printed Carbon Paste Electrodes

    Directory of Open Access Journals (Sweden)

    Hui Xu

    2007-03-01

    Full Text Available A disposable amperometric biosensor for commercial use to detect hydrogenperoxide has been developed. The sensor is based on screen-printed carbon paste electrodesmodified by electropolymerization of pyrrole with horseradish peroxidase (HRP entrapped.The facture techniques of fabricating the enzyme electrodes are suitable for mass productionand quality control. The biosensor shows a linear amperometric response to H2O2 from 0.1to 2.0 mM, with a sensitivity of 33.24 μA mM-1 cm-2. Different operational parameters ofelectropolymerization are evaluated and optimized.

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

    Science.gov (United States)

    Spătaru, N; Bănica, F G

    2001-11-01

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

  7. Data supporting the role of electric field and electrode material on the improvement of the ageing effects in hydrogenated amorphous silicon solar cells.

    Science.gov (United States)

    Scuto, Andrea; Valenti, Luca; Pierro, Silvio; Foti, Marina; Gerardi, Cosimo; Battaglia, Anna; Lombardo, Salvatore

    2015-09-01

    Hydrogenated amorphous Si (a-Si:H) solar cells are strongly affected by the well known Staebler-Wronski effect. This is a worsening of solar cell performances under light soaking which results in a substantial loss of cell power conversion efficiency compared to time zero performance. It is believed not to be an extrinsic effect, but rather a basic phenomenon related to the nature of a-Si:H and to the stability and motion of H-related species in the a-Si:H lattice. This work has been designed in support of the research article entitled "Role of electric field and electrode material on the improvement of the ageing effects in hydrogenated amorphous silicon solar cells" in Solar Energy Materials & Solar Cells (Scuto et al. [1]), which discusses an electrical method based on reverse bias stress to improve the solar cell parameters, and in particular the effect of temperature, electric field intensity and illumination level as a function of the stress time. Here we provide a further set of the obtained experimental data results.

  8. Photoelectrolytic hydrogen production using Bi{sub 2}MNbO{sub 7} (M = Al, Ga) semiconductor film electrodes prepared by dip-coating

    Energy Technology Data Exchange (ETDEWEB)

    Rosas-Barrera, K.L. [Grupo de Investigaciones en Minerales, Biohidrometalurgia y Ambiente - GIMBA, Universidad Industrial de Santander - UIS, Sede Guatiguara, Km. 2 via El Refugio, C.P. 681011, Piedecusta, Santander (Colombia); Pedraza-Avella, J.A. [Centro de Investigaciones en Catalisis - CICAT, Universidad Industrial de Santander - UIS, Sede Guatiguara, Km. 2 via El Refugio, C.P. 681011, Piedecuesta, Santander (Colombia); Ballen-Gaitan, B.P.; Cortes-Pena, J.; Pedraza-Rosas, J.E. [Grupo de Investigaciones en Minerales, Biohidrometalurgia y Ambiente - GIMBA, Universidad Industrial de Santander - UIS, Sede Guatiguara, Km. 2 via El Refugio, C.P. 681011, Piedecusta (Santander) (Colombia); Laverde-Catano, D.A., E-mail: dlaverde@uis.edu.co [Grupo de Investigaciones en Minerales, Biohidrometalurgia y Ambiente - GIMBA, Universidad Industrial de Santander - UIS, Sede Guatiguara, Km. 2 via El Refugio, C.P. 681011, Piedecusta, Santander (Colombia)

    2011-10-25

    The performance of Bi{sub 2}MNbO{sub 7} (M = Al, Ga) films on AISI/SAE 304 stainless steel was evaluated in the photoelectrochemical hydrogen production as a function of the annealing temperature of the films (400, 500 and 600 deg. C) and the composition of the electrolyte solution (containing KOH, KCN and KCl). The films were prepared by sol-gel dip-coating on AISI/SAE 304 stainless steel followed by a thermal annealing. The photoelectrochemical evaluation (UV-Vis, 2.5 V) was carried out in a conventional two-compartment electrochemical cell by using the prepared films as photoanode and a silver plate as cathode. During the process, circulating current was recorded and hydrogen production and cyanide degradation were measured. In both cases, it was found that the higher activity was obtained with the films annealed at 500 deg. C and using an electrolyte solution 0.3 M of KOH and 120 ppm of CN{sup -}. Further works on the subject should involve a cathode evaluation to avoid the electrode polarization in presence of KCl and an experimental design to optimize the evaluated variables.

  9. Discrete kink dynamics in hydrogen-bonded chains: The two-component model

    DEFF Research Database (Denmark)

    Karpan, V.M.; Zolotaryuk, Yaroslav; Christiansen, Peter Leth

    2004-01-01

    We study discrete topological solitary waves (kinks and antikinks) in two nonlinear diatomic chain models that describe the collective dynamics of proton transfers in one-dimensional hydrogen-bonded networks. The essential ingredients of the models are (i) a realistic (anharmonic) ion-proton inte......We study discrete topological solitary waves (kinks and antikinks) in two nonlinear diatomic chain models that describe the collective dynamics of proton transfers in one-dimensional hydrogen-bonded networks. The essential ingredients of the models are (i) a realistic (anharmonic) ion...... principal differences, like a significant difference in the stability switchings behavior for the kinks and the antikinks. Water-filled carbon nanotubes are briefly discussed as possible realistic systems, where topological discrete (anti)kink states might exist....

  10. A ternary nanocomposite electrode of polyoxometalate/carbon nanotubes/gold nanoparticles for electrochemical detection of hydrogen peroxide.

    Science.gov (United States)

    Guo, Shuyue; Xu, Lin; Xu, Bingbing; Sun, Zhixia; Wang, Lihao

    2015-02-01

    In this work, a nanocomposite film electrode containing polyoxometalate (POM) clusters K6P2W18O62 (P2W18), carbon nanotubes (CNTs) and Au nanoparticles (AuNPs) was fabricated by a smart combination of layer-by-layer (LbL) with the self-assembly technique. The synergistic effect of POM, CNTs and AuNPs on the electrocatalysis of H2O2 was investigated to improve the sensitivity of H2O2 detection. The response of (P2W18/CNTs/P2W18/AuNPs)4 electrodes to H2O2 was remarkably enhanced due to large active sites and good electron conducting ability. The sensor exhibited a quick response (less than 1 second) to H2O2 with a high sensitivity (596.1 μAm M(-1) cm(-2)), and a low detection limit (52 nM). Based on the respective advantages of POMs, CNTs and AuNPs, the nanocomposite multilayer POMs/CNTs/POMs/AuNPs will have special properties and high potential for application.

  11. Enhanced methylene blue oxidative removal by copper electrode-based plasma irradiation with the addition of hydrogen peroxide.

    Science.gov (United States)

    Son, Guntae; Kim, Do-Hyung; Lee, Jung Seok; Lee, Hongshin

    2016-08-01

    Submerged plasma irradiation (SPI)-based advanced oxidation processes have been studied for the oxidation of recalcitrant organic compounds because of their various physical and chemical properties. However, SPI technologies still have a few drawbacks such as relatively low efficiency for wastewater treatment and high energy consumption. In order to overcome these drawbacks, in this study, we proposed the combination of SPI and the Cu(II)-catalyzed Fenton-like system. The removal of methylene blue (MB) by the SPI system was significantly enhanced upon the addition of H2O2. The pseudo-first-order rate constants of MB removal increased with the increase of applied voltage. In addition, the optimum H2O2 dose and initial solution pH were 100 mM and 9, respectively. The reactive oxidants responsible for MB removal in copper electrode-based SPI/H2O2 systems are likely to be hydroxyl radicals (OH) or cupryl ion (Cu(III)), wherein Cu(III) is especially important. Furthermore, the copper electrode-based SPI/H2O2 system is a novel advanced oxidation process capable of oxidizing water recalcitrant and toxic organic pollutants at neutral pH.

  12. Hydrogen soil dynamics in northern boreal and subarctic Sweden

    Science.gov (United States)

    Steele, K. J.; Crill, P. M.; Oquist, M. G.; Varner, R. K.

    2011-12-01

    Wetland ecosystems store a large amount of organic carbon in the form of peat and are the largest natural source of CH4. Thawing of northern wetland permafrost results in an increase in the pool of soil carbon that is made available for decomposition processes and CH4 production. Some subarctic mire sites are also getting wetter as the climate warms. An increase in inundated areas in conjunction with increased amounts of organic matter could give rise to potential feedbacks to warming temperatures via increased emissions of reduced trace gases, such as CH4 and H2, to the atmosphere. H2 soil dynamics in peatlands and forests are complex because of the many microbial-mediated reactions driving H2 production and consumption. H2 couples oxidative and reductive processes in anaerobic environments. The aim of this project was to determine if high-latitude boreal and subarctic soils can change from a sink to a source of H2 to the atmosphere by identifying the microbial processes controlling the production and consumption of H2. Does H2 production and emissions to the atmosphere occur under temporary anoxia in organic -rich soils and soil horizons and do episodic weather events, particularly rain and freeze-thaw cycles, drive H2 production and release from natural soils due to the release of labile organic material and anaerobic conditions. Porewater soil gas profiles from different sub-habitats were determined in Stordalen mire in subarctic Sweden using buried ePTFE tubing and samples manually obtained using a stainless steel sipper. Trends in H2 concentration between the microporous tubing and sipper samples generally agree. The H2 concentration is higher in the tubing possibly due to preferential diffusion into the air-filled tubing by H2, which has a low solubility in water. The wettest site dominated by Eriophorum had the highest concentration of H2 with a maximum of 39.3 ppmv H2 at a depth of 30 cm. A mesic site dominated by Sphagnum had the next highest H2

  13. Dynamic flowgraph modeling of process and control systems of a nuclear-based hydrogen production plant

    Energy Technology Data Exchange (ETDEWEB)

    Al-Dabbagh, Ahmad W. [Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario (Canada); Lu, Lixuan [Faculty of Energy Systems and Nuclear Science, Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario (Canada)

    2010-09-15

    Modeling and analysis of system reliability facilitate the identification of areas of potential improvement. The Dynamic Flowgraph Methodology (DFM) is an emerging discrete modeling framework that allows for capturing time dependent behaviour, switching logic and multi-state representation of system components. The objective of this research is to demonstrate the process of dynamic flowgraph modeling of a nuclear-based hydrogen production plant with the copper-chlorine (Cu-Cl) cycle. Modeling of the thermochemical process of the Cu-Cl cycle in conjunction with a networked control system proposed for monitoring and control of the process is provided. This forms the basis for future component selection. (author)

  14. Path integral centroid molecular dynamics simulations of semiinfinite slab and bulk liquid of para-hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kinugawa, Kenichi [Nara Women`s Univ., Nara (Japan). Dept. of Chemistry

    1998-10-01

    It has been unsuccessful to solve a set of time-dependent Schroedinger equations numerically for many-body quantum systems which involve, e.g., a number of hydrogen molecules, protons, and excess electrons at a low temperature, where quantum effect evidently appears. This undesirable situation is fatal for the investigation of real low-temperature chemical systems because they are essentially composed of many quantum degrees of freedom. However, if we use a new technique called `path integral centroid molecular dynamics (CMD) simulation` proposed by Cao and Voth in 1994, the real-time semi-classical dynamics of many degrees of freedom can be computed by utilizing the techniques already developed in the traditional classical molecular dynamics (MD) simulations. Therefore, the CMD simulation is expected to be very powerful tool for the quantum dynamics studies or real substances. (J.P.N.)

  15. Dirac equation, hydrogen atom spectrum and the Lamb shift in dynamical non-commutative spaces

    Indian Academy of Sciences (India)

    S A ALAVI; N REZAEI

    2017-05-01

    We derive the relativistic Hamiltonian of hydrogen atom in dynamical non-commutative spaces (DNCS or $\\tau$ -space). Using this Hamiltonian we calculate the energy shift of the ground state as well the $2P_{1/2}$, $2S_{1/2}$levels. In all the cases, the energy shift depends on the dynamical non-commutative parameter $\\tau$. Using the accuracy of the energy measurement, we obtain an upper bound for $\\tau$. We also study the Lamb shift in DNCS. Both $2P_{1/2}$ and $2S_{1/2}$ levels receive corrections due to dynamical non-commutativity of space which is in contrast with the non-dynamical non-commutative spaces (NDNCS or $\\theta$-space) in which the $2S_{1/2}$ level receives no correction.

  16. Kinetics of the electro-evolution of hydrogen in the presence of substituted phosphonium salts on a mercury electrode

    Energy Technology Data Exchange (ETDEWEB)

    Mikhailik, Yu.V.; Damaskin, B.B.

    1979-01-01

    A study was made of the kinetics of H/sub 3/O/sup +/ release in the presence of tetraphenyl and triphenyldiethylphosphonium salts for the purpose of clarifying the mechanism of the electroevolution of hydrogen in the presence of group V onium compounds. Since the experimental data did produce a completely satisfactory explanation for the catalysis of H/sub 3/O/sup +/ in the presence of Ph/sub 4/P/sup +/ ions, impedance measurements are planned for studying the adsorption properties of the examined systems. 10 references, 4 figures.

  17. Role of catalyst characteristics in electrocatalytic hydrogenation: Reduction of benzaldehyde and acetophenone on carbon felt/Pd electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Polcaro, A.M.; Palmas, S.; Dernini, S. (Univ. di Cagliari, Piazza D' Armi Cagliari (Italy). Dipartimento di Ingegneria Chimica e Materiali)

    1993-07-01

    The hydrogenation of benzaldehyde and acetophenone was investigated at two carbon felt-supported Pd electrocatalysts, prepared by two different methods. The faradaic yield and the selectivity of the reaction were found to be greatly affected by the preparation conditions of the catalyst. A model, based on a reaction electrocatalytic mechanism, involving two parallel steps through which alcohol and hydrocarbon are generated from the reactant adsorbed on different active sites, was performed. The kinetics was described by means of the Langmuir-Hinshelwood rate equations, and the kinetic and equilibrium parameters were determined for both electrocatalysts.

  18. Semiquantal molecular dynamics simulations of hydrogen-bond dynamics in liquid water using multi-dimensional Gaussian wave packets.

    Science.gov (United States)

    Ono, Junichi; Ando, Koji

    2012-11-01

    A semiquantal (SQ) molecular dynamics (MD) simulation method based on an extended Hamiltonian formulation has been developed using multi-dimensional thawed gaussian wave packets (WPs), and applied to an analysis of hydrogen-bond (H-bond) dynamics in liquid water. A set of Hamilton's equations of motion in an extended phase space, which includes variance-covariance matrix elements as auxiliary coordinates representing anisotropic delocalization of the WPs, is derived from the time-dependent variational principle. The present theory allows us to perform real-time and real-space SQMD simulations and analyze nuclear quantum effects on dynamics in large molecular systems in terms of anisotropic fluctuations of the WPs. Introducing the Liouville operator formalism in the extended phase space, we have also developed an explicit symplectic algorithm for the numerical integration, which can provide greater stability in the long-time SQMD simulations. The application of the present theory to H-bond dynamics in liquid water is carried out under a single-particle approximation in which the variance-covariance matrix and the corresponding canonically conjugate matrix are reduced to block-diagonal structures by neglecting the interparticle correlations. As a result, it is found that the anisotropy of the WPs is indispensable for reproducing the disordered H-bond network compared to the classical counterpart with the use of the potential model providing competing quantum effects between intra- and intermolecular zero-point fluctuations. In addition, the significant WP delocalization along the out-of-plane direction of the jumping hydrogen atom associated with the concerted breaking and forming of H-bonds has been detected in the H-bond exchange mechanism. The relevance of the dynamical WP broadening to the relaxation of H-bond number fluctuations has also been discussed. The present SQ method provides the novel framework for investigating nuclear quantum dynamics in the many

  19. Dynamics of rotating and vibrating thin hemispherical shell with mass and damping imperfections and parametrically driven by discrete electrodes

    CSIR Research Space (South Africa)

    Shatalov, M

    2009-05-01

    Full Text Available stream_source_info Shatalov2_2009.pdf.txt stream_content_type text/plain stream_size 22572 Content-Encoding UTF-8 stream_name Shatalov2_2009.pdf.txt Content-Type text/plain; charset=UTF-8 1 DYNAMICS OF ROTATING... AND VIBRATING THIN HEMISPHERICAL SHELL WITH MASS AND DAMPING IMPERFECTIONS AND PARAMETRICALLY DRIVEN BY DISCRETE ELECTRODES Michael Shatalov1,2 and Charlotta Coetzee2 1Sensor Science and Technology (SST) of CSIR Material Science and Manufacturing (MSM...

  20. Ni nanoparticles supported on graphene layers: An excellent 3D electrode for hydrogen evolution reaction in alkaline solution

    Science.gov (United States)

    Wang, Lixin; Li, Yao; Xia, Meirong; Li, Zhiping; Chen, Zhouhao; Ma, Zhipeng; Qin, Xiujuan; Shao, Guangjie

    2017-04-01

    Metal Ni is a plentiful resource that can actively split water toward hydrogen evolution reaction (HER) in alkaline solution, but exploiting high-efficiency Ni-based composite catalysts is still a significant assignment. Therefore, we design a catalytic material with one-step approach to co-electrodeposit Ni nanoparticles and reduced graphene oxide (rGO) sheets on a three-dimensional Ni foam. When the carbon content existed in Ni-rGO composite catalyst is 3.335 at%, the catalyst exhibits excellent activity on HER with a low Tafel slope (b = 77 mV dec-1), a high exchange current density (j0 = 3.408 mA cm-2), small overpotentials of only 36, 129, and 183 mV to drive 10, 60, and 100 mA cm-2 respectively, and high stability under the different current densities. Such remarkable hydrogen evolution performance is attributed to good electrical conductivity, large specific surface area and harmonious synergistic effect between Ni particles and rGO sheets. In addition, density functional theory (DFT) calculations explain that Ni-rGO composite material presents superior interfacial activity in adsorption/desorption of H* compared with pure Ni and rGO sheet.

  1. Electrokinetic and impedimetric dynamics of FeCo-nanoparticles on glassy carbon electrode

    CSIR Research Space (South Africa)

    Ikpo, CO

    2013-01-01

    Full Text Available voltammetric experiments revealed a diffusion-controlled electron transfer process on the GCE/FeCo electrode surface. Further interrogation on the electrochemical properties of the FeCo nanoelectrode in an oxygen saturated 1 M LiClO4 containing 1:1 v/v ethylene...

  2. Dynamic diversity of synthetic supramolecular polymers in water as revealed by hydrogen/deuterium exchange

    Science.gov (United States)

    Lou, Xianwen; Lafleur, René P. M.; Leenders, Christianus M. A.; Schoenmakers, Sandra M. C.; Matsumoto, Nicholas M.; Baker, Matthew B.; van Dongen, Joost L. J.; Palmans, Anja R. A.; Meijer, E. W.

    2017-05-01

    Numerous self-assembling molecules have been synthesized aiming at mimicking both the structural and dynamic properties found in living systems. Here we show the application of hydrogen/deuterium exchange (HDX) mass spectrometry (MS) to unravel the nanoscale organization and the structural dynamics of synthetic supramolecular polymers in water. We select benzene-1,3,5-tricarboxamide (BTA) derivatives that self-assemble in H2O to illustrate the strength of this technique for supramolecular polymers. The BTA structure has six exchangeable hydrogen atoms and we follow their exchange as a function of time after diluting the H2O solution with a 100-fold excess of D2O. The kinetic H/D exchange profiles reveal that these supramolecular polymers in water are dynamically diverse; a notion that has previously not been observed using other techniques. In addition, we report that small changes in the molecular structure can be used to control the dynamics of synthetic supramolecular polymers in water.

  3. Charged particle dynamics and molecular kinetics in the hydrogen postdischarge plasma

    Science.gov (United States)

    Diomede, P.; Longo, S.; Capitelli, M.

    2006-11-01

    The afterglow of a parallel plate radio frequency discharge in hydrogen is studied by numerical modelling to compare ion dynamics and chemical effects on the behavior of negative ions. While the ion dynamics requires a kinetic description of space dependent plasma relaxation (at least 1D), chemical effects require a vibrational kinetics of hydrogen molecules. Since previous models did not include both features it has not been possible until now to realize both effects in a single simulation. We apply an updated version of the 1D Bari model which includes a 1.5D (1Dr2Dv) Particle in Cell/Monte Carlo (PIC/MC) multispecies module coupled to the space and time dependent master equation for H2(X1Σg+,v=0,…,14) vibrational level population. Negative ion fronts are described in hydrogen for the first time and their impact on the plasma limiting surfaces produces a negative ion current evolution compatible with experimental findings. In the same conditions, the attachment rate overshoot is found to contribute about 7% to the average ion density in the plasma.

  4. Electrodes for the hydrogen through water electrolysis using BMI.BF{sub 4} as electrolyte; Eletrodos para a producao de hidrogenio via eletrolise da agua utilizando BMI.BF{sub 4} como eletrolito

    Energy Technology Data Exchange (ETDEWEB)

    Botton, Janine Padilha; Martini, Emilse M.A.; Souza, Michele Oberson de; Souza, Roberto Fernando de [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica. Lab. de Eletroquimica e Catalise]. E-mail: janine@iq.ufrgs.br; Loget, Gabriel [Universite de Rennes 1, Rennes (France). Lab. de Eletroquimica Molecular e Macromolecular. UMR CNRS 6510

    2008-07-01

    The hydrogen production by water electrolysis was tested with different electrocatalysts (nickel, iron alloys containing nickel, chromium and manganese, and molybdenum) in the ionic liquid electrolyte, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF{sub 4}), 10 vol.% in water. The hydrogen evolution reaction (HER) worked at room temperature with a platinum quasi-reference electrode (PtQRE) applying a -1.7 V potential. The experimental conditions used were determined in previous work and such parameters of operation were confirmed with the electrocatalysts employed in this work. A Hoffman cell apparatus was used to perform the water electrolysis. The current density values, j, obtained were between 3.0 mA cm{sup -2} and 77.5 mA cm{sup -2}. The system efficiency was very high for all electrocatalysts tested, between 97.0% and 99.2%. The molybdenum (Mo) electrode was better than others showing the highest current density value in HER. This behavior has been explained by the lower value of activation energy for the electrolysis reaction when Mo is employed comparing with Pt electrode. The energy activation of the HER using platinum (Pt) as electrocatalyst in an aqueous solution of BMI.BF{sub 4} 10 vol.% was 23.40 kJ mol{sup -1}, whereas with electrode of Mo in the same conditions , was 9.22 kJ mol{sup -1}. In an alkaline aqueous electrolyte (usual medium for such reaction), Mo is less efficient than Pt explaining the lack of published citation using pure Mo as cathode for the HER. The excellent results obtained with a Mo electrode employing ionic liquid as electrolyte show that the hydrogen production can be carried out with cheap electrode material at room temperature, which makes this method economically attractive. (author)

  5. Nano-assemblies consisting of Pd/Pt nanodendrites and poly (diallyldimethylammonium chloride)-coated reduced graphene oxide on glassy carbon electrode for hydrogen peroxide sensors

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yanyan; Zhang, Cong; Zhang, Di; Ma, Min; Wang, Weizhen; Chen, Qiang, E-mail: qiangchen@nankai.edu.cn

    2016-01-01

    Non-enzymatic hydrogen peroxide (H{sub 2}O{sub 2}) sensors were fabricated on the basis of glassy carbon (GC) electrode modified with palladium (Pd) core-platinum (Pt) nanodendrites (Pt-NDs) and poly (diallyldimethylammonium chloride) (PDDA)-coated reduced graphene oxide (rGO). A facile wet-chemical method was developed for preparing Pd core-Pt nanodendrites. In this approach, the growth of Pt NDs was directed by Pd nanocrystal which could be regarded as seed. The PDDA-coated rGO could form uniform film on the surface of GC electrode, which provided a support for Pd core- Pt NDs adsorption by self-assembly. The morphologies of the nanocomposites were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction (spectrum). Electrocatalytic ability of the nanocomposites was evaluated by cyclic voltammetry and chronoamperometric methods. The sensor fabricated by Pd core-Pt NDs/PDDA-rGO/GCE exhibited high sensitivity (672.753 μA mM{sup −1} cm{sup −2}), low detection limit (0.027 μM), wider linear range (0.005–0.5 mM) and rapid response time (within 5 s). Besides, it also exhibited superior reproducibility, excellent anti-interference performance and long-term stability. The present work could afford a viable method and efficient platform for fabricating all kinds of amperometric sensors and biosensors. - Highlights: • A facial wet-chemical method was developed for preparing Pd core-Pt nanodendrites. • The morphologies of graphene and Pd core-Pt nanodendrites were characterized. • A novel H{sub 2}O{sub 2} sensor was fabricated by nano-assembly. • The performance of H{sub 2}O{sub 2} sensor was evaluated by cyclic voltammetry and chronoamperometric methods.

  6. Molecular dynamics simulation of the formation of sp3 hybridized bonds in hydrogenated diamondlike carbon deposition processes.

    Science.gov (United States)

    Murakami, Yasuo; Horiguchi, Seishi; Hamaguchi, Satoshi

    2010-04-01

    The formation process of sp3 hybridized carbon networks (i.e., diamondlike structures) in hydrogenated diamondlike carbon (DLC) films has been studied with the use of molecular-dynamics simulations. The processes simulated in this study are injections of hydrocarbon (CH3 and CH) beams into amorphous carbon (a-C) substrates. It has been shown that diamondlike sp3 structures are formed predominantly at a subsurface level when the beam energy is relatively high, as in the "subplantation" process for hydrogen-free DLC deposition. However, for hydrogenated DLC deposition, the presence of abundant hydrogen at subsurface levels, together with thermal spikes caused by energetic ion injections, substantially enhances the formation of carbon-to-carbon sp3 bonds. Therefore, the sp3 bond formation process for hydrogenated DLC films essentially differs from that for hydrogen-free DLC films.

  7. Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

    Science.gov (United States)

    Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

    2014-03-01

    In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

  8. Low-hydrogen Electrode Root Welding Technology of X80 Pipeline Steel%X80管线钢低氢焊条根焊技术

    Institute of Scientific and Technical Information of China (English)

    薛慧; 孔繁荣

    2015-01-01

    目前我国大直径长输管道大部分采用X80管线钢, X80钢根焊道的焊接常采用管道全位置自动焊、 STT和RMD半自动焊、钨极氩弧焊以及焊条电弧焊等工艺。管道全位置自动焊设备昂贵、适应性差。 STT和RMD半自动焊焊接时灵活性较差,必须严格防风措施。钨极氩弧焊的抗风能力差且焊接效率太低。低氢焊条电弧焊虽操作难度大且焊接效率不高,但灵活性强、焊接接头力学性能好且设备简单,适应于返修、连头和不良地段的焊接。详细介绍了X80管线钢低氢焊条根焊焊道的焊前准备、焊接操作技术及焊接工艺参数。%At present, X80 pipeline steel mostly was used in large diameter long-distance pipeline in China. In X80 steel root welding, it usually adopts all position automatic welding, STT and RMD semi-automatic welding, tungsten argon arc welding, shielded metal arc welding, etc. The equipment of pipeline all position automatic welding is expensive, poor adaptability;windproof measures must be strictly controlled in STT and RMD semi-automatic welding;The poor ability to resist the wind for tungsten argon arc welding and its welding efficiency is too low. Although high operation difficulty and low welding efficiency for low hydrogen electrode arc welding, but it is with good flexibility and simple equipment, the mechanical properties of welded joint are good, suitable for welding repair, butt welding and welding in bad location. In this article, it detailedly introduced preparation before welding, welding technology and welding parameters for X80 pipeline steel low-hydrogen electrode root welding bead.

  9. Emergence of hydrogen bonds from molecular dynamics simulation of substituted N-phenylthiourea-catechol oxidase complex.

    Science.gov (United States)

    Park, Kyung-Lae

    2017-01-01

    A series of N-phenylthiourea derivatives was built starting from the X-ray structure in the molecular mechanics framework and the interaction profile in the complex with the catechol oxidase was traced using molecular dynamics simulation. The results showed that the geometry and interactions between ligand and receptor were highly related to the position of the substituted side chains of phenyl moiety. At the end of molecular dynamics run, a concentrated multicenter hydrogen bond was created between the substituted ligand and receptor. The conformation of the ligand itself were also restricted in the receptor pocket. Furthermore, the simulation time of 50 ns were found to be long enough to explore the relevant conformational space and the stationary behavior of the molecular dynamic could be observed.

