WorldWideScience

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. Three-Dimensional Macroporous Polypyrrole-Derived Graphene Electrode Prepared by the Hydrogen Bubble Dynamic Template for Supercapacitors and Metal-Free Catalysts.

    Science.gov (United States)

    Yang, Xiaoqing; Liu, Anran; Zhao, Yuewu; Lu, Huijia; Zhang, Yuanjian; Wei, Wei; Li, Ying; Liu, Songqin

    2015-10-28

    We report a general method for the fabrication of three-dimensional (3D) macroporous graphene/conducting polymer modified electrode and nitrogen-doped graphene modified electrode. This method involves three consecutive steps. First, the 3D macroporous graphene (3D MG) electrode was fabricated electrochemically by reducing graphene oxide dispersion on different conducting substrates and used hydrogen bubbles as the dynamic template. The morphology and pore size of 3D MG could be governed by the use of surfactants and the dynamics of bubble generation and departure. Second, 3D macroporous graphene/polypyrrole (MGPPy) composites were constructed via directly electropolymerizing pyrrole monomer onto the networks of 3D MG. Due to the benefit of the good conductivity of 3D MG and pseudocapacitance of PPy, the composites manifest outstanding area specific capacitance of 196 mF cm(-2) at a current density of 1 mA cm(-2). The symmetric supercapacitor device assembled by the composite materials had a good capacity property. Finally, the nitrogen-doped MGPPy (N-MGPPy or MGPPy-X) with 3D macroporous nanostructure and well-regulated nitrogen doping was prepared via thermal treatment of the composites. The resultant N-MGPPy electrode was explored as a good electrocatalyst for the oxygen reduction reaction (ORR) with the current density value of 5.56 mA cm(-2) (-0.132 V vs Ag/AgCl). Moreover, the fuel tolerance and durability under the electrochemical environment of the N-MGPPy catalyst were found to be superior to the Pt/C catalyst.

  3. Nickel hydrogen bipolar battery electrode design

    Science.gov (United States)

    Puglisi, V. J.; Russell, P.; Verrier, D.; Hall, A.

    1985-01-01

    The preferred approach of the NASA development effort in nickel hydrogen battery design utilizes a bipolar plate stacking arrangement to obtain the required voltage-capacity configuration. In a bipolar stack, component designs must take into account not only the typical design considerations such as voltage, capacity and gas management, but also conductivity to the bipolar (i.e., intercell) plate. The nickel and hydrogen electrode development specifically relevant to bipolar cell operation is discussed. Nickel oxide electrodes, having variable type grids and in thicknesses up to .085 inch are being fabricated and characterized to provide a data base. A selection will be made based upon a system level tradeoff. Negative (hydrpogen) electrodes are being screened to select a high performance electrode which can function as a bipolar electrode. Present nickel hydrogen negative electrodes are not capable of conducting current through their cross-section. An electrode was tested which exhibits low charge and discharge polarization voltages and at the same time is conductive. Test data is presented.

  4. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  5. Dependence of hydrogen arcjet operation on electrode geometry

    Science.gov (United States)

    Pencil, Eric J.; Sankovic, John M.; Sarmiento, Charles J.; Hamley, John A.

    1992-01-01

    The dependence of 2kW hydrogen arcjet performance on cathode to anode electrode spacing was evaluated at specific impulses of 900 and 1000 s. Less than 2 absolute percent change in efficiency was measured for the spacings tested which did not repeat the 14 absolute percent variation reported in earlier work with similar electrode designs. A different nozzle configuration was used to quantify the variation in hydrogen arcjet performance over an extended range of electrode spacing. Electrode gap variation resulted in less than 3 absolute percent change in efficiency. These null results suggested that electrode spacing is decoupled from hydrogen arcjet ignition. The dependence of breakdown voltage on mass flow rate and electrode agreed with Paschen curves for hydrogen. Preliminary characterization of the dependence of hydrogen arcjet ignition on rates of pulse repetition and pulse voltage rise were also included for comparison with previous results obtained using simulated hydrazine.

  6. Dependence of hydrogen arcjet operation on electrode geometry

    Science.gov (United States)

    Pencil, Eric J.; Sankovic, John M.; Sarmiento, Charles J.; Hamley, John A.

    1992-01-01

    The dependence of 2 kW hydrogen arcjet performance on cathode to anode electrode spacing was evaluated at specific impulses of 900 and 1000 s. Less than 2 absolute percent change in efficiency was measured for the spacings tested which did not repeat the 14 absolute percent variation reported in earlier work with similar electrode designs. A different nozzle configuration was used to quantify the variation in hydrogen arcjet performance over an extended range of electrode spacing. Electrode gap variation resulted in less than 3 absolute percent change in efficiency. These null results suggested that electrode spacing is decoupled from hydrogen arcjet performance considerations over the ranges tested. Initial studies were conducted on hydrogen arcjet ignition. The dependence of breakdown voltage on mass flow rate and hydrogen arcjet ignition on rates of pulse repetition and pulse voltage rise were also included for comparison with previous results obtained using simulated hydrazine.

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

    International Nuclear Information System (INIS)

    Fang Zheng; Wang Shaofen; Zhang Zhenghua; Qiu Guanzhou

    2008-01-01

    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 φ 0 * = 0 and ΔS 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) 6 3- /Fe(CN) 6 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

  8. Development of Hydrogen Electrodes for Alkaline Water Electrolysis

    DEFF Research Database (Denmark)

    Kjartansdóttir, Cecilía Kristín

    , 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...... 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...... 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...

  9. Advanced hydrogen electrode for hydrogen-bromide battery

    Science.gov (United States)

    Kosek, Jack A.; Laconti, Anthony B.

    1987-01-01

    Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

  10. Chitosan catalyzes hydrogen evolution at mercury electrodes

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Římánková, Ludmila

    2014-01-01

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

  11. 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.

  12. Submersed sensing electrode used in fuel-cell type hydrogen detector

    Science.gov (United States)

    Niedrach, L. W.; Rudek, F. P.; Rutkoneski, M. D.

    1971-01-01

    Electrode has silicone rubber diffusion barrier with fixed permeation constant for hydrogen. Barrier controls flow of hydrogen to anode and Faraday relationship establishes upper limit for current through cell. Electrode fabrication is described.

  13. Phosphate-bonded composite electrodes for hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

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

    1990-03-01

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

  14. Prussian blue-modified nanoporous gold film electrode for amperometric determination of hydrogen peroxide.

    Science.gov (United States)

    Ghaderi, Seyran; Mehrgardi, Masoud Ayatollahi

    2014-08-01

    In this manuscript, the electrocatalytic reduction of hydrogen peroxides on Prussian blue (PB) modified nanoporous gold film (NPGF) electrode is described. The PB/NPGF is prepared by simple anodizing of a smooth gold film followed by PB film electrodeposition method. The morphology of the PB/NPGF electrode is characterized using scanning electron microscopy (SEM). The effect of solution pH and the scan rates on the voltammetric responses of hydrogen peroxide have also been examined. The amperometric determination of H2O2 shows two linear dynamic responses over the concentration range of 1μM-10μM and 10μM-100μM with a detection limit of 3.6×10(-7)M. Furthermore, this electrode demonstrated good stability, repeatability and selectivity remarkably. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Hydrogen adsorption on skeletal rhodium-tantalum electrodes-catalysts

    International Nuclear Information System (INIS)

    Tsinstevich, V.M.; Krejnina, N.M.

    1975-01-01

    Skeleton rhodium-tantalic catalyst electrodes with a tantalum mass percentage of 0 to 100 have been obtained by the methodology of Crupp and others. The hydrogen adsorption is studied through the method of removing the galvano-static and potentiodynamic curves of charging in sulfuric acid and potassium hydroxide. It has been discovered that the maximum adsorption ability relatively to the hydrogen can be observed in an alloy with a 5% tantalum contents. The energetic characteristics of the alloys are higher in alkali than in acid

  16. Dynamics of hydrogen in hydrogenated amorphous silicon

    Indian Academy of Sciences (India)

    is mobile and can easily move through the material). Hydrogen diffuses ... The determination of the relationship of light-enhanced hydrogen motion to ... term is negligible, and using the thermodynamic relation given below f(c) = kBT .... device-applications problematic but the normal state can be recovered by a thermal an-.

  17. Nickel foam/polyaniline-based carbon/palladium composite electrodes for hydrogen storage

    International Nuclear Information System (INIS)

    Skowronski, Jan M.; Urbaniak, Jan

    2008-01-01

    The sandwich-like nickel/palladium/carbon electrodes exhibiting ability to absorb hydrogen in alkaline solution are presented. Electrodes were prepared by successive deposition of palladium and polyaniline layers on nickel foam substrate followed by heat treatment to give Ni/Pd/C electrode. It was shown that thermal conversion of polymer into carbon layer and subsequent thermal activation of carbon component bring about the modification of the mechanism of reversible hydrogen sorption. It was proven that carbon layer, interacting with Pd catalyst, plays a considerable role in the process of hydrogen storage. In the other series of experiments, Pd particles were dispersed electrochemically on carbon coating leading to Ni/C/Pd system. The adding of the next carbon layer resulted in Ni/C/Pd/C electrodes. Electrochemical properties of the electrodes depend on both the sequence of Pd and C layers and the preparation/activation of carbon coating. Electrochemical behavior of sandwich-like electrodes in the reaction of hydrogen sorption/desorption was characterized in 6 M KOH using the cyclic voltammetry method and the results obtained were compared to those for Ni/Pd electrode. The anodic desorption of hydrogen from electrodes free and containing carbon layer was considered after the potentiodynamic as well as potentiostatic sorption of hydrogen. The influence of the sorption potential and the time of rest of electrodes at a cut-off circuit on the kinetics of hydrogen recovery were examined. The results obtained for Ni/Pd/C electrodes indicate that the displacement of hydrogen between C and Pd phase takes place during the rest at a cut-off circuit. Electrodes containing carbon layer require longer time for hydrogen electrosorption. On the other hand, the presence of carbon layer in electrodes is advantageous because a considerable longer retention of hydrogen is possible, as compared to Pd/Ni electrode. Hydrogen stored in sandwich-like electrodes can instantly be

  18. 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.

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

    KAUST Repository

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

    2017-01-01

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

  20. On the dynamical supersymmetry of atomic hydrogen

    International Nuclear Information System (INIS)

    Slepchenko, L.A.

    1986-01-01

    In the framework of supersymmetric quantum mechanics a dynamical symmetry of the hydrogen atom is considered. New features of spectra for the dynamical supersymmetry of two-dimensional Kepler problem are found

  1. Amperometric biosensor for the detection of hydrogen peroxide using catalase modified electrodes in polyacrylamide.

    Science.gov (United States)

    Varma, Shailly; Mattiasson, Bo

    2005-09-23

    A simple biosensor for the detection of hydrogen peroxide in organic solvents has been developed and coupled to a flow injection analysis (FIA) system. Catalase was entrapped in polyacrylamide gel and placed on the surface of platinum (working electrode) fixed in a Teflon holder with Ag-wire (auxiliary electrode), followed by addition of filter paper soaked in KCl. The entrapped catalase gel was held on the electrode using membranes. The effects of cellulose and polytetrafluroethylene (PTFE) membranes on the electrode response towards hydrogen peroxide have been studied. The modified electrode has been used to study the detection of hydrogen peroxide in solvents like water, dimethyl sulfoxide (DMSO), and 1,4-dioxane using amperometric techniques like cyclic voltammetry (CV) and FIA. The CV of modified catalase electrode showed a broad oxidation peak at -150 mV and a clear reduction peak at -212 mV in the presence of hydrogen peroxide. Comparison of CV with hydrogen peroxide in various solvents has been carried out. The electrode showed an irreversible kinetics with DMSO as the solvent. A flow cell has been designed in order to carry on FIA studies to obtain calibration plots for hydrogen peroxide with the modified electrode. The calibration plots in several solvents such as water, dimethyl sulfoxide, 1,4-dioxane have been obtained. The throughput of the enzyme electrode was 10 injections per hour. Due to the presence of membrane the response time of the electrode is concentration dependent.

  2. Characterizing heterogeneous dynamics at hydrated electrode surfaces

    Science.gov (United States)

    Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

    2013-05-01

    In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

  3. Characterizing heterogeneous dynamics at hydrated electrode surfaces.

    Science.gov (United States)

    Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

    2013-05-14

    In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

  4. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  5. Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

    NARCIS (Netherlands)

    Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

    2000-01-01

    We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

  6. High density plasma productions by hydrogen storage electrode in the Tohoku University Heliac

    International Nuclear Information System (INIS)

    Utoh, H.; Takahashi, H.; Tanaka, Y.; Takenaga, M.; Ogawa, M.; Shinde, J.; Iwazaki, K.; Shinto, K.; Kitajima, S.; Sasao, M.; Nishimura, K.; Inagaki, S.

    2005-01-01

    In the Tohoku University Heliac (TU-Heliac), the influence of a radial electric field on improved modes has been investigated by an electrode biasing. In both positive and negative biasing experiments by the stainless steel (SUS) electrode (cold-electron or ion collection), the improvement of plasma confinement was clearly observed. Furthermore, by negative biasing with a hot cathode (electron injection), the radial electric fields can be actively controlled as a consequence of the control of the electrode current I E . By using the electrode made of a hydrogen storage metal, for example Titanium (Ti) or Vanadium (V), the following possibility can be expected: (1) ions accelerated from the positive biased electrode allow the simulation for the orbit loss of high-energy particles, (2) the electrons/neutral- particles injected from the negative biased electrode provide the production of the high- density plasma, if hydrogen are successfully stored in the electrode. In this present work, several methods were tried as the treatment for hydrogen storage. In the case of the Ti electrode biased positively after the treatment, the improvement of plasma confinement was observed in He plasma, which were same as the experimental results of the SUS electrode. However, in the electron density profiles inside the electrode position there was difference between the biased plasma by the Ti electrode and that by the SUS electrode. In some of Ar discharges biased negatively with the Ti electrode after the treatment, the electron density and the line intensity of H α increased about 10 times of those before biasing. This phenomenon has not been observed in the Ar plasma biased by the SUS electrode. This result suggested that the Ti electrode injected electrons/neutral-hydrogen into the plasma. This high-density plasma productions were observed only 1 ∼ 3 times in the one treatment for hydrogen storage. By using a Vanadium (V) electrode, productions of the high-density plasma

  7. Hydrogen bond dynamics in bulk alcohols.

    Science.gov (United States)

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

    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.

  8. 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.)

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    Oxygen electrodes and steam electrodes are designed and tested to develop improved solid oxide electrolysis cells for H2 production with the cell support on the oxygen electrode. The electrode performance is evaluated by impedance spectroscopy testing of symmetric cells at open circuit voltage (OCV...

  10. Hydrogen storage alloy electrode and the nickel-hydrogen secondary battery using the electrode; Suiso kyuzo gokin denkyoku to sorewo mochiita nikkeru/suiso niji denchi

    Energy Technology Data Exchange (ETDEWEB)

    Ono, T. [Furukawa Electric Co. Ltd., Tokyo (Japan); Furukawa, J. [The Furukawa Battery Co. Ltd., Yokohama (Japan)

    1997-02-14

    With respect to the conventional nickel-hydrogen secondary battery, pulverization of the hydrogen storage alloy due to repetition of charging-discharging cycles can be prevented by using a fluorocarbon resin as a binder in manufacture of the hydrogen storage alloy electrode; however, the inner pressure increase of the battery in case of overcharging can not be fully controlled. The invention relates to control of the inner pressure increase of the nickel-hydrogen secondary battery in case of overcharging. As to the hydrogen storage alloy electrode, the compound comprising the hydrogen storage alloy powder as a main ingredient is supported by a current collector; further, the compound particularly comprises a fluororubber as a binder. The nickel-hydrogen secondary battery equipped with the hydrogen storage alloy electrode can control the inner pressure increase of the battery in case of overcharging, and lessen decrease of the battery capacity due to repetition of charging-discharging cycles over long time. The effects are dependent on the use of the fluororubber as a binder which has good flexibility, and strong binding capacity as well as water repellency. 1 tab.

  11. Hydrogen bond dynamics in bulk alcohols

    International Nuclear Information System (INIS)

    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 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

  12. Hydrogen storage alloy electrode for nickel-hydrogen storage battery use; Nikkeru-suiso chikudenchiyo suiso kyuzo gokin denkyoku

    Energy Technology Data Exchange (ETDEWEB)

    Nagase, H.; Tadokoro, M.

    1995-06-16

    In the conventional hydrogen storage alloy electrode, water soluble polymer is employed as for the binder. Employing the water soluble polymer as for the binder may cause the film formation on the surface of the hydrogen storage alloy to hinder the hydrogen absorption at the alloy surface, resulting in the decrease in activity of electrode and in the discharge characteristic at a low temperature. This invention proposes the addition of Vinylon fiber in the binder of the hydrogen storage alloy electrode made by kneading the hydrogen storage alloy and the binder. The Vinylon fiber improves the strength of the electrode, as it forms a network in the electrode. Furthermore, the point contact between the alloy and the Vinylon fiber in the electrode prevents the film formation which hinders the oxygen absorption and chemical reaction on the surface of the alloy. As for the binder, carboxymethyl cellulose is used. The preferable size of Vinylon fiber is fiber diameter of 0.1 - 0.5 denier and fiber length of 0.5 - 5.0 mm. 4 figs., 4 tabs.

  13. The study of hydrogen electrosorption in layered nickel foam/palladium/carbon nanofibers composite electrodes

    International Nuclear Information System (INIS)

    Skowronski, J.M.; Czerwinski, A.; Rozmanowski, T.; Rogulski, Z.; Krawczyk, P.

    2007-01-01

    In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support

  14. The evaluation of the polarization resistance in a tubular electrode and its application to the hydrogen electrode reaction

    International Nuclear Information System (INIS)

    Montero, M.A.; Marozzi, C.A.; Chialvo, M.R. Gennero de; Chialvo, A.C.

    2007-01-01

    An alternative method for the determination of the kinetic parameters involved in the elementary steps of the reaction mechanism of the hydrogen electrode reaction is proposed. It is based on the determination of the variation of the polarization resistance in a tubular platinum electrode with a laminar flow of electrolyte as a function of the activity of protons of the electrolyte solution. A theoretical expression that relates the experimental variables and the equilibrium polarization resistance is developed, which takes into account the current distribution along the electrode surface. The results are compared with others obtained previously, contributing to the verification of the kinetic mechanism through a completely different experimental procedure

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

    Science.gov (United States)

    Matsuura, Hiroaki; Yamawaki, Yosuke; Sasaki, Kosuke; Uchiyama, Shunichi

    2013-06-01

    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. 10 sec). 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 coulometric method can be used for the determination of the dissolved hydrogen concentration.

  16. 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)

  17. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.; Gogotsi, Yury

    2015-12-01

    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.

  19. Redox Response of Reduced Graphene Oxide-Modified Glassy Carbon Electrodes to Hydrogen Peroxide and Hydrazine

    Directory of Open Access Journals (Sweden)

    Jun-ichi Anzai

    2013-05-01

    Full Text Available The surface of a glassy carbon (GC electrode was modified with reduced graphene oxide (rGO to evaluate the electrochemical response of the modified GC electrodes to hydrogen peroxide (H2O2 and hydrazine. The electrode potential of the GC electrode was repeatedly scanned from −1.5 to 0.6 V in an aqueous dispersion of graphene oxide (GO to deposit rGO on the surface of the GC electrode. The surface morphology of the modified GC electrode was characterized by scanning electron microscopy (SEM and atomic force microscopy (AFM. SEM and AFM observations revealed that aggregated rGO was deposited on the GC electrode, forming a rather rough surface. The rGO-modified electrodes exhibited significantly higher responses in redox reactions of H2O2 as compared with the response of an unmodified GC electrode. In addition, the electrocatalytic activity of the rGO-modified electrode to hydrazine oxidation was also higher than that of the unmodified GC electrode. The response of the rGO-modified electrode was rationalized based on the higher catalytic activity of rGO to the redox reactions of H2O2 and hydrazine. The results suggest that rGO-modified electrodes are useful for constructing electrochemical sensors.

  20. Nickel-hydrogen battery and hydrogen storage alloy electrode; Nikkeru suiso denchi oyobi suiso kyuzo gokin denkyoku

    Energy Technology Data Exchange (ETDEWEB)

    Ono, T. [Furukawa Electric Co. Ltd., Tokyo (Japan); Furukawa, J. [The Furukawa Battery Co. Ltd., Yokohama (Japan)

    1996-03-22

    Hermetically sealed nickel-hydrogen battery has such problem that the inner pressure of the battery elevates when it is overcharged since the oxygen gas evolves from the positive electrode. This invention relates to the hermetically sealed nickel-hydrogen battery consisting of positive electrode composed mainly of nickel hydroxide and negative electrode composed mainly of hydrogen storage alloy. According to the invention, the negative electrode contains organic sulfur compound having carbon-sulfur bond. As a result, the elevation of battery inner pressure due to the hydrogen gas evolution, the decrease in discharge capacity due to the repetition of charge and discharge, and the lowering of voltage after charging can be suppressed. The adequate content of the organic sulfur compound is 0.05 - 1 part in weight to 100 part in weight of hydrogen storage alloy. As for the organic sulfur compound, n-butylthiol, ethylthioethane, phenyldithiobenzene, trimethylsulfonium bromide, thiobenzophenone, 2,4-dinitrobenzenesulfenyl chloride, and ethylene sulphidic acid are employed. 2 figs., 1 tab.

  1. Minimizing fouling at hydrogenated conical-tip carbon electrodes during dopamine detection in vivo.

    Science.gov (United States)

    Chandra, Shaneel; Miller, Anthony D; Bendavid, Avi; Martin, Philip J; Wong, Danny K Y

    2014-03-04

    In this paper, physically small conical-tip carbon electrodes (∼2-5 μm diameter and ∼4 μm axial length) were hydrogenated to develop a probe capable of withstanding fouling during dopamine detection in vivo. Upon hydrogenation, the resultant hydrophobic sp(3) carbon surface deters adsorption of amphiphilic lipids, proteins, and peptides present in extracellular fluid and hence minimizes electrode fouling. These hydrogenated carbon electrodes showed a 35% decrease in sensitivity but little change in the limit of detection for dopamine over a 7-day incubation in a synthetic laboratory solution containing 1.0% (v/v) caproic acid (a lipid), 0.1% (w/v) bovine serum albumin and 0.01% (w/v) cytochrome C (both are proteins), and 0.002% (w/v) human fibrinopeptide B (a peptide). Subsequently, during dopamine detection in vivo, over 70% of the dopamine oxidation current remained after the first 30 min of a 60-min experiment, and at least 50% remained over the next half-period at the hydrogenated carbon electrodes. On the basis of these results, an initial average electrode surface fouling rate of 1.2% min(-1) was estimated, which gradually declined to 0.7% min(-1). These results support minimal fouling at hydrogenated carbon electrodes applied to dopamine detection in vivo.

  2. 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.

  3. 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.

  4. Hydrogen Bond Dynamics in Aqueous Solutions: Ab initio Molecular ...

    Indian Academy of Sciences (India)

    Rate equation for the decay of CHB(t) · Definition of Hydrogen Bonds · Results of Molecular Dynamics · Dynamics of anion-water and water-water hydrogen bonds · Structural relaxation of anion-water & water-water H-bonds · Ab initio Molecular Dynamics : · Slide 14 · Dynamics of hydrogen bonds : CPMD results · Slide 16.

  5. Dynamic simulation of hydrogen isotope distillation unit

    International Nuclear Information System (INIS)

    Le Lann, J.M.; Latge, C.; Joulia, X.; Sere-Peyrigain, P.

    1995-01-01

    Dynamic simulation of hydrogen isotope distillation unit involved in the complex environment of a fusion power plant can be a powerful technique in view to analyze the tritium hazard potential. In this paper, issues related to the development of such a dynamic simulator with model formulation and the numerical treatment of the resulting Differential-Algebraic equation (DAE) system are properly adressed. The typical dynamic characteristics of such columns are quantitatively and qualitatively enlighted on case study with very large disturbances. The developed system has proven to be beneficial for understanding the dynamic behaviour and further for developing control schemes. (orig.)

  6. Dynamic simulation of hydrogen isotope distillation unit

    International Nuclear Information System (INIS)

    Le Lann, J.M.; Joulia, X.; Sere-Peyrigain, P.

    1994-01-01

    Dynamic simulation of hydrogen isotope distillation unit involved in the complex environment of a fusion power plant can be a powerful technique in view to analyze the tritium hazard potential. Issues related to the development of such a dynamic simulator with model formulation and the numerical treatment of the resulting Differential-Algebraic equation (DAE) system are properly addressed. The typical dynamic characteristics of such columns are quantitatively and qualitatively enlightened on case study with very large disturbances. The developed system has proven to be beneficial for understanding the dynamic behaviour and further for developing control schemes. (author) 12 refs.; 4 figs

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  8. Optimization of hydrogen uptake in Ag-CNTs electrodes with charge-discharge cyclic currents

    International Nuclear Information System (INIS)

    Khoshnevisan, B.; Behpour, M.; Kaveh, D.

    2009-01-01

    Electrochemical storage of hydrogen in Ag-CNTs (silver and carbon nanotubes) electrodes has been studied by potentiostat/galvanostat method. Foamed silver has been employed as a mattress for the CNTs and it caused better connections between CNTs and the silver. Therefore the enhancements in the hydrogen storage capacities have been justified. Acidic and thermal methods have been used for purifying the CNTs and the outputs have been characterized by XRD and Raman spectroscopy. It has been observed that in cyclic charge and discharge (C and D) procedures the amount of stored hydrogen in the electrodes (the discharge capacity) is very sensitive to the cyclic regulated currents and it is shown that the optimum value is about 326 mA h/g at 9 mA. This optimization can be attributed to two competitive phenomena: (i) re-alignment of the CNTs, and (ii) oxidation of the electrode's surface.

  9. 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.

  10. Electrochemical modeling of hydrogen storage in hydride-forming electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2009-01-01

    An electrochemical kinetic model (EKM) is developed, describing the electrochemical hydrogen storage in hydride-forming materials under equilibrium conditions. This model is based on first principles of electrochemical reaction kinetics and statistical thermodynamics and describes the complex,

  11. 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)

  12. Non-enzymatic hydrogen peroxide sensor using an electrode modified with iron pentacyanonitrosylferrate nanoparticles

    International Nuclear Information System (INIS)

    Razmi, H.; Mohammad-Rezaei, R.

    2010-01-01

    An electrochemical sensor was developed for determination of hydrogen peroxide (HP) based on a carbon ceramic electrode modified with iron pentacyanonitrosylferrate (FePCNF). The surface of an iron-doped CCE was derivatized in a solution of PCNF by cycling the electrode potential between -0. 2 and +1. 3 V for about 60 times. The morphology and the composition of the resulting electrode were characterized by scanning electron microscopy and Fourier transform infrared techniques. The electrode displayed excellent response to the electro-oxidation of HP which is linearly related to its concentration in the range from 0. 5 μM to 1300 μM. The detection limit is 0. 4 μM, and the sensitivity is 849 A M -1 cm -2 . The modified electrode was used to determination of HP in hair coloring creams as real samples. (author)

  13. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented Electrochemical Kinetic Model (EKM), describing the electrochemical hydrogen storage in hydride-forming materials, has been extended by the description of the solid/electrolyte interface, i.e. the charge transfer kinetics and electrical double layer charging. A complete set of

  14. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented electrochemical kinetic model, describing the electrochemical hydrogen storage in hydride-forming materials, was extended by the description of the solid/electrolyte interface, i.e., the charge-transfer kinetics and electrical double-layer charging. A complete set of equations

  15. Plasma Temperature Determination of Hydrogen Containing High-Frequency Electrode less Lamps by Intensity Distribution Measurements of Hydrogen Molecular Band

    International Nuclear Information System (INIS)

    Gavare, Z.; Revalde, G.; Skudra, A.

    2011-01-01

    The goal of the present work was the investigation of the possibility to use intensity distribution of the Q-branch lines of the hydrogen Fulcher-a diagonal band (d3η u- a3Σg + electronic transition; Q-branch with ν=ν=2) to determine the temperature of hydrogen containing high-frequency electrode less lamps (HFEDLs). The values of the rotational temperatures have been obtained from the relative intensity distributions for hydrogen-helium and hydrogen-argon HFEDLs depending on the applied current. The results have been compared with the method of temperature derivation from Doppler profiles of He 667.8 nm and Ar 772.4 nm lines. The results of both methods are in good agreement, showing that the method of gas temperature determination from the intensity distribution in the hydrogen Fulcher-a (2-2)Q band can be used for the hydrogen containing HFEDLs. It was observed that the admixture of 10% hydrogen in the argon HFEDLs significantly reduces the gas temperature

  16. 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.

  17. Turning Cellulose Waste Into Electricity: Hydrogen Conversion by a Hydrogenase Electrode

    Science.gov (United States)

    Abramov, Sergey M.; Sadraddinova, Elmira R.; Shestakov, Andrey I.; Voronin, Oleg G.; Karyakin, Arkadiy A.; Zorin, Nikolay A.; Netrusov, Alexander I.

    2013-01-01

    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. PMID:24312437

  18. Influence of nonionic surfactants on the potentiometric response of hydrogen ion-selective polymeric membrane electrodes.

    Science.gov (United States)

    Espadas-Torre, C; Bakker, E; Barker, S; Meyerhoff, M E

    1996-05-01

    The influence of poly(ethylene oxide)-based nonionic surfactants (i.e., Triton X-100 and Brij 35) in the sample phase on the response properties of hydrogen ion-selective polymeric membrane electrodes containing mobile (lipophilic amines) or covalently bound (aminated-poly-(vinyl chloride)) hydrogen ion carriers is reported. In the presence of these nonionic surfactants, membrane electrode response toward interfering cation activity (e.g., Na+) in the sample phase is increased substantially and the pH measuring range shortened. The degree of cation interference for pH measurements is shown to correlate with the basicity of the hydrogen ion carrier doped within the membrane phase. The observed deterioration in selectivity arises from the partitioning of the surfactant into the membrane and concomitant extraction of metal cations by the surfactants in the organic phase. The effect of nonionic surfactants on pH electrodes prepared with aminated-PVC membranes is shown to be more complex, with additional large shifts in EMF values apparently arising from multidentate interactions between the surfactant molecules and the polymeric amine in the membrane, leading to a change in the apparent pKa values for the amine sites. The effects induced by nonionic surfactants on the EMF response function of hydrogen ion-selective polymeric membrane electrodes are modeled, and experimental results are shown to correlate well with theoretical predictions.

  19. 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

    the changes in the shape of the total reflection feature. We assume that the change in the morphology of the surface is due to the diffusion of hydrogen in the silicon electrode. This assumption allow us to model the changes in the reflected intensity at two different angles and find the diffusion exponent...

  20. 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.

  1. Redox Control and Hydrogen Production in Sediment Caps Using Carbon Cloth Electrodes

    Science.gov (United States)

    Sun, Mei; Yan, Fei; Zhang, Ruiling; Reible, Danny D.; Lowry, Gregory V.; Gregory, Kelvin B.

    2010-01-01

    Sediment caps that degrade contaminants can improve their ability to contain contaminants relative to sand and sorbent-amended caps, but few methods to enhance contaminant degradation in sediment caps are available. The objective of this study was to determine if, carbon electrodes emplaced within a sediment cap at poised potential could create a redox gradient and provide electron donor for the potential degradation of contaminants. In a simulated sediment cap overlying sediment from the Anacostia River (Washington, DC), electrochemically induced redox gradients were developed within 3 days and maintained over the period of the test (~100 days). Hydrogen and oxygen were produced by water electrolysis at the electrode surfaces and may serve as electron donor and acceptor for contaminant degradation. Electrochemical and geochemical factors that may influence hydrogen production were studied. Hydrogen production displayed zero order kinetics with ~75% coulombic efficiency and rates were proportional to the applied potential between 2.5V to 5V and not greatly affected by pH. Hydrogen production was promoted by increasing ionic strength and in the presence of natural organic matter. Graphite electrode-stimulated degradation of tetrachlorobenzene in a batch reactor was dependent on applied voltage and production of hydrogen to a concentration above the threshold for biological dechlorination. These findings suggest that electrochemical reactive capping can potentially be used to create “reactive” sediments caps capable of promoting chemical or biological transformations of contaminants within the cap. PMID:20879761

  2. 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

  3. 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. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  4. 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)

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2017-10-11

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

  7. 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.

  8. Hydrogen peroxide biosensor based on microperoxidase-11 immobilized in a silica cavity array electrode.

    Science.gov (United States)

    Tian, Shu; Zhou, Qun; Gu, Zhuomin; Gu, Xuefang; Zhao, Lili; Li, Yan; Zheng, Junwei

    2013-03-30

    Hydrogen peroxide biosensor based on the silica cavity array modified indium-doped tin oxide (ITO) electrode was constructed. An array of silica microcavities was fabricated by electrodeposition using the assembled polystyrene particles as template. Due to the resistance gradient of the silica cavity structure, the silica cavity exhibits a confinement effect on the electrochemical reactions, making the electrode function as an array of "soft" microelectrodes. The covalently immobilized microperoxidase-11(MP-11) inside these SiO2 cavities can keep its physiological activities, the electron transfer between the MP-11 and electrode was investigated through electrochemical method. The cyclic voltammetric curve shows a quasi-reversible electrochemical redox behavior with a pair of well-defined redox peaks, the cathodic and anodic peaks are located at -0.26 and -0.15V. Furthermore, the modified electrode exhibits high electrocatalytic activity toward the reduction of hydrogen peroxide and also shows good analytical performance for the amperometric detection of H2O2 with a linear range from 2×10(-6) to 6×10(-4)M. The good reproducibility and long-term stability of this novel electrode not only offer an opportunity for the detection of H2O2 in low concentration, but also provide a platform to construct various biosensors based on many other enzymes. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies

    International Nuclear Information System (INIS)

    Lobyntseva, Elena; Kallio, Tanja; Alexeyeva, Nadezda; Tammeveski, Kaido; Kontturi, Kyoesti

    2007-01-01

    The electrochemical reduction of oxygen on various catalysts was studied using the thin-layer rotating disk electrode (RDE) method. High-surface-area carbon was modified with an anthraquinone derivative and gold nanoparticles. Polytetrafluoroethylene (PTFE) and cationic polyelectrolyte (FAA) were used as binders in the preparation of thin-film electrodes. Our primary goal was to find a good electrocatalyst for the two-electron reduction of oxygen to hydrogen peroxide. All electrochemical measurements were carried out in 0.1 M KOH. Cyclic voltammetry was used in order to characterise the surface processes of the modified electrodes in O 2 -free electrolyte. The RDE results revealed that the carbon-supported gold nanoparticles are active catalysts for the four-electron reduction of oxygen in alkaline solution. Anthraquinone-modified high-area carbon catalyses the two-electron reduction at low overpotentials, which is advantageous for hydrogen peroxide production. In addition, the polymer electrolyte fuel cell technology was used for the generation of hydrogen peroxide. The cell was equipped with a bipolar membrane which consisted of commercial Nafion 117 as a cation-exchange layer and FT-FAA as an anion-exchange layer. The bipolar membranes were prepared by a hot pressing method. Use of the FAA ionomer as a binder for the anthraquinone-modified carbon catalyst resulted in production of hydrogen peroxide

  10. Analysis of the dynamic behavior of porous nickel electrodes in alkaline solutions

    International Nuclear Information System (INIS)

    Real, Silvia G; Visintin, Arnaldo; Castro, Elida B

    2004-01-01

    The nickel electrode is important for its electrocatalytic properties, when it is used in water electrolysis, and for use as a positive terminal in alkaline nickel-cadmium, nickel-iron, nickel-zinc, nickel-hydrogen and nickel-metal hydride batteries. Since there are many factors related to the functioning of these batteries that have still not been clarified, such as the memory effect associated with the change in structure of the nickel hydroxide and the phenomenon of 'battery sudden death', that produce serious problems mostly in spaces uses, this work discusses the dynamic behavior of the porous nickel hydroxide electrode. This electrode possesses outstanding properties such as high power density, good cyclability and elevated specific energy, which make it unique for the above-mentioned applications. The electrochemical storage of energy in this electrode is based on the reversible characteristics of nickel hydroxide/oxhydroxide redox coupling. The reversibility of the process is an important factor in battery materials. In the case of the Ni oxide, during the electrode discharge H + is inserted and this process inverts during the charging. This work presents the results obtained with the use of impedance spectroscopy for different discharge states of the electrode material in order to correlate its electrochemical properties according to the development of physical chemical models. These models include the charging and discharging processes, the process of proton diffusion in the solid and the porous nature of the material. Knowledge about the functioning of the electrode material is obtained by adjusting the experimental data according to the model and the parametric identification to determine values associated with such variables as area of active material, diffusion coefficient of the H + , conductivity of the solid as a function of the discharge state and kinetic constants of the charge transfer process (CW)

  11. Synthesis of nano-sized hydrogen phosphate-imprinted polymer in acetonitrile/water mixture and its use as a recognition element of hydrogen phosphate selective all-solid state potentiometric electrode.

    Science.gov (United States)

    Alizadeh, Taher; Atayi, Khalil

    2018-02-01

    Herein, a new recipe is introduced for the preparation of hydrogen phosphate ion-imprinted polymer nanoparticles (nano-IIP) in acetonitrile/water (63.5:36.5) using phosphoric acid as the template. The nano-IIP obtained was used as the recognition element of a carbon paste potentiometric sensor. The IIP electrode showed a Nernstian response to hydrogen phosphate anion; whereas, the non-imprinted polymer (NIP)-based electrode had no considerable sensitivity to the anion. The presence of both methacrylic acid and vinyl pyridine in the IIP structure, as well as optimization of the functional monomers-template proportion, was found to be important to observe the sensing capability of the IIP electrode. The nano-IIP electrode showed a dynamic linear range of 1 × 10 -5 -1 × 10 -1  mol L-1, Nernstian slope of 30.6 ± (0.5) mV decade -1 , response time of 25 seconds, and detection limit of 4.0 × 10 -6  mol L -1 . The utility of the electrodes was checked by potentiometric titration of hydrogen phosphate with La 3+ solution. Copyright © 2017 John Wiley & Sons, Ltd.

  12. The development of hydrogen storage electrode alloys for nickel hydride batteries

    Science.gov (United States)

    Hong, Kuochih

    The development of hydrogen storage electrode alloys in the 1980s resulted in the birth and growth of the rechargeable nickel hydride (Ni/MH) battery. In this paper we describe briefly a semi-empirical electrochemical/thermodynamic approach to develop/screen a hydrogen storage alloy for electrochemical application. More specifically we will discuss the AB x Ti/Zr-based alloys. Finally, the current state of the Ni/MH batteries including commercial manufacture processes, cell performance and applications is given.

  13. 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.

  14. Changes on iron electrode surface during hydrogen permeation in borate buffer solution

    International Nuclear Information System (INIS)

    Modiano, S.; Carreno, J.A.V.; Fugivara, C.S.; Torresi, R.M.; Vivier, V.; Benedetti, A.V.; Mattos, O.R.

    2008-01-01

    Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E oc ) and in the passive region (+0.30 V ECS ) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L -1 H 3 BO 3 + 0.075 mol L -1 Na 2 B 4 O 7 (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell

  15. 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.

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

    International Nuclear Information System (INIS)

    Ruckman, M.W.; Strongin, M.; Weismann, H.

    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 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 modern electronic devices

  17. Electrochemical investigations of activation and degradation of hydrogen storage alloy electrodes in sealed Ni/MH battery

    Energy Technology Data Exchange (ETDEWEB)

    Chen, W.X.; Xu, Z.D. [Zhejiang University, Hangzhou (China). Dept. of Chemistry; Tu, J.P. [Zhejiang University, Hangzhou (China). Dept. of Materials Science and Engineering

    2002-04-01

    The M1Ni{sub 0.4}Co{sub 0.6}Al{sub 0.4} alloy was treated with hot alkaline solution containing a small amount of KBH{sub 4} and its effect on the activation and degradation behaviors of the hydrogen storage alloy electrodes in sealed Ni/MH batteries was investigated. It was found that the treated alloy electrode exhibited a better activation property than the untreated one in the sealed battery as well as in open cell. For the treated alloy electrode activating, the polarization resistance in the sealed battery was almost equal to that in the open cell. But in the case of the untreated alloy electrode activating, the polarization resistance in the sealed battery was larger than that in the open cell. The reason is that the oxide film on the untreated alloy surface suppressed the combination of the oxygen evolved on the positive electrode with hydrogen on the negative alloy surface. In addition, the decaying of capacity of the untreated alloy electrode was much faster than that of the treated one. The reasons were, that after surface treatment, the Ni-rich and Al-poor layer on the alloy surface not only had a high electrocatalytic activity for hydrogen electrode reaction, but also facilitated the combination of the oxygen with hydrogen and hydrogen adsorption on the alloy surface. (author)

  18. 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.

  19. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-04-15

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

  1. Photo-electrocatalytic hydrogen generation at dye-sensitised electrodes functionalised with a heterogeneous metal catalyst

    International Nuclear Information System (INIS)

    Hoogeveen, Dijon A.; Fournier, Maxime; Bonke, Shannon A.; Fang, Xi-Ya; Mozer, Attila J.; Mishra, Amaresh; Bäuerle, Peter; Simonov, Alexandr N.; Spiccia, Leone

    2016-01-01

    Dye-sensitised photocathodes promoting hydrogen evolution are usually coupled to a catalyst to improve the reaction rate. Herein, we report on the first successful integration of a heterogeneous metal particulate catalyst, viz., Pt aggregates electrodeposited from acidic solutions on the surface of a NiO-based photocathode sensitised with a p-type perylenemonoimid-sexithiophene-triphenylamine dye (PMI-6T-TPA). The platinised dye-NiO electrodes generate photocurrent density of ca −0.03 mA cm −2 (geom.) with 100% faradaic efficiency for the H 2 evolution at 0.059 V vs. reversible hydrogen electrode under 1 sun visible light irradiation (AM1.5G, 100 mW cm −2 , λ > 400 nm) for more than 10 hours in 0.1 M H 2 SO 4 (aq.). The Pt-free dye-NiO and dye-free Pt-modified NiO cathodes show no photo-electrocatalytic hydrogen evolution under these conditions. The performance of these Pt-modified PMI-6T-TPA-based photoelectrodes compares well to that of previously reported dye-sensitised photocathodes for H 2 evolution.

  2. Dynamic environmental transmission electron microscopy observation of platinum electrode catalyst deactivation in a proton-exchange-membrane fuel cell.

    Science.gov (United States)

    Yoshida, Kenta; Xudong, Zhang; Bright, Alexander N; Saitoh, Koh; Tanaka, Nobuo

    2013-02-15

    Spherical-aberration-corrected environmental transmission electron microscopy (AC-ETEM) was applied to study the catalytic activity of platinum/amorphous carbon electrode catalysts in proton-exchange-membrane fuel cells (PEMFCs). These electrode catalysts were characterized in different atmospheres, such as hydrogen and air, and a conventional high vacuum of 10(-5) Pa. A high-speed charge coupled device camera was used to capture real-time movies to dynamically study the diffusion and reconstruction of nanoparticles with an information transfer down to 0.1 nm, a time resolution below 0.2 s and an acceleration voltage of 300 kV. With such high spatial and time resolution, AC-ETEM permits the visualization of surface-atom behaviour that dominates the coalescence and surface-reconstruction processes of the nanoparticles. To contribute to the development of robust PEMFC platinum/amorphous carbon electrode catalysts, the change in the specific surface area of platinum particles was evaluated in hydrogen and air atmospheres. The deactivation of such catalysts during cycle operation is a serious problem that must be resolved for the practical use of PEMFCs in real vehicles. In this paper, the mechanism for the deactivation of platinum/amorphous carbon electrode catalysts is discussed using the decay rate of the specific surface area of platinum particles, measured first in a vacuum and then in hydrogen and air atmospheres for comparison.

