Sample records for electrocatalytic hydrogen oxidation
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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.
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Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators
Badalyan, Artavazd; Stahl, Shannon S.
2016-07-01
The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how
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Energy Technology Data Exchange (ETDEWEB)
Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Akhtari, Keivan [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); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [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); Soltanian, Saied [Department of Physics, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)
2013-07-01
Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO{sub 3}){sub 2}, (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H{sub 2}O{sub 2} and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic
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International Nuclear Information System (INIS)
Hallaj, Rahman; Akhtari, Keivan; Salimi, Abdollah; Soltanian, Saied
2013-01-01
Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO 3 ) 2 , (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H 2 O 2 and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic activity decreased
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International Nuclear Information System (INIS)
Ahmed, Jahangeer; Mao, Yuanbing
2016-01-01
Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.
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Energy Technology Data Exchange (ETDEWEB)
Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.
2018-04-24
A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.
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International Nuclear Information System (INIS)
Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis
2015-01-01
Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.
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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.
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Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe
2014-01-01
The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.
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International Nuclear Information System (INIS)
Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D.
2012-01-01
This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal–oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.
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Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D
2012-11-01
This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.
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Sauter, Waldemar; Bergmann, Olaf L; Schröder, Uwe
2017-08-10
Here, we propose the use of hydroxyacetone, a dehydration product of glycerol, as a platform for the electrocatalytic synthesis of acetone, 1,2-propanediol, and 2-propanol. 11 non-noble metals were investigated as electrode materials in combination with three different electrolyte compositions toward the selectivity, Coulombic efficiency (CE), and reaction rates of the electrocatalytic hydrogenation (formation of 1,2-propanediol) and hydrodeoxygenation (formation of acetone and propanol) of hydroxyacetone. With a selectivity of 84.5 %, a reaction rate of 782 mmol h -1 m -2 and a CE of 32 % (for 0.09 m hydroxyacetone), iron electrodes, in a chloride electrolyte, yielded the best 1,2 propanediol formation. A further enhancement of the performance can be achieved upon increasing the educt concentration to 0.5 m, yielding a reaction rate of 2248.1 mmol h -1 m -2 and a CE of 64.5 %. Acetone formation was optimal at copper and lead electrodes in chloride solution, with lead showing the lowest tendency of side product formation. 2-propanol formation can be achieved using a consecutive oxidation of the formed acetone (at iron electrodes). 1-propanol formation was observed only in traces. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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International Nuclear Information System (INIS)
Santos, D.M.F.; Šljukić, B.; Sequeira, C.A.C.; Macciò, D.; Saccone, A.; Figueiredo, J.L.
2013-01-01
Development of electrocatalytic materials for the hydrogen evolution reaction (HER) is attempted with the aim of reducing the water electrolysis overpotential and increasing its efficiency. Using linear scan voltammetry measurements of the hydrogen discharge enables evaluation of the electrocatalytic activity for the HER of platinum–dysprosium (Pt–Dy) intermetallic alloy electrodes of different compositions. Understanding of materials electrocatalytic performance is based on determination of several crucial kinetic parameters, including the Tafel coefficients, b, charge transfer coefficients, α, exchange current densities, j 0 , and activation energies, E a . Influence of temperature on HER is investigated by performing studies at temperatures ranging from 25 °C to 85 °C. The effect of the Dy amount in the efficiency of the HER on the Pt–Dy alloys is analysed. Results demonstrate that Dy can substantially increase the electrocatalytic activity of the Pt alloys, in comparison to the single Pt electrode. Efforts are made to correlate the microstructure of the alloys with their performance towards the HER. - Highlights: ► Development of electrocatalysts to increase efficiency of electrolytic hydrogen production. ► Synthesis and evaluation of composition and morphology of platinum–dysprosium (Pt–Dy) alloys. ► Hydrogen evolution reaction on Pt–Dy alloys electrodes studied using linear scan voltammetry in alkaline medium. ► Pt–Dy alloy with equiatomic composition enhances kinetics of hydrogen discharge compared to single Pt
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Electrocatalytic hydrogenation of organic molecules on conductive new catalytic material
Energy Technology Data Exchange (ETDEWEB)
Tountian, D. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide; Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Brisach-Wittmeyer, A.; Menard, H. [Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Nkeng, P.; Poillerat, G. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide
2008-07-01
Electrocatalytic hydrogenation (ECH) of organic molecules is a process where chemisorbed hydrogen is produced by electroreduction of water which reacts with the species in bulk. Greater emphasis is being placed on improving the nature of the building material of the electrodes in order to increase ECH efficiency. The effectiveness of the ECH is known to be linked to the nature of electrode materials used and their adsorption properties. This work presented the effect of conductive support material on ECH. The conductive catalysts were obtained from tin dioxide which is chemically stable. Palladium was the catalytic metal used in this study. The production of chemisorbed hydrogen was shown to depend on the quantity of metallic nanoaggregates in electrical contact with the reticulated vitreous carbon use as electrode. The conductive support, F-doped tin dioxide, was obtained by the sol-gel method. The electrocatalysts were characterized by different methods as resistivity measurements, linear sweep voltammetry, XRD, SEM, TGA/DSC, and FTIR analysis. The effects of temperature and time of calcination were also investigated. The study showed that the F-doped SnO2 electrocatalyst appeared to increase the rate of phenol electrohydrogenation. It was concluded that the improved electrocatalytic activity of Pd/F-doped SnO2 can be attributed to the simultaneous polarization of all the metallic Pd nanoaggregates present on the surface as well as in the pores of the matrix by contact with RVC. This results in a better production of chemisorbed atomic hydrogen with a large number of adlienation points. 9 refs., 3 figs.
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Electro-catalytic oxidation of reactive Orange 107 using cerium doped oxides of Nd3+ nanoparticle
International Nuclear Information System (INIS)
Rajkumar, K.; Muthukumar, M.; Mangalaraja, R.V.
2011-01-01
A new rare earth doped cerium oxide powder was used as a catalyst to investigate the removal of colour and TOC from simulated wastewater of Reactive Orange 107. The electro oxidation process was carried out in the reactor in presence of an electrolyte NaCl. Graphite electrode was used as anode and cathode and electrolysis were carried out at a current density of 34.96 mAcm -2 with a catalyst concentration of 0.05g L -1 . In order to find the efficiency of nanocatalyst, experiments were also conducted without catalyst. From the experiment, it was found that complete colour removal was achieved on electrocatalytic oxidation as well as electro oxidation. When comparing the above processes, catalytic oxidation shows more efficient than electro oxidation. With respect to the degradation of the dye, catalytic oxidation shows more TOC removal than the oxidation taken place without catalyst. It infers that even though the electro-catalytic oxidation process achieves complete decolouration but it does not achieve complete mineralisation. The FTIR and GCMS studies confirmed the formation of by-products. (author)
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Tan, Xin; Tahini, Hassan A; Smith, Sean C
2016-12-07
Electrocatalytic, switchable hydrogen storage promises both tunable kinetics and facile reversibility without the need for specific catalysts. The feasibility of this approach relies on having materials that are easy to synthesize, possessing good electrical conductivities. Graphitic carbon nitride (g-C 4 N 3 ) has been predicted to display charge-responsive binding with molecular hydrogen-the only such conductive sorbent material that has been discovered to date. As yet, however, this conductive variant of graphitic carbon nitride is not readily synthesized by scalable methods. Here, we examine the possibility of conductive and easily synthesized boron-doped graphene nanosheets (B-doped graphene) as sorbent materials for practical applications of electrocatalytically switchable hydrogen storage. Using first-principle calculations, we find that the adsorption energy of H 2 molecules on B-doped graphene can be dramatically enhanced by removing electrons from and thereby positively charging the adsorbent. Thus, by controlling charge injected or depleted from the adsorbent, one can effectively tune the storage/release processes which occur spontaneously without any energy barriers. At full hydrogen coverage, the positively charged BC 5 achieves high storage capacities up to 5.3 wt %. Importantly, B-doped graphene, such as BC 49 , BC 7 , and BC 5 , have good electrical conductivity and can be easily synthesized by scalable methods, which positions this class of material as a very good candidate for charge injection/release. These predictions pave the route for practical implementation of electrocatalytic systems with switchable storage/release capacities that offer high capacity for hydrogen storage.
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Energy Technology Data Exchange (ETDEWEB)
Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)
2006-07-01
This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.
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International Nuclear Information System (INIS)
Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong
2015-01-01
A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.
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Zhang, Xiahong; Wu, Genghuang; Cai, Zhixiong; Chen, Xi
2015-03-01
In this study, a facile hydrothermal method was developed to synthesize Pt-on-Pd supported on reduced graphene oxide (Pt-on-Pd/RGO) hybrids. Because of the synergistic effect between Pt-on-Pd and RGO, the obtained Pt-on-Pd/RGO had superior peroxidase-mimic activities in H2O2 reduction and TMB oxidation. The reaction medium was optimized and a sensing approach for H2O2 was developed with a linear range from 0.98 to 130.7 μM of H2O2. In addition, the characteristic of electrocatalytic oxidation of methanol was investigated. The peak current density value, j(f), for the Pt-on-Pd/RGO hybrid (328 mA mg(Pt)(-1)) was about 1.85 fold higher than that of commercial Pt black (177 mA mg(Pt)(-1)) and, also, more durable electrocatalytic activity could be obtained. For the first time, the dual-functional Pt-on-Pd/RGO with peroxidase-mimic activity and an enhanced electrocatalytic oxidation characteristic was reported. Copyright © 2014 Elsevier B.V. All rights reserved.
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Jin, Zhaoyu; Li, Panpan; Xiao, Dan
2017-02-08
Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Electrocatalytic aerobic epoxidation of alkenes: Experimental and DFT investigation
International Nuclear Information System (INIS)
Magdesieva, Tatiana V.; Borisova, Nataliya E.; Dolganov, Alexander V.; Ustynyuk, Yuri A.
2012-01-01
A new method for electrocatalytic aerobic epoxidation of alkenes catalyzed by binuclear Cu(II) complexes with azomethine ligands based on 2,6-diformyl-4-tert-butylphenol is described. In acetonitrile–water (5%), at the potential of Cu II /Cu I redox couple (–0.8 V vs. Ag/AgCl/KCl) at room temperature the epoxide is obtained in an average yield of around 50%. Contrary to the majority of known epoxidations, no strong oxidants are involved and no free hydrogen peroxide is formed in the reaction, thus making it ecologically friendly. The DFT quantum-chemical modeling of the reaction mechanism revealed that a copper hydroperoxo-complex rather than hydrogen peroxide or a copper oxo-complex oxidizes alkene. The process is very selective since neither products of hydroxylation of benzene ring in styrene nor of allylic oxidation of cyclohexene were detected.
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Electrocatalytic oxidation of methanol: study with Pt:Mo dispersed catalysts
Directory of Open Access Journals (Sweden)
Oliveira Neto Almir
2000-01-01
Full Text Available The electrocatalytic oxidation of methanol on Pt:Mo dispersed on carbon prepared using an alternative method recently developed in this laboratory was investigated. The EDX analysis confirmed that the simultaneous reduction of the precursor salts of Pt and Mo leads to the presence of these materials at the nominal composition initially calculated. The addition of Mo to Pt causes an increase of the oxidation currents, but does not improve the catalytic effect for methanol oxidation. Tafel plots for various methanol concentrations showed the presence of two slopes. On line differential electrochemical mass spectrometry (DEMS was used to investigate the distribution of products and intermediates in methanol oxidation.
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Selective electrocatalytic oxidation of sorbitol to fructose and sorbose.
Kwon, Youngkook; de Jong, Ed; van der Waal, Jan Kees; Koper, Marc T M
2015-03-01
A new electrocatalytic method for the selective electrochemical oxidation of sorbitol to fructose and sorbose is demonstrated by using a platinum electrode promoted by p-block metal atoms. By the studying a range of C4, C5 and C6 polyols, it is found that the promoter interferes with the stereochemistry of the polyol and thereby modifies its reactivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.
Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang
2017-08-30
One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.
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Kumar, Sanjeev; Mahajan, Mani; Singh, Rajinder; Mahajan, Aman
2018-02-01
In this report, silver nanoparticles (Ag NPs) anchored reduced graphene oxide (rGO) sheets (rGO/Ag) nanohybrid has been explored as anode material in direct methanol fuel cells (DMFCs). The synthesized rGO/Ag nanohybrid is characterized by XRD, XPS, FTIR spectroscopy and HRTEM techniques. Cyclic voltammograms demonstrate that the rGO/Ag nanohybrid exhibits higher electrocatalytic activity in comparison to rGO sheets for methanol oxidation reaction (MOR). This enhancement is attributed to the synergetic effect produced by the presence of more active sites provided by Ag NPs anchored on a conducting network of large surface area rGO sheets.
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High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst
Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi Zhang
2016-01-01
Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.
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High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.
Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang
2016-12-14
Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.
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High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst
Zheng, Yao
2016-11-28
Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.
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International Nuclear Information System (INIS)
Wu Qinglong; Liao Junsheng; Bai Yun
2010-01-01
Well ordered and uniform titanium dioxide nanotube arrays were fabricated by anodiaing process from a bath containing 1% NaF, 1mol/L Na 2 SO 4 , 0.5 mol/L H 2 SO 4 at room temperature. Surface morphology of titanium dioxide nanotube arrays were observed with SEM. The formation process of titanium dioxide nanotube arrays was suggested by current-time transient. Its catalytic hydrogen evolution behavior was studied by electrochemical measurements in a 5%(mass fraction) H 2 SO 4 solution. The results showed that the titanium dioxide nanotube arrays on titanium had better hydrogen evolution activity and trace palladium lead to the maximum electrocatalytic activity of hydrogen production. (authors)
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Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles
Energy Technology Data Exchange (ETDEWEB)
Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher
2011-01-01
Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.
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International Nuclear Information System (INIS)
Abdel Hameed, R.M.; Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M.
2015-01-01
Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO_2/C-1 and Pt–MnO_2/C-2 electrocatalysts. - Highlights: • Adding MnO_2 to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO_2 improved the kinetics of methanol oxidation reaction. • R_c_t value of Pt–MnO_2/C was about 10 times as low as that at Pt/C. • The removal of CO_a_d_s poisoning species was facilitated at Pt–MnO_2/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO_2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO_2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO_2/C towards methanol oxidation in H_2SO_4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO_2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO_2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO_2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).
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Universal electrode interface for electrocatalytic oxidation of liquid fuels.
Liao, Hualing; Qiu, Zhipeng; Wan, Qijin; Wang, Zhijie; Liu, Yi; Yang, Nianjun
2014-10-22
Electrocatalytic oxidations of liquid fuels from alcohols, carboxylic acids, and aldehydes were realized on a universal electrode interface. Such an interface was fabricated using carbon nanotubes (CNTs) as the catalyst support and palladium nanoparticles (Pd NPs) as the electrocatalysts. The Pd NPs/CNTs nanocomposite was synthesized using the ethylene glycol reduction method. It was characterized using transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, voltammetry, and impedance. On the Pd NPs/CNTs nanocomposite coated electrode, the oxidations of those liquid fuels occur similarly in two steps: the oxidations of freshly chemisorbed species in the forward (positive-potential) scan and then, in the reverse scan (negative-potential), the oxidations of the incompletely oxidized carbonaceous species formed during the forward scan. The oxidation charges were adopted to study their oxidation mechanisms and oxidation efficiencies. The oxidation efficiency follows the order of aldehyde (formaldehyde) > carboxylic acid (formic acid) > alcohols (ethanol > methanol > glycol > propanol). Such a Pd NPs/CNTs nanocomposite coated electrode is thus promising to be applied as the anode for the facilitation of direct fuel cells.
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The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction
Li, Zhengxing
2014-07-01
In the context of the future hydrogen economy, effective production of hydrogen (H2) from readily available and sustainable resources is of crucial importance. Hydrogen generation via water splitting by solar energy or electricity has attracted great attention in recent years. In comparison with photocatalytic water-splitting directly using solar light, which is ideal but the relevant technologies are not yet mature, electrolysis of water with catalyst is more practical at the current stage. The Pt-group noble metals are the most effective electrocatalysts for hydrogen evolution reaction (HER) from water, but their high costs limit their applications. Due to the earth-abundance and low price, MoS2 is expected to be a good alternative of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more investigations are still needed to better understand the structure-performance correlation in this system. In this thesis, we report a new strategy for fabricating MoS2 eletrocatalysts which gives rise to much improved HER performance and allows us to tune the electrocatalytic activity by varying the preparation conditions. Specifically, we sulfurized molybdenum oxide on the surface of a Ti foil electrode via a facile chemical vapor deposition (CVD) method, and directly used the electrode for HER testing. Depending on the CVD temperature, the MoO2-MoS2 nanocomposites show different HER activities. Under the optimal synthesis condition (400ºC), the resulting catalyst exhibited excellent HER activity: an onset potential (overpotential) of 0.095 V versus RHE and the Tafel slope of 40 mv/dec. Such a performance exceeds those of most reported MoS2 based HER electrocatalysts. We demonstrated that the CVD temperature has significant influence on the catalysts in crystallinity degree, particle
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Zhang, Junjun
2017-12-27
A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.
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Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang
2017-01-01
A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.
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Directory of Open Access Journals (Sweden)
SHI Yan-hua
2017-09-01
Full Text Available The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO2, the OH- ion is preferentially absorbed, while Cl- absorption is depressed. OH- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn4+/Mn3+, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100 crystalline plane promotes OH- motion and the escape of newborn O2, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.
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International Nuclear Information System (INIS)
Jinlong, Lv; Tongxiang, Liang; Chen, Wang
2016-01-01
Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H_2SO_4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H_2SO_4 solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.
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Energy Technology Data Exchange (ETDEWEB)
Jinlong, Lv, E-mail: ljlbuaa@126.com [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China); Tongxiang, Liang; Chen, Wang [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China)
2016-03-15
Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.
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Nonaqueous electrocatalytic water oxidation by a surface-bound Ru(bda)(L)₂ complex.
Sheridan, Matthew V; Sherman, Benjamin D; Wee, Kyung-Ryang; Marquard, Seth L; Gold, Alexander S; Meyer, Thomas J
2016-04-21
The rate of electrocatalytic water oxidation by the heterogeneous water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], , (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate) on metal oxide surfaces is greatly enhanced relative to water as the solvent. In these experiments with propylene carbonate (PC) as the nonaqueous solvent, water is the limiting reagent. Mechanistic studies point to atom proton transfer (APT) as the rate limiting step in water oxidation catalysis.
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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.
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Hosseini, Hadi; Ahmar, Hamid; Dehghani, Ali; Bagheri, Akbar; Tadjarodi, Azadeh; Fakhari, Ali Reza
2013-04-15
A novel electrochemical sensor based on Au-SH-SiO₂ nanoparticles supported on metal-organic framework (Au-SH-SiO₂@Cu-MOF) has been developed for electrocatalytic oxidation and determination of L-cysteine. The Au-SH-SiO₂@Cu-MOF was characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction and cyclic voltammetry. The electrochemical behavior of L-cysteine at the Au-SH-SiO₂@Cu-MOF was investigated by cyclic voltammetry. The Au-SH-SiO₂@Cu-MOF showed a very efficient electrocatalytic activity for the oxidation of L-cysteine in 0.1 M phosphate buffer solution (pH 5.0). The oxidation overpotentials of L-cysteine decreased significantly and their oxidation peak currents increased dramatically at Au-SH-SiO₂@Cu-MOF. The potential utility of the sensor was demonstrated by applying it to the analytical determination of L-cysteine concentration. The results showed that the electrocatalytic current increased linearly with the L-cysteine concentration in the range of 0.02-300 μM and the detection limit was 0.008 μM. Finally, the sensor was applied to determine L-cysteine in water and biological samples. Copyright © 2012 Elsevier B.V. All rights reserved.
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Energy Technology Data Exchange (ETDEWEB)
Fathalipour, Soghra, E-mail: fathalipour@pnu.ac.ir [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of); Pourbeyram, Sima; Sharafian, Aziaeh [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of); Tanomand, Asghar [Department of Basic Sciences, Faculty Of Medicine, Maragheh University of Medical Sciences, PO Box: 78151-55158 (Iran, Islamic Republic of); Azam, Parisa [Department of Chemistry, Payame Noor University, PO Box: 19395-3697, Tehran (Iran, Islamic Republic of)
2017-06-01
In this work, an environmentally friendly method was applied for the synthesis of aqueous suspension of L-cysteine modified Ag nanoparticles (NPs)-decorated reduced graphene oxide (rGO) nanocomposite. L-cysteine played a triple role as reducing agent, stabilizer and linker of Ag NPs onto the surface of rGO. The resultant nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction studies (XRD), zeta potential, Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDX). Meanwhile, minimum inhibitory concentration (MIC), minimum bacterial concentration (MBC), agar well diffusion and cyclic voltammetry (CV) techniques were used for the investigation of antibacterial and electrocatalytic behaviors of the nanocomposite, respectively. The obtained nanocomposite showed not only enhanced electrocatalytic activity for glucose but also excellent antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). - Highlights: • Biocompatible reduced graphene oxide/ Ag nanocomposite was synthesized based on cysteine- Ag nanoparticles. • The reaction was carried out at room temperature without any further reducer. • The nanocomposite displayed excellent antibacterial and electrocatalytic activity against glucose.
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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
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Efficient electrocatalytic performance of thermally exfoliated reduced graphene oxide-Pt hybrid
Energy Technology Data Exchange (ETDEWEB)
Antony, Rajini P., E-mail: raji.anna@gmail.com; Preethi, L.K.; Gupta, Bhavana; Mathews, Tom, E-mail: tom@igcar.gov.in; Dash, S.; Tyagi, A.K.
2015-10-15
Highlights: • Synthesis of Pt–RGO nanohybrids of very high electrochemically active surface area. • Electrocatalytic activity-cum-stability: ∼10 times that of commercial Pt-C catalyst. • TEM confirms narrow size distribution and excellent dispersion of Pt nanoparticles. • SAED and XRD indicate (1 1 1) orientation of Pt nanoparticles. • Methanol oxidation EIS reveal decrease in charge transfer resistance with potential - Abstract: High quality thermally exfoliated reduced graphene oxide (RGO) nanosheets decorated with platinum nanocrystals have been synthesized using a simple environmentally benign process. The electrocatalytic behaviour of the Pt–RGO nanohybrid for methanol oxidation was studied using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. High resolution transmission electron microscopy shows uniform dispersion of Pt nanoparticles of ∼2–4 nm size. X-ray diffraction and selected area diffraction studies reveal (1 1 1) orientation of the platinum nanoparticles. The cyclic voltammetry and chronoamperometry results indicate higher catalytic activity and stability for Pt–RGO compared to commercial Pt-C. The electrochemical active surface area of Pt–RGO (52.16 m{sup 2}/g) is found to be 1.5 times that of commercial Pt-C. Impedance spectroscopy shows different impedance behaviour at different potential regions, indicating change in methanol oxidation reaction mechanism with potential. The reversal of impedance pattern to the second quadrant, at potentials higher than ∼0.40 V, indicates change in the rate determining reaction.
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Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei
2017-11-16
The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Energy Technology Data Exchange (ETDEWEB)
Abdel Hameed, R.M., E-mail: randa311eg@yahoo.com [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)
2015-12-30
Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO{sub 2}/C-1 and Pt–MnO{sub 2}/C-2 electrocatalysts. - Highlights: • Adding MnO{sub 2} to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO{sub 2} improved the kinetics of methanol oxidation reaction. • R{sub ct} value of Pt–MnO{sub 2}/C was about 10 times as low as that at Pt/C. • The removal of CO{sub ads} poisoning species was facilitated at Pt–MnO{sub 2}/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO{sub 2}/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO{sub 2} improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO{sub 2}/C towards methanol oxidation in H{sub 2}SO{sub 4} solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO{sub 2} is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO{sub 2}/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO{sub 2}/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).
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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
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Energy Technology Data Exchange (ETDEWEB)
Pang, H.L.; Lu, J.P. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Chen, J.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)], E-mail: chenjinhua@hnu.cn; Huang, C.T.; Liu, B.; Zhang, X.H. [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China)
2009-03-30
SnO{sub 2}-carbon nanotubes (CNTs) composites were prepared by sol-gel method, and characterized by scanning electron microscopy and X-ray diffraction. Due to high stability in diluted acidic solution, SnO{sub 2}-CNTs composites were selected as the catalyst support and second catalyst for ethanol electrooxidation. The electrocatalytic properties of the SnO{sub 2}-CNTs supported platinum (Pt) catalyst (Pt/SnO{sub 2}-CNTs) for ethanol oxidation have been investigated by typical electrochemical methods. Under the same mass loading of Pt, the Pt/SnO{sub 2}-CNTs catalyst shows higher electrocatalytic activity and better long-term cycle stability than Pt/SnO{sub 2} catalyst. Additionally, the effect of the mass ratio of CNTs to SnO{sub 2} on the electrocatalytic activity of the electrode for ethanol oxidation was investigated, and the optimum mass ratio of CNTs to SnO{sub 2} in the Pt/SnO{sub 2}-CNTs catalyst is 1/6.3.
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Energy Technology Data Exchange (ETDEWEB)
Hajjizadeh, M. [Department of Chemistry, Faculty of Science, K. N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of); Jabbari, A. [Department of Chemistry, Faculty of Science, K. N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of)], E-mail: jabbari@kntu.ac.ir; Heli, H.; Moosavi-Movahedi, A.A. [Institute of Biochemistry and Biophysics, University of Tehran, Tehran (Iran, Islamic Republic of); Haghgoo, S. [Center of Quality Control of Drug, Tehran (Iran, Islamic Republic of)
2007-12-31
The electrocatalytic oxidation of several anti-inflammatory drugs (mefenamic acid, diclofenac and indomethacin) was investigated on a nickel hydroxide-modified nickel (NHMN) electrode in alkaline solution. This oxidation process and its kinetics were studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of drugs, the anodic peak current of low-valence nickel species increases, followed by a decrease in the corresponding cathodic current. This pattern indicates that drugs were oxidized on the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. A mechanism based on the electrochemical generation of Ni(III) active sites and their subsequent consumption by drugs was also investigated. The corresponding rate law under the control of charge transfer was developed and kinetic parameters were derived. In this context, the charge-transfer resistance accessible both theoretically and through impedancemetry was used as a criterion. The rate constants of the catalytic oxidation of drugs and the electron-transfer coefficients are reported. A sensitive, simple and time-saving amperometric procedure was developed for the analysis of these drugs in bulk form and for the direct assay of tablets, using the NHMN electrode.
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International Nuclear Information System (INIS)
Hajjizadeh, M.; Jabbari, A.; Heli, H.; Moosavi-Movahedi, A.A.; Haghgoo, S.
2007-01-01
The electrocatalytic oxidation of several anti-inflammatory drugs (mefenamic acid, diclofenac and indomethacin) was investigated on a nickel hydroxide-modified nickel (NHMN) electrode in alkaline solution. This oxidation process and its kinetics were studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of drugs, the anodic peak current of low-valence nickel species increases, followed by a decrease in the corresponding cathodic current. This pattern indicates that drugs were oxidized on the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. A mechanism based on the electrochemical generation of Ni(III) active sites and their subsequent consumption by drugs was also investigated. The corresponding rate law under the control of charge transfer was developed and kinetic parameters were derived. In this context, the charge-transfer resistance accessible both theoretically and through impedancemetry was used as a criterion. The rate constants of the catalytic oxidation of drugs and the electron-transfer coefficients are reported. A sensitive, simple and time-saving amperometric procedure was developed for the analysis of these drugs in bulk form and for the direct assay of tablets, using the NHMN electrode
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Energy Technology Data Exchange (ETDEWEB)
Selvaraj, V.; Alagar, M. [Department of Chemical Engineering, Alagappa College of Technology, Anna University, Chennai 600025 (India); Hamerton, I. [Chemistry Division, School of Biomedical and Molecular Sciences, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom)
2006-10-06
Oxidative electrochemical polymerization of pyrrole at indium-doped tin oxide (ITO) is accomplished from a neat monomer solution with a supporting electrolyte (0.3M n-tetrabutyl ammonium tetrafluoroborate) by multiple-scan cyclic voltammetry. Polypyrrole (Ppy) films containing nanometer-sized platinum and Pt/Pd bimetallic particles are electro-synthesized on ITO glass plates by voltammetric cycling between -0.1 and +1V (versus Ag/AgCl/3M NaCl). The electrocatalytic oxidation of methanol on the nanoparticle-modified polypyrrole films is studied by means of electrochemical techniques. The modified electrode exhibits significant eletrocatalytic activity for methanol oxidation. The enhanced electrocatalytic activities may be due to the uniform dispersion of nanoparticles in the polypyrrole film and a synergistic effect of the highly-dispersed metal particles so that the polypyrrole film reduces electrode poisoning by adsorbed CO species. The monometallic (Pt) and bimetallic (Pt/Pd) nanoparticles are uniformly dispersed in polypyrrole matrixes, as confirmed by scanning electron microscopic and atomic force microscopic analysis. Energy dispersive X-ray analysis is used to characterize the composition of metal present in the nanoparticle-modified electrodes. (author)
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Electrocatalytic oxidation of cellulose at a gold electrode.
Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari
2014-08-01
The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Zhang, Yuting; Huang, Qiwei; Chang, Gang; Zhang, Zaoli; Xia, Tiantian; Shu, Honghui; He, Yunbin
2015-04-01
Homogeneous distribution of cube-shaped Pd nanocrystals on the surface of reduced graphene oxide is obtained via a facile one-step method by employing AA and KBr as the reductant and capping agent, respectively. The experimental factors affecting the morphology and structure of Pd nanoparticles have been systematically investigated to explore the formation mechanism of Pd nanocubes (PdNCs). It is revealed that PdNCs enclosed by active {100} facets with an average side length of 15 nm were successfully synthesized on the surface of reduced graphene oxide. KBr plays the role for facet selection by surface passivation and AA controls the reduction speed of Pd precursors, both of which govern the morphology changes of palladium nanoparticles. In the further electrochemical evaluations, the Pd nanocubes/reduced graphene oxide composites show better electrocatalytic activity and stability towards the electro-oxidation of ethanol than both reduced graphene oxide supported Pd nanoparticles and free-standing PdNCs. It could be attributed to the high electrocatalytic activity of the dominated active {100} crystal facets of Pd nanocubes and the enhanced electron transfer of graphene. The developed approach provide a versatile way for shape-controlled preparation of noble metal nanoparticles, which can work as novel electrocatalysts in the application of direct alcohols fuel cells.
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Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction
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.