  10. Low-temperature metallic liquid hydrogen: an ab-initio path-integral molecular dynamics perspective

    Science.gov (United States)

    Chen, Ji; Li, Xin-Zheng; Zhang, Qianfan; Probert, Matthew; Pickard, Chris; Needs, Richard; Michaelides, Angelos; Wang, Enge

    2013-03-01

    Experiments and computer simulations have shown that the melting temperature of solid hydrogen drops with pressure above about 65 GPa, suggesting that a low temperature liquid state might exist. It has also been suggested that this liquid state might be non-molecular and metallic, although evidence for such behaviour is lacking. Using a combination of ab initio path-integral molecular dynamics and the two-phase methods, we have simulated the melting of solid hydrogen under finite temperatures. We found an atomic solid phase from 500 to 800 GPa which melts at < 200 K. Beyond this and up to pressures of 1,200 GPa a metallic atomic liquid is stable at temperatures as low as 50 K. The quantum motion of the protons is critical to the low melting temperature in this system as ab initio simulations with classical nuclei lead to a considerably higher melting temperature of ~300 K across the entire pressure range considered.

  11. Effects of dimethyl sulfoxide on the hydrogen bonding structure and dynamics of aqueous N-methylacetamide solution

    Indian Academy of Sciences (India)

    APRAMITA CHAND; SNEHASIS CHOWDHURI

    2016-06-01

    Effects of dimethyl-sulfoxide (DMSO) on the hydrogen bonding structure and dynamics in aqueousN-methylacetamide (NMA) solution are investigated by classical molecular dynamics simulations. Themodifications of structure and interaction between water and NMA in presence of DMSO molecules are calculatedby various site-site radial distribution functions and average interaction energies between these speciesin the solution. It is observed that the aqueous peptide hydrogen bond interaction is relatively stronger withincreasing concentration of DMSO, whereas methyl-methyl interaction between NMA and DMSO decreasessignificantly. The DMSO molecule prefers to interact with amide-hydrogen of NMA even at lower DMSO concentration.The lifetimes and structural-relaxation times of NMA-water, water-water and DMSO-water hydrogenbonds are found to increase with increasing DMSO concentration in the solution. The slower translationaland rotational dynamics of NMA is observed in concentrated DMSO solution due to formation of strongerinter-species hydrogen bonds in the solution.

  12. A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

    Science.gov (United States)

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Alavi, Saman; Yasuoka, Kenji

    2015-05-21

    Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5(12)6(4) cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

  13. Investigating the quasiparticle dynamics operating in the electrodes of superconducting tunnel junctions using nanosecond phonon pulses

    CERN Document Server

    Steele, A

    2000-01-01

    this thesis data from phonon experiments are used to directly determine values for the parameters of an STJ such as the quasiparticle loss and tunnel rates in its electrodes. It is also shown how the input energy, in the form of phonons capable of breaking Cooper pairs, and the corresponding charge output from the device can be determined. These values are then compared with those obtained from x-ray absorption data. This thesis is concerned with the use of nanosecond phonon pulses to study quasiparticle behaviour in the electrodes of high-quality niobium superconducting tunnel junctions (STJs). This work is part of a collaboration with the Astrophysics Research and Development Division of the European Space Agency (ESA) at ESTEC. STJs are being widely investigated as photon detectors over a broad range of the electromagnetic spectrum. They potentially offer excellent energy resolution, time response and photon counting capabilities. The primary aim of this research was to use phonon pulses to investigate qua...

  14. Born-Oppenheimer Molecular Dynamics Study on Proton Dynamics of Strong Hydrogen Bonds in Aspirin Crystals, with Emphasis on Differences between Two Crystal Forms.

    Science.gov (United States)

    Brela, Mateusz Z; Wójcik, Marek J; Witek, Łukasz J; Boczar, Marek; Wrona, Ewa; Hashim, Rauzah; Ozaki, Yukihiro

    2016-04-28

    In this study, the proton dynamics of hydrogen bonds for two forms of crystalline aspirin was investigated by the Born-Oppenheimer molecular dynamics (BOMD) method. Analysis of the geometrical parameters of hydrogen bonds using BOMD reveals significant differences in hydrogen bonding between the two crystalline forms of aspirin, Form I and Form II. Analysis of the trajectory for Form I shows spontaneous proton transfer in cyclic dimers, which is absent in Form II. Quantization of the O-H stretching modes allows a detailed discussion on the strength of hydrogen-bonding interactions. The focal point of our study is examination of the hydrogen bond characteristics in the crystal structure and clarification of the influence of hydrogen bonding on the presence of the two crystalline forms of aspirin. In the BOMD method, thermal motions were taken into account. Solving the Schrödinger equation for the snapshots of 2D proton potentials, extracted from MD, gives the best agreement with IR spectra. The character of medium-strong hydrogen bonds in Form I of aspirin was compared with that of weaker hydrogen bonds in aspirin Form II. Two proton minima are present in the potential function for the hydrogen bonds in Form I. The band contours, calculated by using one- and two-dimensional O-H quantization, reflect the differences in the hydrogen bond strengths between the two crystalline forms of aspirin, as well as the strong hydrogen bonding in the cyclic dimers of Form I and the medium-strong hydrogen bonding in Form II.

  15. Developing an electrochemical sensor based on a carbon paste electrode modified with nano-composite of reduced graphene oxide and CuFe2O4 nanoparticles for determination of hydrogen peroxide.

    Science.gov (United States)

    Benvidi, Ali; Nafar, Mohammad Taghi; Jahanbani, Shahriar; Tezerjani, Marzieh Dehghan; Rezaeinasab, Masoud; Dalirnasab, Sudabeh

    2017-06-01

    In this paper, a highly sensitive voltammetric sensor based on a carbon paste electrode with CuFe2O4 nanoparticle (RGO/CuFe2O4/CPE) was designed for determination of hydrogen peroxide (H2O2). The electrocatalytic reduction of H2O2 was examined using various techniques such as cyclic voltammetry (CV), chronoamperometry, amperometry and differential pulse voltammetry (DPV). CuFe2O4 nanoparticles were synthesized by co-precipitation method and characterized with scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) techniques. Then, a high conductive platform based on a carbon paste electrode modified with RGO and CuFe2O4 nanoparticles was prepared as a suitable platform for determination of hydrogen peroxide. Under the optimum conditions (pH5), the modified electrode indicated a fast amperometric response of <2s, good linear range of 2 to 200μM, low detection limit of 0.52μM for determination of hydrogen peroxide. Also, the peak current of differential pulse voltammetry (DPV) of hydrogen peroxide is increased linearly with its concentration in the ranges of 2 to 10μM and 10 to 1000μM. The obtained detection limit for hydrogen peroxide was evaluated to be 0.064μM by DPV. The designed sensor was successfully applied for the assay of hydrogen peroxide in biological and pharmaceutical samples such as milk, green tea, and hair dye cream and mouthwash solution. Copyright © 2017. Published by Elsevier B.V.

  16. Dynamics of a Rydberg hydrogen atom near a metal surface in the electron-extraction scheme

    Energy Technology Data Exchange (ETDEWEB)

    Iñarrea, Manuel [Área de Física Aplicada, Universidad de La Rioja, Logroño (Spain); Lanchares, Víctor [Departamento de Matemáticas y Computación, Universidad de La Rioja, Logroño, La Rioja (Spain); Palacián, Jesús [Departamento de Ingeniería Matemática e Informática, Universidad Pública de Navarra, Pamplona (Spain); Pascual, Ana I. [Departamento de Matemáticas y Computación, Universidad de La Rioja, Logroño, La Rioja (Spain); Salas, J. Pablo, E-mail: josepablo.salas@unirioja.es [Área de Física Aplicada, Universidad de La Rioja, Logroño (Spain); Yanguas, Patricia [Departamento de Ingeniería Matemática e Informática, Universidad Pública de Navarra, Pamplona (Spain)

    2015-01-23

    We study the classical dynamics of a Rydberg hydrogen atom near a metal surface in the presence of a constant electric field in the electron-extraction situation [1], e.g., when the field attracts the electron to the vacuum. From a dynamical point of view, this field configuration provides a dynamics richer than in the usual ion-extraction scheme, because, depending on the values of field and the atom–surface distance, the atom can be ionized only towards the metal surface, only to the vacuum or to the both sides. The evolution of the phase space structure as a function of the atom–surface distance is explored in the bound regime of the atom. In the high energy regime, the ionization mechanism is also investigated. We find that the classical results of this work are in good agreement with the results obtained in the wave-packet propagation study carried out by So et al. [1]. - Highlights: • We study a classical hydrogen atom near a metal surface plus a electric field. • We explore the phase space structure as a function of the field strength. • We find most of the electronic orbits are oriented along the field direction. • We study the ionization of the atom for several atom–surface distances. • This classical study is in good agreement with the quantum results.

  17. Hydrogen Bonding and Dielectric Spectra of Ethylene Glycol–Water Mixtures from Molecular Dynamics Simulations

    Science.gov (United States)

    2016-01-01

    Mixtures of ethylene glycol with water are a prominent example of media with variable viscosity. Classical molecular dynamics simulations at room temperature were performed for mixtures of ethylene glycol (EG) and water with EG mole fractions of xE = 0.0, 0.1, 0.2, 0.4, 0.6, 0.9, 1.0. The calculated dielectric loss spectra were in qualitative agreement with experiment. We found a slightly overestimated slowdown of the dynamics with increasing EG concentration compared to experimental data. Statistics of the hydrogen bond network and hydrogen bond lifetimes were derived from suitable time correlation functions and also show a slowdown in the dynamics with increasing xE. A similar picture is predicted for the time scales of EG conformer changes and for molecular reorientation. A slight blue shift was obtained for the power spectra of the molecular center of mass motion. The results were used to give a qualitative interpretation of the origin of three different relaxation times that appear in experimental complex dielectric spectra and of their change with xE. PMID:27649083

  18. Capsid structure and dynamics of a human rhinovirus probed by hydrogen exchange mass spectrometry.

    Science.gov (United States)

    Wang, Lintao; Smith, David L

    2005-06-01

    Viral capsids are dynamic protein assemblies surrounding viral genomes. Despite the high-resolution structures determined by X-ray crystallography and cryo-electron microscopy, their in-solution structure and dynamics can be probed by hydrogen exchange. We report here using hydrogen exchange combined with protein enzymatic fragmentation and mass spectrometry to determine the capsid structure and dynamics of a human rhinovirus, HRV14. Capsid proteins (VP1-4) were labeled with deuterium by incubating intact virus in D(2)O buffer at neutral pH. The labeled proteins were digested by immobilized pepsin to give peptides analyzed by capillary reverse-phase HPLC coupled with nano-electrospray mass spectrometry. Deuterium levels incorporated at amide linkages in peptic fragments were measured for different exchange times from 12 sec to 30 h to assess the amide hydrogen exchange rates along each of the four protein backbones. Exchange results generally agree with the crystal structure of VP1-4,with extended, flexible terminal and surface-loop regions in fast exchange and folded helical and sheet structures in slow exchange. In addition, three alpha-helices, one from each of VP1-3, exhibited very slow exchange, indicating high stability of the protomeric interface. The beta-strands at VP3 N terminus also had very slow exchange, suggesting stable pentamer contacts. It was noted, however, that the interface around the fivefold axis had fast and intermediate exchange, indicating relatively more flexibility. Even faster exchange rates were found in the N terminus of VP1 and most segments of VP4, suggesting high flexibilities, which may correspond to their potential roles in virus uncoating.

  19. Cathodic stripping voltammetric determination of As(III) with in situ plated bismuth-film electrode using the catalytic hydrogen wave.

    Science.gov (United States)

    Jiajie, Long; Nagaosa, Yukio

    2007-06-12

    A highly sensitive method has been developed for the determination of trace As(III) by a square wave cathodic stripping voltammetry employing in situ plated bismuth-film on edge-plane graphite substrate as working electrode. The presence of As(III) enhanced a cathodic peak corresponding to the catalytic hydrogen wave due to Se(IV) at about -1150 mV. Linear calibration curves for As(III) determination were obtained over the concentration ranges of 0.01-1.0 microg L(-1) and 1.0-12.0 microg L(-1) at deposition times of 30 s and 10 s, respectively. The detection limit (3sigma) was estimated to be as low as 0.7 ng L(-1) As(III) at 30 s deposition time. The optimum experimental parameters and probable interference from foreign ions and organic compounds were investigated. This proposed method could be applied to analyses of certified reference material, synthetic and natural water samples.

  20. Interference Dynamics of Hydrogen Atoms in High-Frequency Dichromatic Laser Fields

    Science.gov (United States)

    Cheng, Tai-Wang; Li, Xiao-Feng; Fu, Pan-Ming; Chen, Shi-Gang

    2002-08-01

    We investigate the ionization and high-order harmonic generation of a hydrogen atom in high-frequency (several atomic units) super strong (up to several tens of atomic units) dichromatic laser fields. An effective iterative method in the framework of high-frequency Floquet theory is used in the calculations. We have considered two kinds of dichromatic laser field, i.e. 1ω-2ω and 1ω-3ω. We find that, in both the cases, the ionization and high-order harmonic generation show evident dependence on the relative phase and strength of the additional harmonic field. The dynamical origin of these interference effects is also discussed.

  1. Interference Dynamics of Hydrogen Atoms in High-Frequency Dichromatic Laser Fields

    Institute of Scientific and Technical Information of China (English)

    程太旺; 李晓峰; 傅盘铭; 陈式刚

    2002-01-01

    We investigate the ionization and high-order harmonic generation of a hydrogen atom in high-frequency (several atomic units) super strong (up to several tens of atomic units) dichromatic laser fields. An effective iterative method in the framework of high-frequency Floquet theory is used in the calculations. We have considered two kinds of dichromatic laser field, i.e. 1ω - 2ω and lω - 3ω. We find that, in both the cases, the ionization and high-order harmonic generation show evident dependence on the relative phase and strength of the additional harmonic field. The dynamical origin of these interference effects is also discussed.

  2. Path Integral Molecular Dynamics for Hydrogen with Orbital-Free Density Functional Theory

    Science.gov (United States)

    Runge, Keith; Karasiev, Valentin; Deymier, Pierre

    2014-03-01

    The computational bottleneck for performing path-integral molecular dynamics (PIMD) for nuclei on a first principles electronic potential energy surface has been the speed with which forces from the electrons can be generated. Recent advances in orbital-free density functional theory (OF-DFT) not only allow for faster generation of first principles forces but also include the effects of temperature on the electron density. We will present results of calculations on hydrogen in warm dense matter conditions where the protons are described by PIMD and the electrons by OF-DFT. Work supported by U.S. Dept. of Energy, grant DE-SC0002139.

  3. The READY program: Building a global potential energy surface and reactive dynamic simulations for the hydrogen combustion.

    Science.gov (United States)

    Mogo, César; Brandão, João

    2014-06-30

    READY (REActive DYnamics) is a program for studying reactive dynamic systems using a global potential energy surface (PES) built from previously existing PESs corresponding to each of the most important elementary reactions present in the system. We present an application to the combustion dynamics of a mixture of hydrogen and oxygen using accurate PESs for all the systems involving up to four oxygen and hydrogen atoms. Results at the temperature of 4000 K and pressure of 2 atm are presented and compared with model based on rate constants. Drawbacks and advantages of this approach are discussed and future directions of research are pointed out.

  4. From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia

    CERN Document Server

    Boese, A D; Martin, J M L; Marx, D; Chandra, Amalendu; Martin, Jan M.L.; Marx, Dominik

    2003-01-01

    The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liq...

  5. Ab initio path-integral molecular dynamics and the quantum nature of hydrogen bonds

    Science.gov (United States)

    Yexin, Feng; Ji, Chen; Xin-Zheng, Li; Enge, Wang

    2016-01-01

    The hydrogen bond (HB) is an important type of intermolecular interaction, which is generally weak, ubiquitous, and essential to life on earth. The small mass of hydrogen means that many properties of HBs are quantum mechanical in nature. In recent years, because of the development of computer simulation methods and computational power, the influence of nuclear quantum effects (NQEs) on the structural and energetic properties of some hydrogen bonded systems has been intensively studied. Here, we present a review of these studies by focussing on the explanation of the principles underlying the simulation methods, i.e., the ab initio path-integral molecular dynamics. Its extension in combination with the thermodynamic integration method for the calculation of free energies will also be introduced. We use two examples to show how this influence of NQEs in realistic systems is simulated in practice. Project supported by the National Natural Science Foundation of China (Grant Nos. 11275008, 91021007, and 10974012) and the China Postdoctoral Science Foundation (Grant No. 2014M550005).

  6. Discrete kink dynamics in hydrogen-bonded chains: the one-component model.

    Science.gov (United States)

    Karpan, V M; Zolotaryuk, Y; Christiansen, P L; Zolotaryuk, A V

    2002-12-01

    We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on-site potential plays the role of the proton potential in the hydrogen bond. The system supports a rich variety of stationary kink solutions with different symmetry properties. We study the stability and bifurcation structure of all these stationary kink states. An exactly solvable model with a piecewise "parabola-constant" approximation of the double-Morse potential is suggested and studied analytically. The dependence of the Peierls-Nabarro potential on the system parameters is studied. Discrete traveling-wave solutions of a narrow permanent profile are shown to exist, depending on the anharmonicity of the Morse potential and the cooperativity of the hydrogen bond (the coupling constant of the interaction between nearest-neighbor protons).

  7. The Electrochemical Performance of Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 Nanocrystalline Hydrogen Storage Alloy as Metal Hydride Electrode

    Institute of Scientific and Technical Information of China (English)

    方守狮; 熊义辉; 等

    2002-01-01

    Ml0.7Mm0.3Ni3.7Co0.7Mn0.4Al0.2 nanocrystalline hydrogen storage materials are prepared by melt-spinning(MS).X-ray diffraction is used for the measurement of the nanocrystalline size.Compared to the electrode of polycrystalline alloys,the property of activation MH9metal hydride)electrode of the alloys with nanometer scale became worse and the inital discharge capacity decreased.It may be ascribed to the decrease of the total amount of rare earth metals and the increase of oxygen on the surface from the analysis of components of the alloys.After heat-treatment,the electrochemical performance of MH electrode of as-spun alloys could be improved,which could be attributed to the alleviation of the lattice strain.

  8. Novel solid oxide cells with SrCo0.8Fe0.1Ga0.1O3-δ oxygen electrode for flexible power generation and hydrogen production

    Science.gov (United States)

    Meng, Xiuxia; Shen, Yichi; Xie, Menghan; Yin, Yimei; Yang, Naitao; Ma, Zi-Feng; Diniz da Costa, João C.; Liu, Shaomin

    2016-02-01

    This work investigates the performance of solid oxide cells as fuel cells (SOFCs) for power production and also as electrolysis cells (SOECs) for hydrogen production. In order to deliver this dual mode flexible operation system, a novel perovskite oxide based on Ga3+ doped SrCo0.8Fe0.1Ga0.1O3-δ (SCFG) is synthesized via a sol-gel method. Its performance for oxygen electrode catalyst was then evaluated. Single solid oxide cell in the configuration of Ni-YSZ|YSZ|GDC|SCFG is assembled and tested in SOFC or SOEC modes from 550 to 850 °C with hydrogen as the fuel or as the product, respectively. GDC is used to avoid the reaction between the electrolyte YSZ and the cobalt-based electrode. Under SOFC mode, a maximum power density of 1044 mW cm-2 is obtained at 750 °C. Further, the cell delivers a stable power output of 650 mW cm-2 up to 125 h at 0.7 V. In the electrolysis mode, when the applied voltage is controlled at 2 V, the electrolysis current density reaches 3.33 A cm-2 at 850 °C with the hydrogen production rate up to 22.9 mL min-1 cm-2 (STP). These results reveal that SCFG is a very promising oxygen electrode material for application in both SOFC and SOEC.

  9. Molecular dynamics simulation of hydrogen dissolution and diffusion in a tungsten grain boundary

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yi; Shu, Xiaolin; Liu, Yi-Nan; Lu, Guang-Hong, E-mail: lgh@buaa.edu.cn

    2014-12-15

    We employ a classic molecular dynamics method to investigate the dissolution and diffusion properties of hydrogen (H) in a Σ5(3 1 0) tilt grain boundary (GB). A maximum binding energy of 2.5 eV and a diffusion barrier of 1.65 eV indicate that GB plays an important role in H trapping. Dynamic simulations with temperature ranging from 600 K to 1200 K verify the diffusion and the aggregation of H in the GB are closely associated with the temperature. Pair radius distribution function analysis suggests a high local GB concentration of H such as 30% at 900 K can lead to a disordered GB structure.

  10. A molecular dynamics simulation of hydrogen atoms collisions on an H-preadsorbed silica surface

    Science.gov (United States)

    Rutigliano, M.; Gamallo, P.; Sayós, R.; Orlandini, S.; Cacciatore, M.

    2014-08-01

    The interaction of hydrogen atoms and molecules with a silica surface is relevant for many research and technological areas. Here, the dynamics of hydrogen atoms colliding with an H-preadsorbed β-cristobalite (0 0 1) surface has been studied using a semiclassical collisional method in conjunction with a recently developed analytical potential energy surface based on density functional theory (DFT) calculations. The atomic recombination probability via an Eley-Rideal (E-R) mechanism, as well as the probabilities for other competitive surface processes, have been determined in a broad range of collision energies (0.04-3.0 eV) for off-normal (θv = 45°) and normal (θv = 0°) incidence and for two different surface temperatures (TS = 300 and 1000 K). H2,gas molecules form in roto-vibrational excited levels while the energy transferred to the solid surface is below 10% for all simulated conditions. Finally, the global atomic recombination coefficient (γE-R) and vibrational state resolved recombination coefficients (γ(v)) were calculated and compared with the available experimental values. The calculated collisional data are of interest in chemical kinetics studies and fluid dynamics simulations of silica surface processes in H-based low-temperature, low-pressure plasmas.

  11. The dynamical properties of Rydberg hydrogen atom near a metal surface

    Institute of Scientific and Technical Information of China (English)

    GE Meihua; ZHANG Yanhui; WANG Dehua; DU Mengli; LIN Shenglu

    2005-01-01

    The dynamical properties of Rydberg hydrogen atom near a metal surface are presented by using the methods of phase space analysis and closed orbit theory. Transforming the coordinates of the Hamiltonian, we find that the phase space of the system is divided into vibrational and rotational region. Both the Poincaré surface of section and the closed orbit theory verify the same conclusion clearly. In this paper we choose the atomic principal quantum number as n = 20. The dynamical character of the exited hydrogen atom depends sensitively on the atom-surface distance d. When d is sufficiently large, the atom-surface potential can be expressed by the traditional van der Waals force and the system is integrable. When d becomes smaller, there exists a critical value dc. For d > dc, the system is near-integrable and the motion is regular. While chaotic motion appears for d < dc, and the system tends to be non-integrable. The trajectories become unstable and the electron might be captured onto the metal surface.

  12. The influence of inclusions and hydrogen on the microstructure and dynamic strength of materials

    Science.gov (United States)

    Silverstein, R.; Glam, B.; Eliezer, D.; Moreno, D.; Eliezer, S.

    2017-01-01

    In this research we investigate different metallurgical effects, such as: inclusions and hydrogen (H) on the dynamic strength of different metals. We also investigate the deformation mechanism evolved from inclusions by metallurgical analysis. The dynamic loading was produced by accelerating Al or steel impactors in a gas gun into different targets (uniaxial plate impact experiments) at a velocity range of 330 to 430 m/s. After impact, the hydrogen-lean duplex stainless steel (H-LDS) system represents the same failure mechanism as in the lower strain rates; increasing strength and decreasing ductility. The Al-Ta and Al-B systems indicate different failure mechanisms compared with the ultra-pure (UP) Al. In addition, the failure mechanism was different when the Ta amount in the Al matrix was higher. Our results show that small amount of inclusions have the same effect on the Al matrix. However, differences can be seen when Ta amount is higher, as opposed to previously published work in the literature.

  13. Dynamics of supercritical methanol of varying density from first principles simulations: hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation.

    Science.gov (United States)

    Yadav, Vivek Kumar; Chandra, Amalendu

    2013-06-14

    A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects

  14. Temperature effects on the capacitance of an imidazolium-based ionic liquid on a graphite electrode: a molecular dynamics simulation.

    Science.gov (United States)

    Liu, Xiaohong; Han, Yining; Yan, Tianying

    2014-08-25

    Temperature-dependent electric double layer (EDL) and differential capacitance-potential (C(d)-U) curves of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)/PF6(-)) were studied on a graphite electrode by molecular dynamics simulations. It was found that all C(d)-U curves were asymmetric camel-shaped with higher C(d) at negative polarization, attributed to the specific adsorption of BMIM(+). In addition, the maxima of Cd at the negative polarization decrease monotonically with temperature due to the thicker EDL, whereas at the positive polarization they gradually increase from 450 to 550 K and decrease at 600 K. Such temperature effects at positive polarization may be understood in terms of the competition between two aspects: the weakening specific adsorption of BMIM(+) allows more effective screening to the positive charge and overall increasing EDL thickness. Although the former dominates from 450 to 550 K, the latter becomes dominant at 600 K.

  15. Dynamic electrochemical impedance spectroscopy of Pt/C-based membrane-electrode assemblies subjected to cycling protocols

    Science.gov (United States)

    Darab, Mahdi; Dahlstrøm, Per Kristian; Thomassen, Magnus Skinlo; Seland, Frode; Sunde, Svein

    2013-11-01

    A PEM fuel cell membrane-electrode assembly (MEA) was characterized by dynamic electrochemical impedance spectroscopy (dEIS) before and after cycling in a single cell configuration. The cell was subjected to 100 cycles between 0.6 V and 1.5 V vs. RHE in N2/5% H2 and 80 °C and 100% RH. Initially, the impedance-plane plots contained first- and fourth-quadrant behavior, which is resulting from a reaction mechanism at the cathode involving adsorbed intermediates. After the cycling, the impedance spectra changed to display first-quadrant behavior only. This is suggested to be due to particle growth and possibly the formation of edges between agglomerated particles. The results show that dEIS is a sensitive technique to detect even very moderate changes in electrocatalyst structure.

  16. Photo-excited hot carrier dynamics in hydrogenated amorphous silicon imaged by 4D electron microscopy

    Science.gov (United States)

    Liao, Bolin; Najafi, Ebrahim; Li, Heng; Minnich, Austin J.; Zewail, Ahmed H.

    2017-09-01

    Charge carrier dynamics in amorphous semiconductors has been a topic of intense research that has been propelled by modern applications in thin-film solar cells, transistors and optical sensors. Charge transport in these materials differs fundamentally from that in crystalline semiconductors owing to the lack of long-range order and high defect density. Despite the existence of well-established experimental techniques such as photoconductivity time-of-flight and ultrafast optical measurements, many aspects of the dynamics of photo-excited charge carriers in amorphous semiconductors remain poorly understood. Here, we demonstrate direct imaging of carrier dynamics in space and time after photo-excitation in hydrogenated amorphous silicon (a-Si:H) by scanning ultrafast electron microscopy (SUEM). We observe an unexpected regime of fast diffusion immediately after photoexcitation, together with spontaneous electron-hole separation and charge trapping induced by the atomic disorder. Our findings demonstrate the rich dynamics of hot carrier transport in amorphous semiconductors that can be revealed by direct imaging based on SUEM.

  17. Dynamics of electrochemical flows 2 Electrochemical flows-through porous electrode

    CERN Document Server

    Xu, Chengjun

    2013-01-01

    The electrolyte (comprising of solute ions and solvents) flow-through the porous media is frequently encountered in nature or in many engineering applications, such as the electrochemical systems, manufacturing of composites, geothermal engineering, soil pollution. In this study, we provide a new general theory for the electrochemical flows-through porous media. We use static method and set up two representative elementary volumes (REVs). One is the macroscopic REV of the mixture of the porous media and the electrolyte, while the other is the microscopic REV in the electrolyte fluid. The establishment of two REVs enables us to investigate the details of transports of mass, heat, electric flied, or momentum in the process of the electrochemical flows-through porous electrode. In this work, the macroscopic governing equations are derived from the conservation laws in the macroscopic REV to describe the electrochemical flows-through porous media. At first, we define the porosity by the volume and surface and div...

  18. Study of the stability of electrode metal melting and transfer in the process of consumable electrode welding powered by supplies with differing dynamic characteristics

    Science.gov (United States)

    Saraev, Y. N.; Chinakhov, D. A.; Il'yashchenko, D. P.; Kiselev, A. S.; Gardiner, A. S.; Raev, I. V.

    2016-11-01

    In the paper we present the results of the study of the power supply characteristics effect upon the stability of electrode metal melting and transfer into the weld pool in the process of consumable electrode welding. It was shown that application of inverter type welding power supplies of the new generation results in changing the characteristics of the heat and mass transfer which has a decisive impact upon the heat content of the weld pool, reduction of residual stresses in the heat-affected zone (HAZ). The authors also substantiate the tendency to the reduction of the structural constituents in the area of the permanent joint.