  3. Hydrogen substituted graphdiyne as carbon-rich flexible electrode for lithium and sodium ion batteries.

    Science.gov (United States)

    He, Jianjiang; Wang, Ning; Cui, Zili; Du, Huiping; Fu, Lin; Huang, Changshui; Yang, Ze; Shen, Xiangyan; Yi, Yuanping; Tu, Zeyi; Li, Yuliang

    2017-10-27

    Organic electrodes are potential alternatives to current inorganic electrode materials for lithium ion and sodium ion batteries powering portable and wearable electronics, in terms of their mechanical flexibility, function tunability and low cost. However, the low capacity, poor rate performance and rapid capacity degradation impede their practical application. Here, we concentrate on the molecular design for improved conductivity and capacity, and favorable bulk ion transport. Through an in situ cross-coupling reaction of triethynylbenzene on copper foil, the carbon-rich frame hydrogen substituted graphdiyne film is fabricated. The organic film can act as free-standing flexible electrode for both lithium ion and sodium ion batteries, and large reversible capacities of 1050 mAh g -1 for lithium ion batteries and 650 mAh g -1 for sodium ion batteries are achieved. The electrode also shows a superior rate and cycle performances owing to the extended π-conjugated system, and the hierarchical pore bulk with large surface area.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  5. Determination of hydrogen peroxide using a Prussian Blue modified macroporous gold electrode

    International Nuclear Information System (INIS)

    Yang, Jiao; Lin, Meng; Cho, MiSuk; Lee, Youngkwan

    2015-01-01

    We describe an electrochemical sensor for hydrogen peroxide (H 2 O 2 ) that is making use of Prussian Blue (PB) electrodeposited on a macroporous (mp) gold skeleton electrode. An mp-Cu film was first prepared as a template and the converted into an mp-Au film through a replacement reaction without destructing the structure. Next, a layer of PB was electrochemically deposited on the surface of the mp-Au film. The surface morphology of the electrode was characterized by scanning electron microscopy. Attenuated total reflection infrared spectroscopy and X-ray photoelectron spectroscopy were applied to confirm the structural features. The mp-PB/Au film electrode displays high electro-catalytic activity for the reduction of H 2 O 2 at a working potential of −50 mV (vs. Ag/AgCl) and is very stable. It has a linear response to H 2 O 2 in the 50 μM to 11.3 mM concentration range and a sensitivity of 767 μA∙mM −1 cm −2 . The electrode also revealed good selectivity in the presence of electro-active species such as ascorbic acid and uric acid. (author)

  6. 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.

  7. Hydrogen peroxide biosensor based on DNA-Hb modified gold electrode

    International Nuclear Information System (INIS)

    Kafi, A.K.M.; Fan Yin; Shin, Hoon-Kyu; Kwon, Young-Soo

    2006-01-01

    A hydrogen peroxide (H 2 O 2 ) biosensor based on DNA-hemoglobin (Hb) modified electrode is described in this paper. The sensor was designed by DNA and hemoglobin dropletting onto gold electrode surface layer by layer. The sensor based on the direct electron transfer of iron of hemoglobin showed a well electrocatalytic response to the reduction of the H 2 O 2 . This sensor offered an excellent electrochemical response for H 2 O 2 concentration below micromole level with high sensitivity and selectivity and short response time. Experimental conditions influencing the biosensor performance such as, pH, potential were optimized and assessed. The levels of the RSD's ( 2 O 2 was observed from 10 to 120 μM with the detection limit of 0.4 μM (based on the S/N = 3)

  8. Mechanisms of improving the cyclic stability of V-Ti-based hydrogen storage electrode alloys

    International Nuclear Information System (INIS)

    Miao He; Wang Weiguo

    2010-01-01

    Research highlights: → The corrosion resistance of V-based phase is much lower than that of C14 Laves phase of V-Ti-based alloys. → The addition of Cr which mostly distributes in V-based phase can effectively increase the anti-corrosion ability of V-Ti-based alloys. → The addition of Cr which mostly distributes in V-based phase can effectively increase the anti-corrosion ability of V-Ti-based alloys. - Abstract: In this work, the mechanisms of improving the cyclic stability of V-Ti-based hydrogen storage electrode alloys were investigated systemically. Several key factors for example corrosion resistance, pulverization resistance and oxidation resistance were evaluated individually. The V-based solid solution phase has much lower anti-corrosion ability than C14 Laves phase in KOH solution, and the addition of Cr in V-Ti-based alloys can suppress the dissolution of the main hydrogen absorption elements of the V-based phase in the alkaline solution. During the charge/discharge cycling, the alloy particles crack or break into several pieces, which accelerates their corrosion/oxidation and increases the contact resistance of the alloy electrodes. Proper decreasing the Vickers hardness and enhancing the fracture toughness can increase the pulverization resistance of the alloy particles. The oxidation layer thickness on the alloy particle surface obviously increases during charge/discharge cycling. This deteriorates their electro-catalyst activation to the electrochemical reaction, and leads to a quick degradation. Therefore, enhancing the oxide resistance can obviously improve the cyclic stability of V-Ti-based hydrogen storage electrode alloys.

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

    International Nuclear Information System (INIS)

    Rau, M.S.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2010-01-01

    The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H 2 SO 4 solution at different rotation rates (ω). 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 ω 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.

  10. 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

    standard hydrogen electrode potential (ASHEP) from the calculated work function. Although conceptually correct, this procedure introduces two sources of errors: (i) the experimental estimate of the ASHEP varies from 4.28 to 4.85 V and, as has been previously shown and is reconfirmed here, (ii...... possess in order for its computed ASHEP to closely match the experimental benchmark. We capture and quantify these three effects by calculating trends in the ASHEP and PZC on eight close-packed transition metals, considering the four most simple and representative water models. Finally, it is also...

  11. 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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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

  13. Hydrogen spillover phenomenon: Enhanced reversible hydrogen adsorption/desorption at Ta{sub 2}O{sub 5}-coated Pt electrode in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Sata, Shunsuke [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Awad, Mohamed I.; El-Deab, Mohamed S. [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Department of Chemistry, Faculty of Science, Cairo University, Cairo (Egypt); Okajima, Takeyoshi [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-5 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-04-01

    The current study is concerned with the preparation and characterization of tantalum oxide-loaded Pt (TaO{sub x}/Pt) electrodes for hydrogen spillover application. XPS, SEM, EDX and XRD techniques are used to characterize the TaO{sub x}/Pt surfaces. TaO{sub x}/Pt electrodes were prepared by galvanostatic electrodeposition of Ta on Pt from LiF-NaF (60:40 mol%) molten salts containing K{sub 2}TaF{sub 7} (20 wt%) at 800 deg. C and then by annealing in air at various temperatures (200, 400 and 600 deg. C). The thus-fabricated TaO{sub x}/Pt electrodes were compared with the non-annealed Ta/Pt and the unmodified Pt electrodes for the hydrogen adsorption/desorption (H{sub ads}/H{sub des}) reaction. The oxidation of Ta to the stoichiometric oxide (Ta{sub 2}O{sub 5}) increases with increasing the annealing temperature as revealed from XPS and X-ray diffraction (XRD) measurements. The higher the annealing temperature the larger is the enhancement in the H{sub ads}/H{sub des} reaction at TaO{sub x}/Pt electrode. The extraordinary increase in the hydrogen adsorption/desorption at the electrode annealed at 600 deg. C is explained on the basis of a hydrogen spillover-reverse spillover mechanism. The hydrogen adsorption at the TaO{sub x}/Pt electrode is a diffusion-controlled process.

  14. Metal hydride electrode and nickel hydrogen storage battery; Suiso kyuzo gokin denkyoku oyobi nikkeru-suiso chikudenchi

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Y.; Tamagawa, H. [Shin-Kobe Electric Machinery Co. Ltd., Tokyo (Japan); Ikawa, A.; Muranaka, R. [Hitachi Ltd., Ibaraki (Japan). Hitachi Research Lab.

    1996-04-16

    Water soluble polymers such as cellulose derivatives and polyvinylalcohol have been used conventionally as binders for metal hydride electrode used for nickel-hydrogen storage batteries. The shortcomings of those binders, however, are low flexibility, and poor binding property for hydrogen absorbing alloy powder and the conductive supporting substrate. This invention relates to the use of ethylene-vinyl copolymer with less than -10{degree}C Tg as the binder for hydrogen absorbing alloy powder. It is desirable that the ethylene-vinylacetate copolymer is selected out of ethylene-vinyl acetate-acryl copolymer and ethylene-vinyl acetate-long chain vinyl ester copolymer, and that the addition is larger than 0.1wt% and less than 1wt% against the weight of hydrogen absorbing alloy in the electrode. The use of this binder results in strong binding of hydrogen absorbing alloy powder to the conductive supporting substrate, providing flexibility as well. 4 figs., 5 tabs.

  15. 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.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  17. Structure of hydrogenated amorphous silicon from ab initio molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Buda, F. (Department of Physics, The Ohio State University, 174 West 18th Avenue, Columbus, Ohio (USA)); Chiarotti, G.L. (International School for Advanced Studies, Strada Costiera 11, I-34014 Trieste (Italy) Laboratorio Tecnologie Avanzate Superfici e Catalisi del Consorzio Interuniversitario Nazionale di Fisica della Materia, Padriciano 99, I-34012 Trieste (Italy)); Car, R. (International School for Advanced Studies, Strada Costiera 11, I-34014 Trieste (Italy) Institut Romard de Recherche Numerique en Physique des Materiaux, CH-1015 Lausanne, Switzerland Department of Condensed Matter Physics, University of Geneva, CH-1211 Geneva (Switzerland)); Parrinello, M. (IBM Research Division, Zurich Research Laboratory, CH-8803 Rueschlikon (Switzerland))

    1991-09-15

    We have generated a model of hydrogenated amorphous silicon by first-principles molecular dynamics. Our results are in good agreement with the available experimental data and provide new insight into the microscopic structure of this material. The calculation lends support to models in which monohydride complexes are prevalent, and indicates a strong tendency of hydrogen to form small clusters.

  18. Quorum sensing alters the microbial community of electrode-respiring bacteria and hydrogen scavengers toward improving hydrogen yield in microbial electrolysis cells

    International Nuclear Information System (INIS)

    Cai, Weiwei; Zhang, Zhaojing; Ren, Ge; Shen, Qiuxuan; Hou, Yanan; Ma, Anzhou; Deng, Ye; Wang, Aijie; Liu, Wenzong

    2016-01-01

    Highlights: • Enhanced hydrogen yield has been achieved with addition of AHL. • AHL regulated exoelectrogens resulting in electrochemical activity enhancement. • Microbial community shift in cathodic biofilm inhibited hydrogen loss. - Abstract: Quorum sensing has been widely applied to enhance the energy recovery of bioelectrochemical system as a sustainable pathway to enhance communication between cells and electrodes. However, how signalling molecules (acyl-homoserine lactones, AHLs) regulate the microbial community to improve hydrogen generation in microbial electrolysis cells (MECs) is not well understood, especially the subsequent influence on interspecies relationships among not only electrode-respiring bacteria but also hydrogen scavengers. Understanding AHL regulation in a complicated and actual biofilm system will be valuable for future applications of microbial electrochemical technology. Herein, we added short-chain AHLs (3OC6) to regulate the biofilm community on bio-electrodes in MECs. As a result, hydrogen yields were enhanced with AHL addition, increasing by 5.57%, 38.68%, and 81.82% with varied external voltages (0.8 V, 0.6 V, and 0.4 V, respectively). Accordingly, overall reactor performance was enhanced, including coulombic efficiency, electron recovery efficiency, and energy efficiency. Based on an electrochemical impedance spectra analysis, the structured biofilm under simple nutrient conditions (acetate) showed a lower internal resistance with AHL addition, indicating that the microbial communities were altered to enhance electron transfer between the biofilm and electrode. The change in the cathodic microbial structure with more electrochemically active bacteria and fewer hydrogen scavengers could contribute to a higher electron recovery and hydrogen yield with AHL addition. The regulation of the microbial community structure by AHLs represents a potential strategy to enhance electron transfer and hydrogen generation in

  19. Passivation behavior of AB{sub 5}-type hydrogen storage alloys for battery electrode application

    Energy Technology Data Exchange (ETDEWEB)

    Meli, F. [Fribourg Univ. (Switzerland). Inst. de Physique; Sakai, T. [Fribourg Univ. (Switzerland). Inst. de Physique; Zuettel, A. [Fribourg Univ. (Switzerland). Inst. de Physique; Schlapbach, L. [Fribourg Univ. (Switzerland). Inst. de Physique

    1995-04-15

    In many applications, AB{sub 5} type hydrogen storage alloys show passivation behavior, i.e. when fully discharged, metal hydride electrodes show (especially at higher temperatures) a decrease in activity and therefore a decrease in capacity at normal discharge currents for ensuing cycles. Passivation may continue to the point where activity becomes so low that the capacity is no longer accessible. Electrochemical measurements were taken of two different AB{sub 5}-type alloys, one with manganese and one without manganese (LaNi{sub 3.4}Co{sub 1.2}Al{sub 0.4} and LaNi{sub 3.4}Co{sub 1.2}Al{sub 0.3}Mn{sub 0.1}). Both alloys showed passivation behavior after remaining in the discharged state. The alloy with manganese showed a stronger tendency to passivation which is in contradiction with earlier observations. Photoelectron spectroscopic analysis together with sputter depth profiling was used to investigate the surface composition of samples which had undergone different surface pretreatments. Surface analysis of electrodes in the passivated state shows a lower content of metallic nickel and a thicker nickel surface oxide film. We attribute the low electrochemical kinetics of the alloys after passivation to the loss of metallic nickel and/or cobalt at the electrode-electrolyte interface. ((orig.))

  20. Performance of Pd on activated carbon as hydrogen electrode with respect to hydrogen yield in a single cell proton exchange membrane (PEM) water electrolyser

    Energy Technology Data Exchange (ETDEWEB)

    Naga Mahesh, K.; Sarada Prasad, J.; Venkateswer Rao, M.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad 500085 (A.P.) (India); Yerramilli, Anjaneyulu [TLGVRC, JSU Box 18739, Jackson State University, Jackson, MS 32917 - 0939 (United States); Raghunathan Rao, P. [Fuel cell section, Heavy Water Division, Bhabha Atomic Research Centre, Trombay, Mumbai - 400 085 (India)

    2009-08-15

    Palladium (Pd) on activated carbon is used as electrocatalyst coated on Nafion 115 membrane as Hydrogen electrode and RuO{sub 2} is coated on other side of membrane used as oxygen electrode. 5 wt% and 10 wt% Pd on activated carbon is prepared as membrane electrode assembly (MEA) and investigated the performance of the same using inhouse prepared 10 cm{sup 2} single cell. The performance of the single cell assembly and the hydrogen yield are reported during electrolysis operation at temperatures 27 C, 45 C and 65 C at 0.1, 0.2, 0.3, 0.4, 0.5 A/cm{sup 2} current densities with respect to voltages. (author)

  1. Development of high temperature reference electrodes for in-pile application: Part I. Feasibility study of the external pressure balanced Ag/AgCl reference electrode (EPBRE) and the cathodically charged Palladium hydrogen electrode

    International Nuclear Information System (INIS)

    Bosch, R.W.; Van Nieuwenhove, R.

    1998-10-01

    The main problems connected with corrosion potential measurements at elevated temperatures and pressures are related to the stability and lifetime of the reference electrode and the correct estimation of the potential related to the Standard Hydrogen Scale (SHE). Under Pressurised Water Reactor (PWR) conditions of 300 degrees Celsius and 150 bar, the choice of materials is also a limiting factor due to the influence of radiation. Investigations on two reference electrodes that can be used under PWR conditions are reported: the cathodically charged palladium hydrogen electrode, and the external pressure balanced silver/silver chloride electrode. Preliminary investigations with the Pd-electrode were focused on the calculation of the required charging time and the influence of dissolved oxygen. High temperature applications are discussed on the basis of results reported in the literature. Investigations with the silver/silver chloride reference electrode mainly dealt with the salt bridge which is necessary to connect the reference electrode with the testing solution. It is shown that the thermal junction potential is independent of the length of the salt bridge. In addition, the high temperature contributes to an increase of the conductivity of the solution, which is beneficial for the salt bridge connection

  2. Hydrogen-bonding effects on film structure and photoelectrochemical properties of porphyrin and fullerene composites on nanostructured TiO 2 electrodes

    NARCIS (Netherlands)

    Kira, Aiko; Tanaka, Masanobu; Umeyama, Tomokazu; Matano, Yoshihiro; Yoshimoto, Naoki; Zhang, Yi; Ye, Shen; Lehtivuori, Heli; Tkachenko, Nikolai V.; Lemmetyinen, Helge; Imahori, Hiroshi

    2007-01-01

    Hydrogen-bonding effects on film structures and photophysical, photoelectrochemical, and photovoltaic properties have been examined in mixed films of porphyrin and fullerene composites with and without hydrogen bonding on nanostructured TiO2 electrodes. The nanostructured TiO2 electrodes modified

  3. Formation dynamics of UV and EUV induced hydrogen plasma

    NARCIS (Netherlands)

    Dolgov, A.A.; Lee, Christopher James; Yakushev, O.; Lopaev, D.V.; Abrikosov, A.; Krivtsun, V.M.; Zotovich, A.; Bijkerk, F.

    2014-01-01

    The comparative study of the dynamics of ultraviolet (UV) and extreme ultraviolet (EUV) induced hydrogen plasma was performed. It was shown that for low H2 pressures and bias voltages, the dynamics of the two plasmas are significantly different. In the case of UV radiation, the plasma above the

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

    Energy Technology Data Exchange (ETDEWEB)

    Asaji, Tetsuo, E-mail: asaji@chs.nihon-u.ac.jp [Nihon University, Department of Chemistry, College of Humanities and Sciences (Japan)

    2016-12-15

    The temperature dependences of {sup 1}H NMR as well as {sup 35}Cl NQR spin-lattice relaxation times T{sub 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{sub B} and the activation energy V/ k{sub 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{sub 1} on the low-temperature side of the T{sub 1} minimum. The NQR T{sub 1} measurements was revealed to be a good probe for the hydrogen transfer dynamics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-02-15

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

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

    International Nuclear Information System (INIS)

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-01-01

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

  7. Production method of hydrogen storage alloy electrode and hydrogen storage alloy for rechageable battery; Suiso kyuzo gokin denkyoku oyobi chikudenchiyo suiso kyuzo gokin no seizo hoho

    Energy Technology Data Exchange (ETDEWEB)

    Mizutaki, F.; Ishimaru, M.

    1995-04-07

    This invention relates to the hydrogen storage alloy electrode in which the misch metal-nickel system hydrogen storage alloy is employed. The grain of the hydrogen storage alloy is controlled so as to reduce the dendrite cell size. Since the hydrogen storage alloy having such small dendrite cell size has no part where the metal structure is too brittle, the alloy has a sufficient mechanical strength. It can stand for the swell and shrink stress associated with the sorption and desorption of hydrogen. The disintegration, therefore, due to the cracking of the alloy is hardly to take place. In addition, the quenching of molten alloy at a cooling rate of 1000{degree}C/sec or faster suppresses the occurrence of segregation of any alloy element at the grain boundary, making it possible to produce the homogeneous and mechanically strong alloy. In other words, it can be achieved to produce a hydrogen storage alloy electrode having an excellent cycle property. 4 figs., 1 tab.

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

    International Nuclear Information System (INIS)

    Ogawa, Hiroshi

    2015-01-01

    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

  9. Decoupling Hydrogen and Oxygen Production in Acidic Water Electrolysis Using a Polytriphenylamine-Based Battery Electrode.

    Science.gov (United States)

    Ma, Yuanyuan; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2018-03-05

    Hydrogen production through water splitting is considered a promising approach for solar energy harvesting. However, the variable and intermittent nature of solar energy and the co-production of H 2 and O 2 significantly reduce the flexibility of this approach, increasing the costs of its use in practical applications. Herein, using the reversible n-type doping/de-doping reaction of the solid-state polytriphenylamine-based battery electrode, we decouple the H 2 and O 2 production in acid water electrolysis. In this architecture, the H 2 and O 2 production occur at different times, which eliminates the issue of gas mixing and adapts to the variable and intermittent nature of solar energy, facilitating the conversion of solar energy to hydrogen (STH). Furthermore, for the first time, we demonstrate a membrane-free solar water splitting through commercial photovoltaics and the decoupled acid water electrolysis, which potentially paves the way for a new approach for solar water splitting. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

    Science.gov (United States)

    Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

    2018-03-01

    Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-03-31

    Highlights: • High Faradic efficiency for CO (95%) is achieved on bulk Ag electrode. • The addition of DTAB contributes to enhanced CO{sub 2} conversion efficiency. • Hydrogen evolution is suppressed by the adsorbed DTAB on Ag electrode. - Abstract: Electrochemical CO{sub 2} reduction provides a desirable pathway to convert greenhouse gas into useful chemicals. It is a great challenge to reduce CO{sub 2} efficiently in aqueous solution, especially on commercial bulk metal electrodes. Here, we report substantial improvement in CO{sub 2} reduction on bulk silver electrode through the introduction of ionic surfactant in aqueous electrolyte. The hydrogen evolution on the electrode surface is greatly suppressed by the surfactant, while the catalytic ability of silver towards CO{sub 2} reduction is maintained. The Faradaic efficiency for CO is greatly enhanced from 50% to 95% after the addition of this low-cost surfactant. This study may provide new pathways towards efficient CO{sub 2} reduction through the inhibition of proton reduction.

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

    Science.gov (United States)

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

    2013-01-09

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-09

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

  14. 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.

  15. The Seebeck coefficient and the Peltier effect in a polymer electrolyte membrane cell with two hydrogen electrodes

    International Nuclear Information System (INIS)

    Kjelstrup, S.; Vie, P.J.S.; Akyalcin, L.; Zefaniya, P.; Pharoah, J.G.; Burheim, O.S.

    2013-01-01

    Highlights: • The heat change associated with the hydrogen electrode in a polymer electrolyte cell is determined from Seebeck coefficient measurements. • When electric current is passed from left to right in the outer circuit, the anode becomes warmer, while the cathode becomes colder in a thermoelectric cell with hydrogen electrodes. • At Soret equilibrium for water in the fuel cell, most of the entropy of the fuel cell reaction is generated at the anode. -- Abstract: We report that the Seebeck coefficient of a Nafion membrane cell with hydrogen electrodes saturated with water vapour, at 1 bar hydrogen pressure and 340 K, is equal to 670 ± 50 μV/K, meaning that the entropy change of the anode reaction at reversible conditions (67 J/(K mol)) corresponds to a reversible heat release of 22 kJ/mol. The transported entropy of protons across the membrane at Soret equilibrium was estimated from this value to 1 ± 5 J/(K mol). The results were supported by the expected variation in the Seebeck coefficient with the hydrogen pressure. We report also the temperature difference of the electrodes, when passing electric current through the cell, and find that the anode is heated (a Peltier heat effect), giving qualitative support to the result for the Seebeck coefficient. The Seebeck and Peltier effects are related by non-equilibrium thermodynamics theory, and the Peltier heat of the cathode in the fuel cell is calculated for steady state conditions to 6 ± 2 kJ/mol at 340 K. The division of the reversible heat release between the anode and the cathode, can be expected to vary with the current density, as the magnitude of the current density can have a big impact on water transport and water concentration profile

  16. 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

  17. New electrodes for hydrogen/oxygen solid polymer electrolyte fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Mosdale, R [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Recherche Fondamentale sur la Matiere Condensee; Stevens, P [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Thermohydraulique et de Physique

    1993-12-31

    A new method of preparation of Electrode/Membrane/Electrode (EME) assemblies for Proton Exchange Membrane Fuel Cells (PEMFC) has been developed. The electrodes are deposited directly onto a Nafion electrolyte membrane from a mixture of platinized carbon, Nafion solution, and PTFE by using a spray technique. By this technique, porous electrodes are obtained with an optimized gas/electrolyte/catalyst interface, and electrode/membrane interface.

  18. A distributed dynamic model of a monolith hydrogen membrane reactor

    International Nuclear Information System (INIS)

    Michelsen, Finn Are; Wilhelmsen, Øivind; Zhao, Lei; Aasen, Knut Ingvar

    2013-01-01

    Highlights: ► We model a rigorous distributed dynamic model for a HMR unit. ► The model includes enough complexity for steady-state and dynamic analysis. ► Simulations show that the model is non-linear within the normal operating range. ► The model is useful for studying and handling disturbances such as inlet changes and membrane leakage. - Abstract: This paper describes a distributed mechanistic dynamic model of a hydrogen membrane reformer unit (HMR) used for methane steam reforming. The model is based on a square channel monolith structure concept, where air flows adjacent to a mix of natural gas and water distributed in a chess pattern of channels. Combustion of hydrogen gives energy to the endothermic steam reforming reactions. The model is used for both steady state and dynamic analyses. It therefore needs to be computationally attractive, but still include enough complexity to study the important steady state and dynamic features of the process. Steady-state analysis of the model gives optimum for the steam to carbon and steam to oxygen ratios, where the conversion of methane is 92% and the hydrogen used as energy for the endothermic reactions is 28% at the nominal optimum. The dynamic analysis shows that non-linear control schemes may be necessary for satisfactory control performance

  19. 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...

  20. Study of hydrogenation for pulverization of rare earth alloys with Nb for metal hydride electrodes

    International Nuclear Information System (INIS)

    Ferreira, Eliner Affonso

    2013-01-01

    In this work were studied La ,7 Mg 0,3 Al 0,3 Mn 0,4 Co (0.5-x) NbxNi 3.8 (x= 0 - 0.5) and La 0,7 Mg 0,3 Al 0,3 Mn 0.4 Nb (05+x) Co 0,5 Ni (3.8-x) . (x=0.3; 0.5;1.3) alloys for negative electrodes of the Nickel-Metal Hydride batteries. The hydrogenation of the alloys was performed varying pressing of H 2 (2 and 9 bar). The discharge capacity of the nickel-metal hydride batteries were analyzed in the Arbin BT-4 electrical test equipment. The as-cast alloys were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and X-Ray diffraction. The increasing Niobium addition in the alloys decreased cycle life and the maximum discharge capacity of the batteries. The maximum discharge capacity was obtained with the La .7 Mg 0.3 Al 0.3 Mn 0,4 Co 0.5 Ni 3.8 (45.36 mAh) and the battery which presented the best performance was La .7 Mg 0.3 Al 0.3 Mn 0.4 Co 0.5 Nb 0.1 Ni 3.8 (44.94 mAh). (author)

  1. Ultrafast Hydrogen-Bonding Dynamics in Amyloid Fibrils.

    Science.gov (United States)

    Pazos, Ileana M; Ma, Jianqiang; Mukherjee, Debopreeti; Gai, Feng

    2018-06-08

    While there are many studies on the subject of hydrogen bonding dynamics in biological systems, few, if any, have investigated this fundamental process in amyloid fibrils. Herein, we seek to add insight into this topic by assessing the dynamics of a hydrogen bond buried in the dry interface of amyloid fibrils. To prepare a suitable model peptide system for this purpose, we introduce two mutations into the amyloid-forming Aβ(16-22) peptide. The first one is a lysine analog at position 19, which is used to help form structurally homogeneous fibrils, and the second one is an aspartic acid derivative (DM) at position 17, which is intended (1) to be used as a site-specific infrared probe and (2) to serve as a hydrogen-bond acceptor to lysine so that an inter-β-sheet hydrogen bond can be formed in the fibrils. Using both infrared spectroscopy and atomic force microscopy, we show that (1) this mutant peptide indeed forms well defined fibrils, (2) when bulk solvent is removed, there is no detectable water present in the fibrils, (3) infrared results obtained with the DM probe are consistent with a protofibril structure that is composed of two antiparallel β-sheets stacked in a parallel fashion, leading to formation of the expected hydrogen bond. Using two-dimensional infrared spectroscopy, we further show that the dynamics of this hydrogen bond occur on a timescale of ~2.3 ps, which is attributed to the rapid rotation of the -NH3+ group of lysine around its Cε-Nζ bond. Taken together, these results suggest that (1) DM is a useful infrared marker in facilitating structure determination of amyloid fibrils and (2) even in the tightly packed core of amyloid fibrils certain amino acid sidechains can undergo ultrafast motions, hence contributing to the thermodynamic stability of the system.

  2. 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.

  3. Dynamics of Molecular Hydrogen in Hypersaline Microbial Mars

    Science.gov (United States)

    Hoehler, Tori M.; Bebout, Brad M.; Visscher, Pieter T.; DesMarais, David J.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Early Earth microbial communities that centered around the anaerobic decomposition of organic molecular hydrogen as a carrier of electrons, regulator of energy metabolism, and facilitator of syntroph'c microbial interactions. The advent of oxygenic photosynthetic organisms added a highly dynamic and potentially dominant term to the hydrogen economy of these communities. We have examined the daily variations of hydrogen concentrations in cyanobacteria-dominated microbial mats from hypersaline ponds in Baja California Sur, Mexico. These mats bring together phototrophic and anaerobic bacteria (along with virtually all other trophic groups) in a spatially ordered and chemically dynamic matrix that provides a good analog for early Earth microbial ecosystems. Hydrogen concentrations in the photic zone of the mat can be three orders of magnitude or more higher than in the photic zone, which are, in turn, an order of magnitude higher than in the unconsolidated sediments underlying the mat community. Within the photic zone, hydrogen concentrations can fluctuate dramatically during the diel (24 hour day-night) cycle, ranging from less than 0.001% during the day to nearly 10% at night. The resultant nighttime flux of hydrogen from the mat to the environment was up to 17% of the daytime oxygen flux. The daily pattern observed is highly dependent on cyanobacterial species composition within the mat, with Lyngbya-dominated systems having a much greater dynamic range than those dominated by Microcoleus; this may relate largely to differing degrees of nitrogen-fixing and fermentative activity in the two mats. The greatest H2 concentrations and fluxes were observed in the absence of oxygen, suggesting an important potential feedback control in the context of the evolution of atmospheric composition. The impact of adding this highly dynamic photosynthetic term to the hydrogen economy of early microbial ecosystems must have been substantial. From an evolutionary standpoint, the H2

  4. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction

    Science.gov (United States)

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

    2015-10-01

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

  5. 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

  6. Hydrogen production from a rectangular horizontal filter press Divergent Electrode-Flow-Through (DEFT™) alkaline electrolysis stack

    Science.gov (United States)

    Gillespie, M. I.; Kriek, R. J.

    2017-12-01

    A membraneless Divergent Electrode-Flow-Through (DEFT™) alkaline electrolyser, for unlocking profitable hydrogen production by combining a simplistic, inexpensive, modular and durable design, capable of overcoming existing technology current density thresholds, is ideal for decentralised renewable hydrogen production, with the only requirement of electrolytic flow to facilitate high purity product gas separation. Scale-up of the technology was performed, representing a deviation from the original tested stack design, incorporating elongated electrodes housed in a filter press assembly. The pilot plant operating parameters were limited to a low flow velocity range (0.03 m s-1 -0.04 m s-1) with an electrode gap of 2.5 mm. Performance of this pilot plant demonstrated repeatability to results previously obtained. Mesh electrodes with geometric area of 344.32 cm2 were used for plant performance testing. A NiO anode and Ni cathode combination developed optimal performance yielding 508 mA cm-2 at 2 VDC in contrast to a Ni anode and cathode combination providing 467 mA cm-2 at 2.26 VDC at 0.04 m s-1, 30% KOH and 80 °C. An IrO2/RuO2/TiO2 anode and Pt cathode combination underwent catalyst deactivation. Owing to the nature of the gas/liquid separation system, gas qualities were inadequate compared to results achieved previously. Future improvements will provide qualities similar to results achieved before.

  7. Ni-Zn electrodes for hydrogen production by acid electrolysis; Eletrodos de Ni-Zn para producao de hidrogenio por eletrolise acida

    Energy Technology Data Exchange (ETDEWEB)

    Torres, C.S.; Malfatti, C.F., E-mail: camilator@gmail.com [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre (Brazil). Departamento de Metalurgia. Lab. de Pesquisa em Corrosao

    2014-07-01

    Hydrogen production by electrolysis of water, have an important role in countries that have great renewable potential for electricity production. The electrolysis of water has been proposed to use the excess capacity of hydroelectric plants. However, to improve process efficiency, research has been undertaken to improve the catalytic reduction reaction of hydrogen from the development of electrodes with better performance. Thus, the selection of low cost electrode materials with good electrocatalytic activity is required. In this work, the hydrogen evolution reaction (HER) employing electrodes of Ni-Zn and Ni was investigated. Morphological characterization of the electrodes was performed using SEM/ EDX and profilometry and electrochemical behavior was evaluated by cathodic polarization curves. The results showed that the addition of Zn promotes the increase the electrocatalytic activity of HER compared to nickel electrode. (author)

  8. ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

    Science.gov (United States)

    Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

  9. An amperometric hydrogen peroxide biosensor based on Co3O4 nanoparticles and multiwalled carbon nanotube modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Kaçar, Ceren; Dalkiran, Berna; Erden, Pınar Esra; Kiliç, Esma

    2014-01-01

    Highlights: • Hydrogen peroxide biosensor was constructed by combining the advantageous properties of MWCNTs and Co 3 O 4 . • Incorporating Co 3 O 4 nanoparticles into MWCNTs/gelatin film increased the electron transfer. • Co 3 O 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 3 O 4 nanoparticles, multiwall carbon nanotubes (MWCNTs) and gelatin. The introduction of MWCNTs and Co 3 O 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 −7 –1.9 × 10 −5 M with a detection limit of 7.4 × 10 −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

  10. 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.

  11. Microscopic dynamics and relaxation processes in liquid hydrogen fluoride

    International Nuclear Information System (INIS)

    Angelini, R.; Giura, P.; Monaco, G.; Sette, F.; Fioretto, D.; Ruocco, G.

    2004-01-01

    Inelastic x-ray scattering and Brillouin light scattering measurements of the dynamic structure factor of liquid hydrogen fluoride have been performed in the temperature range T=214-283 K. The data, analyzed using a viscoelastic model with a two time-scale memory function, show a positive dispersion of the sound velocity c(Q) between the low frequency value c 0 (Q) and the high frequency value c ∞α (Q). This finding confirms the existence of a structural (α) relaxation directly related to the dynamical organization of the hydrogen bonds network of the system. The activation energy E a of the process has been extracted by the analysis of the temperature behavior of the relaxation time τ α (T) that follows an Arrhenius law. The obtained value for E a , when compared with that observed in another hydrogen bond liquid as water, suggests that the main parameter governing the α-relaxation process is the number of hydrogen bonds per molecule

  12. Influence of oxygen on hydrogen storage and electrode properties for micro-designed V-based battery alloys

    Energy Technology Data Exchange (ETDEWEB)

    Tsukahara, M.; Takahashi, K.; Isomura, A. [Mater. R and D Co., Ltd., Aichi (Japan). IMRA; Sakai, T. [Osaka National Research Institute, Midorigaoka, Ikeda-shi, Osaka, 563 (Japan)

    1998-01-30

    The influence of oxygen on micro-structure, hydrogen storage and electrode properties were investigated for the alloy V{sub 3}TiNi{sub 0.56}Co{sub 0.14}Nb{sub 0.047}Ta{sub 0.047}. Since titanium in the alloy worked as a deoxidizer to form the oxide phase, the alloy preserved a large hydrogen capacity in the oxygen concentration range below 5000 mass ppm. More oxygen than 6000 mass ppm caused a remarkable contraction of the unit cell of the vanadium-based main phase and then a decrease in the hydrogen storage capacity. The contraction was accompanied by the precipitation of the Ti-based oxide phase. (orig.) 15 refs.

  13. Fragmentation dynamics of molecular hydrogen in strong ultrashort laser pulses

    International Nuclear Information System (INIS)

    Rudenko, A; Feuerstein, B; Zrost, K; Jesus, V L B de; Ergler, T; Dimopoulou, C; Schroeter, C D; Moshammer, R; Ullrich, J

    2005-01-01

    We present the results of a systematic experimental study of dissociation and Coulomb explosion of molecular hydrogen induced by intense ultrashort (7-25 fs) laser pulses. Using coincident recoil-ion momentum spectroscopy we can distinguish the contributions from dissociation and double ionization even if they result in the same kinetic energies of the fragments. The dynamics of all fragmentation channels drastically depends on the pulse duration, and for 7 fs pulses becomes extremely sensitive to the pulse shape

  14. Photocatalytic properties of PbS/graphene oxide/polyaniline electrode for hydrogen generation.

    Science.gov (United States)

    Shaban, Mohamed; Rabia, Mohamed; El-Sayed, Asmaa M Abd; Ahmed, Aya; Sayed, Somaya

    2017-10-26

    In this work, roll-graphene oxide (Ro-GO), polyaniline (PANI) nano/microparticles, and PbS nanoparticles were prepared by modified Hammer, oxidative polymerization, and chemical bath deposition methods, respectively. These nano/microstructures were characterized, optimized, and designed to form PbS/Ro-GO/PANI nano/microcomposite. Also, the ratios of PbS and Ro-GO were optimized, and the optimized composition of the used composite was 0.4 g PANI, 0.125 g Ro-GO, and 0.075 g PbS. The band gap values for PANI, PbS, Ro-GO, and PbS/Ro-GO/PANI rocomposite were 3, 1.13, 2.86, (1.16, 2) eV, respectively. Two photoelectrode assemblies, Au/PbS/Ro-GO/PANI and PbS/Ro-GO/PANI/ITO/glass were used for the photoelectrochemical (PEC) hydrogen generation. In the first assembly 45 nm- Au layer was sputtered on the surface of a disk of PbS/Ro-GO/PANI composite. For the second assembly, a disk of PbS/Ro-GO/PANI composite was glued on ITO glass using Ag-THF paste. The lifetime efficiency values were 64.2 and 43.4% for the first and second electrode for 2 h, respectively. Finally, the incident photon-to-current conversion efficiency (IPCE) and photon-to-current efficiency (ABPE) were calculated under monochromatic illumination conditions. The optimum IPCE efficiency at 390 nm was 9.4% and 16.17%, whereas ABPE % efficiency was 1.01% and 1.75% for Au/PbS/Ro-GO/PANI and PbS/Ro-GO/PANI/ITO/glass, respectively.

  15. Hydrogenation of the rare earth alloys for production negative electrodes of nickel-metal hydride batteries

    International Nuclear Information System (INIS)

    Casini, Julio Cesar Serafim

    2011-01-01

    In this work were studied of La 0.7-x Mg x Pr 0.3 Al 0.3 Mn 0.4 Co 0.5 Ni 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 2 (2 and 10 bar) and temperature (room and 500 ℃). 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 0.7 Pr 0.3 Al 0.3 Mn 0.4 Co 0.5 Ni 3.8 alloy (60 mAh) and the battery which presented the best performance was La 0.4 Mg 0.3 Pr 0.3 Al 0.3 Mn 0.4 Co 0.5 Ni 3.8 alloy (53 mAh and 150 cycles). The H 2 capability of absorption was diminished for increased Mg addition and no such effect occurs for Mg 0.7 Pr 0.3 Al 0.3 Mn 0.4 Co 0.5 Ni 3.8 alloy. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-06-30

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

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

    Science.gov (United States)

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

    2018-06-01

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

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

    Science.gov (United States)

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

    2010-03-01

    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 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) valid in the limit of thin double layers (compared to typical pore dimensions). We illustrate the theory for 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 with different time scales: (i) in the “supercapacitor regime” of small voltages and/or early times, the porous electrode acts like a transmission line, governed by a linear diffusion equation for the electrostatic potential, scaled to the RC time of a single pore, and (ii) in the “desalination regime” of large voltages and long times, the porous electrode slowly absorbs counterions, governed by coupled, nonlinear diffusion equations for the pore-averaged potential and salt concentration.

  19. A Dynamic Mesh-Based Approach to Model Melting and Shape of an ESR Electrode

    Science.gov (United States)

    Karimi-Sibaki, E.; Kharicha, A.; Bohacek, J.; Wu, M.; Ludwig, A.

    2015-10-01

    This paper presents a numerical method to investigate the shape of tip and melt rate of an electrode during electroslag remelting process. The interactions between flow, temperature, and electromagnetic fields are taken into account. A dynamic mesh-based approach is employed to model the dynamic formation of the shape of electrode tip. The effect of slag properties such as thermal and electrical conductivities on the melt rate and electrode immersion depth is discussed. The thermal conductivity of slag has a dominant influence on the heat transfer in the system, hence on melt rate of electrode. The melt rate decreases with increasing thermal conductivity of slag. The electrical conductivity of slag governs the electric current path that in turn influences flow and temperature fields. The melting of electrode is a quite unstable process due to the complex interaction between the melt rate, immersion depth, and shape of electrode tip. Therefore, a numerical adaptation of electrode position in the slag has been implemented in order to achieve steady state melting. In fact, the melt rate, immersion depth, and shape of electrode tip are interdependent parameters of process. The generated power in the system is found to be dependent on both immersion depth and shape of electrode tip. In other words, the same amount of power was generated for the systems where the shapes of tip and immersion depth were different. Furthermore, it was observed that the shape of electrode tip is very similar for the systems running with the same ratio of power generation to melt rate. Comparison between simulations and experimental results was made to verify the numerical model.

  20. 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

  1. Amperometric biosensor for hydrogen peroxide based on Hemoglobin/DNA/Poly-2,6-pyridinediamine modified gold electrode

    International Nuclear Information System (INIS)

    Tong Zhongqiang; Yuan Ruo; Chai Yaqin; Chen Shihong; Xie Yi

    2007-01-01

    An amperometric biosensor for hydrogen peroxide (H 2 O 2 ) was fabricated based on immobilization of hemoglobin (Hb) on DNA/Poly-2,6-pyridinediamine (PPD) modified Au electrode. PPD thin films were firstly electro-deposited on Au electrode surface which provide a template to attach negatively charged DNA molecules by electrostatic attraction. The adsorbed DNA network provides a good microenvironment for the immobilization of biomolecules and promotes electron transfer between the immobilized Hb and the electrode surface. The fabrication process of the biosensor was characterized by electrochemical impedance spectroscopy. Experimental conditions influencing the biosensor performance such as pH, potential and temperature were assessed and optimized. The proposed biosensor displayed a good electrocatalytic response to the reduction of H 2 O 2 , its linear range is 1.7 μM to 3 mM with a detection limit of 1.0 μM based on the signal-to-noise ratio of 3 (S/N = 3) under the optimized conditions. The Michaelis-Menten constant K m app of Hb immobilized on the electrode surface was found to be 0.8 mM. The biosensor shows high sensitivity and stability. Importantly, this deposition methodology could be further developed for the immobilization of other proteins and biocompounds

  2. Self-Supported Biocarbon-Fiber Electrode Decorated with Molybdenum Carbide Nanoparticles for Highly Active Hydrogen-Evolution Reaction.