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Directory of Open Access Journals (Sweden)
Kwang-Sik Sim
2011-01-01
Full Text Available This paper describes the electrocatalytic activity for CO, MeOH, and EtOH oxidation on the surface of Pt-Ru nanoparticles supported by metal oxide (Nb-TiO2-H prepared for use in a fuel cell. To prepare Nb-TiO2-supported Pt-Ru nanoparticles, first, the Nb-TiO2 supports were prepared by sol-gel reaction of titanium tetraisopropoxide with a small amount of the niobium ethoxide in polystyrene (PS colloids. Second, Pt-Ru nanoparticles were then deposited by chemical reduction of the Pt4+ and Ru3+ ions onto Nb-TiO2 supports (Pt-Ru@Nb-TiO2-CS. Nb element was used to reduce electrical resistance to facilitate electron transport during the electrochemical reactions on a fuel cell electrode. Finally, the Pt-Ru@Nb-TiO2-H catalysts were formed by the removal of core-polystyrene ball from Pt-Ru@TiO2-CS at 500∘C. The successfully prepared Pt-Ru electrocatalysts were confirmed via TEM, XPS, and ICP analysis. The electrocatalytic efficiency of Pt-Ru nanoparticles was evaluated via CO, MeOH, and EtOH oxidation for use in a direct methanol fuel cell (DMFC. As a result, the Pt-Ru@Nb-TiO2-H electrodes showed high electrocatalytic activity for the electrooxidation of CO, MeOH, and EtOH.
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Jana, Rajkumar; Subbarao, Udumula; Peter, Sebastian C.
2016-01-01
Ordered intermetallic nanocrystals with high surface area are highly promising as efficient catalysts for fuel cell applications because of their unique electrocatalytic properties. The present work discusses about the controlled synthesis of ordered intermetallic Pd3Pb nanocrystals in different morphologies at relatively low temperature for the first time by polyol and hydrothermal methods both in presence and absence of surfactant. Here for the first time we report surfactant free synthesis of ordered flower-like intermetallic Pd3Pb nanocrystals in 10 s. The structural characteristics of the nanocrystals are confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The as synthesized ordered Pd3Pb nanocrystals exhibit far superior electrocatalytic activity and durability towards formic acid and ethanol oxidation over commercially available Pd black (Pd/C). The morphological variation of nanocrystals plays a crucial role in the electrocatalytic oxidation of formic acid and ethanol. Among the catalysts, the flower-like Pd3Pb shows enhanced activity and stability in electrocatalytic formic acid and ethanol oxidation. The current density and mass activity of flower-like Pd3Pb catalyst are higher by 2.5 and 2.4 times than that of Pd/C for the formic acid oxidation and 1.5 times each for ethanol oxidation.
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Energy Technology Data Exchange (ETDEWEB)
Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.
2008-03-20
Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.
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International Nuclear Information System (INIS)
Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei
2013-01-01
A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells
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A DNA biosensor based on the electrocatalytic oxidation of amine by a threading intercalator
International Nuclear Information System (INIS)
Gao Zhiqiang; Tansil, Natalia
2009-01-01
An electrochemical biosensor for the detection of DNA based a peptide nucleic acid (PNA) capture probe (CP) modified indium tin oxide electrode (ITO) is described in this report. After hybridization, a threading intercalator, N,N'-bis[(3-propyl)-imidazole]-1,4,5,8-naphthalene diimide (PIND) imidazole complexed with Ru(bpy) 2 Cl (PIND-Ru, bpy = 2,2'-bipyridine), was introduced to the biosensor. PIND-Ru selectively intercalated to double-stranded DNA (ds-DNA) and became immobilized on the biosensor surface. Voltammetric tests showed highly stable and reversible electrochemical oxidation/reduction processes and the peak currents can directly be utilized for DNA quantification. When the tests were conducted in an amine-containing medium, Tris-HCl buffer for example, a remarkable improvement in the voltammetric response and noticeable enhancements of voltammetric and amperometric sensitivities were observed due to the electrocatalytic activity of the [Ru(bpy) 2 Cl] redox moieties. Electrocatalytic current was observed when as little as 3.0 attomoles of DNA was present in the sample solution
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Energy Technology Data Exchange (ETDEWEB)
Al-Enizi, Abdullah M. [Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia); Elzatahry, Ahmed A., E-mail: aelzatahry@ksu.edu.sa [Materials Science and Technology Program, College of Arts and Science, Qatar University, Doha 2713 (Qatar); Advanced Technology and New Materials Research Institute, City of Scientific Research and Technology Applications, New Borg El-Arab City, Alexandria 21934 (Egypt); Abdullah, Aboubakr M., E-mail: bakr@qu.edu.qa [Center for Advanced Materials, Qatar University, Doha 2713 (Qatar); Vinu, Ajayan [Future Industries Institute, University of South Australia, Building X-X2-09, Mawson Lakes Campus, Mawson Lakes 5095 SA (Australia); Iwai, Hideo [Materials Analysis Station, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047 (Japan); Al-Deyab, Salem S. [Petrochemical Research Chair, Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia)
2017-04-15
Highlights: • A mixture of Polyvinylpyrrolidone (PVP), graphene and emeraldine base polyaniline (PANi) was electrospun and used as starting materials to prepare a nitrogen-doped carbon nanofiber (N-CNF). • Nickel oxide was loaded on the N-CNF to form a nanocomposite which was calcined later at different temperatures. • The effect of calcination temperature on the electrocatalytic behavior of the nanocomposite was studied which shows that the nanocomposite calcined at 500 °C was proved to be very high compared to the other calcination temperatures. • The stability of catalyst was excellent and its resistance to the adsorption of the intermediates generated from the methanol oxidation was very high. - Abstract: Nitrogen-Doped Carbon Nanofiber (N-CNF)–supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140–160) nm, and a surface area (393.3 m{sup 2} g{sup −1}). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.
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Study of reactivities of electro-catalytic oxidation of organic substrates with Ru(IV) complex
International Nuclear Information System (INIS)
Madurro, J.M.; Oliveira, S.M. de; Campos, J.L.
1988-01-01
An electrocatalytic procedure for the oxidation of olefines, ketones, heterocycles and ethers using the Ru IV oxidant RuO (bpy) (trpy) 2+ (bpy is 2,2 - bipyridine; trpy is 2,2', 2''' - terpyridine), is described. The relative reactivities of the substrates are determined by analysis of the exponential i x t curves, using simple linear and exponential least-square programme. Mechanistics considerations based on the observed relative reactivities are discussed. (M.J.C.) [pt
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Directory of Open Access Journals (Sweden)
Zhang Li
2011-12-01
Full Text Available Abstract Background The detection of hydrogen peroxide (H2O2 and nitrite ion (NO2- is of great important in various fields including clinic, food, pharmaceutical and environmental analyses. Compared with many methods that have been developed for the determination of them, the electrochemical detection method has attracted much attention. In recent years, with the development of nanotechnology, many kinds of micro/nano-scale materials have been used in the construction of electrochemical biosensors because of their unique and particular properties. Among these catalysts, copper oxide (CuO, as a well known p-type semiconductor, has gained increasing attention not only for its unique properties but also for its applications in many fields such as gas sensors, photocatalyst and electrochemistry sensors. Continuing our previous investigations on transition-metal oxide including cuprous oxide and α-Fe2O3 modified electrode, in the present paper we examine the electrochemical and electrocatalytical behavior of flower like copper oxide modified glass carbon electrodes (CuO/GCE. Results Flower like copper oxide (CuO composed of many nanoflake was synthesized by a simple hydrothermal reaction and characterized using field-emission scanning electron microscopy (FE-SEM and X-ray diffraction (XRD. CuO modified glass carbon electrode (CuO/GCE was fabricated and characterized electrochemically. A highly sensitive method for the rapid amperometric detection of hydrogen peroxide (H2O2 and nitrite (NO2- was reported. Conclusions Due to the large specific surface area and inner characteristic of the flower like CuO, the resulting electrode show excellent electrocatalytic reduction for H2O2 and oxidation of NO2-. Its sensitivity, low detection limit, fast response time and simplicity are satisfactory. Furthermore, this synthetic approach can also be applied for the synthesis of other inorganic oxides with improved performances and they can also be extended to
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International Nuclear Information System (INIS)
Elahi, M. Yousef; Mousavi, M.F.; Ghasemi, S.
2008-01-01
A nano-structured Ni(II)-curcumin (curcumin: 1,7-bis[4-hydroxy-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) film is electrodeposited on a glassy carbon electrode in alkaline solution. The morphology of polyNi(II)-curcumin (NC) was investigated by scanning electron microscopy (SEM). The SEM results show NC has a nano-globular structure in the range 20-50 nm. Using cyclic voltammetry, linear sweep voltammetry, chronoamperometry, steady-state polarization measurements and electrochemical impedance spectroscopy (EIS) showed that the nano-structure NC film acts as an efficient material for the electrocatalytic oxidation of fructose. According to the voltammetric studies, the increase in the anodic peak current and subsequent decrease in the corresponding cathodic current, fructose was oxidized on the electrode surface via an electrocatalytic mechanism. The EIS results show that the charge-transfer resistance has as a function of fructose concentration, time interval and applied potential. The increase in the fructose concentration and time interval in fructose solution results in enhanced charge transfer resistance in Nyquist plots. The EIS results indicate that fructose electrooxidation at various potentials shows different impedance behaviors. At lower potentials, a semicircle is observed in the first quadrant of impedance plot. With further increase of the potential, a transition of the semicircle from the first to the second quadrant occurs. Also, the results obtained show that the rate of fructose electrooxidation depends on concentration of OH - . Electron transfer coefficient, diffusion coefficient and rate constant of the electrocatalytic oxidation reaction are obtained. The modified electrode was used as a sensor for determination of fructose with a good dynamic range and a low detection limit
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Romeiro, Fernanda C.; Rodrigues, Mônica A.; Silva, Luiz A. J.; Catto, Ariadne C.; da Silva, Luis F.; Longo, Elson; Nossol, Edson; Lima, Renata C.
2017-11-01
Reduced graphene oxide-zinc oxide (rGO-ZnO) nanocomposites were successfully synthesized using a facile microwave-hydrothermal method under mild conditions, and their electrocatalytic properties towards O2 evolution were investigated. The microwave radiation played an important role in obtainment of well dispersed ZnO nanoparticles directly on reduced graphene oxide sheets without any additional reducing reagents or passivation agent. X-ray diffraction (XRD), Raman and infrared spectroscopies indicated the reduction of GO as well as the successful synthesis of rGO-ZnO nanocomposites. The chemical states of the samples were shown by XPS analyses. Due to the synergic effect, the resulting nanocomposites exhibited high electronic interaction between ZnO and rGO sheets, which improved the electrocatalytic oxidation of water with low onset potential of 0.48 V (vs. Ag/AgCl) in neutral pH and long-term stability, with high current density during electrolysis. The overpotential for water oxidation decreased in alkaline pH, suggesting useful insight on the catalytic mechanism for O2 evolution.
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CSIR Research Space (South Africa)
Fashedemi, OO
2014-05-01
Full Text Available ) were explored, and compared with those of the Pd/C alone. FeCo@Fe@Pd/C exhibited a remarkable performance in all three alcohols but its best electrocatalytic activity was found in the oxidation of EG where the electrocatalytic rate constant (K...
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Study of the electrocatalytic oxidation of Ethanol over platinum in medium acid
International Nuclear Information System (INIS)
Hoyos, Bibian; Gonzalez, Javier; Sanchez, Carlos
2002-01-01
Electro-catalytic oxidation of ethanol on platinum surfaces in sulfuric acid solutions at different temperatures and concentrations was studied by cyclic voltammetry. The results shown that there is ethanol adsorption at potentials below 0.4V (vs. RHE) with electrode coverage fraction for residues of 0.3 or less. There are also, two irreversible oxidation reactions. Former reaction seems be catalyzed by Pt(OH) species with electronic charge transfer control and the second reaction seems be catalyzed by Pt(OH) 4 with diffusion control while Pt(OH) 2 does not have catalytic activity. The activity and selectivity for total oxidation increases with ethanol concentration and temperature. Finally, a reaction mechanism, which explains the obtained data, is proposed
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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.
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International Nuclear Information System (INIS)
Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao
2014-01-01
The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance
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Institute of Scientific and Technical Information of China (English)
杨苏东; 陈琳
2015-01-01
We report a solvothermal method preparation of dendritic Pd nanoparticles (DPNs) and spherical Pd nanoparticles (SPNs) supported on reduced graphene oxide (RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide (GO) un-der mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.
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Institute of Scientific and Technical Information of China (English)
DAI QiZhou; ZHOU MingHua; LEI LeCheng; ZHANG Xing Wang
2007-01-01
A novel advanced oxidation process-wet electrocatalytic oxidation(WEO)was studied with p-nitrophenol as model pollutant and β-PbO2 electrode as the anode.Compared with the effect of the individual wet air oxidation(WAO)and electrochemical oxidation(EO),the effect of WEO showed synergistic effect on COD removal under the conditions of temperature 160℃,C=1000mg·L-1,PN2=0.50MPa,Po2=0.9 MPa,current density=3 mA·cm-2,Na2SO4 3 g·L-1.And the synergistic factor got the best value of 0.98 within 120 min after 180 min treatment.The synergistic factor was studied after 120 min treatment at 100℃,120℃,140℃and 160℃,and the effect of 120℃was the best with the value of 1.26.Possible mechanism for the synergistic effect was discussed based on the analysis of free-radical generation and intermediates detected by HPLC and GC/MS.
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Directory of Open Access Journals (Sweden)
Amina A. Hamza
2017-01-01
Full Text Available A novel non-precious multiwalled carbon nanotubes (CNTs—supported metal oxide electrocatalyst was developed for methanol electrooxidation in alkaline medium. The catalyst was fabricated by simultaneous electrodeposition of copper-cobalt-nickel ternary nanostructures (CuCoNi on a glassy carbon electrode (GCE modified with CNTs. The proposed electrode was characterized using X-ray diffraction (XRD, energy dispersive X-ray (EDX, and scanning electron microscopy (SEM. The electrochemical behavior and the electrocatalytic performance of the suggested electrode towards the oxidation of methanol were evaluated by cyclic voltammetry (CV, linear sweep voltammetry (LSV, and chronoamperometry (CA in alkaline medium. Several parameters were investigated, e.g., deposition time, potential scan rate, etc. Compared to Cu, Co, or Ni mono electrocatalysts, the electrode based on ternary-metals exhibited superior electrocatalytic activity and stability towards methanol electrooxidation. For instance, CuCoNi@CNTs/GCE has shown at least 2.5 times electrocatalytic activity and stability compared to the mono eletrocatalysts. Moreover, the present study found that the optimized loading level is 1500 s of simultaneous electrodeposition. At this loading level, it was found that the relation between the Ip/ν1/2 function and scan rate gives the characteristic features of a catalytic process. The enhanced activity and stability of CuCoNi@CNTs/GCE was attributed to (i a synergism between three metal oxides coexisting in the same structure; (ii the presence of CNTs as a support for the metal oxides, that offers high surface area for the deposited tertiary alloy and suppresses the aggregation and sintering of the metals oxide with time; as well as (iii the increase of the conductivity of the deposited semiconducting metal oxides.
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International Nuclear Information System (INIS)
Karczmarczyk, Aleksandra; Celebanska, Anna; Nogala, Wojciech; Sashuk, Volodymyr; Chernyaeva, Olga; Opallo, Marcin
2014-01-01
Graphical abstract: - Highlights: • Gold nanoparticulate film electrodes were prepared by layer-by-layer method from oppositely charged nanoparticles. • Positively charged nanoparticles play dominant role in glucose oxidation in alkaline solution. • Gold and gold-carbon nanoparticulate film electrodes exhibit similar glucose oxidation current and onset potential. - Abstract: Electrocatalytic oxidation of glucose was studied at nanoparticulate gold and gold-carbon film electrodes. These electrodes were prepared by a layer-by-layer method without application of any linker molecules. Gold nanoparticles were stabilized by undecane thiols functionalized by trimethyl ammonium or carboxylate groups, whereas the carbon nanoparticles were covered by phenylsulfonate functionalities. The gold nanoparticulate electrodes were characterized by UV-vis and XPS spectroscopy, atomic force microscopy and voltammetry, before and after heat-treatment. Heat-treatment facilitates the aggregation of the nanoparticles and affects the structure of the film. The comparison of the results obtained with film electrodes prepared from gold nanoparticles with the same charge and with gold-carbon nanoparticulate electrodes, proved that positively charged nanoparticles are responsible for the high electrocatalytic activity, whereas negatively charged ones act rather as a linker of the film
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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
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Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong
2015-03-01
Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).
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Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction
Muralikrishna, S.
2015-10-20
Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.
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Hydrothermal synthesis of 2D MoS 2 nanosheets for electrocatalytic hydrogen evolution reaction
Muralikrishna, S.; Manjunath, K.; Samrat, D.; Reddy, Viswanath; Ramakrishnappa, T.; Nagaraju, Doddahalli H.
2015-01-01
Nanostructured molybdenum disulfide (MoS) is a very promising catalyst for producing molecular hydrogen by electrochemical methods. Herein, we have designed and synthesized highly electocatalytically active 2D MoS nanosheets (NS) from molybdenum trioxide (MoO) by a facile hydrothermal method and have compared their electrocatalytic activities for hydrogen evolution reaction (HER). The electrochemical characterization was performed using linear sweep voltammetry (LSV) in acidic medium. The MoS NS show a HER onset potential at about 80 mV vs. reversible hydrogen electrode (RHE) which is much lower than MoO (300 mV). The MoS NS and MoO show a current density of 25 mA cm and 0.3 mA cm, respectively at an overpotential of 280 mV vs. RHE. The MoS NS showed an 83 times higher current density when compared to MoO. The Tafel slopes of the MoS NS and MoO were about 90 mV per dec and 110 mV per dec respectively. This suggests that MoS NS are a better electrocatalyst when compared to MoO and follow the Volmer-Heyrovsky mechanism for HER.
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International Nuclear Information System (INIS)
Jo, Ara; Lee, Youngmi; Lee, Chongmok
2016-01-01
In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1_6) mA mM"−"1 cm"−"2, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.
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Energy Technology Data Exchange (ETDEWEB)
Jo, Ara; Lee, Youngmi, E-mail: youngmilee@ewha.ac.kr; Lee, Chongmok, E-mail: cmlee@ewha.ac.kr
2016-08-24
In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1{sub 6}) mA mM{sup −1} cm{sup −2}, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.
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International Nuclear Information System (INIS)
Dar, Riyaz Ahmad; Naikoo, Gowhar Ahmad; Pitre, Krishna Sadashive
2013-01-01
Graphical abstract: Electrode oxidation mechanism of reserpine at PANI modified-SWCNT/CPE. -- Highlights: • Electropolymerization of polyaniline at SWCNT/CPE. • CV, EIS, CC SEM techniques were used for characterization of electrode. • Electrode showed electrocatalytic activity towards anodic oxidation of reserpine. • Oxidation process as irreversible and adsorption-controlled. • Reserpine in bark of Rauwolfia serpentina and in its pharmaceutical formulations. -- Abstract: In the present work a polyaniline film was successfully deposited by electropolymerization on single walled carbon nanotube paste electrode. The electrode was characterized using cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and scanning electron microscopy. The modified electrode showed electrocatalytic behaviour towards the anodic oxidation of reserpine. The adsorptive stripping voltammetric behaviour of reserpine at polyaniline film modified single walled carbon nanotube paste electrode (modified-SWCNTPE) was investigated and validated in pharmaceuticals and biological fluids by cyclic voltammetry (CV) and adsorptive stripping differential pulse voltammetry (AdSDPV) in 0.02 M phosphate buffer in the pH range of 2.5–8.5. Cyclic voltammetry has shown that the oxidation process is irreversible over the pH range studied and exhibited an adsorption-controlled behaviour. Further, the overall electrode process is mainly diffusion controlled with adsorption effects. The proposed more sensitive AdSDPV method allow quantitation over the range 0.085 μg mL −1 to 0.87 μg mL −1 with the detection limit of 0.407 ng mL −1 and has been successfully used to determine reserpine in bark of Rauwolfia serpentina and in its pharmaceutical formulations
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Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon
International Nuclear Information System (INIS)
Rodriguez, Henry; Hoyos Bibian
2004-01-01
Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon was studied, in acid media at different temperatures and concentrations. During the maturation time of deposited iridium, the surface is covered by an irreversible oxide formation, which affects the behavior of the catalytic mixture. The Pt 7 0 Ir 3 0 and Pt 9 0 Ir 1 0 mixtures seem to be a little more active than the Pt/C electrode at potentials below 800 mV (vs. HRE). In all electrodes appears two reactions: partial ethanol oxidation to produce acetaldehyde (main path of reaction at low temperatures and high electrode coverage with ethanol adsorption residues) and the total oxidation to carbon dioxide which is considerable at potential above 800 mV and it is increased with increasing temperature
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Energy Technology Data Exchange (ETDEWEB)
Liu, Jiang; Wu, Wen-Jie; Fang, Fang [Fudan University, Department of Chemistry (China); Zorin, Nikolay A. [Russian Academy of Sciences, Institute of Basic Biological Problems (Russian Federation); Chen, Meng; Qian, Dong-Jin, E-mail: djqian@fudan.edu.cn [Fudan University, Department of Chemistry (China)
2016-08-15
Immobilization of active enzymes on the surfaces of electrodes and nanomaterials is important in the fields of bioscience, and biotechnology. In this study, we investigated electrocatalytic properties of the interconversion of protons and hydrogen by means of hydrogenase (H{sub 2}ase)-functionalized carbon nanotube polyelectrolyte composites. Multiwalled carbon nanotube polyelectrolytes (MWNT-PEs) were synthesized through a diazonium and an addition reaction with poly(4-vinylpyridine) (P4VP), followed by another addition reaction with either methyl iodide (CH{sub 3}I) or N-methyl-N′-benzyl bromide bipyridinium (VBenBr) to produce MWNT-P4VPMe or MWNT-P4VPBenV polyelectrolytes, respectively. The MWNT-PE@H{sub 2}ase bio-nanocomposites were then prepared by means of MWNT-PEs as substrates to bind with H{sub 2}ase. The redox current density of the MWNT-PE@H{sub 2}ase-modified electrodes increased with a decrease in pH values of the Ar-saturated electrolyte solution owing to the catalytic reduction of protons (H{sub 2} production); further, it increased with the increasing pH values of the H{sub 2}-saturated solution owing to the catalytic oxidation of hydrogen. The reversible color change between blue-colored and colorless viologen (catalyzed by the MWNT-PE@H{sub 2}ase bio-nanocomposites) suggested that they may be developed as nano-biosensors for molecular H{sub 2}. The as-synthesized bio-nanocomposites showed strong long-term stability and high bioactivity.Graphical Abstract.
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Yang, Jenny Y; Smith, Stuart E; Liu, Tianbiao; Dougherty, William G; Hoffert, Wesley A; Kassel, W Scott; Rakowski DuBois, M; DuBois, Daniel L; Bullock, R Morris
2013-07-03
A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex gives three isomers of the doubly protonated Ni(0) complex [Ni(P(Cy)2N(t-Bu)2H)2](BF4)2. Using the pKa values and Ni(II/I) and Ni(I/0) redox potentials in a thermochemical cycle, the free energy of hydrogen addition to [Ni(P(Cy)2N(t-Bu)2)2](2+) was determined to be -7.9 kcal mol(-1). The catalytic rate observed in dry acetonitrile for the oxidation of H2 depends on base size, with larger bases (NEt3, t-BuNH2) resulting in much slower catalysis than n-BuNH2. The addition of water accelerates the rate of catalysis by facilitating deprotonation of the hydrogen addition product before oxidation, especially for the larger bases NEt3 and t-BuNH2. This catalytic pathway, where deprotonation occurs prior to oxidation, leads to an overpotential that is 0.38 V lower compared to the pathway where oxidation precedes proton movement. Under the optimal conditions of 1.0 atm H2 using n-BuNH2 as a base and with added water, a turnover frequency of 58 s(-1) is observed at 23 °C.
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Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju
2014-05-01
A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k
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Jena, Bikash Kumar; Raj, C Retna
2007-03-27
This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).
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Energy Technology Data Exchange (ETDEWEB)
Rutkowska, Iwona A., E-mail: ilinek@chem.uw.edu.pl; Wadas, Anna; Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.pl
2016-12-01
Highlights: • The electrocatalytic system utilizing Pt nanoparticles dispersed on mixed metal oxide (WO{sub 3}/ZrO{sub 2}) system is proposed. • The system is characterized by high activity toward oxidations of ethanol, methanol and acetaldehyde in acid medium. • The enhancement effect is facilitated by presence of hydroxyl groups, high mobility of protons and improved distribution of electrons. • Strong interactions between Pt and the mixed oxide WO{sub 3}/ZrO{sub 2} support are postulated. - Abstract: Nanostructured mixed metal (W, Zr) oxide matrices (in a form of layered intercalated films of WO{sub 3} and ZrO{sub 2}) are considered here for supporting and activating catalytic platinum nanoparticles toward electrooxidation of ethanol. Remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents measured in 0.5 mol dm{sup −3} H{sub 2}SO{sub 4} (containing 0.5 mol dm{sup −3} ethanol) have been observed. Comparison has been made to the behavior of methanol and acetaldehyde under analogous conditions. The enhancement effects are interpreted in terms of specific interactions between platinum nanoparticles and the metal oxide species, high acidity of the mixed oxide sites, as well as high population of surface hydroxyl groups and high mobility of protons existing in close vicinity of Pt catalytic sites. The metal oxide nanostructures are expected to interact competitively (via the surface hydroxyl groups) with adsorbates of the undesirable reaction intermediates, including CO, facilitating their desorption (“third body effect”), or even oxidative removal (e.g., of CO to CO{sub 2}). The fact that the partially reduced tungsten oxide (H{sub x}WO{sub 3}) component is characterized by fast electron transfers coupled to proton displacements tends to improve the overall charge propagation at the electrocatalytic interface.
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Directory of Open Access Journals (Sweden)
Juanito Raphael F. Foronda
2013-01-01
Full Text Available Catalysts in fuel cells are normally platinum based because platinum exhibits high electrocatalytic activity towards ethanol oxidation in acidic medium. However, bulk Pt is expensive and rare in nature. To reduce the consumption of Pt, a support material or matrix is needed to disperse Pt on its surface as micro- or nanoparticles with potential application as anode material in direct ethanol fuel cells (DEFCs. In this study, a composite material consisting of platinum particles dispersed on reduced graphene oxide/poly(3,4-ethylenedioxythiophene (RGO/PEDOT support was electrochemically prepared for ethanol oxidation in sulfuric acid electrolyte. PEDOT, a conductive polymer, was potentiodynamically polymerized from the corresponding monomer, 0.10 M EDOT in 0.10 M HClO4 electrolyte. The PEDOT-modified electrode was used as a substrate for exfoliated graphene oxide (EGO which was prepared by electrochemical exfoliation of graphite from carbon rod of spent batteries and subsequently reduced to form RGO. The Pt/RGO/PEDOT composite gave the highest electrocatalytic activity with an anodic current density of 2688.7 mA·cm−2 at E = 0.70 V (versus Ag/AgCl towards ethanol oxidation compared to bare Pt electrode and other composites. Scanning electron microscopy (SEM revealed the surface morphology of the hybrid composites while energy dispersive X-ray (EDX confirmed the presence of all the elements for the Pt/RGO/PEDOT composite.
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International Nuclear Information System (INIS)
Nicholson, P.G.; Zhou, S.; Hinds, G.; Wain, A.J.; Turnbull, A.
2009-01-01
Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.
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Energy Technology Data Exchange (ETDEWEB)
Uribe-Godinez, J.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro. Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Hernandez-Castellanos, R. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)
2010-11-01
The electrocatalytic activity for oxygen reduction and hydrogen oxidation of a discrete metal carbonyl cluster with a well defined molecular and crystal structure, Rh{sub 6}(CO){sub 16}, is reported. The exchange current density of this compound for oxygen reduction is one order of magnitude higher than that of platinum, and its resistance degree to PEM fuel cell contaminants such as methanol and CO is as high as 2 mol L{sup -1} and 0.5%, respectively. These properties make the metal complex a potential alternative for use as electrode in polymer electrolyte membrane fuel cells. (author)
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Preparation and electrocatalytic property of WC/carbon nanotube composite
International Nuclear Information System (INIS)
Li Guohua; Ma Chunan; Tang Junyan; Sheng Jiangfeng
2007-01-01
Tungsten carbide/carbon nanotube composite was prepared by surface decoration and in situ reduction-carbonization. The samples were characterized by XRD, SEM, EDS, TEM, HRTEM and BET, respectively. The XRD results show that the sample is composed of carbon nanotube, tungsten carbide and tungsten oxide. The EDS results show that the distribution of tungsten oxide is consistent with that of tungsten carbide. SEM, TEM and HRTEM results show that the tungsten carbide nanoparticle with irregular granule grows on the outside surface of carbon nanotube homogenously. The electrocatalytic activity of the sample for p-nitrophenol reduction was tested by a powder microelectrode in a basic solution. The results show that the electrocatalytic activity of the sample is higher than that of granular tungsten carbide, hollow globe tungsten carbide with mesoporosity and carbon nanotube purified. The improvement of the electrocatalytic activity of the sample can be attributed to its components and composite structure. These results indicate that tungsten carbide/carbon nanotube composite is one of the effective ways to improve the electrocatalytic activity of tungsten carbide
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International Nuclear Information System (INIS)
Zhang Lingyan; Yuan Ruo; Chai Yaqing; Li Xuelian
2007-01-01
Positively charged gold nanoparticle (positively charged nano-Au), which was prepared, characterized by ξ-potential and transmission electron microscopy (TEM) was used in combination with L-cysteine to fabricate a modified electrode for electrocatalytic reaction of biomolecules. Compared with electrodes modified by negatively charged gold nanoparticle/L-cysteine, or L-cysteine alone, the electrode modified by the positively charged gold nanoparticle/L-cysteine exhibited excellent electrochemical behavior toward the oxidation of biomolecules such as ascorbic acid, dopamine and hydrogen peroxide. Moreover, the proposed mechanism for electrocatalytic response of positively charged gold nanoparticle was discussed. The immunosensor showed a specific to ascorbic acid in the range 5.1 x 10 -7 -6.7 x 10 -4 M and a low detection limit of 1.5 x 10 -7 M. The experimental results demonstrate that positively charged gold nanoparticle have more efficient electrocatalytic reaction than negatively charged gold nanoparticle, which opens up new approach for fabricating sensor
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Hydrogen sulfide oxidation without oxygen - oxidation products and pathways
International Nuclear Information System (INIS)
Fossing, H.
1992-01-01
Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle
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CSIR Research Space (South Africa)
Maxakato, NW
2010-03-01
Full Text Available Comparative electrocatalytic behavior of functionalized multiwalled carbon nanotubes (fMWCNTs) electrodecorated with Pt/Ru nanoparticles towards the oxidation of methanol (MeOH), ethylene glycol (EG) and formic acid (FA) has been investigated...
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Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts
International Nuclear Information System (INIS)
Li, Zhe-Fei; Wang, Yuxuan; Botte, Gerardine G.