  19. Dynamics of Fluctuations, Flows and Global Stability Under Electrode Biasing in a Linear Plasma Device

    Science.gov (United States)

    Desjardins, Tiffany

    2015-11-01

    Various bias electrodes have been inserted into the Helicon-Cathode (HelCat) device at the University of New Mexico, in order to affect intrinsic drift-wave turbulence and flows. The goal of the experiments was to suppress and effect the intrinsic turbulence and with detailed measurements, understand the changes that occur during biasing. The drift-mode in HelCat varies from coherent at low magnetic field (1kG). The first electrode consists of 6 concentric rings set in a ceramic substrate; these rings act as a boundary condition, sitting at the end of the plasma column 2-m away from the source. A negative bias has been found to have no effect on the fluctuations, but a positive bias (Vr>5Te) is required in order to suppress the drift-mode. Two molybdenum grids can also be inserted into the plasma and sit close to the source. Floating or grounding a grid results in suppressing the drift-mode of the system. A negative bias (>-5Te) is found to return the drift-mode, and it is possible to drive a once coherent mode into a broad-band turbulent one. From a bias voltage of -5Tenew mode, which is identified as a parallel-driven Kelvin-Helmholtz mode. At high positive bias, Vg>10Te, a new large-scale global mode is excited. This mode exhibits fluctuations in the ion saturation current, as well as in the potential, with a magnitude >50%. This mode has been identified as the potential relaxation instability (PRI). In order to better understand the modes and changes observed in the plasma, a linear stability code, LSS, was employed. As well, a 1D3V-PIC code utilizing Braginskii's equations was also utilized to understand the high-bias instability.

  20. APPLICATION OF FLOW-THROUGH THREE-DIMENSIONAL ELECTRODES FOR REGENERATION OF PLATING IRON ELECTROLYTES: 1. MATHEMATICAL MODEL

    Directory of Open Access Journals (Sweden)

    Alexandr Kоshev

    2014-12-01

    Full Text Available The mathematical model of electrochemical processes distribution within the three-dimensional flow-through electrode for the system Fe(III/Fe(II/Fe is described in this paper, considering also the electrochemical reactions of hydrogen and molecular oxygen reduction. Possible dynamic changes in the parameters of electrode, electrolyte and the process are taken into account in the mathematical model, such as electro-conductivity of electrode material, electrolyte flow rate, material porosity and specific electrode surface, concentrations of electro-active substances and other characteristics within the local volume of electrode. Electrode and process characteristics are treated as time and coordinate functions within the electrode volume. The results of calculations and experimental studies of iron electro-reduction are given, the analysis of the numerical modeling is provided.

  1. Preparation of dendritic bismuth film electrodes and their application for detection of trace Pb (II) and Cd (II)

    Institute of Scientific and Technical Information of China (English)

    Huizhu Zhou; Huanhuan Hou; Lei Dai; Yuehua Li; Jing Zhu; Ling Wang

    2016-01-01

    In this paper, dendritic Bi film electrodes with porous structure had successfully been prepared on glassy carbon electrode using a constant current electrolysis method based on hydrogen bubble dynamic templates. The elec-trode prepared using a large applied current density showed an increased internal electroactive area and a signif-icantly improved electrochemical performance. The analytical utility of the prepared dendritic Bi film electrodes for the determination of Pb (II) and Cd (II) in the range of 5–50μg·L−1 were presented in combination with square wave stripping voltammetry in model solution. Compared with non-porous Bi film electrode, the dendrit-ic Bi film electrode exhibited higher sensitivity and lower detection limit. The prepared Bi film electrode with dendritic structure was also successfully applied to real water sample analysis.

  2. The quantum nature of the hydrogen bond: insight from path-integral molecular dynamics

    Science.gov (United States)

    Walker, Brent; Li, Xin-Zheng; Michaelides, Angelos

    2011-03-01

    Hydrogen (H) bonds are weak, generally intermolecular bonds, that hold together much of soft matter, the condensed phases of water, network liquids, and many ferroelectric crystals. The small mass of H means H-bonds are inherently quantum mechanical; effects such as zero point motion and tunneling should be considered, although often are not. In particular, a consistent picture of quantum nuclear effects on the strength of H-bonds and consequently the structure of H-bonded systems is still absent. Here, we report ab initio path-integral molecular dynamics studies on the quantum nature of the H-bond. Systematic examination of a range of H-bonded systems shows that quantum nuclei weaken weak H-bonds but strengthen relatively strong ones. This correlation arises from a competition between anharmonic intermolecular bond bending and intramolecular bond stretching. A simple rule of thumb enables predictions to be made for H-bonded bonded materials in general with merely classical knowledge (e.g. H-bond strength or H-bond length). Our work rationalizes the contrasting influence of quantum nuclear dynamics on a wide variety of materials, including liquid water and HF, and highlights the need for flexible molecules in force-field based studies of quantum nuclear dynamics.

  3. Transport properties of liquid para-hydrogen: The path integral centroid molecular dynamics approach

    Science.gov (United States)

    Yonetani, Yoshiteru; Kinugawa, Kenichi

    2003-11-01

    Several fundamental transport properties of a quantum liquid para-hydrogen (p-H2) at 17 K have been numerically evaluated by means of the quantum dynamics simulation called the path integral centroid molecular dynamics (CMD). For comparison, classical molecular dynamics (MD) simulations have also been performed under the same condition. In accordance with the previous path integral simulations, the calculated static properties of the liquid agree well with the experimental results. For the diffusion coefficient, thermal conductivity, and shear viscosity, the CMD predicts the values closer to the experimental ones though the classical MD results are far from the reality. The agreement of the CMD result with the experimental one is especially good for the shear viscosity with the difference less than 5%. The calculated diffusion coefficient and the thermal conductivity agree with the experimental values at least in the same order. We predict that the ratio of bulk viscosity to shear viscosity for liquid p-H2 is much larger than classical van der Waals simple liquids such as rare gas liquids.

  4. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation.

    Science.gov (United States)

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-28

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm(-1)); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  5. Proton dynamics in the hydrogen bonds of 4-amino-3,5-dihalogenobenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Asaji, Tetsuo, E-mail: asaji@chs.nihon-u.ac.jp [Department of Chemistry, College of Humanities and Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo 156-8550 (Japan); Ueda, Kouhei; Oguni, Masaharu [Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551 (Japan)

    2015-08-18

    Highlights: • 4-Amino-3,5-dichlorobenzoic acid has a symmetric dimer structure. • The compound undergoes a phase transition at 138 K. • The symmetry breaking of the dimer was revealed by {sup 35}Cl NQR. • The proton dynamics was analyzed by coherent and incoherent tunneling models. - Abstract: On the polycrystalline sample of 4-amino-3,5-dihalogenobenzoic acid, 4-NH{sub 2}-3,5-X{sub 2}C{sub 6}H{sub 2}COOH, which has a symmetric dimer structure in the crystal, the proton tunneling in the hydrogen bonds has been investigated by NQR and NMR spin–lattice relaxation times T{sub 1} measurements. Two {sup 35}Cl NQR lines of the X = Cl derivative show the existence of two crystallographically inequivalent chlorine atoms in the high-temperature phase, in consistency with the reported crystal structure. Below 138 K, each splits into a doublet indicating the symmetry breaking of the benzoic acid dimer. The proton dynamics was analyzed by a coherent and incoherent tunneling models, for the high- and low-temperature phases, respectively. The temperature dependence of the correlation time of proton translation was estimated. As for the X = I derivative, the proton dynamics was discussed similarly by {sup 1}H NMR T{sub 1} data by assuming occurrence of a phase transition at low-temperature.

  6. Dynamic modeling efforts for system interface studies for nuclear hydrogen production.

    Energy Technology Data Exchange (ETDEWEB)

    Vilim, R. B.; Nuclear Engineering Division

    2007-08-15

    System interface studies require not only identifying economically optimal equipment configurations, which involves studying mainly full power steady-state operation, but also assessing the operability of a design during load change and startup and assessing safety-related behavior during upset conditions. This latter task is performed with a dynamic simulation code. This report reviews the requirements of such a code. It considers the types of transients that will need to be simulated, the phenomena that will be present, the models best suited for representing the phenomena, and the type of numerical solution scheme for solving the models to obtain the dynamic response of the combined nuclear-hydrogen plant. Useful insight into plant transient behavior prior to running a dynamics code is obtained by some simple methods that take into account component time constants and energy capacitances. Methods for determining reactor stability, plant startup time, and temperature response during load change, and tripping of the reactor are described. Some preliminary results are presented.

  7. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation

    Science.gov (United States)

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-01

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm-1); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  8. Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

    Science.gov (United States)

    Park, Sunghak; Chang, Woo Je; Lee, Chan Woo; Park, Sangbaek; Ahn, Hyo-Yong; Nam, Ki Tae

    2017-01-01

    The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3-) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I- and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

  9. Materials for hydrogen storage: structure and dynamics of borane ammonia complex.

    Science.gov (United States)

    Parvanov, Vencislav M; Schenter, Gregory K; Hess, Nancy J; Daemen, Luke L; Hartl, Monika; Stowe, Ashley C; Camaioni, Donald M; Autrey, Tom

    2008-09-07

    The activation energies for rotations in low-temperature orthorhombic ammonia borane were analyzed and characterized in terms of electronic structure theory. The perdeuterated (11)B-enriched ammonia borane, (11)BD(3)ND(3), sample was synthesized, and the structure was refined from neutron powder diffraction data at 175 K. This temperature has been chosen as median of the range of previously reported nuclear magnetic resonance spectroscopy measurements of these rotations. A representative molecular cluster model was assembled from the refined geometry, and the activation energies were calculated and characterized by analysis of the environmental factors that control the rotational dynamics. The barrier for independent NH(3) rotation, E(a) = 12.7 kJ mol(-1), largely depends on the molecular conformational torsion in the solid-state geometry. The barrier for independent BH(3) rotation, E(a) = 38.3 kJ mol(-1), results from the summation of the effect of molecular torsion and large repulsive intermolecular hydrogen-hydrogen interactions. However, a barrier of E(a) = 31.1 kJ mol(-1) was calculated for internally correlated rotation with preserved molecular conformation. Analysis of the barrier heights and the corresponding rotational pathways shows that rotation of the BH(3) group involves strongly correlated rotation of the NH(3) end of the molecule. This observation suggests that the barrier from previously reported measurement of BH(3) rotation corresponds to H(3)B-NH(3) correlated rotation.

  10. Dynamic Modeling of Hydrogen Sulfide within Enclosed Environments in Biosolids Recovery Facilities.

    Science.gov (United States)

    Matos, Rita Ventura; Matias, Natércia; Ferreira, Filipa; Matos, José Saldanha

    2016-12-01

    Hydrogen sulfide emissions from wastewater affect human health and equipment durability, thus presenting a complex issue for utilities. Several VOC emission models have been used before to predict H2S in collection systems and water resources recovery operations, even if with restrictions. By contrast, fewer studies focus on biosolids emissions and modelling. This paper presents a dynamic modelling approach to predict H2S concentration in a tank headspace of a wastewater biosolids recovery facility. Data from one of the largest Portuguese water resources recovery facilities was collected under different facility operating modes. The developed model adequately predicted H2S concentration, with R2 values of 0.89 and 0.78, for different periods of the year, thus showing how modelling may reliably contribute to utility operation decisions.

  11. Hydrogen bonding-assisted interaction between amitriptyline hydrochloride and hemoglobin: spectroscopic and molecular dynamics studies.

    Science.gov (United States)

    Maurya, Neha; Maurya, Jitendra Kumar; Kumari, Meena; Khan, Abbul Bashar; Dohare, Ravins; Patel, Rajan

    2017-05-01

    Herein, we have explored the interaction between amitriptyline hydrochloride (AMT) and hemoglobin (Hb), using steady-state and time-resolved fluorescence spectroscopy, UV-visible spectroscopy, and circular dichroism spectroscopy, in combination with molecular docking and molecular dynamic (MD) simulation methods. The steady-state fluorescence reveals the static quenching mechanism in the interaction system, which was further confirmed by UV-visible and time-resolved fluorescence spectroscopy. The binding constant, number of binding sites, and thermodynamic parameters viz. ΔG, ΔH, ΔS are also considered; result confirms that the binding of the AMT with Hb is a spontaneous process, involving hydrogen bonding and van der Waals interactions with a single binding site, as also confirmed by molecular docking study. Synchronous fluorescence, CD data, and MD simulation results contribute toward understanding the effect of AMT on Hb to interpret the conformational change in Hb upon binding in aqueous solution.

  12. Hydrogen storage: Lattice dynamics of orthorhombic NaMgH{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Bouhadda, Youcef, E-mail: bouhadda@yahoo.co [Unite de Recherche Appliquee en Energies Renouvelables, BP 88 Ghardaia (Algeria); Fenineche, Noureddine [LERMPS, UTBM, Belfort (France); Boudouma, Youcef [Faculte de Physique, USTHB, Algiers (Algeria)

    2011-02-15

    In this work, we investigate the structural, dynamic and thermodynamic properties of NaMgH{sub 3}, devoted for hydrogen storage. Density functional theory using pseudopotential methods and generalized gradient approximation has been used. A good agreement between the calculated structural parameters and the experimental data was found. A linear-response approach for the density functional theory is used in order to derive the Born effective charge tensors, the dielectric permittivity tensors, the phonon frequencies at the center of the Brillouin zone, the phonon-dispersion curves and the corresponding density of states for NaMgH{sub 3} material. The obtained phonon frequencies at the zone center ({Gamma} point) for the Raman-active and infrared-active modes are analyzed. Thermodynamic functions using the phonon density of states are also calculated.

  13. Hydrogen-bond vibrational and energetic dynamical properties in sI and sII clathrate hydrates and in ice Ih: Molecular dynamics insights.

    Science.gov (United States)

    Chakraborty, Somendra Nath; English, Niall J

    2015-10-21

    Equilibrium molecular dynamics (MD) simulations have been performed on cubic (sI and sII) polymorphs of methane hydrate, and hexagonal ice (ice Ih), to study the dynamical properties of hydrogen-bond vibrations and hydrogen-bond self-energy. It was found that hydrogen-bond energies are greatest in magnitude in sI hydrates, followed by sII, and their energies are least in magnitude in ice Ih. This is consistent with recent MD-based findings on thermal conductivities for these various materials [N. J. English and J. S. Tse, Phys. Rev. Lett. 103, 015901 (2009)], in which the lower thermal conductivity of sI methane hydrate was rationalised in terms of more strained hydrogen-bond arrangements. Further, modes for vibration and energy-transfer via hydrogen bonds in sI hydrate were found to occur at higher frequencies vis-à-vis ice Ih and sII hydrate in both the water-librational and OH⋯H regions because of the more strained nature of hydrogen bonds therein.

  14. Ring opening reaction dynamics in the reaction of hydrogen atoms with ethylene oxide

    Science.gov (United States)

    Shin, S. K.; Jarek, R. L.; Böhmer, E.; Wittig, C.

    1994-10-01

    Ethylene oxide, C2H4O, is a three-membered ring with a single oxygen atom bridging the two carbons. Reactions of H and D atoms with ethylene oxide have been studied in the gas phase to provide insight into the dynamics of three-membered ring opening. H atoms were produced by photolyzing HI in the wavelength range 240-266 nm. The channel leading to OH+C2H4 was monitored via laser-induced fluorescence (LIF) of the OH A 2Σ←X 2Π system. The D atom reaction yields OD with no hydrogen scrambling. With an available energy of 23 000 cm-1, the average OH D rotational energy is ˜350 cm-1 for OH(v=0) and OD(v=0) and ˜250 cm-1 for OD(v=1). OH(v=1) was not observed, while the OD(v=1) population was about one-tenth that of OD(v=0). There was no apparent bias in populations between Λ doublets in each of the spin-orbit states for both OH and OD. Doppler broadening of OH(v=0) rotational lines was measured to evaluate the average center-of-mass (c.m.) translational energy, which was found to be ˜2300 cm-1. On average, the ring opening process deposits ˜10% of the available energy into c.m. translation, ˜2% into OH rotation, and ˜88% into ethylene internal energy. Comparison with CH2CH2OH unimolecular dissociation dynamics and theoretical transition state calculations leads to a likely mechanism in which hydrogen abstracts oxygen via sequential C-O bond fission without involving a long-lived CH2CH2OH intermediate.

  15. Nuclear quantum effect on hydrogen adsorption site of zeolite-templated carbon model using path integral molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Kimichi, E-mail: ki-suzuki@aist.go.jp [Research Institute for Nanosystem, National Institute of Advanced Industrial Science and Technology, Chuo-2, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8568 (Japan); Kayanuma, Megumi [Institut de Chimie, UMR 7177 CNRS/Universite de Strasbourg, 4 rue Blaise Pascal 67000, Strasbourg (France); Tachikawa, Masanori [Quantum Chemistry Division, Graduate School of Science, Yokohama-city University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027 (Japan); Ogawa, Hiroshi [Research Institute for Nanosystem, National Institute of Advanced Industrial Science and Technology, Chuo-2, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8568 (Japan); Nishihara, Hirotomo; Kyotani, Takashi [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Nagashima, Umpei [Research Institute for Nanosystem, National Institute of Advanced Industrial Science and Technology, Chuo-2, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8568 (Japan)

    2011-09-15

    Research highlights: > The stable hydrogen adsorption sites on C{sub 36}H{sub 12} were evaluated at 300 K using path integral molecular dynamics. > In the static MO calculation and conventional MD simulation, five stable adsorption sites of hydrogen atom were found. > In path integral simulation, only four stable adsorption sites were obtained. > The thermal and nuclear quantum effects are key role to settle the hydrogen adsorption sites on carbon materials. - Abstract: To settle the hydrogen adsorption sites on buckybowl C{sub 36}H{sub 12}, which is picked up from zeolite-templated carbon (ZTC), we have performed path integral molecular dynamics (PIMD) simulation including thermal and nuclear quantum fluctuations under semi-empirical PM3 method. In the static PM3 calculation and classical simulation the five stable adsorption sites of hydrogen atom are optimized inside a buckybowl C{sub 36}H{sub 12}, which are labeled as {alpha}-, {beta}{sub 1}-, {beta}{sub 2}-, {gamma}-, and {delta}-carbons from edge to innermost carbon. In PIMD simulation, meanwhile, stable adsorption site is not appeared on {delta}-carbon, but on only {alpha}-, {beta}{sub 1}-, {beta}{sub 2}-, and {gamma}-carbons. This result is due to the fact that the adsorbed hydrogen atom can easily go over the barrier for hydrogen transferring from {delta}- to {beta}{sub 1}-carbons by thermal and nuclear quantum fluctuations. The thermal and nuclear quantum effects are key role to settle the hydrogen adsorption sites on carbon materials.

  16. Hydrogen-bonding structure and dynamics of aqueous carbonate species from car-parrinello molecular dynamics simulations.

    Science.gov (United States)

    Kumar, P Padma; Kalinichev, Andrey G; Kirkpatrick, R James

    2009-01-22

    A comprehensive Car-Parrinello molecular dynamics (CP-MD) study of aqueous solutions of carbonic acid (H(2)CO(3)), bicarbonate (HCO(3)(-)), carbonate (CO(3)(2-)), and carbon dioxide (CO(2)) provides new quantitative insight into the structural and dynamic aspects of the hydrogen-bonding environments for these important aqueous species and their effects on the structure, H-bonding, and dynamical behavior of the surrounding water molecules. The hydration structures of the different carbonate species depend on their ability to accept and donate H-bonds with H(2)O. The H-bonds donated by the C-O-H sites of the carbonate species to water molecules are generally stronger and longer-lived than those accepted by these sites from water molecules. The structural relaxation among the water molecules is dominated by diffusional (translational) motion of H(2)O, whereas the H-bond reorganization is dominated by the librational motion of the water molecules and the carbonate species. The rates of structural relaxation of the H(2)O molecules and the rates of H-bond reorganization among them are slower in systems containing carbonate species, consistent with previous studies of simple salt solutions. The strengths and lifetimes of H-bonds involving the carbonate species positively correlate with the total negative charge on the species. H-bond donation from H(2)O to CO(2) is weak, but the presence of CO(2) noticeably affects the structure and structural relaxation of the surrounding H-bonding network leading to generally stronger H-bonds and slower relaxation rates, the behavior typical of a hydrophobic solute.

  17. Interplay of community dynamics, temperature, and productivity on the hydrogen isotope signatures of lipid biomarkers

    Science.gov (United States)

    Nemiah Ladd, S.; Dubois, Nathalie; Schubert, Carsten J.

    2017-09-01

    The hydrogen isotopic composition (δ2H) of lipid biomarkers has diverse applications in the fields of paleoclimatology, biogeochemistry, and microbial community dynamics. Large changes in hydrogen isotope fractionation have been observed among microbes with differing core metabolisms, while environmental factors including temperature and nutrient availability can affect isotope fractionation by photoautotrophs. Much effort has gone into studying these effects under laboratory conditions with single species cultures. Moving beyond controlled environments and quantifying the natural extent of these changes in freshwater lacustrine settings and identifying their causes is essential for robust application of δ2H values of common short-chain fatty acids as a proxy of net community metabolism and of phytoplankton-specific biomarkers as a paleohydrologic proxy. This work targets the effect of community dynamics, temperature, and productivity on 2H/1H fractionation in lipid biomarkers through a comparative time series in two central Swiss lakes: eutrophic Lake Greifen and oligotrophic Lake Lucerne. Particulate organic matter was collected from surface waters at six time points throughout the spring and summer of 2015, and δ2H values of short-chain fatty acids, as well as chlorophyll-derived phytol and the diatom biomarker brassicasterol, were measured. We paired these measurements with in situ incubations conducted with NaH13CO3, which were used to calculate the production rates of individual lipids in lake surface water. As algal productivity increased from April to June, net discrimination against 2H in Lake Greifen increased by as much as 148 ‰ for individual fatty acids. During the same time period in Lake Lucerne, net discrimination against 2H increased by as much as 58 ‰ for individual fatty acids. A large portion of this signal is likely due to a greater proportion of heterotrophically derived fatty acids in the winter and early spring, which are displaced by

  18. Br?nsted Acid Ionic Liquid Activated Electrodes Catalyze Water Electrolysis for Production of Hydrogen%BrÖnsted酸性离子液体活化电极催化制氢性能研究

    Institute of Scientific and Technical Information of China (English)

    陈佳志; 孟玲祎; 王雅静; 孟晋磊; 江峰; 楚哲; 刘洪涛

    2016-01-01

    分别采用玻碳( GC)、铂( Pt)和金( Au)电极研究了在BrÖnsted酸性离子液体[ HMIm] HSO4中电解水制氢的催化活性,活性大小为Pt > Au >> GC。水中离子液体的含量对析氢电流影响很大,当[ HMIm] HSO4含量为30%(V/V)时,Pt电极催化电解水产氢的阈值电位高达-0.3 V (Ag丝为准参比电极, Ag QRE),在-0.5 V (Ag QRE)处电流密度高达110.52 mA/cm2,为相同条件下Au电极的15倍,GC电极的650倍。计算结果表明,Pt电极在该电解液中的反应活化能为5.68 kJ/mol。电极的高催化活性与[ HMIm] HSO4电离产生的质子有关,使水以H3 O+的形式捕集电子,效率更高。%The water electrolysis for production of hydrogen in the Br?nsted acid ionic liquid [ HMIm] HSO4 aqueous solutions was investigated using glassy carbon ( GC ) , platinum ( Pt ) , and gold ( Au ) electrodes, respectively. It was found that the catalytic activity of the electrodes in the acid ionic liquid electrolytes ranked in sequence as Pt > Au >> GC. The optimal concentration of [ HMIm] HSO4 in aqueous solutions was 30%( V/V ) , and the catalytic current density on Pt electrode for hydrogen evolution reaction ( HER ) at-0. 5 V (Ag QRE) reached 110. 52 mA/cm2. This was 15 and 650-fold larger than the current on the Au and GC electrode, respectively. The Arrhenius activation energy of the Pt electrode in the electrolyte solution was 5. 68 kJ/mol. The high catalytic activity of the electrode was attributed to the [ HMIm] HSO4 that would release protons enabling H2 O molecules ionization, and facilitating the capture of electrons from the electrode.

  19. Neutron Crystallography, Molecular Dynamics, and Quantum Mechanics Studies of the Nature of Hydrogen Bonding in Cellulose I beta

    Science.gov (United States)

    In the crystal structure of cellulose Ibeta, disordered hydrogen (H) bonding can be represented by the average of two mutually exclusive H bonding schemes that have been designated A and B. An unanswered question is whether A and B interconvert dynamically, or whether they are static but present in ...

  20. ELECTROCHEMISTRY OF FUEL CELL ELECTRODES.

    Science.gov (United States)

    optimization of fuel cell electrodes. Hydrogen oxidation and reduction, the reduction of oxygen, and the oxidation of formic acid, a soluble organic...substance, were selected for these studiees because of their relevance to fuel cell systems and because of their relative simplicity. The electrodes

  1. Dynamical systems analysis of electrostatic and aerodynamic forced vibrations of a thin flexible electrode

    Science.gov (United States)

    Madanu, Sushma Bala

    Transverse vibrations of an electrostatically actuated thin flexible cantilever perturbed by low-speed air flow is studied using both experiments and numerical modeling. In the experiments the dynamic characteristics of the cantilever are studied by supplying a DC voltage with an AC component for electrostatic forcing and a constant uniform air flow around the cantilever system for aerodynamic forcing. The maximum voltage applied varies from 1 - 9 kV and air flow speeds range from 0.224 - 3.58 m/s (0.5 - 8 mile/hr). The Reynolds numbers for these speeds lie in the range of 1000 - 20000. A range of control parameters leading to stable vibrations are established using the Strouhal number as the operating parameter whose inverse values change from 100 - 2500. The Numerical results are validated with experimental results. Assuming the amplitude of vibrations are small, then a non-linear dynamic Euler-Bernoulli beam equation with viscous damping and gravitational effects is used to model the vibrations of the dynamical system. Aerodynamic forcing is modeled as a temporally sinusoidal and uniform force acting perpendicular to the beam length. The forcing amplitude is found to be proportional to square of air flow velocity by obtaining relationship between the experimental amplitude of vibrations and air flow velocity. Numerical results strongly agree with those of experiments predicting accurate vibration amplitudes, displacement frequency and quasi-periodic displacements of the cantilever tip.

  2. Bastões de grafite reciclados de baterias comuns e seu uso como eletrodo modificado em hidrogenação eletrocatalítica de alguns substratos orgânicos Graphite sticks recycled from common batteries and their use as a modified electrode in electrocatalytic hydrogenation of some organic substrates

    Directory of Open Access Journals (Sweden)

    Renata C. Z. Lofrano

    2002-12-01

    Full Text Available This paper presents some results on the employ of recycled graphite electrode obtained from used common 1.5 V batteries in the preparation of modified electrode and the electrocatalytical hydrogenation of benzaldehyde and of n-valeraldehyde. This inexpensive and easy to obtain electrode was prepared by coating it with a 1:1 mixed film of poly-(allylfenil ether: poly-[allyl p-(2-ethylammonium benzene ether] and introduction of dispersed platinum particles by ion exchange and reduction of PtCl4-2. Electroreduction of H+ from aqueous H2SO4 using the proposed electrode hydrogenated the substrates in a way comparable with that of vitreous carbon electrode.

  3. Real-time imaging of hydrogen peroxide dynamics in vegetative and pathogenic hyphae of Fusarium graminearum

    Science.gov (United States)

    Mentges, Michael; Bormann, Jörg

    2015-01-01

    Balanced dynamics of reactive oxygen species in the phytopathogenic fungus Fusarium graminearum play key roles for development and infection. To monitor those dynamics, ratiometric analysis using the novel hydrogen peroxide (H2O2) sensitive fluorescent indicator protein HyPer-2 was established for the first time in phytopathogenic fungi. H2O2 changes the excitation spectrum of HyPer-2 with an excitation maximum at 405 nm for the reduced and 488 nm for the oxidized state, facilitating ratiometric readouts with maximum emission at 516 nm. HyPer-2 analyses were performed using a microtiter fluorometer and confocal laser scanning microscopy (CLSM). Addition of external H2O2 to mycelia caused a steep and transient increase in fluorescence excited at 488 nm. This can be reversed by the addition of the reducing agent dithiothreitol. HyPer-2 in F. graminearum is highly sensitive and specific to H2O2 even in tiny amounts. Hyperosmotic treatment elicited a transient internal H2O2 burst. Hence, HyPer-2 is suitable to monitor the intracellular redox balance. Using CLSM, developmental processes like nuclear division, tip growth, septation, and infection structure development were analyzed. The latter two processes imply marked accumulations of intracellular H2O2. Taken together, HyPer-2 is a valuable and reliable tool for the analysis of environmental conditions, cellular development, and pathogenicity. PMID:26446493

  4. Car-Parrinello Molecular Dynamics Simulations of Infrared Spectra of Crystalline Vitamin C with Analysis of Double Minimum Proton Potentials for Medium-Strong Hydrogen Bonds.