    Science.gov (United States)

    Xiao, Jian; Zhang, Yan; Zhang, Zheye; Lv, Qiying; Jing, Feng; Chi, Kai; Wang, Shuai

    2017-07-12

    Devising and facilely synthesizing an efficient noble metal-free electrocatalyst for the acceleration of the sluggish kinetics in the hydrogen-evolution reaction (HER) is still a big challenge for electrolytic water splitting. Herein, we present a simple one-step approach for constructing self-supported biocarbon-fiber cloth decorated with molybdenum carbide nanoparticles (BCF/Mo 2 C) electrodes by a direct annealing treatment of the Mo oxyanions loaded cotton T-shirt. The Mo 2 C nanoparticles not only serve as the catalytic active sites toward the HER but also enhance the hydrophilicity and conductivity of resultant electrodes. As an integrated three-dimensional HER cathode catalyst, the BCF/Mo 2 C exhibits outstanding electrocatalytic performance with extremely low overpotentials of 88 and 115 mV to drive a current density of 20 mA cm -2 in alkaline and acidic media, respectively. In addition, it can continuously work for 50 h with little decrease in the cathodic current density in both alkaline and acidic solutions. Even better, self-supported tungsten carbide and vanadium carbide based electrodes also can be prepared by a similar synthesis process. This work will illuminate an entirely new avenue for the preparation of various self-supported three-dimensional electrodes made of transition-metal carbides for various applications.

  3. Lysine, Arginine, and Histidine Residues in Peptide-Catalyzed Hydrogen Evolution at Mercury Electrodes

    Czech Academy of Sciences Publication Activity Database

    Dorčák, Vlastimil; Vargová, Veronika; Ostatná, Veronika; Paleček, Emil

    2015-01-01

    Roč. 27, č. 4 (2015), s. 910-916 ISSN 1040-0397 R&D Projects: GA ČR(CZ) GA15-15479S; GA ČR(CZ) GA13-00956S Institutional support: RVO:68081707 Keywords : AMALGAM ELECTRODES * STRIPPING CHRONOPOTENTIOMETRY * CARBON ELECTRODES Subject RIV: BO - Biophysics Impact factor: 2.471, year: 2015

  4. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

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

    1996-01-01

    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...... 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......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...

  5. Hydrogen Tunneling Links Protein Dynamics to Enzyme Catalysis

    Science.gov (United States)

    Klinman, Judith P.; Kohen, Amnon

    2014-01-01

    The relationship between protein dynamics and function is a subject of considerable contemporary interest. Although protein motions are frequently observed during ligand binding and release steps, the contribution of protein motions to the catalysis of bond making/breaking processes is more difficult to probe and verify. Here, we show how the quantum mechanical hydrogen tunneling associated with enzymatic C–H bond cleavage provides a unique window into the necessity of protein dynamics for achieving optimal catalysis. Experimental findings support a hierarchy of thermodynamically equilibrated motions that control the H-donor and -acceptor distance and active-site electrostatics, creating an ensemble of conformations suitable for H-tunneling. A possible extension of this view to methyl transfer and other catalyzed reactions is also presented. The impact of understanding these dynamics on the conceptual framework for enzyme activity, inhibitor/drug design, and biomimetic catalyst design is likely to be substantial. PMID:23746260

  6. A reagentless non-enzymatic hydrogen peroxide sensor presented using electrochemically reduced graphene oxide modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Mutyala, Sankararao; Mathiyarasu, Jayaraman

    2016-01-01

    Herein, we report a simple, facile and reproducible non-enzymatic hydrogen peroxide (H 2 O 2 ) sensor using electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). The modified electrode was characterized by Fourier transform infrared (FT-IR), UV–Visible, scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. Cyclic voltammetric (CV) analysis revealed that ERGO/GCE exhibited virtuous charge transfer properties for a standard redox systems and showed excellent performance towards electroreduction of H 2 O 2 . Amperometric study using ERGO/GCE showed high sensitivity (0.3 μA/μM) and faster response upon the addition of H 2 O 2 at an applied potential of − 0.25 V vs. Ag/AgCl. The detection limit is assessed to be 0.7 μM (S/N = 3) and the time to reach a stable study state current is < 3 s for a linear range of H 2 O 2 concentration (1–16 μM). In addition, the modified electrode exhibited good reproducibility and long-term stability. - Graphical abstract: We presented a reagentless non-enzymatic hydrogen peroxide sensor using electrochemically reduced graphene oxide material. - Highlights: • A facile green procedure proposed for high quality graphene synthesis using electrochemical reduction of graphene oxide • A simple, facile and reagentless non-enzymatic hydrogen peroxide sensor developed using ERGO/GCE. • ERGO/GCE exhibited high sensitivity, selectivity and finite limit of detection for H 2 O 2 sensing at low overpotential. • ERGO/GCE exhibited long term stability and good reproducibility.

  7. A reagentless non-enzymatic hydrogen peroxide sensor presented using electrochemically reduced graphene oxide modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Mutyala, Sankararao; Mathiyarasu, Jayaraman, E-mail: al_mathi@yahoo.com

    2016-12-01

    Herein, we report a simple, facile and reproducible non-enzymatic hydrogen peroxide (H{sub 2}O{sub 2}) sensor using electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). The modified electrode was characterized by Fourier transform infrared (FT-IR), UV–Visible, scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. Cyclic voltammetric (CV) analysis revealed that ERGO/GCE exhibited virtuous charge transfer properties for a standard redox systems and showed excellent performance towards electroreduction of H{sub 2}O{sub 2}. Amperometric study using ERGO/GCE showed high sensitivity (0.3 μA/μM) and faster response upon the addition of H{sub 2}O{sub 2} at an applied potential of − 0.25 V vs. Ag/AgCl. The detection limit is assessed to be 0.7 μM (S/N = 3) and the time to reach a stable study state current is < 3 s for a linear range of H{sub 2}O{sub 2} concentration (1–16 μM). In addition, the modified electrode exhibited good reproducibility and long-term stability. - Graphical abstract: We presented a reagentless non-enzymatic hydrogen peroxide sensor using electrochemically reduced graphene oxide material. - Highlights: • A facile green procedure proposed for high quality graphene synthesis using electrochemical reduction of graphene oxide • A simple, facile and reagentless non-enzymatic hydrogen peroxide sensor developed using ERGO/GCE. • ERGO/GCE exhibited high sensitivity, selectivity and finite limit of detection for H{sub 2}O{sub 2} sensing at low overpotential. • ERGO/GCE exhibited long term stability and good reproducibility.

  8. Use of hydrogen peroxide to achieve interference-free stripping voltammetric determination of copper at the bismuth-film electrode

    International Nuclear Information System (INIS)

    Pacheco, Wagner F.; Miguel, Eliane M.; Ramos, Gabriel V.; Cardoso, Carlos E.; Farias, Percio A.M.; Aucelio, Ricardo Q.

    2008-01-01

    In this work, a new approach is presented to allow interference-free determination of Cu (II) by stripping voltammetry using the bismuth-film electrode. The addition of hydrogen peroxide to the electroanalytical cell has promoted complete resolution between re-dissolution peaks of Bi (III) and Cu (II). The absence of interference could be evaluated by the correlation coefficient (r > 0.99) between Cu (II) concentration and its shifted current peak (at +212 mV) while achieving a slightly fluctuation of the bismuth current peak at -180 mV. Studies were performed aiming towards the optimum conditions for trace determination of Cu (II) using hydrogen peroxide. The methodology was applied to a real sample (sugarcane spirits) and the results were compared to those from graphite furnace atomic absorption spectrometry. The analytical parameters of merit and the results of the analysis indicated that the analytical methodology could be readily used for trace determination of Cu (II)

  9. 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.

  10. 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

  11. 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.

  12. A paste type negative electrode using a MmNi{sub 5} based hydrogen storage alloy for a nickel-metal hydride (Ni-MH) battery

    Energy Technology Data Exchange (ETDEWEB)

    Uchida, H.; Matsumoto, T.; Watanabe, S.; Kobayashi, K.; Hoshino, H. [Tokai Univ., Kanagawa (Japan). School of Engineering

    2001-07-01

    Different conducting materials (nickel, copper, cobalt, graphite) were mixed with a MmNi{sub 5} type hydrogen storage alloy, and negative electrodes for a nickel-metal hydride(Ni-MH) rechargeable battery were prepared and examined with respect to the discharge capacity of the electrodes. The change in the discharge capacity of the electrodes with different conducting materials was measured as a function of the number of electrochemical charge and discharge cycles. From the measurements, the electrodes with cobalt and graphite were found to yield much higher discharge capacities than those with nickel or cobalt. From a comparative discharge measurements for an electrode composed of only cobalt powder without the alloy and an electrode with a mixture of cobalt and the alloy, an appreciable contribution of the cobalt surface to the enhancement of charge and discharge capacities was found. (author)

  13. Evaluation of Hydrogen Cracking in Weld Metal Deposited using Cellulosic-Coated Electrodes

    Science.gov (United States)

    2009-06-16

    Cellulosic-coated electrodes (primarily AWS EXX10-type) are traditionally used for "stovepipe" welding of pipelines because they are well suited for deposition of pipeline girth welds and are capable of high deposition rates when welding downhill. De...

  14. Fluorescence quenching studies of potential-dependent DNA reorientation dynamics at glassy carbon electrode surfaces.

    Science.gov (United States)

    Li, Qin; Cui, Chenchen; Higgins, Daniel A; Li, Jun

    2012-09-05

    The potential-dependent reorientation dynamics of double-stranded DNA (ds-DNA) attached to planar glassy carbon electrode (GCE) surfaces were investigated. The orientation state of surface-bound ds-DNA was followed by monitoring the fluorescence from a 6-carboxyfluorescein (FAM6) fluorophore covalently linked to the distal end of the DNA. Positive potentials (i.e., +0.2 V vs open circuit potential, OCP) caused the ds-DNA to align parallel to the electrode surface, resulting in strong dipole-electrode quenching of FAM6 fluorescence. Switching of the GCE potential to negative values (i.e., -0.2 V vs OCP) caused the ds-DNA to reorient perpendicular to the electrode surface, with a concomitant increase in FAM6 fluorescence. In addition to the very fast (submilliseconds) dynamics of the initial reorientation process, slow (0.1-0.9 s) relaxation of FAM6 fluorescence to intermediate levels was also observed after potential switching. These dynamics have not been previously described in the literature. They are too slow to be explained by double layer charging, and chronoamperometry data showed no evidence of such effects. Both the amplitude and rate of the dynamics were found to depend upon buffer concentration, and ds-DNA length, demonstrating a dependence on the double layer field. The dynamics are concluded to arise from previously undetected complexities in the mechanism of potential-dependent ds-DNA reorientation. The possible origins of these dynamics are discussed. A better understanding of these dynamics will lead to improved models for potential-dependent ds-DNA reorientation at electrode surfaces and will facilitate the development of advanced electrochemical devices for detection of target DNAs.

  15. Dynamic model of organic pollutant degradation in three dimensional packed bed electrode reactor.

    Science.gov (United States)

    Pang, Tianting; Wang, Yan; Yang, Hui; Wang, Tianlei; Cai, Wangfeng

    2018-04-21

    A dynamic model of semi-batch three-dimensional electrode reactor was established based on the limiting current density, Faraday's law, mass balance and a series of assumptions. Semi-batch experiments of phenol degradation were carried out in a three-dimensional electrode reactor packed with activated carbon under different conditions to verify the model. The factors such as the current density, the electrolyte concentration, the initial pH value, the flow rate of organic and the initial organic concentration were examined to know about the pollutant degradation in the three-dimensional electrode reactor. The various concentrations and logarithm of concentration of phenol with time were compared with the dynamic model. It was shown that the calculated data were in good agreement with experimental data in most cases. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. 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.

  17. Transient dynamic finite element analysis of hydrogen distribution test chamber structure for hydrogen combustion loads

    International Nuclear Information System (INIS)

    Singh, R.K.; Redlinger, R.; Breitung, W.

    2005-09-01

    Design and analysis of blast resistant structures is an important area of safety research in nuclear, aerospace, chemical process and vehicle industries. Institute for Nuclear and Energy Technologies (IKET) of Research Centre- Karlsruhe (Forschungszentrum Karlsruhe or FZK) in Germany is pursuing active research on the entire spectrum of safety evaluation for efficient hydrogen management in case of the postulated design basis and beyond the design basis severe accidents for nuclear and non-nuclear applications. This report concentrates on the consequence analysis of hydrogen combustion accidents with emphasis on the structural safety assessment. The transient finite element simulation results obtained for 2gm, 4gm, 8gm and 16gm hydrogen combustion experiments concluded recently on the test-cell structure are described. The frequencies and damping of the test-cell observed during the hammer tests and the combustion experiments are used for the present three dimensional finite element model qualification. For the numerical transient dynamic evaluation of the test-cell structure, the pressure time history data computed with CFD code COM-3D is used for the four combustion experiments. Detail comparisons of the present numerical results for the four combustion experiments with the observed time signals are carried out to evaluate the structural connection behavior. For all the combustion experiments excellent agreement is noted for the computed accelerations and displacements at the standard transducer locations, where the measurements were made during the different combustion tests. In addition inelastic analysis is also presented for the test-cell structure to evaluate the limiting impulsive and quasi-static pressure loads. These results are used to evaluate the response of the test cell structure for the postulated over pressurization of the test-cell due to the blast load generated in case of 64 gm hydrogen ignition for which additional sets of computations were

  18. Long life nickel electrodes for a nickel-hydrogen cell: Cycle life tests

    Science.gov (United States)

    Lim, H. S.; Verzwyvelt, S. A.

    1985-01-01

    In order to develop a long life nickel electrode for a Ni/H2 cell, the cycle life of nickel electrodes was tested in Ni/H2 boiler plate cells. A 19 test cell matrix was made of various nickel electrode designs including three levels each of plaque mechanical strength, median pore size of the plaque, and active material loading. Test cells were cycled to the end of their life (0.5v) in a 45 minute low Earth orbit cycle regime at 80% depth-of-discharge. It is shown that the active material loading level affects the cycle life the most with the optimum loading at 1.6 g/cc void. Mechanical strength does not affect the cycle life noticeably in the bend strength range of 400 to 700 psi. It is found that the best plaque is made of INCO nickel powder type 287 and has median pore size of 13 micron.

  19. 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}.

  20. Hydrogen diffusion in La1.5Nd0.5MgNi9 alloy electrodes of the Ni/MH battery

    International Nuclear Information System (INIS)

    Volodin, A.A.; Denys, R.V.; Tsirlina, G.A.; Tarasov, B.P.; Fichtner, M.; Yartys, V.A.

    2015-01-01

    Highlights: • Hydrogen diffusion in the La 1.5 Nd 0.5 MgNi 9 alloy electrode was studied. • Various techniques of low amplitude potentiostatic data treatment were used. • D H demonstrates a maximum (2 × 10 −11 cm 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 1.5 Nd 0.5 MgNi 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 H changes with hydrogen content in the metal hydride anode electrode and has a maximum of ca. 2 × 10 −11 cm 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 x

  1. 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.

  2. 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.

  3. On dynamics of electric spark machining of pieces with the system of non-fixed electrod-tools

    International Nuclear Information System (INIS)

    Timoshenko, B.I.; Morozenko, V.N.

    1976-01-01

    Processing of bodies of revolution by a system of loose electrode-instruments freely resting upon the detail was considered. In this dynamic system correlations were found between the electrode-instrument mass, the angular velocity of the detail, the interelectrode space and the mechanic pulse value which agitated the oscillations of the electrode providing for the most efficient electro-spark treatment. A scheme of the forces acting on the electrode-instrument during the process was presented. An expression was obtained describing the optimum dependence between the oscillation system parametres, and an expression for the maximum number of discharges during an oscillation period of the electrode-inctrument [ru

  4. Ultrafast dynamics of hydrogen bond exchange in aqueous ionic solutions.

    Science.gov (United States)

    Park, Sungnam; Odelius, Michael; Gaffney, Kelly J

    2009-06-04

    The structural and dynamical properties of aqueous ionic solutions influence a wide range of natural and biological processes. In these solutions, water has the opportunity to form hydrogen bonds with other water molecules and anions. Knowing the time scale with which these configurations interconvert represents a key factor to understanding the influence of molecular scale heterogeneity on chemical events in aqueous ionic solutions. We have used ultrafast IR spectroscopy and Car-Parrinello molecular dynamics (CPMD) simulations to investigate the hydrogen bond (H-bond) structural dynamics in aqueous 6 M sodium perchlorate (NaClO4) solution. We have measured the H-bond exchange dynamics between spectrally distinct water-water and water-anion H-bond configurations with 2DIR spectroscopy and the orientational relaxation dynamics of water molecules in different H-bond configurations with polarization-selective IR pump-probe experiments. The experimental H-bond exchange time correlates strongly with the experimental orientational relaxation time of water molecules. This agrees with prior observations in water and aqueous halide solutions, and has been interpreted within the context of an orientational jump model for the H-bond exchange. The CPMD simulations performed on aqueous 6 M NaClO4 solution clearly demonstrate that water molecules organize into two radially and angularly distinct structural subshells within the first solvation shell of the perchlorate anion, with one subshell possessing the majority of the water molecules that donate H-bonds to perchlorate anions and the other subshell possessing predominantly water molecules that donate two H-bonds to other water molecules. Due to the high ionic concentration used in the simulations, essentially all water molecules reside in the first ionic solvation shells. The CPMD simulations also demonstrate that the molecular exchange between these two structurally distinct subshells proceeds more slowly than the H

  5. 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

  6. Electrode characteristics of the (Mm)Ni 5-based hydrogen storage alloys

    Energy Technology Data Exchange (ETDEWEB)

    Han, Dong Soo; Choi, Seung Jun; Chang, Min Ho; Choi, Jeon; Park, Choong Nyun [Chonnam National University, Kwangju (Korea, Republic of)

    1995-06-01

    The MmNi-based alloy electrode was studied for use a negative electrode in Ni-MH battery. Alloys with MmNi{sub 5}-{sub x} M{sub x}(M=Co,Al,Mn) composition were synthesized, and their electrode characteristics of activation rate, temperature dependence, electrode capacity and cycle life were investigated. With increasing Al content and decreasing Mn content in the alloys, the discharge capacity increased while the cycle life decreased. As x in MmNi{sub 5}-{sub x} M{sub x} increased from 1.5 to 2.0, decreasing the Ni content, the discharge capacity, the low temperature property and the rate capability decreased. However its cycle life was improved. Increasing Co content resulted in a prolonged cycle life and decrease of high rate discharge capacity. It can be concluded that the most promising alloy in view of discharge capacity and cycle life is MmNi{sub 3}.5 Co{sub 0}.7 Al{sub 0}.5 Mn{sub 0}.3. (author). 9 refs., 9 figs., 1 tab.

  7. Carbon paste electrode with covalently immobilized thionine for electrochemical sensing of hydrogen peroxide

    Science.gov (United States)

    Thenmozhi, K.; Sriman Narayanan, S.

    2017-11-01

    A water-soluble redox mediator, thionin was covalently immobilized to the functionalized graphite powder and a carbon paste electrode was fabricated from this modified graphite powder. The immobilization procedure proved to be effective in anchoring the thionin mediator in the graphite electrode setup without any leakage problem during the electrochemical studies. The covalent immobilization of the thionin mediator was studied with FT-IR and the electrochemical response of the thionin carbon paste electrode was optimized on varying the supporting electrolyte, pH and scan rate. The modified electrode exhibited well-defined electrocatalytic activity towards the reduction of H2O2 at a lower potential of -0.266 V with good sensitivity. The developed amperometric sensor was efficient towards H2O2 in the linear range from 2.46 × 10-5 M to 4.76 × 10-3 M, with a detection limit of 1.47 × 10-5 M respectively. Important advantages of this sensor are its excellent electrochemical performance, simple fabrication, easy renewability, reproducible analytical results, acceptable accuracy and good operational and long-term stability.

  8. Catalysis of Hydrogen Evolution by Polylysine, Polyarginine and Polyhistidine at Mercury Electrodes

    Czech Academy of Sciences Publication Activity Database

    Vargová, Veronika; Živanovic, Marko; Dorčák, Vlastimil; Paleček, Emil; Ostatná, Veronika

    2013-01-01

    Roč. 25, č. 9 (2013), s. 2130-2135 ISSN 1040-0397 R&D Projects: GA ČR(CZ) GA13-00956S Institutional research plan: CEZ:AV0Z50040702 Institutional support: RVO:68081707 Keywords : CONSTANT-CURRENT CHRONOPOTENTIOMETRY * BOVINE SERUM- ALBUMIN * CARBON ELECTRODES Subject RIV: BO - Biophysics Impact factor: 2.502, year: 2013

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

    Science.gov (United States)

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene; Martinazzo, Rocco

    2015-09-01

    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.

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

    Science.gov (United States)

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H; Burghardt, Irene; Martinazzo, Rocco

    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.

  11. 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.

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

    International Nuclear Information System (INIS)

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene; Martinazzo, Rocco

    2015-01-01

    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

  13. Electron-impact ionization of atomic hydrogen: dynamical variational treatment

    Energy Technology Data Exchange (ETDEWEB)

    Defrance, P.; Lecointre, J. [Institute of Condensed Matter and Nanosciences, Universite Catholique de Louvain, Louvain-la-Neuve (Belgium); Kereselidze, T.; Machavariani, Z.S. [Department of Exact and Natural Sciences, Tbilissi State University, Tbilissi (Georgia)

    2011-10-15

    A simple and straightforward calculating scheme is proposed for electron-impact single and multiple ionization of atoms. The method is based on the application of the Hulthen-Kohn dynamical variational principle. An effective charge seen by the scattered electron is determined for a certain type of trial wave functions mathematically in a rigorous way excluding any empirical assumptions. Validity of the elaborated approach is assessed by calculating triply differential cross section (TDCS) for electron-impact ionization of hydrogen. It is shown that, inclusion of the effective charge into the calculation reduces height of a 'binary peak' in comparison with the first Born approximation result. The height of a 'recoil peak' depends on the sign of the effective charge. The calculated TDCS are compared with the available experimental data and with the results of sophisticated theories and agreement is found. (authors)

  14. Dynamics of premixed hydrogen/air flames in mesoscale channels

    Energy Technology Data Exchange (ETDEWEB)

    Pizza, Gianmarco [Paul Scherrer Institute, Combustion Research, CH-5232, Villigen PSI (Switzerland); Aerothermochemistry and Combustion Systems Laboratory, Swiss Federal Institute of Technology, CH-8092, Zurich (Switzerland); Frouzakis, Christos E.; Boulouchos, Konstantinos [Aerothermochemistry and Combustion Systems Laboratory, Swiss Federal Institute of Technology, CH-8092, Zurich (Switzerland); Mantzaras, John [Paul Scherrer Institute, Combustion Research, CH-5232, Villigen PSI (Switzerland); Tomboulides, Ananias G. [Department of Engineering and Management of Energy Resources, University of Western Macedonia, 50100 Kozani (Greece)

    2008-10-15

    Direct numerical simulation with detailed chemistry and transport is used to study the stabilization and dynamics of lean ({phi}=0.5) premixed hydrogen/air atmospheric pressure flames in mesoscale planar channels. Channel heights of h=2, 4, and 7 mm, and inflow velocities in the range 0.3{<=}U{sub IN}{<=}1100cm/ s are investigated. Six different burning modes are identified: mild combustion, ignition/extinction, closed steady symmetric flames, open steady symmetric flames, oscillating and, finally, asymmetric flames. Chaotic behavior of cellular flame structures is observed for certain values of U{sub IN}. Stability maps delineating the regions of the different flame types are finally constructed. (author)

  15. Molecular dynamics simulation of hydrogen isotope injection into graphene

    International Nuclear Information System (INIS)

    Nakamura, Hiroaki; Takayama, Arimichi; Ito, Atsushi

    2007-07-01

    We reveal the hydrogen isotope effect of three chemical reactions, i.e., the reflection, the absorption and the penetration ratios, by classical molecular dynamics simulation with a modified Brenner's reactive empirical bond order (REBO) potential. We find that the reflection by π-electron does not depend on the mass of the incident isotope, but the peak of the reflection by nuclear moves to higher side of incident energy. In addition to the reflection, we also find that the absorption ratio in the positive z side of the graphene becomes larger, as the mass of the incident isotope becomes larger. On the other hand, the absorption ratio in the negative z side of the graphene becomes smaller. Last, it is found that the penetration ratio does not depend on the mass of the incident isotope because the graphene potential is not affected by the mass. (author)

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

    International Nuclear Information System (INIS)

    Haghighi, Behzad; Khosravi, Mehdi; Barati, Ali

    2014-01-01

    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 2 O 2 . The observed sensitivities for the electrocatalytic oxidation and reduction of H 2 O 2 at the operating potentials of + 0.8 and − 0.2 V were about 13.8 and 18.3 mA M −1 , respectively. The detection limit (S/N = 3) for H 2 O 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 −1 and 30 μM, respectively and better than those obtained (0.2–6 mM, 0.12 mA M −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 2 O 2 reduction and oxidation. • Glucose biosensor was fabricated by immobilization of glucose oxidase on sensor

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

    International Nuclear Information System (INIS)

    Noorbakhsh, Abdollah; Salimi, Abdollah

    2009-01-01

    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 s ) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 x 10 -10 mol cm -2 , 6.12 s -1 , 5.9 x 10 -10 mol cm -2 and 6.58 s -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 3 M -1 s -1 and 5.5 (±0.2) x 10 3 M -1 s -1 , respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 μM, 4.14 nA μM -1 nA μM -1 and 5 μM to 20 mM, and 0.36 μM, 7.62 nA μM -1 , and 1 μM 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 reproducibility, simple preparation procedures and long-term stabilities of signal responses during

  18. Ion dynamics in porous carbon electrodes in supercapacitors using in situ infrared spectroelectrochemistry.

    Science.gov (United States)

    Richey, Francis W; Dyatkin, Boris; Gogotsi, Yury; Elabd, Yossef A

    2013-08-28

    Electrochemical double layer capacitors (EDLCs), or supercapacitors, rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic lifetime compared to batteries. Ionic liquid (IL) electrolytes can broaden the operating voltage window and increase the energy density of EDLCs. Herein, we present direct measurements of the ion dynamics of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide in an operating EDLC with electrodes composed of porous nanosized carbide-derived carbons (CDCs) and nonporous onion-like carbons (OLCs) with the use of in situ infrared spectroelectrochemistry. For CDC electrodes, IL ions (both cations and anions) were directly observed entering and exiting CDC nanopores during charging and discharging of the EDLC. Conversely, for OLC electrodes, IL ions were observed in close proximity to the OLC surface without any change in the bulk electrolyte concentration during charging and discharging of the EDLC. This provides experimental evidence that charge is stored on the surface of OLCs in OLC EDLCs without long-range ion transport through the bulk electrode. In addition, for CDC EDLCs with mixed electrolytes of IL and propylene carbonate (PC), the IL ions were observed entering and exiting CDC nanopores, while PC entrance into the nanopores was IL concentration dependent. This work provides direct experimental confirmation of EDLC charging mechanisms that previously were restricted to computational simulations and theories. The experimental measurements presented here also provide deep insights into the molecular level transport of IL ions in EDLC electrodes that will impact the design of the electrode materials' structure for electrical energy storage.

  19. 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…

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

    KAUST Repository

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

    2014-01-01

    © 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.

  1. 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.

  2. Highly sensitive hydrogen peroxide sensor based on a glassy carbon electrode modified with platinum nanoparticles on carbon nanofiber heterostructures

    International Nuclear Information System (INIS)

    Yang, Yang; Fu, Renzhong; Yuan, Jianjun; Wu, Shiyuan; Zhang, Jialiang; Wang, Haiying

    2015-01-01

    We are presenting a sensor for hydrogen peroxide (H 2 O 2 ) that is based on the use of a heterostructure composed of Pt nanoparticles (NPs) and carbon nanofibers (CNFs). High-density Pt NPs were homogeneously loaded onto a three-dimensional nanostructured CNF matrix and then deposited in a glassy carbon electrode (GCE). The resulting sensor synergizes the advantages of the conducting CNFs and the nanoparticle catalyst. The porous structure of the CNFs also favor the high-density immobilization of the NPs and the diffusion of water-soluble molecules, and thus assists the rapid catalytic oxidation of H 2 O 2 . If operated at a working voltage of −0.2 V (vs. Ag/AgCl), the modified GCE exhibits a linear response to H 2 O 2 in the 5 μM to 15 mM concentration range (total analytical range: 5 μM to 100 mM), with a detection limit of 1.7 μM (at a signal-to-noise ratio of 3). The modified GCE is not interfered by species such as uric acid and glucose. Its good stability, high selectivity and good reproducibility make this electrode a valuable tool for inexpensive amperometric sensing of H 2 O 2 . (author)

  3. 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.

  4. Determination of the level of DNA modification with cisplatin by catalytic hydrogen evolution at mercury-based electrodes.

    Science.gov (United States)

    Horáková, Petra; Tesnohlídková, Lucie; Havran, Ludek; Vidláková, Pavlína; Pivonková, Hana; Fojta, Miroslav

    2010-04-01

    Electrochemical methods proved useful as simple and inexpensive tools for the analysis of natural as well as chemically modified nucleic acids. In particular, covalently attached metal-containing groups usually render the DNA well-pronounced electrochemical activity related to redox processes of the metal moieties, which can in some cases be coupled to catalytic hydrogen evolution at mercury or some types of amalgam electrodes. In this paper we used voltammetry at the mercury-based electrodes for the monitoring of DNA modification with cis-diamminedichloroplatinum (cisplatin), a representative of metallodrugs used in the treatment of various types of cancer or being developed for such purpose. In cyclic voltammetry at the mercury electrode, the cisplatin-modified DNA yielded catalytic currents the intensity of which reflected DNA modification extent. In square-wave voltammetry, during anodic polarization after prereduction of the cisplatinated DNA, a well-developed, symmetrical signal (peak P) was obtained. Intensity of the peak P linearly responded to the extent of DNA modification at levels relevant for biochemical studies (rb = 0.01-0.10, where rb is the number of platinum atoms bound per DNA nucleotide). We demonstrate a correlation between the peak P intensity and a loss of sequence-specific DNA binding by tumor suppressor protein p53, as well as blockage of DNA digestion by a restriction endonuclease Msp I (both caused by the DNA cisplatination). Application of the electrochemical technique in studies of DNA reactivity with various anticancer platinum compounds, as well as for an easy determination of the extent of DNA platination in studies of its biochemical effects, is discussed.

  5. 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).

  6. Covalent attachment of thionine onto gold electrode modified with cadmium sulfide nanoparticles: Improvement of electrocatalytic and photelectrocatalytic reduction of hydrogen peroxide

    International Nuclear Information System (INIS)

    Salimi, Abdollah; Rahmatpanah, Rojzin; Hallaj, Rahman; Roushani, Mahmoud

    2013-01-01

    A newly developed strategy based on gold (Au) electrode modified with cadmium sulfide nanoparticles (CdSnp) and thionine (Th) was proposed toward electrocatalytic and photoelectrocatalytic hydrogen peroxide (H 2 O 2 ) reduction. At first, a thin film of CdS nanoparticles was electrodeposited onto Au electrode. Then, the CdS/Au electrode was modified with mercaptoacetic acid (MAA), which not only acts as a stabilizing agent to prevent the chalcogenide CdS nanocrystals from aggregation but also as a linker for subsequent attachment of Th onto the CdS nanoparticles. The effective covalent immobilization of Th was achieved through amide bond formation reaction between -NH 2 groups of Th and -COOH groups of MAA, using dicyclohexylcarbodiimide (DCC) as condensation agent. The Au/CdS/Th modified electrode showed a well-defined redox couple with surface confined characteristics at wide pH range (2–12). The heterogeneous electron transfer rate constant (k s ) and the surface coverage of immobilized Th on the modified electrode was obtained as 0.12 s −1 and 4.35 × 10 −9 mole cm −2 , respectively. The electrocatalytic activity and stability of the modified electrode toward hydrogen peroxide reduction was investigated and it was found that the Au/CdS/Th electrode illustrates excellent electrocatalytic activity toward H 2 O 2 reduction at reduced overpotential. The detection limit, sensitivity and catalytic rate constant (k cat ) of the modified electrode toward H 2 O 2 were 55 nM, 3.4 μA μM −1 cm −2 and 3.75 (±0.1) × 10 3 M −1 s −1 , respectively, at linear concentration range up to 10 mM. Upon light irradiation, about two-fold improvements were attained in sensitivity and detection limit of the modified electrode toward H 2 O 2 electrocatalytic determination

  7. Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

    Science.gov (United States)

    Nouri-Nigjeh, Eslam; Bruins, Andries P; Bischoff, Rainer; Permentier, Hjalmar P

    2012-10-21

    Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

  8. Molecular dynamics simulation of effect of hydrogen atoms on crack propagation behavior of α-Fe

    Energy Technology Data Exchange (ETDEWEB)

    Song, H.Y., E-mail: gsfshy@sohu.com; Zhang, L.; Xiao, M.X.

    2016-12-16

    The effect of the hydrogen concentration and hydrogen distribution on the mechanical properties of α-Fe with a pre-existing unilateral crack under tensile loading is investigated by molecular dynamics simulation. The results reveal that the models present good ductility when the front region of crack tip has high local hydrogen concentration. The peak stress of α-Fe decreases with increasing hydrogen concentration. The studies also indicate that for the samples with hydrogen atoms, the crack propagation behavior is independent of the model size and boundaries. In addition, the crack propagation behavior is significantly influenced by the distribution of hydrogen atoms. - Highlights: • The distribution of hydrogen plays a critical role in the crack propagation. • The peak stress decrease with the hydrogen concentration increasing. • The crack deformation behavior is disclosed and analyzed.

  9. Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes

    International Nuclear Information System (INIS)

    Paggi, Damian Alvarez; Martin, Diego F.; Kranich, Anja; Hildebrandt, Peter; Marti, Marcelo A.; Murgida, Daniel H.

    2009-01-01

    In this paper we present a combined experimental and theoretical study of the heterogeneous electron transfer reaction of cytochrome c electrostatically adsorbed on metal electrodes coated with monolayers of 6-mercaptohexanoic acid. Molecular dynamics simulations and pathways calculations show that adsorption of the protein leads to a broad distribution of orientations and, thus, to a correspondingly broad distribution of electron transfer rate constants due to the orientation-dependence of the electronic coupling parameter. The adsorbed protein exhibits significant mobility and, therefore, the measured reaction rate is predicted to be a convolution of protein dynamics and tunnelling probabilities for each orientation. This prediction is confirmed by time-resolved surface enhanced resonance Raman which allows for the direct monitoring of protein (re-)orientation and electron transfer of the immobilised cytochrome c. The results provide a consistent explanation for the non-exponential distance-independence of electron transfer rates usually observed for proteins immobilized on electrodes.

  10. Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Paggi, Damian Alvarez; Martin, Diego F. [Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 2, piso 1, C1428EHA Buenos Aires (Argentina); Kranich, Anja; Hildebrandt, Peter [Institut fuer Chemie, Technische Universitaet Berlin, Str. des 17, Juni 135, Sekr. PC14, D-10623 Berlin (Germany); Marti, Marcelo A. [Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 2, piso 1, C1428EHA Buenos Aires (Argentina)], E-mail: marcelo@qi.fcen.uba.ar; Murgida, Daniel H. [Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 2, piso 1, C1428EHA Buenos Aires (Argentina)], E-mail: dhmurgida@qi.fcen.uba.ar

    2009-09-01

    In this paper we present a combined experimental and theoretical study of the heterogeneous electron transfer reaction of cytochrome c electrostatically adsorbed on metal electrodes coated with monolayers of 6-mercaptohexanoic acid. Molecular dynamics simulations and pathways calculations show that adsorption of the protein leads to a broad distribution of orientations and, thus, to a correspondingly broad distribution of electron transfer rate constants due to the orientation-dependence of the electronic coupling parameter. The adsorbed protein exhibits significant mobility and, therefore, the measured reaction rate is predicted to be a convolution of protein dynamics and tunnelling probabilities for each orientation. This prediction is confirmed by time-resolved surface enhanced resonance Raman which allows for the direct monitoring of protein (re-)orientation and electron transfer of the immobilised cytochrome c. The results provide a consistent explanation for the non-exponential distance-independence of electron transfer rates usually observed for proteins immobilized on electrodes.

  11. Biosensing hydrogen peroxide utilizing carbon paste electrodes containing peroxidases naturally immobilized on coconut (Cocus nucifera L.) fibers.

    Science.gov (United States)

    Kozan, J V B; Silva, R P; Serrano, S H P; Lima, A W O; Angnes, L

    2007-05-22

    A novel unmediated hydrogen peroxide biosensor based on the incorporation of fibrous tissue of coconut fruit in carbon paste matrix is presented. Cyclic voltammetry and amperometry were utilized to characterize the main electrochemical parameters and the performance of this new biosensor under different preparation and operation conditions. The resulting H2O2-sensitive biosensors respond rapidly (7 s to attain 90% of the signal), was operated at -0.15 V, presented linear response between 2.0x10(-4) and 3.4x10(-3) mol L(-1), the detection limit was estimated as 4.0x10(-5) mol L(-1). Its operation potential was situated between -0.2 and 0.1 V and the best pH was determined as 5.2. Electrodes containing 5% (w/w) of coconut fiber presented the best signal and their lifetime was extended to 3 months. The apparent Michaelis-Menten constant KM(app) and Vmax were estimated to be 8.90 mmol L(-1) and 6.92 mmol L(-1) microA(-1), respectively. The results obtained for determination of hydrogen peroxide in four pharmaceutical products (antiseptic solution, contact lenses cleaning solution, hair coloring cream and antiseptic dental rinse solution) were in agreement with those obtained by the spectrophotometric method. An additional advantage of these biosensors is the capacity to measure hydrogen peroxide even in samples with relatively low pH. To demonstrate the enzymatic activity of the coconut tissue, a very simple way was created during this work. Coconut fibers were immersed in H2O2 solution between two glass slides. Sequential images were taken to show the rapid generation of O2, attesting the high activity of the enzymes.

  12. Development of new electrode materials for hydrogen production by water electrolysis

    International Nuclear Information System (INIS)

    Rozain, Caroline

    2013-01-01

    It is expected that PEM water electrolysis will play a significant role in the hydrogen society as a key process for producing hydrogen from renewable energy sources but before this, substantial cost reductions are still required. Because of the high acidity of membrane materials used in PEM water electrolysers, expensive noble-metals or their oxides are required as electrocatalysts (platinum for hydrogen evolution and iridium for oxygen evolution). As the oxygen evolution reaction takes place with a large overpotential (anodic potential ≥ 1.6 V) only few materials can be used to avoid corrosion. In state-of-the-art, noble metal oxides are generally used alone in the active layer with typical loadings of 2-3 mg/cm 2 and act as both catalyst and electronic conductor.In order to reduce the noble metal loadings and keep a good electronic conductivity of the catalytic layer, iridium can be supported onto a conductive and electrochemical stable material support. To gain more insights, several MEAs with anodes made of pure iridium oxide or 50 wt % IrO 2 /Ti anodes have been prepared and characterized using cyclic voltammetry and impedance spectroscopy, and by measuring polarization curves at different operating temperatures. Without the catalyst support, anodic loadings can be reduced down to 0,5 mg/cm 2 without any degradation in the electrochemical performances. By using anodes made of iridium oxide and titanium particles, further reductions of anodic loading can be made down to 0.1 mg/cm 2 with performances similar to those obtained with conventional loadings of several mg cm 2 . (author) [fr

  13. Rapid hydrogen charging on metal hydride negative electrode of Fuel Cell/Battery (FCB) systems

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Bokkyu; Lee, Sunmook; Kawai, Hiroyuki; Fushimi, Chihiro; Tsutsumi, Atsushi [Collaborative Research Center for Energy Engineering, Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505 (Japan)

    2009-02-15

    The characteristics of rapid gaseous H{sub 2} charging/electrochemical discharging of the metal hydride negative electrode were investigated for the application in Fuel Cell/Battery (FCB) systems. They were evaluated with the H{sub 2} gas absorption, followed by the subsequent electrochemical discharging in the electrolyte solution (6M KOH). Then, the cyclability of charge-discharge was also examined. It was observed that more than 70% of the theoretical capacity was charged within 10 min with 0.3 MPa and 0.5 MPa of the initial H{sub 2} pressures. The electrochemical discharge curve showed that more than 86% of the absorbed H{sub 2} was discharged. Furthermore, the cycled charge-discharge process indicated that the H{sub 2} gas charge and electrochemical discharge process is an effective way to rapidly charge and activate the metal hydride without degeneration. (author)

  14. Generation mechanism of hydrogen peroxide in dc plasma with a liquid electrode

    Science.gov (United States)

    Takeuchi, Nozomi; Ishibashi, Naoto

    2018-04-01

    The production mechanism of liquid-phase H2O2 in dc driven plasma in O2 and Ar with a water electrode was investigated. When a water anode was used, the concentration of H2O2 increased linearly with the treatment time. The production rate was proportional to the discharge current, and there was no dependence on the gap distance. On the other hand, the production rate was much smaller with a water anode. We concluded that the production of gas-phase H2O2 in the cathode sheath just above a water cathode and diffusion of this H2O2 into the water constitute the key mechanism in the production of liquid-phase H2O2.

  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. Hydrogen bonding analysis of hydroxyl groups in glucose aqueous solutions by a molecular dynamics simulation study

    International Nuclear Information System (INIS)

    Chen, Cong; Li, Wei Zhong; Song, Yong Chen; Weng, Lin Dong; Zhang, Ning

    2012-01-01

    Molecular dynamics simulations have been performed to investigate hydrogen bonding characteristics of hydroxyl groups in glucose aqueous solutions with different concentrations. The hydrogen bonding abilities and strength of different O and H atom types have been calculated and compared. The acceptor/donor efficiencies have been predicted and it has been found that: (1) O2-HO2 and O3-HO3 are more efficient intramolecular hydrogen bonding acceptors than donors; (2) O1-HO1, O4-HO4 and O6-HO6 are more efficient intramolecular hydrogen bonding donors than acceptors; (5) O1-HO1 and O6-HO6 are more efficient intermolecular hydrogen bonding acceptors than donors while hydroxyl groups O2-HO2 and O4-HO4 are more efficient intermolecular hydrogen bonding donors than acceptors. The hydrogen bonding abilities of hydroxyl groups revealed that: (1) the hydrogen bonding ability of OH2-H w is larger than that of hydroxyl groups in glucose; (2) among the hydroxyl groups in glucose, the hydrogen bonding ability of O6-HO6 is the largest and the hydrogen bonding ability of O4-HO4 is the smallest; (3) the intermolecular hydrogen bonding ability of O6-HO6 is the largest; (4) the order for intramolecular hydrogen bonding abilities (from large to small) is O2-HO2, O1-HO1, O3-HO3, O6-HO6 and O4-HO4

  17. 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.

  18. Radiation-electrochemistry of the colloidal gold micro-electrode: Hydrogen formation by organic free radicals

    International Nuclear Information System (INIS)

    Westerhausen, J.; Henglein, A.; Lilie, J.

    1981-01-01

    Various organic free radicals as well as Ni + ions produce hydrogen in the presence of some 10 -4 M of colloidal gold. The gold catalyst was prepared via the reduction of HAuCl 4 either thermally by citrate or by γ-irradiation. The organic radicals were radiolytically produced. The mechanism of H 2 formation includes electron transfer from the organic radicals to the gold particles, storage of a large number of electrons per gold particle, conversion of the electrons into adsorbed H-atoms and desorption of the latter to form H 2 . - The rates of some of these steps were measured using the method of pulse radiolysis. 1-Hydroxy-1-methyl ethyl radicals, (CH 3 ) 2 COH, react with colloidal gold particles almost diffusion controlled provided that the gold particles are not charged with excess electrons. Charged gold particles react at a substantially lower rate. The stored electrons live seconds or even minutes depending on their number per gold particle. In the stationary state, up to 0.38 Coulomb of electrons could be stored per liter of a 2.9x10 -4 molar gold solution, each gold particle carrying about 39 electrons. A comparison is also made between the catalytic activities of colloidal gold and silver. Due to the relative fast conversion of electrons into adsorbed H-atoms, colloidal gold has less capacity for the storage of electrons than colloidal silver. - The dependence of the hydrogen yield on the pH of the solution, the concentration of gold, the size of the gold particles, the concentration of the polyvinyl alcohol stabilizer, and the intensity of radiation was also investigated. At high intensities, some of the radicals are destroyed in a gold catalysed disproportionation. (orig.)