2017-01-01
Highlights: • A procedure to pretreat electrocatalysts to study the ammonia oxidation is provided. • N ads and O/OH ads were identified as the major deactivation species that prevent ammonia oxidatoin. • The electrocatalytic activity, thermodynamics, and possible deactivation mechanisms for ammonia oxidation were elucidated. • The onset potential for ammonia oxidation is related to the hydrogen binding energy of the catalyst. • Ammonia electro-oxidation involves a complex decoupled electron and proton transfer process. - Abstract: The ammonia electro-oxidation reaction (AOR) has been studied due to its promising applications in ammonia electrolysis, wastewater remediation, direct ammonia fuel cells, and sensors. However, it is difficult to compare and analyze the reported electrocatalytic activity of AOR reliably, likely due to the variation in catalyst synthesis, electrode composition, electrode morphology, and testing protocol. In this paper, the electro-oxidation of ammonia on different carbon-supported precious metal nanoparticle catalysts was revisited. The effect of experimental conditions, electrochemical test parameters, electrocatalytic activity, thermodynamics, and possible deactivation mechanism of the catalysts were investigated. Pt/C catalyst possesses the highest electrocatalytic activity, while Ir/C and Rh/C show lower overpotential. The onset potential of the AOR is related to the hydrogen binding energy of the catalyst. N ads is one major cause of deactivation accompanied with the formation of surface O/OH ads at high potentials. The coulombic efficiency of N ads formation on Pt is about 1% initially and gradually decreases with reaction time. Increase in ammonia concentration leads to increase in current density, while increase in hydroxyl ions concentration can enhance the current density and reduce the overpotential simultaneously. The slopes of AOR onset potential and hydrogen adsorption/desorption potential of Pt/C as a function of p
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Institute of Scientific and Technical Information of China (English)
Yuan; Bu; Wenle; Dai; Nan; Li; Xinran; Zhao; Xia; Zuo
2013-01-01
The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid has been investigated by cyclic voltammetry,linear polarization and chronoamperometry.The graphene nanopowder modified electrode was prepared using the drop coating method,which displayed excellent electrocatalytic activity towards the oxidation of dopamine and uric acid compared with the bare glassy carbon electrode in phosphate buffer solution at pH=7.0.Linear responses for dopamine and uric acid were obtained in the ranges of3.3μmol/L to 249.1μmol/L and 6.7μmol/L to 386.3μmol/L with detection limits of 1.5μmol/L and 2.7μmol/L(S/N=3),respectively.The response time was less than 2 s in case of dopamine and 3 s in case of uric acid,respectively.The results demonstrated that the graphene nanopowder had potential for detecting dopamine and uric acid.
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Directory of Open Access Journals (Sweden)
Prabhakarn Arunachalam
2017-04-01
Full Text Available Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO42 nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO42 nanospheres have been examined by powder X-ray diffraction (XRD, Fourier transform-infrared spectroscopy (FT-IR, field emission-scanning electron microscopy (FE-SEM, high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO42 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV and chronopotentiometry (CP techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO42 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO42 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.
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Directory of Open Access Journals (Sweden)
Baoyan Wu
2016-11-01
Full Text Available Here we report a facile eco-friendly one-step electrochemical approach for the fabrication of a polypyrrole (PPy, reduced graphene oxide (RGO, and gold nanoparticles (nanoAu biocomposite on a glassy carbon electrode (GCE. The electrochemical behaviors of PPy–RGO–nanoAu and its application to electrochemical detection of hydrogen peroxide were investigated by cyclic voltammetry. Graphene oxide and pyrrole monomer were first mixed and casted on the surface of a cleaned GCE. After an electrochemical processing consisting of the electrooxidation of pyrrole monomer and simultaneous electroreduction of graphene oxide and auric ions (Au3+ in aqueous solution, a PPy–RGO–nanoAu biocomposite was synthesized on GCE. Each component of PPy–RGO–nanoAu is electroactive without non-electroactive substance. The obtained PPy–RGO–nanoAu/GCE exhibited high electrocatalytic activity toward hydrogen peroxide, which allows the detection of hydrogen peroxide at a negative potential of about −0.62 V vs. SCE. The amperometric responses of the biosensor displayed a sensitivity of 40 µA/mM, a linear range of 32 µM–2 mM, and a detection limit of 2.7 µM (signal-to-noise ratio = 3 with good stability and acceptable reproducibility and selectivity. The results clearly demonstrate the potential of the as-prepared PPy–RGO–nanoAu biocomposite for use as a highly electroactive matrix for an amperometric biosensor.
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Valenti, Giovanni; Boni, Alessandro; Melchionna, Michele; Cargnello, Matteo; Nasi, Lucia; Bertoni, Giovanni; Gorte, Raymond J.; Marcaccio, Massimo; Rapino, Stefania; Bonchio, Marcella; Fornasiero, Paolo; Prato, Maurizio; Paolucci, Francesco
2016-12-01
Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ~130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.
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Synthesis, characterization and electrocatalytic properties of delafossite CuGaO{sub 2}
Energy Technology Data Exchange (ETDEWEB)
Ahmed, Jahangeer [Department of Chemistry, University of Texas Rio Grande Valley, 1201 West University Drive, Edinburg, TX 78539 (United States); Department of Chemistry, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu [Department of Chemistry, University of Texas Rio Grande Valley, 1201 West University Drive, Edinburg, TX 78539 (United States)
2016-10-15
Delafossite CuGaO{sub 2} has been employed as photocatalysts for solar cells, but their electrocatalytic properties have not been extensively studied, especially no comparison among samples made by different synthesis routes. Herein, we first reported the successful synthesis of delafossite CuGaO{sub 2} particles with three different morphologies, i.e. nanocrystalline hexagons, sub-micron sized plates and micron–sized particles by a modified hydrothermal method at 190 °C for 60 h [1–3], a sono-chemical method followed by firing at 850 °C for 48 h, and a solid state route at 1150 °C, respectively. Morphology, composition and phase purity of the synthesized samples was confirmed by powder X-ray diffraction and Raman spectroscopic studies, and then their electrocatalytic performance as active and cost effective electrode materials to the oxygen and hydrogen evolution reactions in 0.5 M KOH electrolyte versus Ag/AgCl was investigated and compared under the same conditions for the first time. The nanocrystalline CuGaO{sub 2} hexagons show enhanced electrocatalytic activity than the counterpart sub-micron sized plates and micron-sized particles. - Graphical abstract: Representative delafossite CuGaO2 samples with sub-micron sized plate and nanocrystalline hexagon morphologies accompanying with chronoamperometric voltammograms for oxygen evolution reaction and hydrogen evolution reaction in 0.5 M KOH electrolyte after purged with N{sub 2} gas. - Highlights: • Delafossite CuGaO{sub 2} with three morphologies has been synthesized. • Phase purity of the synthesized samples was confirmed. • Comparison on their electrocatalytic properties was made for the first time. • Their use as electrodes for oxygen and hydrogen evolution reactions was evaluated. • Nanocrystalline CuGaO{sub 2} hexagons show highest electrocatalytic activity.
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Zhang, Xuan; Zhang, Jia-Wei; Xiang, Ping-Hua; Qiao, Jinli
2018-05-01
Graphene-fullerene hybrids were facilely fabricated by self-assembly of graphene oxide (GO) and multi-substituted fulleropyrrolidines (PyrC60). The hybrids (GO-PyrC60) were applied as support materials to deposit Pd nanoparticle catalyst by a simple hydrothermal co-reduction approach. The as-prepared electrocatalysts (Pd/RGO-PyrC60) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. The RGO-PyrC60 hybrid supported Pd catalyst with the optimal ratio of RGO to PyrC60, exhibited much enhanced electrocatalytic activity and stability toward methanol oxidation reaction (MOR) compared to the RGO alone supported Pd as well as commercial Pd/C. The introduction of fulleropyrrolidine as spacer between graphene layers could increase the electrocatalytic activity and improve the long-term stability. This strategy may contribute to developing graphene-fullerene hydrids as effective support materials for advanced electrocatalysts.
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Energy Technology Data Exchange (ETDEWEB)
Majidi, Mir Reza [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of); Jouyban, Abolghasem [Faculty of Pharmacy and Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz 51664 (Iran, Islamic Republic of); Asadpour-Zeynali, Karim [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of)]. E-mail: asadpour@tabrizu.ac.ir
2007-06-20
Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 {mu}M, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.
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Energy Technology Data Exchange (ETDEWEB)
Wang, Pengcheng; Zhou, Yingke, E-mail: zhouyk888@hotmail.com; Hu, Min; Chen, Jian
2017-01-15
Highlights: • Nitrogen-doped carbon nanotube supporting ultrafine NiO nanoparticles with high dispersity are facile synthesized. • The nitrogen doping, calcination temperature and NiO loading present great effects on the catalyst morphology, structure and electrochemical performance. • NiO-NCNT-3x-400 demonstrates remarkable catalytic activity and stability for the methanol electrolytic oxidation reaction. - Abstract: Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.
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International Nuclear Information System (INIS)
Nalini, B.; Sriman Narayanan, S.
1998-01-01
Ruthenium(III) diphenyldithiocarbamate was used as mediator to modify graphite electrode by abrasive method. The modified electrode was characterized electrochemically by cyclic voltammetry. The electrode was scanned between 0.0 V to +0.8 V. An anodic peak at + 0.39 V and a cathodic peak at +0.24 V have been observed for a scan rate of 100 mV/s. The electrode has been characterized at various scan rate and pHs in 0.1 M KNO 3 solution. Sulfhydryl compounds, cysteine and glutathione, were electro catalytically oxidised at the modified electrode. pH variation was studied to optimize the conditions for their estimation. Linear response for cysteine is in the range of 0.00-15.20 ppm, with a correlation coefficient (r), of 0.9993. The linear range for glutathione is 0.00-30.40 ppm, with a value of 0.999 for r. The electrocatalytic oxidation of both cysteine and glutathione gave reproducible current values with a standard deviation of 0.1686 for 10 repetitive determinations. The stability and reproducibility of the electrode for the determination of cysteine and glutathione were also discussed. The electrocatalytic oxidation of the sulfhydryl compounds were also studied in hydrodynamic environment. (author)
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Shinagawa, Tatsuya
2016-12-17
Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. The electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances where water splitting reaction is conducted, required solution conditions such as the identity and molarity of ions may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate developing efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), electrode stability, and/or indirectly impacts the performance by influencing concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.
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Shinagawa, Tatsuya; Takanabe, Kazuhiro
2016-01-01
Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. The electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances where water splitting reaction is conducted, required solution conditions such as the identity and molarity of ions may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate developing efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), electrode stability, and/or indirectly impacts the performance by influencing concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.
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Energy Technology Data Exchange (ETDEWEB)
Golikand, Ahmad Nozad; Maragheh, Mohammad Ghannadi; Irannejad, Leila [Jaber Ibn Hayan Research Lab., Atomic Energy Organization of Iran (AEOI), Tehran (Iran); Golabi, Seyed Mehdi [Electroanalytical Chemistry Lab., Faculty of Chemistry, University of Tabriz, Tabriz (Iran)
2005-08-18
The electrocatalytic oxidation of methanol at a (Pb) lead electrode modified by Pt, Pt-Ru and Pt-Sn microparticles dispersed into poly(o-phenylenediamine) (PoPD) film has been investigated using cyclic voltammetry as analytical technique and 0.5M sulfuric acid as supporting electrolyte. It has been shown that the presence of PoPD film increases considerably the efficiency of deposited Pt and Pt alloys microparticles toward the electrocatalytic oxidation of methanol. The catalytic activity of Pt particles is further enhanced when Ru and especially Sn, is co-deposited in the polymer film. The effects of various parameters such as concentration of methanol, medium temperature as well as the long term stability of modified electrodes have also been investigated. (author)
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Shinagawa, Tatsuya; Takanabe, Kazuhiro
2017-04-10
Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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Novel antimony doped tin oxide/carbon aerogel as efficient electrocatalytic filtration membrane
Directory of Open Access Journals (Sweden)
Zhimeng Liu
2016-05-01
Full Text Available A facile method was developed to prepare antimony doped tin oxide (Sb-SnO2/carbon aerogel (CA for use as an electrocatalytic filtration membrane. The preparation process included synthesis of a precursor sol, impregnation, and thermal decomposition. The Sb-SnO2, which was tetragonal in phase with an average crystallite size of 10.8 nm, was uniformly distributed on the CA surface and firmly attached via carbon-oxygen-tin chemical bonds. Preliminary filtration tests indicated that the Sb-SnO2/CA membrane had a high rate of total organic carbon removal for aqueous tetracycline owing to its high current efficiency and electrode stability.
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A novel hydrogen oxidizer amidst the sulfur-oxidizing Thiomicrospira lineage
Hansen, Moritz; Perner, Mirjam
2015-01-01
Thiomicrospira species are ubiquitously found in various marine environments and appear particularly common in hydrothermal vent systems. Members of this lineage are commonly classified as sulfur-oxidizing chemolithoautotrophs. Although sequencing of Thiomicrospira crunogena's genome has revealed genes that encode enzymes for hydrogen uptake activity and for hydrogenase maturation and assembly, hydrogen uptake ability has so far not been reported for any Thiomicrospira species. We isolated a Thiomicrospira species (SP-41) from a deep sea hydrothermal vent and demonstrated that it can oxidize hydrogen. We show in vivo hydrogen consumption, hydrogen uptake activity in partially purified protein extracts and transcript abundance of hydrogenases during different growth stages. The ability of this strain to oxidize hydrogen opens up new perspectives with respect to the physiology of Thiomicrospira species that have been detected in hydrothermal vents and that have so far been exclusively associated with sulfur oxidation. PMID:25226028
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Chen, Batian
2016-05-17
Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties
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Energy Technology Data Exchange (ETDEWEB)
Chu, H.-W.; Thangamuthu, R. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China); Chen, S.-M. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China)], E-mail: smchen78@ms15.hinet.net
2008-02-15
Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H{sub 2}SO{sub 4} solution containing Zn(NO{sub 3}){sub 2}, RuCl{sub 3} and K{sub 3}[Fe(CN){sub 6}] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of Ru{sup II/III} redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and L-cysteine, and reduction of S{sub 2}O{sub 8}{sup 2-} and SO{sub 5}{sup 2-} as well as IO{sub 3}{sup -} using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques.
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Nano cobalt oxides for photocatalytic hydrogen production
Mangrulkar, Priti A.
2012-07-01
Nano structured metal oxides including TiO 2, Co 3O 4 and Fe 3O 4 have been synthesized and evaluated for their photocatalytic activity for hydrogen generation. The photocatalytic activity of nano cobalt oxide was then compared with two other nano structured metal oxides namely TiO 2 and Fe 3O 4. The synthesized nano cobalt oxide was characterized thoroughly with respect to EDX and TEM. The yield of hydrogen was observed to be 900, 2000 and 8275 mmol h -1 g -1 of photocatalyst for TiO 2, Co 3O 4 and Fe 3O 4 respectively under visible light. It was observed that the hydrogen yield in case of nano cobalt oxide was more than twice to that of TiO 2 and the hydrogen yield of nano Fe 3O 4 was nearly four times as compared to nano Co 3O 4. The influence of various operating parameters in hydrogen generation by nano cobalt oxide was then studied in detail. Copyright © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
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Directory of Open Access Journals (Sweden)
Liu Xiuping
2018-01-01
Full Text Available Two novel water stable metal-organic frameworks, [Cu(L·(4,4′-bipy·(ClO4]n (1, [Cu(L·(phen·(ClO4·(H2O]2 (2, have been constructed by HL=[5-Mercapto-1-methyl] tetrazole acetic acid and Cu (II salt in the presence of assistant N-containing ligands. MOF 1 and MOF 2 with open CuII sites, resulting the framework 1 and 2 show electrocatalytic activity for water oxidation in alkaline solution. The electrochemical properties of complex for oxygen evolution reaction (OER were evaluated by linear sweep voltammetry (LSV and the Tafel slopes. Complex 1 has a higher LSV activity with a lower over potential of 1.54 V and a much higher increase in current density. Meanwhile, the Tafel slope of complex 1 (122.0 mV dec-1 is much lower than complex 2 (243.5 mV dec-1. This phenomenon makes complex 1 a promising porous material for electrocatalytic activity.
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Directory of Open Access Journals (Sweden)
Ali Ourari
2017-11-01
Full Text Available Nickel(II-DHS complex was obtained from N,N′-bis(2,5-dihydroxybenzylidene-1,2-diaminoethane (H2DHS ligand and nickel acetate tetrahydrated in ethanolic solution with stirring under reflux. This complex, dissolved in an alkaline solution, was oxidized to form electroactive films strongly adhered on the ITO (indium tin oxide electrode surface. In this alkaline solution, the poly-[NiII-DHS]/ITO films showed the typical voltammetric response of (Ni2+/Ni3+ redox couple centers which are immobilized in the polymer-film. The modified electrodes (MEs obtained were also characterized by several techniques such as scanning electronic microscopy, atomic force microscopy and electrochemical methods. The electrocatalytic behavior of these MEs toward the oxidation reaction of some aliphatic alcohols such as methanol, ethanol, 2-Methyl-1-propanol and isopropanol was investigated. The voltammograms recorded with these alcohols showed good electrocatalytic efficiency. The electrocatalytic currents were at least 80 times higher than those obtained for the oxidation of methanol on electrodes modified with nickel hydroxide films in alkaline solutions. We noticed that these electrocatalytic currents are proportional to the concentration of methanol (0.050–0.30 μM. In contrast, those recorded for the oxidation of other aliphatic short chain alcohols such as ethanol, 2-methyl-1-propanol and isopropanol are rather moderately weaker. In all cases the electrocatalytic currents presented a linear dependence with the concentration of alcohol. These modified electrodes could be applied as alcohol sensors.
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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.
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International Nuclear Information System (INIS)
Cai, Zhi-xiong; Liu, Cong-cong; Wu, Geng-huang; Chen, Xiao-mei; Chen, Xi
2014-01-01
Graphical abstract: - Highlights: • Porous 3D dendrite-like structure of Pt-on-Pd bimetallic nanostructures supported on graphene were prepared. • The surface of nanostructures was very “clean” because of the surfactant-free formation process and the use of green reagent. • The hetero-nanostructures showed excellent electrocatalytic performance in methanol oxidation. - Abstract: A green synthesis of Pt-on-Pd bimetallic nanodendrites supported on graphene (GPtPdNDs) with a Pd interior and a dendrite-like Pt exterior was achieved using a two-step preparation, mixing graphene and PdCl 4 2− first, then adding PtCl 4 2− and ethanol without any other solvent. The morphology, structure and composition of the thus-prepared GPtPdNDs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no halide ions (refer in particular to Br - , I − ) or surfactant was involved in the synthesis, the prepared GPtPdNDs were directly modified onto a glassy carbon electrode and showed excellent electrocatalytic performance in methanol oxidation without any pretreatments. Moreover, with the special structure of PtPdNDs and the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the GPtPdNDs composites exhibited higher electrocatalytic activity and better tolerance to Pt nanoparticles supported on graphene (GPtNPs) and Pt/C for methanol oxidation
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Hydrogen evolution by a metal-free electrocatalyst
Zheng, Yao
2014-04-28
Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics. © 2014 Macmillan Publishers Limited. All rights reserved.
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CSIR Research Space (South Africa)
Ramulifho, T
2013-04-01
Full Text Available Electrocatalytic oxidation of ethylene glycol (EG) in alkaline medium using nano-scaled palladium-based bimetallic catalysts (PdM, where M = Ni and Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) is compared. The bimetallic...
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Diffusion of hydrogen in iron oxides
International Nuclear Information System (INIS)
Bruzzoni, P.
1993-01-01
The diffusion of hydrogen in transitions metals oxides has been recently studied at room temperature through the permeability electrochemical technique. This work studies thin oxide layers grown in air or in presence of oxidizing atmospheres at temperatures up to 200 deg C. The substrate was pure iron with different superficial treatments. It was observed that these oxides reduce up to three magnitudes orders, the hydrogen stationary flux through membranes of usual thickness in comparison with iron membranes free of oxide. (Author)
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Energy Technology Data Exchange (ETDEWEB)
Chen, Aishi; Cui, Renjie; He, Yanna; Wang, Qi [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); Zhang, Jian, E-mail: iamjzhang@njupt.edu.cn [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); Yang, Jianping [School of Science, Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 (China); Li, Xing’ao, E-mail: lxahbmy@126.com [Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023 (China); School of Science, Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 (China)
2017-07-31
Highlights: • A new hollow MoS{sub 2} microflakes are prepared by hydrothermal synthesis firstly. • SEM and TEM study show the structural nature of hollow microflakes in depth. • The unique hollow structures have large surface area owing to the cavity. • The hollow microflakes show better HER performance than their solid counterparts. - Abstract: Molybdenum disulfide (MoS{sub 2}) has emerged as a promising non-precious metal catalyst for hydrogen evolution reaction (HER) in recent years. Some strategies including nanotechnology as well as atom doping have been employed in the preparing of electrocatalysts for high-activity and stability. To the best of our knowledge, hollow MoS{sub 2} microflakes assembled from ultrathin nanosheets have not been prepared previously. In this work, a simple, facile and environmentally friendly hydrothermal synthesis was utilized for the fabrication of hollow MoS{sub 2} microflakes for the first time. The unique hollow structures have fascinating properties, such as the large surface and low density. The morphology and structure of MoS{sub 2} microflakes were confirmed by XRD, SEM, TEM and Raman. The composition of these materials was identified by the X-ray photoelectron spectroscopy. Notably, the as-prepared hollow MoS{sub 2} microflakes showed better electrocatalytic activity than other samples. The hollow flake-like structure can not only increase the active edge sites owing to the large specific surface area, but also enhance the electron transport to improve the electrocatalytic activity. Benefiting from these factors, the hollow MoS{sub 2} microflakes exhibited electrocatalytic activity and excellent stability with a low overpotential about 85 mV and a Tafel slope of 59 mV per decade.
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International Nuclear Information System (INIS)
Ju, HyungKuk; Giddey, Sarbjit; Badwal, Sukhvinder P.S.; Mulder, Roger J.
2016-01-01
Highlights: • Ethanol assisted water electrolysis reduces electric energy input by more than 50%. • Partial oxidation of ethanol leads to formation of undesired chemicals. • Degradation occurs due to formation of by-products and poisoning of catalyst. • Better catalyst has the potential to increase ethanol to H_2 conversion efficiency. • A plausible ethanol electro-oxidation mechanism has been proposed - Abstract: The global interest in hydrogen/fuel cell systems for distributed power generation and transport applications is rapidly increasing. Many automotive companies are now bringing their pre-commercial fuel cell vehicles in the market, which will need extensive hydrogen generation, distribution and storage infrastructure for fueling of these vehicles. Electrolytic water splitting coupled to renewable sources offers clean on-site hydrogen generation option. However, the process is energy intensive requiring electric energy >4.2 kWh for the electrolysis stack and >6 kWh for the complete system per m"3 of hydrogen produced. This paper investigates using ethanol as a renewable fuel to assist with water electrolysis process to substantially reduce the energy input. A zero-gap cell consisting of polymer electrolyte membrane electrolytic cells with Pt/C and PtSn/C as anode catalysts were employed. Current densities up to 200 mA cm"−"2 at 70 °C were achieved at less than 0.75 V corresponding to an energy consumption of about 1.62 kWh m"−"3 compared with >4.2 kWh m"−"3 required for conventional water electrolysis. Thus, this approach for hydrogen generation has the potential to substantially reduce the electric energy input to less than 40% with the remaining energy provided by ethanol. However, due to performance degradation over time, the energy consumption increased and partial oxidation of ethanol led to lower conversion efficiency. A plausible ethanol electro-oxidation mechanism has been proposed based on the Faradaic conversion of ethanol and
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Directory of Open Access Journals (Sweden)
Ling Ding
2015-03-01
Full Text Available The electrocatalytic oxidation of venlafaxine (VEN was investigated at a glassy carbon electrode (GCE, the modified electrode by a gel containing multiwall carbon nanotubes (MWCNTs and a room-temperature ionic liquid (RTIL, 1-butyl-3-methylimidazolium hexafluorophate (BMIMPF6 in 0.10 mol L−1 phosphate buffer solution (PBS, pH 6.8. It was found that an irreversible anodic oxidation peak of VEN with the peak potential (Epa as 0.780 V appeared at MWCNTs-RTIL/GCE. The electrode reaction process was a diffusion-controlled one and the electrochemical oxidation involved two electrons transferring and two protons participation. Furthermore, the charge-transfer coefficient (α, and the electrode reaction rate constant (kf of VEN were found to be 0.91 and 3.04×10−2 s−1, respectively. Under the optimized conditions, the electrocatalytic oxidation peak currents were linearly dependent on the concentration of VEN in the concentration range from 2.0×10−6 mol L−1 ~ 2.0×10−3 mol L−1 with the limit of detection (S / N = 3 as 1.69×10−6 mol L−1. The proposed method has been successfully applied in the electrochemical quantitative determination of VEN content in commercial venlafaxine hydrochloride capsules and the determination results could meet the requirement of the quantitative determination.
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Tan, De-Xin; Wang, Yan-Li
2018-03-01
Sea anemone-like palladium (Pd)/polyaniline (PANI) nanocomposites were synthesized via visible-light-assisted swollen liquid crystals (SLCs) template method. The resulting samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive spectrometer (EDS), x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet-visible (UV–vis) absorption spectroscopy and Fourier transform infrared (FT-IR) spectroscopy, respectively. The electrocatalytic properties of Pd/PANI nanocomposites modified glass carbon electrode (GCE) for methane oxidation were investigated by cycle voltammetry (CV) and chronoamperometry. Those dispersed sea anemone-like Pd/PANI nanocomposites had an average diameter of 320 nm. The obtained Pd nanoparticles with an average diameter of about 45 nm were uniformly distributed in PANI matrix. Sea anemone-like Pd/PANI nanocomposites exhibited excellent electrocatalytic activity and stability for oxidation of methane (CH4).
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Directory of Open Access Journals (Sweden)
Jinbao He
2018-01-01
Full Text Available MoS2 is a promising material to replace Pt-based catalysts for the hydrogen evolution reaction (HER, due to its excellent stability and high activity. In this work, MoS2 nanoparticles supported on graphitic carbon (about 20 nm with a preferential 002 facet orientation have been prepared by pyrolysis of alginic acid films on quartz containing adsorbed (NH42MoS4 at 900 °C under Ar atmosphere. Although some variation of the electrocatalytic activity has been observed from batch to batch, the MoS2 sample exhibited activity for HER (a potential onset between 0.2 and 0.3 V vs. SCE, depending on the concentrations of (NH42MoS4 precursor used in the preparation process. The loading and particle size of MoS2, which correlate with the amount of exposed active sites in the sample, are the main factors influencing the electrocatalytic activity.
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Yuan, Qiang
2014-01-01
Well-defined Pd-Pt@Pd core-shell nanocrystals with a Pd-Pt alloy core and a conformal Pd shell of ~2-3 nm were directly synthesized through a one-pot, aqueous solution approach without any preformed Pd or Pt seeds. These Pd-Pt@Pd core-shell nanocrystals show an enhanced electrocatalytic activity for formic acid oxidation compared with commercial Pd black. This journal is © 2014 The Royal Society of Chemistry.
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Pt nanoparticles embedded on reduced graphite oxide with excellent electrocatalytic properties
Energy Technology Data Exchange (ETDEWEB)
Saravanan, Gengan, E-mail: saravanan3che@gmail.com [Central University of Tamil Nadu, Department of Chemistry, Thiruvarur, 610101 (India); Mohan, Subramanian, E-mail: sanjnamohan@yahoo.com [EMFT Division, CSIR-Central Electrochemical Research Institute, Tamilnadu, Karaikudi 630 006 (India)
2016-11-15
Graphical abstract: RGO/Nano Pt: This study explore the electrocatalytic oxidation performance of reduced graphite oxide (RGO) anchored with nano Pt. This graphene composite reveal superior electrooxidation performance that is associated with the flexible RGO matrix and the uniform distribution of Pt particles, which enhances surface area, fast electron transfer, uniform particle size distribution; consequently, the RGO matrix provides more stability to Pt particles during electrooxidation process. Display Omitted - Highlights: • Greener electrochemical method applied to prepare well-dispersed Pt-rGO. • Pt-rGO large surface area excellent charge transfer better catalytic activity. • Low-cost highly efficient carbon-based electrodes for direct formic acid fuel cell. • rGO an excellent support to anchor Pt nanoparticles on its surface. • Pt-rGO distinctly enhanced current density towards formic acid electrooxidation. - Abstract: Economically viable electrochemical approach has been developed for the synthesis of Pt nanoparticles through electrodeposition technique on the surface of Reduced Graphite Oxide (RGO). Pt nanoparticles embedded Reduced Graphite Oxide on Glassy Carbon Electrode are employed (Pt-rGO/GCE) for electrooxidation of formic acid. Scanning Electron Microscopy (SEM) image and Transmission Electron Microscopy (TEM) image shows that reduced graphite oxide act as an excellent support to anchor the Pt nanoparticles. Cyclic voltammetry results confirmed that Pt-rGO/GCE enhanced current density as many folds than that of bare platinum electrode for electrooxidation of formic acid. X-ray diffraction (XRD) patterns for Pt-graphene composites illustrate that peaks at 69.15 and 23° for Pt (220) and graphene carbon (002) respectively. {sup 13}C NMR spectrum of the electrochemically reduced graphite oxide resonance contains only one peak at 133 ppm which retains graphitic sp{sup 2} carbon and does not contain any oxygenated carbon and the carbonyl
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International Nuclear Information System (INIS)
Jo, Kyung Min; Kang, Hyun Ju; Yang, Hae Sik
2011-01-01
We have recently shown that the electrocatalytic activity of Au nanoparticles (AuNPs) can be enhanced via NaBH 4 treatment and cathodic treatment and that the enhanced activity slowly decreases with aging. We have also demonstrated that the electrocatalytic activity of the AuNPs freshly prepared by electrochemical or chemical reduction slowly decreases with aging in both air and solution. Likewise, the electrocatalytic activity of anodically treated Au electrodes or AuNPs might change with aging. Herein, we report that the electrocatalytic activity of long-aged AuNPs can be enhanced via anodic treatment and that the enhanced electrocatalytic activity decreases with aging in air. The change in the electrocatalytic activity of AuNPs was evaluated by comparing cyclic voltammograms for the electrooxi-dation of hydrogen peroxide (H 2 O 2 ) and formic acid
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International Nuclear Information System (INIS)
Jiang Zhongqing; Jiang Zhongjie
2011-01-01
Graphical abstract: A H 2 plasma, that aims at reducing the fraction of the oxidized species at the outermost perimeter of metal particles, has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, reduced charge transfer resistance, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. Highlights: → A H 2 plasma technique is used to treat the PtRu nanoparticles. → The H 2 plasma treated PtRu/PS-MWCNTs exhibit improved electrocatalytic activity. → The H 2 plasma treated PtRu/PS-MWCNTs have significantly reduced charge transfer resistance. → The H 2 plasma treated PtRu/PS-MWCNTs show the increased stability. → The Pt:Ru atomic ratio of PtRu nanoparticles has a significant effect on the electrochemical activity. - Abstract: A H 2 plasma has been used to treat the PtRu nanoparticles supported on the plasma functionalized multi-walled carbon nanotubes (PtRu/PS-MWCNTs). The plasma treatment does not change the size and crystalline structure of PtRu nanoparticles, but reduces the fraction of the oxidized species at the outermost perimeter of particles. The electrochemical results show that these plasma treated PtRu/PS-MWCNTs exhibit increased electrochemically active surface area, improved electrocatalytic activity and long term stability toward methanol and formic acid oxidation, and enhanced tolerance to carbonaceous species relative to the sample untreated with the H 2 plasma. The electrocatalytic activities of the plasma treated PtRu/PS-MWCNTs are found to be dependent upon the Pt:Ru atomic ratios of PtRu nanoparticles. The catalysts with a Pt:Ru atomic ratio close to 1:1 show superior properties in the electrooxidation of methanol and formic acid
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Hydrogen oxidation in Azospirillum brasilense
Energy Technology Data Exchange (ETDEWEB)
Tibelius, K.