    Science.gov (United States)

    Brela, Mateusz Z; Wójcik, Marek J; Boczar, Marek; Witek, Łukasz; Yasuda, Mitsuru; Ozaki, Yukihiro

    2015-06-25

    We studied proton dynamics of a hydrogen bonds of the crystalline l-ascorbic acid. Our approach was based on the Car-Parrinello molecular dynamics. The focal point of our study was simulation of the infrared spectra of l-ascorbic acid associated with the O-H stretching modes that are very sensitive to the strength of hydrogen bonding. In the l-ascorbic acid there are four kinds of hydrogen bonds. We calculated their spectra by using anharmonic approximation and the time course of the dipole moment function as obtained from the Car-Parrinello simulation. The quantization of the nuclear motion of the protons was made to perform detailed analysis of strength and properties of hydrogen bonds. We presented double minimum proton potentials with small value of barriers for medium-strong hydrogen bonds. We have also shown the difference character of medium-strong hydrogen bonds compared to weaker hydrogen bonds in the l-ascorbic acid.

  5. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah, E-mail: absalimi@uok.ac.i [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Mahdioun, Monierosadat; Noorbakhsh, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Abdolmaleki, Amir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156/83111 (Iran, Islamic Republic of); Ghavami, Raoof [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2011-03-30

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20-100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1-12). The surface coverages and heterogeneous electron transfer rate constants (k{sub s}) of immobilized Mn-complex were approximately 1.58 x 10{sup -10} mole cm{sup -2} and 48.84 s{sup -1}. The modified electrode showed excellent electrocatalytic activity toward H{sub 2}O{sub 2} reduction. Detection limit, sensitivity, linear concentration range and k{sub cat} for H{sub 2}O{sub 2} were, 0.2 {mu}M and 692 nA {mu}M{sup -1} cm{sup -2}, 1 {mu}M to 1.5 mM and 7.96({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1}, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.

  6. A molecular dynamics calculation of solid phase of malonic acid: role of hydrogen-bond chains and the elastic constants

    Indian Academy of Sciences (India)

    SATHYA S R R PERUMAL; YASHONATH SUBRAMANIAN

    2017-07-01

    Recent studies suggest that hydrogen bonds, in particular, hydrogen bond chains play an important role in determining the properties of a substance.We report an investigation into the triclinic phase of crystalline malonic acid. One of two intermolecular interaction potentials proposed here is seen to predict the lattice parameters as well as the enthalpy of the triclinic phase in good agreement with experimental data. Structural and dynamic properties are reported. Also reported are the lifetime of the hydrogen bond and hydrogen bondchains of length l along [011] direction where l = 1 to 5. From the temperature dependence of the lifetime we have obtained the activation energies of the chains. We also report the elements of elastic constant tensor. Theresults show that the presence of the hydrogen bond chain along [011] direction leads to higher value for elastic tensor Cyyzz suggesting a strong correlation between hydrogen bond chains and the elastic constant along thatdirection. This is consistent with the recent report of Azuri I et al. 2015 Angew. Chem. Int. Ed. Engl. 54 13566 who reported that rather large Young’s modulus for certain amino acid crystals.

  7. A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water-Ice: Defining Adsorption in Classical Molecular Dynamics

    CERN Document Server

    Dupuy, John L; Stancil, P C

    2016-01-01

    Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g. a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H$_2$) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics (MD) simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking ...

  8. Protein structural dynamics at the gas/water interface examined by hydrogen exchange mass spectrometry.

    Science.gov (United States)

    Xiao, Yiming; Konermann, Lars

    2015-08-01

    Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N(2) bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N(2) bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N(2) sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, "semi-unfolded" ↔ "native" ↔ "globally unfolded" → "aggregated". This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS.

  9. Investigation of coupling between chemistry and discharge dynamics in radio frequency hydrogen plasmas in the Torr regime

    Energy Technology Data Exchange (ETDEWEB)

    Kalache, B [LPICM, UMR 7647 (CNRS), Ecole Polytechnique, 91128 Palaiseau Cedex (France); Novikova, T [LPICM, UMR 7647 (CNRS), Ecole Polytechnique, 91128 Palaiseau Cedex (France); Morral, A Fontcuberta i [LPICM, UMR 7647 (CNRS), Ecole Polytechnique, 91128 Palaiseau Cedex (France); Cabarrocas, P Roca i [LPICM, UMR 7647 (CNRS), Ecole Polytechnique, 91128 Palaiseau Cedex (France); Morscheidt, W [LIMHP, UPR 1311 (CNRS), UPN, Av. J. B. Clement, 93430 Villetaneuse (France); Hassouni, K [LIMHP, UPR 1311 (CNRS), UPN, Av. J. B. Clement, 93430 Villetaneuse (France)

    2004-07-07

    We present the results of a study of a capacitively coupled hydrogen discharge by means of a one-dimensional numerical fluid model and experiments. The model includes a detailed description of the gas-phase chemistry taking into account the production of H{sup -} ions by dissociative attachment of H{sub 2} vibrational levels. The population of these levels is described by a Boltzmann vibrational distribution function characterized by a vibrational temperature T{sub V}. The effect of the dissociative-attachment reaction on the discharge dynamics was investigated by varying the vibrational temperature, which was used as a model input parameter. Increasing the vibrational temperature from 1000 to 6000 K affects both the chemistry and the dynamics of the electrical discharge. Because of dissociative attachment, the H{sup -} ion density increases by seven orders of magnitude and the H{sup -} ion density to electron density ratio varies from 10{sup -7} to 6, while the positive ion density increases slightly. As a consequence, the atomic hydrogen density increases by a factor of three, and the sheath voltage drops from 95 to 75 V. Therefore, clear evidence of a strong coupling between chemistry and electrical dynamics through the production of H{sup -} ions is demonstrated. Moreover, satisfactory agreement between computed and measured values of atomic hydrogen and H{sup -} ion densities gives further support to the requirement of a detailed description of the hydrogen vibrational kinetics for capacitively coupled radio frequency discharge models in the Torr regime.

  10. Ultrafast Dynamics of Hole Injection and Recombination in Organometal Halide Perovskite Using Nickel Oxide as p-Type Contact Electrode.

    Science.gov (United States)

    Corani, Alice; Li, Ming-Hsien; Shen, Po-Shen; Chen, Peter; Guo, Tzung-Fang; El Nahhas, Amal; Zheng, Kaibo; Yartsev, Arkady; Sundström, Villy; Ponseca, Carlito S

    2016-04-01

    There is a mounting effort to use nickel oxide (NiO) as p-type selective electrode for organometal halide perovskite-based solar cells. Recently, an overall power conversion efficiency using this hole acceptor has reached 18%. However, ultrafast spectroscopic investigations on the mechanism of charge injection as well as recombination dynamics have yet to be studied and understood. Using time-resolved terahertz spectroscopy, we show that hole transfer is complete on the subpicosecond time scale, driven by the favorable band alignment between the valence bands of perovskite and NiO nanoparticles (NiO(np)). Recombination time between holes injected into NiO(np) and mobile electrons in the perovskite material is shown to be hundreds of picoseconds to a few nanoseconds. Because of the low conductivity of NiO(np), holes are pinned at the interface, and it is electrons that determine the recombination rate. This recombination competes with charge collection and therefore must be minimized. Doping NiO to promote higher mobility of holes is desirable in order to prevent back recombination.

  11. {sup 2}H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H{sub 2}ca

    Energy Technology Data Exchange (ETDEWEB)

    Asaji, Tetsuo, E-mail: asaji@chs.nihon-u.ac.jp; Hara, Masamichi; Fujimori, Hiroki [Nihon University, Department of Chemistry, College of Humanities and Sciences (Japan); Hagiwara, Shoko [Nihon University, Department of Chemistry, Graduate School of Integrated Basic Sciences (Japan)

    2016-12-15

    Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5’-dimethyl-2,2’-bipyridine (55DMBP) and chloranilic acid (H{sub 2}ca), was investigated by use of {sup 2}H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N{sup +}-H …O{sup −} in the antiferroelectric phase were clearly observed as the splitting of the side band of the {sup 2}H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D {sub 2}ca. The temperature dependence of the spin-lattice relaxation time was measured of the N{sup +}-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N{sup +}-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol{sup −1}.

  12. Molecular dynamics simulation of amorphous indomethacin-poly(vinylpyrrolidone) glasses: solubility and hydrogen bonding interactions.

    Science.gov (United States)

    Xiang, Tian-Xiang; Anderson, Bradley D

    2013-03-01

    Amorphous drug dispersions are frequently employed to enhance solubility and dissolution of poorly water-soluble drugs and thereby increase their oral bioavailability. Because these systems are metastable, phase separation of the amorphous components and subsequent drug crystallization may occur during storage. Computational methods to determine the likelihood of these events would be very valuable, if their reliability could be validated. This study investigates amorphous systems of indomethacin (IMC) in poly(vinylpyrrolidone) (PVP) and their molecular interactions by means of molecular dynamics (MD) simulations. IMC and PVP molecules were constructed using X-ray diffraction data, and force-field parameters were assigned by analogy with similar groups in Amber-ff03. Five assemblies varying in PVP and IMC composition were equilibrated in their molten states then cooled at a rate of 0.03 K/ps to generate amorphous glasses. Prolonged aging dynamic runs (100 ns) at 298 K and 1 bar were then carried out, from which solubility parameters, the Flory-Huggins interaction parameter, and associated hydrogen bonding properties were obtained. Calculated glass transition temperature (T(g)) values were higher than experimental results because of the faster cooling rates in MD simulations. Molecular mobility as characterized by atomic fluctuations was substantially reduced below the T(g) with IMC-PVP systems exhibiting lower mobilities than that found in amorphous IMC, consistent with the antiplasticizing effect of PVP. The number of IMC-IMC hydrogen bonds (HBs) formed per IMC molecule was substantially lower in IMC-PVP mixtures, particularly the fractions of IMC molecules involved in two or three HBs with other IMC molecules that may be potential precursors for crystal growth. The loss of HBs between IMC molecules in the presence of PVP was largely compensated for by the formation of IMC-PVP HBs. The difference (6.5 MPa(1/2)) between the solubility parameters in amorphous IMC

  13. Real-time monitoring of cellular dynamics using a microfluidic cell culture system with integrated electrode array and potentiostat

    DEFF Research Database (Denmark)

    Zor, Kinga; Vergani, M.; Heiskanen, Arto

    2011-01-01

    A versatile microfluidic, multichamber cell culture and analysis system with an integrated electrode array and potentiostat suitable for electrochemical detection and microscopic imaging is presented in this paper. The system, which allows on-line electrode cleaning and modification, was develope...

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

    Science.gov (United States)

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

    2016-08-01

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

  15. Optimization of caesium dynamics in large and powerful RF sources for negative hydrogen ions

    Energy Technology Data Exchange (ETDEWEB)

    Mimo, Alessandro; Wimmer, Christian; Wuenderlich, Dirk; Fantz, Ursel [Max-Planck-Institut fuer Plasmaphysik, 85748 Garching (Germany)

    2015-05-01

    The development of large and powerful RF sources for negative hydrogen and deuterium ions is mandatory for the realization of the Neutral Beam Injection system at ITER. Caesium seeding into negative ion sources is necessary to obtain the required ion current with a tolerable level of co-extracted electrons. The caesium dynamics, during both plasma and vacuum phases, was investigated by means of the Monte Carlo transport code CsFlow3D, which is used to simulate the time evolution of the distribution of neutral and ionic caesium in the IPP prototype RF ion source. Simulations were performed for different durations of plasma-on and plasma-off phases, with the purpose of understanding how the duty cycle influences the caesium distribution and hence the source performance. In order to investigate asymmetry effects in the caesium distribution, caused by the positioning of caesium evaporator, the caesium coverage on the top and on the bottom part of the plasma grid was simulated and data were compared to the caesium density measured by laser absorption in the prototype source. The next step will be to introduce in the code the simulation of diagnostics such as laser absorption spectroscopy and optical emission spectroscopy, in order to achieve a direct benchmark of the code with experimental data.

  16. Dynamics of bluff-body-stabilized premixed hydrogen/air flames in a narrow channel

    KAUST Repository

    Lee, Bok Jik

    2015-06-01

    Two-dimensional direct numerical simulations were conducted for bluff-body stabilized flames of a lean hydrogen/air mixture at near-blowoff conditions in a meso-scale channel. Parametric simulations were conducted by incrementally varying the inflow velocity in the vicinity of the blowoff limit, and the corresponding flame response was monitored. The present study is a showcase of combustion DNS with embedded boundary representation, and full demonstration of the detailed visualization of the near-blowoff flame characteristics. As the inflow velocity approaches blowoff limit, the flame dynamics exhibit a complex sequence of events, such as periodic local extinction and recovery, and regrowth of the bulk flame by the flame segments attached behind the bluff-body. The total extinction is observed as the attached flames shrink down and are no longer able to regrow the bulk flames. Despite the disparity in the physical scale under study, the observed sequence of the extinction pathway shows a strong similarity with experimental observations at larger scale combustion systems. © 2015 The Combustion Institute.

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

    Science.gov (United States)

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

    2016-12-01

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

  18. Single discharge of the matrix source of negative hydrogen ions: Influence of the neutral particle dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Paunska, Ts.; Todorov, D., E-mail: dimitar-tdrv@phys.uni-sofia.bg; Shivarova, A. [Faculty of Physics, Sofia University, BG-1164 Sofia (Bulgaria); Tarnev, Kh. [Department of Applied Physics, Technical University–Sofia, BG-1000 Sofia (Bulgaria)

    2015-04-08

    The study presents two-dimensional (2D) fluid-plasma-model description of a planar-coil inductively-driven discharge, considered as a single element of a matrix source of volume-produced negative hydrogen ions. Whereas the models developed up to now have been directed towards description of the charged particle behavior in the discharge, including that of the negative ions, this model stresses on the role of the neutral particle dynamics and of the surface processes in the formation of the discharge structure. The latter is discussed based on comparison of results obtained for discharges in a flowing gas and at a constant gas pressure as well as for different values of the coefficient of atom recombination on the walls. The conclusions are that the main plasma parameters – electron density and temperature and plasma potential – determining the gas discharge regime stay stable, regardless of changes in the redistribution of the densities of the neutral particles and of the positive ions. With regards to the volume production of the ions, which requires high density of (vibrationally excited) molecules, the impact on the degree of dissociation of the coefficient of atom recombination on the wall is discussed.

  19. Dynamic nuclear polarization and relaxation of H and D atoms in solid mixtures of hydrogen isotopes

    CERN Document Server

    Sheludiakov, S; Järvinen, J; Vainio, O; Lehtonen, L; Vasiliev, S; Lee, D M; Khmelenko, V V

    2016-01-01

    We report on a study of Dynamic Nuclear Polarization and electron and nuclear spin relaxation of atomic hydrogen and deuterium in solid molecular matrices of H$_{2}$, D$_{2}$, and HD mixtures. The electron and nuclear spin relaxation times ($T_{1e}$ and $T_{1N}$) were measured within the temperature range 0.15-2.5$\\,$K in a magnetic field of 4.6 T, conditions which ensure a high polarization of electron spins. We found that $T_{1e}$ is nearly temperature independent in this temperature range, while $T_{1N}$ decreased by 2 orders of magnitude. Such strong temperature dependence is typical for the nuclear Orbach mechanism of relaxation via the electron spins. We found that the nuclear spins of H atoms in solid D$_{2}$ and D$_{2}:$HD can be efficiently polarized by the Overhauser effect. Pumping the forbidden transitions of H atoms also leads to DNP, with the efficiency strongly dependent on the concentration of D atoms. This behaviour indicates the Cross effect mechanism of the DNP and nuclear relaxation, which...

  20. Formation of a robust and stable film comprising ionic liquid and polyoxometalate on glassy carbon electrode modified with multiwalled carbon nanotubes: Toward sensitive and fast detection of hydrogen peroxide and iodate

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Behzad, E-mail: haghighi@iasbs.ac.i [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195 - 1159, Gava Zang, Zanjan (Iran, Islamic Republic of); Hamidi, Hassan [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195 - 1159, Gava Zang, Zanjan (Iran, Islamic Republic of); Gorton, Lo [Institute of Chemistry, Lund University, P.O. Box 124, S-221 00 Lund (Sweden)

    2010-06-30

    A robust and stable film comprising n-octylpyridinum hexafluorophosphate ([C{sub 8}Py][PF{sub 6}]) and 1:12 phosphomolybdic acid (PMo{sub 12}) was prepared on glassy carbon electrodes modified with multiwall carbon nanotubes (GCE/MWCNTs) by dip-coating. The cyclic voltammograms of the GCE/MWCNTs/[C{sub 8}Py][PF{sub 6}]-PMo{sub 12} showed three well-defined pairs of redox peaks due to the PMo{sub 12} system. The surface coverage for the immobilized PMo{sub 12} and the average values of the electron transfer rate constant for three pairs of redox peaks were evaluated. The GCE/MWCNTs/[C{sub 8}Py][PF{sub 6}]-PMo{sub 12} showed great electrocatalytic activity towards the reduction of H{sub 2}O{sub 2} and iodate. The kinetic parameters of the catalytic reduction of hydrogen peroxide and iodate at the electrode surface and analytical features of the sensor for amperometric determination of hydrogen peroxide and iodate were evaluated.

  1. Application of Hydrogen-storage Alloy Electrode in Electrochemical Reduction of Glucose%贮氢合金电极在葡萄糖电化学还原中的应用

    Institute of Scientific and Technical Information of China (English)

    陈惠; 唐有根; 唐征

    2003-01-01

    Electrolysis of glucose was performed at constant potential using hydrogen-storage alloy as catalytic reduction electrode. It was found that the superficial treatment and activation of hydrogen-storage alloy powder had obvious effects on improving the current efficiency of sorbitol. Under the optimums, current efficiency of sorbitol by electrolyzing glucose was over 94%. The yield of sorbitol was over 80%, the lifespan of electrode was tested and analyzed, the ways of regeneration were discussed.%以贮氢合金电极作催化还原电极,恒电位电解葡萄糖,发现合金经表面处理及电极的活化后,即可提高电流效率,在最优条件下,电解葡萄糖制山梨醇电流效率高达90%,葡萄糖转化率达80%以上.测试了电极的使用寿命,同时对电极中毒及再生方法进行了探讨.

  2. Quasi-Elastic Neutron Scattering (QENS) Studies of Hydrogen Dynamics for Nano-Confined NaAlH4

    Science.gov (United States)

    Dobbins, Tabbetha; Narasegowda, Shathabish; Brown, Craig; Tyagi, Madhusudan; Jenkins, Timothy

    The hydrogen dynamics of nano-confined sodium alanate (NaAlH4) has been studied using quasi-elastic neutron scattering (QENS). Results indicate thermodynamic destabilization is responsible for reduced desorption temperatures of NaAlH4 upon confinement within the nanopores of a metal organic framework (MOF). Both the bulk (microscale) NaAlH4 and the nanoconfined NaAlH4 data were fitted to re-orientation models which yielded corresponding percent mobile hydrogen and jump lengths. The jump lengths calculated from the nano-NaAlH4 were ~2.5 Å, and in conformity with those jump lengths determined for bulk NaAlH4 of ~2.3 Å. As much as 18 % of the hydrogen atoms were estimated to be mobile in the nano-NaAlH4 sample even at relatively low temperatures of 350 K. In contrast, bulk NaAlH4 shows less than 7 % mobile H-atoms even at higher temperatures of ~450 K. The activation energy for the long range is 3.1meV. Quasi-Elastic Neutron Scattering (QENS) Studies of Hydrogen Dynamics for Nano-Confined NaAlH4.

  3. Hydrogen-bond and solvent dynamics in transition metal complexes: a combined simulation and NMR-investigation.

    Science.gov (United States)

    Huang, Jing; Häussinger, Daniel; Gellrich, Urs; Seiche, Wolfgang; Breit, Bernhard; Meuwly, Markus

    2012-12-13

    Self-assembling ligands through complementary hydrogen-bonding in the coordination sphere of a transition metal provides catalysts with unique properties for carbon-carbon and carbon-heteroatom formation. Their most distinguishing chemical bonding pattern is a double-hydrogen-bonded motif, which determines much of the chemical functionality. Here, we discuss the possibility of double proton transfer (DPT) along this motif using computational and experimental methods. The infrared and NMR spectral signatures for the double-hydrogen-bonded motif are analyzed. Atomistic simulations and experiments suggest that the dynamics of the catalyst is surprisingly complex and displays at least three different dynamical regimes which can be distinguished with NMR spectroscopy and analyzed from computation. The two hydrogen bonds are kept intact and in rapid tautomeric exchange down to 125 K, which provides an estimate of 5 kcal/mol for the barrier for DPT. This is confirmed by the simulations which predict 5.8 kcal/mol for double proton transfer. A mechanistic interpretation is provided and the distribution of the solvent shell surrounding the catalyst is characterized from extensive simulations.

  4. On detonation dynamics in hydrogen-air-steam mixtures: Theory and application to Olkiluoto reactor building

    Energy Technology Data Exchange (ETDEWEB)

    Silde, A.; Lindholm, I. [VTT Energy, Espoo (Finland)

    2000-02-01

    This report consists of the literature study of detonation dynamics in hydrogen-air-steam mixtures, and the assessment of shock pressure loads in Olkiluoto 1 and 2 reactor building under detonation conditions using the computer program DETO developed during this work at VTT. The program uses a simple 1-D approach based on the strong explosion theory, and accounts for the effects of both the primary or incident shock and the first (oblique or normal) reflected shock from a wall structure. The code results are also assessed against a Balloon experiment performed at Germany, and the classical Chapman-Jouguet detonation theory. The whole work was carried out as a part of Nordic SOS-2.3 project, dealing with severe accident analysis. The initial conditions and gas distribution of the detonation calculations are based on previous severe accident analyses by MELCOR and FLUENT codes. According to DETO calculations, the maximum peak pressure in a structure of Olkiluoto reactor building room B60-80 after normal shock reflection was about 38.7 MPa if a total of 3.15 kg hydrogen was assumed to burned in a distance of 2.0 m from the wall structure. The corresponding pressure impulse was about 9.4 kPa-s. The results were sensitive to the distance used. Comparison of the results to classical C-J theory and the Balloon experiments suggested that DETO code represented a conservative estimation for the first pressure spike under the shock reflection from a wall in Olkiluoto reactor building. Complicated 3-D phenomena of shock wave reflections and focusing, nor the propagation of combustion front behind the shock wave under detonation conditions are not modeled in the DETO code. More detailed 3-D analyses with a specific detonation code are, therefore, recommended. In spite of the code simplifications, DETO was found to be a beneficial tool for simple first-order assessments of the structure pressure loads under the first reflection of detonation shock waves. The work on assessment

  5. Measurement and Calculation of Electrochemical Potentials in Hydrogenated High Temperature Water, including an Evaluation of the Yttria-Stabilized Zirconia/Iron-Iron Oxide (Fe/Fe3O4) Probe as Reference Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Steven A. Attanasio; David S. Morton; Mark A. Ando

    2001-10-22

    The importance of knowing the electrochemical corrosion potential (ECP, also referred to as E{sub con}) of nickel-base alloys in hydrogenated water is related to the need to understand the effects of dissolved (i.e., aqueous) hydrogen concentration ([H{sub 2}]) on primary water stress corrosion cracking (PWSCC). Also, the use of a reference electrode (RE) can improve test quality by heightening the ability to detect instances of out-of-specification or unexpected chemistry. Three methods are used to measure and calculate the ECP of nickel-based alloys in hydrogenated water containing {approx} 1 to 150 scc/kg H{sub 2} (0.1 to 13.6 ppm H{sub 2}) at 260 to 360 C. The three methods are referred to as the specimen/component method, the platinum (Pt) method, and the yttria-stabilized zirconia/iron-iron oxide (YSZ/Fe-Fe{sub 3}O{sub 4}) RE method. The specimen/component method relies upon the assumption that the specimen or component behaves as a hydrogen electrode, and its E{sub corr} is calculated using the Nernst equation. The present work shows that this method is valid for aqueous H{sub 2} levels {ge} {approx} 5 to 10 scc/kg H{sub 2}. The Pt method uses a voltage measurement between the specimen or component and a Pt electrode, with the Pt assumed to behave as a hydrogen electrode; this method is valid as long as the aqueous H{sub 2}level is known. The YSZ/Fe-Fe{sub 3}O{sub 4}, which represents a relatively new approach for measuring E{sub corr} in this environment, can be used even if the aqueous H{sub 2} level is unknown. The electrochemical performance of the YSZ/Fe-Fe{sub 3}O{sub 4} probe supports its viability as a RE for use in high temperature hydrogenated water. Recent design modifications incorporating a teflon sealant have improved the durability of this RE (however, some of the REs do still fail prematurely due to water in-leakage). The Pt method is judged to represent the best overall approach, though there are cases where the other methods are superior

  6. Hydrogen Bond Dynamics of Histamine Monocation in Aqueous Solu-tion: How Geometric Parameters Influence the Hydrogen Bond Strength

    OpenAIRE

    Pirc, Gordana; Stare, Jernej; Mavri, Janez; Vianello, Robert

    2014-01-01

    Chemometric statistical approaches involving multiple linear regression (MLR) and principal compo-nent analysis (PCA) were employed on a set of 42 distinct snapshot structures of the physiological histamine monocation in aqueous solution along the Car-Parrinello molecular dynamics trajectory, in order to obtain a better insight into the relationship between the geometry parameters of the system and the resulting νNH stretching frequencies. A simple 2D linear regression of νNH with Namino•••Ow...

  7. 氢电极预烧温度对丝网印刷YSZ电解质薄膜的影响%Effect of Presintering Temperature of Hydrogen Electrode on Screen-Printed YSZ Films

    Institute of Scientific and Technical Information of China (English)

    梁明德; 章德铭; 张鑫; 冀晓娟; 沈婕; 任先京

    2013-01-01

    Yttria-stabilized zirconia (YSZ) electrolyte film was prepared by screen-printing technology. The presintering temperature of porous NiO-YSZ hydrogen electrode substrates used in solid oxide electrolysis cells (SOEC) was optimized. A single fuel cell of Ni-YSZ/YSZ (10 μm)/LSM-YSZ was successfully prepared by screen-printing method. The results show that the optimum presintering temperature of NiO-YSZ hydrogen electrode is 1 000 ℃, and the hydrogen production rate of single SOEC is 386 mL/(cm2 · h) , 255 mL/(cm2 · h) , and 142 mL/(cm2 · h), at 800 ℃ , 850 ℃ and 900 ℃ , respectively. The ohmic resistance of the electrolytic cell can be effectively reduced through thinning down of YSZ electrolyte membrane with screen-printing technology.%采用丝网印刷法制备了Y2O3稳定ZrO2(YSZ)电解质薄膜,并对固体氧化物电解池(SOEC)的NiO-YSZ氢电极预烧温度进行了优化.结果表明,NiO-YSZ氢电极适宜的预烧温度为1000℃,YSZ电解质薄膜化后制备的SOEC在800℃、850℃和900℃三种电解温度下,1.50 V时的产氢速率分别为386 mL/(cm2·h)、255 mL/(cm2·h)和142 mL/(cm2·h).采用丝网印刷法将YSZ电解质薄膜化制备后可以有效降低电解池的欧姆阻抗.

  8. Thermodynamic and dynamic dielectric properties of one-dimensional hydrogen bonded ferroelectric of PbHPO4-type

    Directory of Open Access Journals (Sweden)

    I.R. Zachek

    2014-12-01

    Full Text Available Within the modified model of proton ordering of one-dimensional ferroelectric having hydrogen bonds of PbHPO4-type, their thermodynamic and dynamic characteristics are studied and calculated taking into account the linear (by crystal deformations ϵi (i=1,3 and ϵ4 contributions into the energy of a proton system but without taking into account the tunneling in the two-particle cluster approximation. There has been obtained a good quantitative description of the temperature dependence of polarization, static dielectric permittivity, heat capacity and frequency dependence of dynamic dielectric permittivity at different temperatures for PbHPO4 and PbHDO4 crystals.

  9. Characterizing the dynamics of alpha-synuclein oligomers using hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Betzer, Cristine; Jensen, Poul H;

    2013-01-01

    hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS), we have analyzed the structural dynamics of soluble αSN oligomers. The analyzed oligomers were metastable, slowly dissociating to monomers over a period of 21 days, after excess monomer had been removed. The C-terminal region of α......-shielded structure. The protected regions were interspersed by two somewhat more dynamic regions (residues 18-38 and 55-70). In the oligomeric state, the isotopic exchange pattern of the region of residues 35-95 of αSN corresponded well with previous nuclear magnetic resonance and electron paramagnetic resonance...