  19. 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.

  20. 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...

  1. Feasibility of solid oxide fuel cell dynamic hydrogen coproduction to meet building demand

    Science.gov (United States)

    Shaffer, Brendan; Brouwer, Jacob

    2014-02-01

    A dynamic internal reforming-solid oxide fuel cell system model is developed and used to simulate the coproduction of electricity and hydrogen while meeting the measured dynamic load of a typical southern California commercial building. The simulated direct internal reforming-solid oxide fuel cell (DIR-SOFC) system is controlled to become an electrical load following device that well follows the measured building load data (3-s resolution). The feasibility of the DIR-SOFC system to meet the dynamic building demand while co-producing hydrogen is demonstrated. The resulting thermal responses of the system to the electrical load dynamics as well as those dynamics associated with the filling of a hydrogen collection tank are investigated. The DIR-SOFC system model also allows for resolution of the fuel cell species and temperature distributions during these dynamics since thermal gradients are a concern for DIR-SOFC.

  2. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Dyatkin, Boris [Drexel Univ., Philadelphia, PA (United States); Zhang, Yu [Vanderbilt Univ., Nashville, TN (United States); Mamontov, Eugene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kolesnikov, Alexander I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cheng, Yongqiang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meyer, III, Harry M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cummings, Peter T. [Vanderbilt Univ., Nashville, TN (United States); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

    2016-04-07

    Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces and enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.

  3. Development of an operation strategy for hydrogen production using solar PV energy based on fluid dynamic aspects

    Directory of Open Access Journals (Sweden)

    Amores Ernesto

    2017-06-01

    Full Text Available Alkaline water electrolysis powered by renewable energy sources is one of the most promising strategies for environmentally friendly hydrogen production. However, wind and solar energy sources are highly dependent on weather conditions. As a result, power fluctuations affect the electrolyzer and cause several negative effects. Considering these limiting effects which reduce the water electrolysis efficiency, a novel operation strategy is proposed in this study. It is based on pumping the electrolyte according to the current density supplied by a solar PV module, in order to achieve the suitable fluid dynamics conditions in an electrolysis cell. To this aim, a mathematical model including the influence of electrode-membrane distance, temperature and electrolyte flow rate has been developed and used as optimization tool. The obtained results confirm the convenience of the selected strategy, especially when the electrolyzer is powered by renewable energies.

  4. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. 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.

  6. Charging and Transport Dynamics of a Flow-Through Electrode Capacitive Deionization System.

    Science.gov (United States)

    Qu, Yatian; Campbell, Patrick G; Hemmatifar, Ali; Knipe, Jennifer M; Loeb, Colin K; Reidy, John J; Hubert, Mckenzie A; Stadermann, Michael; Santiago, Juan G

    2018-01-11

    We present a study of the interplay among electric charging rate, capacitance, salt removal, and mass transport in "flow-through electrode" capacitive deionization (CDI) systems. We develop two models describing coupled transport and electro-adsorption/desorption which capture salt removal dynamics. The first model is a simplified, unsteady zero-dimensional volume-averaged model which identifies dimensionless parameters and figures of merits associated with cell performance. The second model is a higher fidelity area-averaged model which captures both spatial and temporal responses of charging. We further conducted an experimental study of these dynamics and considered two salt transport regimes: (1) advection-limited regime and (2) dispersion-limited regime. We use these data to validate models. The study shows that, in the advection-limited regime, differential charge efficiency determines the salt adsorption at the early stage of the deionization process. Subsequently, charging transitions to a quasi-steady state where salt removal rate is proportional to applied current scaled by the inlet flow rate. In the dispersion-dominated regime, differential charge efficiency, cell volume, and diffusion rates govern adsorption dynamics and flow rate has little effect. In both regimes, the interplay among mass transport rate, differential charge efficiency, cell capacitance, and (electric) charging current governs salt removal in flow-through electrode CDI.

  7. 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.

  8. FIRST OPERATING RESULTS OF A DYNAMIC GAS BEARING TURBINE IN AN INDUSTRIAL HYDROGEN LIQUEFIER

    International Nuclear Information System (INIS)

    Bischoff, S.; Decker, L.

    2010-01-01

    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.

  9. Study on stainless steel electrode based on dynamic aluminum liquid corrosion mechanism.

    Science.gov (United States)

    Hou, Hua; Yang, Ruifeng

    2009-01-01

    Scanning electrion microscope (SEM) was performed for investigations on the corrosion mechanism of stainless steel electrode in dynamic melting aluminum liquid. Microstructures and composition analysis was made by electron probe analysis (EPA) combined with metallic phase analysis. It can be concluded that the corrosion process is mainly composed of physical corrosion (flowing and scouring corrosion) and chemical corrosion (forming FeAl and Fe2Al5) and the two mechanisms usually exist simultaneously. The corrosion interface thickness is about 10 μm, which is different to usual interface width of hundreds μm in the static melting Al with iron matrix.

  10. Controlling laser ablation plasma with external electrodes. Application to sheath dynamics study and beam physics

    International Nuclear Information System (INIS)

    Isono, Fumika; Nakajima, Mitsuo; Hasegawa, Jun; Kawamura, Tohru; Horioka, Kazuhiko

    2013-01-01

    The potential of laser ablation plasma was controlled successfully by using external ring electrodes. We found that an electron sheath is formed at the plasma boundary, which plays an important role in the potential formation. When the positively biased plasma reaches a grounded grid, electrons in the plasma are turned away and ions are accelerated, which leads to the formation of a virtual anode between the grid and an ion probe. We think that this device which can raise the plasma potential up to order of kV can be applied to the study of sheath dynamics and to a new type of ion beam extraction. (author)

  11. Evaluation of hydrogen production system coupling with HTTR using dynamic analysis code

    International Nuclear Information System (INIS)

    Sato, Hiroyuki; Ohashi, Hirofumi; Inaba, Yoshitomo; Nishihara, Tetsuo; Hayashi, Koji; Inagaki, Yoshiyuki

    2006-01-01

    The Japan Atomic Energy Agency (JAEA) was entrusted 'Development of Nuclear Heat Utilization Technology' by Ministry of Education, Culture, Sports, Science and Technology. In this development, the JAEA investigated the system integration technology to couple the hydrogen production system by steam reforming with the High Temperature Engineering Test Reactor (HTTR). Prior to the construction of the hydrogen production system coupling with the HTTR, a dynamic analysis code had to be developed to evaluate the system transient behaviour of the hydrogen production system because there are no examples of chemical facilities coupled with nuclear reactor in the world. This report describes the evaluation of the hydrogen production system coupling with HTTR using analysis code, N-HYPAC, which can estimate transient behaviour of the hydrogen production system by steam reforming. The results of this investigation provide that the influence of the thermal disturbance caused by the hydrogen production system on the HTTR can be estimated well. (author)

  12. Dynamic Reference Electrode development for redox potential measurements in fluoride molten salt at high temperature

    International Nuclear Information System (INIS)

    Durán-Klie, Gabriela; Rodrigues, Davide; Delpech, Sylvie

    2016-01-01

    Measurement of redox potential in fluoride media is a major problem due to the difficulty to design a reference electrode with high stability, high mechanical resistance and high accuracy. In the frame of molten salt reactor studies, a dynamic reference electrode (DRE) is developed to measure redox potential in fluoride molten salt at high temperature. DRE is based on the in-situ generation of a transient redox system. The choice of the redox couple corresponds to the cathodic limit of the molten salt considered. As a preliminary step, the demonstration of feasibility of generating a DRE was done in LiF-NaF-KF (46.5–11.5–42 mol%) media at 500 °C. In this salt, the reference redox system generated by coulometry at applied current is KF/K, metallic potassium being electrodeposited on a tungsten wire electrode. The validation of the DRE response and the experimental optimization parameters for DRE generation were realized by following the NiF 2 /Ni redox potential evolution as a function of NiF 2 concentration in the fused salt. The current value applied for DRE generation was optimized. It depends on the amount of metallic cations contained in the fused salt and which can be electrochemically reduced simultaneously during the DRE generation. The current corresponding to the DRE generation has to be 4 times greater than the current corresponding to the reduction of the other elements.

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

    Science.gov (United States)

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

    2017-02-01

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

  14. Hydrogen bubble dynamic template fabrication of nanoporous Cu film supported by graphene nanaosheets: A highly sensitive sensor for detection of nitrite.

    Science.gov (United States)

    Majidi, Mir Reza; Ghaderi, Seyran

    2017-12-01

    High surface area nanoporous Cu film (NPCF) has been successfully synthesized using a hydrogen bubble dynamic template on the graphene nanosheets (GNs) modified glassy carbon electrode (GCE). The effect of different synthesis conditions such as applied potential and deposition time on the NPCF morphology was investigated. The structure and constituent of the NPCF-GNs/GCE were characterized by scanning electron microscopy (SEM), energy-dispersive x-ray (EDX), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and electrochemical methods. The study on electrocatalytic performance of the NPCF-GNs/GCE demonstrated that this electrode has excellent catalytic activity toward nitrite oxidation. The quantitative measurement of nitrite by amperometric method showed a wide concentration range (0.1-100µmolL -1 ) with a detection limit and a sensitivity of 8.87 × 10 -8 molL -1 and 3.1 AL/molcm 2 , respectively. The excellent electrochemical response and high sensitivity of the proposed electrode were attributed to the 3D structure of NPCF and the synergic effect of NPCF and GNs. Furthermore, this electrode showed some other advantages including good repeatability, high reproducibility, long-term stability and anti-interference performance toward nitrite sensing. The applicability of the proposed electrode was proved by successful determination of nitrite in real samples (tap water, river water and sausage samples). Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

    Science.gov (United States)

    Srivastava, Abhinav; Debnath, Ananya

    2018-03-01

    Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations

  16. Nonlinear Dynamic Behavior of a Bi-Axial Torsional MEMS Mirror with Sidewall Electrodes

    Directory of Open Access Journals (Sweden)

    Mehmet Ozdogan

    2016-03-01

    Full Text Available Nonlinear dynamic responses of a Micro-Electro-Mechanical Systems (MEMS mirror with sidewall electrodes are presented that are in close agreement with previously-reported experimental data. An analysis of frequency responses reveals softening behavior, and secondary resonances originated from the dominant quadratic nonlinearity. The quadratic nonlinearity is an electromechanical coupling effect caused by the electrostatic force. This effect is reflected in our mathematical model used to simulate the dynamic response of the micro-mirror. The effects of increased forcing and decreased damping on the frequency response are investigated as the mirrors are mostly used in vacuum packages. The results can predict MEMS mirror behaviors in optical devices better than previously-reported models.

  17. Influence of Pt Gate Electrode Thickness on the Hydrogen Gas Sensing Characteristics of Pt/In2O3/SiC Hetero-Junction Devices

    Directory of Open Access Journals (Sweden)

    S. Kandasamy

    2007-09-01

    Full Text Available Hetero-junction Pt/In2O3/SiC devices with different Pt thickness (30, 50 and 90nm were fabricated and their hydrogen gas sensing characteristics have been studied. Pt and In2O3 thin films were deposited by laser ablation. The hydrogen sensitivity was found to increase with decreasing Pt electrode thickness. For devices with Pt thickness of 30 nm, the sensitivity gradually increased with increasing temperature and reached a maximum of 390 mV for 1% hydrogen in air at 530°C. Atomic force microscopy (AFM analysis revealed a decrease in Pt grain size and surface roughness for increasing Pt thickness. The relationship between the gas sensing performance and the Pt film thickness and surface morphology is discussed.

  18. Dynamic conductivity and partial ionization in dense fluid hydrogen

    Science.gov (United States)

    Zaghoo, Mohamed

    2018-04-01

    A theoretical description for optical conduction experiments in dense fluid hydrogen is presented. Different quantum statistical approaches are used to describe the mechanism of electronic transport in hydrogen's high-temperature dense phase. We show that at the onset of the metallic transition, optical conduction could be described by a strong rise in atomic polarizability, due to increased ionization, whereas in the highly degenerate limit, the Ziman weak scattering model better accounts for the observed saturation of reflectance. The inclusion of effects of partial ionization in the highly degenerate region provides great agreement with experimental results. Hydrogen's fluid metallic state is revealed to be a partially ionized free-electron plasma. Our results provide some of the first theoretical transport models that are experimentally benchmarked, as well as an important guide for future studies.

  19. Hydrogen bond dynamics governs the effective photoprotection mechanism of plant phenolic sunscreens.

    Science.gov (United States)

    Liu, Fang; Du, Likai; Lan, Zhenggang; Gao, Jun

    2017-02-15

    Sinapic acid derivatives are important sunscreen species in natural plants, which could provide protection from solar UV radiation. Using a combination of ultrafast excited state dynamics, together with classical molecular dynamics studies, we demonstrate that there is direct coupling of hydrogen bond motion with excited state photoprotection dynamics as part of the basic mechanism in solution. Beyond the intra-molecular degree of freedom, the inter-molecular motions on all timescales are potentially important for the photochemical or photophysical events, ranging from the ultrafast hydrogen bond motion to solvent rearrangements. This provides not only an enhanced understanding of the anomalous experimental spectroscopic results, but also the key idea in the development of sunscreen agents with improved photo-chemical properties. We suggest that the hydrogen bond dynamics coupled excited state photoprotection mechanism may also be possible in a broad range of bio-related molecules in the condensed phase.

  20. MWCNT-cysteamine-Nafion modified gold electrode based on myoglobin for determination of hydrogen peroxide and nitrite.

    Science.gov (United States)

    Canbay, Erhan; Şahin, Berika; Kıran, Müge; Akyilmaz, Erol

    2015-02-01

    In this work, a novel amperometric biosensor of hydrogen peroxide (H2O2) was developed based on the immobilization of myoglobin (Mb) on the surface of the multi-walled carbon nanotube (MWCNT) -Nafion-cysteamine (CA) modified gold electrode (Au) and its electrocatalytic activity was used for the determination of nitrite (NO2(-)). In the optimization studies, the best MWCNT and myoglobin amount were investigated. It was discovered at the experiments for the optimization of the working conditions that the buffer at this study as 50.0mM, pH7.0 phosphate buffer (PBS) and working temperature as 30°C for the H2O2 biosensor. It was determined at the characterization studies on the biosensor that linear results are obtained between the ranges of 0.1μM to 70.0μM for H2O2 concentration and 1-250μM for NO2(-). The reproducibility of the biosensor was determined both H2O2 and nitrite. From the experiments, average value, standard deviation (SD) and coefficients of variation (CV%) were calculated to be 10.02±0.43μM, and 4.29% for 10.0μM H2O2 (n=6) and 52.0±2.1μM, and 3.89% for 50.0μM nitrite (n=8), respectively. At the same time the sample was analyzed for NO2(-) in drinking and mineral waters. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  2. Hydrogen evolution reaction catalyst

    Science.gov (United States)

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

    2016-02-09

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

  3. Development of sensitive amperometric hydrogen peroxide sensor using a CuNPs/MB/MWCNT-C_6_0-Cs-IL nanocomposite modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Roushani, Mahmoud; Bakyas, Kobra; Zare Dizajdizi, Behruz

    2016-01-01

    A sensitive hydrogen peroxide (H_2O_2) sensor was constructed based on copper nanoparticles/methylene blue/multiwall carbon nanotubes–fullerene–chitosan–ionic liquid (CuNPs/MB/MWCNTs–C_6_0–Cs–IL) nanocomposites. The MB/MWCNTs–C_6_0–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_6_0–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_2O_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_2O_2 concentration in human blood serum sample with satisfactory results. - Highlights: • CuNPs/MB/MWCNT-C_6_0-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_2O_2. • The CuNPs/MB/MWCNT-C_6_0-Cs-IL/GC electrode demonstrated high stability for the detection of H_2O_2.

  4. 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}.

  5. Derivation of basic equations for rigorous dynamic simulation of cryogenic distillation column for hydrogen isotope separation

    International Nuclear Information System (INIS)

    Kinoshita, Masahiro; Naruse, Yuji

    1981-08-01

    The basic equations are derived for rigorous dynamic simulation of cryogenic distillation columns for hydrogen isotope separation. The model accounts for such factors as differences in latent heat of vaporization among the six isotopic species of molecular hydrogen, decay heat of tritium, heat transfer through the column wall and nonideality of the solutions. Provision is also made for simulation of columns with multiple feeds and multiple sidestreams. (author)

  6. 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.

    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,

  7. Molecular dynamics study of grain boundary diffusion of hydrogen in tungsten

    International Nuclear Information System (INIS)

    Von Toussaint, U; Gori, S; Manhard, A; Höschen, T; Höschen, C

    2011-01-01

    Understanding the influence of the microstructure of tungsten on hydrogen transport is crucial for the use of tungsten as first-wall material in fusion reactors. Here, we report the results of molecular dynamics and transition state studies on the influence of grain boundaries in tungsten on the transport of hydrogen. An exhaustive mapping of possible minimum activation energy migration trajectories for hydrogen as the trace impurity reveals a strongly modified activation energy distribution in the neighborhood of grain boundaries together with an altered connectivity matrix. The results indicate that grain boundaries in polycrystalline tungsten may provide an important transport channel, especially for neutron-damaged tungsten.

  8. Study on the hydrogen demand in China based on system dynamics model

    International Nuclear Information System (INIS)

    Ma, Tao; Ji, Jie; Chen, Ming-qi

    2010-01-01

    Reasonable estimation of hydrogen energy and other renewable energy demand of China's medium and long-term energy is of great significance for China's medium and long-term energy plan. Therefore, based on both China's future economic development and relative economic theory and system dynamics theory, this article analyzes qualitatively the internal factors and external factors of hydrogen energy demand system, and makes the state high and low two assumptions about China's medium and long-term hydrogen demand according to the different speed of China's economic development. After the system dynamic model setting up export and operation, the output shows the data changes of the total hydrogen demand and the four kinds of hydrogen demand. According to the analysis of the output, two conclusions are concluded: The secondary industry, not the tertiary industry (mainly the transportation), should be firstly satisfied by the hydrogen R and D and support of Government policy. Change of Chinese hydrogen demand scale, on basis of its economic growth, can not be effective explained through Chinese economic growth rate, and other influencing factor and mechanism should be probed deeply. (author)

  9. Influence of electrolyte composition and temperature on behaviour of AB5 hydrogen storage alloy used as negative electrode in Ni-MH batteries

    Science.gov (United States)

    Karwowska, Malgorzata; Jaron, Tomasz; Fijalkowski, Karol J.; Leszczynski, Piotr J.; Rogulski, Zbigniew; Czerwinski, Andrzej

    2014-10-01

    The AB5-type metal alloy (Mm-Ni4.1Al0.2Mn0.4Co0.45) has been investigated in different electrolytes (LiOH, NaOH, KOH, RbOH, CsOH). All of the electrochemical measurements have been performed using limited volume electrode technique (LVE). Thickness of the working electrode is nearly equal to the diameter of the grain (ca. 50 μm). Hydrogen diffusion coefficient has been determined using chronoamperometry. Hydrogen diffusion coefficient calculated for 100% state of charge reaches maximum value in KOH (DH = 4.65·10-10 cm2 s-1). We have obtained the highest value of capacity for the electrode in KOH and the lowest - in CsOH. The temperature influence on alloy capacity has been also tested. The alloy has been also characterised with SEM coupled with EDS, TGA/DSC and powder XRD. The unit cell of MmNi4.1Al0.2Mn0.4Co0.45 have been refined in the Cu5.4Yb0.8 structure type (a modified LaNi5 structure); the structure is unaffected by the electrochemical treatment.

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

    International Nuclear Information System (INIS)

    Bae, Jeong Hwan; Cho, Gyeong-Lyeob

    2010-01-01

    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 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 2 emission in Korea when considering dynamic general equilibrium effects. (author)

  11. Hydrogen storage alloy electrode for metal-hydride alkaline storage battery its production method; Kinzoku-suisokabutsu aruakri chikudenchiyo no suiso kyuzo gokin denkyoku oyobi sono seizo hoho

    Energy Technology Data Exchange (ETDEWEB)

    Matsuura, Y.; Nogami, K.; Kimoto, M.; Higashiyama, N.; Kuroda, Y.; Yonezu, I.; Nishio, K.

    1997-03-28

    Recently, it is proposed to employ the hydrogen storage alloy produced by means of rapidly solidifying single roll method, i.e., a method of projecting the molten alloy onto the surface of roll rotating in high speed as for the negative electrode material of the metal hydride alkaline battery. However, the hydrogen storage alloy produced by the single roll method has a heterogeneous grain size. So that the utilization of the hydrogen storage alloy is limited. This invention solves the problem. The rare earth-nickel system hydrogen storage alloy ribbon with average thickness of 0.08 - 0.35 mm is produced by means of single roll method. The grain size of the alloy is over 0.2 micrometer on roll surface side and below 20 micrometers on open surface side. The above said alloy is ground to average particle size of 25 - 70 micrometers to be used for the hydrogen absorbent. In this way, the metal hydride alkaline battery with excellent high rate discharge characteristic at the initial stage of charge-discharge cycle, excellent charge-discharge cycle characteristic, and excellent inner pressure characteristic can be produced. 2 figs., 5 tabs.

  12. Dynamics of dissociative adsorption of hydrogen on Ni(100)

    International Nuclear Information System (INIS)

    Hamza, A.V.; Madix, R.J.

    1985-01-01

    Nearly monoenergetic beams of hydrogen and deuterium were used to determine dissociative sticking probabilities for H 2 and D 2 on Ni(100) at various energies. Variation of the surface temperature between 90 and 300 K had no effect on the dissociative sticking probability of H 2 at 3.6 and 5.8 kJ/mol incident beam energy, indicating a direct mechanism of dissociation. A four fold increase in the initial dissociative sticking probability for H 2 from 0.2 to 0.8 was observed by increasing the translational kinetic energy from 0.7 to 7.0 kJ/mol. The initial dissociative sticking probability for D 2 was slightly lower, increasing from 0.15 to 0.75 with increasing translational kinetic energy from 1.3 to 10.5 kJ/mol. The form of the increase with kinetic energy was explained by tunnelling through a low activation barrier, accounting as well for the high dissociation probability at low kinetic energies. The dissociative sticking probability decreased with hydrogen or deuterium adatom coverage at all energies. The decline in sticking probability with hydrogen coverage was fit to a s(theta) = s 0 (1 - a theta)/sup n/ functional form. From this relationship it was deduced that hydrogen adatoms block only single sites and that four vacant sites are needed for dissociation. The dissociative sticking probability for H 2 declined precipitously from 0.77 to 0.16 with oxygen adatom coverage from 0 to 5% of a monolayer at a translational energy of 9.6 kJ.mol. 36 references, 8 figures

  13. Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

    Science.gov (United States)

    Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

    2010-05-05

    A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

  14. 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.

  15. Glassy carbon electrode modified with gold nanoparticles and hemoglobin in a chitosan matrix for improved pH-switchable sensing of hydrogen peroxide

    International Nuclear Information System (INIS)

    Liu, Yang; Shi, Liang; Gong, Jin; Fang, Yu-Ting; Bao, Ning; Gu, Hai-Ying; Zeng, Jiang

    2015-01-01

    Hemoglobin (Hb) has been demonstrated to endow electrochemical sensors with pH-switchable response because of the presence of carboxyl and amino groups. Hb was deposited in a chitosan matrix on a glassy carbon electrode (GCE) that was previously coated with clustered gold nanoparticles (Au-NPs) by electrodeposition. The switching behavior is active (“on”) to the negatively charged probe [Fe(CN) 6 3− ] at pH 4.0, but inactive (“off”) to the probe at pH 8.0. This switch is fully reversible by simply changing the pH value of the solution and can be applied for pH-controlled reversible electrochemical reduction of H 2 O 2 catalyzed by Hb. The modified electrode was tested for its response to the different electroactive probes. The response to these species strongly depends on pH which was cycled between 4 and 8. The effect is also attributed to the presence of pH dependent charges on the surface of the electrode which resulted in either electrostatic attraction or repulsion of the electroactive probes. The presence of Hb, in turn, enhances the pH-controllable response, and the electrodeposited Au-NPs improve the capability of switching. This study reveals the potential of protein based pH-switchable materials and also provides a simple and effective strategy for fabrication of switchable chemical sensors as exemplified in a pH-controllable electrode for hydrogen peroxide. (author)

  16. Electron beam dynamics in an ultrafast transmission electron microscope with Wehnelt electrode.

    Science.gov (United States)

    Bücker, K; Picher, M; Crégut, O; LaGrange, T; Reed, B W; Park, S T; Masiel, D J; Banhart, F

    2016-12-01

    High temporal resolution transmission electron microscopy techniques have shown significant progress in recent years. Using photoelectron pulses induced by ultrashort laser pulses on the cathode, these methods can probe ultrafast materials processes and have revealed numerous dynamic phenomena at the nanoscale. Most recently, the technique has been implemented in standard thermionic electron microscopes that provide a flexible platform for studying material's dynamics over a wide range of spatial and temporal scales. In this study, the electron pulses in such an ultrafast transmission electron microscope are characterized in detail. The microscope is based on a thermionic gun with a Wehnelt electrode and is operated in a stroboscopic photoelectron mode. It is shown that the Wehnelt bias has a decisive influence on the temporal and energy spread of the picosecond electron pulses. Depending on the shape of the cathode and the cathode-Wehnelt distance, different emission patterns with different pulse parameters are obtained. The energy spread of the pulses is determined by space charge and Boersch effects, given by the number of electrons in a pulse. However, filtering effects due to the chromatic aberrations of the Wehnelt electrode allow the extraction of pulses with narrow energy spreads. The temporal spread is governed by electron trajectories of different length and in different electrostatic potentials. High temporal resolution is obtained by excluding shank emission from the cathode and aberration-induced halos in the emission pattern. By varying the cathode-Wehnelt gap, the Wehnelt bias, and the number of photoelectrons in a pulse, tradeoffs between energy and temporal resolution as well as beam intensity can be made as needed for experiments. Based on the characterization of the electron pulses, the optimal conditions for the operation of ultrafast TEMs with thermionic gun assembly are elaborated. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Dynamic combinatorial libraries based on hydrogen-bonde molecular boxes

    NARCIS (Netherlands)

    Kerckhoffs, J.M.C.A.; Mateos timoneda, Miguel; Reinhoudt, David; Crego Calama, Mercedes

    2007-01-01

    This article describes two different types of dynamic combinatorial libraries of host and guest molecules. The first part of this article describes the encapsulation of alizarin trimer 2 a3 by dynamic mixtures of up to twenty different self-assembled molecular receptors together with the

  18. 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.

  19. 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...... defect motion in sodium alanate could result from vacancy-mediated sodium diffusion....

  20. A novel flow battery: A lead acid battery based on an electrolyte with soluble lead(II). Part IX: Electrode and electrolyte conditioning with hydrogen peroxide

    Science.gov (United States)

    Collins, John; Li, Xiaohong; Pletcher, Derek; Tangirala, Ravichandra; Stratton-Campbell, Duncan; Walsh, Frank C.; Zhang, Caiping

    Extended cycling of a soluble lead acid battery can lead to problems due to an imbalance in the coulombic efficiency leading to deposits of Pb and PbO2 on the electrodes. Periodic addition of hydrogen peroxide to the electrolyte of the soluble lead acid flow battery largely overcomes several operational problems seen during extended cycling, using a 10 cm × 10 cm parallel plate flow cell. It is shown that this treatment greatly extends the number of cycles that can be achieved with a reasonable energy-, voltage-, and charge efficiency of 54-66%, 71%, and 77-91%.

  1. A novel flow battery: A lead acid battery based on an electrolyte with soluble lead(II). Part IX: Electrode and electrolyte conditioning with hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Collins, John; Stratton-Campbell, Duncan [C-Tech Innovation Ltd., Capenhurst, Chester CH1 6EH (United Kingdom); Li, Xiaohong; Tangirala, Ravichandra; Walsh, Frank C.; Zhang, Caiping [Energy Technology Research Group, School of Engineering Sciences, University of Southampton, Highfield, University Road, Southampton SO17 1BJ (United Kingdom); Pletcher, Derek [Electrochemistry and Surface Science Group, School of Chemistry, University of Southampton, Southampton SO17 1BJ (United Kingdom)

    2010-05-01

    Extended cycling of a soluble lead acid battery can lead to problems due to an imbalance in the coulombic efficiency leading to deposits of Pb and PbO2 on the electrodes. Periodic addition of hydrogen peroxide to the electrolyte of the soluble lead acid flow battery largely overcomes several operational problems seen during extended cycling, using a 10 cm x 10 cm parallel plate flow cell. It is shown that this treatment greatly extends the number of cycles that can be achieved with a reasonable energy-, voltage-, and charge efficiency of 54-66%, 71%, and 77-91%. (author)

  2. Glass and antimony electrodes for long-term pH monitoring: a dynamic in vitro comparison

    NARCIS (Netherlands)

    Geus, W. P.; Smout, A. J.; Kooiman, J. C.; Lamers, C. B.; Gues, J. W.

    1995-01-01

    OBJECTIVE: To compare the performance of combined glass microelectrodes with monocrystalline and polycrystalline antimony electrodes with external reference in a 24-h dynamic in vitro study. DESIGN AND METHODS: In an artificial stomach, the pH of the contents titrated from pH1-7 and back by NaOH and

  3. Cellular automaton model for hydrogen transport dynamics through metallic surface

    International Nuclear Information System (INIS)

    Shimura, K.; Yamaguchi, K.; Terai, T.; Yamawaki, M.

    2002-01-01

    Hydrogen re-emission and re-combination at the surface of first wall materials are a crucial issue for the understanding of the fuel recycling and for the tritium inventory in plasma facing materials. It is know to be difficult to model the transient behaviour of those processes due to their complex time-transient nature. However, cellular automata (CA) are powerful tools to model such complex systems because of their nature of discreteness in both dependent and independent variables. Then the system can be represented by the fully local interactions between cells. For that reason, complex physical and chemical systems can be described by fairly simple manner. In this study, the kinetics of desorption of adsorbed hydrogen from an ideal metallic surface is modelled in CA. Thermal desorption is simulated with this model and the comparison with the theory of rate processes is performed to identify the validity of this model. The overall results show that this model is reasonable to express the desorption kinetics

  4. 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...

  5. A COMPREHENSIVE STUDY OF HYDROGEN ADSORBING TO AMORPHOUS WATER ICE: DEFINING ADSORPTION IN CLASSICAL MOLECULAR DYNAMICS

    Energy Technology Data Exchange (ETDEWEB)

    Dupuy, John L.; Lewis, Steven P.; Stancil, P. C. [Department of Physics and Astronomy and the Center for Simulational Physics, University of Georgia, Athens, GA 30602 (United States)

    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 (H{sub 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 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.

  6. Hydrogen bond dynamical properties of adsorbed liquid water monolayers with various TiO2 interfaces

    Science.gov (United States)

    English, Niall J.; Kavathekar, Ritwik S.; MacElroy, J. M. D.

    2012-12-01

    Equilibrium classical molecular dynamics (MD) simulations have been performed to investigate the hydrogen-bonding kinetics of water in contact with rutile-(110), rutile-(101), rutile-(100), and anatase-(101) surfaces at room temperature (300 K). It was observed that anatase-(101) exhibits the longest-lived hydrogen bonds in terms of overall persistence, followed closely by rutile-(110). The relaxation times, defined as the integral of the autocorrelation of the hydrogen bond persistence function, were also longer for these two cases, while decay of the autocorrelation function was slower. The increased number and overall persistence of hydrogen bonds in the adsorbed water monolayers at these surfaces, particularly for anatase-(101), may serve to promote possible water photolysis activity thereon.

  7. Molecular dynamics simulation of chemical sputtering of hydrogen atom on layer structured graphite

    International Nuclear Information System (INIS)

    Ito, A.; Wang, Y.; Irle, S.; Morokuma, K.; Nakamura, H.

    2008-10-01

    Chemical sputtering of hydrogen atom on graphite was simulated using molecular dynamics. Especially, the layer structure of the graphite was maintained by interlayer intermolecular interaction. Three kinds of graphite surfaces, flat (0 0 0 1) surface, armchair (1 1 2-bar 0) surface and zigzag (1 0 1-bar 0) surface, are dealt with as targets of hydrogen atom bombardment. In the case of the flat surface, graphene layers were peeled off one by one and yielded molecules had chain structures. On the other hand, C 2 H 2 and H 2 are dominant yielded molecules on the armchair and zigzag surfaces, respectively. In addition, the interaction of a single hydrogen isotope on a single graphene is investigated. Adsorption, reflection and penetration rates are obtained as functions of incident energy and explain hydrogen retention on layered graphite. (author)

  8. Effects of buffer agents on hydrogen adsorption and desorption at/within activated carbon for the negative electrode of aqueous asymmetric supercapacitors

    International Nuclear Information System (INIS)

    Chien, Hsiu-Chuan; Wu, Tzu-Ho; Rajkumar, Muniyandi; Hu, Chi-Chang

    2016-01-01

    Highlights: • H adsorption causes local pH increase and negatively shifts the double-layer potential window. • The local pH variation at AC/electrolyte interface can be controlled via adding buffer agents. • H adsorption potential on AC in buffer electrolytes follows the Nernstian dependence. • The pseudocapacitive reversibility of H adsorption/desorption at/within AC is too poor. - Abstract: In this work, the effects of adding buffer agents into aqueous electrolytes on the hydrogen adsorption/desorption behaviour at/within activated carbon are systematically investigated for the negative electrode of asymmetric supercapacitors. Due to the poor electrochemical reversibility of hydrogen adsorption/desorption at/within activated carbon, the hydrogen responses at/within activated carbon are not suitable for pseudo-capacitive energy storage of high-performance asymmetric supercapacitor. The electrochemical adsorption of H atoms consumes protons and causes the local pH change at the activated carbon/electrolyte interface, leading to the negative shift in the H adsorption potential when weakly acidic, neutral, and weakly basic electrolytes without buffer agents are employed. The addition of buffer agents into electrolytes significantly improves the rate of proton supply and promotes the rate of hydrogen adsorption at/within AC. Interestingly, the onset potential of significant H adsorption obtained from the buffered electrolytes generally follows the Nernstian dependence, suggesting the Nerstian dependence of H"+/H_a_d_s on AC at all pH values. In order to obtain the energy storage devices with high coulombic and energy efficiencies, the onset potential of significant H adsorption obtained from the electrolyte containing buffer agents is a reliable lower potential limit of the AC-coated negative electrode for aqueous asymmetric supercapacitors.

  9. Hydrogen storage alloy electrode for a metal-hydride alkaline battery; Kinzoku-suisokabutsu arukari chikudenchiyo no suiso kyuzo gokin denkyoku

    Energy Technology Data Exchange (ETDEWEB)

    Matsuura, Y.; Kuroda, Y.; Higashiyama, N.; Kimoto, M.; Nogami, M.; Nishio, K.; Saito, T.

    1996-07-16

    This invention aims to present a hydrogen storage alloy electrode which gives a metal-hydride alkaline battery with a high discharge characteristics at an initial stage of the charge and discharge cycle and excellent charge and discharge cycle characteristics. Thin belt-like misch metal(Mm)-nickel hydrogen storage alloy lumps with a CaCu5 type crystal structure and with dissolved boron or carbon as replaced atoms of nickel in a supersaturated state are obtained by quenching and solidification of molten Mm-Ni hydrogen storage alloy with addition of boron or carbon in 0.005 to 0.150 molar ratio to 1 mole of Mm by a single or dual role method, and annealed in an inert gas or in vacuum at a temperature of 620 to 1000{degree}C for a prescribed time to separate out a boron compound as a second phase, followed by pulverization to produce the alloy powder which is used as a hydrogen storage alloy material. The presence of the second phase promotes cracking of the alloy at an early stage of the charge and discharge cycle and suppresses generation of fine powder in the following charge and discharge cycles. 2 figs., 5 tabs.

  10. Efficient electrocatalytic reduction and detection of hydrogen peroxide at an IrIVOx·H2O nanostructured electrode prepared by electroflocculation

    International Nuclear Information System (INIS)

    Liu, Pei-Yin; Sun, Sin-Cih; Chen, Yi-Shiang; Chuang, Min-Chieh

    2016-01-01

    An Ir IV Ox·nH 2 O nanostructured electrode prepared by electroflocculation is reported; the electrode efficiently catalyzes the electrochemical reduction of hydrogen peroxide (H 2 O 2 ). Linear sweep voltammograms reveal that the potential onset arising due to the reduction of H 2 O 2 (1 mM) occurs at -0.1 V (vs. Ag/AgCl), which is more anodic than the onset potential occurring on the glassy carbon electrode by 400 mV, thereby substantiating the catalytic utility of Ir IV Ox·nH 2 O. The number of electrons transferred in the process, estimated via the Koutecky-Levich equation, is 1.89 ± 0.30. The Tafel slope obtained from polarization measurements is ca. 240.9 mV/dec. Furthermore, the Ir IV Ox·nH 2 O nanostructured electrode exhibits response with linear relationship against H 2 O 2 concentrations ranging over 0-1 mM (when agitated) and 0-150 μM (in flow injection analysis); the limit of detection (3σ), as determined under flow injection analysis, is 5 μM. The as-fabricated electrode is insensitive to the oxidation of ascorbic acid (0.1 mM) and acetaminophen (0.1 mM) and exhibits stable amperometric response (over twenty successive trials), albeit a slight drift in the sensor response is observed during the initial six evaluations. Based on the results, the electrocatalytic mechanism involving the following steps is proposed: (1) the reduction of Ir from Ir IV to Ir III , (2) catalytic cleavage of the O-O bond to generate OH· radicals, and (3) the reduction of the OH· radicals to OH − via the reoxidation of Ir III to Ir IV .

  11. 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.

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

    KAUST Repository

    Panos, C.; Kouramas, K.I.; Georgiadis, M.C.; Pistikopoulos, E.N.

    2010-01-01

    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.

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

    Science.gov (United States)

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H; Burghardt, Irene; Martinazzo, Rocco

    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.

  14. 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.

  15. 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.

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

    International Nuclear Information System (INIS)

    Tian Dexiang; Jin Baokang

    2011-01-01

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

  17. Towards a unified description of the hydrogen bond network of liquid water: A dynamics based approach

    International Nuclear Information System (INIS)

    Ozkanlar, Abdullah; Zhou, Tiecheng; Clark, Aurora E.

    2014-01-01

    The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed

  18. 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.

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

    KAUST Repository

    Masri, Karim M.; Younis, Mohammad I.

    2014-01-01

    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.

  20. 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.

  1. 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.

  2. 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.

  3. Electron beam dynamics in an ultrafast transmission electron microscope with Wehnelt electrode

    Energy Technology Data Exchange (ETDEWEB)

    Bücker, K.; Picher, M.; Crégut, O. [Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS, Université de Strasbourg, 23 rue du Loess, 67034 Strasbourg (France); LaGrange, T. [Interdisciplinary Centre for Electron Microscopy, École Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland); Reed, B.W.; Park, S.T.; Masiel, D.J. [Integrated Dynamic Electron Solutions, Inc., 5653 Stoneridge Drive 117, Pleasanton, CA 94588 (United States); Banhart, F., E-mail: florian.banhart@ipcms.unistra.fr [Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS, Université de Strasbourg, 23 rue du Loess, 67034 Strasbourg (France)

    2016-12-15

    High temporal resolution transmission electron microscopy techniques have shown significant progress in recent years. Using photoelectron pulses induced by ultrashort laser pulses on the cathode, these methods can probe ultrafast materials processes and have revealed numerous dynamic phenomena at the nanoscale. Most recently, the technique has been implemented in standard thermionic electron microscopes that provide a flexible platform for studying material's dynamics over a wide range of spatial and temporal scales. In this study, the electron pulses in such an ultrafast transmission electron microscope are characterized in detail. The microscope is based on a thermionic gun with a Wehnelt electrode and is operated in a stroboscopic photoelectron mode. It is shown that the Wehnelt bias has a decisive influence on the temporal and energy spread of the picosecond electron pulses. Depending on the shape of the cathode and the cathode-Wehnelt distance, different emission patterns with different pulse parameters are obtained. The energy spread of the pulses is determined by space charge and Boersch effects, given by the number of electrons in a pulse. However, filtering effects due to the chromatic aberrations of the Wehnelt electrode allow the extraction of pulses with narrow energy spreads. The temporal spread is governed by electron trajectories of different length and in different electrostatic potentials. High temporal resolution is obtained by excluding shank emission from the cathode and aberration-induced halos in the emission pattern. By varying the cathode-Wehnelt gap, the Wehnelt bias, and the number of photoelectrons in a pulse, tradeoffs between energy and temporal resolution as well as beam intensity can be made as needed for experiments. Based on the characterization of the electron pulses, the optimal conditions for the operation of ultrafast TEMs with thermionic gun assembly are elaborated. - Highlights: • A detailed characterization of electron

  4. Origin and dynamics of expanding neutral hydrogen supershells

    International Nuclear Information System (INIS)

    Kolesnik, I.G.; Silich, S.A.

    1987-01-01

    The evolutionary model of expanding supershells regulated by induced star formation is proposed. It is suggested that giant expanding shells are formed n superclouds at late evolutionary stage of star complexes. To understand the dynamics of the most huge supershells it is necessary to take into account that expanding shells can trigger star formation in cold dense pre-exosting cloudlets. Efficiency of induced star formation must be less than one percent to fit observational properties of supershells

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. On dewetting dynamics of solid films of hydrogen isotopes and its influence on tritium β spectroscopy

    International Nuclear Information System (INIS)

    Fleischmann, L.; Bonn, J.; Bornschein, B.; Otten, E.W.; Przyrembel, M.; Weinheimer, Ch.

    2000-01-01

    The dewetting dynamics of solid films of hydrogen isotopes, quench-condensed on a graphite substrate, was measured at various temperatures below desorption by observing the stray light from the film. A schematic model describing the dewetting process by surface diffusion is presented, which agrees qualitatively with our data. The activation energies of different hydrogen isotopes for surface diffusion were determined. The time constant for dewetting of a quench-condensed T 2 film at the working temperature of 1.86 K of the mainz neutrino mass experiment was extrapolated. (orig.)

  11. Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke; Li, Yifan; Yu, Shule; Cullen, David A.; Retterer, Scott T.; Toops, Todd J.; Bender, Guido; Pivovar, Bryan S.; Green, Johney B.; Zhang, Feng-Yuan

    2018-05-01

    Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layers at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.

  12. 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.

  13. Near-infrared selective dynamic windows controlled by charge transfer impedance at the counter electrode.

    Science.gov (United States)

    Pattathil, Praveen; Scarfiello, Riccardo; Giannuzzi, Roberto; Veramonti, Giulia; Sibillano, Teresa; Qualtieri, Antonio; Giannini, Cinzia; Cozzoli, P Davide; Manca, Michele

    2016-12-08

    Recent developments in the exploitation of transparent conductive oxide nanocrystals paved the way to the realization of a new class of electrochemical systems capable of selectively shielding the infrared heat loads carried by sunlight and prospected the blooming of a key enabling technology to be implemented in the next generation of "zero-energy" building envelopes. Here we report the fabrication of a set of electrochromic devices embodying an engineered nanostructured electrode made by high aspect-ratio tungsten oxide nanorods, which allow for selectively and dynamically controlling sunlight transmission over the near-infrared to visible range. Varying the intensity of applied voltage makes the spectral response of the device change across three different optical regimes, namely fully transparent, near-infrared only blocking and both visible and near-infrared blocking. It is demonstrated that the degree of reversible modulation of the thermal radiation entering the glazing element can approach a remarkable 85%, accompanied by only a modest reduction in the luminous transmittance.