1984-01-01
Hydrogen oxidation by Azospirillum brasilense Sp7 was studied in N/sub 2/-fixing and NH/sub 4//sup +/-grown batch cultures. The K/sub m/ for H/sub 2/ of O/sub 2/-dependent H/sup 3/H oxidation in whole cells was 9 uM. The rates of H/sup 3/H and H/sub 2/ oxidation were very similar, indicating that the initial H/sub 2/ activation step in the overall H/sub 2/ oxidation reaction was not rate-limiting and that H/sup 3/H oxidation was a valid measure of H/sub 2/-oxidation activity. Hydrogen-oxidation activity was inhibited irreversibly by air. In N-free cultures the O/sub 2/ optima for O/sub 2/-dependent H/sub 2/ oxidation, ranging from 0.5-1.25% O/sub 2/ depending on the phase of growth, were significantly higher than those of C/sub 2/H/sub 2/ reduction, 0.15-0.35%, suggesting that the H/sub 2/-oxidation system may have a limited ability to aid in the protection of nitrogenase against inactivation by O/sub 2/. Oxygen-dependent H/sub 2/ oxidation was inhibited by NO/sub 2//sup +/, NO, CO, and C/sub 2/H/sub 2/ with apparent K/sub 1/ values of 20, 0.4, 28, and 88 uM, respectively. Hydrogen-oxidation activity was 50 to 100 times higher in denitrifying cultures when the terminal electron acceptor for growth was N/sub 2/O rather than NO/sub 3//sup -/, possibly due to the irreversible inhibition of hydrogenase by NO/sub 2//sup -/ and NO in NO/sub 3//sup -/-grown cultures.
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Microwave-polyol synthesis and electrocatalytic performance of Pt/graphene nanocomposites
International Nuclear Information System (INIS)
Liao, Chien-Shiun; Liao, Chien-Tsao; Tso, Ching-Yu; Shy, Hsiou-Jeng
2011-01-01
Highlights: · One-pot microwave-polyol synthesis of Pt/graphene electrocatalyst. · Simultaneous formation of Pt nanoparticles and reduction of graphene oxide. · Electrocatalytic activities depend on the morphology of the deposited Pt particles. · Dense dispersion of isolated Pt particles with high electrochemical active surface. · Few particle clusters of Pt have large number of active sites for methanol oxidation. - Abstract: Graphene oxide (GO) prepared by the modified Hummers method is used as a support in the formation of a Pt/GO nanocomposite electrocatalyst by microwave-polyol synthesis. The effects of microwave reaction times on particle size, dispersion, and electrocatalytic performance of Pt nanoparticles are studied using wide-angle X-ray diffractometery, Raman spectroscopy, transmission electron microscopy and three-electrode electrochemical measurements. The results indicate that Pt nanoparticles nucleation and growth occur, and the particles are uniformly deposited on the GO nanosheets within a short time. The maximum electrochemical active surface area 85.71 m 2 g -1 for a Pt/GO reaction time of 5 min, is a result of the deposition of a dense dispersion of small Pt particles. The highest methanol oxidation peak current density, I f , of 0.59 A mg -1 occurs for a Pt/GO reaction time of 10 min and is due to the formation of interconnecting Pt particles clusters. This novel Pt/GO nanocomposite electrocatalyst with high electrocatalytic activities has the potential for use as an anode material in fuel cells.
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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.
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International Nuclear Information System (INIS)
Samiee, L.; Shoghi, F.; Vinu, A.
2013-01-01
Highlights: ► Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. ► Novel electrocatalytic activity of functionalized nanoporous carbon material. ► Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N 2 adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe 2 O 3 -Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.
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Energy Technology Data Exchange (ETDEWEB)
Samiee, L., E-mail: Leila.Samiee83@gmail.com [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Shoghi, F. [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Vinu, A., E-mail: a.vinu@uq.edu.au [Australian Institute for Bioengineering and Nanotechnology(AIBN), University of Queensland, Corner College and Cooper Roads (Bld75), Brisbane, Qld 4072 (Australia)
2013-01-15
Highlights: Black-Right-Pointing-Pointer Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. Black-Right-Pointing-Pointer Novel electrocatalytic activity of functionalized nanoporous carbon material. Black-Right-Pointing-Pointer Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N{sub 2} adsorption-desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe{sub 2}O{sub 3}-Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.
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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.
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Directory of Open Access Journals (Sweden)
Mingyan Wang
2017-07-01
Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin âMtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and ÏâÏ stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst
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Electro-catalytic degradation of sulfisoxazole by using graphene anode.
Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng
2016-05-01
Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants. Copyright © 2015. Published by Elsevier B.V.
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Confinement dependence of electro-catalysts for hydrogen evolution from water splitting
Directory of Open Access Journals (Sweden)
Mikaela Lindgren
2014-02-01
Full Text Available Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE, where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.
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Energy Technology Data Exchange (ETDEWEB)
Manivannan, Shanmugam; Ramaraj, Ramasamy, E-mail: ramarajr@yahoo.com [Madurai Kamaraj University, Centre for Photoelectrochemistry, School of Chemistry (India)
2013-10-15
A facile method for fabrication of raspberry-like Au nanostructures (Au NRBs)-modified electrode by electrodeposition and its applications toward the electrocatalytic oxidation of methanol (MOR) in alkaline medium and oxygen reduction reaction (ORR) in both alkaline and acidic media are demonstrated. The Au NRBs are characterized by UV-Vis absorption spectra, SEM, X-ray diffraction, and electrochemical measurements. The growth of Au NRBs was monitored by recording the in-situ absorption spectral changes during electrodeposition using spectroelectrochemical technique. Here we systematically studied the MOR by varying several reaction parameters such as potential scan rate and methanol concentration. The electrocatalytic poisoning effect due to the MOR products are not observed at the Au NRBs-modified electrode. At the alkaline medium the Au NRBs-modified electrode shows the better catalytic activities toward the MOR and ORR when compared to the poly crystalline gold and bare glassy carbon electrodes. The Au NRBs-modified electrode is a promising and inexpensive electrode material for other electrocatalytic applications.Graphical AbstractRaspberry-like Au nanostructures modified electrode is prepared and used for electrocatalytic applications.
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International Nuclear Information System (INIS)
Kiyani, Roya; Rowshanzamir, Soosan; Parnian, Mohammad Javad
2016-01-01
In this work, palladium and palladium-cobalt supported on nitrogen doped graphene as anode materials in direct methanol fuel cells is reported. A simple and low temperature solvothermal method is used to directly prepare nanoflower-like NG and then, Pd and Pd−Co nanoparticles are precipitated onto the surface of NG using a modified polyol reduction method. The synthesized electrocatalysts are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) are used to measure electrocatalytic methanol oxidation activity and the durability of electrocatalysts. The results show that Pd−Co/NG has better electrocatalytic activity than Pd/NG toward methanol oxidation reaction (MOR) in alkaline media that is related at the presence of cobalt atoms. In addition, chronoamperometric results indicate that Pd−Co/NG is more stable than commercial Pt/C for MOR. - Highlights: • Nitrogen doped graphene (NG) was prepared by a simple solvothermal method. • Pd and Pd−Co nanoparticles were deposited on NG by polyol reduction method. • Promoting effects of cobalt over Pd/NG for MOR were investigated. • Higher activity and enhanced durability was observed for Pd−Co/NG catalyst.
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Mechanisms of wet oxidation by hydrogen peroxide
International Nuclear Information System (INIS)
Baxter, R.A.
1987-08-01
A research programme is currently under way at BNL and MEL to investigate the possible use of Hydrogen Peroxide with metal ion catalysts as a wet oxidation treatment system for CEGB organic radioactive wastes. The published literature relating to the kinetics and mechanism of oxidation and decomposition reactions of hydrogen peroxide is reviewed and the links with practical waste management by wet oxidation are examined. Alternative wet oxidation systems are described and the similarities to the CEGB research effort are noted. (author)
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International Nuclear Information System (INIS)
Gu Zhiguo; Yang Shuping; Li Zaijun; Sun Xiulan; Wang Guangli; Fang Yinjun; Liu Junkang
2011-01-01
Graphical abstract: We first reported an ultrasensitive hydrogen peroxide biosensor in this work, which was fabricated by coating graphene-gold nanocomposite, CdTe-CdS core-shell quantum dots, gold nanoparticles and horseradish peroxidase in sequence on the surface of gold electrode. Since a promising their electrocatalytic synergy towards hydrogen peroxide was achieved, the biosensor displayed very high sensitivity, low detection limit (S/N = 3) (3.2 x 10 -11 M) and good long-term stability (20 weeks). Highlights: · We for the first time integrated novel hydrogen peroxide biosensor based on G-AuNP, CdTe-CdS and AuNPs. · Three nanomaterials show remarkable synergistic electrocatalysis towards hydrogen peroxide. · The biosensor provides the best sensitivity in all biosensors based on graphene for detection of glucose up to now. - Abstract: We first reported an ultrasensitive hydrogen peroxide biosensor in this work. The biosensor was fabricated by coating graphene-gold nanocomposite (G-AuNP), CdTe-CdS core-shell quantum dots (CdTe-CdS), gold nanoparticles (AuNPs) and horseradish peroxidase (HRP) in sequence on the surface of gold electrode (GE). Cyclic voltammetry and differential pulse voltammetry were used to investigate electrochemical performances of the biosensor. Since promising electrocatalytic synergy of G-AuNP, CdTe-CdS and AuNPs towards hydrogen peroxide was achieved, the biosensor displayed a high sensitivity, low detection limit (S/N = 3) (3.2 x 10 -11 M), wide calibration range (from 1 x 10 -10 M to 1.2 x 10 -8 M) and good long-term stability (20 weeks). Moreover, the effects of omitting G-AuNP, CdTe-CdS and AuNP were also examined. It was found that sensitivity of the biosensor is more 11-fold better if G-AuNP, CdTe-CdS and AuNPs are used. This could be ascribed to improvement of the conductivity between graphene nanosheets in the G-AuNP due to introduction of the AuNPs, ultrafast charge transfer from CdTe-CdS to the graphene sheets and AuNP due to
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Energy Technology Data Exchange (ETDEWEB)
Shafaie, Fahimeh [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Hadadzadeh, Hassan, E-mail: hadad@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Behnamfar, Mohammad Taghi [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 (Iran, Islamic Republic of); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan, 81746-73441 (Iran, Islamic Republic of)
2016-12-01
A new mononuclear yttrium(III) complex, [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}] (where MO{sup –} is methyl orange anion (4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate)), was synthesized in an aqueous solution. The complex was characterized by elemental analysis, UV/Vis, FT-IR, and single-crystal X-ray crystallography. The yttrium oxysulfate nanoparticles (Y{sub 2}O{sub 2}SO{sub 4}) were then prepared by calcination of [Y(MO){sub 3}(DMF){sub 3}(H{sub 2}O){sub 2}]. The obtained nanoparticles were characterized by FT-IR, X-ray diffraction analysis (XRD), and field-emission scanning electron microscopy (FE-SEM). The hydrogen adsorption/desorption (H{sub ads}/H{sub des}) behavior of the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles was studied at a carbon paste electrode (CPE) in H{sub 2}SO{sub 4} by cyclic voltammetry (CV). The recorded voltammograms exhibited a pair of peaks corresponding to the adsorption/desorption of hydrogen for the Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. The results show a reversible hydrogen adsorption/desorption reaction for both compounds. The voltammograms of the nanoparticles indicate an excellent cycling stability for the adsorption/desorption of hydrogen. In addition, the linear sweep voltammetry (LSV) technique was used to investigate the electrocatalytic activity of both compounds for the hydrogen adsorption reaction. The linear voltammograms of both compounds demonstrate the excellent electrocatalytic activity for the hydrogen adsorption reaction. - Highlights: • Preparation of a new Y(III) complex and Y{sub 2}O{sub 2}SO{sub 4} nanoparticles. • Investigation of the H{sub ads}/H{sub des} reaction for both compounds by voltammetry. • Observation of two peaks corresponding to the H{sub ads}/H{sub des} in both compounds. • An excellent cycling stability for the nanoparticles in H{sub 2}SO{sub 4}.
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Directory of Open Access Journals (Sweden)
Xiaoying Wang
2015-07-01
Full Text Available A facile, rapid and green method based on potentiostatic electrodeposition is developed to synthesize a novel H3PMo12O40-Pt/reduced graphene oxide (denoted as PMo12-Pt/rGO composite. The as-prepared PMo12-Pt/rGO is characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM and X-ray photoelectron spectroscopy (XPS. The results reveal that graphene oxide (GO is reduced to the rGO by electrochemical method and POMs clusters are successfully located on the rGO as the modifier. Furthermore, the PMo12-Pt/rGO composite shows higher electrocatalytic activity, better tolerance towards CO and better stability than the conventional pure Pt catalyst.
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Development of hydrogen oxidizing bacteria using hydrogen from radiolysis or metal corrosion
International Nuclear Information System (INIS)
Libert, M.F.; Sellier, R.; Marty, V.; Camaro, S.
2000-01-01
The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H 2 production in a bituminized nuclear waste environment were simulated in the present study: - H 2 production by iron corrosion under anaerobic conditions was simulated by adding 10% of H 2 in the atmosphere; - H 2 production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H 2 in water allows the growth of hydrogen oxidizing bacteria leading to: - CO 2 and N 2 production; - H 2 consumption; - lower NO 3 - concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO 3 - release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H 2 instead of hydrocarbons. (authors)
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Hydrogen storage inside graphene-oxide frameworks
International Nuclear Information System (INIS)
Chan Yue; Hill, James M
2011-01-01
In this paper, we use applied mathematical modelling to investigate the storage of hydrogen molecules inside graphene-oxide frameworks, which comprise two parallel graphenes rigidly separated by perpendicular ligands. Hydrogen uptake is calculated for graphene-oxide frameworks using the continuous approximation and an equation of state for both the bulk and adsorption gas phases. We first validate our approach by obtaining results for two parallel graphene sheets. This result agrees well with an existing theoretical result, namely 1.85 wt% from our calculations, and 2 wt% arising from an ab initio and grand canonical Monte Carlo calculation. This provides confidence to the determination of the hydrogen uptake for the four graphene-oxide frameworks, GOF-120, GOF-66, GOF-28 and GOF-6, and we obtain 1.68, 2, 6.33 and 0 wt%, respectively. The high value obtained for GOF-28 may be partly explained by the fact that the benzenediboronic acid pillars between graphene sheets not only provide mechanical support and porous spaces for the molecular structure but also provide the higher binding energy to enhance the hydrogen storage inside graphene-oxide frameworks. For the other three structures, this binding energy is not as large in comparison to that of GOF-28 and this effect diminishes as the ligand density decreases. In the absence of conflicting data, the present work indicates GOF-28 as a likely contender for practical hydrogen storage.
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Directory of Open Access Journals (Sweden)
Jianping Yong
2014-01-01
Full Text Available Five new structural ferrocene derivatives (2a~2e were firstly synthesized and characterized by 1H NMR, 13C NMR, ESI-MS, and XRD. Subsequently, the preliminarily electrocatalytic oxidation of L-cysteine (L-Cys at nafion-ferrocene derivatives modified glassy carbon electrode (GCE has also been investigated by cyclic voltammetry. The results showed that 2e can dramatically electrocatalyze the oxidation of L-cysteine at its modified GCE in 0.1 mol L−1 NaNO3 aqueous solution with a quasireversible process with ΔEp≈55 mV.
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Directory of Open Access Journals (Sweden)
Hongjun Wu
2011-01-01
Full Text Available Ti-supported RuO2-Co3O4-CeO2 (Ru0.3Co0.7−xCex oxide, 0≤x≤0.7 electrodes were prepared by sol-gel process. The phase structure, surface morphology, and microstructure of the oxide layer were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Electrocatalytic activity and oxygen evolution reaction (OER kinetics on these electrodes in 1.0 mol⋅dm−3 KOH solution were studied by recording open-circuit potential, cyclic voltammetry, and polarisation curves. The results showed that the appropriate content of CeO2 could reduce the grain size and increase active surface area. The electrocatalytic activity shows a strong dependence on the CeO2 content in the film. Catalytic performance of mixed oxide electrodes with 40 mol % CeO2 was the best, with the greatest voltammetric charge, 86.23 mC⋅cm−2, and the smallest apparent activation energy for OER at 0.60 V was 22.76 kJ⋅mol−1.
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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.
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Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts
Energy Technology Data Exchange (ETDEWEB)
Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment
1975-11-01
Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.
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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.
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Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
DEFF Research Database (Denmark)
Man, Isabela Costinela; Su, Hai-Yan; Vallejo, Federico Calle
2011-01-01
with the computational standard hydrogen electrode (SHE) model. We showed that by the discovery of a universal scaling relation between the adsorption energies of HOO* vs HO*, it is possible to analyze the reaction free energy diagrams of all the oxides in a general way. This gave rise to an activity volcano......Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination...
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Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion
DEFF Research Database (Denmark)
Glarborg, Peter; Marshall, Paul
2017-01-01
Hydrogen isocyanide (HNC) has been proposed as an important intermediate in oxidation of hydrogen cyanide (HCN) in combustion, but details of its chemistry are still in discussion. At higher temperatures, HCN and HNC equilibrate rapidly, and being more reactive than HCN, HNC offers a fast alterna...... HNCO is the major consumption path for HCN. Under lean conditions, HNC is shown to be less important than indicated by the early work by Lin and co-workers, but it acts to accelerate HCN oxidation and promotes the formation of HNCO.......Hydrogen isocyanide (HNC) has been proposed as an important intermediate in oxidation of hydrogen cyanide (HCN) in combustion, but details of its chemistry are still in discussion. At higher temperatures, HCN and HNC equilibrate rapidly, and being more reactive than HCN, HNC offers a fast...
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High-temperature oxidation of Zircaloy in hydrogen-steam mixtures
International Nuclear Information System (INIS)
Chung, H.M.; Thomas, G.R.
1982-09-01
Oxidation rates of Zircaloy-4 cladding tubes have been measured in hydrogen-steam mixtures at 1200 to 1700 0 C. For a given isothermal oxidation temperature, the oxide layer thicknesses have been measured as a function of time, steam supply rate, and hydrogen overpressure. The oxidation rates in the mixtures were compared with similar data obtained in pure steam and helium-steam environments under otherwise identical conditions. The rates in pure steam and helium-steam mixtures were equivalent and comparable to the parabolic rates obtained under steam-saturated conditions and reported in the literature. However, when the helium was replaced with hydrogen of equivalent partial pressure, a significantly smaller oxidation rate was observed. For high steam-supply rates, the oxidation kinetics in a hydrogen-steam mixture were parabolic, but the rate was smaller than for pure steam or helium-steam mixtures. Under otherwise identical conditions, the ratio of the parabolic rate for hydrogen-steam to that for pure steam decreased with increasing temperature and decreasing steam-supply rate
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Zhu, Chengzhou; Guo, Shaojun; Dong, Shaojun
2012-05-02
A facile and general method has been developed to synthesize well-defined PdPt and PdAu alloy nanowires, which exhibit significantly enhanced activity towards small molecules, such as ethanol, methanol, and glucose electro-oxidation in an alkaline medium. Considering the important role of one-dimensional alloy nanowires in electrocatalytic systems, the present Pd-based alloy nanostructures could offer a promising new class of advanced electrocatalysts for direct alcohol fuel cells and electrochemical sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Figueiredo-Filho, Luiz C S; Brownson, Dale A C; Fatibello-Filho, Orlando; Banks, Craig E
2013-08-21
We explore the recent reports that the use of graphene modified electrodes gives rise to the electrocatalytic oxidation of kojic acid. It is demonstrated that large quantifiable voltammetric signatures are observed on bare/unmodified graphitic electrodes, which are shown to be analytically useful and superior to those observed at graphene modified alternatives. This work is of importance as it shows that control experiments are critical and must be undertaken before "electrocatalysis" is conferred when investigating graphene in electrochemistry. In terms of the electroanalytical response of graphene modified electrodes, a bare edge plane pyrolytic graphite electrode is shown to give rise to an improved linear range and limit of detection, questioning the need to modify electrodes with graphene.
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Gold nanoparticles-decorated fluoroalkylsilane nano-assemblies for electrocatalytic applications
Energy Technology Data Exchange (ETDEWEB)
Ballarin, Barbara, E-mail: barbara.ballarin@unibo.it [Department of Industrial Chemistry “Toso Montanari”, UdR INSTM of Bologna and CIRI MAM, Alma Mater Studiorum – University of Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy); Barreca, Davide [CNR-IENI and INSTM, Department of Chemistry, Padova University, Via Marzolo 1, 35131 Padova (Italy); Cassani, Maria Cristina, E-mail: maria.cassani@unibo.it [Department of Industrial Chemistry “Toso Montanari”, UdR INSTM of Bologna and CIRI MAM, Alma Mater Studiorum – University of Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy); Carraro, Giorgio; Maccato, Chiara [Department of Chemistry, Padova University and INSTM, Via Marzolo 1, 35131 Padova (Italy); Mignani, Adriana [Center for Industrial Research – Advanced Applications in Mechanical Engineering and Materials Technology (CIRI-MAM), University of Bologna, Viale del Risorgimento 2, 40136 Bologna (Italy); Lazzari, Dario; Bertola, Maurizio [Miteni S.p.A., Località Colombara 91, 36070 Trissino, VI (Italy)
2016-01-30
Graphical abstract: - Highlights: • Au{sub NPs}/short-chain fluoroalkylsilane (FAS) layers/indium tin oxide (ITO) sandwich structures were prepared by a two-step method. • The FAS-embedded amide functional group enhances the Au{sub NPs} surface coverage. • The Au{sub NPs}/FAS/ITO systems are electrocatalytically active toward methanol oxidation. - Abstract: Metal/organosilane/oxide sandwich structures were prepared via a two-step self-assembly method. First, indium tin oxide (ITO) substrates were functionalized with the following fluoroalkylsilanes (FAS): R{sub F}C(O)N(H)(CH{sub 2}){sub 3}Si(OMe){sub 3} (1, R{sub F} = C{sub 5}F{sub 11}), containing an embedded amide between the perfluoroalkyl chain and the syloxanic moiety, and R{sub F}(CH{sub 2}){sub 2}Si(OEt){sub 3} (2, R{sub F} = C{sub 6}F{sub 13}). Subsequently, Au nanoparticles (Au{sub NPs}) introduction in the obtained systems was carried out by controlled immersion into a solution of citrate-stabilized Au{sub NPs}. The physico-chemical properties of the target materials were thoroughly investigated by using various complementary techniques. Finally, the application of such systems as catalysts for methanol electro-oxidation under alkaline conditions was investigated, revealing the synergistical role played by FAS and Au{sub NPs} in promoting a remarkable electrocatalytic activity.
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International Nuclear Information System (INIS)
Gómez-Anquela, C.; Revenga-Parra, M.; Abad, J.M.; Marín, A. García; Pau, J.L.; Pariente, F.; Piqueras, J.; Lorenzo, E.
2014-01-01
Electroactive films containing redox active phenothiazine moieties are covalently bound onto gold and graphene oxide gold hybrid electrodes, using reductive redox grafting of N’,N’-dimethylphenothiazin-5-ium-3,7-diamine (Azure A) diazonium salt. The grafting procedure is based on continuous voltammetric potential sweep of solutions containing the phenothiazine diazonium salt previously generated in situ. Control of the film thickness, electroactivity and stability can easily be exerted through appropriate choice of the concentration and number of potential scans performed. Cyclic Voltammetry, Electrochemical Quartz Crystal Microbalance (EQCM) and Spectroscopic Ellipsometry are used to characterize the growth process as well as the viscoelastic properties of the resulting stable electrografted films. The electron transfer reactions through the films are mediated by the presence of the Azure A redox moieties, which show a quasi-reversible electrochemical response and exhibit a potent electrocatalytic effect toward the oxidation of NADH. This electrocatalytic model has been used to compare the properties of Azure A electrografted films generated on gold electrodes with those obtained on hybrid electrodes composed by graphene oxide modified gold electrodes
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Megarajan, Sengan; Ayaz Ahmed, Khan Behlol; Rajendra Kumar Reddy, G; Suresh Kumar, P; Anbazhagan, Veerappan
2016-02-01
Herein, we present a simple and green method for the synthesis of gold nanoparticles (AuNPs) using the phytoproteins of spinach leaves. Under ambient sunlight irradiation, the isolated phytoprotein complex from spinach leaves reduces the gold chloride aqueous solution and stabilizes the formed AuNPs. As prepared nanoparticles were characterized by UV-visible spectroscopy, Fourier transform infra-red (FTIR) spectroscopy, zeta potential, transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDS). The surface plasmon resonance (SPR) maximum for AuNPs was observed at 520 nm. The zeta potential value estimated for the AuNPs is -27.0 mV, indicating that the NPs are well separated. Transmission electron micrographs revealed that the particles are spherical in nature with the size range from 10 to 15 nm. AuNPs act as a catalyst in the degradation of an azo dye, methyl orange in an aqueous environment. The reduction rate was determined to be pseudo-first order. Electrocatalytic efficiency of the synthesized AuNPs via this green approach was studied by chronoamperometry using ascorbic acid and hydrogen peroxide as a model compound for oxidation and reduction, respectively. Electrocatalytic studies indicate that the gold nanoparticles can be used to detect ascorbic acid and hydrogen peroxide in micromolar concentrations with response time less than 3s. Copyright © 2015 Elsevier B.V. All rights reserved.
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High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters
Energy Technology Data Exchange (ETDEWEB)
Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.
2017-01-18
The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.
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Hydrogen evolution by a metal-free electrocatalyst
Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Luhua; Han, Yu; Chen, Ying; Du, Aijun; Jaronieć, Mietek; Qiao, Shizhang
2014-01-01
Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All
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Voloshin, Y Z; Belov, A S; Vologzhanina, A V; Aleksandrov, G G; Dolganov, A V; Novikov, V V; Varzatskii, O A; Bubnov, Y N
2012-05-28
The cycloaddition of the mono- and dichloroglyoximes to the cobalt(II) bis-α-benzyldioximate afforded the cobalt(II) mono- and dichloroclathrochelates in moderate yields (40-60%). These complexes undergo nucleophilic substitution of their reactive chlorine atoms with aliphatic amines, alcohols and thiolate anions. In the case of ethylenediamine and 1,2-ethanedithiol, only the macrobicyclic products with α,α'-N(2)- and α,α'-S(2)-alicyclic six-numbered ribbed fragments were obtained. The cobalt(II) cage complexes with terminal mercapto groups were synthesized using aliphatic dithiols. The crystal and molecular structures of the six cobalt(II) clathrochelates were obtained by X-ray diffraction. Their CoN(6)-coordination polyhedra possess a geometry intermediate between a trigonal prism and a trigonal antiprism, and the encapsulated cobalt(II) ions are shifted from their centres due to the structural Jahn-Teller effect with the Co-N distances varying significantly (by 0.10-0.26 Å). The electrochemistry of the complexes obtained was studied by cyclic voltammetry (CV). The anodic waves correspond to the quasi-reversible Co(2+/3+) oxidations, whereas the cathodic ranges contain the quasi-reversibile waves assigned to the Co(2+/+) reductions; all the cobalt(i)-containing clathrochelate anions formed are stable in the CV time scale. The electrocatalytic properties of the cobalt complexes obtained were studied in the production of hydrogen from H(+) ions: the addition of HClO(4) resulted in the formation of the same catalytic cathodic reduction Co(2+/+) waves. The controlled-potential electrolysis with gas chromatography analysis confirmed the production of H(2) in high Faraday yields. The efficiency of this electrocatalytic process was enhanced by an immobilization of the complexes with terminal mercapto groups on a surface of the working gold electrode.
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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.
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International Nuclear Information System (INIS)
Xie, Xiang; Mu, Wanjun; Li, Xingliang; Wei, Hongyuan; Jian, Yuan; Yu, Qianhong; Zhang, Rui; Lv, Kai; Tang, Hui; Luo, Shunzhong
2014-01-01
WO 3 has been identified as a promising candidate electrocatalyst for hydrogen evolution reaction (HER), because it can form a tungsten bronze (HxWO 3 ) which is highly electron and proton conducting. In this paper, we report that the electrocatalytic activity of WO 3 for HER can be enhanced by incorporation of tantalum ions (Ta 5+ ) into the lattice of WO 3 . The most active performance is achieved with the molar ratio of Ta/W being 0.01, which is two times more active than that of undoped WO 3 at an overpotential of -0.52 V. It is shown that incorporation of proper Ta 5+ into WO 3 can induce moderate defects and oxygen vacancies, as well as intercalate a higher amount of protons, which enhance the electron transfer and short the protons diffusion paths. These changes correlated positively with the enhanced catalytic HER activity. This study demonstrates, for the first time, that metal ions-doped WO 3 nanowires are promising electrocatalysts for HER
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Nano cobalt oxides for photocatalytic hydrogen production
Mangrulkar, Priti A.; Joshi, Meenal M.; Tijare, Saumitra N.; Polshettiwar, Vivek; Labhsetwar, Nitin K.; Rayalu, Sadhana Suresh
2012-01-01
of various operating parameters in hydrogen generation by nano cobalt oxide was then studied in detail. Copyright © 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
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International Nuclear Information System (INIS)
Jung, Inhwa; Kim, Doyeon; Yun, Yongsik; Chung, Suengyoung; Lee, Jaeyoung; Tak, Yongsug
2004-01-01
Methanol crossover rate through proton exchange membrane (Nafion 117) was investigated with a newly designed electrochemical stripping cell. Nanosize Pt electrode was prepared by the electroless deposition. Distinct electrocatalytic oxidation behaviors of methanol inside membrane were similar to the methanol oxidation in aqueous electrolyte, except adsorption/desorption of hydrogen. The amount of methanol diffused through membrane was calculated from the charge of methanol oxidation during repetitive cyclic voltammetry (CV) and methanol crossover rate was estimated to be 0.69 nmol/s
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International Nuclear Information System (INIS)
Liu, Ran; Ye, Ke; Gao, Yinyi; Long, Ziyao; Cheng, Kui; Zhang, Wenping; Wang, Guiling; Cao, Dianxue
2016-01-01
Highlights: • A binder-free Cu/Cu foam electrode is prepared by an electrochemical method. • The electrode owns a novel three-dimensional porous structure. • The electrode exhibits superior catalytic activity for hydrazine electrooxidation. - Abstract: A three-dimensional porous copper film is directly deposited on Cu foam by an electrodeposition method using hydrogen bubbles as dynamic template (denoted as Cu/Cu foam). Its electrocatalytic activity toward hydrazine electrooxidation is tested by linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Compared with Cu foam, hydrazine electrooxidation on the Cu/Cu foam electrode shows that the onset oxidation potential displays a ~100 mV negative shift, the current density at −0.6 V raises about 14 times, the apparent activation energy and the charge transfer resistance reduce significantly. The increasing electrocatalytic performance for hydrazine electrooxidation is mainly caused by the highly porous structure of the Cu/Cu foam electrode which can provide a large surface area and make electrolyte access the electrocatalyst surfaces more easily. Hydrazine electrooxidation on the Cu/Cu foam electrode proceeds through a near 4-electron process.