  10. Three-body dynamics in single ionization of atomic hydrogen by 75 keV proton impact.

    Science.gov (United States)

    Laforge, A C; Egodapitiya, K N; Alexander, J S; Hasan, A; Ciappina, M F; Khakoo, M A; Schulz, M

    2009-07-31

    Doubly differential cross sections for single ionization of atomic hydrogen by 75 keV proton impact have been measured and calculated as a function of the projectile scattering angle and energy loss. This pure three-body collision system represents a fundamental test case for the study of the reaction dynamics in few-body systems. A comparison between theory and experiment reveals that three-body dynamics is important at all scattering angles and that an accurate description of the role of the projectile-target-nucleus interaction remains a major challenge to theory.

  11. INFLUENCE OF SOLVENT ON INTRAMOLECULAR PROTON-TRANSFER IN HYDROGEN MALONATE - MOLECULAR-DYNAMICS SIMULATION STUDY OF TUNNELING BY DENSITY-MATRIX EVOLUTION AND NONEQUILIBRIUM SOLVATION

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC; VANGUNSTEREN, WF

    1993-01-01

    A density matrix evolution (DME) method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. the preceding paper in this issue) in combination with classical molecular dynamics simulation was applied to calculate the rate of proton tunneling in the intramolecular double-well hydrogen bond of hydrogen malo

  12. Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal.

    Science.gov (United States)

    Ueda, Akira; Yamada, Shota; Isono, Takayuki; Kamo, Hiromichi; Nakao, Akiko; Kumai, Reiji; Nakao, Hironori; Murakami, Youichi; Yamamoto, Kaoru; Nishio, Yutaka; Mori, Hatsumi

    2014-08-27

    A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

  13. Dynamics of urokinase receptor interaction with Peptide antagonists studied by amide hydrogen exchange and mass spectrometry

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J D; Gårdsvoll, Henrik; Danø, Keld

    2004-01-01

    Using amide hydrogen exchange combined with electrospray ionization mass spectrometry, we have in this study determined the number of amide hydrogens on several peptides that become solvent-inaccessible as a result of their high-affinity interaction with the urokinase-type plasminogen activator r...

  14. Structure and dynamics of hydrogen in nanocomposite solid acids for fuel cell applications

    NARCIS (Netherlands)

    Chan, W.K.

    2011-01-01

    The transition to sustainable energy sources is inevitable. A possible future scenario could be the hydrogen economy, where the fuel cell plays an important role in the conversion of hydrogen back to electricity. The technology behind the fuel cell however, still has significant room for improvement

  15. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    Science.gov (United States)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

  16. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  17. Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Franz, James A.; O' Hagan, Molly J.; Ho, Ming-Hsun; Liu, Tianbiao L.; Helm, Monte L.; Lense, Sheri; DuBois, Daniel L.; Shaw, Wendy J.; Appel, Aaron M.; Raugei, Simone; Bullock, R. Morris

    2013-12-09

    The [Ni(PR2NR’2)2]2+ catalysts, (where PR2NR´2 is 1,5-R´-3,7-R-1,5-diaza-3,7-diphosphacyclooctane), are some of the fastest reported for hydrogen production and oxidation, however, chair/boat isomerization and the presence of a fifth solvent ligand have the potential to slow catalysis by incorrectly positioning the pendant amines or blocking the addition of hydrogen. Here, we report the structural dynamics of a series of [Ni(PR2NR’2)2]n+ complexes, characterized by NMR spectroscopy and theoretical modeling. A fast exchange process was observed for the [Ni(CH3CN)(PR2NR’2)2]2+ complexes which depends on the ligand. This exchange process was identified to occur through a three step mechanism including dissociation of the acetonitrile, boat/chair isomerization of each of the four rings identified by the phosphine ligands (including nitrogen inversion), and reassociation of acetonitrile on the opposite side of the complex. The rate of the chair/boat inversion can be influenced by varying the substituent on the nitrogen atom, but the rate of the overall exchange process is at least an order of magnitude faster than the catalytic rate in acetonitrile demonstrating that the structural dynamics of the [Ni(PR2NR´2)2]2+ complexes does not hinder catalysis. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under FWP56073. Research by J.A.F., M.O., M-H. H., M.L.H, D.L.D. A.M.A., S. R. and R.M.B. was carried out in the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. W.J.S. and S.L. were funded by the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences. T.L. was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences

  18. Learning probabilistic models of hydrogen bond stability from molecular dynamics simulation trajectories

    KAUST Repository

    Chikalov, Igor

    2011-02-15

    Background: Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. They form and break while a protein deforms, for instance during the transition from a non-functional to a functional state. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor.Methods: This paper describes inductive learning methods to train protein-independent probabilistic models of H-bond stability from molecular dynamics (MD) simulation trajectories of various proteins. The training data contains 32 input attributes (predictors) that describe an H-bond and its local environment in a conformation c and the output attribute is the probability that the H-bond will be present in an arbitrary conformation of this protein achievable from c within a time duration ?. We model dependence of the output variable on the predictors by a regression tree.Results: Several models are built using 6 MD simulation trajectories containing over 4000 distinct H-bonds (millions of occurrences). Experimental results demonstrate that such models can predict H-bond stability quite well. They perform roughly 20% better than models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a conformation. In most tests, about 80% of the 10% H-bonds predicted as the least stable are actually among the 10% truly least stable. The important attributes identified during the tree construction are consistent with previous findings.Conclusions: We use inductive learning methods to build protein-independent probabilistic models to study H-bond stability, and demonstrate that the models perform better than H-bond energy alone. 2011 Chikalov et al; licensee BioMed Central Ltd.

  19. Learning Probabilistic Models of Hydrogen Bond Stability from Molecular Dynamics Simulation Trajectories

    KAUST Repository

    Chikalov, Igor

    2011-04-02

    Hydrogen bonds (H-bonds) play a key role in both the formation and stabilization of protein structures. H-bonds involving atoms from residues that are close to each other in the main-chain sequence stabilize secondary structure elements. H-bonds between atoms from distant residues stabilize a protein’s tertiary structure. However, H-bonds greatly vary in stability. They form and break while a protein deforms. For instance, the transition of a protein from a nonfunctional to a functional state may require some H-bonds to break and others to form. The intrinsic strength of an individual H-bond has been studied from an energetic viewpoint, but energy alone may not be a very good predictor. Other local interactions may reinforce (or weaken) an H-bond. This paper describes inductive learning methods to train a protein-independent probabilistic model of H-bond stability from molecular dynamics (MD) simulation trajectories. The training data describes H-bond occurrences at successive times along these trajectories by the values of attributes called predictors. A trained model is constructed in the form of a regression tree in which each non-leaf node is a Boolean test (split) on a predictor. Each occurrence of an H-bond maps to a path in this tree from the root to a leaf node. Its predicted stability is associated with the leaf node. Experimental results demonstrate that such models can predict H-bond stability quite well. In particular, their performance is roughly 20% better than that of models based on H-bond energy alone. In addition, they can accurately identify a large fraction of the least stable H-bonds in a given conformation. The paper discusses several extensions that may yield further improvements.

  20. Dynamic Nuclear Polarization and Relaxation of H and D Atoms in Solid Mixtures of Hydrogen Isotopes

    Science.gov (United States)

    Sheludiakov, S.; Ahokas, J.; Järvinen, J.; Vainio, O.; Lehtonen, L.; Vasiliev, S.; Lee, D. M.; Khmelenko, V. V.

    2016-12-01

    We report on a study of dynamic nuclear polarization and electron and nuclear spin relaxation of atomic hydrogen and deuterium in solid molecular matrices of H2, D2 , and HD mixtures. The electron and nuclear spin relaxation times (T_{1e} and T_{1N} ) were measured within the temperature range 0.15-2.5 K in a magnetic field of 4.6 T, conditions which ensure a high polarization of electron spins. We found that T_{1e} is nearly temperature independent in this temperature range, while T_{1N} decreased by two orders of magnitude upon raising temperature. Such strong temperature dependence is typical for the nuclear Orbach mechanism of relaxation via the electron spins. We found that the nuclear spins of H atoms in solid D2 and D2{:}HD can be efficiently polarized by the Overhauser effect. Pumping the forbidden transitions of H atoms also leads to DNP, with the efficiency strongly dependent on the concentration of D atoms. This behavior indicates the cross effect mechanism of the DNP and nuclear relaxation, which turns out to be well resolved in the conditions of our experiments. Efficient DNP of H atoms was also observed when pumping the middle D line located in the center of the ESR spectrum. This phenomenon can be explained in terms of clusters or pairs of H atoms with a strong exchange interaction. These clusters have partially allowed transitions in the center of the ESR spectrum, and DNP may be created via the resolved cross effect.

  1. Effect of the geometric phase on the dynamics of the hydrogen-exchange reaction.

    Science.gov (United States)

    Juanes-Marcos, Juan Carlos; Althorpe, Stuart C; Wrede, Eckart

    2007-01-28

    A recent puzzle in nonadiabatic quantum dynamics is that geometric phase (GP) effects are present in the state-to-state opacity functions of the hydrogen-exchange reaction, but cancel out in the state-to-state integral cross sections (ICSs). Here the authors explain this result by using topology to separate the scattering amplitudes into contributions from Feynman paths that loop in opposite senses around the conical intersection. The clockwise-looping paths pass over one transition state (1-TS) and scatter into positive deflection angles; the counterclockwise-looping paths pass over two transition states (2-TS) and scatter into negative deflection angles. The interference between the 1-TS and 2-TS paths thus integrates to a very small value, which cancels the GP effects in the ICS. Quasiclassical trajectory (QCT) calculations reproduce the scattering of the 1-TS and 2-TS paths into positive and negative deflection angles and show that the 2-TS paths describe a direct insertion mechanism. The inserting atom follows a highly constrained "S-bend" path, which allows it to avoid both the other atoms and the conical intersection and forces the product diatom to scatter into high rotational states. By contrast, the quantum 2-TS paths scatter into a mainly statistical distribution of rotational states, so that the quantum 2-TS total ICS is roughly twice the QCT ICS at 2.3 eV total energy. This suggests that the S-bend constraint is relaxed by tunneling in the quantum system. These findings on H+H(2) suggest that similar cancellations or reductions in GP effects are likely in many other reactions.

  2. On the impedance of galvanic cells XXVII. The temperature-dependence of the kinetic parameters of the hydrogen electrode reaction on mercury in concentrated HI

    NARCIS (Netherlands)

    Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1969-01-01

    The impedance of a dropping mercury electrode in 57% HI (7.6 M) was measured at temperatures between −35° and +25°C. In a certain potential and temperature region, two reactions were found to be proceeding simultaneously: the reversible Hg/HgI4−2 reaction and the irreversible H+/H2(Hg) reaction. Ana

  3. Electrochemical determination of sulphide at multi-walled carbon nanotubes-dihexadecyl hydrogen phosphate composite film modified electrodes based on in situ synthesis of methylene blue

    Institute of Scientific and Technical Information of China (English)

    An Min Xiang; Li Zhou; Cheng Guo Hu; Sheng Shui Hu

    2008-01-01

    A novel electrochemical method for the determination of sulphide at a multi-walled carbon nanotube-dihexadecyl hydrogenphosphate composite film coated glassy carbon electrode (MWNTs-DHP/GCE) based on in situ synthesis of methylene blue (MB)was established.

  4. Hydrogen bond dynamics of histamine monocation in aqueous solution: Car-Parrinello molecular dynamics and vibrational spectroscopy study.

    Science.gov (United States)

    Stare, Jernej; Mavri, Janez; Grdadolnik, Jože; Zidar, Jernej; Maksić, Zvonimir B; Vianello, Robert

    2011-05-19

    Hydration of histamine was examined by infrared spectroscopy and Car-Parrinello molecular dynamics simulation. Histamine is a neurotransmitter and inflammation mediator, which at physiological pH conditions is present mainly in monocationic form. Our focus was on the part of vibrational spectra that corresponds to histamine N-H stretching, since these degrees of freedom are essential for its interactions with either water molecules or transporters and receptors. Assignment of the experimental spectra revealed a broad feature between 3350 and 2300 cm(-1), being centered at 2950 cm(-1), which includes a mixed contribution from the ring N-H and the aminoethyl N-H stretching vibrations. Computational analysis was performed in two ways: first, by making Fourier transformation on the autocorrelation function of all four N-H bond distances recorded during CPMD run, and second, and most importantly, by incorporating quantum effects through applying an a posteriori quantization of all N-H stretching motions utilizing our snapshot analysis of the fluctuating proton potential. The one-dimensional vibrational Schrödinger equation was solved numerically for each snapshot, and the N-H stretching envelopes were calculated as a superposition of the 0→1 transitions. The agreement with the experiment was much better in the case of the second approach. Our calculations clearly demonstrated that the ring amino group absorbs at higher frequencies than the remaining three amino N-H protons of the protonated aminoethyl group, implying that the chemical bonding in the former group is stronger than in the three amino N-H bonds, thus forming weaker hydrogen bonding with the surrounding solvent molecules. In this way the results of the simulation complemented the experimental spectrum that cannot distinguish between the two sets of protons. The effects of deuteration were also considered. The resulting N-D absorption is narrower and red-shifted. The presented methodology is of general

  5. Magnetohydrodynamic electrode

    Science.gov (United States)

    Boquist, Carl W.; Marchant, David D.

    1978-01-01

    A ceramic-metal composite suitable for use in a high-temperature environment consists of a refractory ceramic matrix containing 10 to 50 volume percent of a continuous high-temperature metal reinforcement. In a specific application of the composite, as an electrode in a magnetohydrodynamic generator, the one surface of the electrode which contacts the MHD fluid may have a layer of varying thickness of nonreinforced refractory ceramic for electrode temperature control. The side walls of the electrode may be coated with a refractory ceramic insulator. Also described is an electrode-insulator system for a MHD channel.

  6. Potential of hydrogen bond in water. Comparison of the theory with vibrational spectra and results of molecular dynamics simulations.

    Science.gov (United States)

    Efimov, Yuri Ya; Naberukhin, Yuri I

    2011-02-01

    Potential of hydrogen bond is the function which relates its energy to geometrical parameters of hydrogen bridge: its length R(O…O) and angles between direction O…O and OH group [φ (H-O…O)] and/or lone pair of proton accepting oxygen atom [χ(-O…O)]. Previously we have suggested an approach to design such potentials based on the approximate numerical solution of a reverse problem of the spectrum band shape in the frames of the fluctuation theory of hydrogen bonding. In the given work this method is applied to construction of the two-parameter potentials that depend on parameters {R(O…O), φ (H-O…O} or {φ (H-O…O), χ (-O…O)}. Using them, the spectra of OH vibrations of HOD molecules in a liquid phase are calculated theoretically in good agreement with experiment in the temperature range up to 200 °C. Distributions of angles P(φ, T), P(χ, T), and energies P(E) are calculated also. The same distributions and spectra are independently calculated on the basis of the geometrical parameters of the hydrogen bridges obtained from molecular dynamics models of water. The shapes of the spectral contours and their temperature evolution calculated for computer models turned out to be similar to experimental ones only for the potential that includes the length of H-bond R(O…O).

  7. A mechanistic model of hydrogen-methanogen dynamics in the rumen.

    Science.gov (United States)

    Wang, Yuancheng; Janssen, Peter H; Lynch, Tammy A; Brunt, Bruce van; Pacheco, David

    2016-03-21

    Existing mathematical models to estimate methane production in the rumen are based on calculation of hydrogen balances without considering the presence of methanogens. In this study, a mechanistic model of methane production is proposed that depicts the interaction between hydrogen concentration and methanogens in the rumen. Analytical results show that it meets biological expectations, namely increased fractional passage rate leads to a greater growth rate of methanogens, and a greater steady state hydrogen concentration. This model provides a basis on which to develop a more comprehensive model of methane production in the rumen that includes thermodynamics and feed fermentation pathways.

  8. Hydrogen-deuterium exchange mass spectrometry for investigation of backbone dynamics of oxidized and reduced cytochrome P450cam.

    Science.gov (United States)

    Hamuro, Yoshitomo; Molnar, Kathleen S; Coales, Stephen J; OuYang, Bo; Simorellis, Alana K; Pochapsky, Thomas C

    2008-02-01

    Backbone dynamics of the camphor monoxygenase cytochrome P450(cam) (CYP101) as a function of oxidation/ligation state of the heme iron were investigated via hydrogen/deuterium exchange (H/D exchange) as monitored by mass spectrometry. Main chain amide NH hydrogens can exchange readily with solvent and the rate of this exchange depends upon, among other things, dynamic fluctuations in local structural elements. A fluxional region of the polypeptide will exchange more quickly with solvent than one that is more constrained. In most regions of the enzyme, exchange rates were similar between oxidized high-spin camphor-bound and reduced camphor- and CO-bound CYP101 (CYP-S and CYP-S-CO, respectively). However, in regions of the protein that have previously been implicated in substrate access by structural and molecular dynamics investigations, the reduced enzyme shows significantly slower exchange rates than the oxidized CYP-S. This observation corresponds to increased flexibility of the oxidized enzyme relative to the reduced form. Structural features previously found to be perturbed in CYP-S-CO upon binding of the biologically relevant effector and reductant putidaredoxin (Pdx) as determined by nuclear magnetic resonance are also more protected from exchange in the reduced state. To our knowledge, this study represents the first experimental investigation of backbone dynamics within the P450 family using this methodology.

  9. Dynamical Properties of Hydrogen in ZnO:H Treated by H2/Ar Plasma under Atmospheric Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jun Kue; Kwon, Hyeok-Jung; Kim, Han-Sung; Kim, Dae-Il; Cho, Yong Sub [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    ZnO is a wide-band-gap semiconductor with many technological applications, including catalysis, gas sensing, and the fabrication of microelectronic devices. The geometric, electronic, and defect surface structures play a role in many applications of ZnO. Electron spin resonance (ESR) measurement on temperature was made to identify occupied energy states of H in ZnO:H, the g-value of H being revealed to be 1.96. The dynamical properties of ZnO:H are discussed in view of conversion to hydrogen molecule by analyzing the spin-lattice relaxation time of 1H nuclear magnetic resonance (NMR) spectroscopy. We have investigated the diffusional properties of hydrogen adsorbed on ZnO surface (ZnO:H) by a H{sub 2}/Ar mixed plasma treatment installed at KOMAC. Electron spin resonance measurement identified occupied energy states of H in ZnO:H, the g-value of H being revealed to be 1.96. In further work, the proton dynamics of ZnO:H would be discussed in view of conversion to hydrogen molecule by analyzing the spin-lattice relaxation time of 1H nuclear magnetic resonance spectroscopy.

  10. Chemical Reactivity Dynamics and Quantum Chaos in Highly Excited Hydrogen Atoms in an External Field: A Quantum Potential Approach

    Directory of Open Access Journals (Sweden)

    B. Maiti

    2002-04-01

    Full Text Available Abstract: Dynamical behavior of chemical reactivity indices like electronegativity, hardness, polarizability, electrophilicity and nucleophilicity indices is studied within a quantum fluid density functional framework for the interactions of a hydrogen atom in its ground electronic state (n = 1 and an excited electronic state (n = 20 with monochromatic and bichromatic laser pulses. Time dependent analogues of various electronic structure principles like the principles of electronegativity equalization, maximum hardness, minimum polarizability and maximum entropy have been found to be operative. Insights into the variation of intensities of the generated higher order harmonics on the color of the external laser field are obtained. The quantum signature of chaos in hydrogen atom has been studied using a quantum theory of motion and quantum fluid dynamics. A hydrogen atom in the electronic ground state (n = 1 and in an excited electronic state ( n = 20 behaves differently when placed in external oscillating monochromatic and bichromatic electric fields. Temporal evolutions of Shannon entropy, quantum Lyapunov exponent and Kolmogorov – Sinai entropy defined in terms of the distance between two initially close Bohmian trajectories for these two cases show marked differences. It appears that a larger uncertainty product and a smaller hardness value signal a chaotic behavior.

  11. Modelling of hydrogen thermal desorption spectrum in nonlinear dynamical boundary-value problem

    Science.gov (United States)

    Kostikova, E. K.; Zaika, Yu V.

    2016-11-01

    One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary-value problem of thermal desorption and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

  12. Photoelectrochemical performance of multi-layered BiOx-TiO2/Ti electrodes for degradation of phenol and production of molecular hydrogen in water.

    Science.gov (United States)

    Park, Hyunwoong; Bak, Ayoung; Ahn, Yong Yoon; Choi, Jina; Hoffmannn, Michael R

    2012-04-15

    Multi-layered BiO(x)-TiO(2) electrodes were used for the oxidation of chemical contaminants coupled with the production of H(2) characterized by a synergistic enhancement. The BiO(x)-TiO(2) electrodes were composed of a mixed-metal oxide array involving an under layer of TaO(x)-IrO(x), a middle layer of BiO(x)-SnO(2), and a top layer of BiO(x)-TiO(2) deposited in a series on both sides of Ti foil. Cyclic voltammograms showed that the BiO(x)-TiO(2) electrodes had an electrocatalytic activity for oxidation of phenol that was enhanced by 70% under illumination with AM 1.5 light. When the BiO(x)-TiO(2) anode was coupled with a stainless steel cathode in a Na(2)SO(4) electrolyte with phenol and irradiated with UV light at an applied DC voltage, the anodic phenol oxidation rate and the cathodic H(2) production rates were enhanced by factors of four and three, respectively, as compared to the sum of each light irradiation and direct DC electrolysis. These synergistic effects depend on the specific electrode composition and decrease on TaO(x)-IrO(x) and BiO(x)-SnO(2) anodes in the absence of a top layer of BiO(x)-TiO(2). These results indicate that the BiO(x)-TiO(2) layer functions as the key photo-electrocatalyst. The heavy doping level of Bi (25 mol%) in TiO(2) increases the electric conductivity of the parent TiO(2).

  13. Three-dimensionally Ordered Macroporous (3DOM) Gold-nanoparticle Doped Titanium Dioxide (GTD) Photonic Crystals Modified Electrodes for Hydrogen Peroxide Biosensor

    Institute of Scientific and Technical Information of China (English)

    Wei NanNan; Han Tao; Li JianLin; Xin Xin; Du JiangYan

    2009-01-01

    @@ The design and fabrication of simply,sensitively electrochemical biosensors have been of high interest for their widespread applications such as drug discovery,disease diagnostics,environmental monitoring and food safety.Using the 3DOM GTD/ITO electrode,we developed a new HRP-based H_2O_2 biosensor.This novel H_2O_2 biosensor displayed high sensitivity,acceptable stability and reproducibility.These provide a fundamental theory principle for the new biosensor application.

  14. Car-Parrinello and path integral molecular dynamics study of the hydrogen bonds in 2-acetyl-1,8-dihydroxy-3,6-dimethylnaphthalene

    Science.gov (United States)

    Durlak, Piotr; Latajka, Zdzisław

    2010-10-01

    Theoretical studies of the structure and proton motion in the intramolecular O-H…O hydrogen bonds in 2-acetyl-1,8-dihydroxy-3,6-dimethylnapthlane were carried out at the DFT and molecular dynamics levels. Geometry optimization at the PBE1PBE/6-311++G(2d,2p) level demonstrate the existence of two tautomers on the potential energy surface. Dynamics of proton motion in intramolecular hydrogen bonds was investigated in vacuo at 100 K using Car-Parrinello and path integral molecular dynamics. For the strong intramolecular hydrogen bond very large delocalization of bridging proton is noted, especially in the path integral simulation where quantum effects are taken into account. No tautomerism was found for this intramolecular hydrogen bond.

  15. A path integral molecular dynamics study of the hyperfine coupling constants of the muoniated and hydrogenated acetone radicals

    Science.gov (United States)

    Oba, Yuki; Kawatsu, Tsutomu; Tachikawa, Masanori

    2016-08-01

    The on-the-fly ab initio density functional path integral molecular dynamics (PIMD) simulations, which can account for both the nuclear quantum effect and thermal effect, were carried out to evaluate the structures and "reduced" isotropic hyperfine coupling constants (HFCCs) for muoniated and hydrogenated acetone radicals (2-muoxy-2-propyl and 2-hydoxy-2-propyl) in vacuo. The reduced HFCC value from a simple geometry optimization calculation without both the nuclear quantum effect and thermal effect is -8.18 MHz, and that by standard ab initio molecular dynamics simulation with only the thermal effect and without the nuclear quantum effect is 0.33 MHz at 300 K, where these two methods cannot distinguish the difference between muoniated and hydrogenated acetone radicals. In contrast, the reduced HFCC value of the muoniated acetone radical by our PIMD simulation is 32.1 MHz, which is about 8 times larger than that for the hydrogenated radical of 3.97 MHz with the same level of calculation. We have found that the HFCC values are highly correlated with the local molecular structures; especially, the Mu—O bond length in the muoniated acetone radical is elongated due to the large nuclear quantum effect of the muon, which makes the expectation value of the HFCC larger. Although our PIMD result calculated in vacuo is about 4 times larger than the measured experimental value in aqueous solvent, the ratio of these HFCC values between muoniated and hydrogenated acetone radicals in vacuo is in reasonable agreement with the ratio of the experimental values in aqueous solvent (8.56 MHz and 0.9 MHz); the explicit presence of solvent molecules has a major effect on decreasing the reduced muon HFCC of in vacuo calculations for the quantitative reproduction.

  16. Seasonal dynamics in dissolved organic matter, hydrogen peroxide, and cyanobacterial blooms in Lake Erie

    Directory of Open Access Journals (Sweden)

    Rose M. Cory

    2016-04-01

    Full Text Available Hydrogen peroxide (H2O2 has been suggested to influence cyanobacterial community structure and toxicity. However, no study has investigated H2O2 concentrations in freshwaters relative to cyanobacterial blooms when sources and sinks of H2O2 may be highly variable. For example, photochemical production of H2O2 from chromophoric dissolved organic matter (CDOM may vary over the course of the bloom with changing CDOM and UV light in the water column, while microbial sources and sinks of H2O2 may change with community biomass and composition. To assess relationships between H2O2 and harmful algal blooms dominated by toxic cyanobacteria in the western basin of Lake Erie, we measured H2O2 weekly at six stations from June – November, 2014 and 2015, with supporting physical, chemical, and biological water quality data. Nine additional stations across the western, eastern, and central basins of Lake Erie were sampled during August and October, 2015. CDOM sources were quantified from the fluorescence fraction of CDOM using parallel factor analysis (PARAFAC. CDOM concentration and source were significantly correlated with specific conductivity, demonstrating that discharge of terrestrially-derived CDOM from rivers can be tracked in the lake. Autochthonous sources of CDOM in the lake increased over the course of the blooms. Concentrations of H2O2 in Lake Erie ranged from 47 ± 16 nM to 1570 ± 16 nM (average of 371 ± 17 nM; n = 225, and were not correlated to CDOM concentration or source, UV light, or estimates of photochemical production of H2O2 by CDOM. Temporal patterns in H2O2 were more closely aligned with bloom dynamics in the lake. In 2014 and 2015, maximum concentrations of H2O2 were observed prior to peak water column respiration and chlorophyll a, coinciding with the onset of the widespread Microcystis blooms in late July. The spatial and temporal patterns in H2O2 concentrations suggested that production and decay of H2O2 from aquatic

  17. Vibrational lifetimes of hydrogen on lead films: An ab initio molecular dynamics with electronic friction (AIMDEF) study

    Energy Technology Data Exchange (ETDEWEB)

    Saalfrank, Peter [Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam (Germany); Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Juaristi, J. I. [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20018 Donostia-San Sebastián (Spain); Alducin, M.; Muiño, R. Díez [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián (Spain); Blanco-Rey, M. [Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, 20018 Donostia-San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas UPV/EHU, Apartado 1072, 20018 Donostia-San Sebastián (Spain)

    2014-12-21

    Using density functional theory and Ab Initio Molecular Dynamics with Electronic Friction (AIMDEF), we study the adsorption and dissipative vibrational dynamics of hydrogen atoms chemisorbed on free-standing lead films of increasing thickness. Lead films are known for their oscillatory behaviour of certain properties with increasing thickness, e.g., energy and electron spillout change in discontinuous manner, due to quantum size effects [G. Materzanini, P. Saalfrank, and P. J. D. Lindan, Phys. Rev. B 63, 235405 (2001)]. Here, we demonstrate that oscillatory features arise also for hydrogen when chemisorbed on lead films. Besides stationary properties of the adsorbate, we concentrate on finite vibrational lifetimes of H-surface vibrations. As shown by AIMDEF, the damping via vibration-electron hole pair coupling dominates clearly over the vibration-phonon channel, in particular for high-frequency modes. Vibrational relaxation times are a characteristic function of layer thickness due to the oscillating behaviour of the embedding surface electronic density. Implications derived from AIMDEF for frictional many-atom dynamics, and physisorbed species will also be given.