  14. Design, commissioning and operational results of wide dynamic range BPM switched electrode electronics

    International Nuclear Information System (INIS)

    Powers, T.; Doolittle, L.; Ursic, R.; Wagner, J.

    1997-01-01

    The Continuous Electron Beam Accelerator Facility (CEBAF) is a high-intensity, continuous-wave electron accelerator for nuclear physics. Total acceleration of 4 GeV is achieved by recirculating the beam through two 400-MeV linacs. The operating currents over which the linac beam position monitoring system must meet specifications are 1 μA to 1000 μA. A system was developed in 1994 and installed in the spring of 1995 that switches four electrode signals at 120 kHz through two signal-conditioning chains that use computer-controlled variable gain amplifiers with a dynamic range greater than 80 dB. The system timing was tuned to the machine recirculation period of 4.2 μs so that components of the multipass beam could be resolved in the linacs. Other features of this VME-based system include long-term stability and high-speed data acquisition, which make it suitable for use as both a time-domain diagnostic tool and as part of a variety of beam feedback systems. The computer interface has enough control over the hardware to make a thorough self-calibration and verification-of-operation routine possible. copyright 1997 American Institute of Physics

  15. Dynamic Compression Experiments on Hydrogen and Deuterium in the Warm Dense Liquid.

    Science.gov (United States)

    Desjarlais, Michael; McCoy, Chad; Cochrane, Kyle; Mattsson, Thomas; Knudson, Marcus; Redmer, Ronald

    2017-06-01

    Recently a shock-ramp platform has been developed on the Z Accelerator to access off-Hugoniot states in liquids. The accelerator delivers a two-step current pulse; the first accelerates the electrode to a constant velocity, which upon impact with the sample cell creates a well-defined shock, the subsequent current rise produces ramp compression from the initially shocked state producing relatively cool (1-2 kK), high pressure (>300 GPa), high compression (10 to 15-fold compression) states. This technique allows experimental access to the region of phase space where hydrogen is predicted to undergo a first-order phase transition from an insulating molecular-like to a conducting atomic-like liquid. Here we discuss the experimental platform, survey various theoretical predictions for the liquid-liquid, insulator-to-metal transition in hydrogen, and present results of experiments on both deuterium and hydrogen that clearly show an abrupt transition to a metallic state. We also present results from recent experiments at higher temperatures (3-4 kK) and compare the observations to both first-principles theory and previous step-wise loading experiments that exhibited a minimum metallic conductivity. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  16. Hydrogen storage alloy electrode of metal hydride alkaline storage battery and its production method; Kinzoku-suisokabutsu arukari chikudenchiyo no suiso kyuzo gokin denkyoku oyobi sono seizo hoho

    Energy Technology Data Exchange (ETDEWEB)

    Matsuura, Y.; Nogami, K.; Kimoto, M.; Higashiyama, N.; Kuroda, Y.; Yonezu, I.; Nishio, K.

    1997-03-28

    Recently, a proposal was made of employing the hydrogen storage alloy produced by means f rapidly solidifying single roll method, i.e., a method of projecting the molten alloy onto the surface of roll rotating in high speed as for the negative electrode material of the metal hydride alkaline battery. However, the hydrogen storage alloy produced by the single roll method has a heterogeneous grain size. This invention solves the problem. The Mm{center_dot}Ni{center_dot}Co{center_dot}Al{center_dot}Mn alloy ribbon with average thickness of 0.08 - 0.35 mm is produced by means of single roll method. The grain size of the alloy is over 0.2 micrometer on roll surface side and below 18 micrometers on open surface side. The alloy is ground to be used for the hydrogen absorbent. The general formula of this alloy is MmR(x) (Mm = mischmetal, R = Ni, Co, Al, Mn). In this way, the metal hydride alkaline battery with excellent high rate discharge characteristic at the initial stage of charge-discharge cycle, excellent charge-discharge cycle characteristic, and excellent inner pressure characteristic can be produced. 2 figs., 5 tabs.

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

    International Nuclear Information System (INIS)

    Nakano, H.; Goto, M.; Tsumori, K.; Kisaki, M.; Ikeda, K.; Nagaoka, K.; Osakabe, M.; Takeiri, Y.; Kaneko, O.; Nishiyama, S.; Sasaki, K.

    2015-01-01

    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

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

    International Nuclear Information System (INIS)

    Feng Yexin; Chen Ji; Wang Enge; Li Xin-Zheng

    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. (topical review)

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

    International Nuclear Information System (INIS)

    Wimmer, Christian

    2014-01-01

    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. 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.

  1. 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.

  2. Dynamic effects on the acceptance of hydrogen technologies - an international comparison

    International Nuclear Information System (INIS)

    Heinz, Boris; Erdmann, Georg

    2008-01-01

    Social acceptance plays an important role for the future hydrogen economy and a broad market launch of hydrogen technologies. Neglecting the aspect of public acceptance and attitude may become a serious obstacle for the establishment of a mass market infrastructure. With a standardized questionnaire and a standardized procedure, personal interviews were conducted with at least 300 persons in Amsterdam, Barcelona, Berlin, Hamburg, London, Luxembourg, Madrid and Reykjavik, in total with 3352 persons. Thus the dynamics of the public attitude toward hydrogen were analyzed, whereby the possibility of setbacks and accidents was taken into consideration. Whereas 68% of the interviewed persons would be supportive of the aforementioned technologies, an amount of 31% was determined to be volatile. An amount of 77% stated that they would use a hydrogen bus instead of a conventional one if they could choose, but an amount of 21% was indifferent. It will be shown how these amounts can affect the balance of acceptance and how stable the acceptance of hydrogen technologies can be considered in the evaluated six countries. (author)

  3. A molecular dynamics study of nuclear quantum effect on the diffusion of hydrogen in condensed phase

    International Nuclear Information System (INIS)

    Nagashima, Hiroki; Tokumasu, Takashi; Tsuda, Shin-ichi; Tsuboi, Nobuyuki; Koshi, Mitsuo; Hayashie, A. Koichi

    2014-01-01

    In this paper, the quantum effect of hydrogen molecule on its diffusivity is analyzed using Molecular Dynamics (MD) method. The path integral centroid MD (CMD) method is applied for the reproduction method of time evolution of the molecules. The diffusion coefficient of liquid hydrogen is calculated using the Green-Kubo method. The simulation is performed at wide temperature region and the temperature dependence of the quantum effect of hydrogen molecule is addressed. The calculation results are compared with those of classical MD results. As a result, it is confirmed that the diffusivity of hydrogen molecule is changed depending on temperature by the quantum effect. It is clarified that this result can be explained that the dominant factor by quantum effect on the diffusivity of hydrogen changes from the swollening the potential to the shallowing the potential well around 30 K. Moreover, it is found that this tendency is related to the temperature dependency of the ratio of the quantum kinetic energy and classical kinetic energy

  4. A dynamic simulation tool for the battery-hybrid hydrogen fuel cell vehicle

    Energy Technology Data Exchange (ETDEWEB)

    Moore, R.M. [Hawaii Natural Energy Institute, University of Hawaii, Manoa (United States); Ramaswamy, S.; Cunningham, J.M. [California Univ., Berkeley, CA (United States); Hauer, K.H. [xcellvision, Major-Hirst-Strasse 11, 38422 Wolfsburg (Germany)

    2006-10-15

    This paper describes a dynamic fuel cell vehicle simulation tool for the battery-hybrid direct-hydrogen fuel cell vehicle. The emphasis is on simulation of the hybridized hydrogen fuel cell system within an existing fuel cell vehicle simulation tool. The discussion is focused on the simulation of the sub-systems that are unique to the hybridized direct-hydrogen vehicle, and builds on a previous paper that described a simulation tool for the load-following direct-hydrogen vehicle. The configuration of the general fuel cell vehicle simulation tool has been previously presented in detail, and is only briefly reviewed in the introduction to this paper. Strictly speaking, the results provided in this paper only serve as an example that is valid for the specific fuel cell vehicle design configuration analyzed. Different design choices may lead to different results, depending strongly on the parameters used and choices taken during the detailed design process required for this highly non-linear and n-dimensional system. The primary purpose of this paper is not to provide a dynamic simulation tool that is the ''final word'' for the ''optimal'' hybrid fuel cell vehicle design. The primary purpose is to provide an explanation of a simulation method for analyzing the energetic aspects of a hybrid fuel cell vehicle. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  5. Dynamically polarized hydrogen target as a broadband, wavelength-independent thermal neutron spin polarizer

    International Nuclear Information System (INIS)

    Zhao Jinkui; Garamus, Vasil M.; Mueller, Wilhelm; Willumeit, Regine

    2005-01-01

    A hydrogen-rich sample with dynamically polarized hydrogen nuclei was tested as a wavelength-independent neutron transmission spin polarizer. The experiment used a modified setup of the dynamic nuclear polarization target station at the GKSS research center. The standard solvent sample at the GKSS DNP station was used. It is 2.8mm thick and consists of 43.4wt% water, 54.6wt% glycerol, and 2wt% of EHBA-Cr(v) complex. The wavelength of the incident neutrons for the transmission experiment was λ=8.1A with Δλ/λ=10%. The polarization of neutron beam after the target sample was analyzed with a supermirror analyzer. A neutron polarization of -52% was achieved at the hydrogen polarization of -69%. Further experiments will test the feasibility of other hydrogen-rich materials, such as methane, as the polarizer. A theoretical calculation shows that a polarized methane target would allow over 95% neutron polarizations with more than 30% transmission

  6. 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 CuFe 2 O 4 nanoparticle (RGO/CuFe 2 O 4 /CPE) was designed for determination of hydrogen peroxide (H 2 O 2 ). The electrocatalytic reduction of H 2 O 2 was examined using various techniques such as cyclic voltammetry (CV), chronoamperometry, amperometry and differential pulse voltammetry (DPV). CuFe 2 O 4 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 CuFe 2 O 4 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 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.

  7. The hydrogen atom in a magnetic field. Spectrum from the Coulomb dynamical group approach

    International Nuclear Information System (INIS)

    Delande, D.; Gay, J.C.

    1986-01-01

    Some sample results are presented for the problems of the hydrogen atom in a magnetic field. The energies have been computed for a typical Rydberg situation of atomic physics interest using limited computer facilities. The use of the Coulomb dynamical group allows a complete description of the symmetries and a rational choice of a Sturmian type basis set. Moreover, comparison with Rayleigh-Schrodinger perturbative expansions of the energies is performed. (author)

  8. 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

  9. Photoelectrochemical performance of multi-layered BiOx–TiO2/Ti electrodes for degradation of phenol and production of molecular hydrogen in water

    International Nuclear Information System (INIS)

    Park, Hyunwoong; Bak, Ayoung; Ahn, Yong Yoon; Choi, Jina; Hoffmannn, Michael R.

    2012-01-01

    Highlights: ► We demonstrated that the electrocatalytic performance of BiO x –TiO 2 anodes for the degradation of aqueous phenol could be highly boosted by light irradiation. ► Although BiO x –TiO 2 anodes have been originally developed as the electrocatalytic anodes that operate in the absence of light by degeneratively doping Bi in TiO 2 , the presence of TiO 2 made them retain photoelectrocatalytic activity as well. ► Such dual functionality of BiO x –TiO 2 electrodes with high synergy effects may be directly used for water treatment with simultaneous hydrogen production from water. - Abstract: 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 .

  10. Utilization of the molecular dynamic to study the effect of hydrogen in the stress corrosion

    International Nuclear Information System (INIS)

    Arnoux, P.

    2007-01-01

    Many microscopic and theoretical models of stress corrosion have been proposed, in particularly to explain the grain boundary cracking of stainless steels and nickel base. In this work calculus of molecular dynamic have been used to propose a mechanism of stress corrosion at the atomic scale. The author aims to reproduce, by molecular dynamic, the mechanism of an open crack in irradiated stainless steel in PWR reactor and show that the growth of the oxide at the crack back produce hydrogen. (A.L.B.)

  11. 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)

  12. Iron(III) protoporphyrin IX-single-wall carbon nanotubes modified electrodes for hydrogen peroxide and nitrite detection

    International Nuclear Information System (INIS)

    Turdean, Graziella L.; Popescu, Ionel Catalin; Curulli, Antonella; Palleschi, Giuseppe

    2006-01-01

    Iron(III) protoporphyrin IX (Fe(III)P), adsorbed either on single-walled carbon nanotubes (SWCNT) or on hydroxyl-functionalized SWCNT (SWCNT-OH), was incorporated within a Nafion matrix immobilized on the surface of a graphite electrode. From cyclic voltammetric measurements, performed under different experimental conditions (pH and potential scan rate), it was established that the Fe(III)P/Fe(II)P redox couple involves 1e - /1H + . The heterogeneous electron transfer process occurred faster when Fe(III)P was adsorbed on SWCNT-OH (∼11 s -1 ) than on SWCNT (∼4.9 s -1 ). Both the SWCNT-Fe(III)P- and SWCNT-OH-Fe(III)P-modified graphite electrodes exhibit electrocatalytic activity for H 2 O 2 and nitrite reduction. The modified electrodes sensitivities were found varying in the following sequences: S SWCNT-OH-Fe(III)P = 2.45 mA/M ∼ S SWCNT-Fe(III)P = 2.95 mA/M > S Fe(III)P = 1.34 mA/M for H 2 O 2 , and S SWCNT-Fe(III)P = 3.54 mA/M > S Fe(III)P 1.44 mA/M > S SWCNT-OH-Fe(III)P = 0.81 mA/M for NO 2 -

  13. Rhodium-Prussian Blue modified carbon paste electrode (Rh-PBMCPE for amperometric detection of hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Ivama Viviane Midori

    2003-01-01

    Full Text Available Prussian Blue was deposited at carbon paste electrode surface from a solution containing 2.0 x 10-3 mol L-1 K3[Fe(CN6], 3.0 x 10-3 mol L-1 FeCl3 and 1.0 x 10-2 mol L-1 HCl using two controlled potentials. To improve the stability of the modified electrode it was 50 times cycled in a solution containing 1.0 x 10-3 mol L-1 RhCl3, 0.50 mol L-1 KCl and 0.010 mol L-1 HCl in the potential range from - 0.40 V to 0.60 V at 60 mV s-1. The Rh - Prussian Blue carbon paste modified electrode (Rh-PBMCPE showed good stability during amperometric catalytic determination of H2O2 at 0.040 V, without ascorbic and uric acids interferences. The current changed linearly with H2O2 concentrations in the range of 5.0 x 10-5 - 8.6 x 10-4 mol L-1. The estimated detection limit was 2.8 x 10-5 mol L-1 with sensibility changing from 1.32 to 0.96 A mol-1 L cm-2 along five days (180 determinations.

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

    KAUST Repository

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

    2015-01-01

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

  15. 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.)

  16. 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.

  17. Selective hydrogen detection at high temperature by using yttria-stabilized zirconia-based sensor with coupled metal-oxide-based sensing electrodes

    International Nuclear Information System (INIS)

    Yamaguchi, Mami; Anggraini, Sri Ayu; Fujio, Yuki; Breedon, Michael; Plashnitsa, Vladimir V.; Miura, Norio

    2012-01-01

    A selective and sensitive hydrogen (H 2 ) sensor capable of working at a high operating temperature was developed by using a pair of metal-oxide-based SEs formed on a yttria-stabilized zirconia (YSZ) tube, operating as a mixed-potential type sensor. The utilization of SnO 2 (+30 wt.% YSZ) electrode together with NiO-TiO 2 electrode configured as a combined-type sensor, successfully diminished the response of the examined interfering gases (especially propene), while maintaining high response toward H 2 at an operating temperature of 600 °C under humid operating conditions. The developed sensor exhibited quick response to 100 ppm H 2 , as the 90% response time was observed to be 9 s. The sensing performance of the combined-type sensor was barely affected by changes in water vapor concentration within the range of 1–4 vol.%, suggesting the resilience of the sensor to function in realistic working conditions. This sensor exhibited a linear relationship between sensitivity and H 2 concentration on a logarithmic scale.

  18. 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.

  19. Multiple enhancement of luminol electrochemiluminescence using electrodes functionalized with titania nanotubes and platinum black: ultrasensitive determination of hydrogen peroxide, resveratrol, and dopamine

    International Nuclear Information System (INIS)

    Ming, Liang; Peng, Tingting; Tu, Yifeng

    2016-01-01

    We describe a substantial improvement of the electrochemiluminescence (ECL) of luminol which is widely used in flow injection analysis (FIA). It is based on synchronous dual sensitization of ECL by using titania nanotubes (TiNTs) and platinum black (PB). A piece of indium tin oxide (ITO) glass functionalized with TiNTs acts as the first working electrode, and a PB-modified platinum plate serves as the second one. By applying two constant potentials to the two electrodes, strong and consecutive ECL emission of luminol is obtained. The system works well in assays as shown for the successful quantitation of hydrogen peroxide (H 2 O 2 ), of the antioxidant resveratrol, and of the neutrotransmitter dopamine (DA) in spiked human serum samples. The detection limits for these three species (at a signal-to-noise ratio of 3) are as low as 66 pM (H 2 O 2 ), 22 nM (resveratrol), and 30 nM (DA). Recoveries in assays of DA in spiked serum range from 97.3 to 105.4 %. In our perception, the technique of dual sensitization represents a substantial improvement of the detection limits of ECL assays. (author)

  20. 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.

  1. 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.

  2. Dynamic simulation of pure hydrogen production via ethanol steam reforming in a catalytic membrane reactor

    International Nuclear Information System (INIS)

    Hedayati, Ali; Le Corre, Olivier; Lacarrière, Bruno; Llorca, Jordi

    2016-01-01

    Ethanol steam reforming (ESR) was performed over Pd-Rh/CeO 2 catalyst in a catalytic membrane reactor (CMR) as a reformer unit for production of fuel cell grade pure hydrogen. Experiments were performed at 923 K, 6–10 bar, and fuel flow rates of 50–200 μl/min using a mixture of ethanol and distilled water with steam to carbon ratio of 3. A static model for the catalytic zone was derived from the Arrhenius law to calculate the total molar production rates of ESR products, i.e. CO, CO 2 , CH 4 , H 2 , and H 2 O in the catalytic zone of the CMR (coefficient of determination R 2  = 0.993). The pure hydrogen production rate at steady state conditions was modeled by means of a static model based on the Sieverts' law. Finally, a dynamic model was developed under ideal gas law assumptions to simulate the dynamics of pure hydrogen production rate in the case of the fuel flow rate or the operating pressure set point adjustment (transient state) at isothermal conditions. The simulation of fuel flow rate change dynamics was more essential compared to the pressure change one, as the system responded much faster to such an adjustment. The results of the dynamic simulation fitted very well to the experimental values at P = 7–10 bar, which proved the robustness of the simulation based on the Sieverts' law. The simulation presented in this work is similar to the hydrogen flow rate adjustments needed to set the electrical load of a fuel cell, when fed online by the pure hydrogen generating reformer studied. - Highlights: • Ethanol steam reforming (ESR) experiments were performed in a Pd-Ag membrane reactor. • The model of the catalytic zone of the reactor was derived from the Arrhenius law. • The permeation zone (membrane) was modeled based on the Sieverts' law. • The Sieverts' law model showed good results for the range of P = 7–10 bar. • Pressure and fuel flow rate adjustments were considered for dynamic simulation.

  3. Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

    Science.gov (United States)

    Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

    2009-06-08

    Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

  4. 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.

  5. Study into the mechanisms of hydrogen contamination of niobium as a material for superconducting radiofrequency cavities. Molecular dynamics studies for simulation of the hydrogen diffusion processes

    International Nuclear Information System (INIS)

    Roux, B.

    1993-01-01

    Superconducting radiofrequency cavities were chosen for most of the future particle accelerators. In the case of pure niobium cavities, several laboratories have observed degradation of superconducting properties related to the conditions of the cooling down process. This effect seems to stem from hydrogen contamination which occurs during surface treatments. With the aim to study the influence of different surface treatments on the hydrogen contamination depth concentration profiling of the near surface region (the first 200 nm) was first carried out by the classical ERDA technique with 30 nm depth resolution. In order to better localize hydrogen, the initial particle selecting device (Teflon foil) was replaced by an electromagnetic (ExB) filter improving then the depth resolution by a factor three. This study reveals an hydrogen segregation at the niobium surface. Such a result is in contradiction with the relative high experimental value of the hydrogen diffusion coefficient given by the literature. To understand the trapping mechanism of hydrogen, a simulation by molecular dynamics of this impurity diffusion process was performed. This approach requires the knowledge of the interatomic potential. The potential parameters were fitted with static and dynamic tests. Nb-Nb interaction is based on many body potential. Nb-H is represented by two body potential. The Arrhenius diagram of the diffusion coefficient achieved by dynamic for a single crystal provides too small activation energy in comparison with experimental results. However, in presence of defects, a simulation proves a large increase of these values. It is only around 1000 K that the diffusion of hydrogen is not altered by defects. This conclusion confirms the experimental results concerning a good characteristic of superconducting cavities after thermal treatments. (orig.)

  6. Determination of the level of DNA modification with cisplatin by catalytic hydrogen evolution at mercury-based electrodes

    Czech Academy of Sciences Publication Activity Database

    Horáková Brázdilová, Petra; Těsnohlídková, Lucie; Havran, Luděk; Vidláková, Pavlína; Pivoňková, Hana; Fojta, Miroslav

    2010-01-01

    Roč. 82, č. 7 (2010), s. 2969-2976 ISSN 0003-2700 R&D Projects: GA ČR(CZ) GP204/07/P476; GA AV ČR(CZ) IAA500040701; GA AV ČR(CZ) 1QS500040581; GA MŠk(CZ) LC06035 Grant - others:GA AV ČR(CZ) IAA400040903 Program:IA Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : cisplatin * electrochemical analysis of DNA * mercury electrode Subject RIV: BO - Biophysics Impact factor: 5.874, year: 2010

  7. Immobilization of [Cu(bpy)2]Br2 complex onto a glassy carbon electrode modified with alpha-SiMo12O40(4-) and single walled carbon nanotubes: application to nanomolar detection of hydrogen peroxide and bromate.

    Science.gov (United States)

    Salimi, Abdollah; Korani, Aazam; Hallaj, Rahman; Khoshnavazi, Roshan; Hadadzadeh, Hasan

    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)(2)]Br(2) was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, alpha-SiMo(12)O(40)(4-) and single walled carbon nanotubes (SWCNTs). 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(12)O(40)(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(12)O(40)(4-) modified electrodes shows excellent electrocatalytic activity toward reduction H(2)O(2) and BrO(3)(-) at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5(+/-0.2)x10(3) M(-1) s(-1) and 3.0(+/-0.10)x10(3) M(-1) s(-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(-1), 10 nM-20 microM, 1 nM, 5.5 nA nM(-1) and 10 nM-18 microM, respectively.

  8. 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...... chain subject to a substrate with two optical bands), both providing a bistability of the hydrogen-bonded proton. Exact two-component (kink and antikink) discrete solutions for these models are found numerically. We compare the soliton solutions and their properties in both the one- (when the heavy ions...... 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....

  9. Molecular dynamics simulations of interactions between hydrogen and fusion-relevant materials

    International Nuclear Information System (INIS)

    Rooij, Dagmar de

    2010-01-01

    In a thermonuclear reactor fusion between hydrogen isotopes takes place, producing helium and energy. The so-called divertor is the part of the fusion reactor vessel where the plasma is neutralized in order to exhaust the helium. The surface plates of the divertor are subjected to high heat loads and high fluxes of energetic hydrogen and helium. In the next generation fusion device - the tokamak ITER - the expected conditions at the plates are particle fluxes exceeding 10 24 per second and square metre, particle energies ranging from 1 to 100 eV and an average heat load of 10 MW per square metre. Two materials have been identified as candidates for the ITER divertor plates: carbon and tungsten. Since there are currently no fusion devices that can create these harsh conditions, it is unknown how the materials will behave in terms of erosion and hydrogen retention. To gain more insight in the physical processes under these conditions molecular dynamics simulations have been conducted. Since diamond has been proposed as possible plasma facing material, we have studied erosion and hydrogen retention in diamond and amorphous hydrogenated carbon (a-C:H). As in experiments, diamond shows a lower erosion yield than a-C:H, however the hydrogen retention in diamond is much larger than in a-C:H and also hardly depending on the substrate temperature. This implies that simple heating of the surface is not sufficient to retrieve the hydrogen from diamond material, whereas a-C:H readily releases the retained hydrogen. So, in spite of the higher erosion yield carbon material other than diamond seems more suitable. Experiments suggest that the erosion yield of carbon material decreases with increasing flux. This was studied in our simulations. The results show no flux dependency, suggesting that the observed reduction is not a material property but is caused by external factors as, for example, redeposition of the erosion products. Our study of the redeposition showed that the

  10. 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.

  11. Incident angle dependence of reactions between graphene and hydrogen atom by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Saito, Seiki; Nakamura, Hiroaki; Ito, Atsushi

    2010-01-01

    Incident angle dependence of reactions between graphene and hydrogen atoms are obtained qualitatively by classical molecular dynamics simulation under the NVE condition with modified Brenner reactive empirical bond order (REBO) potential. Chemical reaction depends on two parameters, i.e., polar angle θ and azimuthal angle φ of the incident hydrogen. From the simulation results, it is found that the reaction rates strongly depend on polar angle θ. Reflection rate becomes larger with increasing θ, and the θ dependence of adsorption rate is also found. The θ dependence is caused by three dimensional structure of the small potential barrier which covers adsorption sites. φ dependence of penetration rate is also found for large θ. (author)

  12. High performance ceramic carbon electrode-based anodes for use in the Cu-Cl thermochemical cycle for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Ranganathan, Santhanam; Easton, E. Bradley [Faculty of Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada)

    2010-02-15

    A high performance ceramic carbon electrode (CCE) was fabricated by the sol-gel method to study the CuCl electrolysis in Cu-Cl thermochemical cycle. The electrochemical behavior and stability of the CCE was investigated by polarization experiments at different concentrations of CuCl/HCl system. The CCE displayed excellent anodic performance and vastly outperformed the bare carbon fiber paper (CFP) even at high concentrations of CuCl (0.5 M) and HCl (6 M), which is explained in terms of increased active area and enhanced anion transport properties. Further enhancement of activity was achieved by coating the CCE layer onto both sides of the CFP substrate. (author)

  13. 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.

  14. 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...

  15. 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...

  16. Molecular scale structure and dynamics at an ionic liquid/electrode interface

    DEFF Research Database (Denmark)

    Reichert, Peter; Kjær, Kasper Skov; Brandt van Driel, Tim

    2018-01-01

    After a century of research, the potential-dependent ion distribution at electrode/electrolyte interfaces is still under debate. In particular for solvent-free electrolytes such as room-temperature ionic liquids, classical theories for the electrical double layer are not applicable. Using a combi...

  17. 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)

  18. 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. Copyright © 2014 Wiley Periodicals, Inc.

  19. 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.

  20. A non-enzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with cuprous oxide and nitrogen-doped graphene in a nafion matrix

    International Nuclear Information System (INIS)

    Jiang, Bin-Bin; Wei, Xian-Wen; Wu, Fang-Hui; Chen, Le; Yuan, Guo-Zan; Wu, Kong-Lin; Dong, Chao; Ye, Yin

    2014-01-01

    We have modified a glassy carbon electrode (GCE) with copper(I) oxide nanoparticles (NPs), nitrogen-doped graphene (N-graphene) and Nafion to obtain a novel sensing platform for the non-enzymatic detection of hydrogen peroxide. The deposition of the Cu 2 O NPs on N-graphene was accomplished by single-step chemical reduction. The nanocomposite was characterized by using X-ray diffraction and scanning electron microscopy which revealed the successful attachment of monodispersed Cu 2 O NPs to the N-graphene. Electrochemical studies revealed that the composite possesses excellent electrocatalytic activity toward the reduction of H 2 O 2 in pH 7.4 phosphate buffer solution at a working potential of −0.60 V. Nafion obviously enhances the stability of the modified GCE and repels any negatively charged species. Compared to a conventional Cu 2 O/Nafion-modified GCE, the modified GCE presented here exhibits (a) a higher catalytic activity for the reduction of H 2 O 2 (1.94 times), (b) a wider linear range (from 5.0 μM to 3.57 mM), (c) a lower detection limit (0.8 μM at an S/N of 3), (d) higher sensitivity (26.67 μA mM −1 ) and (e) a shorter response time (2 s). Moreover, the new GCE exhibits good selectivity and stability. These properties make the new hybrid electrode a promising tool for to the development of electrochemical sensors, molecular bioelectronic devices, biosensors, and biofuel cells. (author)

  1. Mobility of hydrogen-helium clusters in tungsten studied by molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Grigorev, Petr, E-mail: grigorievpit@gmail.com [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol, 2400 (Belgium); Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnologies, and Telecommunications, Peter the Great St.Petersburg Polytechnic University, St. Petersburg (Russian Federation); Terentyev, Dmitry; Bonny, Giovanni [SCK-CEN, Nuclear Materials Science Institute, Boeretang 200, Mol, 2400 (Belgium); Zhurkin, Evgeny E. [Department of Experimental Nuclear Physics K-89, Institute of Physics, Nanotechnologies, and Telecommunications, Peter the Great St.Petersburg Polytechnic University, St. Petersburg (Russian Federation); Oost, Guido van [Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Noterdaeme, Jean-Marie [Ghent University, Applied Physics EA17 FUSION-DC, St.Pietersnieuwstraat, 41 B4, B-9000, Gent (Belgium); Max-Planck-Institut für Plasmaphysik, Garching (Germany)

    2016-06-15

    Tungsten is a primary candidate material for plasma facing components in fusion reactors. Interaction of plasma components with the material is unavoidable and will lead to degradation of the performance and the lifetime of the in-vessel components. In order to gain better understanding the mechanisms driving the material degradation at atomic level, atomistic simulations are employed. In this work we study migration, stability and self-trapping properties of pure helium and mixed helium-hydrogen clusters in tungsten by means of molecular dynamics simulations. We test two versions of an embedded atom model interatomic potential by comparing it with ab initio data regarding the binding properties of He clusters. By analysing the trajectories of the clusters during molecular dynamics simulations at finite temperatures we obtain the diffusion parameters. The results show that the diffusivity of mixed clusters is significantly lower, than that of pure helium clusters. The latter suggest that the formation of mixed clusters during mixed hydrogen helium plasma exposure will affect the helium diffusivity in the material.

  2. The electrochemical properties of Zr-Ti-V-Ni-Mn hydrogen storage alloys with various compositions for an electrode of Ni-MH secondary battery

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Seung Jun; Jung, So Yi; Park, Choong Nyeon [Dept. of Metallurgical Engineering, Chonnam National University, Kwangju (Korea)

    1999-12-01

    Effects of alloy modification for the Zr{sub 0.7}Ti{sub 0.3}V{sub 0.4}Ni{sub 1.2}Mn{sub 0.4} alloy as an electrode materials have been investigated. When Ti in the alloy was partially substituted by Zr, the hydrogen storage capacity and subsequently the discharge capacity increased significantly, however, the activation characteristic and rate capability decreased. By substituting Mn with other elements (Cr, Co and Fe) in the alloy, discharge capacity decreased but the cycle life and rate capability were improved. Considering both the discharge capacity, the high rate discharge property and cycle life, the Zaire.{sub 7}Ti{sub 0.3}V{sub 0.4}Ni{sub 1.2}Mn{sub 0.3}Cr{sub 0.1} alloy among the alloys subjected to the test was found to be a prominent alloy for a practical usage. 11 refs., 5 figs., 2 tabs.

  3. Hydrogen peroxide biosensor based on hemoglobin immobilized at graphene, flower-like zinc oxide, and gold nanoparticles nanocomposite modified glassy carbon electrode.

    Science.gov (United States)

    Xie, Lingling; Xu, Yuandong; Cao, Xiaoyu

    2013-07-01

    In this work, a highly sensitive hydrogen peroxide (H2O2) biosensor based on immobilization of hemoglobin (Hb) at Au nanoparticles (AuNPs)/flower-like zinc oxide/graphene (AuNPs/ZnO/Gr) composite modified glassy carbon electrode (GCE) was constructed, where ZnO and Au nanoparticles were modified through layer-by-layer onto Gr/GCE. Flower-like ZnO nanoparticles could be easily prepared by adding ethanol to the precursor solution having higher concentration of hydroxide ions. The Hb/AuNPs/ZnO/Gr composite film showed a pair of well-defined, quasi-reversible redox peaks with a formal potential (E(0)) of -0.367 V, characteristic features of heme redox couple of Hb. The electron transfer rate constant (k(s)) of immobilized Hb was 1.3 s(-1). The developed biosensor showed a very fast response (<2 s) toward H2O2 with good sensitivity, wide linear range, and low detection limit of 0.8 μM. The fabricated biosensor showed interesting features, including high selectivity, acceptable stability, good reproducibility, and repeatability along with excellent conductivity, facile electron mobility of Gr, and good biocompatibility of ZnO and AuNPs. The fabrication method of this biosensor was simple and effective for determination of H2O2 in real samples with quick response, good sensitivity, high selectivity, and acceptable recovery. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Thermal and dynamic loads on the EPR containment due to hydrogen combustion

    International Nuclear Information System (INIS)

    Eyink, J.; Movahed, M.; Petzold, K.G.; Kotchourko, A.; Royl, P.; Travis, J.R.

    2001-01-01

    A major aspect of the EPR safety concept is to cope with severe accidents including core melt and to maintain the integrity of the containment even for those hypothetical events. One potential threat for the containment is related to the combustion of hydrogen, which may be produced in a large amount during core degradation. The European Pressurized Water Reactor (EPR) hydrogen mitigation concept consists of about 44 recombiners, located mainly in the equipment rooms (only 4 recombiners are located in the dome area). This paper is devoted to two important potential threats on the containment related to hydrogen removal: - Thermal loads resulting from recombiner action and/or combustion are of importance also with respect to the integrity of the local composite liner foreseen at some crucial locations of the containment; - Dynamic loads resulting from fast deflagration may impair containment wall or internal walls even if the AICC (adiabatic isochoric complete combustion) pressure is below the design pressure. Two types of combustion calculations have been performed: a) In cases, where fast deflagration cannot be excluded, combustion has been calculated with COM3D, a special CFD code developed to calculate dynamic pressure loads on walls, and b) 'Standing flame' combustion as well as recombination processes have been calculated with GASFLOW for bounding scenarios in order to evaluate maximum containment wall surface temperatures for cases of long-lasting combustion, mainly with emphasis on the application of a partial liner. Because of the depressurization of the reactor coolant system directly into the containment atmosphere via a relief tank and rupture discs a high concentration of steam is available for nearly all scenarios. For these scenarios no threat to internal walls is expected based on the combustion loads identified by the analyses presented here. In case of fast secondary cool-down a large amount of energy is removed to the secondary side of the SG and

  5. 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.

  6. Tunable hydrogen separation in porous graphene membrane: first-principle and molecular dynamic simulation.

    Science.gov (United States)

    Tao, Yehan; Xue, Qingzhong; Liu, Zilong; Shan, Meixia; Ling, Cuicui; Wu, Tiantian; Li, Xiaofang

    2014-06-11

    First-principle density functional theory (DFT) calculation and molecular dynamic (MD) simulation are employed to investigate the hydrogen purification performance of two-dimensional porous graphene material (PG-ESX). First, the pore size of PG-ES1 (3.2775 Å) is expected to show high selectivity of H2 by DFT calculation. Then MD simulations demonstrate the hydrogen purification process of the PG-ESX membrane. The results indicate that the selectivity of H2 over several other gas molecules that often accompany H2 in industrial steam methane reforming or dehydrogenation of alkanes (such as N2, CO, and CH4) is sensitive to the pore size of the membrane. PG-ES and PG-ES1 membranes both exhibit high selectivity for H2 over other gases, but the permeability of the PG-ES membrane is much lower than the PG-ES1 membrane because of the smaller pore size. The PG-ES2 membrane with bigger pores demonstrates low selectivity for H2 over other gases. Energy barrier and electron density have been used to explain the difference of selectivity and permeability of PG-ESX membranes by DFT calculations. The energy barrier for gas molecules passing through the membrane generally increase with the decreasing of pore sizes or increasing of molecule kinetic diameter, due to the different electron overlap between gas and a membrane. The PG-ES1 membrane is far superior to other carbon membranes and has great potential applications in hydrogen purification, energy clean combustion, and making new concept membrane for gas separation.

  7. Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

    Science.gov (United States)

    Wetzel, David J; Malone, Marvin A; Haasch, Richard T; Meng, Yifei; Vieker, Henning; Hahn, Nathan T; Gölzhäuser, Armin; Zuo, Jian-Min; Zavadil, Kevin R; Gewirth, Andrew A; Nuzzo, Ralph G

    2015-08-26

    Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

  8. Cyanobacterial and microcystins dynamics following the application of hydrogen peroxide to waste stabilisation ponds

    Science.gov (United States)

    Barrington, D. J.; Ghadouani, A.; Ivey, G. N.

    2013-06-01

    Cyanobacteria and cyanotoxins are a risk to human and ecological health, and a hindrance to biological wastewater treatment. This study investigated the use of hydrogen peroxide (H2O2) for the removal of cyanobacteria and cyanotoxins from within waste stabilization ponds (WSPs). The daily dynamics of cyanobacteria and microcystins (commonly occurring cyanotoxins) were examined following the addition of H2O2 to wastewater within both the laboratory and at the full scale within a maturation WSP, the final pond in a wastewater treatment plant. Hydrogen peroxide treatment at concentrations ≥ 0.1 mg H2O2 μg-1 total phytoplankton chlorophyll a led to the lysis of cyanobacteria, in turn releasing intracellular microcystins to the dissolved state. In the full-scale trial, dissolved microcystins were then degraded to negligible concentrations by H2O2 and environmental processes within five days. A shift in the phytoplankton assemblage towards beneficial Chlorophyta species was also observed within days of H2O2 addition. However, within weeks, the Chlorophyta population was significantly reduced by the re-establishment of toxic cyanobacterial species. This re-establishment was likely due to the inflow of cyanobacteria from ponds earlier in the treatment train, suggesting that whilst H2O2 may be a suitable short-term management technique, it must be coupled with control over inflows if it is to improve WSP performance in the longer term.

  9. Cyanobacterial and microcystins dynamics following the application of hydrogen peroxide to waste stabilisation ponds

    Directory of Open Access Journals (Sweden)

    D. J. Barrington

    2013-06-01

    Full Text Available Cyanobacteria and cyanotoxins are a risk to human and ecological health, and a hindrance to biological wastewater treatment. This study investigated the use of hydrogen peroxide (H2O2 for the removal of cyanobacteria and cyanotoxins from within waste stabilization ponds (WSPs. The daily dynamics of cyanobacteria and microcystins (commonly occurring cyanotoxins were examined following the addition of H2O2 to wastewater within both the laboratory and at the full scale within a maturation WSP, the final pond in a wastewater treatment plant. Hydrogen peroxide treatment at concentrations ≥ 0.1 mg H2O2 μg−1 total phytoplankton chlorophyll a led to the lysis of cyanobacteria, in turn releasing intracellular microcystins to the dissolved state. In the full-scale trial, dissolved microcystins were then degraded to negligible concentrations by H2O2 and environmental processes within five days. A shift in the phytoplankton assemblage towards beneficial Chlorophyta species was also observed within days of H2O2 addition. However, within weeks, the Chlorophyta population was significantly reduced by the re-establishment of toxic cyanobacterial species. This re-establishment was likely due to the inflow of cyanobacteria from ponds earlier in the treatment train, suggesting that whilst H2O2 may be a suitable short-term management technique, it must be coupled with control over inflows if it is to improve WSP performance in the longer term.

  10. 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.

  11. Communication: Dynamical and structural analyses of solid hydrogen under vapor pressure

    Energy Technology Data Exchange (ETDEWEB)

    Hyeon-Deuk, Kim, E-mail: kim@kuchem.kyoto-u.ac.jp [Department of Chemistry, Kyoto University, Kyoto 606-8502 (Japan); Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Ando, Koji [Department of Chemistry, Kyoto University, Kyoto 606-8502 (Japan)

    2015-11-07

    Nuclear quantum effects play a dominant role in determining the phase diagram of H{sub 2}. With a recently developed quantum molecular dynamics simulation method, we examine dynamical and structural characters of solid H{sub 2} under vapor pressure, demonstrating the difference from liquid and high-pressure solid H{sub 2}. While stable hexagonal close-packed lattice structures are reproduced with reasonable lattice phonon frequencies, the most stable adjacent configuration exhibits a zigzag structure, in contrast with the T-shape liquid configuration. The periodic angular distributions of H{sub 2} molecules indicate that molecules are not a completely free rotor in the vapor-pressure solid reflecting asymmetric potentials from surrounding molecules on adjacent lattice sites. Discrete jumps of librational and H–H vibrational frequencies as well as H–H bond length caused by structural rearrangements under vapor pressure effectively discriminate the liquid and solid phases. The obtained dynamical and structural information of the vapor-pressure H{sub 2} solid will be useful in monitoring thermodynamic states of condensed hydrogens.

  12. Functional Dynamics of Hexameric Helicase Probed by Hydrogen Exchange and Simulation

    Science.gov (United States)

    Radou, Gaël; Dreyer, Frauke N.; Tuma, Roman; Paci, Emanuele

    2014-01-01

    The biological function of large macromolecular assemblies depends on their structure and their dynamics over a broad range of timescales; for this reason, it is a significant challenge to investigate these assemblies using conventional experimental techniques. One of the most promising experimental techniques is hydrogen-deuterium exchange detected by mass spectrometry. Here, we describe to our knowledge a new computational method for quantitative interpretation of deuterium exchange kinetics and apply it to a hexameric viral helicase P4 that unwinds and translocates RNA into a virus capsid at the expense of ATP hydrolysis. Room-temperature dynamics probed by a hundred nanoseconds of all-atom molecular dynamics simulations is sufficient to predict the exchange kinetics of most sequence fragments and provide a residue-level interpretation of the low-resolution experimental results. The strategy presented here is also a valuable tool to validate experimental data, e.g., assignments, and to probe mechanisms that cannot be observed by x-ray crystallography, or that occur over timescales longer than those that can be realistically simulated, such as the opening of the hexameric ring. PMID:25140434

  13. Algebraic theory of Stark-Zeeman dynamic effect in hydrogen-like atom

    International Nuclear Information System (INIS)

    Fursa, D.V.; Yudin, G.L.

    1990-01-01

    The problems of calculating time evolution operator within the given n-shell (here n is main quantum number) for the hydrogen atom located in non-stationary electric and magnetic fields is under investigation. Making use of the Fock SO(4) group reduces this problem to the set of problems with linear realization of the dynamic symmetry group for which the evolution operator is the operator of corresponding groups representation. The types of evolution operator parametrization in the form of exponents product (the Wei-Norman method) any by means of D-functions connected with Euler angles and Cayley-Klein parameters are discussed. It is shown that the problem of evolution operator calculation can be reduced to investigation of a pair of two-level systems. 35 refs

  14. A-site order–disorder in the NdBaMn2O5+δ SOFC electrode material monitored in situ by neutron diffraction under hydrogen flow

    KAUST Repository

    Tonus, Florent

    2017-05-11

    The A-site disordered perovskite manganite, Nd0.5Ba0.5MnO3, has been obtained by heating the A-site-ordered and vacancy ordered layered double perovskite, NdBaMn2O5, in air at 1300 °C for 5 h. Combined transmission electron microscopy (TEM) images and neutron powder diffraction (NPD) analysis at 25 °C revealed that Nd0.5Ba0.5MnO3 has a pseudotetragonal unit cell with orthorhombic symmetry (space group Imma, √2ap × 2ap × √2ap) at 20 °C with the cell dimensions a = 5.503(1) Å, b = 7.7962(4) Å, c = 5.502(1) Å, in contrast to Pm[3 with combining macron]m or Cmcm that have been previously stated from X-ray diffraction studies. The in situ neutron diffraction study carried out on Nd0.5Ba0.5MnO3 in hydrogen flow up to T ∼ 900 °C, allows monitoring the A-site cation disorder–order structural phase transition of this representative member of potential SOFC anode materials between air sintering conditions and hydrogen working conditions. Oxygen loss from Nd0.5Ba0.5MnO3 proceeds with retention of A-site disorder until the oxygen content reaches the Nd0.5Ba0.5MnO2.5 composition at 600 °C. The phase transition to layered NdBaMn2O5 and localization of the oxygen vacancies in the Nd layer proceeds at 800 °C with retention of the oxygen content. Impedance spectroscopy measurements for the oxidized A-site ordered electrode material, NdBaMn2O6, screen printed on a Ce0.9Gd0.1O2−δ (CGO) electrolyte showed promising electrochemical performance in air at 700 °C with a polarization resistance of 1.09 Ω cm2 without any optimization.