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International Nuclear Information System (INIS)
Polgikh, L.Y.; Golodets, G.I.; Il'chenko, N.I.
1985-01-01
On the basis of data on the kinetics of the reaction 2H 2 + O 2 = 2H 2 O isotope exchange H 2 + D 2 = 2HD under the conditions of oxidative catalysis, and the kinetic isotope effect, a mechanism is proposed for the oxidation of hydrogen on cobalt monoxide-oxide. At low temperatures the reaction proceeds according to a mechanism of alternating reduction-reoxidation of the surface with the participation of hydrogen adsorbed in molecular form; at increased temperature and low P 02 /P /SUB H2/ ratios, a significant contribution to the observed rate is made by a mechanism including dissociative chemisorption of hydrogen
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Lu, Bang-An; Du, Jia-Huan; Sheng, Tian; Tian, Na; Xiao, Jing; Liu, Li; Xu, Bin-Bin; Zhou, Zhi-You; Sun, Shi-Gang
2016-06-01
Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts.Concave nanocubes are enclosed by high-index facets and have negative curvature; they are expected to have enhanced reactivity, as compared to nanocubes with flat surfaces. Herein, we propose and demonstrate a new strategy for the synthesis of concave Pt nanocubes with {hk0} high-index facets, by using a hydrogen adsorption-mediated electrochemical square-wave potential method. It was found that Pt atoms prefer to deposit on edge sites rather than terrace sites on Pt surfaces with intensive hydrogen adsorption, resulting in the formation of concave structures. The as-prepared concave Pt nanocubes exhibit enhanced catalytic activity and stability towards oxidation of ethanol and formic acid in acidic solutions, compared to commercial Pt/C catalysts. Electronic supplementary information (ESI) available: Details of DFT calculation, SEM images of concave Pt nanocubes, mass activity and stability characterization of the catalysts. See DOI: 10.1039/c6nr02349e
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Metal oxide/hydrogen battery; Kinzoku sankabutsu/suiso denchi
Energy Technology Data Exchange (ETDEWEB)
Kanda, M.; Niki, H. [Toshiba Research and Development Centre, Komukai, Kawasaki (Japan)
1995-07-04
The metal oxide-hydrogen battery consisting mainly of hydrogen storage alloy has high energy density and high volume efficiency. However, it is disadvantageous that the self-discharge takes place since the discharge capacity is lowered due to the delivery of stored hydrogen from the hydrogen electrode. This invention relates to the metal oxide-hydrogen battery consisting of hydrogen storage alloy. Hydrogen storage alloy which is composed of LaNi5 system homogeneous solid solution having an equilibrium plateau pressure of less than 1 atm at 20{degree}C is used. As a result, the battery voltage change and the self-discharge can be reduced, and the cell performance can be improved. Examples of LaNi5 system hydrogen storage alloy are ANi(5-x)Mx (A = La, Mm, and Ca, M = Al, Mn, Si, Ge, Fe, B, Ga, Cu, In, and Co). LaNi(4.7)Al(0.3) and MmNi(4.2)Mn(0.8) are preferable. 3 figs.
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Hydrogenation and high temperature oxidation of Zirconium claddings
International Nuclear Information System (INIS)
Novotny, T.; Perez-Feró, E.; Horváth, M.
2015-01-01
In the last few years a new series of experiments started for supporting the new LOCA criteria, considering the proposals of US NRC. The effects which can cause the embrittlement of VVER fuel claddings were reviewed and evaluated in the framework of the project. The purpose of the work was to determine how the fuel cladding’s hydrogen uptake under normal operating conditions, effect the behavior of the cladding under LOCA conditions. As a first step a gas system equipment with gas valves and pressure gauge was built, in which the zirconium alloy can absorb hydrogen under controlled conditions. In this apparatus E110 (produced by electrolytic method, currently used at Paks NPP) and E110G (produced by a new technology) alloys were hydrogenated to predetermined hydrogen contents. According the results of ring compression tests the E110G alloys lose their ductility above 3200 ppm hydrogen content. This limit can be applied to determine the ductile-brittle transition of the nuclear fuel claddings. After the hydrogenation, high temperature oxidation experiments were carried out on the E110G and E110 samples at 1000 °C and 1200 °C. 16 pieces of E110G and 8 samples of E110 with 300 ppm and 600 ppm hydrogen content were tested. The oxidation of the specimens was performed in steam, under isothermal conditions. Based on the ring compression tests load-displacement curves were recorded. The main objective of the compression tests was to determine the ductile-brittle transition. These results were compared to the results of our previous experiments where the samples did not contain hydrogen. The original claddings showed more ductile behavior than the samples with hydrogen content. The higher hydrogen content resulted in a more brittle mechanical behavior. However no significant difference was observed in the oxidation kinetics of the same cladding types with different hydrogen content. The experiments showed that the normal operating hydrogen uptake of the fuel claddings
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Energy Technology Data Exchange (ETDEWEB)
Ma, Juanjuan, E-mail: majj0518@hotmail.com [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Liu, Lin; Chen, Qian; Yang, Min [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Wang, Danping [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Tong, Zhiwei [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Chen, Zhong, E-mail: aszchen@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore)
2017-03-31
Highlights: • Crumpled CoTMPyP/ERGO hybrid was successfully prepared by a facile two-step process. • CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. • CoTMPyP/ERGO hybrid film shows good electrocatalytic activity and stability for HER. - Abstract: Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.
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Electrocatalytic activity of self-doped polyaniline
International Nuclear Information System (INIS)
Shieh, Yeong-Tarng; Jung, Jeng-Ji; Lin, Rong-Hsien; Yang, Chien-Hsin; Wang, Tzong-Liu
2012-01-01
Self-doped conducting polyaniline-modified indium tin oxide (ITO) electrodes were prepared by cyclic voltammetry on ITO substrates in aniline (AN) and o-aminobenzene sulfonic acid (OSA) mixed monomer solutions with AN/OSA mole ratios of 25/75, 50/50, and 75/25, followed by investigations on electrocatalytic activities of the copolymers to redox reactions of Fe(CN) 6 3−/4− as a probe in aqueous solutions of different pH using cyclic voltammetry. For a given pH, the P(25AN-co-75OSA)-modified ITO electrode demonstrated the highest current density, followed by the P(50AN-co-50OSA)- and by the P(75AN-co-25OSA)-modified ITO electrodes. It can be concluded that a higher content of OSA (sulfonate) in the copolymer exhibited a higher extent of self-doping in the copolymer, leading to a higher electrocatalytic activity to redox reactions of the probe. The electrocatalytic activities of the copolymers decreased with increasing pH. The P(25AN-co-75OSA)-modified ITO electrode was electroactive for sensing the redox reactions of the probe in aqueous solutions of up to pH 7, the P(50AN-co-50OSA)-modified ITO electrode was electroactive for up to only pH 5, but the P(75AN-co-25OSA)-modified ITO electrode was not electroactive in aqueous solution of pH even as low as 2.
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Electrocatalytic oxidation of alcohols on single gold particles in highly ordered SiO2 cavities
International Nuclear Information System (INIS)
Li, Na; Zhou, Qun; Tian, Shu; Zhao, Hong; Li, Xiaowei; Adkins, Jason; Gu, Zhuomin; Zhao, Lili; Zheng, Junwei
2013-01-01
In the present work, we report a new and simple approach for preparing a highly ordered Au (1 1 1) nanoparticle (NP) array in SiO 2 cavities on indium-doped tin oxide (ITO) electrodes. We fabricated a SiO 2 cavity array on the surface of an ITO electrode using highly ordered self-assembly of polystyrene spheres as a template. Gold NPs were electrodeposited at the bottom of the SiO 2 cavities, and single gold NPs dominated with (1 1 1) facets were generated in each cavity by annealing the electrode at a high temperature. Such (1 1 1) facets were the predominate trait of the single gold particle which exhibited considerable electrocatalytic activity toward oxidation of methanol, ethanol, and glycerol. This has been attributed to the formation of incipient hydrous oxides at unusually low potential on the specific (1 1 1) facet of the gold particles. Moreover, each cavity of the SiO 2 possibly behaves as an independent electrochemical cell in which the methanol molecules are trapped; this produces an environment advantageous to catalyzing electrooxidation. The oxidation of methanol on the electrodes is a mixed control mechanism (both by diffusion and electrode kinetics). This strategy both provided an approach to study electrochemical reactions on a single particle in a microenvironment and may supply a way to construct alcohols sensors
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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)
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Zircaloy-oxidation and hydrogen-generation rates in degraded-core accident situations
International Nuclear Information System (INIS)
Chung, H.M.; Thomas, G.R.
1983-02-01
Oxidation of Zircaloy cladding is the primary source of hydrogen generated during a degraded-core accident. In this paper, reported Zircaloy oxidation rates, either measured at 1500 to 1850 0 C or extrapolated from the low-temperature data obtained at 0 C, are critically reviewed with respect to their applicability to a degraded-core accident situation in which the high-temperature fuel cladding is likely to be exposed to and oxidized in mixtures of hydrogen and depleted steam, rather than in an unlimited flux of pure steam. New results of Zircaloy oxidation measurements in various mixtures of hydrogen and steam are reported for >1500 0 C. The results show significantly smaller oxidation and, hence, hydrogen-generation rates in the mixture, compared with those obtained in pure steam. It is also shown that a significant fraction of hydrogen, generated as a result of Zircaloy oxidation, is dissolved in the cladding material itself, which prevents that portion of hydrogen from reaching the containment building space. Implications of these findings are discussed in relation to a more realistic method of quantifying the hydrogen source term for a degraded-core accident analysis
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Ehsani, Ali; Jaleh, Babak; Nasrollahzadeh, Mahmoud
2014-07-01
Reduced graphene oxide (rGO) was used to support Cu nanoparticles. As electro-active electrodes for supercapacitors composites of reduced graphene oxide/Cu nanoparticles (rGO/CuNPs) and polytyramine (PT) with good uniformity are prepared by electropolymerization. Composite of rGO/CuNPs-PT was synthesized by cyclic voltammetry (CV) methods and electrochemical properties of film were investigated by using electrochemical techniques. The results show that, the rGO/CuNPs-PT/G has better capacitance performance. This is mainly because of the really large surface area and the better electronic and ionic conductivity of rGO/CuNPs-PT/G, which lead to greater double-layer capacitance and faradic pseudo capacitance. Modified graphite electrodes (rGO/CuNPs-PT/G) were examined for their redox process and electrocatalytic activities towards the oxidation of methanol in alkaline solutions. The methods of cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) were employed. In comparison with a Cu-PT/G (Graphite), rGO/CuNPs-PT/G modified electrode shows a significantly higher response for methanol oxidation. A mechanism based on the electro-chemical generation of Cu(III) active sites and their subsequent consumptions by methanol have been discussed.
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International Nuclear Information System (INIS)
Liu, Baocang; Huo, Lili; Zhang, Geng; Zhang, Jun
2016-01-01
Highlights: • A novel hollow mesoporous ternary @M-TiN/N-G/Pt electrocatalysts were synthesized. • The @M-TiN/N-G/Pt electrocatalysts displayed outstanding activity and stability toward MOR and ORR. • The activity and stability of @M-TiN/N-G/Pt electrocatalysts were higher than Pt/TiN, @M-TiN/Pt, and Pt/C catalysts. • The excellent electrocatalytic performance rooted in its unique configuration. • Several reasons were proposed to explain the enhanced electrocatalytic performance of @M-TiN/N-G/Pt. - Abstract: A novel hollow mesoporous TiN/N-graphene (N-G) hybrid architecture (@M-TiN/N-G) composed of N-doped graphene wrapped mesoporous TiN nanoparticle shells was constructed for the first time. It can be used as an efficient support for creating a highly efficient ternary @M-TiN/N-G/Pt electrocatalyst with superior catalytic activity and stability for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) through decorating well-dispersed Pt nanoparticles on @M-TiN/N-G surface. By optimizing the content of N-G in catalysts, the @M-TiN/N-G/Pt catalysts display superior catalytic activity and stability toward MOR and ORR to traditional Pt/C and graphene-free Pt/TiN and @M-TiN/Pt catalysts. The various characterization results reveal that the outstanding electrocatalytic performance of @M-TiN/N-G/Pt catalyst roots in its large surface area, high porosity, strong interaction among Pt, TiN, and N-G, excellent electron transfer property facilitated by N-doped graphene, and small size of Pt and TiN nanocrystals. The synthetic approach may be available for constructing other graphene based hollow metal nitrides, carbides, and phosphides for various electrocatalytic applications.
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International Nuclear Information System (INIS)
Jafarian, M.; Mahjani, M.G.; Heli, H.; Gobal, F.; Khajehsharifi, H.; Hamedi, M.H.
2003-01-01
Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour
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Reaction between vanadium trichloride oxide and hydrogen sulfide
International Nuclear Information System (INIS)
Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo
1978-01-01
The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)
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Energy Technology Data Exchange (ETDEWEB)
Song Yan; Ma Yuting; Wang Yuan [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China); Di Junwei, E-mail: djw@suda.edu.c [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China); Tu Yifeng [Department of Chemistry, Soochow University, Suzhou, Jiangsu 215123 (China)
2010-07-01
Gold-platinum (Au-Pt) hybrid nanoparticles (Au-PtNPs) were successfully deposited on an indium tin oxide (ITO) surface using a direct electrochemical method. The resulting nanoparticles were characterized by scanning electron microscopy (SEM), UV-vis spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and electrochemical methods. It was found that the size of the Au-PtNPs depends on the number of electrodeposition cycles. Au-PtNPs obtained by 20 electrodeposition cycles had a cauliflower-shaped structure with an average diameter of about 60 nm. These Au-PtNPs exhibited alloy properties. Electrochemical measurements showed that the charge transfer resistivity was significantly decreased for the Au-PtNPs/ITO electrode. Additionally, the Au-PtNPs displayed an electrocatalytic activity for nitrite oxidation and oxygen reduction. The Au-PtNPs/ITO electrodes reported herein could possibly be used as electrocatalysts and sensors.
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Interactions of hydrogen isotopes and oxides with metal tubes
International Nuclear Information System (INIS)
Longhurst, G. R.; Cleaver, J.
2008-01-01
Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)
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Interactions of hydrogen isotopes and oxides with metal tubes
Energy Technology Data Exchange (ETDEWEB)
Longhurst, G. R. [Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415-3860 (United States); Cleaver, J. [Idaho State Univ., 921 South 8th Avenue, Pocatello, ID 83201 (United States)
2008-07-15
Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)
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Interactions of Hydrogen Isotopes and Oxides with Metal Tubes
International Nuclear Information System (INIS)
Longhurst, Glen R.
2008-01-01
Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results
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Energy Technology Data Exchange (ETDEWEB)
Spătaru, Tanţa; Preda, Loredana; Osiceanu, Petre; Munteanu, Cornel; Anastasescu, Mihai; Marcu, Maria; Spătaru, Nicolae, E-mail: nspataru@icf.ro
2014-01-01
A new hybrid system with improved photocatalytic and electrocatalytic performances was obtained by two-step potentiostatic deposition on highly boron-doped diamond (BDD) substrate. First, hydrated TiO{sub 2} was anodically deposited from a TiCl{sub 3} aqueous solution, both in the presence and in the absence of sodium dodecyl sulfate (SDS). The study of the UV irradiation effect evidenced that titanium oxide coatings obtained by surfactant-assisted electrodeposition (TiO{sub 2}:SDS) exhibit enhanced photocurrent, due to its very rough texonsture and presumably to better efficiency of charge carrier separation. Electrochemical deposition of platinum on the oxide-coated BDD was carried out in a second step and AFM, SEM and XPS measurements have shown that, on the TiO{sub 2}:SDS substrate, Pt particles are smaller, more uniformly distributed, and tend to form clusters, leading to a specific surface area of the electrocatalyst of ca. 6.55 m{sup 2} g{sup −1}. Carbon monoxide stripping experiments demonstrated that, when deposited on TiO{sub 2}:SDS, Pt particles are also less sensitive to CO-poisoning during methanol anodic oxidation.
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Hydrogen interaction with oxidized Si(111) probed with positrons
International Nuclear Information System (INIS)
Lynn, K.G.; Nielsen, B.; Welch, D.O.
1989-01-01
A variable-energy positron beam was utilized to study the interface action of hydrogen with Si(111) covered by an ultrahigh-vacuum thermally grown oxide of 2-3 nm thickness. It was observed that positrons implanted at shallow depth (< 100 nm) after diffusion are trapped either at the interface between the oxide and the Si or in the oxide. The positron-annihilation characteristics of these trapped positrons are found to be very sensitive to hydrogen exposure. The momentum distribution of the annihilating positron-electron pair, as observed in the Doppler broadening of the annihilation line, broadens considerably after exposure to hydrogen. The effect recovers after annealing at ≅ 1100 K, suggesting a hydrogen binding at the interface of ∼ 3 ± 0.3 eV. (author). 18 refs., 3 figs
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Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers
International Nuclear Information System (INIS)
Jensen, Henriette Stokbro; Lens, Piet N.L.; Nielsen, Jeppe L.; Bester, Kai; Nielsen, Asbjorn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes
2011-01-01
Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d -1 and 1.33 d -1 as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.
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[Characteristics of proteins synthesized by hydrogen-oxidizing microorganisms].
Volova, T G; Barashkov, V A
2010-01-01
The study was conducted to determine the biological value of proteins synthesized by hydrogen-oxidizing microorganisms--the hydrogen bacteria Alcaligenes eutrophus Z1 and Ralstonia eutropha B5786 and the CO-resistant strain of carboxydobacterium Seliberia carboxydohydrogena Z1062. Based on a number of significant parameters characterizing the biological value of a product, the proteins of hydrogen-oxidizing microorganisms have been found to occupy an intermediate position between traditional animal and plant proteins. The high total protein in biomass of these microorganisms, their complete amino acid content, and availability to proteolytic enzymes allow for us to consider these microorganisms as potential protein producers.
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International Nuclear Information System (INIS)
Xia Yue; Liu Jun; Huang Wei; Li Zelin
2012-01-01
Highlights: ► A smooth Au surface was rebuilt into clean dendrite via square wave potential pulses. ► It was performed in blank H 2 SO 4 solution without Au(III) species and other additives. ► Dendritic Au provided certain advantage for dispersing Pt due to its unique structure. ► Pt-decorated dendritic Au demonstrated high activity for the HCOOH electrooxidation. - Abstract: We report here the fabrication of clean dendritic gold (DG) directly on a smooth Au electrode via square wave potential pulses (SWPPs) in a blank H 2 SO 4 solution containing no Au(III) species and additives. The effects of potential range, frequency and duration time of SWPPs and H 2 SO 4 concentration on the construction of DG were systematically investigated. A possible mechanism was proposed to explain the growth of DG. The whole process was templateless and surfactantless, and therefore effectively avoided possible contaminations that occurred in other synthetic routes. Further, the prepared DG electrode functioned as a scaffold to support electrodeposited Pt clusters, producing Pt-decorated DG (Pt-DG) electrodes. The electrocatalytic properties of Pt-DG electrodes with various Pt loadings were examined for the oxidation of formic acid. The low Pt loading Pt-DG demonstrated different electrochemical behavior from that on Pt-decorated smooth gold (Pt-SG) and on Pt-decorated gold nanoparticles because there were more defect sites like steps and edges on the DG surface. Ensemble effect, as well as electronic effect, accounts for the improved electrocatalytic activity of low Pt loading Pt-DG.
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Energy Technology Data Exchange (ETDEWEB)
Gentil, Solène [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Laboratoire de Chimie et Biologie des Métaux, Univ. Grenoble Alpes, CNRS UMR5249, CEA, 38000 Grenoble France; Lalaoui, Noémie [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Dutta, Arnab [Pacific Northwest National Laboratory, Richland WA 99532 USA; Current address: Chemistry Department, IIT Gandhinagar, Gujarat 382355 India; Nedellec, Yannig [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Cosnier, Serge [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France; Shaw, Wendy J. [Pacific Northwest National Laboratory, Richland WA 99532 USA; Artero, Vincent [Laboratoire de Chimie et Biologie des Métaux, Univ. Grenoble Alpes, CNRS UMR5249, CEA, 38000 Grenoble France; Le Goff, Alan [Univ. Grenoble Alpes, CNRS, DCM UMR 5250, 38000 Grenoble France
2017-01-12
A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with a multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.
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Kondratenko, E.V.; Mul, Guido; Baltrusaitis, Jonas; Larrazábal, G.O.; Pérez-Ramírez, J.
2013-01-01
This review highlights recent developments and future perspectives in carbon dioxide usage for the sustainable production of energy and chemicals and to reduce global warming. We discuss the heterogeneously catalysed hydrogenation, as well as the photocatalytic and electrocatalytic conversion of CO2
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International Nuclear Information System (INIS)
Liu, Yong; Liu, Lan; Shan, Jun; Zhang, Jingdong
2015-01-01
Highlights: • Pd and reduced graphene oxide are deposited on foam-Ni via electrodeposition. • Pd particles supported on RGO possess large active surface area. • Pd/RGO/foam-Ni shows high electrocatalytic activity for dechlorination of 4-CP. • 100% 4-CP can be removed on Pd/RGO/foam-Ni under optimum ECH conditions. - Abstract: A high-performance palladium (Pd) and reduced graphene oxide (RGO) composite electrode was prepared on foam-nickel (foam-Ni) via two-step electrodeposition processes. The scanning electron microscopic (SEM) observation showed that the obtained Pd/RGO/foam-Ni composite electrode displayed a uniform and compact morphology. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopic (XPS) analysis confirmed the successful deposition of Pd and RGO on nickel substrate. The cyclic voltammetric (CV) measurements indicated that the presence of RGO greatly enhanced the active surface area of Pd particles deposited on foam-Ni. The as-deposited Pd/RGO/foam-Ni electrode was applied to electrocatalytic hydrodechlorination (ECH) of 4-chlorophenol (4-CP). Various factors influencing the dechlorination of 4-CP such as dechlorination current, initial concentration of 4-CP, Na 2 SO 4 concentration and initial pH were systematically investigated. The thermodynamic analysis showed that the dechlorination reaction of 4-CP at different temperatures followed the first-order kinetics and the activation energy for 4-CP dechlorination on Pd/RGO/foam-Ni electrode was calculated to be 51.96 kJ mol −1 . Under the optimum conditions, the dechlorination efficiency of 4-CP could reach 100% after 60-min ECH treatment. Moreover, the prepared Pd/RGO/foam-Ni composite electrode showed good stability for recycling utilization in ECH of 4-CP
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Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering
Yan, Yong; Qian, Shuo; Garrison, Ben; Smith, Tyler; Kim, Peter
2018-04-01
A nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0 wt. % at 1100 °C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness, and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.
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Li, Shuwen; Dong, Zhengping; Yang, Honglei; Guo, Shujing; Gou, Galian; Ren, Ren; Zhu, Zhejun; Jin, Jun; Ma, Jiantai
2013-02-11
A new catalyst consisting of ionic liquid (IL)-functionalized carbon nanotubes (CNTs) obtained through 1,3-dipolar cycloaddition support-enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl(-))-CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl(-))-CNTs were systematic characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL-CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl(-))-CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Highly efficient and stable MoP-RGO nanoparticles as electrocatalysts for hydrogen evolution
International Nuclear Information System (INIS)
Wu, Zexing; Wang, Jie; Zhu, Jing; Guo, Junpo; Xiao, Weiping; Xuan, Cuijuan; Lei, Wen; Wang, Deli
2017-01-01
Graphical abstract: Graphene supported MoP (MoP-RGO) was synthesized through a facile solvothermal reaction followed by high-temperature phosphating treatment method. The material exhibits an outstanding HER performance in both acid and alkaline media. RGO act as a substrate which can not only avoid the nanoparticles aggregation, but also facilitate the electron transfer during the electrocatalytic process. - Abstract: Electrochemical splitting of water to obtain hydrogen plays a vital role in high energy density devices, especially for fuel cells. In this work, reduced graphene oxide supported molybdenum phosphide nanoparticles (MoP-RGO) were prepared via a facile solvothermal reaction followed by high-temperature phosphating treatment. The electrochemical measurement results indicate that the MoP-RGO nanocomposite obtained at 900 °C exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER) with overpotentials of 117 mV and 150 mV at a current density of 10 mA cm"−"2 in acid and alkaline media, respectively. Furthermore, the instability of the catalyst in basic medium was systemically investigated. This work provides a facile strategy for the synthesis of cost-effective carbon supported metal phosphide as HER electrocatalyst.
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A sensitive hydrogen peroxide sensor based on leaf-like silver
International Nuclear Information System (INIS)
Meng, Zuchao; Zhang, Mingyin; Zhang, Hongfang; Zheng, Jianbin
2014-01-01
A novel non-enzymatic hydrogen peroxide sensor based on leaf-like silver was constructed. The leaf-like silver was synthesized on the surface of L-cysteine (L-cys) by electrodeposition. Scanning electron microscopy and electrochemical techniques were used to characterize the leaf-like silver nanoparticles. The sensor showed high electrocatalytic activity towards the reduction of hydrogen peroxide. A wide linear range of 2.5–1.5 mM with a low detection limit of 0.7 µM was obtained. Excellent electrocatalytic activity, large surface-to-volume ratio and efficient electron transport properties of leaf-like silver have enabled stable and highly sensitive performance for the non-enzymatic hydrogen peroxide sensor. (paper)
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High pressure oxidation of sponge-Zr in steam/hydrogen mixtures
International Nuclear Information System (INIS)
Kim, Y.S.
1997-01-01
A thermogravimetric apparatus for operation in 1 and 70 atm steam-hydrogen or steam-helium mixtures was used to investigate the oxidation kinetics of sponge-Zr containing 215 ppm Fe. Weight-gain rates, reflecting both oxygen and hydrogen uptake, were measured in the temperature range 350-400 C. The specimens consisted of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk. The edges of the disk specimens were coated with a thin layer of pure gold to avoid the deleterious effect of corners. Following each experiment, the specimens were examined metallographically to reveal the morphology of the oxide and/or hydride formed. Two types of oxide, one black and uniform and the other white and nodular, were observed on sponge-Zr surfaces oxidized in steam environments at 70 atm. The oxidation rate when white-nodular oxide formed was a factor of two higher than that of black-uniform oxide at 400 C for steam contents above 1 mol%. The oxidation rate was independent of total pressure, the carrier gas (H 2 or He) and steam content above ∝1 mol%. The oxidation kinetics of sponge-Zr follows a linear law for maximum reaction times up to ∝6 days. The oxidation rate in steam-hydrogen mixtures at 70 atm total pressure decreases when the steam content approaches the steam-starved region (∝0.5 mol% steam at 400 C and ∝0.02 mol% steam at 350 C). Lower steam concentrations cause massive hydriding of the specimens. Even at steam concentrations above the critical value, direct hydrogen absorption from the gas was manifest by hydrogen pickup fractions greater than unity. (orig.)
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Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J
2017-04-05
The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.
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A study of hydrogen permeation in aluminum alloy treated by various oxidation processes
International Nuclear Information System (INIS)
Song Wenhai; Long Bin
1997-01-01
A set of oxide coatings was formed on the surface of an Al alloy (wt%: Fe, 0.24; Si, 1.16; Cu, 0.05-0.2; Zn, 0.1; Al, residual) by means of various oxidation processes. The hydrogen permeability through the aluminum alloy and its coating materials was determined by a vapor phase permeation technique at temperatures ranging from 400 to 500 C using high-purity H 2 (99.9999%) gas with an upstream hydrogen pressure of 10 4 -10 5 Pa. The experimental results show that the hydrogen permeability through aluminum oxide coating is 100-2000 times lower than that through the aluminum alloy substrate. This means that the aluminum oxide is a significant hydrogen permeation barrier. A high hydrogen permeation resistance was observed in an oxide layer prefilmed in 200 C water, while an anodized aluminum oxide film had a less obstructive effect, possibly caused by the porous structure of the anodic oxide. The hydrogen permeability through films of aluminum oxide was not a simple function of the aluminum-oxide phase configuration. (orig.)
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Zhang, Jin; Cheng, Yi; Lu, Shanfu; Jia, Lichao; Shen, Pei Kang; Jiang, San Ping
2014-11-18
The inner tubes of carbon nanotubes (CNTs) have a significant promotion effect on the electrocatalytic activity of Pd nanoparticles (NPs) for the ethanol oxidation of direct alcohol fuel cells (DAFCs) and Pd NPs supported on CNTs with 3-7 walls show a much higher activity as compared to that supported on typical single-walled and multi-walled CNTs.
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Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun
2018-05-01
Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.
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Effective Degradation of Aqueous Tetracycline Using a Nano-TiO2/Carbon Electrocatalytic Membrane
Directory of Open Access Journals (Sweden)
Zhimeng Liu
2016-05-01
Full Text Available In this work, an electrocatalytic membrane was prepared to degrade aqueous tetracycline (TC using a carbon membrane coated with nano-TiO2 via a sol-gel process. SEM, XRD, EDS, and XPS were used to characterize the composition and structure of the electrocatalytic membrane. The effect of operating conditions on the removal rate of tetracycline was investigated systematically. The results show that the chemical oxygen demand (COD removal rate increased with increasing residence time while it decreased with increasing the initial concentration of tetracycline. Moreover, pH had little effect on the removal of tetracycline, and the electrocatalytic membrane could effectively remove tetracycline with initial concentration of 50 mg·L−1 (pH, 3.8–9.6. The 100% tetracycline and 87.8% COD removal rate could be achieved under the following operating conditions: tetracycline concentration of 50 mg·L−1, current density of 1 mA·cm−2, temperature of 25 °C, and residence time of 4.4 min. This study provides a new and feasible method for removing antibiotics in water with the synergistic effect of electrocatalytic oxidation and membrane separation. It is evident that there will be a broad market for the application of electrocatalytic membrane in the field of antibiotic wastewater treatment.