  18. Thermodynamics of hydration of fullerols [C60(OH)n] and hydrogen bond dynamics in their hydration shells

    Science.gov (United States)

    Keshri, Sonanki; Tembe, B. L.

    2017-02-01

    Molecular dynamics simulations of fullerene and fullerols [C60(OH)n, where n = 2-30] in aqueous solutions have been performed for the purpose of obtaining a detailed understanding of the structural and dynamic properties of these nanoparticles in water. The structures, dynamics and hydration free energies of the solute molecules in water have been analysed. Radial distribution functions, spatial density distribution functions and hydrogen bond analyses are employed to characterize the solvation shells of water around the central solute molecules. We have found that water molecules form two solvation shells around the central solute molecule. Hydrogen bonding in the bulk solvent is unaffected by increasing n. The large decrease in solvation enthalpies of these solute molecules for n > 14 enhances solubilisation. The diffusion constants of solute molecules decrease with increasing n. The solvation free energy of C60 in water is positive (52.8 kJ/mol), whereas its value for C60(OH)30 is highly negative (-427.1 kJ/mol). The effects of surface hydroxylation become more dominant once the fullerols become soluble.

  19. Comparison of Proximally Versus Distally Placed Spatially Distributed Sequential Stimulation Electrodes in a Dynamic Knee Extension Task.

    Science.gov (United States)

    Laubacher, Marco; Aksöz, Efe A; Binder-Macleod, Stuart; Hunt, Kenneth J

    2016-06-13

    Spatially distributed sequential stimulation (SDSS) has demonstrated substantial power output and fatigue benefits compared to single electrode stimulation (SES) in the application of functional electrical stimulation (FES). This asymmetric electrode setup brings new possibilities but also new questions since precise placement of the electrodes is one critical factor for good muscle activation. The aim of this study was to compare the power output, fatigue and activation properties of proximally versus distally placed SDSS electrodes in an isokinetic knee extension task simulating knee movement during recumbent cycling. M. vastus lateralis and medialis of seven able-bodied subjects were stimulated with rectangular bi-phasic pulses of constant amplitude of 40 mA and at an SDSS frequency of 35 Hz for 6 min on both legs with both setups (i.e. n=14). Torque was measured during knee-extension movement by a dynamometer at an angular velocity of 110 deg/s. Mean power, peak power and activation time were calculated and compared for the initial and final stimulation phases, together with an overall fatigue index. Power output values (Pmean, Ppeak) were scaled to a standardised reference input pulse width of 100 μs (Pmean,s, Ppeak,s). The initial evaluation phase showed no significant differences between the two setups for all outcome measures. Ppeak and Ppeak,s were both significantly higher in the final phase for the distal setup (25.4 ± 8.1 W vs. 28.2 ± 6.2 W, p=0.0062 and 34.8 ± 9.5 W vs. 38.9 ± 6.7 W, p=0.021, respectively). With distal SDSS, there was modest evidence of higher Pmean and Pmean,s (p=0.071, p=0.14, respectively) but of longer activation time (p=0.096). The rate of fatigue was similar for both setups. For practical FES applications, distal placement of the SDSS electrodes is preferable.

  20. Molecular collective dynamics in solid para-hydrogen and ortho-deuterium: The Parrinello-Rahman-type path integral centroid molecular dynamics approach

    Science.gov (United States)

    Saito, Hiroaki; Nagao, Hidemi; Nishikawa, Kiyoshi; Kinugawa, Kenichi

    2003-07-01

    The single-particle and collective dynamics of hydrogen/deuterium molecules in solid hcp para-hydrogen (p-H2) and ortho-deuterium (o-D2) has been investigated by using the path integral centroid molecular dynamics (CMD) simulations at zero-pressure and 5.4 and 5.0 K, respectively. For this purpose, we have newly unified the standard CMD method with the Parrinello-Rahman-Nosé-Hoover-chain-type isothermal-isobaric technique. The phonon density of states have been obtained and the dynamic structure factors have been calculated to observe the phonon dispersion relations of both crystals. For solid p-H2, the high energy edge of the phonon energies of solid p-H2 is >13 meV, and the calculated phonon energies are significantly higher than those observed in Nielsen's previous neutron scattering experiments in the energy region >9 meV. The relationship between the present results and the data reported so far is discussed to resolve the outstanding controversy regarding the phonon energies in solid p-H2. On the other hand, the excitation energies for solid o-D2 are in fairly good agreement with those of the neutron experiments. The calculated isothermal compressibility of solid p-H2 is found to be very close to the experimental result.

  1. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama

    2016-09-29

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  2. Molecular dynamics studies of electron-ion temperature equilibration in hydrogen plasmas within the coupled-mode regime

    Science.gov (United States)

    Benedict, Lorin X.; Surh, Michael P.; Stanton, Liam G.; Scullard, Christian R.; Correa, Alfredo A.; Castor, John I.; Graziani, Frank R.; Collins, Lee A.; Čertík, Ondřej; Kress, Joel D.; Murillo, Michael S.

    2017-04-01

    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 =1026cm-3 , Ti=105K , and 107K 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.

  3. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Yukie, E-mail: mori.yukie@ocha.ac.jp; Masuda, Yuichi

    2015-09-08

    Highlights: • MD simulations were performed to study dynamics of strong hydrogen bonds. • Nuclear magnetic relaxation times of proton were measured in solution. • The hydrogen bond of dibenzoylmethane enol is asymmetric in methanol solution. • Formation or breakage of intermolecular hydrogen bonds can trigger proton transfer. • Dimethylsulfoxide may form a bifurcated hydrogen bond with a hydrogen-bonded system. - Abstract: Hydrogen phthalate anion has a short strong O–H–O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl{sub 4}, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the {sup 17

  4. Response to 'Comment on 'The electrochemical Peltier heat of the standard hydrogen electrode reaction' by Zheng Fang et al.' [Thermochimica Acta V 490 (1-2) (2009) 82-84

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zheng, E-mail: zfang@csu.edu.cn [Chemistry and Chemical Engineering College, Central South University, Changsha 410083 (China)

    2009-12-10

    In response to Rockwood's query about the standard state of electron and the handling of the entropy of electron on the absolute scale, an answer is made. Usually, the standard state for a chemical substance is specified based on a classical physical law. The standard state of electron on the absolute scale is determined according to the free electron model on the Fermi-Dirac statistics. However, the thermodynamic handling of the same particle on the different scales must be completely identical, and the difference is only designated values of the thermodynamic parameters. For the standard hydrogen electrode reaction, the electron entropy and the partial molar entropy of hydrogen ion, respectively, are 65.29 J mol{sup -1}K{sup -1} and zero on the conventional scale, and zero and about -22.3 J mol{sup -1} K{sup -1} on the absolute scale at 298.15 K. The other query, related to units used for fugacity, the conversion entropy of electron from gas-phase to metal-phase, the partial molar entropy of electron in the platinum, and the Peltier heat at the platinum/copper joint, is also expatiated.

  5. A hydrogen-evolving Ni(P2N2)2 electrocatalyst covalently attached to a glassy carbon electrode: preparation, characterization, and catalysis. comparisons with the homogeneous analogue.

    Science.gov (United States)

    Das, Atanu K; Engelhard, Mark H; Bullock, R Morris; Roberts, John A S

    2014-07-01

    A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined system shows that a single species predominates with a surface density of 1.3 × 10(-10) mol cm(-2), approaching the value estimated for a densely packed monolayer. With the Ni(II) system, both photoemission and voltammetric data show speciation to unidentified products on coupling, and the surface density is 6.7 × 10(-11) mol cm(-2). The surface-confined Ni(0) complex is an electroctalyst for hydrogen evolution, showing the onset of catalytic current at the same potential as the soluble parent complex. Decomposition of the surface-confined species is observed in acidic acetonitrile. This is interpreted to reflect the lability of the Ni(II)-phosphine interaction and the basicity of the free phosphine and bears on concurrent efforts to implement surface-confined Ni(P2N2)2 complexes in electrochemical or photoelectrochemical devices.

  6. Cathodic H2 gas production through Pd alloy membrane electrodes

    Science.gov (United States)

    Shirogami, T.; Murata, K.

    A rechargeable H2-NiOOH cell with hydrogen-permeable membrane electrode was tested, and its cathodic hydrogen gas production through the membrane electrode investigated. When a Pd-Pt, catalyzed electrolyte-facing surface was cathodically polarized in a concentrated KOH solution, it was found that hydrogen gas was evolved in the chamber through dissolved hydrogen atoms' penetrating of the membrane to exit at the other, palladized surface as free gas.

  7. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

  8. A microbial fuel cell with the three-dimensional electrode applied an external voltage for synthesis of hydrogen peroxide from organic matter

    Science.gov (United States)

    Chen, Jia-yi; Zhao, Lin; Li, Nan; Liu, Hang

    2015-08-01

    The study experimentally investigates the changing performance of three-dimensional electrode H2O2-producting MFCs coupled with simultaneous wastewater treatment at various external cell voltages from 0.1 V to 0.8 V, in order to explore the optimal applied voltage and its reasons. The graphite particle electrodes made of graphite powders with polytetrafluoroethene (PTFE) as the binder are used as three-dimensional cathode. The results indicate that applied voltage is demonstrated to increase the productive rate and output of H2O2 and the efficiency of acetate degradation. Besides, a relatively high current density caused by a high applied voltage has a positive impact on anode performance in terms of organic degradation and coulombic efficiency. In addition, a relatively high voltage leads to the reduction of H2O2 and the evolution of H2. Considering H2O2 concentration, anodic COD removal and current efficiencies of MFCs at various voltages, the optimal voltage is chosen to be 0.4 V, achieving the H2O2 generation of 705.6 mg L-1 at a rate of 2.12 kg m-3 day-1 and 76% COD removal in 8 h, with energy input of 0.659 kWh per kg H2O2. Coulombic efficiency, faradic efficiency and COD conversion efficiency are 92%, 96%, and 88% respectively.

  9. Analysis of protein conformation and dynamics by hydrogen/deuterium exchange MS.

    Science.gov (United States)

    Engen, John R

    2009-10-01

    Understanding as much as possible about proteins in the shortest amount of time has long been a goal of hydrogen exchange (HX) MS. Recent technological advances have led to improvements in the technique, but has this goal yet been achieved? (To listen to a podcast about this Feature, please go to the Analytical Chemistry Web site at pubs.acs.org/journal/ancham.).

  10. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: excitation dynamics and ion flux asymmetry

    NARCIS (Netherlands)

    Bruneau, B.; Diomede, P.; Economou, D. J.; Longo, S.; Gans, T.; O’Connell, D.; Greb, A.; Johnson, E.; Booth, J. P.

    2016-01-01

    Parallel plate capacitively coupled plasmas in hydrogen at relatively high pressure ( 1 Torr) are excited with tailored voltage waveforms containing up to five frequencies. Predictions of a hybrid model combining a particle-in-cell simulation with Monte Carlo collisions and a fluid model

  11. Dynamics of flames near the rich-flammability limit of hydrogen-air mixtures

    Science.gov (United States)

    Kailasanath, K.; Ganguly, K.; Patnaik, G.

    1993-01-01

    Flames near the rich-flammability limit of hydrogen-air mixtures are studied using a detailed, time-dependent, one-dimensional Lagrangian model. Results from the numerical simulations indicate that a steady burning velocity is not obtained for very rich hydrogen-air mixtures. As the amount of hydrogen is increased, a damped oscillation is observed in the flame and burning velocities, and then, with further increase in the amount of hydrogen, an undamped oscillation with a complex set of frequencies is observed. Simulations with a simplified one-step irreversible chemical reaction do not show these oscillations, suggesting that chemical kinetics plays a strong role in inducing these oscillations. Further analysis shows that the oscillations are due to a competition for H atoms between chain branching and chain-terminating reactions. Simulations of spherically expanding flames suggest that stretch effects (due to curvature) will cause the oscillations to occur in less rich mixtures than that observed for planar flames. The implications of these oscillations on the rich-flammability limit as well as the role of chemical kinetics in creating a fundamental flammability limit is discussed.

  12. Resonant Scattering of Muonic Hydrogen Atoms and Dynamics of Muonic Molecular Complex

    CERN Document Server

    Fujiwara, M C; Bailey, J M; Beer, G A; Beveridge, J L; Faifman, M P; Huber, T M; Kammel, P; Kim, S K; Knowles, P E; Kunselman, A R; Maier, M; Markushin, V E; Marshall, G M; Martoff, C J; Mason, G R; Mulhauser, F; Olin, A; Petitjean, C; Porcelli, T A; Wozniak, J; Zmeskal, J

    2001-01-01

    Resonant scattering of muonic hydrogen atoms via back decay of molecular complex, a key process in the understanding of epithermal muonic molecular formation, is analyzed. The limitations of the effective rate approximation are discussed and the importance of the explicit treatment of the back decay is stressed. An expression of the energy distribution for the back-decayed atoms is given.

  13. Car-Parrinello and path integral molecular dynamics study of the hydrogen bond in the chloroacetic acid dimer system.

    Science.gov (United States)

    Durlak, Piotr; Morrison, Carole A; Middlemiss, Derek S; Latajka, Zdzislaw

    2007-08-14

    We have studied the double proton transfer (DPT) reaction in the cyclic dimer of chloroacetic acid using both classical and path integral Car-Parrinello molecular dynamics. We also attempt to quantify the errors in the potential energy surface that arise from the use of a pure density functional. In the classical dynamics a clear reaction mechanism can be identified, where asynchronized DPT arises due to coupling between the O-H stretching oscillator and several low energy intermolecular vibrational modes. This mechanism is considerably altered when quantum tunneling is permitted in the simulation. The introduction of path integrals leads to considerable changes in the thermally averaged molecular geometry, leading to shorter and more centered hydrogen bond linkages.

  14. Car-Parrinello and path integral molecular dynamics study of the hydrogen bond in the chloroacetic acid dimer system

    Science.gov (United States)

    Durlak, Piotr; Morrison, Carole A.; Middlemiss, Derek S.; Latajka, Zdzislaw

    2007-08-01

    We have studied the double proton transfer (DPT) reaction in the cyclic dimer of chloroacetic acid using both classical and path integral Car-Parrinello molecular dynamics. We also attempt to quantify the errors in the potential energy surface that arise from the use of a pure density functional. In the classical dynamics a clear reaction mechanism can be identified, where asynchronized DPT arises due to coupling between the O-H stretching oscillator and several low energy intermolecular vibrational modes. This mechanism is considerably altered when quantum tunneling is permitted in the simulation. The introduction of path integrals leads to considerable changes in the thermally averaged molecular geometry, leading to shorter and more centered hydrogen bond linkages.

  15. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols

    Science.gov (United States)

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K.

    2017-02-01

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  16. Study of the dynamics of the electrode plasma in a high-current magnetically insulated transmission line

    Science.gov (United States)

    Bakshaev, Yu. L.; Bartov, A. V.; Blinov, P. I.; Chernenko, A. S.; Dan'ko, S. A.; Kalinin, Yu. G.; Kingsep, A. S.; Korolev, V. D.; Mizhiritskiĭ, V. I.; Smirnov, V. P.; Shashkov, A. Yu.; Sasorov, P. V.; Tkachenko, S. I.

    2007-04-01

    A series of experiments was carried out in the S-300 facility (3 MA, 0.15 Θ, 100 ns) to study the behavior of a section of a magnetically insulated transmission line (MITL) at current densities of up to 500 MA/cm2 and linear current densities of up to 6 MA/cm (i.e., at parameters close to those expected in a fast Z-pinch fusion reactor projected in Sandia National Laboratories). The surface explosion of the ohmically heated MITL electrode is accompanied by the formation of a plasma layer on its surface. This can deteriorate of the transmission properties of the line because the vacuum gap is short-circuited by the plasma produced. The parameters of the electrode plasma and its effect on the MITL transmission properties were investigated experimentally. Possible consequences of the above effects are evaluated, and MHD simulations of the electrode explosion and the subsequent spread of the plasma layer are performed. It is shown that the time during which an MITL segment preserves its transmission properties conforms to the requirements of the conceptual fusion reactor.

  17. Modelling (1 0 0) hydrogen-induced platelets in silicon with a multi-scale molecular dynamics approach

    Energy Technology Data Exchange (ETDEWEB)

    Moras, G. [Department of Physics, King' s College London, Strand, London WC2R 2LS (United Kingdom)], E-mail: gianpietro.moras@kcl.ac.uk; Colombi Ciacchi, L. [Fraunhofer Institut fuer Werkstoffmechanik, Woehlerstrasse 11, 79108 Freiburg (Germany); Institut fuer Zuverlaessigkeit von Bauteilen und Systemen, University of Karlsruhe, Kaiserstrasse 12, 76131 Karlsruhe (Germany); Csanyi, G. [Department of Engineering, Centre for Micromechanics, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ (United Kingdom); De Vita, A. [Department of Physics, King' s College London, Strand, London WC2R 2LS (United Kingdom); INFM-DEMOCRITOS National Simulation Centre and Centre of Excellence for Nanostructured Materials (CENMAT), University of Trieste (Italy)

    2007-12-15

    We introduce a multiscale molecular dynamics (MD) approach to study the thermal evolution of (1 0 0) hydrogen-induced platelets (HIPs) in silicon. The HIPs are modeled by {approx}10 nm long planar defects in a periodically repeated crystalline model system containing {approx}25,000 silicon atoms. The initial defect models are created either by cleavage of atomic planes or by planar assemblies of vacancies, and are stabilized by saturating the resulting surface dangling bonds with hydrogen atoms. The time evolution of the defects is studied by finite-temperature MD using the 'Learn On The Fly' (LOTF) technique. This hybrid scheme allows us to perform accurate density-functional-tight-binding (DFTB) force calculations only on the chemically reactive platelet zone, while the surrounding silicon crystal is described by the Stillinger-Weber (SW) classical potential. Reliable dynamical trajectories are obtained by choosing the DFTB zone in a way which minimizes the errors on the atomic forces.

  18. Comparison of Proximally Versus Distally Placed Spatially Distributed Sequential Stimulation Electrodes in a Dynamic Knee Extension Task

    Science.gov (United States)

    Laubacher, Marco; Aksöz, Efe A.; Binder-Macleod, Stuart; Hunt, Kenneth J.

    2016-01-01

    Spatially distributed sequential stimulation (SDSS) has demonstrated substantial power output and fatigue benefits compared to single electrode stimulation (SES) in the application of functional electrical stimulation (FES). This asymmetric electrode setup brings new possibilities but also new questions since precise placement of the electrodes is one critical factor for good muscle activation. The aim of this study was to compare the power output, fatigue and activation properties of proximally versus distally placed SDSS electrodes in an isokinetic knee extension task simulating knee movement during recumbent cycling. M. vastus lateralis and medialis of seven able-bodied subjects were stimulated with rectangular bi-phasic pulses of constant amplitude of 40 mA and at an SDSS frequency of 35 Hz for 6 min on both legs with both setups (i.e. n=14). Torque was measured during knee-extension movement by a dynamometer at an angular velocity of 110 deg/s. Mean power, peak power and activation time were calculated and compared for the initial and final stimulation phases, together with an overall fatigue index. Power output values (Pmean, Ppeak) were scaled to a standardised reference input pulse width of 100 μs (Pmean,s, Ppeak,s). The initial evaluation phase showed no significant differences between the two setups for all outcome measures. Ppeak and Ppeak,s were both significantly higher in the final phase for the distal setup (25.4 ± 8.1 W vs. 28.2 ± 6.2 W, p=0.0062 and 34.8 ± 9.5 W vs. 38.9 ± 6.7 W, p=0.021, respectively). With distal SDSS, there was modest evidence of higher Pmean and Pmean,s (p=0.071, p=0.14, respectively) but of longer activation time (p=0.096). The rate of fatigue was similar for both setups. For practical FES applications, distal placement of the SDSS electrodes is preferable. PMID:27478563

  19. Comparison of proximally versus distally placed spatially distributed sequential stimulation electrodes in a dynamic knee extension task

    Directory of Open Access Journals (Sweden)

    Marco Laubacher

    2016-06-01

    Full Text Available Spatially distributed sequential stimulation (SDSS has demonstrated substantial power output and fatigue benefits compared to single electrode stimulation (SES in the application of functional electrical stimulation (FES. This asymmetric electrode setup brings new possibilities but also new questions since precise placement of the electrodes is one critical factor for good muscle activation. The aim of this study was to compare the power output, fatigue and activation properties of proximally versus distally placed SDSS electrodes in an isokinetic knee extension task simulating knee movement during recumbent cycling. M. vastus lateralis and medialis of seven able-bodied subjects were stimulated with rectangular bi-phasic pulses of constant amplitude of 40 mA and at an SDSS frequency of 35 Hz for 6 min on both legs with both setups (i.e. n=14. Torque was measured during knee-extension movement by a dynamometer at an angular velocity of 110 deg/s. Mean power, peak power and activation time were calculated and compared for the initial and final stimulation phases, together with an overall fatigue index. Power output values (Pmean, Ppeak were scaled to a standardised reference input pulse width of 100 μs (Pmean,s, Ppeak,s. The initial evaluation phase showed no significant differences between the two setups for all outcome measures. Ppeak and Ppeak,s were both significantly higher in the final phase for the distal setup (25.4 ± 8.1 W vs. 28.2 ± 6.2 W, p=0.0062 and 34.8 ± 9.5 W vs. 38.9 ± 6.7 W, p=0.021, respectively. With distal SDSS, there was modest evidence of higher Pmean and Pmean,s (p=0.071, p=0.14, respectively but of longer activation time (p=0.096. The rate of fatigue was similar for both setups. For practical FES applications, distal placement of the SDSS electrodes is preferable.

  20. A planar microfabricated electrolyzer for hydrogen and oxygen generation

    Science.gov (United States)

    Jiang, L.; Myer, B.; Tellefsen, K.; Pau, S.

    We present the design, fabrication and testing of a microfabricated planar reactor for the hydrogen evolution reaction (HER) using thin film Pt electrodes and polydimethylsiloxane (PDMS) fluidic chamber. The reactor is designed to separate gases by flow dynamics and reactor flow is analyzed by three-dimensional finite element analysis. The planar geometry is scalable, compact and stackable. Using KOH 28 wt% electrolyte, we have achieved a hydrogen generation density of 0.23 kg h -1 m -3 and an efficiency of 48% with a flow rate of 10 ml min -1 and cell voltage of 3 V.

  1. Investigation of cryogenic hydrogen storage on high surface area activated carbon. Equilibrium and dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Paggiaro, Ricardo Gaspar

    2008-11-29

    This thesis investigates cryo-adsorptive systems for hydrogen storage for mobile applications. By means of macroscopic and microscopic balance models, an extensive analysis is carried out, including among others the investigation of the thermal effects during high-pressure system filling, venting losses during normal operation and inactivity, time-course of system pressure and temperature and gas delivery under various operating conditions. Model results were compared with experimental data, good agreement was obtained. The analysis also includes a comparison to other storage technologies such as cryo-compressed gas and liquefaction storage. The results show that cryo-adsorptive systems have storage characteristics comparable to compressed gas systems, but at a much lower pressure. They are also energetically more efficient than liquid hydrogen systems. However, the necessity of cryotemperatures and thermal management during operation and filling might limit their application. (orig.)

  2. Spectroscopy and Dynamics of Molecular and Ionic Impurities Embedded in Solid Hydrogen

    Science.gov (United States)

    1993-09-01

    hexagonal close packed (hcp) or face centered cubic ( fcc ) structure . Fundamental properties of solid hydrogen are sum- marized in a review by Silvera... fcc structure in which each molecular site is a center of symmetry. This is because each neighbor molecule has its counterpart at the position diamet...and found no other spectral features. This indicates that our crystal has a purely hcp structure. A crystal with mixed hcp and fcc structure would give

  3. On the lattice dynamics of metallic hydrogen and other Coulomb systems

    Science.gov (United States)

    Beck, H.; Straus, D.

    1975-01-01

    Numerical results for the phonon spectra of metallic hydrogen and other Coulomb systems in cubic lattices are presented. In second order in the electron-ion interaction, the behavior of the dielectric function of the interacting electron gas for arguments around the seond Fermi harmonic leads to drastic Kohn anomalies and even to imaginary phonon frequencies. Third-order band-structure corrections are also calculated. Properties of self-consistent phonons and the validity of the adiabatic approximation are discussed.

  4. Femtosecond Hydrogen Bond Dynamics of Bulk-like and Bound Water at Positively and Negatively Charged Lipid Interfaces Revealed by 2D HD-VSFG Spectroscopy.

    Science.gov (United States)

    Singh, Prashant Chandra; Inoue, Ken-Ichi; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Tahara, Tahei

    2016-08-26

    Interfacial water in the vicinity of lipids plays an important role in many biological processes, such as drug delivery, ion transportation, and lipid fusion. Hence, molecular-level elucidation of the properties of water at lipid interfaces is of the utmost importance. We report the two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) study of the OH stretch of HOD at charged lipid interfaces, which shows that the hydrogen bond dynamics of interfacial water differ drastically, depending on the lipids. The data indicate that the spectral diffusion of the OH stretch at a positively charged lipid interface is dominated by the ultrafast (dynamics, while the dynamics at a negatively charged lipid interface exhibit sub-picosecond dynamics almost exclusively, implying that fast hydrogen bond fluctuation is prohibited. These results reveal that the ultrafast hydrogen bond dynamics at the positively charged lipid-water interface are attributable to the bulk-like property of interfacial water, whereas the slow dynamics at the negatively charged lipid interface are due to bound water, which is hydrogen-bonded to the hydrophilic head group.

  5. Dynamic response of a carbon nanotube-based rotary nano device with different carbon-hydrogen bonding layout

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Hang [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Cai, Kun, E-mail: caikun1978@163.com [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Wan, Jing [College of Water Resources and Architectural Engineering, Northwest A& F University, Yangling 712100 (China); Gao, Zhaoliang, E-mail: coopcg@163.com [Institute of Soil and Water Conservation, Northwest A& F University, Yangling, 712100 (China); Chen, Zhen [State Key Laboratory of Structural Analysis for Industrial Equipment, Department of Engineering Mechanics, Faculty of Vehicle Engineering and Mechanics, Dalian University of Technology, Dalian 116024 (China)

    2016-03-01

    Graphical abstract: - Highlights: • The rotational transmission performance of a rotational transmission system (RTS) with different types of C−H bonding layouts on the edge of motor and rotor is investigated using MD simulation method. • The L–J interaction between covalently bonded hydrogen atoms and sp1 carbon atoms is too weak to support a stable rotational transmission when only the motor or rotor has bonded hydrogen atoms. • When both the motor and rotor have the same C−H bonding layout on their adjacent ends, a stable output rotational speed of rotor can be obtained. • A low input rotational speed (e.g., 100 GHz) would lead to a synchronous rotational transmission if the system has (+0.5H) C−H bonding layout. - Abstract: In a nano rotational transmission system (RTS) which consists of a single walled carbon nanotube (SWCNT) as the motor and a coaxially arranged double walled carbon nanotube (DWCNT) as a bearing, the interaction between the motor and the rotor in bearing, which has great effects on the response of the RTS, is determined by their adjacent edges. Using molecular dynamics (MD) simulation, the interaction is analyzed when the adjacent edges have different carbon-hydrogen (C−H) bonding layouts. In the computational models, the rotor in bearing and the motor with a specific input rotational speed are made from the same armchair SWCNT. Simulation results demonstrate that a perfect rotational transmission could happen when the motor and rotor have the same C−H bonding layout on their adjacent ends. If only half or less of the carbon atoms on the adjacent ends are bonded with hydrogen atoms, the strong attraction between the lower speed (100 GHz) motor and rotor leads to a synchronous rotational transmission. If only the motor or the rotor has C−H bonds on their adjacent ends, no rotational transmission happens due to weak interaction between the bonded hydrogen atoms on one end with the sp{sup 1} bonded carbon atoms on the other

  6. The microstructures and electrochemical performances of La0.6Gd0.2Mg0.2Ni3.0Co0.5-xAlx (x=0-0.5) hydrogen storage alloys as negative electrodes for nickel/metal hydride secondary batteries

    Science.gov (United States)

    Li, Rongfeng; Xu, Peizhen; Zhao, Yamin; Wan, Jing; Liu, Xiaofang; Yu, Ronghai

    2014-12-01

    La0.6Gd0.2Mg0.2Ni3.0Co0.5-xAlx (x = 0-0.5) hydrogen storage alloys were prepared by induction melting followed by annealing treatment at 1173 K for 8 h. The effects of substitution Al for Co on the microstructures and electrochemical performances were studied systematically. The structure analyses show that all alloys consist of multiphase structures such as (La, Mg)2Ni7 phase, (La, Mg) Ni3 phase and LaNi5 phase. The abundance of (La, Mg)2Ni7 phase decreases while the abundance of LaNi5 phase and (La, Mg)Ni3 phase increases directly as the Al content increasing. The electrochemical tests show that the maximum discharge capacity of alloy electrodes are almost unchanged when x ≤ 0.2 while the cyclic stability of the alloy electrode are improved significantly after proper amount of Al substitution for Co. The alloy electrode with x = 0.1 exhibits the better balance between discharge capacity and cycling life than any others. Moreover, at the discharge current density of 900 mA g-1, the high rate dischargeability (HRD) of the alloy electrodes decreases with increasing Al substitution and the relative analyses reveal that the charge transfer on alloy surface is more important than the hydrogen diffusion in alloy bulk for the kinetic properties of the alloy electrodes.