  15. Dynamic Electrochemical Impedance Spectroscopy of a Three-Electrode Lithium-Ion Battery during Pulse Charge and Discharge

    International Nuclear Information System (INIS)

    Huang, Jun; Ge, Hao; Li, Zhe; Zhang, Jianbo

    2015-01-01

    Highlights: • Dynamic EIS is performed on a three-electrode pouch cell; • Charge transfer resistance during insertion is generally larger than that during deinsertion due to the surface concentration change; • An inductive behavior is revealed at low frequencies due to the violation of stationary condition in DEIS measurement; • Electrochemical models of a single active particle in both time and frequency domain are developed. • The model predicts a positive correlation between the lower frequency limit and the DC current. - Abstract: The dynamic electrochemical impedance spectroscopy (DEIS) of a three-electrode pouch type lithium-ion battery is measured using a series of sine wave perturbations super-imposed on pulse charge and discharge. The DEIS reveals noticeable differences between charge and discharge at frequencies corresponding to the charge transfer reaction. The charge transfer resistance during intercalation is generally found to be larger than that during deintercalation for the battery chemistry in this study. This result is mainly attributed to the decreased Li ion concentration in the electrolyte during intercalation. At low frequencies, an abnormal inductive behavior is also observed. Such abnormality is found to result from the violation of stationary condition, i.e. the state of the battery under pulse charge or discharge deviates significantly from its initial condition for the perturbation of low frequencies. To analytically define the stationary condition, we develop electrochemical models of a single active particle in both time and frequency domain, which describes the transport of lithium ions in both active particle and electrolyte phase and the interfacial charge transfer reactions at their interface. The lower frequency limit is a key parameter to ensure a quasistationary state during the DEIS measurement. An explicit formulation of the stationary condition predicts a positive correlation between the lower frequency limit and

  16. Hydrogen bonding in protic ionic liquids: structural correlations, vibrational spectroscopy, and rotational dynamics of liquid ethylammonium nitrate

    Science.gov (United States)

    Zentel, Tobias; Overbeck, Viviane; Michalik, Dirk; Kühn, Oliver; Ludwig, Ralf

    2018-02-01

    The properties of the hydrogen bonds in ethylammonium nitrate (EAN) are analyzed by using molecular dynamics simulations and infrared as well as nuclear magnetic resonance experiments. EAN features a flexible three-dimensional network of hydrogen bonds with moderate strengths, which makes it distinct from related triethylammonium-based ionic liquids. First, the network’s flexibility is manifested in a not very pronounced correlation of the hydrogen bond geometries, which is caused by rapid interchanges of bonding partners. The large flexibility of the network also leads to a substantial broadening of the mid-IR absorption band, with the contributions due to N-H stretching motions ranging from 2800 to 3250 cm-1. Finally, the different dynamics are also seen in the rotational correlation of the N-H bond vector, where a correlation time as short as 16.1 ps is observed.

  17. Interplay of community dynamics, temperature, and productivity on the hydrogen isotope signatures of lipid biomarkers

    Directory of Open Access Journals (Sweden)

    S. N. Ladd

    2017-09-01

    Full Text Available 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

  18. A gold electrode modified with hemoglobin and the chitosan Fe3O4 nanocomposite particles for direct electrochemistry of hydrogen peroxide

    International Nuclear Information System (INIS)

    Wang, Yuan-Hong; Yu, Chun-Mei; Pan, Zhong-Qin; Wang, Yu-Fei; Guo, Jian-Wei; Gu, Hai-Ying

    2013-01-01

    We report on a novel electrochemical biosensor that was fabricated by immobilizing hemoglobin (Hb) onto the surface of a gold electrode modified with a chitosan Fe 3 O 4 nano-composite. The Fe 3 O 4 nanoparticles were prepared by co-precipitation and have an average size of 25 nm. They were dispersed in chitosan solution to obtain the chitosan Fe 3 O 4 nano-composite particles with an average diameter of 35 nm as verified by transmission electron microscopy. X-ray diffraction patterns and Fourier transform IR spectroscopy confirmed that the crystallite structure of the Fe 3 O 4 particles in the nano-composite has remained unchanged. At pH 7.0, Hb gives a pair of redox peaks with a potential of about −0.21 V and −0.36 V. The Hb on the film maintained its biological activity and displays good electrocatalytic reduction activity towards hydrogen peroxide. The linear range for the determination of H 2 O 2 is from 2.3 μM to 9.6 mM, with a detection limit at 1.1 μM concentration (at S/N = 3). The apparent Michaelis-Menten constant is 3.7 mM and indicates the high affinity of Hb for H 2 O 2 . This biosensor also exhibits good reproducibility and long-term stability. Thus, it is expected to possess potential applications in the development of the third-generation electrochemical biosensors (author)

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

    Science.gov (United States)

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

    2018-05-01

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

  20. 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 ...

  1. Intra- und intermolecular hydrogen bonds. Spectroscopic, quantum chemical and molecular dynamics studies

    International Nuclear Information System (INIS)

    Simperler, A.

    1999-03-01

    Intra- and intermolecular H-bonds have been investigated with spectroscopic, quantum chemical, and molecular dynamics methods. The work is divided into the following three parts: 1. Intramolecular interactions in ortho-substituted phenols. Theoretical and experimental data that characterizes the intramolecular hydrogen bonds in 48 different o-substituted phenols are discussed. The study covers various kinds of O-H ... Y -type interactions (Y= N, O, S, F, Cl, Br, I, C=C, C=-C, and C-=N). The bond strength sequences for several series of systematically related compounds as obtained from IR spectroscopy data (i.e., v(OH) stretching frequencies) are discussed and reproduced with several theoretical methods (B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3LYP/6-31++G(d,p), B3LYP/DZVP, MP2/6-31G(d,p), and MP2/6-31++G(d,p) levels of theory). The experimentally determined sequences are interpreted in terms of the intrinsic properties of the molecules: hydrogen bond distances, Mulliken partial charges, van der Waals radii, and electron densities of the Y-proton acceptors. 2. Competitive hydrogen bonds and conformational equilibria in 2,6-disubstituted phenols containing two different carbonyl substituents. The rotational isomers of ten unsymmetrical 2,6-disubstituted phenols as obtained by combinations of five different carbonyl substituents (COOH, COOCH 3 , CHO, COCH 3 , and CONH 2 ) have been theoretically investigated at the B3LYP/6-31G(d,p) level of theory. The relative stability of four to five conformers of each compound were determined by full geometry optimization for free molecules as well as for molecules in reaction fields with dielectric constants up to ε=37.5. A comparison with IR spectroscopic data of available compounds revealed excellent agreement with the theoretically predicted stability sequences and conformational equilibria. The stability of a conformer could be interpreted to be governed by the following two contributions: (i) an attractive hydrogen bond

  2. A dynamic study on the sulfuric acid distillation column for VHTR-assisted hydrogen production systems

    International Nuclear Information System (INIS)

    Youngjoon, Shin; Heesung, Shin; Jiwoon, Jang; Kiyoung, Lee; Jonghwa, Chang

    2007-01-01

    The sulfur-iodine (SI) cycle and the Westinghouse sulfur hybrid cycle coupled to a very high temperature gas-cooled reactor (VHTR) are well known as a feasible technology to produce hydrogen. The concentration of the sulfuric acid solution and its decomposition are essential parts in both cycles. In this paper, the thermophysical properties which are the boiling point, latent heat, and the partial pressures of water, sulfuric acid, and sulfur trioxide have been correlated as a function of the sulfuric acid concentration for the H 2 SO 4 and H 2 O binary chemical system, based on the data in Perry's chemical engineers' hand-book and other experimental data. By using these thermophysical correlations, a dynamic analysis of a sulfuric acid distillation column has been performed to establish the column design requirements and its optimum operation condition. From the results of the dynamic analysis, an optimized column system is anticipated for a distillation column equipped with 2 ideal plates and a second plate feeding system from the bottom plate. The effects of the hold-up of the re-boiler and the reflux ratio from the top product stream on the elapsing time when the system progresses toward a steady state have been analyzed. (authors)

  3. Real-time imaging of hydrogen peroxide dynamics in vegetative and pathogenic hyphae of Fusarium graminearum.

    Science.gov (United States)

    Mentges, Michael; Bormann, Jörg

    2015-10-08

    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.

  4. Statics and dynamics of free and hydrogen-bonded OH groups at the air/water interface.

    Science.gov (United States)

    Vila Verde, Ana; Bolhuis, Peter G; Campen, R Kramer

    2012-08-09

    We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

  5. Molecular Dynamics Investigation of the Effects of Concentration on Hydrogen Bonding in Aqueous Solutions of Methanol, Ethylene Glycol and Glycerol

    International Nuclear Information System (INIS)

    Zhang, Ning; Li, Weizhong; Chen, Cong; Zuo, Jianguo; Weng, Lindong

    2013-01-01

    Hydrogen bonding interaction between alcohols and water molecules is an important characteristic in the aqueous solutions of alcohols. In this paper, a series of molecular dynamics simulations have been performed to investigate the aqueous solutions of low molecular weight alcohols (methanol, ethylene glycol and glycerol) at the concentrations covering a broad range from 1 to 90 mol %. The work focuses on studying the effect of the alcohols molecules on the hydrogen bonding of water molecules in binary mixtures. By analyzing the hydrogen bonding ability of the hydroxyl (-OH) groups for the three alcohols, it is found that the hydroxyl group of methanol prefers to form more hydrogen bonds than that of ethylene glycol and glycerol due to the intra-and intermolecular effects. It is also shown that concentration has significant effect on the ability of alcohol molecule to hydrogen bond water molecules. Understanding the hydrogen bonding characteristics of the aqueous solutions is helpful to reveal the cryoprotective mechanisms of methanol, ethylene glycol and glycerol in aqueous solutions

  6. 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. © 2015 The Protein Society.

  7. Thermophysical properties of hydrogen-helium mixtures: re-examination of the mixing rules via quantum molecular dynamics simulations.

    Science.gov (United States)

    Wang, Cong; He, Xian-Tu; Zhang, Ping

    2013-09-01

    Thermophysical properties of hydrogen, helium, and hydrogen-helium mixtures have been investigated in the warm dense matter regime at electron number densities ranging from 6.02 × 10^{29} ∼ 2.41 × 10^{30} m^{-3} and temperatures from 4000 to 20000 K via quantum molecular dynamics simulations. We focus on the dynamical properties such as the equation of states, diffusion coefficients, and viscosity. Mixing rules (density matching, pressure matching, and binary ionic mixing rules) have been validated by checking composite properties of pure species against that of the fully interacting mixture derived from quantum molecular dynamics simulations. These mixing rules reproduce pressures within 10% accuracy, while it is 75% and 50% for the diffusion and viscosity, respectively. The binary ionic mixing rule moves the results into better agreement. Predictions from one component plasma model are also provided and discussed.

  8. Investigation of coupling between chemistry and discharge dynamics in radio frequency hydrogen plasmas in the Torr regime

    International Nuclear Information System (INIS)

    Kalache, B; Novikova, T; Morral, A Fontcuberta i; Cabarrocas, P Roca i; Morscheidt, W; Hassouni, K

    2004-01-01

    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 - ions by dissociative attachment of H 2 vibrational levels. The population of these levels is described by a Boltzmann vibrational distribution function characterized by a vibrational temperature T 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 - ion density increases by seven orders of magnitude and the H - ion density to electron density ratio varies from 10 -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 - ions is demonstrated. Moreover, satisfactory agreement between computed and measured values of atomic hydrogen and H - 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

  9. Hydrogen dynamics in the low temperature phase of LiBH{sub 4} probed by quasielastic neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Remhof, Arndt, E-mail: arndt.remhof@empa.ch [Empa, Swiss Federal Institute for Materials Science and Technology, Hydrogen and Energy, CH-8600 Dübendorf (Switzerland); Züttel, Andreas [Empa, Swiss Federal Institute for Materials Science and Technology, Hydrogen and Energy, CH-8600 Dübendorf (Switzerland); Ramirez-Cuesta, Timmy; García-Sakai, Victoria [ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Frick, Bernhard [Institut Laue-Langevin, F-38002 Grenoble (France)

    2013-12-12

    Highlights: • Inelastic fixed window sans offer new possibilities in neutron backscattering spectrometers. • Two different kind of reorientational motion were identified in the low temperature phase of LiBH{sub 4}. • Thermally activated jump rotation. - Abstract: LiBH{sub 4} contains 18.5 wt% hydrogen and undergoes a structural phase transition (orthorhombic → hexagonal) at 381 K which is associated with a large increase in hydrogen and lithium solid-state mobility. We investigated the hydrogen dynamics in the low temperature phase of LiBH{sub 4} by quasielastic neutron scattering, including a new kind of inelastic fixed window scan (IFWS). In the temperature range from 175 to 380 K the H-dynamics is dominated by thermally activated rotational jumps of the [BH{sub 4}]{sup −} anion around the c3 axis with an activation energy of about 162 meV. In agreement with earlier NMR data, a second type of thermally activated motion with an activation energy of about 232 meV could be identified using the IFWS. The present study of hydrogen dynamics in LiBH{sub 4} illustrates the feasibility of using IFWS on neutron backscattering spectrometers as a probe of localised motion.

  10. A new time-frequency method to reveal quantum dynamics of atomic hydrogen in intense laser pulses: Synchrosqueezing transform

    International Nuclear Information System (INIS)

    Sheu, Yae-lin; Hsu, Liang-Yan; Wu, Hau-tieng; Li, Peng-Cheng; Chu, Shih-I

    2014-01-01

    This study introduces a new adaptive time-frequency (TF) analysis technique, the synchrosqueezing transform (SST), to explore the dynamics of a laser-driven hydrogen atom at an ab initio level, upon which we have demonstrated its versatility as a new viable venue for further exploring quantum dynamics. For a signal composed of oscillatory components which can be characterized by instantaneous frequency, the SST enables rendering the decomposed signal based on the phase information inherited in the linear TF representation with mathematical support. Compared with the classical type of TF methods, the SST clearly depicts several intrinsic quantum dynamical processes such as selection rules, AC Stark effects, and high harmonic generation

  11. Population dynamics and current-generation mechanisms in cassette-electrode microbial fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Kazuya [ERATO/JST, Tokyo (Japan). Hashimoto Light Energy Conversion Project; Tokyo Univ. (Japan). Research Center for Advanced Science and Technology; Tokyo Univ. of Pharmacy and Life Sciences (Japan). School of Life Sciences; Miyahara, Morio [ERATO/JST, Tokyo (Japan). Hashimoto Light Energy Conversion Project; Shimoyama, Takefumi [Tokyo Univ. (Japan). Research Center for Advanced Science and Technology; Hashimoto, Kazuhito [ERATO/JST, Tokyo (Japan). Hashimoto Light Energy Conversion Project; Tokyo Univ. (Japan). Dept. of Applied Chemistry

    2011-12-15

    Cassette-electrode microbial fuel cells (CE-MFCs) have been demonstrated useful to treat biomass wastes and recover electric energy from them. In order to reveal electricity-generation mechanisms in CE-MFCs, the present study operated a bench-scale reactor (1 l in capacity; approximately 1,000 cm{sup 2} in anode and cathode areas) for treating a high-strength model organic wastewater (comprised of starch, peptone, and fish extract). Approximately 1 month was needed for the bench reactor to attain a stable performance, after which volumetric maximum power densities persisted between 120 and 150 mW/l throughout the experiment (for over 2 months). Temporal increases in the external resistance were found to induce subsequent increases in power outputs. After electric output became stable, electrolyte and anode were sampled from the reactor for evaluating their current-generation abilities; it was estimated that most of current (over 80%) was generated by microbes in the electrolyte. Cyclic voltammetry of an electrolyte supernatant detected several electron shuttles with different standard redox potentials at high concentrations (equivalent to or more than 100 {mu}M 5-hydroxy-1,4-naphthoquinone). Denaturing gradient gel electrophoresis and quantitative real-time PCR of 16S ribosomal RNA gene fragments showed that bacteria related to the genus Dysgonomonas occurred abundantly in association with the increases in power outputs. These results suggest that mediated electron transfer was the main mechanism for electricity generation in CE-MFC, where high-concentration electron shuttles and Dysgonomonas bacteria played important roles. (orig.)

  12. {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}.

  13. Hydrogen molecules inside fullerene C70: quantum dynamics, energetics, maximum occupancy, and comparison with C60.

    Science.gov (United States)

    Sebastianelli, Francesco; Xu, Minzhong; Bacić, Zlatko; Lawler, Ronald; Turro, Nicholas J

    2010-07-21

    Recent synthesis of the endohedral complexes of C(70) and its open-cage derivative with one and two H(2) molecules has opened the path for experimental and theoretical investigations of the unique dynamic, spectroscopic, and other properties of systems with multiple hydrogen molecules confined inside a nanoscale cavity. Here we report a rigorous theoretical study of the dynamics of the coupled translational and rotational motions of H(2) molecules in C(70) and C(60), which are highly quantum mechanical. Diffusion Monte Carlo (DMC) calculations were performed for up to three para-H(2) (p-H(2)) molecules encapsulated in C(70) and for one and two p-H(2) molecules inside C(60). These calculations provide a quantitative description of the ground-state properties, energetics, and the translation-rotation (T-R) zero-point energies (ZPEs) of the nanoconfined p-H(2) molecules and of the spatial distribution of two p-H(2) molecules in the cavity of C(70). The energy of the global minimum on the intermolecular potential energy surface (PES) is negative for one and two H(2) molecules in C(70) but has a high positive value when the third H(2) is added, implying that at most two H(2) molecules can be stabilized inside C(70). By the same criterion, in the case of C(60), only the endohedral complex with one H(2) molecule is energetically stable. Our results are consistent with the fact that recently both (H(2))(n)@C(70) (n = 1, 2) and H(2)@C(60) were prepared, but not (H(2))(3)@C(70) or (H(2))(2)@C(60). The ZPE of the coupled T-R motions, from the DMC calculations, grows rapidly with the number of caged p-H(2) molecules and is a significant fraction of the well depth of the intermolecular PES, 11% in the case of p-H(2)@C(70) and 52% for (p-H(2))(2)@C(70). Consequently, the T-R ZPE represents a major component of the energetics of the encapsulated H(2) molecules. The inclusion of the ZPE nearly doubles the energy by which (p-H(2))(3)@C(70) is destabilized and increases by 66% the

  14. The Electrode Characteristics of the Sintered AB{sub 5}-type Metal Hydrogen Storage Alloy for Ni-MH Secondary Battery

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Sang Min; Park, Won; Choi, Seung Jun; Park, Choong Nyeon [Department of Metallurgical Engineering, Chonnam National University, Kawngju, (Korea, Republic of); Noh, Hak [Autombile Reseach Center, Chonnom National University, Kwangju (Korea, Republic of); Choi, Jeon [Department. of Iron and Metallurgical Engineering., Hanlyo Sanup University, Kwangyang (Korea, Republic of)

    1996-12-15

    The AB{sub 5} type metal hydride electrodes using (LM)Ni{sub 4.49}C0{sub 0.1}Mn{sub 0.205}Al{sub 0.205}(LM : Lanthanium rich Mischmetal) alloy powders({<=}200mesh) which were coated with 25wt% copper in an acidic bath were prepared with or without addition of 10wt% PTFE as a binder. Prior to electrochemical measurements, the electrode were sintered at 40 for 1 and 2hrs in vacuum with Mm(mischmetal) and sponge type Ti getters. The properties such as maximum capacity, cycle life and mechanical strength of the negative electrode have been investigated. The surface analysis of the electrode was also obtained before and after charge-discharge cycling using scanning election microscope(SEM). From the observations of electrochemical behavior, it was found that the sintered electrode shows a lower maximum discharge capacity compared with non-sintered electrode but it shows a better cycle life. For the both electrode with or without addition of PTFE binder, the values of mechanical strength were obtained, and their values increasing sintering time. However, there is little difference of discharge capacity for both electrodes. (author). 9 refs., 2 tabs., 4 figs., 2 ills.

  15. Horseradish Peroxidase (HRP Immobilized Poly(aniline-co-m-aminophenol Film Electrodes–fabrication and Evaluation as Hydrogen Peroxide Sensor

    Directory of Open Access Journals (Sweden)

    Seong-Ho Choi

    2007-05-01

    Full Text Available Enzyme modified electrodes were fabricated with poly(aniline-co-m-aminophenol. Electrochemical polymerization of aniline and m-aminophenol wasperformed to get the film of copolymer on the surface of gold electrode. Modifiedelectrodes were fabricated by two methods, physical entrapment and covalent cross-linking.In one of the method, gold nanoparticles were loaded into the copolymer film andhorseradish peroxidase (HRP was immobilized into the Au nanoparticle loaded copolymerfilm through physical entrapment. In the other method, the amino and -OH groups in thecopolymer are utilized to form covalent functionalization with HRP via glutaric dialdehydeas cross-linker/mediator. The conducting copolymer/enzyme modified electrodes preparedby physical entrapment/covalent functionalization of enzyme were tested forelectrocatalytic activities towards sensing of H2O2. Amperometric results indicate thatenzyme modified electrode via physical entrapment possesses better electrocatalyticperformance over covalent functionalized enzyme electrode.

  16. Multi-arrangement quantum dynamics in 6D: cis-trans isomerization and 1,3-hydrogen transfer in HONO

    International Nuclear Information System (INIS)

    Luckhaus, David

    2004-01-01

    The overtone spectrum and wave packet dynamics of nitrous acid (HONO) are studied with a global six-dimensional potential energy function interpolated directly from density functional calculations together with the corresponding dipole hypersurfaces. The quantum dynamics for the cis-trans isomerization and the symmetric 1,3-hydrogen transfer are treated in full dimensionality in terms of the generalized Z-matrix discrete variable representation. For the quantum mechanical description of complicated rearrangements a new approach to multi-arrangement quantum dynamics is introduced and applied to the symmetric hydrogen exchange tunneling in cis-HONO. The cis-trans isomerization is found to be dominated by adiabatic barrier crossing with only minor tunneling contributions, but with pronounced mode selectivity. The OH-stretching overtones of trans-HONO are adiabatically almost completely separated from the OH torsional dynamics with extremely slow intramolecular energy redistribution. The 1,3-hydrogen transfer, by contrast, proceeds largely via coherent tunneling even significantly below the barrier. The process is clearly non-adiabatic (at least in terms of valence coordinates) but remains highly state specific. While the absorption spectrum of trans-HONO remains largely unaffected, OH-stretching overtones of cis-HONO (above the barrier between 2ν OH and 3ν OH ) decompose into highly fragmented absorption patterns with corresponding tunneling periods on the picosecond time scale

  17. Nuclear dynamics in the metastable phase of the solid acid caesium hydrogen sulfate.

    Science.gov (United States)

    Krzystyniak, Maciej; Drużbicki, Kacper; Fernandez-Alonso, Felix

    2015-12-14

    High-resolution spectroscopic measurements using thermal and epithermal neutrons and first-principles calculations within the framework of density-functional theory are used to investigate the nuclear dynamics of light and heavy species in the metastable phase of caesium hydrogen sulfate. Within the generalised-gradient approximation, extensive calculations show that both 'standard' and 'hard' formulations of the Perdew-Burke-Ernzerhof functional supplemented by Tkatchenko-Scheffler dispersion corrections provide an excellent description of the known structure, underlying vibrational density of states, and nuclear momentum distributions measured at 10 and 300 K. Encouraged by the agreement between experiment and computational predictions, we provide a quantitative appraisal of the quantum contributions to nuclear motions in this solid acid. From this analysis, we find that only the heavier caesium atoms reach the classical limit at room temperature. Contrary to naïve expectation, sulfur exhibits a more pronounced quantum character relative to classical predictions than the lighter oxygen atom. We interpret this hitherto unexplored nuclear quantum effect as arising from the tighter binding environment of this species in this technologically relevant material.

  18. Probing Conformational Dynamics of Tau Protein by Hydrogen/Deuterium Exchange Mass Spectrometry

    Science.gov (United States)

    Huang, Richard Y.-C.; Iacob, Roxana E.; Sankaranarayanan, Sethu; Yang, Ling; Ahlijanian, Michael; Tao, Li; Tymiak, Adrienne A.; Chen, Guodong

    2018-01-01

    Fibrillization of the microtubule-associated protein tau has been recognized as one of the signature pathologies of the nervous system in Alzheimer's disease, progressive supranuclear palsy, and other tauopathies. The conformational transition of tau in the fibrillization process, tau monomer to soluble aggregates to fibrils in particular, remains unclear. Here we report on the use of hydrogen/deuterium exchange mass spectrometry (HDX-MS) in combination with other biochemical approaches, including Thioflavin S fluorescence measurements, enzyme-linked immunosorbent assay (ELISA), and Western blotting to understand the heparin-induced tau's fibrillization. HDX-MS studies including anti-tau antibody epitope mapping experiments provided molecular level details of the full-length tau's conformational dynamics and its regional solvent accessibility upon soluble aggregates formation. The results demonstrate that R3 region in the full-length tau's microtubule binding repeat region (MTBR) is stabilized in the aggregation process, leaving both N and C terminal regions to be solvent exposed in the soluble aggregates and fibrils. The findings also illustrate the practical utility of orthogonal analytical methodologies for the characterization of protein higher order structure. [Figure not available: see fulltext.

  19. Laccase-13 Regulates Seed Setting Rate by Affecting Hydrogen Peroxide Dynamics and Mitochondrial Integrity in Rice

    Directory of Open Access Journals (Sweden)

    Yang Yu

    2017-07-01

    Full Text Available Seed setting rate is one of the most important components of rice grain yield. To date, only several genes regulating setting rate have been identified in plant. In this study, we showed that laccase-13 (OsLAC13, a member of laccase family genes which are known for their roles in modulating phenylpropanoid pathway and secondary lignification in cell wall, exerts a regulatory function in rice seed setting rate. OsLAC13 expressed in anthers and promotes hydrogen peroxide production both in vitro and in the filaments and anther connectives. Knock-out of OsLAC13 showed significantly increased seed setting rate, while overexpression of this gene exhibited induced mitochondrial damage and suppressed sugar transportation in anthers, which in turn affected seed setting rate. OsLAC13 also induced H2O2 production and mitochondrial damage in the root tip cells which caused the lethal phenotype. We also showed that high abundant of OsmiR397, the suppressor of OsLAC13 mRNA, increased the seed setting rate of rice plants, and restrains H2O2 accumulation in roots during oxidative stress. Our results suggested a novel regulatory role of OsLAC13 gene in regulating seed setting rate by affecting H2O2 dynamics and mitochondrial integrity in rice.

  20. 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.

  1. 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.

  2. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Salimi, Abdollah; Mahdioun, Monierosadat; Noorbakhsh, Abdollah; Abdolmaleki, Amir; Ghavami, Raoof

    2011-01-01

    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 s ) of immobilized Mn-complex were approximately 1.58 x 10 -10 mole cm -2 and 48.84 s -1 . The modified electrode showed excellent electrocatalytic activity toward H 2 O 2 reduction. Detection limit, sensitivity, linear concentration range and k cat for H 2 O 2 were, 0.2 μM and 692 nA μM -1 cm -2 , 1 μM to 1.5 mM and 7.96(±0.2) x 10 3 M -1 s -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.

  3. Self adaptive internal combustion engine control for hydrogen mixtures using piezoelectric transducers for dynamic cylinder pressure monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Courteau, R.; Bose, T.K. [Quebec Univ., Trois-Rivieres, PQ (Canada). Institut de recherche sur l' hydrogene

    2004-07-01

    Hydrogen internal combustion engine research at the Hydrogen Research Institute includes the following infrastructure: a 20 square metre test cell, an engine preparation room, a 150 hp dynamometer, exhaust gas analysers and a hydrogen supply. The goal of the research is to develop internal combustion engine technologies that can use hydrogen as a fuel without knocking, backfires, excessive engine wear, and with low emissions. As well as hydrogen, fuels such as biogas are also investigated. Technologies under investigation include adaptive control algorithms, as well as advanced sensors and actuators. The latter include piezolelectrics, optical fibres, nitrogen oxide detectors, and chemical composition detectors. Developments include microprocessor-controlled injection and ignition control systems for both single cylinder and multicylinder engines. Research on the influence of fuel composition on best ignition timing is presented. There is also dynamic cylinder pressure monitoring to prevent knocking make engine state assessments and perform engine calibration. Piezoelectric cylinder pressure sensors are employed, either integrated with the spark plugs, or stand-alone, inserted through separate holes through the cylinder head. tabs, figs.

  4. Vibrational signatures of cation-anion hydrogen bonding in ionic liquids: a periodic density functional theory and molecular dynamics study.

    Science.gov (United States)

    Mondal, Anirban; Balasubramanian, Sundaram

    2015-02-05

    Hydrogen bonding in alkylammonium based protic ionic liquids was studied using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Normal-mode analysis within the harmonic approximation and power spectra of velocity autocorrelation functions were used as tools to obtain the vibrational spectra in both the gas phase and the crystalline phases of these protic ionic liquids. The hydrogen bond vibrational modes were identified in the 150-240 cm(-1) region of the far-infrared (far-IR) spectra. A blue shift in the far-IR mode was observed with an increasing number of hydrogen-bonding sites on the cation; the exact peak position is modulated by the cation-anion hydrogen bond strength. Sub-100 cm(-1) bands in the far-IR spectrum are assigned to the rattling motion of the anions. Calculated NMR chemical shifts of the acidic protons in the crystalline phase of these salts also exhibit the signature of cation-anion hydrogen bonding.

  5. A study of the dynamics of hydrogen in yttrium using inelastic neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Bennington, S M; Benham, M J; Ross, D K [Birmingham Univ. (UK). School of Physics and Space Research; Taylor, A D; Bowden, Z A [Rutherford Appleton Lab., Chilton (UK)

    1989-01-01

    The results of several high resolution inelastic scattering experiments on {alpha}-phase yttrium-hydrogen are presented including measurements of energy levels up to the fourth and a study of the splitting of certain states due to hydrogen-hydrogen interactions. An attempt is made to model the energy levels by using perturbed simple harmonic oscillator wavefunctions. This can account for most of the major features of the spectrum. (orig.).

  6. On detonation dynamics in hydrogen-air-steam mixtures: Theory and application to Olkiluoto reactor building

    International Nuclear Information System (INIS)

    Silde, A.; Lindholm, I.

    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

  7. Probing the hydrogen equilibrium and kinetics in zeolite imidazolate frameworks via molecular dynamics and quasi-elastic neutron scattering experiments.

    Science.gov (United States)

    Pantatosaki, Evangelia; Jobic, Hervé; Kolokolov, Daniil I; Karmakar, Shilpi; Biniwale, Rajesh; Papadopoulos, George K

    2013-01-21

    The problem of simulating processes involving equilibria and dynamics of guest sorbates within zeolitic imidazolate frameworks (ZIF) by means of molecular dynamics (MD) computer experiments is of growing importance because of the promising role of ZIFs as molecular "traps" for clean energy applications. A key issue for validating such an atomistic modeling attempt is the possibility of comparing the MD results, with real experiments being able to capture analogous space and time scales to the ones pertained to the computer experiments. In the present study, this prerequisite is fulfilled through the quasi-elastic neutron scattering technique (QENS) for measuring self-diffusivity, by elaborating the incoherent scattering signal of hydrogen nuclei. QENS and MD experiments were performed in parallel to probe the hydrogen motion, for the first time in ZIF members. The predicted and measured dynamics behaviors show considerable concentration variation of the hydrogen self-diffusion coefficient in the two topologically different ZIF pore networks of this study, the ZIF-3 and ZIF-8. Modeling options such as the flexibility of the entire matrix versus a rigid framework version, the mobility of the imidazolate ligand, and the inclusion of quantum mechanical effects in the potential functions were examined in detail for the sorption thermodynamics and kinetics of hydrogen and also of deuterium, by employing MD combined with Widom averaging towards studying phase equilibria. The latter methodology ensures a rigorous and efficient way for post-processing the dynamics trajectory, thereby avoiding stochastic moves via Monte Carlo simulation, over the large number of configurational degrees of freedom a nonrigid framework encompasses.

  8. Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Ahmed, Farouq; Nagumo, Ryo; Miura, Ryuji; Ai, Suzuki; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Miyamoto, Akira

    2011-01-01

    The notion of 'active sites' is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.

  9. 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...

  10. 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.

  11. 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...

  12. 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.

  13. 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.

  14. Effect of hydrogenation disproportionation conditions on magnetic anisotropy in Nd-Fe-B powder prepared by dynamic hydrogenation disproportionation desorption recombination

    Directory of Open Access Journals (Sweden)

    Masao Yamazaki

    2017-05-01

    Full Text Available Various anisotropic Nd-Fe-B magnetic powders were prepared by the dynamic hydrogenation disproportionation desorption recombination (d-HDDR treatment with different hydrogenation disproportionation (HD times (tHD. The resulting magnetic properties and microstructural changes were investigated. The magnetic anisotropy was decreased with increasing tHD. In the d-HDDR powders with higher magnetic anisotropy, fine (200–600 nm and coarse (600–1200 nm Nd2Fe14B grains were observed. The coarse Nd2Fe14B grains showed highly crystallographic alignment of the c-axis than fine Nd2Fe14B grains. In the highly anisotropic Nd2Fe14B d-HDDR powder, a large area fraction of lamellar-like structures consisting of NdH2 and α-Fe were observed after HD treatment. Furthermore, the mean diameter of the lamellar-like regions, where lamellar-like structures orientate to the same direction in the HD-treated alloys was close to that of coarse Nd2Fe14B grains after d-HDDR treatment. Thus, the lamellar-like regions were converted into the crystallographically aligned coarse Nd2Fe14B grains during desorption recombination treatment, and magnetic anisotropy is closely related to the volume fraction of lamellar-like regions observed after HD treatment.

  15. Statistical properties of the dense hydrogen plasma: An ab initio molecular dynamics investigation

    International Nuclear Information System (INIS)

    Kohanoff, J.; Hansen, J.P.

    1995-12-01

    The hydrogen plasma is studied in the very high density (atomic and metallic) regime by extensive ab initio Molecular Dynamics simulations. Protons are treated classically, and electrons in the Born-Oppenheimer framework, within the local density approximation (LDA). Densities and temperatures studied fall within the strong coupling regime of the protons. We address the question of the validity of linear screening, and we find it to yield a reasonably good description up to r s approx. 0.5, but already too crude for r s = 1 (with r s = (3/4πρ) 1/3 the ion sphere radius). Finite-size and Brillouin zone sampling effects in metallic systems are studied and shown to be very delicate also in the fluid (liquid metal) phase. We analyse the low-temperature phase diagram and the melting transition. A remarkably fast decrease of the melting temperature with decreasing density is found, up to a point when it becomes comparable to the Fermi temperature of the protons. The possible vicinity of a triple point bcc-hcp(fcc)- liquid is discussed in the region of r s approx. 1.1 and T approx. 100 - 200K. The fluid phase is studied in detail for several temperatures. Proton-electron correlations show a weak temperature dependence, and proton-proton correlations exhibit a well-defined first coordination shell, thus characterizing fluid H in this regime as an atomic liquid. Diffusion coefficients are compared to the values for the one-component plasma. Vibrational densities of states (VDOS) show a plasmon renormalization due to electron screening, and the presence of a plasmon-coupled single-particle mode up to very high temperatures. Collective modes are studied through dynamical structure factors. In close relationship with the VDOS, the simulations reveal the remarkable persistent of a weakly damped high-frequency ion acoustic mode, even under conditions of strong electron screening. The possibility of using this observation as a diagnostic for the plasma phase transition to the

  16. Microscopic dynamics of the hydrogen bonded systems studied by quasi-elastic slow neutron scattering

    International Nuclear Information System (INIS)

    Padureanu, I.; Aranghel, D.; Radulescu, A.; Ion, M.; Lechner, R. E.; Desmedt, A.; Pieper, J.

    2002-01-01

    The detailed understanding of the dynamical properties in highly viscous liquids such as glycerol, as well the supercooled and glassy state has attracted a great deal of attention. Glycerol is a hydrogen bonded forming system considered as intermediate between fragile and strong glasses with a glass transition temperature T g ∼ 185 K, melting temperature T m 290 K and a sound velocity V S ∼ 3330 m/s. Incoherent neutron scattering experiments from glasses generally show a broad feature with a maximum around 2 to 10 meV. This large contribution of such unusual low frequency excitations obeying the Bose-Einstein statistics to the density of states is referred to as 'boson peak' (BP) with a maximum near a frequency of 1 THz. A very much-debated question is the dramatic changes in the properties as well as the nature of the boson peak and the acoustic modes occurring in the neighborhood of this frequency. So far the experiments were not able to give a definite answer concerning the excitations giving rise to the boson peak. The inelastic X-ray scattering across the liquid glass transition in glycerol revealed propagating collective excitations in the whole liquid-glass transition temperature range. This conclusion challenges the present understanding of glasses and supercooled liquids particularly with their thermal properties. New experiments at lower temperatures than those investigated so far where the phonon scattering processes are less hard have been proposed. The relationship between the low frequency features, the microscopic structure, the nature of the forces and the atomic motions taking place at low frequencies is still an open question. According to the mode coupling theory (MCT) the glass transition is interpreted as a two-step process where the glass structure is softened by fast local motions (β - process) until some temperature T c >T g , where the structure breaks down leading to diffusion (α-process). It is an open question, whether MCT can

  17. Hydrogen absorbing alloy electrode for metal-hydride alkali storage battery and hydrogen absorbing particles for metal-hydride alkali storage battery; Kinzoku-suisokabutsu arukari chikudenchiyo no suiso kyuzo gokin denkyoku oyobi kinzoku-suisokabutsu arukari chikudenchiyo no suiso kyuzo gokin ryushi

    Energy Technology Data Exchange (ETDEWEB)

    Niiyama, K.; Konno, Y.; Maeda, R.; Nogami, K.; Nishio, K.; Saito, T.

    1996-02-02

    For preventing degradation due to oxidation of hydrogen absorbing alloy to elongate the life of batteries, a proposal has been made to coat the surface of hydrogen absorbing alloy with electroless nickel plated film. When the surfaces of hydrogen absorbing alloy particles are coated with such electroless nickel plated films having low phosphoric acid content, however, absorption of the oxygen gas produced by overcharge delays to increase the pressure inside the battery because the plated film is unporous dense coat with high crystallinity. This invention relates to phosphoric acid containment in the ratios from 11 to 14wt% in the electroless nickel plated layer of the hydrogen absorbing alloy electrode for the metal-hydride alkali storage battery. Long time is required for the initial activation when the phosphoric acid content is less than 11wt% because the crystallinity of the plated film is too high and forms a dense unporous film. On the other hand, the plated film becomes brittle and tends to peel off from the hydrogen absorbing alloy if phosphoric acid content exceeds 14wt%. 3 figs., 2 tabs.

  18. Influence of Nafion film on oxygen reduction reaction and hydrogen peroxide formation on Pt electrode for proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Ohma, Atsushi; Fushinobu, Kazuyoshi; Okazaki, Ken

    2010-01-01

    The influence of Nafion film on ORR kinetics and H 2 O 2 formation on a Pt electrode was investigated using RRDE in 0.1 M HClO 4 . It was found that the Nafion-coated Pt system showed lower apparent ORR activity and more H 2 O 2 production than the bare Pt electrode system. From the temperature sensitivity, it was revealed that the apparent activation energies of ORR in the Nafion-coated Pt system were lower than the bare Pt electrode system, and the H 2 O 2 formation was suppressed with the increase of the temperature. In order to analyze the results furthermore, other systems (0.1/1.0 M, HClO 4 /CF 3 SO 3 H) with the bare Pt electrodes were also examined as references. It was exhibited that the ORR kinetic current, the H 2 O 2 formation, and the apparent activation energies of 1.0 M CF 3 SO 3 H system were close to those of the Nafion-coated Pt system. We concluded that the orientation of anion species of Nafion and CF 3 SO 3 H to the Pt surface via water molecules, as well as a fluorocarbon polymer network of Nafion, might block O 2 adsorption, resulting in the smaller effective surface area of the Pt electrode for ORR, the smaller ORR kinetic current, and the more H 2 O 2 production.

  19. 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...... receptor (uPAR). These experiments reveal that at least six out of eight amide hydrogens in a synthetic nine-mer peptide antagonist (AE105) become sequestered upon engagement in uPAR binding. Various uPAR mutants with decreased affinity for this peptide antagonist gave similar results, thereby indicating...... that deletion of the favorable interactions involving the side chains of these residues in uPAR does not affect the number of hydrogen bonds established by the main chain of the peptide ligand. The isolated growth factor-like domain (GFD) of the cognate serine protease ligand for uPAR showed 11 protected amide...

  20. The dynamics of hydrogen atoms dissolved in Zr Cr2 alloy

    International Nuclear Information System (INIS)

    Moura, J.I. de.

    1992-01-01

    The localized vibration modes of hydrogen in the Zr Cr 2 H x compound were studied for three hydrogen concentrations, namely x=0.45, 2 and 3, by inelastic neutron scattering with the beryllium filter-time of flight facility installed at the IEA-R1 research reactor at IPEN-CNEN/SP. It was observed four frequencies of localized hydrogen vibrations, three of which with 28 MeV full width at a half maximum (FWHM) at neutron energy transfers of 184, 151 and 134 MeV with no perceptible changes as a function of hydrogen concentration. The fourth mode is observed at neutron energy transfer of 106 MeV for x=o.45 and x=2 whereas it decreases to 98 MeV for x=3. (author)

  1. Modelling for Near-Surface Transport Dynamics of Hydrogen of Plasma Facing Materials by use of Cellular Automaton

    International Nuclear Information System (INIS)

    Shimura, K.; Terai, T.; Yamawaki, M.

    2003-01-01

    In this study, the kinetics of desorption of adsorbed hydrogen from an ideal metallic surface is modelled in Cellular Automaton (CA). The modelling is achieved by downgrading the surface to one dimension. The model consists of two parts that are surface migration and desorption. The former is attained by randomly sorting the particles at each time, the latter is realised by modelling the thermally-activated process. For the verification of this model, thermal desorption is simulated then the comparison with the chemical kinetics is carried out. Excellent agreement is observed from the result. The results show that this model is reasonable to express the recombinative desorption of two chemisorbed adatoms. Though, the application of this model is limited to the second-order reaction case. But it can be believed that the groundwork of modelling the transport dynamics of hydrogen through the surface under complex conditions is established

  2. Directly calculated electrical conductivity of hot dense hydrogen from molecular dynamics simulation beyond Kubo-Greenwood formula

    Science.gov (United States)

    Ma, Qian; Kang, Dongdong; Zhao, Zengxiu; Dai, Jiayu

    2018-01-01

    Electrical conductivity of hot dense hydrogen is directly calculated by molecular dynamics simulation with a reduced electron force field method, in which the electrons are represented as Gaussian wave packets with fixed sizes. Here, the temperature is higher than electron Fermi temperature ( T > 300 eV , ρ = 40 g / cc ). The present method can avoid the Coulomb catastrophe and give the limit of electrical conductivity based on the Coulomb interaction. We investigate the effect of ion-electron coupled movements, which is lost in the static method such as density functional theory based Kubo-Greenwood framework. It is found that the ionic dynamics, which contributes to the dynamical electrical microfield and electron-ion collisions, will reduce the conductivity significantly compared with the fixed ion configuration calculations.