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Energy Technology Data Exchange (ETDEWEB)
Uribe-Godinez, J.; Jimenez-Sandoval, O.; Borja-Arco, E.; Altamirano-Gutierrez, A. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional, Queritaro (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Queretaro (Mexico)
2008-07-01
Rhodium (Rh6(CO)16) and novel Rh-based clusters were prepared using thermolysis techniques under different conditions in N2 and H2 reaction media, as well as in n-nonane, o-xylene, 1,2-dichlorobenzene and dimethylsulfoxide. The clusters were used as novel electrocatalysts for oxygen reduction reaction (ORR) in the absence and presence of 1.0 and 2.0 M methanol solutions. The catalysts were also used for hydrogen oxidation reaction (HOR) with pure hydrogen (H2) and in the presence of carbon monoxide (CO). Rotating disk electrode measurements were used to analyze the materials. The study showed that the electrocatalyst support ratio plays a significant role in the electrochemical behaviour of the materials. Rh6(CO)16 and Rh2(1,2-DCB) presented the best electrocatalytic behaviour for ORR and HOR in the absence and presence of methanol and CO. The study demonstrated that the rhodium-based materials are capable of performing ORR and HOR while being tolerant of both methanol and CO. 3 refs., 3 figs.
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Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application
Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik
2017-09-01
Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.
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Metal oxide-hydrogen secondary battery; Kinzoku sankabutsu-suiso niji denchi
Energy Technology Data Exchange (ETDEWEB)
Hosobuchi, H.; Edoi, M.; Katsumata, T.
1995-06-06
Recently, the metal oxide - hydrogen secondary battery characterized by employing the hydrogen storage alloy as the hydrogen negative electrode draws attention. However, the secondary batteries equipped with the negative electrode composed of hydrogen storage alloy powder have such shortcoming that the charge-discharge cycle life is rather short and it changes widely from battery to battery, as the hydrogen storage alloy is disintegrated. This invention solves the problem. Employing the alloy having a composition expressed as LmNi(w)Co(X)Mn(y)Al(z) (Lm = rare earth elements including La) can suppress the disintegration of hydrogen storage alloy powder during the charge-discharge cycle. In addition, controlling the oxygen content in the hydrogen storage alloy powder to 500 - 1500ppm can reduce the oxidation corrosion of the hydrogen storage alloy, resulting in suppression of its deterioration. 1 fig., 2 tabs.
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International Nuclear Information System (INIS)
Zhu Zanzan; Wang Jianlong; Munir, Ahsan; Zhou, H. Susan
2010-01-01
Recently, bamboo shaped carbon nanotubes (BCNTs) have received increased attention for its bamboo shaped structure associated properties and its application in direct methanol/ethanol fuel cell. In this work, the potential to use BCNTs as the support material of high loaded Pt nanoparticles for improving the efficiency of ethanol/methanol fuel cell is explored. The structure and nature of the resulting Pt-BCNTS composite were characterized by transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) spectrum, it was found that Pt nanoparticles were homogeneously dispersed on the BCNTs surfaces with 23.5% by weight. Cyclic voltammogram (CV) indicated that the Pt-BCNTs catalyst displayed excellent electrocatalytic activity and long-term stability toward ethanol oxidation. The excellent performance may be attributed to the high dispersion of nanoscale Pt catalysts and the unique nature of BCNTs. The results imply that doping N atom introduces some defective sites and active sites onto the surface of CNTs. In general, this paper demonstrates that BCNTs are promising support material for Pt-nanoparticles catalyst and can be used to enhance the efficiency of fuel cell.
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International Nuclear Information System (INIS)
Yang, Lulu; Lu, Shunkai; Wang, Hui; Shao, Qi; Liao, Fan; Shao, Mingwang
2017-01-01
Highlights: • Amorphous Re nanoparticle modified Si nanowire nanocomposites were prepared. • An interesting self-activation phenomenon was observed in HER process. • Re/SiNW showed synergy in HER process. • The optimal mass ratio of Re: Si was determined to be 31.1: 68.9. - Abstract: Amorphous rhenium nanoparticles modified silicon nanowires were prepared via reducing Re ion by Si−H bonds, which were employed to electrocatalysize the hydrogen evolution reaction because amorphous structure may have excellent catalytic activity. It is interesting that an obvious self-activation for Re/Si catalysts was observed with the current density enhanced by 2.2 times its previous value at 400 mV after a 3,000 s of continuous cyclic voltammetry scanning, and the catalytic performance remained steady thereafter. The optimal electrocatalytic performance was found with the Re: Si mass ratio of 31.1: 68.9, resulting in a Tafel slope of 81 mV·dec −1 and overpotential of 100 mV at current density of 10 mA·cm −2 .
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Energy Technology Data Exchange (ETDEWEB)
Yao, Fubing; Zhong, Yu [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, E-mail: dongbowang@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); Chen, Fei; Zhao, Jianwei; Xie, Ting; Jiang, Chen; An, Hongxue; Zeng, Guangming; Li, Xiaoming [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)
2017-02-05
Highlights: • Pd/Pt-NACF served as an adsorption/electrocatalysis electrode to reduce perchlorate. • The possible mechanisms involved in the reaction process were explained. • The reusability and stability of Pd/Pt-NACF bifunctional material was evaluated. - Abstract: In this work, Pd/Pt supported on N-doped activated carbon fiber (Pd/Pt-NACF) was employed as the electrode for electrocatalytic degradation of perchlorate through adsorption/electroreduction process. Perchlorate in solution was firstly adsorbed on Pd/Pt-NACF and then reduced to non-toxic chloride by the catalytic function of Pd/Pt at a constant current (20 mA). Compared with Pd/Pt-ACF, the adsorption capacity and electrocatalytic degradation efficiency of Pd/Pt-NACF for perchlorate increased 161% and 28%, respectively. Obviously, positively charged N-functional groups on NACF surface enhanced the adsorption capacity of Pd/Pt-NACF, and the dissociation of hydrogen to atomic H* by the Pd/Pt nanostructures on the cathode might drastically promote the electrocatalytic reduction of perchlorate. The role of atomic H* in the electroreduction process was identified by tertiary butanol inhibition test. Meanwhile, the perchlorate degradation performance was not substantially lower after three successive adsorption/electrocatalytic degradation experiments, demonstrating the electrochemical reusability and stability of the as-prepared electrode. These results showed that Pd/Pt-NACF was effective for electrocatalytic degradation of perchlorate and had great potential in perchlorate removal from water.
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Directory of Open Access Journals (Sweden)
Henrique E. Toma
2010-01-01
Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.
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Garcia Esparza, Angel T.; Limkrailassiri, Kevin; Leroy, Fré dé ric; Rasul, Shahid; Yu, Weili; Lin, Liwei; Takanabe, Kazuhiro
2014-01-01
We report the use of a facile and highly scalable synthesis process to control growth products of earth-abundant Cu-based oxides and their application in relevant photoelectrochemical and electrochemical solar fuel generation systems. Characterization of the synthesized Cu(I)/Cu(II) oxides indicates that their surface morphology and chemical composition can be simply tuned by varying two synthesis parameters (time and temperature). UV-Vis spectroscopy and impedance spectroscopy studies are performed to estimate the band structures and electronic properties of these p-type semiconductor materials. Photoelectrodes made of Cu oxides possess favorable energy band structures for production of hydrogen from water; the position of their conduction band is ≈1 V more negative than the water-reduction potential. High acceptor concentrations on the order of 1018-1019 cm-3 are obtained, producing large electric fields at the semiconductor-electrolyte interface and thereby enhancing charge separation. The highly crystalline pristine samples used as photocathodes in photoelectrochemical cells exhibit high photocurrents under AM 1.5G simulated illumination. When the samples are electrochemically reduced under galvanostatic conditions, the co-existence of the oxide with metallic Cu on the surface seems to function as an effective catalyst for the selective electrochemical reduction of CO2. © the Partner Organisations 2014.
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International Nuclear Information System (INIS)
Micić, Darko; Šljukić, Biljana; Zujovic, Zoran; Travas-Sejdic, Jadranka; Ćirić-Marjanović, Gordana
2014-01-01
Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO 2 − oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis
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Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation
DEFF Research Database (Denmark)
Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.
2015-01-01
evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates...... sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively....
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Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid
2018-01-01
The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.
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Electrocatalytic activity of carbon-supported catalysts for direct ethanol fuel cell applications
Energy Technology Data Exchange (ETDEWEB)
Rodriguez Varela, F.J. [CINVESTAV-Unidad Saltillo, Coahuila, (Mexico). Grupo de Investigacion en Energia; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie
2008-07-01
Proton exchange membrane fuel cells (PEMFCs) can be fueled with hydrogen, alcohols, hydrocarbons and acetals. Ethanol is an important fuel candidate because it can be electro-oxidized to carbon dioxide on platinum (Pt)-based electrocatalysts in a direct ethanol fuel cell (DEFC) at relatively low temperatures. This study investigated the electrocatalytic activity of some carbon-supported electrocatalysts towards the ethanol oxidation (EOR) and the oxygen reduction reaction (ORR) in the presence of ethanol. Compared to other anode catalysts such as Pt, PtRu and Pt oxide, anodes based on PtSn alloys have a higher catalytic activity for the EOR. When tested in a DEFC, the current density at 0.4V and 90 degrees C based on a PtSn/C anode and a Pt/C cathode was 2 times higher than that of a cell based on a PtRu/C-Pt/C membrane electrode assembly (MEA) configuration. In addition, cathode catalysts based on Ru/C had good catalytic activity for the ORR and exhibited high selectivity for this reaction in the presence of ethanol. The results showed that in the presence of 0.125, 0.25 or 0.5 M ethanol concentrations, a decrease in onset potential of about 60, 62 and 68 mV emerged, respectively. These values were about 10 times lower than those measured for some Pt-based cathode catalysts tested in this study in the presence of 0.125 M EtOH. 20 refs., 5 figs.
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International Nuclear Information System (INIS)
Schumacher, L.C.; Holzheuter, I.B.; Nucara, M.C.; Dignam, M.J.
1989-01-01
Sputter-deposited films of silver with lead, manganese and nickel have been studied as possible oxygen reduction electrocatalysts using cyclic voltammetry, rotating disc studies, steady-state polarization and Auger analysis. In general, the Ag-Pb and Ag-Mn films display superior electrocatalytic activity for O 2 reduction, while the Ag-Ni films' performance is inferior to that of pure Ag. For the Ag-Pb films, which show the highest electrocatalytic activity, the mixed metal films display oxidation-reduction behavior which is not simply a superposition of that of the separate metals, and suggests a mechanism for the improved behavior
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Ma, Xiaohui; Luo, Liqiang; Zhu, Limei; Yu, Liming; Sheng, Leimei; An, Kang; Ando, Yoshinori; Zhao, Xinluo
2013-11-01
Single-wall carbon nanotubes (SWCNTs) supported Pt-Fe nanoparticles have been prepared by one-step hydrogen arc discharge evaporation of carbon electrode containing both Pt and Fe metal elements. The formation of SWCNTs and Pt-Fe nanoparticles occur simultaneously during the evaporation process. High-temperature hydrogen treatment and hydrochloric acid soaking have been carried out to purify and activate those materials in order to obtain a new type of Pt-Fe/SWCNTs catalyst for methanol oxidation. The Pt-Fe/SWCNTs catalyst performs much higher electrocatalytic activity for methanol oxidation, better stability and better durability than a commercial Pt/C catalyst according to the electrochemical measurements, indicating that it has a great potential for applications in direct methanol fuel cells.
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Mohamed, Ibrahim M. A.; Yasin, Ahmed S.; Barakat, Nasser A. M.; Song, Seung A.; Lee, Ha Eun; Kim, Seong Su
2018-03-01
A nanocomposite of Ni/Pd supported by carbonized poly-vinyl alcohol (PVA) nanofibers (NFs) was synthesized via electrospinning followed by calcination under an argon atmosphere. The as-synthesized NFs were studied using physicochemical analyses, such as field-emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTsbnd IR) and X-ray photoelectron spectroscopy (XPS), to investigate the morphology, crystallinity, effect of carbonization and surface chemistry of the NFs, respectively. Cyclic voltammetry (CV) and chronoamperometry (CA) were utilized to study the performance of the NFs towards electrooxidation reactions. The designed NFs present superior electrocatalytic behavior in an acid medium towards formic acid oxidation, as well as urea and ethanol oxidation in an alkaline medium. The electrocatalytic performance of the bimetallic NFs appears to arise from the assembly of bimetallic Ni/Pd@NFs based on PVA, which has hydroxyl groups. These hydroxyl groups can decrease the negative processes that occur as a result of metal-metal interactions, such as the aggregation process. This study introduces a novel non-precious electrocatalyst to facilitate the commercialization of fuel cells based on formic acid, urea and ethanol.
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The oxidation of hydrogen cyanide and related chemistry
DEFF Research Database (Denmark)
Dagaut, Philippe; Glarborg, Peter; Alzueta, Maria U.
2008-01-01
For modeling the formation of nitrogen oxides in combustion via both the prompt-NO and the fuel-NO mechanisms, as well as for modeling the reduction of nitrogen oxides via reburning, a good knowledge of the kinetics of oxidation of hydrogen cyanide (HCN) is required. The formation routes to HCN a...
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International Nuclear Information System (INIS)
Fukumoto, Michihisa; Hara, Motoi; Kaneko, Hiroyuki; Sakuraba, Takuya
2015-01-01
The oxidation behavior of Zircaloy-4 at high temperatures in a flowing Ar-H_2O (saturated at 323 K) mixed gas was investigated using hydrogen and oxygen sensors installed at a gas outlet, and the utility of the gas sensing methods by using both sensors was examined. The generated amount of hydrogen was determined from the hydrogen partial pressure continuously measured by the hydrogen sensor, and the resultant calculated oxygen amount that reacted with the specimen was in close agreement with the mass gain gravimetrically measured after the experiment. This result demonstrated that the hydrogen partial pressure measurement using a hydrogen sensor is an effective method for examining the steam oxidation of this metal as well as monitoring the hydrogen evolution. The advantage of this method is that the oxidation rate of the metal at any time as a differential quantity is able to be obtained, compared to the oxygen amount gravimetrically measured as an integral quantity. When the temperature was periodically changed in the range of 1173 K to 1523 K, highly accurate measurements could be carried out using this gas monitoring method, although reasonable measurements were not gravimetrically performed due to the fluctuating thermo-buoyancy during the experiment. A change of the oxidation rate was clearly detected at a monoclinic tetragonal transition temperature of ZrO_2. From the calculation of the water vapor partial pressure during the thermal equilibrium condition using the hydrogen and oxygen partial pressures, it became clear that a thermal equilibrium state is maintained when the isothermal condition is maintained, but is not when the temperature increases or decreases with time. Based on these results, it was demonstrated that the gas monitoring system using hydrogen and oxygen sensors is very useful for investigating the oxidation process of the Zircaloy in steam. (author)
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Stability aspects of hydrogen-doped indium oxide
Jost, Gabrielle; Hamri, Alexander Nordin; Köhler, Florian; Hüpkes, Jürgen
2015-01-01
Transparent conductive oxides play an important role as contact layers in various opto-electronic devices such as solar cells or LEDs. Whilst crystalline materials e.g. zinc oxide (ZnO), tin oxide (Sn2O3) or tin doped indium oxide (ITO) have already been vastly investigated and applied [1] hydrogen doped indium oxide (In2O3:H) entered the scene a while ago as a new material with a superior trade-off between electrical and optical performance. In2O3:H is commonly deposited at room temperature...
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Two-dimensional metal dichalcogenides and oxides for hydrogen evolution
DEFF Research Database (Denmark)
Pandey, Mohnish; Vojvodic, Aleksandra; Thygesen, Kristian Sommer
2015-01-01
We explore the possibilities of hydrogen evolution by basal planes of 2D metal dichalcogenides and oxides in the 2H and 1T class of structures using the hydrogen binding energy as a computational activity descriptor. For some groups of systems like the Ti, Zr, and Hf dichalcogenides the hydrogen...
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Effect of hydrogen on stresses in anodic oxide film on titanium
International Nuclear Information System (INIS)
Kim, Joong-Do; Pyun, Su-Il; Seo, Masahiro
2003-01-01
Stresses in anodic oxide film on titanium thin film/glass electrode in pH 8.4 borate solution were investigated by a bending beam method. The increases in compressive stress observed with cathodic potential sweeps after formation of anodic oxide film were attributed to the volume expansion due to the compositional change of anodic oxide film from TiO 2 to TiO 2-x (OH) x . The instantaneous responses of changes in stress, Δσ, in the anodic oxide film to potential steps demonstrated the reversible characteristic of the TiO 2-x (OH) x formation reaction. In contrast, the transient feature of Δσ for the titanium without anodic oxide film represented the irreversible formation of TiH x at the metal/oxide interphase. The large difference in stress between with and without the oxide film, has suggested that most of stresses generated during the hydrogen absorption/desorption reside in the anodic oxide film. A linear relationship between changes in stress, Δ(Δσ) des , and electric charge, ΔQ des , during hydrogen desorption was found from the current and stress transients, manifesting that the stress changes were crucially determined by the amount of hydrogen desorbed from the oxide film. The increasing tendency of -Δ(Δσ) des with increasing number of potential steps and film formation potential were discussed in connection with the increase in desorption amount of hydrogen in the oxide film with increasing absorption/desorption cycles and oxide film thickness
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Energy Technology Data Exchange (ETDEWEB)
Huang, Jianqiu, E-mail: jianqiu@vt.edu [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Tea, Eric; Li, Guanchen [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Hin, Celine [Department of Mechanical Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road - MC 0238, Blacksburg, VA 24061 (United States); Department of Material Science and Engineering, Virginia Tech, Goodwin Hall, 635 Prices Fork Road-MC 0238, Blacksburg, VA 24061 (United States)
2017-06-01
Highlights: • Hydrogen release process at the Al/SiO{sub 2} metal-oxide interface has been investigated. • A mathematical model that estimates the hydrogen release potential has been proposed. • Al atoms, Al−O bonds, and Si−Al bonds are the major hydrogen traps at the Al/SiO{sub 2} interface. • Hydrogen atoms are primarily release from Al−H and O−H bonds at the Al/SiO{sub 2} metal-oxide interface. - Abstract: The Anode Hydrogen Release (AHR) mechanism at interfaces is responsible for the generation of defects, that traps charge carriers and can induce dielectric breakdown in Metal-Oxide-Semiconductor Field Effect Transistors. The AHR has been extensively studied at Si/SiO{sub 2} interfaces but its characteristics at metal-silica interfaces remain unclear. In this study, we performed Density Functional Theory (DFT) calculations to study the hydrogen release mechanism at the typical Al/SiO{sub 2} metal-oxide interface. We found that interstitial hydrogen atoms can break interfacial Al−Si bonds, passivating a Si sp{sup 3} orbital. Interstitial hydrogen atoms can also break interfacial Al−O bonds, or be adsorbed at the interface on aluminum, forming stable Al−H−Al bridges. We showed that hydrogenated O−H, Si−H and Al−H bonds at the Al/SiO{sub 2} interfaces are polarized. The resulting bond dipole weakens the O−H and Si−H bonds, but strengthens the Al−H bond under the application of a positive bias at the metal gate. Our calculations indicate that Al−H bonds and O−H bonds are more important than Si−H bonds for the hydrogen release process.
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Bramhaiah, K.; Pandey, Indu; Singh, Vidya N.; Kavitha, C.; John, Neena S.
2018-03-01
Hybrid films of reduced graphene oxide-osmium nanoparticles (rGO-Os NPs) synthesized at a liquid/liquid interface are explored for their electrocatalytic activity towards the oxidation of rhodamine B (RhB), a popular colourant found in textile industry effluents and a non-permitted food colour. The free-standing nature of the films enables them to be lifted directly on to electrodes without the aid of any binders. The films consist of aggregates of ultra-small Os NPs interspersed with rGO layers. The hybrid film exhibits enhanced RhB oxidation when compared to its constituents arising from the synergic effect between rGO and Os NPs, Os contributing to electrocatalysis and rGO contributing to high surface area and conductance as well as stabilization of Os nanoparticles. The electrochemical sensor based on rGO-Os NP hybrid film on pencil graphite electrode shows a remarkable performance for the quantitative detection of RhB with a linear variation in a wide range of concentrations, 4-1300 ppb (8.3 nM-2.71 μM). The modified electrode presents good stability over more than 6 months, reproducibility and anti-interference capability. The use of developed sensor for adequate detection of RhB in real samples such as food samples and pen markers is also demonstrated.
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CATALYTIC OXIDATION OF ALCOHOLS AND EPOXIDATION OF OLEFINS WITH HYDROGEN PEROXIDE AS OXIDANT
Hydrogen peroxide (H2O2) is an ideal oxidant of choice for these oxidations due to economic and environmental reasons by giving water as a by-product. Two catalysts used are vanadium phosphorus oxide (VPO) and Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a...
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Fang, Zhiwei; Peng, Lele; Qian, Yumin; Zhang, Xiao; Xie, Yujun; Cha, Judy J; Yu, Guihua
2018-04-18
Seeking earth-abundant electrocatalysts with high efficiency and durability has become the frontier of energy conversion research. Mixed-transition-metal (MTM)-based electrocatalysts, owing to the desirable electrical conductivity, synergistic effect of bimetal atoms, and structural stability, have recently emerged as new-generation hydrogen evolution reaction (HER) electrocatalysts. However, the correlation between anion species and their intrinsic electrocatalytic properties in MTM-based electrocatalysts is still not well understood. Here we present a novel approach to tuning the anion-dependent electrocatalytic characteristics in MTM-based catalyst for HER, using holey Ni/Co-based phosphides/selenides/oxides (Ni-Co-A, A = P, Se, O) as the model materials. The electrochemical results, combined with the electrical conductivity measurement and DFT calculation, reveal that P substitution could modulate the electron configuration, lower the hydrogen adsorption energy, and facilitate the desorption of hydrogen on the active sites in Ni-Co-A holey nanostructures, resulting in superior HER catalytic activity. Accordingly we fabricate the NCP holey nanosheet electrocatalyst for HER with an ultralow onset overpotential of nearly zero, an overpotential of 58 mV, and long-term durability, along with an applied potential of 1.56 V to boost overall water splitting at 10 mA cm -2 , among the best electrocatalysts reported for non-noble-metal catalysts to date. This work not only presents a deeper understanding of the intrinsic HER electrocatalytic properties for MTM-based electrocatalyst with various anion species but also offers new insights to better design efficient and durable water-splitting electrocatalysts.
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Hydrogen traps in the oxide/alloy interface region of Zr-Nb alloys
International Nuclear Information System (INIS)
Khatamian, D.
1995-03-01
In this study the 1 H( 15 N,αγ) 12 C nuclear reaction has been used to measure hydrogen profiles of anodically oxidized Zr-Nb specimens containing various amounts of niobium. The profiles have been correlated with oxygen profiles, obtained using a Scanning Auger Microprobe (SAM), and with X-ray diffraction patterns. In addition, unoxidized Zr-2.5Nb (Zr-2.5 wt% Nb) samples were implanted with oxygen and hydrogen to study the interaction between these two species when dissolved in the alloy. All the anodically oxidized specimens, except the pure Zr and the single-phase β-Zr (Zr-20Nb) samples, displayed hydrogen peaks beneath the oxide layer. These results, in conjunction with the results from the implanted specimens, indicate that the hydrogen moves under the influence of a stress gradient to the sub-oxide region, where the metal lattice has been expanded due to superficial oxide growth. The results show that dissolved oxygen sites in Zr-2.5Nb alloy do not trap hydrogen. (author). 16 refs., 6 figs
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Oxidation mechanism of porous Zr_2Fe used as a hydrogen getter
International Nuclear Information System (INIS)
Cohen, Dror; Nahmani, Moshe; Rafailov, Genadi; Attia, Smadar; Shamish, Zorik; Landau, Miron; Merchuk, Jose; Zeiri, Yehuda
2016-01-01
We determined the oxidation mechanism of porous ST-198, which mainly comprises Zr_2Fe. Oxidation kinetics depended on temperature, oxygen partial pressure, and oxidation extent. The passivation role of oxidation in hydrogen scavenging is probably due to the development of a surface oxide, independent of oxygen concentration. Zr_2Fe would be a superior hydrogen getter in oxygen-contaminated environments at high temperatures, as most oxygen will be consumed at the outer shell by mass transfer limitations, protecting the bulk of the getter for hydrogen scavenging. - Highlights: • Porous Zr_2Fe–O_2 interactions are characterized in detail. • Gettering efficiency at low temperature is hampered by oxide layer formation. • Gettering is better at high temperatures as outer shell consumes maximum oxygen.
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Bates, Michael
electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).
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Synthesis of Platinum-Nickel Hydroxide Nanocomposites for Electrocatalytic Reduction of Water
Wang, Lei
2016-11-25
Water electrolysis represents a promising solution for storage of renewable but intermittent electrical energy in hydrogen molecules. This technology is however challenged by the lack of efficient electrocatalysts for the hydrogen and oxygen evolution reactions. Here we report on the synthesis of platinum-nickel hydroxide nanocomposites and their electrocatalytic applications for water reduction. An in situ reduction strategy taking advantage of the Ni(II)/Ni(III) redox has been developed to enable and regulate the epitaxial growth of Pt nanocrystals on single-layer Ni(OH)2 nanosheets. The obtained nanocomposites (denoted as Pt@2D-Ni(OH)2) exhibit an improvement factor of 5 in catalytic activity and a reduction of up to 130 mV in overpotential compared to Pt for the hydrogen evolution reaction (HER). A combination of electron microscopy/spectroscopy characterization, electrochemical studies and density functional calculations was employed to uncover the structures of the metal-hydroxide interface and understand the mechanisms of catalytic enhancement.
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Synthesis of Platinum-Nickel Hydroxide Nanocomposites for Electrocatalytic Reduction of Water
Wang, Lei; Zhu, Yihan; Zeng, Zhenhua; Lin, Chong; Giroux, Michael; Jiang, Lin; Han, Yu; Greeley, Jeffrey; Wang, Chao; Jin, Jian
2016-01-01
Water electrolysis represents a promising solution for storage of renewable but intermittent electrical energy in hydrogen molecules. This technology is however challenged by the lack of efficient electrocatalysts for the hydrogen and oxygen evolution reactions. Here we report on the synthesis of platinum-nickel hydroxide nanocomposites and their electrocatalytic applications for water reduction. An in situ reduction strategy taking advantage of the Ni(II)/Ni(III) redox has been developed to enable and regulate the epitaxial growth of Pt nanocrystals on single-layer Ni(OH)2 nanosheets. The obtained nanocomposites (denoted as Pt@2D-Ni(OH)2) exhibit an improvement factor of 5 in catalytic activity and a reduction of up to 130 mV in overpotential compared to Pt for the hydrogen evolution reaction (HER). A combination of electron microscopy/spectroscopy characterization, electrochemical studies and density functional calculations was employed to uncover the structures of the metal-hydroxide interface and understand the mechanisms of catalytic enhancement.
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Nurlaela, Ela; Shinagawa, Tatsuya; Qureshi, Muhammad; Dhawale, Dattatray Sadashiv; Takanabe, Kazuhiro
2016-01-01
The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER
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Contribution to the determination of total hydrogen in oxide nuclear fuels
International Nuclear Information System (INIS)
Bartscher, W.; Kutter, H.
1979-01-01
Normally the total hydrogen content of a fast breeder mixed oxide fuel is calculated from the results of the determinations of free hydrogen and water. Thermodynamic considerations, coupled with kinetic results for room temperature and 1000 0 C and taken from the literature indicate, that the normal method for the determination of water by heating in a carrier gas stream and subsequent coulometric determination of the expelled water must give low results. A modification of this method involving the introduction of a copper oxide furnace into the system for the oxidation of hydrogen has been studied. The resulting method for the determination of total hydrogen gives about ten times higher values than those calculated from the normal water determination. These total hydrogen values and the oxygen to metal ratios which are obtained by gravimetric methods and not corrected for the water content, reflect more realistically the in-pile conditions in the fuel pin. (Auth.)
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DEFF Research Database (Denmark)
Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine Anton
2016-01-01
A detailed understanding of the electrochemical reduction of CO2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO2(1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO2 reduction...... and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits...
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Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma
Energy Technology Data Exchange (ETDEWEB)
Vesel, Alenka, E-mail: alenka.vesel@guest.arnes.si [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Mozetic, Miran [Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana (Slovenia); Balat-Pichelin, Marianne [PROMES-CNRS Laboratory, 7 Rue du four solaire, 66120 Font Romeu Odeillo (France)
2016-11-30
Highlights: • Oxidized Inconel alloy was exposed to hydrogen at temperatures up to 1500 K. • Oxide reduction in hydrogen plasma started at approximately 1300 K. • AES depth profiling revealed complete reduction of oxides in plasma. • Oxides were not reduced, if the sample was heated just in hydrogen atmosphere. • Surface of reduced Inconel preserved the same composition as the bulk material. - Abstract: Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.
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Electrocatalytic Activity and Selectivity - a Density Functional Theory Study
DEFF Research Database (Denmark)
Karamad, Mohammadreza
-catalysts towards two appealing electrochemical reactions: 1)electroreduction of CO2 to hydrocarbons and alcohols, and 2) electrochemical production of hydrogen peroxide, i.e. H2O2, from its elements i.e. H2 and O2. The thesis is divided into three parts: In the first part, electro-catalytic activity of different...... metallic and functionalized graphene catalysts. Secondly, we considered CO2 reduction on RuO2, which has a distinctive catalytic activity and selectivity compared to Cu to get insight into mechanistic pathway of the CO2 reduction. Finally, in the last part, we have taken advantage of the isolated active...
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Do Carmo, Devaney Ribeiro; Fernandes, Daniela Silvestrini
2017-09-01
Graphene oxide (GO) was chemically modified with a poly(propylene)imine Generation 3.0 dendrimer (DAB-Am-16). The characterization, structure and properties of hybrid graphene oxide/DAB-Am-16 dendrimer was studied by Raman spectroscopy, Fourier-Transforming Infrared Spectroscopy (FT-IR), X-Ray Photoelectron Spectroscopic (XPS), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Thermogravimetric analysis. After functionalized the hybrid material (GOD) can interact with copper and subsequently with hexacyanoferrate (III) ions (GODHCu). The GODHCu incorporated into a graphite paste electrode (20% w/w) was applied to an electrocatalytic detection of neurotransmitter L-dopamine using differential pulse voltammetry. The analytical curve showed a linear response in the concentration range from 1.0 × 10-7 to 1.0 × 10-5 mol L-1 with a corresponding equation Y(A) = 1.706 × 10-5 + 0.862 [L-dopamine] and a correlation coefficient r2 = 0.998. The detection limit was 6.36 × 10-7 mol L-1 with a relative standard deviation of ±4% (n = 3) and an amperometric sensitivity of 0.862 A/mol L-1.