  7. Interactions of hydrogen with amorphous hafnium oxide

    Science.gov (United States)

    Kaviani, Moloud; Afanas'ev, Valeri V.; Shluger, Alexander L.

    2017-02-01

    We used density functional theory (DFT) calculations to study the interaction of hydrogen with amorphous hafnia (a -HfO2 ) using a hybrid exchange-correlation functional. Injection of atomic hydrogen, its diffusion towards electrodes, and ionization can be seen as key processes underlying charge instability of high-permittivity amorphous hafnia layers in many applications. Hydrogen in many wide band gap crystalline oxides exhibits negative-U behavior (+1 and -1 charged states are thermodynamically more stable than the neutral state) . Our results show that in a -HfO2 hydrogen is also negative-U, with charged states being the most thermodynamically stable at all Fermi level positions. However, metastable atomic hydrogen can share an electron with intrinsic electron trapping precursor sites [Phys. Rev. B 94, 020103 (2016)., 10.1103/PhysRevB.94.020103] forming a [etr -+O -H ] center, which is lower in energy on average by about 0.2 eV. These electron trapping sites can affect both the dynamics and thermodynamics of the interaction of hydrogen with a -HfO2 and the electrical behavior of amorphous hafnia films in CMOS devices.

  8. A study of hydrogen-bond dynamics in carboxylic acids by NMR T1 measurements: isotope effects and hydrogen-bond length dependence

    Science.gov (United States)

    Agaki, T.; Imashiro, F.; Terao, T.; Hirota, N.; Hayashi, S.

    1987-08-01

    Proton (deuteron) transfer of hydrogen bonds in benzoic, glutaric and p-formylbenzoic acids was studied by proton (deuteron) T1 measurements. Deuteration of carboxylic protons was found to increase the barriers to classical proton jumping as well as quantum-mechanical tunneling. The former barriers increase as the hydrogen-bond distance increases.

  9. Electrode structures and surfaces for Li batteries

    Energy Technology Data Exchange (ETDEWEB)

    Thackeray, Michael M.; Kang, Sun-Ho; Balasubramanian, Mahalingam; Croy, Jason

    2017-03-14

    This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.

  10. Hydrogen-based electrochemical energy storage

    Science.gov (United States)

    Simpson, Lin Jay

    2013-08-06

    An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

  11. Synchrotron infrared spectroscopy at megabar pressures - Vibrational dynamics of hydrogen to 180 GPa

    Science.gov (United States)

    Hanfland, M.; Hemley, R. J.; Mao, H. K.; Williams, G. P.

    1992-01-01

    New techniques for measuring infrared spectra at megabar pressures using synchrotron radiation have been developed and applied to study the Q1(1), Qi(1) + Si(0), and QR(J) vibrational transitions of solid hydrogen to 180 GPa. The frequency difference between the Q1(1) infrared and Raman vibrons increases from 3/cm (zero pressure) to 510/cm (180 GPa), indicating a dramatic increase in intermolecular coupling with pressure. A negative frequency shift is observed for the infrared vibron above 140 GPa. A significant increase in frequency and LO-TO splitting of the lattice phonon is also documented.

  12. Path integral molecular dynamics simulation of solid para-hydrogen with an aluminum impurity

    Science.gov (United States)

    Mirijanian, Dina T.; Alexander, Millard H.; Voth, Gregory A.

    2002-11-01

    The equilibrium properties of an aluminum impurity trapped in solid para-hydrogen have been studied. The results were compared to those of a previous study by Krumrine et al. [J. Chem. Phys. 113 (2000) 9079] with an atomic boron. In the presence of vacancy defect, when the orientation-dependent Al- pH 2 potential is used, the Al atom is displaced to a position half way between its original substituted site and the vacancy site. Thermodynamic results also indicate that the presence of a neighboring vacancy helps to stabilize the Al impurity to a far greater extent than in the case of the B impurity.

  13. Neutron Scattering of Residual Hydrogen in 1,4-Dioxane-D8 Liquid. Understanding Measurements with Molecular Dynamics Simulations

    Energy Technology Data Exchange (ETDEWEB)

    de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Liu, Hongjun [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Herwig, Kenneth W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kidder, Michelle [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-01-25

    That incoherent scattering from protiated molecular liquids adds a constant background to the measured scattering intensity is well known, but less appreciated is the fact that coherent scattering is also induced by the presence of hydrogen in a deuterated liquid. In fact, the scattering intensity can be very sensitive, in the small-q region, with respect to the amounts and distribution of residual H in the system. We used 1,4-dioxane liquid to demonstrate that the partial structure factors of the HD and DD atom pairs contribute significantly to inter-molecular scattering and that uncertainty in the extent of deuteration account for discrepancies between simulations and measurements. Both contributions to uncertainty have similar magnitudes: scattering interference of the hydrogen-deuterium pair, and complementary interference from the deuterium-deuterium pair by virtue of chemical inhomogeneity. This situation arises in practice since deuteration of liquids is often 99% or less. A combined experimental and extensive computational study of static thermal neutron scattering of 1,4-dioxane demonstrates the foregoing. We show, through simulations, that the reason for the differences is the content of protiated dioxane (vendors quote 1%). We estimate that up to 5% (at 298K and at 343K) protiated mole fraction may be involved in generating the scattering differences. Finally, we find that the particular distribution of hydrogen in the protiated molecules affects the results significantly; here we considered molecules to be either fully protiated or fully deuterated. This scenario best reconciles the computational and experimental results, and leads us to speculate that the deuteration synthesis process tends to leave a molecule either fully deuterated or fully protiated. Although we have used 1,4-dioxane as a model liquid, the effects described in this study extend to similar liquids and similar systematic experimental/computational studies can be performed to either

  14. Visualization and Interpretation of Attosecond Electron Dynamics in Laser-Driven Hydrogen Molecular Ion using Bohmian Trajectories

    CERN Document Server

    Takemoto, Norio

    2010-01-01

    We analyze the attosecond electron dynamics in hydrogen molecular ion driven by an external intense laser field using ab-initio numerical simulations of the corresponding time-dependent Schr{\\"{o}}dinger equation and Bohmian trajectories. To this end, we employ a one-dimensional model of the molecular ion in which the motion of the protons is frozen. The results of the Bohmian trajectory calculations do agree well with those of the ab-initio simulations and clearly visualize the electron transfer between the two protons in the field. In particular, the Bohmian trajectory calculations confirm the recently predicted attosecond transient localization of the electron at one of the protons and the related multiple bunches of the ionization current within a half cycle of the laser field. Further analysis based on the quantum trajectories shows that the electron dynamics in the molecular ion can be understood via the phase difference accumulated between the Coulomb wells at the two protons. Modeling of the dynamics ...

  15. Grasping hydrogen adsorption and dynamics in metal-organic frameworks using (2)H solid-state NMR.

    Science.gov (United States)

    Lucier, Bryan E G; Zhang, Yue; Lee, Kelly J; Lu, Yuanjun; Huang, Yining

    2016-06-18

    Record greenhouse gas emissions have spurred the search for clean energy sources such as hydrogen (H2) fuel cells. Metal-organic frameworks (MOFs) are promising H2 adsorption and storage media, but knowledge of H2 dynamics and adsorption strengths in these materials is lacking. Variable-temperature (VT) (2)H solid-state NMR (SSNMR) experiments targeting (2)H2 gas (i.e., D2) shed light on D2 adsorption and dynamics within six representative MOFs: UiO-66, M-MOF-74 (M = Zn, Mg, Ni), and α-M3(COOH)6 (M = Mg, Zn). D2 binding is relatively strong in Mg-MOF-74, Ni-MOF-74, α-Mg3(COOH)6, and α-Zn3(COOH)6, giving rise to broad (2)H SSNMR powder patterns. In contrast, D2 adsorption is weaker in UiO-66 and Zn-MOF-74, as evidenced by the narrow (2)H resonances that correspond to rapid reorientation of the D2 molecules. Employing (2)H SSNMR experiments in this fashion holds great promise for the correlation of MOF structural features and functional groups/metal centers to H2 dynamics and host-guest interactions.

  16. Photoelectrochemical Hydrogen Production

    CERN Document Server

    Krol, R van de

    2012-01-01

    Photoelectrochemical Hydrogen Production describes the principles and materials challenges for the conversion of sunlight into hydrogen through water splitting at a semiconducting electrode. Readers will find an analysis of the solid state properties and materials requirements for semiconducting photo-electrodes, a detailed description of the semiconductor/electrolyte interface, in addition to the photo-electrochemical (PEC) cell. Experimental techniques to investigate both materials and PEC device performance are outlined, followed by an overview of the current state-of-the-art in PEC materia

  17. Bulk Hydrogen Content OF High-Silica Rocks in Gale Crater With the Active Dynamic Albedo of Neutrons Experiment

    Science.gov (United States)

    Gabriel, T. S. J.; Hardgrove, C.; Litvak, M.; Mitrofanov, I.; Boynton, W. V.; Fedosov, F.; Golovin, D.; Jun, I.; Mischna, M.; Tate, C. G.; Moersch, J.; Harshman, K.; Kozyrev, A. S.; Malakhov, A.; Mokrousov, M.; Nikiforov, S.; Sanin, A. B.; Vostrukhin, A.; Archer, P. D., Jr.; Franz, H. B.; Thompson, L.

    2017-01-01

    The Mars Science Laboratory (MSL) Curiosity rover recently traversed over plateaus of mafic aeolian sandstones (the 'Stimson' formation) that overlie mudstones (the 'Murray' formation). Within the Stimson formation we observed many lighter-toned, halo-forming features, that are potentially indicative of fluid alteration (see Fig. 1). These halo features extend for tens of meters laterally and are approx.1 meter wide. The halo features were characterized by Curiosity's geochemical instruments: Alpha Proton X-Ray Spectrometer (APXS), Chemin, Chemcam and Sample Analysis at Mars (SAM). With respect to the host (unaltered) Stimson rocks, fracture halos were significantly enriched in silicon and low in iron [1]. Changes in hydrogen abundance (due to its large neutron scattering cross section) greatly influence the magnitude of the thermal neutron response from the Dynamic Albedo of Neutrons (DAN) instrument [2]. There are also some elemental species, e.g. chlorine, iron, and nickel, that have significant microscopic neutron absorption cross sections. These elements can be abundant and variable results provide a useful estimate of the lower bound for bulk hydrogen content (assuming a homogeneous distribution).

  18. Light-field-characterization in a continuous hydrogen-producing photobioreactor by optical simulation and computational fluid dynamics.

    Science.gov (United States)

    Krujatz, Felix; Illing, Rico; Krautwer, Tobias; Liao, Jing; Helbig, Karsten; Goy, Katharina; Opitz, Jörg; Cuniberti, Gianaurelio; Bley, Thomas; Weber, Jost

    2015-12-01

    Externally illuminated photobioreactors (PBRs) are widely used in studies on the use of phototrophic microorganisms as sources of bioenergy and other photobiotechnology research. In this work, straightforward simulation techniques were used to describe effects of varying fluid flow conditions in a continuous hydrogen-producing PBR on the rate of photofermentative hydrogen production (rH2 ) by Rhodobacter sphaeroides DSM 158. A ZEMAX optical ray tracing simulation was performed to quantify the illumination intensity reaching the interior of the cylindrical PBR vessel. 24.2% of the emitted energy was lost through optical effects, or did not reach the PBR surface. In a dense culture of continuously producing bacteria during chemostatic cultivation, the illumination intensity became completely attenuated within the first centimeter of the PBR radius as described by an empirical three-parametric model implemented in Mathcad. The bacterial movement in chemostatic steady-state conditions was influenced by varying the fluid Reynolds number. The "Computational Fluid Dynamics" and "Particle Tracing" tools of COMSOL Multiphysics were used to visualize the fluid flow pattern and cellular trajectories through well-illuminated zones near the PBR periphery and dark zones in the center of the PBR. A moderate turbulence (Reynolds number = 12,600) and fluctuating illumination of 1.5 Hz were found to yield the highest continuous rH2 by R. sphaeroides DSM 158 (170.5 mL L(-1) h(-1) ) in this study.

  19. Charge Transfer Dynamics in Semiconductor Quantum Dots Relevant to Solar Hydrogen Production

    Science.gov (United States)

    Krauss, Todd

    Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. For example, in light-driven proton reduction to molecular hydrogen, a light-absorbing molecule (the photosensitizer) rapidly transfers a photoexcited electron to a catalyst for reducing protons. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. To understand why this system has such extraordinary catalytic behavior, ultrafast transient absorption (TA) spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts were performed. CdSe QDs transfer photoexcited electrons to a Ni-dihydrolipoic acid (Ni-DHLA) catalyst complex extremely fast and with high efficiency. Even under high fluence, the relative fraction of TA signal due to ET remains well over 80%, and depopulation from exciton-exciton annihilation is minimal (6%). We also found that increasing QD size and/or shelling the core CdSe QDs with a shell of CdS slowed the ET rate, in agreement with the relative efficiency of photochemical H2 generation. The extremely fast ET provides a fundamental explanation for the exceptional photocatalytic H2 activity of the CdSe QD/Ni-DHLA system and guides new directions for further improvements.

  20. A TDDFT/EFP1 study on hydrogen bonding dynamics of coumarin 151 in water

    Science.gov (United States)

    Ramegowda, Mariyappa

    2015-02-01

    Change in energy of hydrogen bonds (HBs) upon excitation, plays an important role on the spectra of chemical and biological molecules. Effective fragment potential (EFP) method of explicit water molecules embedded in polarizable continuum medium (PCM) is used for the solvation of 7-Amino-4-(trifluoromethyl)coumarin (C151). Time dependent density functional theory (TDDFT) calculations combined with EFP/PCM had been carried out to study the electronic structure and the exited state properties of C151 with five water molecules (C151-(H2O)5 complex). S0 state and S1 state geometries were optimized using DFT/TDDFT with PBE0 functional combined with cc-pVDZ basis set, the transition energies are computed with same basis set and functional. Change in HB energy is calculated using the procedure proposed by T. Nagata et al. to calculate solute-solvent interaction energy in Nagata et al. (2011). Upon photoexcitation of C151-(H2O)5 complex, A type (N⋯Hsbnd O) HB is weakened with decrease of energy by 4.37 kJ/mol, whereas B and C type (Cdbnd O⋯Hsbnd O and Nsbnd H⋯O) HBs are strengthened with increase of 5.62 and 10.21 kJ/mol energy, respectively. This study again confirmed that the intermolecular hydrogen bonds between C151 chromophore and aqueous solvents are strengthened, not cleaved upon electronic excitation.

  1. Dynamics of two interacting hydrogen bubbles in liquid aluminum under the influence of a strong acoustic field

    Science.gov (United States)

    Lebon, Gerard S. B.; Pericleous, Koulis; Tzanakis, Iakovos; Eskin, Dmitry G.

    2015-10-01

    Ultrasonic melt processing significantly improves the properties of metallic materials. However, this promising technology has not been successfully transferred to the industry because of difficulties in treating large volumes of melt. To circumvent these difficulties, a fundamental understanding of the efficiency of ultrasonic treatment of liquid metals is required. In this endeavor, the dynamics of two interacting hydrogen bubbles in liquid aluminum are studied to determine the effect of a strong acoustic field on their behavior. It is shown that coalescence readily occurs at low frequencies in the range of 16 to 20 kHz; forcing frequencies at these values are likely to promote degassing. Emitted acoustic pressures from relatively isolated bubbles that resonate with the driving frequency are in the megapascal range and these cavitation shock waves are presumed to promote grain refinement by disrupting the growth of the solidification front.

  2. Low-temperature phases of dense hydrogen and deuterium by first-principles path-integral molecular dynamics

    Science.gov (United States)

    Torrent, Marc; Geneste, Gregory

    2012-02-01

    The low-temperature phases of dense hydrogen and deuterium have been investigated using first-principles path-integral molecular dynamics, a technique that we have recently implemented in the ABINIT code and that allows to account for the quantum fluctuations of atomic nuclei. A massively parallelized scheme is applied to produce trajectories of several tens of thousands steps using a 64-atom supercell and a Trotter number of 64. The so-called phases I, II and III are studied and compared to the structures proposed in the literature. The quantum fluctuations produce configurational disorder and are shown to systematically enhance the symmetry of the system: a continuous gain of symmetry in the angular density of probability of the molecules is found from classical particles to quantum D2 and finally to quantum H2. Particular emphasis is made on the ``broken-symmetry'' phase (phase II).

  3. π-Hydrogen Bonding of Aromatics on the Surface of Aerosols: Insights from Ab Initio and Molecular Dynamics Simulation.

    Science.gov (United States)

    Feng, Ya-Juan; Huang, Teng; Wang, Chao; Liu, Yi-Rong; Jiang, Shuai; Miao, Shou-Kui; Chen, Jiao; Huang, Wei

    2016-07-14

    Molecular level insight into the interaction between volatile organic compounds (VOCs) and aerosols is crucial for improvement of atmospheric chemistry models. In this paper, the interaction between adsorbed toluene, one of the most significant VOCs in the urban atmosphere, and the aqueous surface of aerosols was studied by means of combined molecular dynamics simulations and ab initio quantum chemistry calculations. It is revealed that toluene can be stably adsorbed on the surface of aqueous droplets via hydroxyl-π hydrogen bonding between the H atoms of the water molecules and the C atoms in the aromatic ring. Further, significant modifications on the electrostatic potential map and frontier molecular orbital are induced by the solvation effect of surface water molecules, which would affect the reactivity and pathway of the atmospheric photooxidation of toluene. This study demonstrates that the surface interactions should be taken into consideration in the atmospheric chemical models on oxidation of aromatics.

  4. Dynamics of the atmospheric pressure diffuse dielectric barrier discharge between cylindrical electrodes in roll-to-roll PECVD reactor

    Science.gov (United States)

    Starostin, Sergey A.; Welzel, Stefan; Liu, Yaoge; van der Velden-Schuermans, Bernadette; Bouwstra, Jan B.; van de Sanden, Mauritius C. M.; de Vries, Hindrik W.

    2015-07-01

    The high current diffuse dielectric barrier discharge (DBD) was operated in a bi-axial cylindrical electrode configuration using nitrogen, oxygen and argon gas flow with the addition of tetraethyl orthosilicate as precursor for silica-like film deposition. The behaviour of the transient plasma was visualized by means of fast imaging from two orthogonal directions. The formation and propagation (~3 × 104 m s-1) of lateral ionization waves with the transverse light emission structure similar to the low pressure glow discharge was observed at time scales below 1 µs. Despite plasma non-uniformity at nanosecond time scale the deposition process on the web-rolled polymer results in smooth well adherent films with good film uniformity and excellent gas diffusion barrier properties. Contribution to the topical issue "The 14th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE XIV)", edited by Nicolas Gherardi, Ronny Brandenburg and Lars Stollenwark

  5. Investigations of an O-H...S hydrogen bond via Car-Parrinello and path integral molecular dynamics.

    Science.gov (United States)

    Jezierska, Aneta; Panek, Jarosław J

    2009-06-01

    The presence of intramolecular hydrogen bonds influences the binding energy, tautomeric equilibrium, and spectroscopic properties of various classes of organic molecules. This article discusses the O-H...S bridge, one of the less commonly investigated types of intramolecular interactions. 3-mercapto-1,3-diphenylprop-2-en-1-one was considered as the model structure. This compound exhibits photochromic properties. Car-Parrinello molecular dynamics (CPMD) was applied to investigate the spectroscopic and molecular properties of this compound in the gas phase and in the solid state. The second part of the study is devoted to the effects of the quantization of nuclear motions, with special attention to the O-H...S moiety. Path integral molecular dynamics (PIMD) of the molecular crystal of 3-mercapto-1,3-diphenylprop-2-en-1-one was carried out for this purpose. The employment of this fully quantum mechanical technique enables one to study, in a time-averaged sense, the zero-point motion important for flat potential energy surfaces. Finally, the potentials of mean force (Pmfs) were calculated from the CPMD and PIMD data obtained for the solid-state calculations. The effect of including quantum nuclear motion was investigated. In the studied compound, quantum effects shortened the H-bridge and provided a better description of the free energy minimum. The computational results place this uncommon intramolecular H-bonding among the class of strong hydrogen bonds with large red shifts of O-H stretching modes, which correspond well with previously presented experimental data in the literature concerning this structure. 2008 Wiley Periodicals, Inc.

  6. A novel nonenzymatic sensor based on LaNi{sub 0.6}Co{sub 0.4}O{sub 3} modified electrode for hydrogen peroxide and glucose

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Zhen [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); School of Chemistry and Chemical Engineering, Linyi University, 18 TongDa Road, Linyi 276005 (China); Gu Shuqing [Department of Chemistry, Shanghai University, Shanghai 200444 (China); School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Ding Yaping, E-mail: wdingyp@sina.com [Department of Chemistry, Shanghai University, Shanghai 200444 (China); School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Jin Jindi [Department of Chemistry, Shanghai University, Shanghai 200444 (China)

    2012-10-01

    Graphical abstract: CVs recorded on the bare CPE (a) and LNC/CPE (c) with 0.3 mM H{sub 2}O{sub 2}, LNC/CPE (b) without H{sub 2}O{sub 2} in 0.1 M NaOH. Scan rate: 100 mV s{sup -1}. Highlights: Black-Right-Pointing-Pointer The sensor exhibited wide linear range and low detection limit. Black-Right-Pointing-Pointer The sensor possesses high sensitivity and fast response. Black-Right-Pointing-Pointer The sensor was used for detection of hydrogen peroxide and glucose. Black-Right-Pointing-Pointer The proposed sensor has good stability and reproducibility. Black-Right-Pointing-Pointer The sensor was applied in toothpaste and serum samples with satisfactory results. - Abstract: In this paper, LaNi{sub 0.6}Co{sub 0.4}O{sub 3} (LNC) nanoparticles were synthesized by the sol-gel method, and the structure and morphology of LNC nanoparticles were characterized by X-ray diffraction spectrum, scanning electron microscopy and transmitting electron microscopy. And then, LNC was used to modify carbon paste electrode (CPE) without any adhesive to fabricate hydrogen peroxide and glucose sensor, and the results demonstrated that LNC exhibited strong electrocatalytical activity by cyclic voltammetry and amperometry. In H{sub 2}O{sub 2} determination, linear response was obtained in the concentration range of 10 nM-100 {mu}M with a detection limit of 1.0 nM. In glucose determination, there was the linear region of 0.05-200 {mu}M with a detection limit of 8.0 nM. Compared with other reports, the proposed sensor also displayed high sensitivity toward H{sub 2}O{sub 2} (1812.84 {mu}A mM{sup -1} cm{sup -2}) and glucose (643.0 {mu}A mM{sup -1} cm{sup -2}). Moreover, this prepared sensor was applied to detect glucose in blood serum and hydrogen peroxide in toothpaste samples with satisfied results, indicating its possibility in practical application.

  7. FUEL CELL ELECTRODES FOR ACID MEDIA

    Science.gov (United States)

    fuel cell electrodes for acid media. Activated carbon electrodes were prepared, wetproofed with paraffin or Teflon, and catalyzed with platinum. The wetproofing agent was applied by immersion or electrodeposition and the catalyst applied by chemical decomposition of H2P+Cl6 solutions. Half cell studies with hydrogen anodes and oxygen (air) cathodes showed that electrochemical performance is essentially the same for paraffin and Teflontreated electrodes; however, the life of the Teflon-treated electrodes under equal conditions of load is greater than that for

  8. Carbon aerogel electrodes for direct energy conversion

    Science.gov (United States)

    Mayer, Steven T.; Kaschmitter, James L.; Pekala, Richard W.

    1997-01-01

    A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome.

  9. Ab initio molecular dynamics study of hydrogen removal by ion-surface interactions

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, Johanna [Materials Chemistry, RWTH-Aachen, D-52056 Aachen (Germany); Larsson, Karin [Department of Materials Chemistry, Angstroem Laboratory, Uppsala University, Box 538, 751 21 Uppsala (Sweden); Schneider, Jochen M [Materials Chemistry, RWTH-Aachen, D-52056 Aachen (Germany)

    2005-04-20

    The energy dependence of surface reactions has been investigated through ab initio MD simulations for collisions between Al{sup 1+} and a gibbsite surface. No change in surface composition was observed for 0 eV initial kinetic energy of Al{sup 1+}. An increase in energy to 3.5 eV resulted in extended surface migration of hydrogen, subsequent H{sub 2} formation and desorption from the surface. These results may be understood based on thermodynamics and an increase in entropy upon H{sub 2} formation. They are of fundamental importance for an increased understanding of thin film growth through the correlation between ion energy and film composition. They may also indicate a pathway to affect impurity incorporation during film growth. (letter to the editor)

  10. Classical Dynamics of Harmonic Generation of the Hydrogen Molecular Ion Interacting with Ultrashort Intense Laser Pulses

    Institute of Scientific and Technical Information of China (English)

    LI Chao-Hong; DUAN Yi-Wu; Wing-Ki Liu; Jian-Min Yuan

    2001-01-01

    Within Born-Oppenheimer approximation, by using the classical trajectory theory, a description for the high order harmonic generation of the hydrogen molecular ion interacting with ultrashort laser pulses has been pre sented. The Coulomb singularities have been remedied by the regularization. The action-angle variables have been used to generate the initial inversion symmetry microcanonical distribution. Within a proper intensity range, a harmonic plateau with only odd harmonics appears. For a larger intensity, because of the existence of chaos, the harmonic spectra become noisier. For a large enough intensity, the ionization takes place and the harmonics disappear. So the chaos causes the noises, the ionization suppresses the harmonic generation, and the onset of the ionization follows the onset of chaos.

  11. Dynamics of Weak, Bifurcated and Strong Hydrogen Bonds in Lithium Nitrate Trihydrate

    Energy Technology Data Exchange (ETDEWEB)

    Werhahn, Jasper C.; Pandelov, S.; Xantheas, Sotiris S.; Iglev, H.

    2011-07-07

    The properties of three distinct types of hydrogen bonds, namely a weak, a bifurcated and a strong one, all present in/the LiNO3 (HDO)(D2O)2 hydrate lattice unit cell are studied using steady-state and time-resolved spectroscopy. The lifetimes of the OH stretching vibrations for the three individual bonds are 2.2 ps (weak), 1.7 ps (bifurcated), and 1.2 ps (strong), respectively. For the first time the properties of bifurcated H bonds can thus be unambiguously directly compared to those of weak and strong H bonds in the same system. The values of their OH stretching vibration lifetime, anharmonicity, red shift and bond strength lie between those for the strong and weak H bonds. The experimentally observed inhomogeneous broadening of their spectral signature is attributed to the coupling with a low frequency intermolecular wagging vibration/

  12. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    Science.gov (United States)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

    Hydrogen phthalate anion has a short strong O-H-O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl4, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17O and 1H nuclei monitoring the nuclear magnetic relaxation times of 1H. The experimental results indicated that the H-bond geometry of 2 is influenced by the interactions with dimethylsulfoxide, suggesting the formation of a bifurcated H-bond, which was supported by the DFT calculations. The MD simulations for the methanol solution of 2 showed that the asymmetry of the OH distance is correlated with the asymmetry in the electrostatic field of the

  13. Transport dynamics of a high-power-density matrix-type hydrogen-oxygen fuel cell

    Science.gov (United States)

    Prokopius, P. R.; Hagedorn, N. H.

    1974-01-01

    Experimental transport dynamics tests were made on a space power fuel cell of current design. Various operating transients were introduced and transport-related response data were recorded with fluidic humidity sensing instruments. Also, sampled data techniques were developed for measuring the cathode-side electrolyte concentration during transient operation.

  14. Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics

    Science.gov (United States)

    Walker, Brent; Michaelides, Angelos

    2010-11-01

    The impact of quantum nuclear effects on hydrogen (H-) bond strength has been inferred in earlier work from bond lengths obtained from path integral molecular dynamics (PIMD) simulations. To obtain a direct quantitative assessment of such effects, we use constrained-centroid PIMD simulations to calculate the free energy changes upon breaking the H-bonds in dimers of HF and water. Comparing ab initio simulations performed using PIMD and classical nucleus molecular dynamics (MD), we find smaller dissociation free energies with the PIMD method. Specifically, at 50 K, the H-bond in (HF)2 is about 30% weaker when quantum nuclear effects are included, while that in (H2O)2 is about 15% weaker. In a complementary set of simulations, we compare unconstrained PIMD and classical nucleus MD simulations to assess the influence of quantum nuclei on the structures of these systems. We find increased heavy atom distances, indicating weakening of the H-bond consistent with that observed by direct calculation of the free energies of dissociation.