  3. 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.

  4. Sandwich-type electrode

    Science.gov (United States)

    Lu, Wen-Tong P.; Garcia, Earl R.

    1983-01-01

    Disclosed is an improvement on a method of making an electrode wherein a suspension in a liquid is prepared of a powdered catalyst containing a noble metal, carbon powder and a binder, and the suspension is poured over a carbon substrate dried, compressed and sintered to form a solid catalyst layer bonded to the carbon substrate. The improvement is placing a carbon paper on the catalyst layer prior to compressing. The improved electrode can be used as either a cathode or an anode in a sulfur dioxide depolarized electrolyzer in a process for producing hydrogen from water.

  5. The hydrogen dynamics of CsH5(PO4)2 studied by means of nuclear magnetic resonance

    International Nuclear Information System (INIS)

    Gradisek, A; Dimnik, B; Vrtnik, S; Dolinsek, J; Wencka, M; Zdanowska Fraczek, M; Lavrova, G V

    2011-01-01

    We have investigated the hydrogen dynamics of cesium pentahydrogen diphosphate, CsH 5 (PO 4 ) 2 , by means of nuclear magnetic resonance (NMR) spectroscopy, in order to address the question of why there is no superprotonic phase transition in this compound, in contrast to other structurally similar hydrogen-bonded ionic salts, where a superprotonic transition is frequently found to be present. The analysis of the NMR spectrum and the spin-lattice relaxation rate revealed that the temperature-dependent hydrogen dynamics of CsH 5 (PO 4 ) 2 involves motional processes (the intra-H-bond jumps and the inter-H-bond jumps at elevated temperatures, as a mechanism of the ionic conductivity) identical to those for the other H-bonded superprotonic salts. The considerably stronger H-bond network in CsH 5 (PO 4 ) 2 prompts the search for a higher superprotonic transition temperature. However, due to the relatively weak bonding between the {[H 2 PO 4 ]} ∞ planes in the [100] direction of the CsH 5 (PO 4 ) 2 structure by means of the ionic bonding via the cesium atoms and the small number of H bonds in that direction (where out of five H bonds in the unit cell, four are directed within the {[H 2 PO 4 ]} ∞ planes and only one is between the planes), the bonds between the planes become thermally broken and the crystal melts before the H-bond network rearranges via water release into an open structure typical of the superprotonic phase. Were the coupling between the {[H 2 PO 4 ]} ∞ planes in the CsH 5 (PO 4 ) 2 somewhat stronger, the superprotonic transition would occur in the same manner as it does in other structurally related hydrogen-bonded ionic salts.

  6. A path integral molecular dynamics study of the hyperfine coupling constants of the muoniated and hydrogenated acetone radicals

    Energy Technology Data Exchange (ETDEWEB)

    Oba, Yuki; Kawatsu, Tsutomu; Tachikawa, Masanori, E-mail: tachi@yokohama-cu.ac.jp [Quantum Chemistry Division, Yokohama City University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027 (Japan)

    2016-08-14

    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.

  7. A path integral molecular dynamics study of the hyperfine coupling constants of the muoniated and hydrogenated acetone radicals

    International Nuclear Information System (INIS)

    Oba, Yuki; Kawatsu, Tsutomu; Tachikawa, Masanori

    2016-01-01

    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.

  8. Localised electrochemical impedance measurements of a polymer electrolyte fuel cell using a reference electrode array to give cathode-specific measurements and examine membrane hydration dynamics

    Science.gov (United States)

    Engebretsen, Erik; Hinds, Gareth; Meyer, Quentin; Mason, Tom; Brightman, Edward; Castanheira, Luis; Shearing, Paul R.; Brett, Daniel J. L.

    2018-04-01

    Advances in bespoke diagnostic techniques for polymer electrolyte fuel cells continue to provide unique insight into the internal operation of these devices and lead to improved performance and durability. Localised measurements of current density have proven to be extremely useful in designing better fuel cells and identifying optimal operating strategies, with electrochemical impedance spectroscopy (EIS) now routinely used to deconvolute the various losses in fuel cells. Combining the two techniques provides another dimension of understanding, but until now each localised EIS has been based on 2-electrode measurements, composed of both the anode and cathode responses. This work shows that a reference electrode array can be used to give individual electrode-specific EIS responses, in this case the cathode is focused on to demonstrate the approach. In addition, membrane hydration dynamics are studied under current load steps from open circuit voltage. A three-stage process is identified associated with an initial rapid reduction in membrane resistance after 10 s of applying a current step, followed by a slower ramp to approximately steady state, which was achieved after ∼250 s. These results support previously published work that has looked at membrane swelling dynamics and reveal that membrane hydration/membrane resistance is highly heterogeneous.

  9. Bubble dynamic templated deposition of three-dimensional palladium nanostructure catalysts: Approach to oxygen reduction using macro-, micro-, and nano-architectures on electrode surfaces

    International Nuclear Information System (INIS)

    Yang Guimei; Chen Xing; Li Jie; Guo Zheng; Liu Jinhuai; Huang Xingjiu

    2011-01-01

    Highlights: → We synthesize the Pd nanostructures by bubbles dynamic templated. → We obtain Pd nanobuds and Pd nanodendrites by changing the reaction precursor. → We obtain Pd macroelectrode voltammertric behavior using small amount of Pd materials. → We proved a ECE process. → The Pd nanostructures/GCE for O 2 reduction is a 2-step 4-electron process. - Abstract: Three-dimensional (3D) palladium (Pd) nanostructures (that is, nano-buds or nano-dendrites) are fabricated by bubble dynamic templated deposition of Pd onto a glassy carbon electrode (GCE). The morphology can be tailored by changing the precursor concentration and reaction time. Scanning electron microscopy images reveal that nano-buds or nano-dendrites consist of nanoparticles of 40-70 nm in diameter. The electrochemical reduction of oxygen is reported at such kinds of 3D nanostructure electrodes in aqueous solution. Data were collected using cyclic voltammetry. We demonstrate the Pd macroelectrode behavior of Pd nanostructure modified electrode by exploiting the diffusion model of macro-, micro-, and nano-architectures. In contrast to bare GCE, a significant positive shift and splitting of the oxygen reduction peak (vs Ag/AgCl/saturated KCl) at Pd nanostructure modified GCE was observed.

  10. 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

  11. 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.

  12. A bioinspired copper 2,2-bipyridyl complex immobilized MWCNT modified electrode prepared by a new strategy for elegant electrocatalytic reduction and sensing of hydrogen peroxide

    International Nuclear Information System (INIS)

    Mayuri, Pinapeddavari; Saravanan, Natarajan; Senthil Kumar, Annamalai

    2017-01-01

    Owing to facile electron-transfer reaction, metal complex based molecular architecture has attracted much interest in electrochemistry, especially for bioinspired electrocatalytic and electrochemical sensor applications. Indeed, preparation of stable surface-confined molecular system is a challenging task. In general, derivatization methodology, in which, a specific functional groups such as thiol, carboxylic acid, pyrene and amino bearing inorganic complexes synthesized discreetly by chemical approach have been attached suitably on electrode surface via any one of the following techniques; self-assembly, covalent immobilization, electrostatic interaction, ionic exchange and encapsulation. Herein, we report a copper-bipyridyl complex immobilized multiwalled carbon nanotube (MWCNT)-Nafion (Nf) modified glassy carbon electrode (GCE/Nf-MWCNT@bpy-Cu"2"+) prepared by a new strategy in which sequential modification of bipyridyl (bpy) ligand on MWCNT via π-π interaction followed by in-situ complexation with copper ion for efficient electrochemical reduction of H_2O_2. The copper species chemically modified electrode showed highly stable and well-defined surface-confined Cu"2"+"/"1"+ redox peak response, without any Cu"1"+"/"0 redox transition, at an equilibrium potential, E_1_/_2 = −135 mV vs Ag/AgCl in a pH 7 phosphate buffer solution. Detailed physico-chemical characterization by SEM, FT-IR, Raman and ESI-MS and electrochemical characterization reveals that [Cu(bpy)_2(H_2O)_2]"+ (molecular weight 413.4) like species was immobilized as a major species on the modified electrode. A bioinspired electro-catalytic reduction of H_2O_2 was studied using cyclic voltammetric and rotating disc electrode techniques. In further, electrochemical sensing of H_2O_2 by amperometric i-t and flow injection analysis methods with a detection limit values 4.5 and 0.49 μM respectively were demonstrated.

  13. 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.

  14. Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

    Science.gov (United States)

    Hofer, Thomas S.; Hünenberger, Philippe H.

    2018-06-01

    The absolute intrinsic hydration free energy GH+,w a t ◦ of the proton, the surface electric potential jump χwa t ◦ upon entering bulk water, and the absolute redox potential VH+,w a t ◦ of the reference hydrogen electrode are cornerstone quantities for formulating single-ion thermodynamics on absolute scales. They can be easily calculated from each other but remain fundamentally elusive, i.e., they cannot be determined experimentally without invoking some extra-thermodynamic assumption (ETA). The Born model provides a natural framework to formulate such an assumption (Born ETA), as it automatically factors out the contribution of crossing the water surface from the hydration free energy. However, this model describes the short-range solvation inaccurately and relies on the choice of arbitrary ion-size parameters. In the present study, both shortcomings are alleviated by performing first-principle calculations of the hydration free energies of the sodium (Na+) and potassium (K+) ions. The calculations rely on thermodynamic integration based on quantum-mechanical molecular-mechanical (QM/MM) molecular dynamics (MD) simulations involving the ion and 2000 water molecules. The ion and its first hydration shell are described using a correlated ab initio method, namely resolution-of-identity second-order Møller-Plesset perturbation (RIMP2). The next hydration shells are described using the extended simple point charge water model (SPC/E). The hydration free energy is first calculated at the MM level and subsequently increased by a quantization term accounting for the transformation to a QM/MM description. It is also corrected for finite-size, approximate-electrostatics, and potential-summation errors, as well as standard-state definition. These computationally intensive simulations provide accurate first-principle estimates for GH+,w a t ◦, χwa t ◦, and VH+,w a t ◦, reported with statistical errors based on a confidence interval of 99%. The values obtained

  15. 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

  16. Dynamic Covalent Self-Assembly of Mono-, Bi- and Trimacro-cycles from Hydrogen Bonded Preorganized Templates

    Institute of Scientific and Technical Information of China (English)

    LIN Jianbin; WU Jing; JIANG Xikui; LI Zhanting

    2009-01-01

    This paper describes the dynamic covalent assembly of three mono-, bi- and trimacrocycles by utilizing hydro-gen bonding-driven zigzag anthranilamides as "leading" components. The monomacrocycle, a tetraamino molecule, was prepared from the [24+2] coupling reaction of a "'U"-shaped dialdehyde and a porphyrin diamine, followed by the reduction of the macrocyclic tetraimine by NaBH3CN, while the bi-and trimacrocycles were obtained through two six-component coupling reactions with rigid tri- and tetraamino-appended oligomers as templates.

  17. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama; Alandini, Nurtalya; Rueping, Magnus

    2016-01-01

    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

  18. 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

  19. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    International Nuclear Information System (INIS)

    Mori, Yukie; Masuda, Yuichi

    2015-01-01

    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 4 , acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17 O and 1

  20. Influence of the concentration of borohydride towards hydrogen production and escape for borohydride oxidation reaction on Pt and Au electrodes - experimental and modelling insights

    Science.gov (United States)

    Olu, Pierre-Yves; Bonnefont, Antoine; Braesch, Guillaume; Martin, Vincent; Savinova, Elena R.; Chatenet, Marian

    2018-01-01

    The Borohydride Oxidation Reaction (BOR), the anode reaction in a Direct borohydride fuel cell (DBFC), is complex and still poorly understood, which impedes the development and deployment of the DBFC technology. In particular, no practical electrocatalyst is capable to prevent gaseous hydrogen generation and escape from its anode upon operation, which lowers the fuel-efficiency of the DBFC and raises safety issues in operation. The nature of the anode electrocatalysts strongly influences the hydrogen escape characteristics of the DBFC, which demonstrates how important it is to isolate the BOR mechanism in conditions relevant to DBFC operation. In this paper, from a selected literature review and BOR experiments performed in differential electrochemical mass spectrometry (DEMS) in a wide range of NaBH4 concentration (5-500 mM), a microkinetic model of the BOR for both Pt and Au surfaces is proposed; this model takes into account the hydrogen generation and escape.

  1. Design and development of a highly stable hydrogen peroxide biosensor on screen printed carbon electrode based on horseradish peroxidase bound with gold nanoparticles in the matrix of chitosan.

    Science.gov (United States)

    Tangkuaram, Tanin; Ponchio, Chatchai; Kangkasomboon, Thippayawadee; Katikawong, Panadda; Veerasai, Waret

    2007-04-15

    The design and development of a screen printed carbon electrode (SPCE) on a polyvinyl chloride substrate as a disposable sensor is described. Six configurations were designed on silk screen frames. The SPCEs were printed with four inks: silver ink as the conducting track, carbon ink as the working and counter electrodes, silver/silver chloride ink as the reference electrode and insulating ink as the insulator layer. Selection of the best configuration was done by comparing slopes from the calibration plots generated by the cyclic voltammograms at 10, 20 and 30 mM K(3)Fe(CN)(6) for each configuration. The electrodes with similar configurations gave similar slopes. The 5th configuration was the best electrode that gave the highest slope. Modifying the best SPCE configuration for use as a biosensor, horseradish peroxidase (HRP) was selected as a biomaterial bound with gold nanoparticles (AuNP) in the matrix of chitosan (HRP/AuNP/CHIT). Biosensors of HRP/SPCE, HRP/CHIT/SPCE and HRP/AuNP/CHIT/SPCE were used in the amperometric detection of H(2)O(2) in a solution of 0.1M citrate buffer, pH 6.5, by applying a potential of -0.4V at the working electrode. All the biosensors showed an immediate response to H(2)O(2). The effect of HRP/AuNP incorporated with CHIT (HRP/AuNP/CHIT/SPCE) yielded the highest performance. The amperometric response of HRP/AuNP/CHIT/SPCE retained over 95% of the initial current of the 1st day up to 30 days of storage at 4 degrees C. The biosensor showed a linear range of 0.01-11.3mM H(2)O(2), with a detection limit of 0.65 microM H(2)O(2) (S/N=3). The low detection limit, long storage life and wide linear range of this biosensor make it advantageous in many applications, including bioreactors and biosensors.

  2. Coherent dynamics of the localized vibrational modes of hydrogen in CaF2

    NARCIS (Netherlands)

    Wells, J. P. R.; Rella, C. W.; Bradley, I. V.; Galbraith, I.; Pidgeon, C. R.

    2000-01-01

    We report the observation of giant quantum coherence effects in the localized modes of ionized hydrogen in synthetic fluorite. Infrared free induction decay experiments on the substitutional H+ center thew dramatic modulations at negative delay times due to interference between multiple vibrational

  3. Dynamic Monte-Carlo modeling of hydrogen retention and chemical erosion from Tore Supra deposits

    International Nuclear Information System (INIS)

    Rai, A.; Schneider, R.; Warrier, M.; Roubin, P.; Martin, C.

    2009-01-01

    A multi-scale model has been developed to study the hydrogen retention [A. Rai, R. Schneider, M. Warrier, J. Nucl. Mater. 374 (2008) 304] and chemical erosion of porous graphite. To model the chemical erosion process due to thermal hydrogen ions, Kueppers cycle [J. Kueppers, Surf. Sci. Rep. 22 (1995) 249; M. Wittmann, J. Kueppers, J. Nucl. Mater. 227 (1996) 186] has been introduced. The model is applied to study hydrogen transport in deposits collected from the leading edge of neutralizers of Tore Supra. The effect of internal structure on chemical erosion is studied. The MD study [E. Salonen et al., J. Nucl. Mater. 290-293 (2001) 144] shows that the experimentally observed decrease of erosion yield at higher fluxes is due to the decrease of carbon collision cross-section at a surface due to shielding by hydrogen atom already present on the surface. Inspired by this study, a simple multi-scale model is developed to describe the flux dependence of chemical erosion. The idea is to use the local chemistry effect from the Kueppers model to calculate the hydrocarbon molecule formation process and then to find the release probability of the produced hydrocarbon based on the purely geometrical constraints. The model represents quite well the trends in experimental data.

  4. Ejection dynamics of hydrogen molecular ions from methanol in intense laser fields

    International Nuclear Information System (INIS)

    Okino, T; Furukawa, Y; Liu, P; Ichikawa, T; Itakura, R; Hoshina, K; Yamanouchi, K; Nakano, H

    2006-01-01

    The ejection of hydrogen molecular ions from two-body Coulomb explosion processes of methanol (CH 3 OH, CD 3 OH and CH 3 OD) in an intense laser field (800 nm, 60 fs, 0.2 PW cm -2 ) is investigated by a coincidence momentum imaging method. From the coincidence momentum maps, the ejection processes of hydrogen molecular ions, CH 3 OH 2+ → H m + + CH (3-m) OH + (m = 2, 3), CD 3 OH 2+ → D m + + CH (3-m) OH + (m = 2, 3) and CH 3 OD 2+ → H m + + CH (3-m) OD + (m = 2, 3), are identified. Based on the results obtained with isotopically substituted methanol, the isotope effect on the ejection process of hydrogen molecular ions is discussed. Furthermore, the ejection of H/D exchanged hydrogen molecular ions (HD + , HD 2 + and H 2 D + ) is identified, and the timescales for the H/D exchanging processes are estimated from the extent of anisotropy in the ejection directions

  5. Hydrogen atom injection into carbon surfaces by comparison between Monte-Carlo, molecular dynamics and ab-initio calculations

    International Nuclear Information System (INIS)

    Ito, A.; Kenmotsu, T.; Kikuhara, Y.; Inai, K.; Ohya, K.; Wang, Y.; Irle, S.; Morokuma, K.; Nakamura, H.

    2009-01-01

    Full text: To understand the plasma-wall interaction on divertor plates, we investigate the interaction of hydrogen atoms and carbon materials used in the high heat flux components by the use of the following simulations. Monte-Carlo (MC) method based on binary collision approximation can calculate the sputtering process of hydrogen atoms on the carbon material quickly. Classical molecular dynamics (MD) method employs multi-body potential models and can treat realistic structures of crystal and molecule. The ab-initio method can calculate electron energy in quantum mechanics, which is regarded as realistic potential for atoms. In the present paper, the interaction of the hydrogen and the carbon material is investigated using the multi-scale (MC, MD and ab-initio) methods. The bombardment of hydrogen atoms onto the carbon material is simulated by the ACAT-code of the MC method, which cannot represent the structure of crystal, and the MD method using modified reactive empirical bond order (REBO) potential, which treats single crystal graphite and amorphous carbon. Consequently, we clarify that the sputtering yield and the reflection rate calculated by the ACAT-code agree with those on the amorphous carbon calculated by the MD. Moreover, there are many kinds of REBO potential for the MD. Adsorption, reflection and penetration rates between a hydrogen atom and a graphene surface are calculated by the MD simulations using the two kinds of potential model. For the incident energy of less than 1 eV, the MD simulation using the modified REBO potential, which is based on Brenner's REBO potential in 2002, shows that reflection is dominant, while the most popular Brenner's REBO potential in 1990 shows that adsorption is dominant. This reflection of the low energy injection is caused by a small potential barrier for the hydrogen atom in the modified REBO potential. The small potential barrier is confirmed by the ab-initio calculations, which are hybrid DFT (B3LYP/cc-pVDZ), ab

  6. Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics

    Science.gov (United States)

    Brela, Mateusz Z.; Boczar, Marek; Malec, Leszek M.; Wójcik, Marek J.; Nakajima, Takahito

    2018-05-01

    Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers.

  7. Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

    Science.gov (United States)

    Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

    2009-12-31

    Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

  8. Hydrogen Detection With a Gas Sensor Array – Processing and Recognition of Dynamic Responses Using Neural Networks

    Directory of Open Access Journals (Sweden)

    Gwiżdż Patryk

    2015-03-01

    Full Text Available An array consisting of four commercial gas sensors with target specifications for hydrocarbons, ammonia, alcohol, explosive gases has been constructed and tested. The sensors in the array operate in the dynamic mode upon the temperature modulation from 350°C to 500°C. Changes in the sensor operating temperature lead to distinct resistance responses affected by the gas type, its concentration and the humidity level. The measurements are performed upon various hydrogen (17-3000 ppm, methane (167-3000 ppm and propane (167-3000 ppm concentrations at relative humidity levels of 0-75%RH. The measured dynamic response signals are further processed with the Discrete Fourier Transform. Absolute values of the dc component and the first five harmonics of each sensor are analysed by a feed-forward back-propagation neural network. The ultimate aim of this research is to achieve a reliable hydrogen detection despite an interference of the humidity and residual gases.

  9. 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.)

  10. A measurement of hydrogen transport in deuterium discharges using the dynamic response of the effective mass

    International Nuclear Information System (INIS)

    Dudok de Wit, T.; Duval, B.P.; Joye, B.; Lister, J.B.

    1992-02-01

    Particle tagging in a tokamak provides an attractive method for studying transport mechanisms. The injection of test particles at the plasma edge and the subsequent measurement of the evolution of their concentration at the centre can be used to quantify the underlying transport mechanisms. This has been carried out on the TCA tokamak by injecting hydrogen into a deuterium discharge, and simultaneously measuring the temporal evolution of the effective mass and the edge ionisation rate. (author) 3 figs., 9 refs

  11. Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell. Part 4. Electrode Compartments of Cell Modified and Tested in Scaled-Up Mobile Unit

    Science.gov (United States)

    2013-09-03

    The catholyte is the water fed to the cathode compartment and it must be free from hardness ions such as calcium (Ca +2 ) and magnesium (Mg +2...4NaOH + 2H2 (6) Overall: 6H2O + 4NaCl  4HClIX + 4 NaOH  + 2H2Cathode + O2Anode (7) The amount of H + generated by the cathode...electrode that is operating as the cathode. Ions that impart hardness to seawater include calcium (Ca +2 ) and magnesium (Mg +2 ) ions, and their total

  12. Dynamic plasma screening effects on electron capture process in hydrogenic ion fully stripped ion collisions in dense plasmas

    International Nuclear Information System (INIS)

    Jung, Y.

    1997-01-01

    In dense plasmas, dynamic plasma screening effects are investigated on electron capture from hydrogenic ions by past fully stripped ions. The classical Bohr Lindhard model has been applied to obtain the electron capture probability. The interaction potential in dense plasmas is represented in terms of the longitudinal dielectric function. The classical straight-line trajectory approximation is applied to the motion of the projectile ion in order to visualize the electron capture probability as a function of the impact parameter, projectile energy, and plasma parameters. The electron capture probability including the dynamic plasma screening effect is always greater than that including the static plasma screening effect. When the projectile velocity is smaller than the electron thermal velocity, the dynamic polarization screening effect becomes the static plasma screening effect. When the projectile velocity is greater than the plasma electron thermal velocity, the interaction potential is almost unshielded. The difference between the dynamic and static plasma screening effects is more significant for low energy projectiles. It is found that the static screening formula obtained by the Debye Hueckel model overestimates the plasma screening effects on the electron capture processes in dense plasmas. copyright 1997 American Institute of Physics

  13. A survey of reference electrodes for high temperature waters

    International Nuclear Information System (INIS)

    Molander, A.; Eriksson, Sture; Pein, K.

    2000-11-01

    In nuclear power plants, corrosion potential measurements are used to follow the conditions for different corrosion types in reactor systems, particularly IGSCC in BWRs. The goal of this work has been to give a survey of reference electrodes for high temperature water, both those that are used for nuclear environments and those that are judged to possible future development. The reference electrodes that are used today in nuclear power plants for corrosion potential measurements are of three types. Silver chloride electrodes, membrane electrodes and platinum electrodes (hydrogen electrodes). The principals for their function is described as well as the conversion of measured potentials to the SHE scale (Standard Hydrogen Electrode). Silver chloride electrodes consist of an inner reference system of silver chloride in equilibrium with a chloride solution. The silver chloride electrode is the most common reference electrode and can be used in several different systems. Platinum electrodes are usually more robust and are particularly suitable to use in BWR environment to follow the hydrogen dosage, but have limitations at low and no hydrogen dosage. Ceramic membrane electrodes can be with different types of internal reference system. They were originally developed for pH measurements in high temperature water. If pH is constant, the membrane electrode can be used as reference electrode. A survey of ceramic reference electrodes for high temperature water is given. A ceramic membrane of the type used works as an oxygen conductor, so the potential and pH in surrounding medium is in equilibrium with the internal reference system. A survey of the lately development of electrodes is presented in order to explain why the different types of electrodes are developed as well as to give a background to the possibilities and limitations with the different electrodes. Possibilities of future development of electrodes are also given. For measurements at low or no hydrogen dosage

  14. Dynamic behaviour of Li batteries in hydrogen fuel cell power trains

    Science.gov (United States)

    Veneri, O.; Migliardini, F.; Capasso, C.; Corbo, P.

    A Li ion polymer battery pack for road vehicles (48 V, 20 Ah) was tested by charging/discharging tests at different current values, in order to evaluate its performance in comparison with a conventional Pb acid battery pack. The comparative analysis was also performed integrating the two storage systems in a hydrogen fuel cell power train for moped applications. The propulsion system comprised a fuel cell generator based on a 2.5 kW polymeric electrolyte membrane (PEM) stack, fuelled with compressed hydrogen, an electric drive of 1.8 kW as nominal power, of the same typology of that installed on commercial electric scooters (brushless electric machine and controlled bidirectional inverter). The power train was characterized making use of a test bench able to simulate the vehicle behaviour and road characteristics on driving cycles with different acceleration/deceleration rates and lengths. The power flows between fuel cell system, electric energy storage system and electric drive during the different cycles were analyzed, evidencing the effect of high battery currents on the vehicle driving range. The use of Li batteries in the fuel cell power train, adopting a range extender configuration, determined a hydrogen consumption lower than the correspondent Pb battery/fuel cell hybrid vehicle, with a major flexibility in the power management.

  15. 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

  16. The dynamics of highly excited hydrogen atoms in microwave fields: Application of the Floquet picture of quantum mechanics

    International Nuclear Information System (INIS)

    Holthaus, M.

    1990-04-01

    The study of short-time phenomena in strongly interacting quantum systems requires on the theoretical side the development of methods, which are both non-perturbative and 'dynamical', which thus regard the change of outer parameters in the slope of time. For systems with a periodic, fast and a further slow, parametric time dependence both requirements are fulfilled by the Floquet picture of quantum mechanics. This picture, which starts from the adiabatic evolution on effective quasi-energy surfaces, is presented in the first chapter of the present thesis, whereby especially the term of the adiabaticity for periodically time dependent systems is explained. In the second chapter the Floquet theory is applied to the description of microwave experiments with highly excited hydrogen atoms. Here it is shown that the Floquet picture permits to understand a manifold of experimental observations under a unified point of view. Really these microwave experiments offer an ideal possibility for the test of the Floquet picture: On the one hand there is the strength of the outer field of the same order of magnitude as that of the nuclear field, by which the highly excited electron is bound, on the other hand in the experiment an extremely precise control of amplitude, frequency, and pulse shape is possible, so that the conditions for a detailed comparison of theory and experiment are given. The insights, which model calculations yield in the dynamics of highly excited hydrogen atoms in strong alternating fields, allow a prediction of further effects, for which it is to be looked for in new experiments. In the following third chapter some further aspects of these model calculations are discussed, whereby also common properties of the dynamics of excited atoms in microwave fields and that of atoms under the influence of strong laser pulses are discussed. (orig./HSI) [de

  17. Facile fabrication of polyaniline nanotubes using the self-assembly behavior based on the hydrogen bonding: a mechanistic study and application in high-performance electrochemical supercapacitor electrode

    International Nuclear Information System (INIS)

    Wu, Wenling; Pan, Duo; Li, Yanfeng; Zhao, Guanghui; Jing, Lingyun; Chen, Suli

    2015-01-01

    At present, the in situ synthesis of polyaniline (PANI) nanotubes via self-assembly of organic dopant acid is a particularly charming task in supercapacitors. Herein, we report the formation of uniform PANI nanotubes doped with malic acid (MA) and other organic acids, such as propionic acid (PA), succinic acid (SA), tartaric acid (TA) and citric acid (CA), which simultaneously acts as a dopant acid as well as a structure-directing agent. The morphology, structure and thermal stability of PANI nanotubes were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectra, Ultraviolet-visible spectra (UV–vis), X-ray diffraction (XRD), thermogravimetric analysis (TGA). Meanwhile, the electrochemical performance of the fabricated electrodes was evaluated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS). Furthermore, the PANI-MA and PANI-CA nanotubes, with [aniline]/[acid] molar ratio of 4:1, possessed highest specific capacitance of 658 F/g and 617 F/g at the current density of 0.1 A/g in 1.0 M H 2 SO 4 electrolyte due to their unique nanotubular structures. It makes PANI nanotubes a promising electrode material for high performance supercapacitors

  18. 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...

  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. Dynamic response of physisorbed hydrogen molecules on lanthanide-modified zirconia nanoparticles

    International Nuclear Information System (INIS)

    Loong, C.K.; Trouw, F.; Ozawa, Masakuni; Suzuki, Suguru

    1997-01-01

    Ultrafine lanthanide (Ln = Ce and Nd)-modified zirconia powders synthesized by a coprecipitation method exhibit high surface areas and adsorption sites that are essential for catalytic applications. We report a study of the surface chemistry of Ce 0.1 Zr 0.9 O 2 and Nd 0.1 Zr 0.9 O 1.95 powders. First, the specific surface area and porosity are characterized by nitrogen isotherm-adsorption measurements. Second, the motion of hydrogen molecules physisorbed on Ce- and Nd-doped zirconias is studied by inelastic neutron scattering. Nitrogen adsorption-desorption isotherm measurements yield a BET surface area (26.1 m 2 /g) and mesopore size (∼5 nm radius) in Ce 0.1 Zr 0.9 O 2 as compared to those (72.3 m 2 /g and ∼3 nm) in Nd 0.1 Zr 0.9 O 1.95 . The vibrational densities of states of H 2 on Ce 0.1 Zr 0.9 O 2 and Nd 0.1 Zr 0.9 O 1.95 were measured at 20 K over the 0-200 meV energy range for three hydrogen coverage. The spectra for both samples consist of two parts: a sharp peak at ∼14.5 meV and a broad component extending beyond 200 meV. The sharp peak corresponds to transitions from the J=0 to J=1 rotational states of bulk hydrogen molecules, and its intensity decreases with decreasing H 2 coverage. The broad component corresponds to overdamped motion of surface adsorbed hydrogen molecules. The major difference in the latter component between the Ce- and Nd-doped samples is an excess of intensities in the 5-14 meV region in Nd 0.1 Zr 0.9 O 1.95 . The confined motion of adsorbed H 2 on the different micropore and mesopore surfaces of Ce 0.1 Zr 0.9 O 2 and Nd 0.1 Zr 0.9 O 1.95 is discussed

  1. 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

  2. Comment on "Theoretical study of the dynamics of atomic hydrogen adsorbed on graphene multilayers"

    Science.gov (United States)

    Bonfanti, Matteo; Martinazzo, Rocco

    2018-03-01

    It is shown that the theoretical prediction of a transient magnetization in bilayer and multilayer graphene (M. Moaied et al., Phys. Rev. B 91, 155419 (2015), 10.1103/PhysRevB.91.155419) relies on an incorrect physical scenario for adsorption, namely, one in which H atoms adsorb barrierless on graphitic substrates and form a random adsorption pattern of monomers. Rather, according to experimental evidence, H atom sticking is an activated process, and adsorption is under kinetic control, largely ruled by a preferential sticking mechanism that leads to stable, nonmagnetic dimers at all but the smallest coverages (Theory and experiments are reconciled by reconsidering the hydrogen atom adsorption energetics with the help of van der Waals-inclusive density functional calculations that properly account for the basis set superposition error. It is shown that today van der Waals-density functional theory predicts a shallow physisorption well that nicely agrees with available experimental data and suggests that the hydrogen atom adsorption barrier in graphene is 180 meV high, within ˜5 meV accuracy.

  3. Dynamic study of excited state hydrogen-bonded complexes of harmane in cyclohexane-toluene mixtures.

    Science.gov (United States)

    Carmona, Carmen; Balón, Manuel; Galán, Manuel; Guardado, Pilar; Muñoz, María A

    2002-09-01

    Photoinduced proton transfer reactions of harmane or 1-methyl-9H-pyrido[3,4-b]indole (HN) in the presence of the proton donor hexafluoroisopropanol (HFIP) in cyclohexane-toluene mixtures (CY-TL; 10% vol/vol of TL) have been studied. Three excited state species have been identified: a 1:2 hydrogen-bonded proton transfer complex (PTC), between the pyridinic nitrogen of the substrate and the proton donor, a hydrogen-bonded cation-like exciplex (CL*) with a stoichiometry of at least 1:3 and a zwitterionic exciplex (Z*). Time-resolved fluorescence measurements evidence that upon excitation of ground state PTC, an excited state equilibrium is established between PTC* and the cationlike exciplex, CL*, lambdaem approximately/= 390 nm. This excited state reaction is assisted by another proton donor molecule. Further reaction of CL* with an additional HFIP molecule produces the zwitterionic species, Z*, lambda(em) approximately/= 500 nm. From the analysis of the multiexponential decays, measured at different emission wavelengths and as a function of HFIP concentration, the mechanism of these excited state reactions has been established. Thus, three rate constants and three reciprocal lifetimes have been determined. The simultaneous study of 1,9-dimethyl-9H-pyrido[3,4-b]indole (MHN) under the same experimental conditions has helped to understand the excited state kinetics of these processes.

  4. Dynamic high pressure induced strong and weak hydrogen bonds enhanced by pre-resonance stimulated Raman scattering in liquid water.

    Science.gov (United States)

    Wang, Shenghan; Fang, Wenhui; Li, Fabing; Gong, Nan; Li, Zhanlong; Li, Zuowei; Sun, Chenglin; Men, Zhiwei

    2017-12-11

    355 nm pulsed laser is employed to excite pre-resonance forward stimulated Raman scattering (FSRS) of liquid water at ambient temperature. Due to the shockwave induced dynamic high pressure, the obtained Raman spectra begin to exhibit double peaks distribution at 3318 and 3373 cm -1 with the input energy of 17 mJ,which correspond with OH stretching vibration with strong and weak hydrogen (H) bonds. With laser energy rising from 17 to 27 mJ, the Stokes line at 3318 cm -1 shifts to 3255 and 3230 cm -1 because of the high pressure being enlarged. When the energy is up to 32 mJ, only 3373 cm -1 peak exists. The strong and weak H bond exhibit quite different energy dependent behaviors.

  5. 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.

  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. Dynamics of the reaction of the N+ ion with hydrogen isotopes and helium

    International Nuclear Information System (INIS)

    Ruska, W.E.W.

    1976-01-01

    Molecular beam techniques were used to study the reactive and non-reactive scattering of the nitrogen positive ion from hydrogen isotopes and helium, at energies above the stability limit for spectator stripping. Reactive scattering was observed from H 2 and HD targets. Non-reactive scattering was observed from H 2 and D 2 targets, and from He at one energy. A correlation diagram for the system is presented and compared with the available a priori calculations. Two surfaces are expected to lead to reaction. One is a 3 A 2 - 3 PI surface, the other, a 3 B 1 - 3 Σ - surface. Collinear approaches are expected to be most reactive on the 3 B 1 - 3 Σ - surface; noncollinear, on the 3 A 1 - 3 PI surface. Theoretical models are presented in which an incident hard sphere A, representing the projectile ion, strikes one of a pair of hard spheres B-C representing the B hydrogen molecule. After an impulsive A-B collision, an impulsive B-C collision may take place. The relative energy of A to B is then examined, and a reactive event is considered to have occurred if the energy is less than the dissociation energy for the A-B molecule. This model is treated both in the collinear case and in three dimensions. A graphical technique for the collinear case is summarized and applied to reaction on the 3 B 1 - 3 Σ - surface. An integral equation for the three-dimensional case is developed. A synthesis of two treatments, representing the behavior of the system on both reactive surfaces, and considering the charge-exchange channel, correctly predicts the observed product distribution. Predictions are also presented for the as yet unobserved case of reactive scattering from a D 2 target

  8. Self adaptive internal combustion engine control for hydrogen mixtures based on piezoelectric dynamic cylinder pressure transducers

    International Nuclear Information System (INIS)

    Courteau, R.; Bose, T.K.

    2004-01-01

    Piezoelectric transducers offer an effective, non-intrusive way to monitor dynamic cylinder pressure in internal combustion engines. Devices dedicated to this purpose are appearing on the market, often in the form of spark plugs with embedded piezo elements. Dynamic cylinder pressure is typically used to provide diagnostic functions, or to help map an engine after it is designed. With the advent of powerful signal processor chips, it is now possible to embed enough computing power in the engine controller to perform auto tuning based on the signals provided by such transducers. Such functionality is very useful if the fuel characteristics vary between fill ups, as is often the case with alternative fuels. We propose here an algorithm for self-adaptive tuning based on a Kalman filter operating on a few selected metrics of the dynamic pressure curve. (author)

  9. Self adaptive internal combustion engine control for hydrogen mixtures based on piezoelectric dynamic cylinder pressure transducers

    Energy Technology Data Exchange (ETDEWEB)

    Courteau, R.; Bose, T. K. [Universite du Quebec a Trois-Rivieres, Hydrogen Research Institute, Trois-Rivieres, PQ (Canada)

    2004-07-01

    An algorithm for self-adaptive tuning of an internal combustion engine is proposed, based on a Kalman filter operating on a few selected metrics of the dynamic pressure curve. Piezoelectric transducers are devices to monitor dynamic cylinder pressure; spark plugs with embedded piezo elements are now available to provide diagnostic engine functions. Such transducers are also capable of providing signals to the engine controller to perform auto tuning, a function that is considered very useful particularly in vehicles using alternative fuels whose characteristics frequently show variations between fill-ups. 2 refs., 2 figs.

  10. A dynamic model of a 100 kW micro gas turbine fuelled with natural gas and hydrogen blends and its application in a hybrid energy grid

    International Nuclear Information System (INIS)

    Di Gaeta, Alessandro; Reale, Fabrizio; Chiariello, Fabio; Massoli, Patrizio

    2017-01-01

    The paper deals with the development of a dynamic model of a commercial 100 kW Micro Gas Turbine (MGT) fuelled with mixtures of standard (i.e. natural gas or methane) and alternative fuels (i.e. hydrogen). The model consists of a first-order differential equation (ODE) describing the dominant dynamics of the MGT imposed by its own control system during production electrical power. The differential equation is coupled to a set of nonlinear maps derived numerically from a detailed 0D thermodynamic matching model of the MGT evaluated over a wide range of operating conditions (i.e. mechanical power, fraction of hydrogen and ambient temperature). The efficiency of the electrical machine with power inverter and power absorbed by auxiliary devices is also taken into account. The resulting model is experimentally validated for a sequence of power step responses of the MGT at different ambient conditions and with different fuel mixtures. The model is suited for simulation and control of hybrid energy grids (HEGs) which rely on advanced use of MGT and hydrogen as energy carrier. In this regard, the MGT model is used in the simulation of an HEG based on an appropriate mix of renewable (non-programmable) and non-renewable (programmable) energy sources with hydrogen storage and its reuse in the MGT. Here, the MGT is used as a programmable energy vector for compensating the deficits of renewable energies (such as solar and wind) with respect to user demand, while excess renewable energy is used to produce hydrogen via electrolysis of water. The simulated HEG comprises a solar PhotoVoltaic (PV) plant (300 kW), an MGT (100 kW) fuelled with natural gas and hydrogen blends, a water electrolyzer (WE) system (8 bar, 56 Nm 3 /h), a hydrogen tank (54 m 3 ), and an Energy Management Control System (EMCS). - Highlights: • A dynamic model of a commercial 100 kW MGT fuelled with natural gas and hydrogen blends is developed. • The model reproduces the electrical power generated by

  11. Hydrogen research and development in Hawaii: Hawaii natural energy institute's hydrogen from renewable resources research program

    International Nuclear Information System (INIS)

    McKinley, K.R.; Rocheleau, R.E.; Takahashi, P.K.; Jensen, C.M.

    1993-01-01

    Hawaii, an energy-vulnerable state, has launched a Renewable Resources Research Program, focusing on hydrogen production and storage; the main tasks of this effort are: photoelectrochemical production of hydrogen through the use of coated silicon electrodes; solar conversion and the production of hydrogen with cyanobacteria; improved hydrogen storage through the use of nonclassical poly-hydride metal complexes. 10 refs

  12. Liquid electrode

    Science.gov (United States)

    Ekechukwu, A.A.

    1994-07-05

    A dropping electrolyte electrode is described for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions. 2 figures.

  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. 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.

  15. Hydrogen migration dynamics in hydrated Al clusters: The Al17(−)·H2O system as an example

    International Nuclear Information System (INIS)

    Álvarez-Barcia, S.; Flores, J. R.

    2014-01-01

    The Al m (−) ·(H 2 O) n systems are known to undergo water splitting processes in the gas phase giving H k Al m (OH) k (−) ·(H 2 O) n−k systems, which can generate H 2 . The migration of H atoms from one Al atom to another on the cluster's surface is of critical importance to the mechanism of the complete H 2 production process. We have applied a combination of Molecular Dynamics and Rice-Ramsperger-Kassel-Marcus theory including tunneling effects to study the gas-phase evolution of HAl 17 (OH) (−) , which can be considered a model system. First, we have performed an extensive search for local minima and the connecting saddle points using a density functional theory method. It is found that in the water-splitting process Al 17 (−) ·(H 2 O) → HAl 17 (OH) (−) , the H atom which bonds to the Al cluster losses rather quickly its excess energy, which is easily “absorbed” by the cluster because of its flexibility. This fact ultimately determines that long-range hydrogen migration is not a very fast process and that, probably, tunneling only plays a secondary role in the migration dynamics, at least for moderate energies. Reduction of the total energy results in the process being very much slowed down. The consequences on the possible mechanisms of H 2 generation from the interaction of Al clusters and water molecules are discussed

  16. Dynamics of the reaction of the N/sup +/ ion with hydrogen isotopes and helium

    Energy Technology Data Exchange (ETDEWEB)

    Ruska, W.E.W.