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Phenol oxidation with hydrogen peroxide
Energy Technology Data Exchange (ETDEWEB)
Ramiez Cortina, R.C.; Hernadez Perez, I. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico); Ortiz Lozoya, C.E. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico)]|[Inst. Mexicano del Petroleo (Mexico); Alonso Gutierrez, M.S. [Inst. National Polytechnique, ENSCT, Lab. of Chimie Agro-Industrielle, Toulouse (France)
2003-07-01
In this work the process application of advanced oxidation is investigated with hydrogen peroxide, for the phenol destruction. The experiments were carried out in a glass reactor of 750 mL. Three phenol concentrations were studied (2000, 1000 and 500 ppm) being oxidized with H{sub 2}O{sub 2} (1, 2 and 3 M). The tests of oxidation had a reaction time of 48 h at ambient temperature and pressure. The phenol degradation was determined as COD at different reaction times and intermediate oxidation products were analyzed by chromatography. The results of this study show that it is possible to degrade phenol (1000 ppm) until 90% with H{sub 2}O{sub 2} 2M. Being achieved the best efficiency with a good molar relationship of H{sub 2}O{sub 2}/phenol. Intends a reaction outline in the degradation of the phenol. (orig.)
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Directory of Open Access Journals (Sweden)
A. C. Gómez-Monsiváis
2017-03-01
Full Text Available Currently, the ethanol electro-oxidation reaction has attracted considerable attention in fuel cells because of new green ethanol synthetic methods based on biomass processes that have emerged. In this study, PtFe/C and Pt/C nanoparticles were synthesized by a chemical reduction method and tested in the ethanol electro-oxidation reaction. Furthermore, the electrocatalytic effect of the PtFe bimetallic catalyst was analyzed by in situ surface-enhanced Raman spectroscopy (SERS coupled to an electrochemical cell. X-ray diffractograms showed typical face-centered cubic structures with crystallite sizes of 3.31 and 3.94 for Pt/C and PtFe/C, respectively. TEM micrographs revealed nanoparticle sizes of 2 ± 0.4 nm and 3 ± 0.6 nm for Pt/C and PtFe/C respectively. PtFe/C exhibited a Pt90Fe10 composition by both X-ray fluorescence and energy-dispersive X-ray spectroscopy. A better electrocatalytic activity as function of concentration was obtained through the incorporation of a small amount of Fe into the Pt lattice and the presence of Fe2+/Fe3+ (observed by X-ray photoelectron spectroscopy. According to SERS experiments, the presence of these iron species promotes the chemisorption of ethanol, the formation of formic acid as main product and renewal of the catalytic sites, resulting in current densities that were at least three fold higher than the values obtained for the Pt/C nanocatalyst.
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Steijns, M.; Derks, F.; Verloop, A.; Mars, P.
1976-01-01
The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we
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Synthesis and characterization of cobalt-nichel oxides for the oxygen formation reaction
International Nuclear Information System (INIS)
Morales G, P.
2001-01-01
In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co 3 O 4 and the Ni O as the mixtures Ni O/Co 3 O 4 were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co 3 O 4 and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co 3 O 4 mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)
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Energy Technology Data Exchange (ETDEWEB)
Qiu, Weiwei; Zhu, Qionghua; Gao, Fei; Gao, Feng [College of Chemistry and Environment, Fujian Province Key Laboratory of Morden Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou 363000 (China); Huang, Jiafu; Pan, Yutian [College of Biological Science and Technology, Minnan Normal University, Zhangzhou 363000 (China); Wang, Qingxiang, E-mail: axiang236@126.com [College of Chemistry and Environment, Fujian Province Key Laboratory of Morden Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou 363000 (China)
2017-03-01
A novel electrochemical non-enzymatic hydrogen peroxide (H{sub 2}O{sub 2}) sensor has been developed based on Prussian blue (PB) and electrochemically reduced graphene oxide (ERGO). The GO was covalently modified on glassy carbon electrode (GCE), and utilized as a directing platform for in-situ synthesis of electroactive PB. Then the GO was electrochemically treated to reduction form to improve the effective surface area and electroactivity of the sensing interface. The fabrication process was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM). The results showed that the rich oxygen containing groups play a crucial role for the successful synthesis of PB, and the obtained PB layer on the covalently immobilized GO has good stability. Electrochemical sensing assay showed that the modified electrode had tremendous electrocatalytic property for the reduction of H{sub 2}O{sub 2}. The steady-state current response increased linearly with H{sub 2}O{sub 2} concentrations from 5 μM to 1 mM with a fast response time (less than 3 s). The detection limit was estimated to be 0.8 μM. When the sensor was applied for determination of H{sub 2}O{sub 2} released from living cells of macrophages, satisfactory results were achieved. - Highlights: • Covalent method was applied for immobilization of GO on glassy carbon electrode. • GO directed in-situ synthesis of electroactive PB. • PB-ERGO composite shows high electrocatalytic activity toward H{sub 2}O{sub 2}. • The modified biosensor is capable of detecting H{sub 2}O{sub 2} released from living macrophages.
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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
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Meguerdichian, Andrew G; Jafari, Tahereh; Shakil, Md R; Miao, Ran; Achola, Laura A; Macharia, John; Shirazi-Amin, Alireza; Suib, Steven L
2018-02-19
Electrocatalytic decomposition of urea for the production of hydrogen, H 2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH 4 ]NiPO 4 ·6H 2 O and β-Ni 2 P 2 O 7 using in situ prepared [NH 4 ] 2 HPO 4 . The [NH 4 ]NiPO 4 ·6H 2 O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH 4 ]NiPO 4 ·6H 2 O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm 2 /mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.
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Rettew, Robert E; Allam, Nageh K; Alamgir, Faisal M
2011-02-01
The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO(2) nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO(2) nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO(2) substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.
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CHALLENGES IN GENERATING HYDROGEN BY HIGH TEMPERATURE ELECTROLYSIS USING SOLID OXIDE CELLS
Energy Technology Data Exchange (ETDEWEB)
M. S. Sohal; J. E. O' Brien; C. M. Stoots; M. G. McKellar; J. S. Herring; E. A. Harvego
2008-03-01
Idaho National Laboratory’s (INL) high temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells is presented in this paper. The research results reported here have been obtained in a laboratory-scale apparatus. These results and common scale-up issues also indicate that for the technology to be successful in a large industrial setting, several technical, economical, and manufacturing issues have to be resolved. Some of the issues related to solid oxide cells are stack design and performance optimization, identification and evaluation of cell performance degradation parameters and processes, integrity and reliability of the solid oxide electrolysis (SOEC) stacks, life-time prediction and extension of the SOEC stack, and cost reduction and economic manufacturing of the SOEC stacks. Besides the solid oxide cells, balance of the hydrogen generating plant also needs significant development. These issues are process and ohmic heat source needed for maintaining the reaction temperature (~830°C), high temperature heat exchangers and recuperators, equal distribution of the reactants into each cell, system analysis of hydrogen and associated energy generating plant, and cost optimization. An economic analysis of this plant was performed using the standardized H2A Analysis Methodology developed by the Department of Energy (DOE) Hydrogen Program, and using realistic financial and cost estimating assumptions. The results of the economic analysis demonstrated that the HTE hydrogen production plant driven by a high-temperature helium-cooled nuclear power plant can deliver hydrogen at a cost of $3.23/kg of hydrogen assuming an internal rate of return of 10%. These issues need interdisciplinary research effort of federal laboratories, solid oxide cell manufacturers, hydrogen consumers, and other such stakeholders. This paper discusses research and development accomplished by INL on such issues and highlights associated challenges that need to
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Effect of the oxidation front penetration on in-clad hydrogen migration
Feria, F.; Herranz, L. E.
2018-03-01
In LWR fuel claddings the embrittlement due to hydrogen precipitates (i.e., hydrides) is a degrading mechanism that concerns in nuclear safety, particularly in dry storage. A relevant factor is the radial distribution of the hydrogen absorbed, especially the hydride rim formed. Thus, a reliable assessment of fuel performance should account for hydrogen migration. Based on the current state of modelling of hydrogen dynamics in the cladding, a 1D radial model has been derived and coupled with the FRAPCON code. The model includes the effect of the oxidation front progression on in-clad hydrogen migration, based on experimental observations found (i.e., dissolution/diffusion/re-precipitation of the hydrogen in the matrix ahead of the oxidation front). A remarkable quantitative impact of this new contribution has been shown by analyzing the hydrogen profile across the cladding of several high burnup fuel scenarios (>60 GW d/tU); other potential contributions like thermodiffusion and diffusion in the hydride phase hardly make any difference. Comparisons against PIE measurements allow concluding that the model accuracy notably increases when the effect of the oxidation front is accounted for in the hydride rim formation. In spite of the promising results, further validation would be needed.
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International Nuclear Information System (INIS)
Sivanesan, A.; Kannan, P.; Abraham John, S.
2007-01-01
This paper describes the electrocatalytic oxidation of ascorbic acid (AA) in phosphate buffer solution by the immobilized citrate capped gold nanoparticles (AuNPs) on 1,6-hexanedithiol (HDT) modified Au electrode. X-ray photoelectron spectrum (XPS) of HDT suggests that it forms a monolayer on Au surface through one of the two -SH groups and the other -SH group is pointing away from the electrode surface. The free -SH groups of HDT were used to covalently attach colloidal AuNPs. The covalent attachment of AuNPs on HDT monolayer was confirmed from the observed characteristic carboxylate ion stretching modes of citrate attached with AuNPs in the infra-red reflection absorption spectrum (IRRAS) in addition to a higher reductive desorption charges obtained for AuNPs immobilized on HDT modified Au (Au/HDT/AuNPs) electrode in 0.1 M KOH when compared to HDT modified Au (Au/HDT) electrode. The electron transfer reaction of [Fe(CN) 6 ] 4-/3- was markedly hindered at the HDT modified Au (Au/HDT) electrode while it was restored with a peak separation of 74 mV after the immobilization of AuNPs on Au/HDT (Au/HDT/AuNPs) electrode indicating a good electronic communication between the immobilized AuNPs and the underlying bulk Au electrode through a HDT monolayer. The Cottrell slope obtained from the potential-step chronoamperometric measurements for the reduction of ferricyanide at Au/HDT/AuNPs was higher than that of bare Au electrode indicating the increased effective surface area of AuNPs modified electrode. The Au/HDT/AuNPs electrode exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA) by enhancing the oxidation peak current to more than two times with a 210 mV negative shift in the oxidation potential when compared to a bare Au electrode. The standard heterogeneous electron transfer rate constant (k s ) calculated for AA oxidation at Au/HDT/AuNPs electrode was 5.4 x 10 -3 cm s -1 . The oxidation peak of AA at Au/HDT/AuNPs electrode was
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Mechanical test of E110 cladding material oxidized in hydrogen rich steam atmosphere
International Nuclear Information System (INIS)
Windberg, P.; Perez-Fero, E.
2005-01-01
The behavior of the fuel cladding under accidental conditions has been studied at the AEKI for more than a decade. Earlier, the effect of oxygen and hydrogen content on the mechanical properties was studied separately. The present experiments can help to understand what kind of processes took place in the cleaning tank at Paks NPP (2003). The purpose of our experiments was to investigate high temperature oxidation of E110 cladding in steam + hydrogen mixture. A high temperature tube furnace was used for oxidation of the samples. The oxidation was carried out at three different temperatures (900 0 C, 1000 0 C, 1100 0 C). The hydrogen content in the steam was varied between 19-36 vol%. The oxygen content of the sample was defined as oxidation ratio. Two sizes (length: 2 and 8 mm) of cladding rings and 100 mm long E110 cladding tubes were oxidized. After the oxidation we made compression and tensile tests for rings, and ballooning experiments for 100 mm long tube. The most important conclusions were the following. Oxidation in H-rich steam atmosphere need longer time to get the same oxidation ratio compared to the steam oxidation without hydrogen. The shorter oxidation time results in a more compact oxide layer. The longer oxidation time leads to a cracked oxide layer. (author)
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International Nuclear Information System (INIS)
Couet, Adrien; Motta, Arthur T.; Ambard, Antoine; Livigni, Didier
2017-01-01
Highlights: • In-situ electrochemistry on zirconium alloys in 360 °C pure water show oxide layer resistivity changes during corrosion. • A linear relationship is observed between oxide resistivity and instantaneous hydrogen pickup fraction. • The resistivity of the oxide layer formed on Zircaloy-4 (and thus its hydrogen pickup fraction) is higher than on Zr-2.5Nb. - Abstract: Hydrogen pickup during nuclear fuel cladding corrosion is a critical life-limiting degradation mechanism for nuclear fuel. Following a program dedicated to zirconium alloys, corrosion, it has been hypothesized that oxide electronic resistivity determines hydrogen pickup. In-situ electrochemical impedance spectroscopy experiments were performed on Zircaloy-4 and Zr-2.5Nb alloys in 360 °C water. The oxide resistivity was measured as function of time. The results show that as the oxide resistivity increases so does the hydrogen pickup fraction. The resistivity of the oxide layer formed on Zircaloy-4 is higher than on Zr-2.5Nb, resulting in a higher hydrogen pickup fraction of Zircaloy-4, compared to Zr-2.5Nb.
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CSIR Research Space (South Africa)
Adekunle, AS
2010-06-01
Full Text Available of the electrodes with the Ni and NiO nanoparticles was confirmed by techniques such as FTIR, FESEM, HRSEM, TEM, XRD, EDX and cyclic voltammetry (CV). The electrocatalytic oxidation of DEAET and hydrazine on the modified electrodes was investigated using CV...
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Modifications for the improvement of catalyst materials for hydrogen evolution
Directory of Open Access Journals (Sweden)
DRAGAN SLAVKOV
2006-02-01
Full Text Available The structural and electrocatalytic characteristics of composite materials based on non-precious metals were studied. Precursors of metallic phase (Ni, Co or CoNi and oxide phase (TiO2 were grafted on a carbon substrate (Vulcan XC-72 by the sol-gel procedure and thermally treated at 250 ºC. Ni and CoNi crystals of 10–20 nm were produced, in contrast the Co and TiO2 were amorphous. The dissimilar electronic character of the components gives rise to a significant electrocatalytic activity for the hydrogen evolution reaction (HER, even in the basic series of prepared materials. Further improvement of the catalysts was achieved by modification of all three components. Hence, Mo was added into the metallic phase, TiO2 was converted into the crystalline form and multiwall carbon nanotubes (MWCNTs were used instead of carbon particles. The improvement, expressed in terms of the lowering the hydrogen evolution overpotential at 60 mA cm–2, was the most pronounced in the Ni-based systems grafted on MWCNTs (120 mV lower HER overpotential compared to 60 mV in case of Ni-based systems grafted on crystalline TiO2 (TiO2 prepared at 450 ºC and of Ni-based systems containing 25 at.% Mo. Nevertheless, even with the realized enhancement, of all the fested materials, the Co-based systems remained superior HER catalysts.
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Hydrogen peroxide oxidant fuel cell systems for ultra-portable applications
Valdez, T. I.; Narayanan, S. R.
2001-01-01
This paper will address the issues of using hydrogen peroxide as an oxidant fuel in a miniature DMFC system. Cell performance for DMFC based fuel cells operating on hydrogen peroxide will be presented and discussed.
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Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui
2017-08-01
Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.
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Energy Technology Data Exchange (ETDEWEB)
Roy, Protiva Rani [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Saha, Madhu Sudan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Okajima, Takeyoshi [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)]. E-mail: ohsaka@echem.titech.ac.jp
2006-06-01
Multinegatively charged metal complex, hexacyanoferrate ([Fe(CN){sub 6}]{sup 4-}), was electrostatically trapped in the cationic polymer film of N,N-dimethylaniline (PDMA) which was electrochemically deposited on the boron-doped diamond (BDD) electrode by controlled-potential electro-oxidation of the monomer. This ferrocyanide-trapped PDMA film was used to catalyze the oxidation of ascorbic acid (AA). Increase in the oxidation current response with a negative shift of the anodic peak potential was observed at the cationic PDMA film-coated BDD (PDMA|BDD) electrode, compared with that at the bare BDD electrode. A more drastic enhancement in the oxidation peak current as well as more negative shift of oxidation potential was found at the ferrocyanide-trapped PDMA film-coated BDD ([Fe(CN){sub 6}]{sup 3-/4-}|PDMA|BDD) electrode. This [Fe(CN){sub 6}]{sup 3-/4-}|PDMA|BDD electrode can be used as an amperometric sensor of AA. Ferrocyanide, electrostatically trapped in the polymer film shows more electrocatalytic activity than that coordinatively attached to the polymer film or dissolved in the solution phase. The electrocatalytic current depends on the surface coverage of ferricyanide, {gamma} {sub Fe}, within the polymer film. Diffusion coefficient (D) of AA in the solution was estimated by rotating disk electrode voltammetry: D = (5.8 {+-} 0.3) x 10{sup -6} cm{sup 2} s{sup -1}. The second-order rate constant for the catalytic oxidation of AA by ferricyanide was also estimated to be 9.0 x 10{sup 4} M{sup -1} s{sup -1}. In the hydrodynamic amperometry using the [Fe(CN){sub 6}]{sup 3-/4-}|PDMA|BDD electrode, a successive addition of 1 {mu}M AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.233 {mu}A cm{sup -2} {mu}M{sup -1}.
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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 .
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Energy Technology Data Exchange (ETDEWEB)
Ullah, Nehar, E-mail: nehar.ullah@mail.mcgill.ca; Ali, Irshad; Omanovic, Sasha
2015-01-15
A thermally prepared iridium/ruthenium-oxide coating (Ir{sub 0.8}Ru{sub 0.2}-oxide) formed on a titanium substrate was investigated as a possible electrode for direct electrochemical regeneration of enzymatically-active 1,4-NADH from its oxidized form NAD{sup +}, at various electrode potentials, in a batch electrochemical reactor. The coating surface was characterized by ‘cracked mud’ morphology, yielding a high surface roughness. The NADH regeneration results showed that the percentage of enzymatically-active 1,4-NADH present in the product mixture (i.e. recovery) is strongly dependent on the electrode potential, reaching a maximum (88%) at −1.70 V vs. MSE. The relatively high recovery was explained on the basis of availability of adsorbed ‘active’ hydrogen (H{sub ads}) on the Ir/Ru-oxide surface, i.e. on the basis of electrochemical hydrogenation. - Highlights: • Ir{sub 0.8}Ru{sub 0.2}-oxide coating was formed thermally on a Ti substrate. • Electrochemical regeneration of enzymatically-active 1,4-NADH was investigated. • The 1,4-NADH recovery percentage is strongly dependent on the electrode potential. • A highest recovery, 88%, was obtained at −1.70 V vs. MSE. • The NADH regeneration process involved electrochemical hydrogenation.
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Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals
Energy Technology Data Exchange (ETDEWEB)
Song, Yang; Sanyal, Udishnu; Pangotra, Dhananjai; Holladay, Jamelyn D.; Camaioni, Donald M.; Gutierrez-Tinoco, Oliver Y.; Lercher, Johannes A.
2018-03-01
Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and
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Directory of Open Access Journals (Sweden)
Žerađanin Aleksandar R.
2014-01-01
Full Text Available The efficiency of electrocatalytic gas evolving reactions (hydrogen, chlorine and oxygen evolution is a key challenge for the important industrial processes, such as chlor-alkali electrolysis or water electrolysis. Central issue for the aforementioned electrocatalytic processes is huge power consumption. Experimental results accumulated in the past, as well as some predictive models ("volcano" plots indicate that altering the nature of the electrode material cannot significantly increase the activity of mentioned reactions. Consequently, it is necessary to find a qualitatively different strategy for improving the energy efficiency of electrocatalytic gas evolving reactions. Usually disregarded fact is that the gas evolution is an oscillatory phenomenon. Given the oscillatory behavior, a key parameter of macrokinetics of gas electrode is the frequency of gas-bubble detachment. Bearing in mind that the gas evolution greatly depends on the surface morphology, a methodology is proposed that establishes a rational link between the morphological pattern of electrode with electrode activity and stability. Characterization was performed using advanced analytical tools. Frequency of gas-bubble detachment is obtained in the configuration of scanning electrochemical microscopy (SECM while the corrosion stability is analyzed using miniaturized scanning flow electrochemical cell connected to the mass spectrometer (SFC-ICPMS.
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Gold nanoparticles-decorated fluoroalkylsilane nano-assemblies for electrocatalytic applications
Ballarin, Barbara; Barreca, Davide; Cassani, Maria Cristina; Carraro, Giorgio; Maccato, Chiara; Mignani, Adriana; Lazzari, Dario; Bertola, Maurizio
2016-01-01
Metal/organosilane/oxide sandwich structures were prepared via a two-step self-assembly method. First, indium tin oxide (ITO) substrates were functionalized with the following fluoroalkylsilanes (FAS): RFC(O)N(H)(CH2)3Si(OMe)3 (1, RF = C5F11), containing an embedded amide between the perfluoroalkyl chain and the syloxanic moiety, and RF(CH2)2Si(OEt)3 (2, RF = C6F13). Subsequently, Au nanoparticles (AuNPs) introduction in the obtained systems was carried out by controlled immersion into a solution of citrate-stabilized AuNPs. The physico-chemical properties of the target materials were thoroughly investigated by using various complementary techniques. Finally, the application of such systems as catalysts for methanol electro-oxidation under alkaline conditions was investigated, revealing the synergistical role played by FAS and AuNPs in promoting a remarkable electrocatalytic activity.
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International Nuclear Information System (INIS)
You, Jung-Min; Kim, Daekun; Jeon, Seungwon
2012-01-01
Highlights: ► Novel thiolated carbon nanostructures – platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. ► The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H 2 O 2 for the first time. ► The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H 2 O 2 . ► The proposed H 2 O 2 biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures – multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H 2 O 2 . The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors’ performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H 2 O 2 analysis.
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Methodologies for hydrogen determination in metal oxides by prompt gamma activation analysis
International Nuclear Information System (INIS)
Alvarez, E.; Biegalski, S.R.; Landsberger, S.
2007-01-01
Prompt gamma activation analysis (PGAA), available at University of Texas at Austin (UT), has been employed for the direct determination of hydrogen content in a series of metal oxide materials typically used as cathodes in lithium ion battery systems. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. PGAA has proven to be a novel and precise technique for the determination of hydrogen in metal oxides. This type of investigation could provide valuable insight regarding the factors that limit the practical capacities of lithium ion oxide cathodes
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International Nuclear Information System (INIS)
Amblard, J.; Belloni, J.; Platzer, O.
1991-01-01
We show how to utilize the radiolytic pathway for grafting metal nanoaggregates upon anodes or cathodes involved in the chlorine-soda process, thus enhancing their electrochemical behaviour. In both cases important overpotentials are usually measured on unmodified electrodes. The electrocatalytic efficiency of bimetallic nanoparticles (such as Pt-Ru and Ni-Ru), once grafted onto bulk metal electrodes (Ti or Ni), has been investigated by measuring the overpotential for chlorine or hydrogen evolution, respectively. Experimental conditions are similar to those of the industrial process. A synergistic effect is shown when Pt and Ru are alloyed in a 2: 1 atomic ratio. Then the chlorine overpotential is minimum. Conversely, there is no synergy between Ni and Ru, although a minimum amount of Ru in Ru-Ni (50% atomic) ensures a very low hydrogen overpotential [fr
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Energy Technology Data Exchange (ETDEWEB)
Murugavelu, M.; Karthikeyan, B., E-mail: bkarthi_au@yahoo.com
2017-01-01
The Ag-Au core-shell bimetal nanoparticles (BNPs) was prepared using chemical reduction method. The prepared Ag-Au core-shell BNPs were characterized by UV–Visible (UV–Vis) spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) pattern. These results showed the Ag-Au BNPs exhibited core-shell shape. The Ag-Au core-shell BNPs was examined towards electrocatalytic oxidation of L-methionine (L-Met) by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry. According to the results, L-Met is determined with detection limit of 30 μM. Interference studies in biological buffer was also studied. - Highlights: • The Ag-Au core-shell BNPs are synthesized and characterized • Ag-Au core-shell BNPs modified (Ag-Au/GCE) has been examined for L-methionine oxidation/sensing by using electrochemical method. • The Ag-Au/GCE exhibited good performance for the detection of L-methionine.
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Mechanistic insight into oxide-promoted palladium catalysts for the electro-oxidation of ethanol.
Martinez, Ulises; Serov, Alexey; Padilla, Monica; Atanassov, Plamen
2014-08-01
Recent advancements in the development of alternatives to proton exchange membrane fuel cells utilizing less-expensive catalysts and renewable liquid fuels, such as alcohols, has been observed for alkaline fuel cell systems. Alcohol fuels present the advantage of not facing the challenge of storage and transportation encountered with hydrogen fuel. Oxidation of alcohols has been improved by the promotion of alloyed or secondary phases. Nevertheless, currently, there is no experimental understanding of the difference between an intrinsic and a synergistic promotion effect in high-pH environments. This report shows evidence of different types of promotion effects on palladium electrocatalysts obtained from the presence of an oxide phase for the oxidation of ethanol. The correlation of mechanistic in situ IR spectroscopic studies with electrochemical voltammetry studies on two similar electrocatalytic systems allow the role of either an alloyed or a secondary phase on the mechanism of oxidation of ethanol to be elucidated. Evidence is presented for the difference between an intrinsic effect obtained from an alloyed system and a synergistic effect produced by the presence of an oxide phase. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Carbon catalysts for electrochemical hydrogen peroxide production in acidic media
DEFF Research Database (Denmark)
Čolić, Viktor; Yang, Sungeun; Révay, Zsolt
2018-01-01
Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run...... the reaction in an acidic electrolyte with high performance is particularly important, as it would allow the use of polymer solid electrolytes and the production of pH-neutral hydrogen peroxide. Carbon catalysts, which are cheap, abundant, durable and can be highly selective show promise as potential catalysts...... for such systems. In this work, we examine the electrocatalytic performance and properties of seven commercially available carbon materials for H2O2 production by oxygen electroreduction. We show that the faradaic efficiencies for the reaction lie in a wide range of 18-82% for different carbon catalysts. In order...
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Effect of hydrogen on the integrity of aluminium–oxide interface at elevated temperatures
Li, Meng; Xie, De-Gang; Ma, Evan; Li, Ju; Zhang, Xixiang; Shan, Zhi-Wei
2017-01-01
Hydrogen can facilitate the detachment of protective oxide layer off metals and alloys. The degradation is usually exacerbated at elevated temperatures in many industrial applications; however, its origin remains poorly understood. Here by heating hydrogenated aluminium inside an environmental transmission electron microscope, we show that hydrogen exposure of just a few minutes can greatly degrade the high temperature integrity of metal–oxide interface. Moreover, there exists a critical temperature of ∼150 °C, above which the growth of cavities at the metal–oxide interface reverses to shrinkage, followed by the formation of a few giant cavities. Vacancy supersaturation, activation of a long-range diffusion pathway along the detached interface and the dissociation of hydrogen-vacancy complexes are critical factors affecting this behaviour. These results enrich the understanding of hydrogen-induced interfacial failure at elevated temperatures.
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Effect of hydrogen on the integrity of aluminium–oxide interface at elevated temperatures
Li, Meng
2017-02-20
Hydrogen can facilitate the detachment of protective oxide layer off metals and alloys. The degradation is usually exacerbated at elevated temperatures in many industrial applications; however, its origin remains poorly understood. Here by heating hydrogenated aluminium inside an environmental transmission electron microscope, we show that hydrogen exposure of just a few minutes can greatly degrade the high temperature integrity of metal–oxide interface. Moreover, there exists a critical temperature of ∼150 °C, above which the growth of cavities at the metal–oxide interface reverses to shrinkage, followed by the formation of a few giant cavities. Vacancy supersaturation, activation of a long-range diffusion pathway along the detached interface and the dissociation of hydrogen-vacancy complexes are critical factors affecting this behaviour. These results enrich the understanding of hydrogen-induced interfacial failure at elevated temperatures.
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International Nuclear Information System (INIS)
Luo, Liqiang; Zhang, Yuting; Li, Fang; Si, Xiaojing; Ding, Yaping; Deng, Dongmei; Wang, Tianlin
2013-01-01
Graphical abstract: -- Highlights: •Spinel-type Co x Ni 1−x Fe 2 O 4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) were synthesized. •Co x Ni 1−x Fe 2 O 4 were first employed as novel enzyme mimic sensing materials of H 2 O 2 . •Co 0.5 Ni 0.5 Fe 2 O 4 /CPE showed excellent electrocatalytic activity to H 2 O 2 . •Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was successfully applied to determine H 2 O 2 in toothpastes. -- Abstract: A series of spinel-type Co x Ni 1−x Fe 2 O 4 (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) magnetic nanomaterials were solvothermally synthesized as enzyme mimics for the eletroctrocatalytic oxidation of H 2 O 2 . X-ray diffraction and scanning electron microscope were employed to characterize the composition, structure and morphology of the material. The electrochemical properties of spinel-type Co x Ni 1−x Fe 2 O 4 with different (Co/Ni) molar ratio toward H 2 O 2 oxidation were investigated, and the results demonstrated that Co 0.5 Ni 0.5 Fe 2 O 4 modified carbon paste electrode (Co 0.5 Ni 0.5 Fe 2 O 4 /CPE) possessed the best electrocatalytic activity for H 2 O 2 oxidation. Under optimum conditions, the calibration curve for H 2 O 2 determination on Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was linear in a wide range of 1.0 × 10 −8 –1.0 × 10 −3 M with low detection limit of 3.0 × 10 −9 M (S/N = 3). The proposed Co 0.5 Ni 0.5 Fe 2 O 4 /CPE was also applied to the determination of H 2 O 2 in commercial toothpastes with satisfactory results, indicating that Co x Ni 1−x Fe 2 O 4 is a promising hydrogen peroxidase mimics for the detection of H 2 O 2
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DEFF Research Database (Denmark)
Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip
2015-01-01
step towards accurate identification and prediction of a variety of oxide/electrode interfacial structure-properties relationships, but also provides the foundation for rational design and control of ‘targeted active phases’ at catalytic interfaces. The successful design of bifunctional......In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... under alkaline electrochemical conditions. We demonstrate that the structure and oxidation state of the films can be systematically tuned by changing the applied electrode potential and/or the nature of substrates. Structural features determined from the theoretical calculations provide a wealth...