  15. Synthesis of Cobalt Phosphide Nanoparticles Supported on Pristine Graphene by Dynamically Self-Assembled Graphene Quantum Dots for Hydrogen Evolution.

    Science.gov (United States)

    Wang, Xiaoyan; Yuan, Weiyong; Yu, Yanan; Li, Chang Ming

    2017-03-09

    A highly active, durable, and low-cost hydrogen evolution reaction (HER) catalyst is desirable for energy storage through water splitting but its fabrication presents great challenges. Herein, mediated by dynamically self-assembled graphene quantum dots (GQDs), small, uniform, high-density, and well-dispersed CoP nanoparticles were grown in situ on pristine graphene for the first time. This hybrid nanostructure was then employed as HER electrocatalyst, showing an onset potential of 7 mV, an overpotential of 91.3 mV to achieve 10 mA cm(-2) , a Tafel slope of 42.6 mV dec(-1) , and an exchange current density of 0.1225 mA cm(-2) , all of which compare favorably to those of most reported non-noble-metal catalysts. The developed catalyst also exhibits excellent durability with negligible current loss after 2000 cyclic voltammetry cycles (+0.01 to -0.17 V vs. RHE) or 34 h of chronoamperometric measurement at an overpotential of 91.3 mV. This work not only develops a new strategy for the fabrication of high-performance and inexpensive electrocatalysts for HER but also provides scientific insight into the mechanism of the dynamically self-assembled GQDsmediated synthesis process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Applications of hydrogen deuterium exchange (HDX for the characterization of conformational dynamics in light-activated photoreceptors

    Directory of Open Access Journals (Sweden)

    Robert eLindner

    2015-06-01

    Full Text Available Rational design of optogenetic tools is inherently linked to the understanding of photoreceptor function. Structural analysis of elements involved in signal integration in individual sensor domains provides an initial idea of their mode of operation, but understanding how local structural rearrangements eventually affect signal transmission to output domains requires inclusion of the effector regions in the characterization. However, the dynamic nature of these assemblies renders their structural analysis challenging and therefore a combination of high- and low-resolution techniques is required to appreciate functional aspects of photoreceptors.This review focuses on the potential of Hydrogen-Deuterium exchange coupled to mass spectrometry (HDX-MS for complementing the structural characterization of photoreceptors. In this respect, the ability of HDX-MS to provide information on the conformational dynamics and the possibility to address multiple functionally relevant states in solution render this methodology ideally suitable. We highlight recent examples demonstrating the potential of HDX-MS and discuss how these results can help to improve existing optogenetic systems or guide the design of novel optogenetic tools.

  17. Ion-orbital coupling in Car-Parrinello calculations of hydrogen-bond vibrational dynamics: case study with the NH3-HCl dimer.

    Science.gov (United States)

    Ong, S W; Lee, B X B; Kang, H C

    2011-09-14

    We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH(3)-HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH(3)-HCl dimer because of interest in its vibrational spectrum, in particular the magnitude of the frequency shift of the H-Cl stretch due to the anharmonic interactions when the hydrogen bond is formed. We find that an orbital mass of about 100 a.u. or smaller is required in order for the ion-orbital coupling to be linear in orbital mass, and the results for which can be accurately extrapolated to the adiabatic limit of zero orbital mass. We argue that this is general for hydrogen-bonded systems, suggesting that typical orbital mass values used in CPMD are too high to accurately describe vibrational dynamics in hydrogen-bonded systems. Our results also show that the usual application of a scaling factor to the CPMD frequencies to correct for the effects of orbital mass is not valid. For the dynamics of the dimer, we find that the H-Cl stretch and the N-H-Cl bend are significantly coupled, suggesting that it is important to include the latter degree of freedom in quantum dynamical calculations. Results from our calculations with deuterium-substitution show that both these degrees of freedom have significant anharmonic interactions. Our calculated frequency for the H-Cl stretch using the Becke-exchange Lee-Yang-Parr correlation functional compares reasonably well with a previous second-order Møller-Plesset calculation with anharmonic corrections, although it is low compared to the experimental value for the dimer trapped in a neon-matrix. © 2011 American Institute of Physics

  18. Car-Parrinello and path integral molecular dynamics study of the intramolecular hydrogen bonds in the crystals of benzoylacetone and dideuterobenzoylacetone.

    Science.gov (United States)

    Durlak, Piotr; Latajka, Zdzisław

    2014-11-14

    The dynamics of the intramolecular short hydrogen bond in the molecular crystal of benzoylacetone and its deuterated analogue are investigated using ab initio molecular dynamics simulations. A study on intramolecular hydrogen bonding in 1-phenyl-1,3-butadione (I) and 1-deuteroxy-2-deutero-1-phenylbut-1-en-3-one (II) crystals has been carried out at 160 K and 300 K on the CPMD method level and at 300 K on the PIMD method level. The analysis of the two-dimensional free-energy landscape of reaction coordinate δ-parameter and ROO distances shows that the hydrogen (deuter) between the two oxygen atoms adopts a slightly asymmetrical position in the single potential well. When the nuclear quantum effects are taken into account, very large delocalization of the bridging proton is observed. These studies indicate that hydrogen bonds in the crystal of benzoylacetone have characteristic properties for the type of bonding model resonance-assisted hydrogen bonds (RAHB) without existing the equilibrium of the two tautomers. The infrared spectrum has been calculated, and a comparative vibrational analysis has been performed. The CPMD vibrational results appear to qualitatively agree with the experimental ones.

  19. Investigations of the very short hydrogen bond in the crystal of nitromalonamide via Car-Parrinello and path integral molecular dynamics.

    Science.gov (United States)

    Durlak, Piotr; Mierzwicki, Krzysztof; Latajka, Zdzisław

    2013-05-09

    In this paper are presented the results of theoretical studies of the structure in proton motion in a very short O···O and two weak N-H···O intramolecular hydrogen bonds in the nitromalonamide crystal. The dynamics of proton motion in hydrogen bonds were investigated in the NVT ensemble at 298 K using the Car-Parrinello and the path integral molecular dynamics. A very large delocalization of proton in the slightly asymmetrical single well of free energy potential of O-H···O intramolecular hydrogen bond was noted especially in the path integral simulation where quantum effects are taken into account. This hydrogen bond is very strong with the estimated energy of hydrogen bond ca. -27 kcal/mol. The nature of intra- and intermolecular interactions was studied by means of quantum theory of atoms in molecules. The infrared spectra were calculated and compared with available experimental data. CPMD vibrational results appear to be in good agreement with the experimental ones.

  20. Interaction of hydrogen with metallic nanojunctions

    Energy Technology Data Exchange (ETDEWEB)

    Halbritter, Andras; Csonka, Szabolcs; Makk, Peter; Mihaly, Gyoergy [Electron Transport Research Group of the Hungarian Academy of Sciences and Department of Physics, Budapest University of Technology and Economics, 1111 Budapest (Hungary)

    2007-03-15

    We study the behavior of hydrogen molecules between atomic-sized metallic electrodes using the mechanically controllable break junction technique. We focus on the interaction H{sub 2} with monoatomic gold chains demonstrating the possibility of a hydrogen molecule being incorporated in the chain. We also show that niobium is strongly reactive with hydrogen, which enables molecular transport studies between superconducting electrodes. This opens the possibility for a full characterization of the transmission properties of molecular junctions with superconducting subgap structure measurements.

  1. Microvoltammetric Electrodes.

    Science.gov (United States)

    1985-09-25

    Microvoltammetric Electrodes, J. 0. Howell, R. M. Wightman, Anal. Chem., 56, 524-529 (1984). 2. Flow Rate Independent Amperometric Cell , W. L. Caudill...Electroanal. Chem., 182, 113-122 (1985). C. List of all publications 1. Flow Rate Independent Amperometric Cell , W. L. Caudill, J. 0. Howell, R. M

  2. Temperature-controlled bidirectional enantioselectivity in a dynamic catalyst for asymmetric hydrogenation.

    Science.gov (United States)

    Storch, Golo; Trapp, Oliver

    2015-03-16

    Asymmetric catalysis using enantiomerically pure catalysts is one of the most widely used methods for the preparation of enantiomerically pure compounds. The separate synthesis of both enantiomerically pure compounds requires tedious and time-consuming preparation of both enantiomerically pure catalysts or chiral separation of the racemic products. Here, we report a stereochemically flexible diastereomeric rhodium(I) catalyst for asymmetric hydrogenations of prochiral (Z)-α-acetamidocinnamates and α-substituted acrylates, which changes its enantioselectivity depending on the temperature to produce each enantiomerically pure compound in high yield with constant high enantioselectivity over time. The same axially chiral rhodium(I) catalyst produces (R)-phenylalanine derivatives in enantiomeric ratios of up to 87:13 (R/S) at low temperature and up to 3:97 (R/S) of the corresponding S enantiomers after re-equilibration of the same catalyst at elevated temperature. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Multidimensional modeling of biofilm development and fluid dynamics in a hydrogen-based, membrane biofilm reactor (MBfR).

    Science.gov (United States)

    Martin, Kelly J; Picioreanu, Cristian; Nerenberg, Robert

    2013-09-01

    A two-dimensional, particle-based biofilm model coupled with mass transport and computational fluid dynamics was developed to simulate autotrophic denitrification in a spiral-wound membrane biofilm reactor (MBfR), where hydrogen is supplied via hollow-fiber membrane fabric. The spiral-wound configuration consists of alternating layers of plastic spacer net and membrane fabric that create rows of flow channels, with the top and bottom walls comprised of membranes. The transversal filaments of the spacer partially obstruct the channel flow, producing complex mixing and shear patterns that require multidimensional representation. This study investigated the effect of hydrogen and nitrate concentrations, as well as spacer configuration, on biofilm development and denitrification fluxes. The model results indicate that the cavity spacer filaments, which rest on the bottom membranes, cause uneven biofilm growth. Most biofilm resided on the bottom membranes, only in the wake of the filaments where low shear zones formed. In this way, filament configuration may help achieve a desired biofilm thickness. For the conditions tested in this study, the highest nitrate fluxes were attained by minimizing the filament diameter and maximizing the filament spacing. This lowered the shear stress at the top membranes, allowing for more biofilm growth. For the scenarios studied, biomass limitation at the top membranes hindered performance more significantly than diffusion limitation in the thick biofilms at the bottom membranes. The results also highlighted the importance of two-dimensional modeling to capture uneven biofilm growth on a substratum with geometrical complexity. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Density dependence of hydrogen bonding and the translational-orientational structural order in supercritical water: a molecular dynamics study.

    Science.gov (United States)

    Ma, Haibo; Ma, Jing

    2011-08-07

    Molecular dynamics simulation have been performed with a wide range of densities along a near critical isotherm of supercritical water (SCW) in order to study the density dependence of the structure order and hydrogen bonding (HB). It is revealed that the translational structure order is nearly invariant while the orientational tetrahedral structure order is very sensitive to the bulk density under supercritical conditions. Meanwhile, some energetically unfavorable intermediate water dimer structures are found to appear under supercritical conditions due to the reduced energy difference and the enhanced energy fluctuation. As a consequence, a general geometrical criterion or the inclusion of a energy-based criterion instead of currently widely adopted pure r(OH)-based geometric criterion is suggested to be used in the HB statistics under supercritical conditions. It is found that the average HB number per H(2)O molecule (n(HB)) reduces with the decreasing SCW bulk density although a given pair of H(2)O molecules are shown to have a stronger ability to form a hydrogen bond under lower SCW bulk densities. Accordingly, the orientational tetrahedral structure order q decreases with the reducing bulk density under supercritical conditions. However, when the fluid is dilute with ρ ≤ 0.19ρ(c) (ρ(c) = 0.322 g/cm(3)), the energy fluctuation increases sharply and the short-range order is destroyed, signifying the supercritical fluid (SCF)-gas state transition. Accordingly, the orientational tetrahedral structure order q gets reversal around ρ = 0.19ρ(c) and approaches zero under very dilute conditions. The sensitivity of the orientational order to the density implies the microscopic origin of the significant dependence of SCF's physicochemical properties on the pressure.

  5. Biomimetic hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Krassen, Henning

    2009-05-15

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

  6. Dynamical resonances in the fluorine atom reaction with the hydrogen molecule.

    Science.gov (United States)

    Yang, Xueming; Zhang, Dong H

    2008-08-01

    [Reaction: see text]. The concept of transition state has played a crucial role in the field of chemical kinetics and reaction dynamics. Resonances in the transition state region are important in many chemical reactions at reaction energies near the thresholds. Detecting and characterizing isolated reaction resonances, however, have been a major challenge in both experiment and theory. In this Account, we review the most recent developments in the study of reaction resonances in the benchmark F + H 2 --> HF + H reaction. Crossed molecular beam scattering experiments on the F + H 2 reaction have been carried out recently using the high-resolution, highly sensitive H-atom Rydberg tagging technique with HF rovibrational states almost fully resolved. Pronounced forward scattering for the HF (nu' = 2) product has been observed at the collision energy of 0.52 kcal/mol in the F + H 2 (j = 0) reaction. Quantum dynamical calculations based on two new potential energy surfaces, the Xu-Xie-Zhang (XXZ) surface and the Fu-Xu-Zhang (FXZ) surface, show that the observed forward scattering of HF (nu' = 2) in the F + H 2 reaction is caused by two Feshbach resonances (the ground resonance and first excited resonance). More interestingly, the pronounced forward scattering of HF (nu' = 2) at 0.52 kcal/mol is enhanced considerably by the constructive interference between the two resonances. In order to probe the resonance potential more accurately, the isotope substituted F + HD --> HF + D reaction has been studied using the D-atom Rydberg tagging technique. A remarkable and fast changing dynamical picture has been mapped out in the collision energy range of 0.3-1.2 kcal/mol for this reaction. Quantum dynamical calculations based on the XXZ surface suggest that the ground resonance on this potential is too high in comparison with the experimental results of the F + HD reaction. However, quantum scattering calculations on the FXZ surface can reproduce nearly quantitatively the resonance

  7. Hydrogen Ionic Plasma and Particle Dynamics in Negative Ion Source for NBI

    Science.gov (United States)

    Tsumori, Katsuyoshi

    2013-10-01

    Three negative-ion-based neutral beam injectors (NBIs) have been developed for plasma heating in the Large Helical Device. The NBIs achieve successfully the nominal injection power and beam energy, and understanding of the production and transport mechanisms of H- ion is required to obtain more stable high power beam. In the ion source development, we have found hydrogen ionic plasmas with extremely low electron density are produced in the beam extraction region. The plasma is measured with a combination of an electrostatic probe, millimeter-wave interferometer and cavity ring down (CRD). It has been observed for the first time that the charge neutrality of the ionic plasma is broken with H- extraction and electrons compensate the extracted H- charge. The influence of the extraction field widely affects to the ionic plasma in the extraction region. Two-dimensional particle-in-cell simulation (2D-PIC) has been applied to investigate the particle transport and reproduces the production of the ionic plasma and electron compensation due to H- extraction. In particle model, produced H- ions leave from the Cs covered PG surface in opposite direction to beam extraction. The direction can be changed with the electric field and collective effect due to the presence of plasma. A new technique using CCD camera with H α filter applied to measure the two-dimensional distribution of H- density. In the ionic plasma, H α light is emitted via electron-impact excitation and mutual neutralization processes with H- ion and proton. Comparing the results obtained with optical emission spectroscopy, electrostatic probe and CRD, it is shown the H α emission is dominated with the mutual neutralization. By subtracting the CCD images with and without beam extraction, it becomes clear that H- ions are extracted not directly from the PG surface but from the bulk of the ionic plasma. The result suggests the initial energy of H- ion is dumped rapidly in the ionic plasma.

  8. Microfield dynamics in dense hydrogen plasmas with high-Z impurities

    Science.gov (United States)

    Hau-Riege, Stefan P.; Weisheit, Jon

    2017-01-01

    We use large-scale classical molecular dynamics to determine microfield properties for several dense plasma mixtures. By employing quantum statistical potentials (QSPs) to regularize the Coulomb interaction, our simulations follow motions of electrons as well as ions for times long enough to track relaxation phenomena involving both types of particles. Coulomb coupling, relative to temperature, of different pairs of species in the hot, dense matter being simulated ranges from weak to strong. We first study the effect of such coupling differences, along with composition and QSP differences, on the roles of electrons and various mixture components in determining probability distributions of instantaneous, total microfields experienced by the ions. Then, we address two important dynamical questions: (1) How is the quasistatic part of the total field to be extracted from the time-dependent simulation data? (2) Under what conditions does the commonly used approximation of ions with fixed Yukawa-like screening by free electrons accurately describe quasistatic fields? We identify a running, short-time average of the total field at each ion as its slowly evolving, quasistatic part. We consider several ways to specify the averaging interval, and note the influence of ion dynamics in this issue. When all species are weakly coupled, the quasistatic fields have probability distributions agreeing well with those we obtain from simulations of Yukawa-screened ions. However, agreement deteriorates as the coupling between high-Z ions increases well beyond unity, principally because the Yukawa model tends to underestimate the true screening of close high-Z pairs. Examples of this fact are given, and some consequences for the high-field portions of probability distributions are discussed.

  9. Dynamic tunneling ionization of excited hydrogen atoms: A precise experiment versus theories

    Science.gov (United States)

    Sauer, B. E.; Yoakum, S.; Moorman, L.; Koch, P. M.; Richards, D.; Dando, P. A.

    1992-01-01

    New data for n0=24,...,32 H atoms ionized by a linearly polarized, 9.908-GHz electric field are compared with calculations. Being more precise than laser multiphoton ionization experiments with tightly bound atoms, our experiments distinguish between tunneling through and classical escape over a slowly oscillating barrier and between one- and many-state dynamical processes. Formulas used to interpret low-frequency laser multiphoton ionization data poorly describe our results. Our data delineate ranges of validity of other partly successful models and are best reproduced by a new 3D semiclassical model.

  10. Dynamic tunneling ionization of excited hydrogen atoms: A precise experiment versus theories

    Energy Technology Data Exchange (ETDEWEB)

    Sauer, B.E.; Yoakum, S.; Moorman, L.; Koch, P.M. (Department of Physics, State University of New York at Stony Brook, Stony Brook, New York 11794-3800 (United States)); Richards, D.; Dando, P.A. (Mathematics Faculty, Open University, Milton Keynes MK7 6AA (United Kingdom))

    1992-01-27

    New data for {ital n}{sub 0}=24,...,32 H atoms ionized by a linearly polarized, 9.908-GHz electric field are compared with calculations. Being more precise than laser multiphoton ionization experiments with tightly bound atoms, our experiments distinguish between tunneling {ital through} and classical escape {ital over} a slowly oscillating barrier and between one- and many-state dynamical processes. Formulas used to interpret low-frequency laser multiphoton ionization data poorly describe our results. Our data delineate ranges of validity of other partly successful models and are best reproduced by a new 3D semiclassical model.

  11. Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy.

    Science.gov (United States)

    Ghosh, Hirendra N; Verma, Sandeep; Nibbering, Erik T J

    2011-02-10

    Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

  12. Immobilization of [Cu(bpy){sub 2}]Br{sub 2} complex onto a glassy carbon electrode modified with {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes: Application to nanomolar detection of hydrogen peroxide and bromate

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)], E-mail: absalimi@uok.ac.ir; Korani, Aazam; Hallaj, Rahman; Khoshnavazi, Roshan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hadadzadeh, Hasan [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2009-03-02

    A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy){sub 2}]Br{sub 2} was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes (SWCNTs){sub .} Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} modified electrodes shows excellent electrocatalytic activity toward reduction H{sub 2}O{sub 2} and BrO{sub 3}{sup -} at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1} and 3.0({+-}0.10) x 10{sup 3} M{sup -1} s{sup -1}, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM{sup -1}, 10 nM-20 {mu}M, 1 nM, 5.5 nA nM{sup -1} and 10 nM-18 {mu}M, respectively.

  13. Thermodynamic functions from lattice dynamic of KMgH{sub 3} for hydrogen storage applications

    Energy Technology Data Exchange (ETDEWEB)

    Bouhadda, Youcef, E-mail: bouhadda@yahoo.com [Unite de Recherche Appliquee en Energies Renouvelables, BP 88, Ghardaia (Algeria); Kheloufi, Nawal; Bentabet, Abdelouahab [Centre universistaire Bordj Bouariej (Algeria); Boudouma, Youcef [Faculte de Physique USTHB, Alger (Algeria); Fenineche, Noureddine [LERMPS, UTBM, Belfort (France); Benyalloul, Kamel [Unite de Recherche Appliquee en Energies Renouvelables, BP 88, Ghardaia (Algeria)

    2011-09-15

    Highlights: > The dynamical and thermodynamic properties of KMgH{sub 3} are presented. > The density of state is calculated and shows that the KMgH{sub 3} is an insulator. > Formation energy of the KMgH{sub 3} is calculated for different possible reaction pathways. > The phonon frequencies at gamma point for the infrared and Raman modes are assigned. > The thermodynamic functions of KMgH{sub 3} are determined for the first time in this study. - Abstract: The dynamic and the thermodynamic properties of KMgH{sub 3} have been investigated by density functional theory (DFT). We have found that the calculated lattice parameters differ from the experimental data by less than 0.6% and the electronic density of states (DOS) reveals that the KMgH{sub 3} is an insulator. The formation energy of KMgH{sub 3} from binary hydrides (MgH{sub 2} and KH) has been calculated. Using density-functional perturbation theory, we have calculated the phonon dispersion curves, the phonon density of states, the Born effective charge tensors, the dielectric permittivity tensors and the phonon frequencies at the center of the Brillouin zone of KMgH{sub 3}. Also we have assigned the calculated phonon frequencies at the gamma point for Infrared-active and Raman-active modes. For the first time, the thermodynamic functions are computed using the phonon density of states.

  14. Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

    Energy Technology Data Exchange (ETDEWEB)

    Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, Minnesota 55455 (United States); Coulston, Emma; Cole, George C. [Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD (United Kingdom); Legon, Anthony C., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu; Tew, David P., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS (United Kingdom)

    2015-09-14

    a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.

  15. Hydrogenation of the rare earth alloys for production negative electrodes of nickel-metal hydride batteries; Hidrogenacao de ligas a base de terras raras para fabricacao de eletrodos negativos de baterias de niquel-hidreto metalico

    Energy Technology Data Exchange (ETDEWEB)

    Casini, Julio Cesar Serafim

    2011-07-01

    In this work were studied of La{sub 0.7-x}Mg{sub x} Pr{sub 0.3}Al{sub 0.3}Mn{sub 0.4}Co{sub 0.5}Ni{sub 3.8} (X = 0 and 0.7) alloys for negative electrodes of the nickel-metal hydride batteries. The hydrogenation of the alloys was performed varying pressing of H{sub 2} (2 and 10 bar) and temperature (room and 500 Degree-Celsius ). The discharge capacity of the nic kel-metal hydride batteries were analyzed in ARBIN BT- 4 electrical test equipment. The as-cast alloys were analyzed by scanning electron microscopy (SEM), energy disperse spectroscopy (EDX) and X-Ray diffraction. The increasing Mg addition in the alloy increases maximum discharge capacity but decrease cycle life of the batteries. The maximum discharge capacity was obtained with the Mg{sub 0.7}Pr{sub 0.3}Al{sub 0.3}Mn{sub 0.4}Co{sub 0.5}Ni{sub 3.8} alloy (60 mAh) and the battery which presented the best performance was La{sub 0.4}Mg{sub 0.3}Pr{sub 0.3}Al{sub 0.3}Mn{sub 0.4}Co{sub 0.5}Ni{sub 3.8} alloy (53 mAh and 150 cycles). The H{sub 2} capability of absorption was diminished for increased Mg addition and no such effect occurs for Mg{sub 0.7}Pr{sub 0.3}Al{sub 0.3}Mn{sub 0.4}Co{sub 0.5}Ni{sub 3.8} alloy. (author)

  16. Impact of electrode kinetics on the dynamic response of a DMFC to change of methanol feed concentration

    Science.gov (United States)

    Schultz, Thorsten; Krewer, Ulrike; Sundmacher, Kai

    A dynamic one-dimensional rigorous process model of a single-cell direct methanol fuel cell (DMFC) is presented. Multi-component mass transport in the diffusion layers and the polymer electrolyte membrane (PEM) is described using the generalised Maxwell-Stefan equation for porous structures. In the PEM, local swelling behaviour and non-idealities are accounted for by a Flory-Huggins activity model. This model is used as basis of a model family with different anode and cathode reaction mechanisms (single-step and multi-step with and without adsorption to catalyst surface sites). The model variants were used to simulate the dynamic (transient) response of the DMFC to stepwise changes in the methanol feed concentration from typical operating levels down to zero, while maintaining the cell current. For validation, similar experiments were carried out. In the experiments, the cell voltage broke down only after an unexpectedly long period of time, and for a variety of operating conditions even a cell voltage overshoot could be observed. Such overshoot behaviour is also predicted by those model variants, which feature anode reaction mechanisms with reaction intermediates (e.g. CO) adsorbed to the anode catalyst, while models without such detailed anode reaction mechanisms fail in this respect. The model-based analysis reveals that the observed overshoots result from the different time constants of the responses of the anode and cathode overpotentials to the feed change.

  17. Effect of grain size on the behavior of hydrogen/helium retention in tungsten: a cluster dynamics modeling

    Science.gov (United States)

    Zhao, Zhe; Li, Yonggang; Zhang, Chuanguo; Pan, Guyue; Tang, Panfei; Zeng, Zhi

    2017-08-01

    Reducing ion retention in materials is a key factor in the management of tritium inventory, the selection of compatible plasma-facing materials (PFMs), and thus the future development of fusion reactors. In this work, by introducing the cellular sink strength of grain boundaries (GBs) into the cluster dynamics model, the behavior of hydrogen (H) and helium (He) retention in W with different grain sizes is studied under various irradiation conditions systematically. It is found that the H/He retention increases dramatically with decreasing grain size at typical service temperatures, due to the enhancement of H/He capture ratio by GBs. Generally, He retention exists in three forms: He in GBs, in dislocations and in clusters (He m V n , He n and He n I). Our further study shows that, under the irradiation of low energy and low fluence ions, the contribution of He in clusters is negligible. The total He retention is thus dominated by the competing absorption of GBs and dislocations, that is, changing from the dislocation-based to grain boundary-based retention with decreasing grain size. H retention also presents the same behavior. In view of these grain size-related behaviors of H/He retention in W, it is suggested that coarse-grained crystals should be selected for W-based PFMs in practice.

  18. NEAR-BLOWOFF DYNAMICS OF BLUFF-BODY-STABILIZED PREMIXED HYDROGEN/AIR FLAMES IN A NARROW CHANNEL

    KAUST Repository

    Lee, Bok Jik

    2015-06-07

    The flame stability is known to be significantly enhanced when the flame is attached to a bluff-body. The main interest of this study is on the stability of the flame in a meso-scale channel, considering applications such as combustion-based micro power generators. We investigate the dynamics of lean premixed hydrogen/air flames stabilized behind a square box in a two-dimensional meso-scale channel with high-fidelity numerical simulations. Characteristics of both non-reacting flows and reacting flows over the bluff-body are studied for a range of the mean inflow velocity. The flame stability in reacting flows is investigated by ramping up the mean inflow velocity step by step. As the inlet velocity is increased, the initially stable steady flames undergo a transition to an unsteady mode of regular asymmetric fluctuation. When the inlet velocity is further increased, the flame is eventually blown off. Between the regular fluctuation mode and blowoff limit, there exists a narrow range of the inlet velocity where the flames exhibit periodic local extinction and recovery. Approaching further to blowoff limit, the local extinction and recovery becomes highly transient and a failure of recovery leads blowoff and extinction of the flame kernel.

  19. Hydrogen Filling Station

    Energy Technology Data Exchange (ETDEWEB)

    Boehm, Robert F; Sabacky, Bruce; Anderson II, Everett B; Haberman, David; Al-Hassin, Mowafak; He, Xiaoming; Morriseau, Brian

    2010-02-24

    future. Project partners also conducted a workshop on hydrogen safety and permitting. This provided an opportunity for the various permitting agencies and end users to gather to share experiences and knowledge. As a result of this workshop, the permitting process for the hydrogen filling station on the Las Vegas Valley Water District’s land was done more efficiently and those who would be responsible for the operation were better educated on the safety and reliability of hydrogen production and storage. The lessons learned in permi