    1976-06-28

    Molecular beam techniques were used to study the reactive and non-reactive scattering of the nitrogen positive ion from hydrogen isotopes and helium, at energies above the stability limit for spectator stripping. Reactive scattering was observed from H/sub 2/ and HD targets. Non-reactive scattering was observed from H/sub 2/ and D/sub 2/ targets, and from He at one energy. A correlation diagram for the system is presented and compared with the available a priori calculations. Two surfaces are expected to lead to reaction. One is a /sup 3/A/sub 2/ - /sup 3/PI surface, the other, a /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface. Collinear approaches are expected to be most reactive on the /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface; noncollinear, on the /sup 3/A/sub 1/ - /sup 3/PI surface. Theoretical models are presented in which an incident hard sphere A, representing the projectile ion, strikes one of a pair of hard spheres B-C representing the B hydrogen molecule. After an impulsive A-B collision, an impulsive B-C collision may take place. The relative energy of A to B is then examined, and a reactive event is considered to have occurred if the energy is less than the dissociation energy for the A-B molecule. This model is treated both in the collinear case and in three dimensions. A graphical technique for the collinear case is summarized and applied to reaction on the /sup 3/B/sub 1/ - /sup 3/..sigma../sup -/ surface. An integral equation for the three-dimensional case is developed. A synthesis of two treatments, representing the behavior of the system on both reactive surfaces, and considering the charge-exchange channel, correctly predicts the observed product distribution. Predictions are also presented for the as yet unobserved case of reactive scattering from a D/sub 2/ target.

  17. 21 CFR 876.1400 - Stomach pH electrode.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Stomach pH electrode. 876.1400 Section 876.1400...) MEDICAL DEVICES GASTROENTEROLOGY-UROLOGY DEVICES Diagnostic Devices § 876.1400 Stomach pH electrode. (a) Identification. A stomach pH electrode is a device used to measure intragastric and intraesophageal pH (hydrogen...

  18. electrode array

    African Journals Online (AJOL)

    PROF EKWUEME

    A geoelectric investigation employing vertical electrical soundings (VES) using the Ajayi - Makinde Two-Electrode array and the ... arrangements used in electrical D.C. resistivity survey. These include ..... Refraction Tomography to Study the.

  19. A nuclear magnetic relaxation study of hydrogen exchange and water dynamics in aqueous systems

    International Nuclear Information System (INIS)

    Lankhorst, D.

    1983-01-01

    In this thesis exchange of water protons in solutions of some weak electrolytes and polyelectrolytes is studied. Also the dynamical behaviour of water molecules in pure water is investigated. For these purposes nuclear magnetic resonance relaxation measurements, in solutions of oxygen-17 enriched water, are interpreted. The exchange rate of the water protons is derived from the contribution of 1 H- 17 O scalar coupling to the proton transverse relaxation rate. This rate is measured by the Carr-Purcell technique. (Auth.)

  20. Square-wave adsorptive stripping voltammetric determination of nanomolar levels of bezafibrate using a glassy carbon electrode modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film.

    Science.gov (United States)

    Ardila, Jorge Armando; Oliveira, Geiser Gabriel; Medeiros, Roberta Antigo; Fatibello-Filho, Orlando

    2014-04-07

    A highly sensitive method for bezafibrate determination using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film based on square-wave adsorptive stripping voltammetry (SWAdSV) is proposed. The electrochemical behaviour of bezafibrate has been studied by cyclic voltammetry, showing an irreversible anodic peak at a potential of 1.09 V in 0.1 mol L(-1) phosphate buffer solution (pH 2.0). A study of the scan rate showed that the oxidation of bezafibrate is an adsorptive-controlled process, involving the transfer of two electrons and two protons per molecule. The analytical curve was linear over a bezafibrate concentration range from 50 to 910 nmol L(-1), with a detection limit of 16 nmol L(-1). This analytical method was successfully applied for benzafibrate determination in pharmaceutical formulations, with results showing good agreement with those obtained using a comparative spectrophotometric method, and has the potential for field application.

  1. Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation

    International Nuclear Information System (INIS)

    Smith, Kyle K. G.; Rossky, Peter J.; Poulsen, Jens Aage; Cunsolo, A.

    2014-01-01

    The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm −3 ) and (T = 23.0 K, n = 24.61 nm −3 ), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm −1 . At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm −1 para-hydrogen provides a test case for improved approximations to quantum dynamics

  2. Hydrogen bond dynamics and water structure in glucose-water solutions by depolarized Rayleigh scattering and low-frequency Raman spectroscopy

    Science.gov (United States)

    Paolantoni, Marco; Sassi, Paola; Morresi, Assunta; Santini, Sergio

    2007-07-01

    The effect of glucose on the relaxation process of water at picosecond time scales has been investigated by depolarized Rayleigh scattering (DRS) experiments. The process is assigned to the fast hydrogen bonding dynamics of the water network. In DRS spectra this contribution can be safely separated from the slower relaxation process due to the sugar. The detected relaxation time is studied at different glucose concentrations and modeled considering bulk and hydrating water contributions. As a result, it is found that in diluted conditions the hydrogen bond lifetime of proximal water molecules becomes about three times slower than that of the bulk. The effect of the sugar on the hydrogen bond water structure is investigated by analyzing the low-frequency Raman (LFR) spectrum sensitive to intermolecular modes. The addition of glucose strongly reduces the intensity of the band at 170cm-1 assigned to a collective stretching mode of water molecules arranged in cooperative tetrahedral domains. These findings indicate that proximal water molecules partially lose the tetrahedral ordering typical of the bulk leading to the formation of high density environments around the sugar. Thus the glucose imposes a new local order among water molecules localized in its hydration shell in which the hydrogen bond breaking dynamics is sensitively retarded. This work provides new experimental evidences that support recent molecular dynamics simulation and thermodynamics results.

  3. Plasma sheath dynamics and parameters in focus and defocus conditions. Vol. 2

    International Nuclear Information System (INIS)

    Masoud, M.M.; Soliman, H.M.; El-Aragi, G.M.

    1996-01-01

    The study deals with the effect of the inner electrode polarity on the dynamic behaviour and parameters of plasma sheath in a coaxial discharge. The experimental investigations presented here were carried out in a coaxial plasma focus discharge device of mather geometry. It consisted of coaxial stainless steel hollow cylindrical electrodes with inner electrode 18.2 cm length and outer-electrode 31.5 cm length. The diameter of the inner and outer electrodes are 3.2 cm and 6.6 cm, respectively. The two electrodes are separated by a teflon disc at the breech. The outer electrode muzzle is connected to stainless steel expansion chamber of 23 cm length and 17 cm diameter. The discharge takes place in hydrogen gas with a base pressure of 1 torr. The experiments were conducted with 10 kV bank voltage, which corresponds to 100 K A peak discharge current. By using a double electric probe, It was found that the plasma electron density was higher near the negative electrode. Investigations using a miniature rogovsky coil have shown that, the radial and azimuthal current density increased with radial distance from negative electrode to positive electrode. The shape and the axial velocity of plasma sheath were measured using a magnetic probe. The experimental results indicate that, the plasma is thick near the negative electrode, in both cases of the outer or the inner electrode. Also it has been found that the axial plasma sheath velocity reaches its maximum value at the muzzle for positive and negative inner electrode. The magnitude of maximum axial velocity reaches 1.7 x 10 60 cm/s for positive inner electrode and decreased by 25% for negative inner electrode further investigations revealed that on interchanging the polarity from normal operation (positive inner electrode), it was found that with negative inner electrode the soft x-ray emission intensity dropped by three orders of magnitude from that with positive inner electrode. 9 figs

  4. Plasma sheath dynamics and parameters in focus and defocus conditions. Vol. 2

    Energy Technology Data Exchange (ETDEWEB)

    Masoud, M M; Soliman, H M; El-Aragi, G M [Plasma Physics and Nuclear Fusion Department, Nuclear Research Centre, Atomic Energy Aurhority, Cairo (Egypt)

    1996-03-01

    The study deals with the effect of the inner electrode polarity on the dynamic behaviour and parameters of plasma sheath in a coaxial discharge. The experimental investigations presented here were carried out in a coaxial plasma focus discharge device of mather geometry. It consisted of coaxial stainless steel hollow cylindrical electrodes with inner electrode 18.2 cm length and outer-electrode 31.5 cm length. The diameter of the inner and outer electrodes are 3.2 cm and 6.6 cm, respectively. The two electrodes are separated by a teflon disc at the breech. The outer electrode muzzle is connected to stainless steel expansion chamber of 23 cm length and 17 cm diameter. The discharge takes place in hydrogen gas with a base pressure of 1 torr. The experiments were conducted with 10 kV bank voltage, which corresponds to 100 K A peak discharge current. By using a double electric probe, It was found that the plasma electron density was higher near the negative electrode. Investigations using a miniature rogovsky coil have shown that, the radial and azimuthal current density increased with radial distance from negative electrode to positive electrode. The shape and the axial velocity of plasma sheath were measured using a magnetic probe. The experimental results indicate that, the plasma is thick near the negative electrode, in both cases of the outer or the inner electrode. Also it has been found that the axial plasma sheath velocity reaches its maximum value at the muzzle for positive and negative inner electrode. The magnitude of maximum axial velocity reaches 1.7 x 10{sup 60} cm/s for positive inner electrode and decreased by 25% for negative inner electrode further investigations revealed that on interchanging the polarity from normal operation (positive inner electrode), it was found that with negative inner electrode the soft x-ray emission intensity dropped by three orders of magnitude from that with positive inner electrode. 9 figs.

  5. Non-enzymatic hydrogen peroxide detection at NiO nanoporous thin film- electrodes prepared by physical vapor deposition at oblique angles

    International Nuclear Information System (INIS)

    Salazar, Pedro; Rico, Victor; González-Elipe, Agustín R.

    2017-01-01

    Highlights: • A non-enzymatic sensor for H 2 O 2 detection based on nickel thin film is reported. • Nanostructured nickel thin films are prepared by physical vapor deposition at oblique angles. • Main analytical parameters were obtained under optimal operation conditions. • Sensors depict an outstanding selectivity and a high stability. • Sensors are successfully used to determine H 2 O 2 in antiseptic solutions. - Abstract: In this work we report a non-enzymatic sensor for hydrogen peroxide (H 2 O 2 ) detection based on nanostructured nickel thin films prepared by physical vapor deposition at oblique angles. Porous thin films deposited on ITO substrates were characterized by X-ray diffraction analysis, scanning electron microcopy (SEMs), X-ray photoelectron spectroscopy (XPS) and electrochemical techniques such as Cyclic Voltammetry (CV) and Constant Potential Amperometry (CPA). The microstructure of the thin films consisted of inclined and separated Ni nanocolumns forming a porous thin layer of about 500 nm thickness. Prior to their use, the films surface was electrochemically modified and the chemical state studied by CV and XPS analysis. These techniques also showed that Ni 2+ /Ni 3+ species were involved in the electrochemical oxidation and detection of H 2 O 2 in alkaline medium. Main analytical parameters such as sensitivity (807 mA M −1 cm −2 ), limit of detection (3.22 μM) and linear range (0.011–2.4 mM) were obtained under optimal operation conditions. Sensors depicted an outstanding selectivity and a high stability and they were successfully used to determine H 2 O 2 concentration in commercial antiseptic solutions.

  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. 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.

  8. 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

  9. Molecular dynamics study of some non-hydrogen-bonding base pair DNA strands

    Science.gov (United States)

    Tiwari, Rakesh K.; Ojha, Rajendra P.; Tiwari, Gargi; Pandey, Vishnudatt; Mall, Vijaysree

    2018-05-01

    In order to elucidate the structural activity of hydrophobic modified DNA, the DMMO2-D5SICS, base pair is introduced as a constituent in different set of 12-mer and 14-mer DNA sequences for the molecular dynamics (MD) simulation in explicit water solvent. AMBER 14 force field was employed for each set of duplex during the 200ns production-dynamics simulation in orthogonal-box-water solvent by the Particle-Mesh-Ewald (PME) method in infinite periodic boundary conditions (PBC) to determine conformational parameters of the complex. The force-field parameters of modified base-pair were calculated by Gaussian-code using Hartree-Fock /ab-initio methodology. RMSD Results reveal that the conformation of the duplex is sequence dependent and the binding energy of the complex depends on the position of the modified base-pair in the nucleic acid strand. We found that non-bonding energy had a significant contribution to stabilising such type of duplex in comparison to electrostatic energy. The distortion produced within strands by such type of base-pair was local and destabilised the duplex integrity near to substitution, moreover the binding energy of duplex depends on the position of substitution of hydrophobic base-pair and the DNA sequence and strongly supports the corresponding experimental study.

  10. 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.

  11. Ultrafine hydrogen storage powders

    Science.gov (United States)

    Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

    2000-06-13

    A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

  12. A Space-Based Observational Strategy for Hydrogen Cosmology Using Dynamic Polarimetry and Pattern Recognition

    Science.gov (United States)

    Burns, Jack O.; Nhan, Bang; Bradley, Richard F.; Tauscher, Keith A.; Rapetti, David; Switzer, Eric

    2018-06-01

    The redshifted 21-cm monopole is expected to be a powerful probe of the epoch of the first stars and galaxies (10 polarimetry that separates the polarized foreground from the unpolarized 21-cm signal. Initial results from a ground-based prototype called the Cosmic Twilight Polarimeter will be described which tentatively reveal the presence of the expected polarization signature from the foreground. Dynamic polarimetry, when combined with sophisticated pattern recognition techniques based on training sets, machine learning, and statistical information criteria offer promise for precise extraction of the 21-cm spectrum. We describe a new SmallSat mission concept, the Dark Ages Polarimetry Pathfinder (DAPPer), that will utilize these novel approaches for extending the recent detection of a 78 MHz signal down to lower frequencies where we can uniquely probe evidence for the first stars and dark matter.

  13. Numerical simulation of dynamic quenching of dual-split fluorescence of molecules with intramolecular hydrogen bonds

    International Nuclear Information System (INIS)

    Morozov, V.A.; Chuvulkin, N.D.; Smolenskij, E.A.; Dubina, Yu.M.

    2014-01-01

    The dynamic quenching of intensity pulses of the dual-split fluorescence (DSF) has been simulated using numerical solutions of the equations for the population matrix of five states of the model fluorescent molecule (FM). The state with the highest energy is considered as resonantly excited by irradiation, and two other excited states populated by subsequent relaxation processes are taken as initial states for the FM transitions with emission of the DSF photons. The FM model parameters are selected to fit typical parameters of the molecules with intramolecular proton photo transfer. Quenching is considered as a consequence of non-radiative decay of the FM excited states due to collisions with the quencher molecules. Examples of two types of the DSF quenching of the FM are given. The first type leads to an intramolecular radiationless decay of particular excited states of the FM, and the second one results in radiationless transitions from the same states to the quencher molecule states. (authors)

  14. Cermet electrode

    Science.gov (United States)

    Maskalick, Nicholas J.

    1988-08-30

    Disclosed is a cermet electrode consisting of metal particles of nickel, cobalt, iron, or alloys or mixtures thereof immobilized by zirconia stabilized in cubic form which contains discrete deposits of about 0.1 to about 5% by weight of praseodymium, dysprosium, terbium, or a mixture thereof. The solid oxide electrode can be made by covering a substrate with particles of nickel, cobalt, iron, or mixtures thereof, growing a stabilized zirconia solid oxide skeleton around the particles thereby immobilizing them, contacting the skeleton with a compound of praseodymium, dysprosium, terbium, or a mixture thereof, and heating the skeleton to a temperature of at least 500.degree. C. The electrode can also be made by preparing a slurry of nickel, cobalt, iron, or mixture and a compound of praseodymium, dysprosium, terbium, or a mixture thereof, depositing the slurry on a substrate, heating the slurry to dryness, and growing a stabilized zirconia skeleton around the metal particles.

  15. Study on the fluid dynamics of nitrogen and hydrogen gases subjected to wires element in monolithic channel

    Directory of Open Access Journals (Sweden)

    Rashidi Amirah

    2017-01-01

    Full Text Available Ammonia has a very significant value in the fertilizer industry where it was being synthesized via Haber-Bosch process in the early 19th century. As the process utilize high operating conditions, it imposes high capital cost and is an energy-consuming process. Due to this unsustainable process, researchers have initiated an alternative to overcome this drawback by performing a simulation in microfluidic environment using ambient temperature and pressure (25°C and 1 atm. Wires element configured in a 50 mm x 10 mm, (L x D dimension monolithic channel with different spacing and number of wires, arranged axially in 60o pitch have been introduced to investigate the dynamic mixing of nitrogen and hydrogen for ammonia synthesis. As the wires are configured in a different manner, the results show dissimilar volume fraction profile, contours and mixing index. Creating suitable obstruction with larger obstruction space enhanced the mixing. Reducing spacing from 2 mm to 1.5 mm illustrates fluctuating velocity at the centre of the channel causing the flow velocity become less than the set velocity 0.05ms-1. By substituting from 19 wires to 13 wires to the flow, chaotic advection occurs lead to the increased of mixing index up to 94%.

  16. Dual-level direct dynamics studies for the hydrogen abstraction reaction of 1,1-difluoroethane with O( 3P)

    Science.gov (United States)

    Liu, Jing-yao; Li, Ze-sheng; Dai, Zhen-wen; Zhang, Gang; Sun, Chia-chung

    2004-01-01

    We present dual-level direct dynamics calculations for the CH 3CHF 2 + O( 3P) hydrogen abstraction reaction in a wide temperature range, based on canonical variational transition-state theory including small curvature tunneling corrections. For this reaction, three distinct transition states, one for α-abstraction and two for β-abstraction, have been located. The potential energy surface information is obtained at the MP2(full)/6-311G(d,p) level of theory, and higher-level single-point calculations for the stationary points are preformed at several levels, namely QCISD(T)/6-311+G(3df,3pd), G2, and G3 using the MP2 geometries, as well as at the G3//MP4SDQ/6-311G(d,p) level. The energy profiles are further refined with the interpolated single-point energies method at the G3//MP2(full)/6-311G(d,p) level. The total rate constants match the experimental data reasonable well in the measured temperature range 1110-1340 K. It is shown that at low temperature α-abstraction may be the major reaction channel, while β-abstraction will have more contribution to the whole reaction rate as the temperature increases.

  17. 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.

  18. Dynamical screening of AMM and QED effects for large- Z hydrogen-like atoms

    Science.gov (United States)

    Roenko, A. A.; Sveshnikov, K. A.

    2018-01-01

    The effective interaction Δ U AMM of the anomalous magnetic moment (AMM) of an electron with the Coulomb field of an extended nucleus is analyzed. As soon as the q 2 dependence of the electron formfactor F 2( q 2)is taken into account from the beginning, the AMM is found to be dynamically screened at small distances of r ≪ 1/ m. The Δ U AMM effects on the low-lying electronic levels of a superheavy extended nucleus with Zα > 1are analyzed using the nonperturbative approach. The growth rate of the Δ U AMM contribution with increasing Z is shown to be essentially nonmonotonic. At the same time, the energy shifts of electronic levels in the vicinity of the threshold of the lower continuum monotonically decrease in the region Z ≫ Z cr,1 s . The latter result is generalized to the whole self-energy contribution to energy shifts of electronic levels, thus also referring to the possible behavior of QED radiative effects with virtual-photon exchange, considered beyond the framework of the perturbative expansion in Zα.

  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 permitting the filling station and conducting this workshop provided a basis for future hydrogen projects in the region. Continuing efforts to increase the working pressure of electrolysis and efficiency have been pursued. Research was also performed on improving the cost, efficiency and durability of Proton Exchange Membrane (PEM) hydrogen technology. Research elements focused upon PEM membranes, electrodes/catalysts, membrane-electrode assemblies, seals, bipolar plates, utilization of renewable power, reliability issues, scale, and advanced conversion topics. Additionally, direct solar-to-hydrogen conversion research to demonstrate stable and efficient photoelectrochemistry (PEC) hydrogen production systems based on a number of optional concepts was performed. Candidate PEC concepts included technical obstacles such as inefficient photocatalysis, inadequate photocurrent due to non-optimal material band gap energies, rapid electron-hole recombination, reduced hole mobility and diminished operational lifetimes of surface materials exposed to electrolytes. Project Objective 1: Design, build, operate hydrogen filling station Project Objective 2: Perform research and development for utilizing solar technologies on the hydrogen filling station and convert two utility vehicles for use by the station operators Project Objective 3: Increase capacity of hydrogen filling station; add additional vehicle; conduct safety workshop; develop a roadmap for

  20. Dramatic effect of pore size reduction on the dynamics of hydrogen adsorbed in metal–organic materials

    KAUST Repository

    Nugent, Patrick

    2014-07-21

    The effects of pore size reduction on the dynamics of hydrogen sorption in metal-organic materials (MOMs) were elucidated by studying SIFSIX-2-Cu and its doubly interpenetrated polymorph SIFSIX-2-Cu-i by means of sorption, inelastic neutron scattering (INS), and computational modeling. SIFSIX-2-Cu-i exhibits much smaller pore sizes, which possess high H2 sorption affinity at low loadings. Experimental H2 sorption measurements revealed that the isosteric heat of adsorption (Qst) for H2 in SIFSIX-2-Cu-i is nearly two times higher than that for SIFSIX-2-Cu (8.6 vs. 4.6 kJ mol-1). The INS spectrum for H2 in SIFSIX-2-Cu-i is rather unique for a porous material, as only one broad peak appears at low energies near 6 meV, which simply increases in intensity with loading until the pores are filled. The value for this rotational transition is lower than that in most neutral metal-organic frameworks (MOFs), including those with open Cu sites (8-9 meV), which is indicative of a higher barrier to rotation and stronger interaction in the channels of SIFSIX-2-Cu-i than the open Cu sites in MOFs. Simulations of H2 sorption in SIFSIX-2-Cu-i revealed two hydrogen sorption sites in the MOM: direct interaction with the equatorial fluorine atom (site 1) and between two equatorial fluorine atoms on opposite walls (site 2). The calculated rotational energy levels and rotational barriers for the two sites in SIFSIX-2-Cu-i are in good agreement with INS data. Furthermore, the rotational barriers and binding energies for site 2 are slightly higher than that for site 1, which is consistent with INS results. The lowest calculated transition for the primary site in SIFSIX-2-Cu is also in good agreement with INS data. In addition, this transition in the non-interpenetrating material is higher than any of the sites in SIFSIX-2-Cu-i, which indicates a significantly weaker interaction with the host as a result of the larger pore size. This journal is © the Partner Organisations 2014.

  1. Magnetohydrodynamic electrode

    International Nuclear Information System (INIS)

    1980-01-01

    The object of the invention is the provision of a material capable of withstanding a high-temperature, corrosive and erosive environment for use as a ceramic-metal composite electrode current collector in the channel of a magnetohydrodynamic generator. (U.K.)

  2. Effect of the La/Mg ratio on the structure and electrochemical properties of La xMg 3- xNi 9 ( x=1.6-2.2) hydrogen storage electrode alloys for nickel-metal hydride batteries

    Science.gov (United States)

    Liao, B.; Lei, Y. Q.; Chen, L. X.; Lu, G. L.; Pan, H. G.; Wang, Q. D.

    Effect of La/Mg ratio on the structure and electrochemical properties of La xMg 3- xNi 9 ( x=1.6-2.2) ternary alloys was investigated. All alloys are consisted of a main phase with hexagonal PuNi 3-type structure and a few impurity phases (mainly LaNi 5 and MgNi 2). The increase of La/Mg ratio in the alloys leads to an increase in both the cell volume and the hydride stability. The discharge capacity of the alloys at 100 mA/g increases with the increase of La/Mg ratio and passes though a maximum of 397.5 mAh/g at x=2.0. As the La/Mg ratio increases, the high-rate dischargeability of the alloy electrodes at 1200 mA/g HRD 1200 decreases from 66.7% ( x=1.6) to 26.5% ( x=2.2). The slower decrease of HRD 1200 (from 66.7 to 52.7%) of the alloys with x=1.6-2.0 is mainly attributed to the decrease of electrocatalytic activity of the alloys for charge-transfer reaction, the more rapid decrease of HRD 1200 of the alloys with x>2.0 is mainly attributed to the lowering of the hydrogen diffusion rate in the bulk of alloy. The cycling capacity degradation of the alloys is rather fast for practical application due to the corrosion of La and Mg and the large VH in the hydride phase.

  3. Hydrogen energy

    International Nuclear Information System (INIS)

    2005-03-01

    This book consists of seven chapters, which deals with hydrogen energy with discover and using of hydrogen, Korean plan for hydrogen economy and background, manufacturing technique on hydrogen like classification and hydrogen manufacture by water splitting, hydrogen storage technique with need and method, hydrogen using technique like fuel cell, hydrogen engine, international trend on involving hydrogen economy, technical current for infrastructure such as hydrogen station and price, regulation, standard, prospect and education for hydrogen safety and system. It has an appendix on related organization with hydrogen and fuel cell.

  4. Bridging the European Wind Energy Market and a Future Renewable Hydrogen-Inclusive Economy. A Dynamic Techno-economic Assessment

    International Nuclear Information System (INIS)

    Shaw, S.; Peteves, S.D.

    2006-01-01

    The study establishes the link between the growing wind market and the emerging hydrogen market of the European Union, in a so-called 'wind-hydrogen strategy'. It considers specifically the diversion of wind electricity, as a wind power control mechanism in high wind penetration situations, for the production of renewable electrolytic hydrogen - a potentially important component of a renewable hydrogen-inclusive economy. The analysis examines the long-term competitiveness of a wind-hydrogen strategy via cost-benefit assessment. It indicates the duration and extent to which (financial) support, if any, would need to be provided in support of such a strategy, and the influence over time of certain key factors on the outcome

  5. Electrode Processes in Porous Electrodes.

    Science.gov (United States)

    1985-11-26

    F104470 2.0 MASS SPECTROMETRY One part of activity for this year is an investigation of the behavior of silver electrodes through the distribution of...al. (2)). These, in some cases, involve tedious and time comsuming procedures and discrepencies of as much as 15% have been observed in the results. As

  6. Probing the importance of hydrogen bonds in the active site of the subtilisin nattokinase by site-directed mutagenesis and molecular dynamics simulation.

    Science.gov (United States)

    Zheng, Zhong-liang; Ye, Mao-qing; Zuo, Zhen-yu; Liu, Zhi-gang; Tai, Keng-chang; Zou, Guo-lin

    2006-05-01

    Hydrogen bonds occurring in the catalytic triad (Asp32, His64 and Ser221) and the oxyanion hole (Asn155) are very important to the catalysis of peptide bond hydrolysis by serine proteases. For the subtilisin NK (nattokinase), a bacterial serine protease, construction and analysis of a three-dimensional structural model suggested that several hydrogen bonds formed by four residues function to stabilize the transition state of the hydrolysis reaction. These four residues are Ser33, Asp60, Ser62 and Thr220. In order to remove the effect of these hydrogen bonds, four mutants (Ser33-->Ala33, Asp60-->Ala60, Ser62-->Ala62, and Thr220-->Ala220) were constructed by site-directed mutagenesis. The results of enzyme kinetics indicated that removal of these hydrogen bonds increases the free-energy of the transition state (DeltaDeltaG(T)). We concluded that these hydrogen bonds are more important for catalysis than for binding the substrate, because removal of these bonds mainly affects the kcat but not the K(m) values. A substrate, SUB1 (succinyl-Ala-Ala-Pro-Phe-p-nitroanilide), was used during enzyme kinetics experiments. In the present study we have also shown the results of FEP (free-energy perturbation) calculations with regard to the binding and catalysis reactions for these mutant subtilisins. The calculated difference in FEP also suggested that these four residues are more important for catalysis than binding of the substrate, and the simulated values compared well with the experimental values from enzyme kinetics. The results of MD (molecular dynamics) simulations further demonstrated that removal of these hydrogen bonds partially releases Asp32, His64 and Asn155 so that the stability of the transition state decreases. Another substrate, SUB2 (H-D-Val-Leu-Lys-p-nitroanilide), was used for FEP calculations and MD simulations.

  7. Hydrogen atom model for nucleon and pion

    International Nuclear Information System (INIS)

    Baiquni, A.

    1976-01-01

    Discussion on Dion as double charge particle, covering that on semi classical model, proton Dionium model consequence, symmetry group in hydrogen, hydrogen atom dynamic group, and discussion on relativistic dynamic group, covering relativistic equation for hydrogen, operator extension of SO(4, 2), application of SO(4,2)O SO(4,2), and hydrogen complete equation, are given. (author)

  8. Lactose Binding Induces Opposing Dynamics Changes in Human Galectins Revealed by NMR-Based Hydrogen-Deuterium Exchange.

    Science.gov (United States)

    Chien, Chih-Ta Henry; Ho, Meng-Ru; Lin, Chung-Hung; Hsu, Shang-Te Danny

    2017-08-16

    Galectins are β-galactoside-binding proteins implicated in a myriad of biological functions. Despite their highly conserved carbohydrate binding motifs with essentially identical structures, their affinities for lactose, a common galectin inhibitor, vary significantly. Here, we aimed to examine the molecular basis of differential lactose affinities amongst galectins using solution-based techniques. Consistent dissociation constants of lactose binding were derived from nuclear magnetic resonance (NMR) spectroscopy, intrinsic tryptophan fluorescence, isothermal titration calorimetry and bio-layer interferometry for human galectin-1 (hGal1), galectin-7 (hGal7), and the N-terminal and C-terminal domains of galectin-8 (hGal8 NTD and hGal8 CTD , respectively). Furthermore, the dissociation rates of lactose binding were extracted from NMR lineshape analyses. Structural mapping of chemical shift perturbations revealed long-range perturbations upon lactose binding for hGal1 and hGal8 NTD . We further demonstrated using the NMR-based hydrogen-deuterium exchange (HDX) that lactose binding increases the exchange rates of residues located on the opposite side of the ligand-binding pocket for hGal1 and hGal8 NTD , indicative of allostery. Additionally, lactose binding induces significant stabilisation of hGal8 CTD across the entire domain. Our results suggested that lactose binding reduced the internal dynamics of hGal8 CTD on a very slow timescale (minutes and slower) at the expense of reduced binding affinity due to the unfavourable loss of conformational entropy.

  9. Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

    International Nuclear Information System (INIS)

    Briere, M.A.

    1993-07-01

    Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

  10. Effect of temperature on compact layer of Pt electrode in PEMFCs by first-principles molecular dynamics calculations

    Energy Technology Data Exchange (ETDEWEB)

    He, Yang [Department of Materials Science and Engineering, China University of Petroleum (Beijing), Beijing 102249 (China); Beijing Key Laboratory of Failure, Corrosion and Protection of Oil/gas Facilities, China University of Petroleum (Beijing), Beijing 102249 (China); Chen, Changfeng, E-mail: chen_c_f@163.com [Department of Materials Science and Engineering, China University of Petroleum (Beijing), Beijing 102249 (China); Beijing Key Laboratory of Failure, Corrosion and Protection of Oil/gas Facilities, China University of Petroleum (Beijing), Beijing 102249 (China); Yu, Haobo [Department of Materials Science and Engineering, China University of Petroleum (Beijing), Beijing 102249 (China); Beijing Key Laboratory of Failure, Corrosion and Protection of Oil/gas Facilities, China University of Petroleum (Beijing), Beijing 102249 (China); Lu, Guiwu [Department of Materials Science and Engineering, China University of Petroleum (Beijing), Beijing 102249 (China)

    2017-01-15

    Highlights: • The structures of water compact layer on Pt(111) at different temperature were calculated. • The feature of chemical bond between water molecules and Pt (111) surface was discussed with temperature increased. • Temperature dependence of electrical strengths and capacitances of compact layer on Pt (111) surface was calculated. - Abstract: Formation of the double-layer electric field and capacitance of the water-metal interface is of significant interest in physicochemical processes. In this study, we perform first- principles molecular dynamics simulations on the water/Pt(111) interface to investigate the temperature dependence of the compact layer electric field and capacitance based on the calculated charge densities. On the Pt (111) surface, water molecules form ice-like structures that exhibit more disorder along the height direction with increasing temperature. The O−H bonds of more water molecules point toward the Pt surface to form Pt−H covalent bonds with increasing temperature, which weaken the corresponding O−H bonds. In addition, our calculated capacitance at 300 K is 15.2 mF/cm{sup 2}, which is in good agreement with the experimental results. As the temperature increases from 10 to 450 K, the field strength and capacitance of the compact layer on Pt (111) first increase and then decrease slightly, which is significant for understanding the water/Pt interface from atomic level.

  11. The description of dense hydrogen with Wave Packet Molecular Dynamics (WPMD) simulations; Die Beschreibung von dichtem Wasserstoff mit der Methode der Wellenpaket-Molekulardynamik (WPMD)

    Energy Technology Data Exchange (ETDEWEB)

    Jakob, B.

    2006-10-10

    In this work the wave packet molecular dynamics (WPMD) is presented and applied to dense hydrogen. In the WPMD method the electrons are described by a slater determinant of periodic Gaussian wave packets. Each single particle wave function can parametrised through 8 coordinates which can be interpreted as the position and momentum, the width and its conjugate momentum. The equation of motion for these coordinates can be derived from a time depended variational principle. Properties of the equilibrium can be ascertained by a Monte Carlo simulation. With the now completely implemented antisymmetrisation the simulation yields a fundamental different behavior for dense hydrogen compare to earlier simplified models. The results show a phase transition to metallic hydrogen with a higher density than in the molecular phase. This behavior has e.g. a large implication to the physics of giant planets. This work describes the used model and explains in particular the calculation of the energy and forces. The periodicity of the wave function leads to a description in the Fourier space. The antisymmetrisation is done by Matrix operations. Moreover the numerical implementation is described in detail to allow the further development of the code. The results provided in this work show the equation of state in the temperature range 300K - 50000K an density 10{sup 23}-10{sup 24} cm{sup -3}, according a pressure 1 GPa-1000 GPa. In a phase diagram the phase transition to metallic hydrogen can be red off. The electrical conductivity of both phases is destined. (orig.)

  12. Study of hydrogen-molecule guests in type II clathrate hydrates using a force-matched potential model parameterised from ab initio molecular dynamics

    Science.gov (United States)

    Burnham, Christian J.; Futera, Zdenek; English, Niall J.

    2018-03-01

    The force-matching method has been applied to parameterise an empirical potential model for water-water and water-hydrogen intermolecular interactions for use in clathrate-hydrate simulations containing hydrogen guest molecules. The underlying reference simulations constituted ab initio molecular dynamics (AIMD) of clathrate hydrates with various occupations of hydrogen-molecule guests. It is shown that the resultant model is able to reproduce AIMD-derived free-energy curves for the movement of a tagged hydrogen molecule between the water cages that make up the clathrate, thus giving us confidence in the model. Furthermore, with the aid of an umbrella-sampling algorithm, we calculate barrier heights for the force-matched model, yielding the free-energy barrier for a tagged molecule to move between cages. The barrier heights are reasonably large, being on the order of 30 kJ/mol, and are consistent with our previous studies with empirical models [C. J. Burnham and N. J. English, J. Phys. Chem. C 120, 16561 (2016) and C. J. Burnham et al., Phys. Chem. Chem. Phys. 19, 717 (2017)]. Our results are in opposition to the literature, which claims that this system may have very low barrier heights. We also compare results to that using the more ad hoc empirical model of Alavi et al. [J. Chem. Phys. 123, 024507 (2005)] and find that this model does very well when judged against the force-matched and ab initio simulation data.

  13. Dynamics of hydrogen induced blistering of a low carbon steel sheet by lamb waves analysis; Ramuha no teiryo kaiseki ni yoru hakubanteitansoko no suiso hare no dainamikkusu

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Teruyoshi.; Takemoto, Mikio. [Aoyama Gakuin University, Tokyo (Japan). Faculty of Science and Engineering

    1999-06-15

    With the aim of studying the fracture dynamics of environmentally assisted fractures in thin plates, we developed a new source simulation method of the zeroth-order symmetric (or S{sub 0}-) Lamb wave using the experimental overall-transfer function of the system. The transfer function was determined by the time-domain deconvolution of detected S{sub 0}-Lamb component by the artificial fracture source of a compression -type PZT element whose vibration kinetics was estimated by the iteration so that the S{sub o}-waveform detected. Hydrogen induced blistering was found to be caused by the succession of fast Mode-I fracture with source rise times from 0.6 to 1.0{mu}s. The crack volume estimated by the source simulation corresponded to that of fine blistering with an opening displacement of 5{mu}m. As the estimated fracture kinetics of hydrogen blistering coincide with those of delayed fracture of high tension low alloy steel under tensile loading, the kinetics of first and micro-fractures and blistering induced by hydrogen gas precipitation appears to be independent on the hydrogen solubility and strength of steels, the applied stresses and the orientation of cracks. (author)

  14. On the room-temperature phase diagram of high pressure hydrogen: An ab initio molecular dynamics perspective and a diffusion Monte Carlo study

    International Nuclear Information System (INIS)

    Chen, Ji; Ren, Xinguo; Li, Xin-Zheng; Alfè, Dario; Wang, Enge

    2014-01-01

    The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results

  15. A survey of reference electrodes for high temperature waters; Oeversikt av referenselektroder i hoegtemperaturvatten

    Energy Technology Data Exchange (ETDEWEB)

    Molander, A.; Eriksson, Sture; Pein, K. [Studsvik Nuclear, Nykoeping (Sweden)

    2000-11-01

    In nuclear power plants, corrosion potential measurements are used to follow the conditions for different corrosion types in reactor systems, particularly IGSCC in BWRs. The goal of this work has been to give a survey of reference electrodes for high temperature water, both those that are used for nuclear environments and those that are judged to possible future development. The reference electrodes that are used today in nuclear power plants for corrosion potential measurements are of three types. Silver chloride electrodes, membrane electrodes and platinum electrodes (hydrogen electrodes). The principals for their function is described as well as the conversion of measured potentials to the SHE scale (Standard Hydrogen Electrode). Silver chloride electrodes consist of an inner reference system of silver chloride in equilibrium with a chloride solution. The silver chloride electrode is the most common reference electrode and can be used in several different systems. Platinum electrodes are usually more robust and are particularly suitable to use in BWR environment to follow the hydrogen dosage, but have limitations at low and no hydrogen dosage. Ceramic membrane electrodes can be with different types of internal reference system. They were originally developed for pH measurements in high temperature water. If pH is constant, the membrane electrode can be used as reference electrode. A survey of ceramic reference electrodes for high temperature water is given. A ceramic membrane of the type used works as an oxygen conductor, so the potential and pH in surrounding medium is in equilibrium with the internal reference system. A survey of the lately development of electrodes is presented in order to explain why the different types of electrodes are developed as well as to give a background to the possibilities and limitations with the different electrodes. Possibilities of future development of electrodes are also given. For measurements at low or no hydrogen dosage

  16. Hydrogen isotope dynamic effects on partially reduced paramagnetic six-atom Ag clusters in low-symmetry cage of zeolite A

    Directory of Open Access Journals (Sweden)

    Amgalanbaatar Baldansuren

    2016-12-01

    Full Text Available A well-defined, monodisperse Ag6+ cluster was prepared by mild chemical treatments including aqueous ion-exchange, dehydration, oxygen calcination at 673 K and hydrogen reduction 293 K, rather than autoreduction and irradiations with γ-ray and X-ray. H2 reduction was proved as a crucial step to form the nanosize cluster with six equivalent silver atoms. Hydrogen isotope exchange and dynamics were probed by EPR and HYSCORE to provide information relevant to the cluster geometry, size, charge state and spin state. Desorption experiments result in the deuterium desorption energy of 0.78 eV from the cluster, exceeding the experimental value of 0.38 eV for the single crystal Ag(111 surface. These experiments indicate that the EPR-active clusters are in delicate equilibrium with EPR-silent clusters.

  17. Electrocatalysts for hydrogen energy

    CERN Document Server

    Losiewicz, Bozena

    2015-01-01

    This special topic volume deals with the development of novel solid state electrocatalysts of a high performance to enhance the rates of the hydrogen or oxygen evolution. It contains a description of various types of metals, alloys and composites which have been obtained using electrodeposition in aqueous solutions that has been identified to be a technologically feasible and economically superior technique for the production of the porous electrodes. The goal was to produce papers that would be useful to both the novice and the expert in hydrogen technologies. This volume is intended to be us

  18. Hydrogen exchange mass spectrometry of bacteriorhodopsin reveals light-induced changes in the structural dynamics of a biomolecular machine.

    Science.gov (United States)

    Pan, Yan; Brown, Leonid; Konermann, Lars

    2011-12-21

    Many proteins act as molecular machines that are fuelled by a nonthermal energy source. Examples include transmembrane pumps and stator-rotor complexes. These systems undergo cyclic motions (CMs) that are being driven along a well-defined conformational trajectory. Superimposed on these CMs are thermal fluctuations (TFs) that are coupled to stochastic motions of the solvent. Here we explore whether the TFs of a molecular machine are affected by the occurrence of CMs. Bacteriorhodopsin (BR) is a light-driven proton pump that serves as a model system in this study. The function of BR is based on a photocycle that involves trans/cis isomerization of a retinal chromophore, as well as motions of transmembrane helices. Hydrogen/deuterium exchange (HDX) mass spectrometry was used to monitor the TFs of BR, focusing on the monomeric form of the protein. Comparative HDX studies were conducted under illumination and in the dark. The HDX kinetics of BR are dramatically accelerated in the presence of light. The isotope exchange rates and the number of backbone amides involved in EX2 opening transitions increase roughly 2-fold upon illumination. In contrast, light/dark control experiments on retinal-free protein produced no discernible differences. It can be concluded that the extent of TFs in BR strongly depends on photon-driven CMs. The light-induced differences in HDX behavior are ascribed to protein destabilization. Specifically, the thermodynamic stability of the dark-adapted protein is estimated to be 5.5 kJ mol(-1) under the conditions of our work. This value represents the free energy difference between the folded state F and a significantly unfolded conformer U. Illumination reduces the stability of F by 2.2 kJ mol(-1). Mechanical agitation caused by isomerization of the chromophore is transferred to the surrounding protein scaffold, and subsequently, the energy dissipates into the solvent. Light-induced retinal motions therefore act analogously to an internal heat

  19. From solar energy to hydrogen via magnesium: a challenging approach

    International Nuclear Information System (INIS)

    Abdel-Aal, H.K.

    2006-01-01

    In the proposed scheme, solar energy is used first to vaporize a dynamic stream of sea water flowing along an inclined Preferential Salt Separator (P S S). Magnesium chloride salts - soluble in seawater - will separate as end products. Once obtained, anhydrous magnesium chloride is to be electrolysed to produce magnesium metal, a reliable source of stored energy. When shipped to remote locations, it is used as electrode to construct a 'galvanic - electrolytic' cell, in which water is electrolysed producing hydrogen as end product. Small scale experimental results are presented. Reference to the work reported by Pacheco is made. (authors)

  20. Capacitance enhancement via electrode patterning

    International Nuclear Information System (INIS)

    Ho, Tuan A.; Striolo, Alberto

    2013-01-01

    The necessity of increasing the energy density in electric double layer capacitors to meet current demand is fueling fundamental and applied research alike. We report here molecular dynamics simulation results for aqueous electrolytes near model electrodes. Particular focus is on the effect of electrode patterning on the structure of interfacial electrolytes, and on the potential drop between the solid electrodes and the bulk electrolytes. The latter is estimated by numerically integrating the Poisson equation using the charge densities due to water and ions accumulated near the interface as input. We considered uniform and patterned electrodes, both positively and negatively charged. The uniformly charged electrodes are modeled as graphite. The patterned ones are obtained by removing carbon atoms from the top-most graphene layer, yielding nanoscopic squares and stripes patterns. For simplicity, the patterned electrodes are effectively simulated as insulators (the charge remains localized on the top-most layer of carbon atoms). Our simulations show that the patterns alter the structure of water and the accumulation of ions at the liquid-solid interfaces. Using aqueous NaCl solutions, we found that while the capacitance calculated for three positively charged electrodes did not change much, that calculated for the negatively charged electrodes significantly increased upon patterning. We find that both water structure and orientation, as well as ion accumulation affect the capacitance. As electrode patterning affects differently water structure and ion accumulation, it might be possible to observe ion-specific effects. These results could be useful for advancing our understanding of electric double layer capacitors, capacitive desalination processes, as well as of fundamental interfacial electrolytes properties