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International Nuclear Information System (INIS)
Raynaud, Pierre
1980-01-01
This research thesis addresses the study of the oxidation reaction in the case of corrosion of iron by oxygen, hydrogen sulphide or hydrogen-water vapour mixes, and in the case of oxidation of titanium and of titanium nitride by hydrogen-water vapour mixes. It first addresses the corrosion of iron by oxygen with an experiment performed in cylinder symmetry: description of operational conditions, discussion of kinetic curves, development of a law of generation of multiple layers in cylinder symmetry, analytical exploitation of experimental results. The second part addresses the oxidation of iron by hydrogen-water vapour mixes: experimental conditions, influence of temperature on kinetics, micrographic study (oxide morphology, coating morphology, interpretation of differences with the case of plane symmetry), discussion of the influence of cylinder symmetry on oxidation kinetics. The third part addresses the oxidation of titanium by hydrogen-water vapour mixes: global kinetic evolution, reaction products and micrographic examination, morphology and texture studies, discussion of the oxidation mechanism and of cylinder symmetry [fr
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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.)
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The role of surface oxides on hydrogen sorption kinetics in titanium thin films
Hadjixenophontos, Efi; Michalek, Lukas; Roussel, Manuel; Hirscher, Michael; Schmitz, Guido
2018-05-01
Titanium is presently discussed as a catalyst to accelerate the hydrogenation kinetics of hydrogen storage materials. It is however known that H absorption in Ti decisively depends on the surface conditions (presence or absence of the natural surface oxide). In this work, we use Ti thin films of controlled thickness (50-800 nm) as a convenient tool for quantifying the atomic transport. XRD and TEM investigations allow us to follow the hydrogenation progress inside the film. Hydrogenation of TiO2/Ti bi-layers is studied at 300 °C, for different durations (10 s to 600 min) and at varying pressures of pure H2 atmosphere. Under these conditions, the hydrogenation is found to be linear in time. By comparing films with and without TiO2, as well as by studying the pressure dependence of hydrogenation, it is demonstrated that hydrogen transport across the oxide represents the decisive kinetic barrier rather than the splitting of H2 molecules at the surface. Hydrogenation appears by a layer-like reaction initiated by heterogeneous nucleation at the backside interface to the substrate. The linear growth constant and the H diffusion coefficient inside the oxide are quantified, as well as a reliable lower bound to the hydrogen diffusion coefficient in Ti is derived. The pressure dependence of hydrogen absorption is quantitatively modelled.
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Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts
Anis, Shaheen Fatima; Hashaikeh, Raed
2018-02-01
Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50-150 nm range) and micro-zeolite Y (500-800 nm range) were loaded with WO3, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO3 were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO3 loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO3. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO3, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.
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Nurlaela, Ela
2016-01-25
The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.
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Energy Technology Data Exchange (ETDEWEB)
Libert, M F; Sellier, R; Marty, V; Camaro, S [CEA Cadarache, Dept. d' Entreposage et de Stockage des Dechets (DCC/DESD/SEP), 13 - Saint-Paul-lez-Durance (France)
2000-07-01
The effect of many parameters need to be studied to characterize the long term behavior of nuclear waste in a deep repository. These parameters concern the chemical effects, radiolytic effects, mechanical properties, water composition, and microbiological activity. To evaluate microbial activity in such an environment, work was focused on an inventory of key nutrients (C, H, 0, N, P, S) and energy sources required for bacterial growth. The production of hydrogen in the nuclear waste environment leads to the growth of hydrogen oxidizing bacteria, which modify the gas production balance. A deep repository containing bituminized waste drums implies several sources of hydrogen: - water radiolysis; -corrosion of metal containers; - radiolysis of the embedding matrix (bitumen). Two deep geological disposal conditions leading to H{sub 2} production in a bituminized nuclear waste environment were simulated in the present study: - H{sub 2} production by iron corrosion under anaerobic conditions was simulated by adding 10% of H{sub 2} in the atmosphere; - H{sub 2} production by radiolysis of bitumen matrix was approached by subjecting this material to external gamma irradiation with a dose rate near real conditions (6 Gy/h). The presence of dissolved H{sub 2} in water allows the growth of hydrogen oxidizing bacteria leading to: - CO{sub 2} and N{sub 2} production; - H{sub 2} consumption; - lower NO{sub 3}{sup -} concentration caused by reduction to nitrogen. In the first case, hydrogen consumption is limited by the NO{sub 3}{sup -} release rate from the bitumen matrix. In the second case, however, under gamma radiation at a low dose rate, hydrogen production is weak, and the hydrogen is completely consumed by microorganisms. Knowledge about these hydrogen oxidizing bacteria is just beginning to emerge. Heterotrophic denitrifying bacteria adapt well to hydrogen metabolism (autotrophic metabolism) by oxidizing H{sub 2} instead of hydrocarbons. (authors)
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Oxide characterization and hydrogen behaviors of Zr-based alloys
International Nuclear Information System (INIS)
Kim, Y. S.; Kim, D. J.; Kwon, S. H.; Lee, H. S.; Oh, S. J.; Yim, B. J.; Son, S. B.; Yun, S. P.
2006-03-01
The work scope and contents of the research are as follows : basic properties of zirconium alloys, hydrogen pick-up mechanism of zirconium alloy, effects of hydride on the corrosion behaviors of zirconium alloys, estimation on stress of oxide layer in the zirconium alloy, microstructure and characteristic of oxide in pre-hydrided zirconium alloys
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Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction
Energy Technology Data Exchange (ETDEWEB)
Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)
2015-04-15
Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.
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Solid oxide fuel cells and hydrogen production
International Nuclear Information System (INIS)
Dogan, F.
2009-01-01
'Full text': A single-chamber solid oxide fuel cell (SC-SOFC), operating in a mixture of fuel and oxidant gases, provides several advantages over the conventional SOFC such as simplified cell structure (no sealing required). SC-SOFC allows using a variety of fuels without carbon deposition by selecting appropriate electrode materials and cell operating conditions. The operating conditions of single chamber SOFC was studied using hydrocarbon-air gas mixtures for a cell composed of NiO-YSZ / YSZ / LSCF-Ag. The cell performance and catalytic activity of the anode was measured at various gas flow rates. The results showed that the open-circuit voltage and the power density increased as the gas flow rate increased. Relatively high power densities up to 660 mW/cm 2 were obtained in a SC-SOFC using porous YSZ electrolytes instead of dense electrolytes required for operation of a double chamber SOFC. In addition to propane- or methane-air mixtures as a fuel source, the cells were also tested in a double chamber configuration using hydrogen-air mixtures by controlling the hydrogen/air ratio at the cathode and the anode. Simulation of single chamber conditions in double chamber configurations allows distinguishing and better understanding of the electrode reactions in the presence of mixed gases. Recent research efforts; the effect of hydrogen-air mixtures as a fuel source on the performance of anode and cathode materials in single-chamber and double-chamber SOFC configurations,will be presented. The presentation will address a review on hydrogen production by utilizing of reversible SOFC systems. (author)
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International Nuclear Information System (INIS)
Du, Cheng; Gao, Xiaohui; Zhuang, Zhihua; Cheng, Chunfeng; Zheng, Fuqin; Li, Xiaokun; Chen, Wei
2017-01-01
Highlights: • PtAu nanoalloy surface is heteroepitaxially grown on the pre-synthesized Au nano-pentagrams. • The PtAu/Au nano-pentagrams exhibit excellent electrocatalytic activity for ethanol oxidation. • The charge transfer resistance of PtAu/Au is lower than that of commercial Pt/C. • The durability and anti-poisoning ability of PtAu/Au is much better than those of commercial Pt/C - Abstract: Improving Pt utilization is of fundamental importance for many significant processes in energy conversion, which is strongly dependent on the surface structure of used catalysts. Based on the traditional Pt-on-Au system which has been proved to be an ideal nanostructure for improving the catalytic activity and stability of Pt, and the recent follow-up studies on this system, we introduce here a new strategy for fabricating Pt surface with high-index facets over the Pt-on-Au system. To achieve this goal, we elaborately designed and fabricated a unique zigzag PtAu alloy nanosurface on Au nano-pentagrams (PtAu/Au NPs) through epitaxial growth of Pt along the high-index facets on the pre-synthesized Au nano-pentagrams. Owing to the surface electronic interaction between Au and Pt and the exposed high-index facets from the unique morphology of zigzag PtAu alloy nanosurface, the as-prepared PtAu/Au NPs exhibited excellent electrocatalytic performance toward ethanol oxidation reaction (EOR) in alkaline condition. The specific activity (8.3 mA cm"−"2) and mass activity (4.4 A mg"−"1) obtained from PtAu/Au NPs are about 5.2 and 5.5 times, respectively, higher than those from commercial Pt/C for EOR.
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Hydrogen Production via Steam Reforming of Ethyl Alcohol over Palladium/Indium Oxide Catalyst
Directory of Open Access Journals (Sweden)
Tetsuo Umegaki
2009-01-01
Full Text Available We report the synergetic effect between palladium and indium oxide on hydrogen production in the steam reforming reaction of ethyl alcohol. The palladium/indium oxide catalyst shows higher hydrogen production rate than indium oxide and palladium. Palladium/indium oxide affords ketonization of ethyl alcohol with negligible by-product carbon monoxide, while indium oxide mainly affords dehydration of ethyl alcohol, and palladium affords decomposition of ethyl alcohol with large amount of by-product carbon monoxide. The catalytic feature of palladium/indium oxide can be ascribed to the formation of palladium-indium intermetallic component during the reaction as confirmed by X-ray diffraction and X-ray photoelectron spectroscopic measurements.
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Suspension Hydrogen Reduction of Iron Oxide Concentrates
Energy Technology Data Exchange (ETDEWEB)
H.Y. Sohn
2008-03-31
The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.
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Oxide film defects in Al alloys and the formation of hydrogen- related porosity
International Nuclear Information System (INIS)
Griffiths, W D; Yue, Y; Gerrard, A J
2016-01-01
Double oxide film defects have also been held responsible for the origins of hydrogen porosity, where hydrogen dissolved in the Al melt passes into the interior atmosphere of the double oxide film defect causing it to inflate. However, this is in opposition to long- established evidence that H cannot readily diffuse through aluminium oxide. To investigate this further, samples of commercial purity Al were first degassed to remove their initial H content, and then heated to above their melting point and held in atmospheres of air and nitrogen respectively, to determine any differences in H pick-up. The experiment showed that samples held in an oxidising atmosphere, and having an oxide skin, picked up significantly less H than when the samples were held in a nitrogen atmosphere, which resulted in the formation of AlN in cracks in the oxide skin of the sample. It is suggested that double oxide film defects can give rise to hydrogen-related porosity, but this occurs more quickly when the oxygen in the original oxide film defect has been consumed by reaction with the surrounding melt and nitrogen reacts to form AlN, which is more permeable to H than alumina, more easily allowing the oxide film defect to give rise to a hydrogen pore. This is used to interpret results from an earlier synchrotron experiment, in which a small pore was seen to grow into a larger pore, while an adjacent large pore remained at a constant size. (paper)
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Nouri-Nigjeh, Eslam; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.
2012-01-01
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
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Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures
International Nuclear Information System (INIS)
De Hollander, W.R.; Nivas, Y.
1975-01-01
Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)
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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.
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Energy Technology Data Exchange (ETDEWEB)
Singh, R.N.; Singh, A.; Anindita; Mishra, D. [Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005 (India)
2008-12-15
The study of electrochemical behaviour of dispersed Ni on graphite, glassy carbon, and Ti electrodes, obtained by an electro-deposition method, is carried out in 1 M KOH + 1 M CH{sub 3}OH at 25 C. Results show that the nature of substrate influences the apparent electrocatalytic activities of the Ni over layer greatly. It is observed that at E = 0.50 V vs. Hg/HgO (25 C), the dispersed Ni on graphite is approx. 300 times more active than that dispersed on Ti and is approx. 260 times more active than that dispersed on glassy carbon. Further, these electrodes show quite good resistance against electrode poisoning by the methanol oxidation intermediates/products. (author)
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Oxidation of lignin-carbohydrate complex from bamboo with hydrogen peroxide catalyzed by Co(salen
Directory of Open Access Journals (Sweden)
Zhou Xue-Fei
2014-01-01
Full Text Available The reactivity of salen complexes toward hydrogen peroxide has been long recognized. Co(salen was tested as catalyst for the aqueous oxidation of a refractory lignin-carbohydrate complex (LCC isolated from sweet bamboo (Dendrocalamushamiltonii in the presence of hydrogen peroxide as oxidant. Co(salen catalyzed the reaction of hydrogen peroxide with LCC. From the spectra analyses, lignin units in LCC were undergoing ring-opening, side chain oxidation, demethoxylation, β-O-4 cleavage with Co(salen catalytic oxidation. The degradation was also observed in the carbohydrate of LCC. The investigation on the refractory LCC degradation catalyzed by Co(salen may be an important aspect for environmentally-oriented biomimetic bleaching in pulp and paper industry.
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DEFF Research Database (Denmark)
Zong, Xu; Chen, Hongjun; Seger, Brian
2014-01-01
A solar-to-chemical conversion process is demonstrated using a photoelectrochemical cell without external bias for selective oxidation of hydrogen sulfide (H2S) to produce hydrogen peroxide (H2O2) and sulfur (S). The process integrates two redox couples anthraquinone/anthrahydroquinone and I−/I3......−, and conceptually illustrates the remediation of a waste product for producing valuable chemicals....
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Energy Technology Data Exchange (ETDEWEB)
Shumba, Munyaradzi; Mashazi, Philani; Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za
2016-02-15
Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences.
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International Nuclear Information System (INIS)
Shumba, Munyaradzi; Mashazi, Philani; Nyokong, Tebello
2016-01-01
Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates were characterized by absorption spectroscopy, transmission electron microscopy, fluorescence spectroscopy, X-ray diffraction, thermo gravimetric analysis and X-ray photon spectroscopy. The presence of reduced graphene oxide or graphene oxide resulted in the quenching (turn on) of Zn octacarboxy phthalocyanine fluorescence which can be explained by photoinduced electron transfer. Zn octacarboxy phthalocyanine-reduced graphene oxide or graphene oxide conjugates “turned on” fluorescence showed a linear response to hydrogen peroxide hence their potential to be used as sensors. The nanoprobe developed showed high selectivity towards hydrogen peroxide in the presence of physiological interferences.
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Kumar, Suneel; Reddy, Nagappagari Lakshmana; Kushwaha, Himmat Singh; Kumar, Ashish; Shankar, Muthukonda Venkatakrishnan; Bhattacharyya, Kaustava; Halder, Aditi; Krishnan, Venkata
2017-09-22
The development of noble metal-free catalysts for hydrogen evolution is required for energy applications. In this regard, ternary heterojunction nanocomposites consisting of ZnO nanoparticles anchored on MoS 2 -RGO (RGO=reduced graphene oxide) nanosheets as heterogeneous catalysts show highly efficient photocatalytic H 2 evolution. In the photocatalytic process, the catalyst dispersed in an electrolytic solution (S 2- and SO 3 2- ions) exhibits an enhanced rate of H 2 evolution, and optimization experiments reveal that ZnO with 4.0 wt % of MoS 2 -RGO nanosheets gives the highest photocatalytic H 2 production of 28.616 mmol h -1 g cat -1 under sunlight irradiation; approximately 56 times higher than that on bare ZnO and several times higher than those of other ternary photocatalysts. The superior catalytic activity can be attributed to the in situ generation of ZnS, which leads to improved interfacial charge transfer to the MoS 2 cocatalyst and RGO, which has plenty of active sites available for photocatalytic reactions. Recycling experiments also proved the stability of the optimized photocatalyst. In addition, the ternary nanocomposite displayed multifunctional properties for hydrogen evolution activity under electrocatalytic and photoelectrocatalytic conditions owing to the high electrode-electrolyte contact area. Thus, the present work provides very useful insights for the development of inexpensive, multifunctional catalysts without noble metal loading to achieve a high rate of H 2 generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles
Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele
2011-11-01
By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.
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Hydrogen Bonding in Phosphine Oxide/Phosphate-Phenol Complexes
Cuypers, R.; Sudhölter, E.J.R.; Zuilhof, H.
2010-01-01
To develop a new solvent-impregnated resin (SIR) system for the removal of phenols and thiophenols from water, complex formation by hydrogen bonding of phosphine oxides and phosphates is studied using isothermal titration calorimetry (ITC) and quantum chemical modeling. Six different computational
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Removing of oxides from Fe-Ni alloys by hydrogen plasma treatment
International Nuclear Information System (INIS)
Vesel, A.; Drenik, A.; Mozetic, M.
2007-01-01
Plasma wall interaction is one of the key issues in fusion research for ITER application. The first-wall materials in tokamaks and in other high temperature plasma reactors are subject to and to continuous degradation due to the ion bombardment. Furthermore the release of the eroded wall material leads to their redeposition to other parts of the fusion reactor and they can be even transported into the core plasma where they cause dilution of the plasma fuel and cooling of the plasma itself. One possible solution for removal of deposits formed during operation of the fusion devices is oxygen plasma treatment. A drawback of the oxygen plasma is that it causes formation of oxides on the surface of the materials. These oxides can be reduced by further hydrogen plasma treatment. A study on reduction of an oxide layer from Fe-Ni alloys was performed. The samples were exposed to low pressure weakly ionized hydrogen plasma for different periods. A density of hydrogen plasma was 8x10 15 m -3 , an electron temperature was 6 eV, and a degree of dissociation was about 30%. After plasma treatment the samples were analyzed by Auger Electron Spectroscopy (AES). The results showed that the complete reduction of an initial oxide layer with the thickness of about 30 nm occurred after 20 s of exposure to hydrogen plasma, when AES showed no more oxygen on the surface of Fe-Ni alloy. During the exposure of the samples to the plasma their temperature was measured. The temperature first rised with time, reached the maximum value, and than dropped as soon as the layer of an oxide on the surface was reduced. (author)
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CSIR Research Space (South Africa)
Akinbulu, IA
2011-10-01
Full Text Available characteristics of the films were interrogated by cyclic voltammetry. Significant passivation of voltammetry processes associated with bare gold surface (gold oxidation and underpotential deposition of copper) confirmed formation of the films. Electrocatalytic...
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Reduced graphene oxide supported gold nanoparticles for electrocatalytic reduction of carbon dioxide
Saquib, Mohammad; Halder, Aditi
2018-02-01
Electrochemical reduction of carbon dioxide is one of the methods which have the capability to recycle CO2 into valuable products for energy and industrial applications. This research article describes about a new electrocatalyst "reduced graphene oxide supported gold nanoparticles" for selective electrochemical conversion of carbon dioxide to carbon monoxide. The main aim for conversion of CO2 to CO lies in the fact that the latter is an important component of syn gas (a mixture of hydrogen and carbon monoxide), which is then converted into liquid fuel via well-known industrial process called Fischer-Tropsch process. In this work, we have synthesized different composites of the gold nanoparticles supported on defective reduced graphene oxide to evaluate the catalytic activity of reduced graphene oxide (RGO)-supported gold nanoparticles and the role of defective RGO support towards the electrochemical reduction of CO2. Electrochemical and impedance measurements demonstrate that higher concentration of gold nanoparticles on the graphene support led to remarkable decrease in the onset potential of 240 mV and increase in the current density for CO2 reduction. Lower impedance and Tafel slope values also clearly support our findings for the better performance of RGOAu than bare Au for CO2 reduction.
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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
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Niessen, J; Schröder, U; Harnisch, F; Scholz, F
2005-01-01
To exploit the fermentative hydrogen generation and direct hydrogen oxidation for the generation of electric current from the degradation of cellulose. Utilizing the metabolic activity of the mesophilic anaerobe Clostridium cellulolyticum and the thermophilic Clostridium thermocellum we show that electricity generation is possible from cellulose fermentation. The current generation is based on an in situ oxidation of microbially synthesized hydrogen at platinum-poly(tetrafluoroaniline) (Pt-PTFA) composite electrodes. Current densities of 130 mA l(-1) (with 3 g cellulose per litre medium) were achieved in poised potential experiments under batch and semi-batch conditions. The presented results show that electricity generation is possible by the in situ oxidation of hydrogen, product of the anaerobic degradation of cellulose by cellulolytic bacteria. For the first time, it is shown that an insoluble complex carbohydrate like cellulose can be used for electricity generation in a microbial fuel cell. The concept represents a first step to the utilization of macromolecular biomass components for microbial electricity generation.
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International Nuclear Information System (INIS)
Safavi, Afsaneh; Maleki, Norouz; Momeni, Safieh; Tajabadi, Fariba
2008-01-01
The electrocatalytic oxidation of sulfite was investigated at carbon ionic liquid electrode (CILE). This electrode is a very good alternative to previously described electrodes because the electrocatalytic effect is achieved without any electrode modification. Comparative experiments were carried out using carbon paste electrode (CPE) and glassy carbon electrode (GCE). At CILE, highly reproducible and well-defined cyclic voltammograms were obtained for sulfite with a peak potential of 0.55 V vs. Ag/AgCl. Sulfite oxidation at CILE does not result in deactivation of the electrode surface. The kinetic parameters for this irreversible heterogeneous electron transfer process were determined. Under optimal experimental conditions, the peak current response increased linearly with sulfite concentration over the range of 6-1000 μM. The detection limit of the method was 4 μM. The method was applied to the determination of sulfite in mineral water, grape juice and non-alcoholic beer samples
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International Nuclear Information System (INIS)
Gmucova, Katarina; Weis, Martin; Nadazdy, Vojtech; Capek, Ignac; Satka, Alexander; Chitu, Livia; Cirak, Julius; Majkova, Eva
2008-01-01
Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe 3 O 4 /Fe 2 O 3 ) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their 'orientation ordering' in an energetically favourable position
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Free standing graphene oxide film for hydrogen peroxide sensing
Ranjan, Pranay; Balakrishnan, Jayakumar; Thakur, Ajay D.
2018-05-01
We report hydrogen peroxide (H2O2)sensing using free standing graphene oxide thin films prepared using a cost effective scalable approach. Such sensors may find application in pharmaceutical and food processing industries.
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Directory of Open Access Journals (Sweden)
Ramayeni Elsa
2018-01-01
Full Text Available One of the methods to improve the oxidation stability of palm biodiesel is through partially hydrogenation. The production using Nickel/Carbon catalyst to speed up the reaction rate. Product is called Palm H-FAME (Hydrogenated FAME. Partial hydrogenation breaks the unsaturated bond on FAME (Fatty Acid Methyl Ester, which is a key component of the determination of oxidative properties. Changes in FAME composition by partial hydrogenation are predicted to change the oxidation stability so it does not cause deposits that can damage the injection system of diesel engine, pump system, and storage tank. Partial hydrogenation is carried out under operating conditions of 120 °C and 6 bar with 100:1, 100:3, 100:5, 100:10 % wt catalyst in the stirred batch autoclave reactor. H-FAME synthesis with 100:5 % wt Ni/C catalyst can decrease the iodine number which is the empirical measure of the number of unsaturated bonds from 91.78 to 82.38 (g-I2/100 g with an increase of oxidation stability from 585 to 602 minutes.
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Energy Technology Data Exchange (ETDEWEB)
Liu, Ruirui, E-mail: liurui1114@outlook.com; Lv, Meng, E-mail: lm199133@126.com; Wang, Qianbin, E-mail: material_wqb@163.com; Li, Hongliang, E-mail: lhl@qdu.edu.cn; Guo, Peizhi, E-mail: pzguo@qdu.edu.cn; Zhao, X.S., E-mail: chezxs@qdu.edu.cn
2017-02-15
Three ZnFe{sub 2}O{sub 4} colloidal nanocrystal assemblies (CNAs), namely CNA1, CNA2 and CNA3, have been synthesized solvothermally with the size of 560 nm, 460 nm and 330 nm and are formed by the self-assembly of primary nanocrystals with the crystallite sizes of 19.2 nm, 15.5 nm and 21.8 nm, respectively. It was found that CNA2 performed superparamagnetic behavior with a saturation magnetization value of 36.9 emu g{sup −1} while either CNA1 or CNA3 exhibited weak ferromagnetic with a small hysteresis loop and large saturation magnetization. Electrochemical sensing measurements toward the reduction of hydrogen peroxide showed that the peak currents of the CNAs in cyclic voltammograms showed a linear relationship with the concentration of hydrogen peroxide in the experimental conditions and the peak potentials were increased with the order of CNA3, CNA2 and CNA1. The formation mechanism of ZnFe{sub 2}O{sub 4} CNAs had been discussed based on the experimental data. The magnetism and electrocatalysis of the ZnFe{sub 2}O{sub 4} CNAs were supposed to be dependent on the size of primary nanoparticles and the structure of the CNAs. - Highlights: • Size-tunable ZnFe{sub 2}O{sub 4} colloidal nanocrystal assemblies were synthesized solvothermally. • Magnetic properties of ZnFe{sub 2}O{sub 4} assemblies are depended on the size and self-assembly of primary nanoparticles. • Electrocatalytic activity of ZnFe{sub 2}O{sub 4} assemblies is determined by their structure.
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Energy Technology Data Exchange (ETDEWEB)
Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)
2014-12-15
Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.
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International Nuclear Information System (INIS)
Nagaraju, D.H.; Devaraj, S.; Balaya, P.
2014-01-01
Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd 2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl 2 . X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells
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Charge transfer mediator based systems for electrocatalytic oxygen reduction
Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.
2017-07-18
Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.
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Charge transfer mediator based systems for electrocatalytic oxygen reduction
Energy Technology Data Exchange (ETDEWEB)
Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.
2017-11-07
Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.
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Cheng, Wei; Compton, Richard G
2016-02-12
We report the electrocatalytic dehalogenation of trichloroethylene (TCE) by single soft nanoparticles in the form of Vitamin B12 -containing droplets. We quantify the turnover number of the catalytic reaction at the single soft nanoparticle level. The kinetic data shows that the binding of TCE with the electro-reduced vitamin in the Co(I) oxidation state is chemically reversible. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Hydrogen in oxides and nitrides: unexpected physics and impact on devices
International Nuclear Information System (INIS)
Van De Walle, Chris G; Janotti, Anderson
2010-01-01
Controlling the conductivity of wide-band-gap semiconductors is key to enabling applications in electronics and optoelectronics. Many oxides exhibit unintentional n-type conductivity, and oxygen vacancies have been widely discussed as the source of this conductivity. Based on first-principles investigations we have shown that this cannot be true in ZnO and SnO 2 . We suggest that the conductivity is due to unintentional incorporation of donor impurities, with hydrogen being a likely candidate. Both interstitial and substitutional hydrogen act as shallow donors in a number of oxides. The atomic and electronic structures of these centers is discussed.
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Energy Technology Data Exchange (ETDEWEB)
Ranganathan, Suresh; Raju, Prabu; Arunachalam, Vijayaraj; Krishnamoorty, Giribabu; Ramadoss, Manigandan; Arumainathan, Stephen; Vengidusamy, Narayanan [University of Madras, Guindy Maraimalai Campus, Chennai (India)
2012-06-15
Poly(anthranilic acid) was synthesized by rapid mixing method using 5-sulphosalicylic acid as a dopant. The synthesized polymer was characterized by various techniques like FT-IR, UV-Visible, and X-ray diffraction etc., The FT-IR studies reveal that the 5-sulphosalicylic acid is well doped within the polymer. The morphological property was characterized by field emission scanning electron microscopic technique. The electrochemical properties of the polymer were studied by cyclic voltammetric method. The synthesized polymer was used to modify glassy carbon electrode (GCE) and the modified electrode was found to exhibit electrocatalytic activity for the oxidation of uric acid (UA)
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International Nuclear Information System (INIS)
Ranganathan, Suresh; Raju, Prabu; Arunachalam, Vijayaraj; Krishnamoorty, Giribabu; Ramadoss, Manigandan; Arumainathan, Stephen; Vengidusamy, Narayanan
2012-01-01
Poly(anthranilic acid) was synthesized by rapid mixing method using 5-sulphosalicylic acid as a dopant. The synthesized polymer was characterized by various techniques like FT-IR, UV-Visible, and X-ray diffraction etc., The FT-IR studies reveal that the 5-sulphosalicylic acid is well doped within the polymer. The morphological property was characterized by field emission scanning electron microscopic technique. The electrochemical properties of the polymer were studied by cyclic voltammetric method. The synthesized polymer was used to modify glassy carbon electrode (GCE) and the modified electrode was found to exhibit electrocatalytic activity for the oxidation of uric acid (UA)
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DEFF Research Database (Denmark)
Sun, Hongyu; Zhao, Yanyan; Mølhave, Kristian
2017-01-01
Three dimensional (3D) hierarchical architectures based onmolybdenum disulfide (MoS2) an d reduced graphene oxide (rGO) are synthesized through a mixed solvothermal method.By simply increasing the amount of graphene oxide (GO) during the synthesis, the 3D assembly of MoS2 can be tunedfrom nanoflo...
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Energy Technology Data Exchange (ETDEWEB)
You, Jung-Min; Kim, Daekun [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Jeon, Seungwon [Department of Chemistry and Institute of Basic Science, Chonnam National University, Gwangju 500-757 (Korea, Republic of)
2012-03-30
Highlights: Black-Right-Pointing-Pointer Novel thiolated carbon nanostructures - platinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. Black-Right-Pointing-Pointer The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H{sub 2}O{sub 2} for the first time. Black-Right-Pointing-Pointer The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H{sub 2}O{sub 2}. Black-Right-Pointing-Pointer The proposed H{sub 2}O{sub 2} biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s. - Abstract: Glassy carbon electrodes were coated with thiolated carbon nanostructures - multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H{sub 2}O{sub 2}. The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors' performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H{sub 2}O{sub 2} analysis.
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Gold-catalyzed oxidation of substituted phenols by hydrogen peroxide
Cheneviere, Yohan; Caps, Valerie; Tuel, Alain
2010-01-01
Gold nanoparticles deposited on inorganic supports are efficient catalysts for the oxidation of various substituted phenols (2,6-di-tert-butyl phenol and 2,3,6-trimethyl phenol) with aqueous hydrogen peroxide. By contrast to more conventional
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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
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Mechanism of calcium oxide excitation by atom hydrogen
International Nuclear Information System (INIS)
Kharlamov, V.F.
1991-01-01
Heterogeneous recombination of hydrogen atoms on the surface of calcium oxide proceeds according to the Langmuir-Hinshelwood mechanism with participation of atoms in two different states, belonging to adsorption centres of the same type. CaO excitation is broughty about by vibration-electron transitions during associative desorption of H 2 molecules
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Electrocatalytic glucose sensor
Energy Technology Data Exchange (ETDEWEB)
Gebhardt, U; Luft, G; Mund, K; Preidel, W; Richter, G J
1983-01-01
An artificial pancreas consists of an insulin depot, a dosage unit and a glucose sensor. The measurement of the actual glucose concentration in blood is still an unsolved problem. Two methods are described for an electrocatalytic glucose sensor. Under the interfering action of amino acids and urea in-vitro measurements show an error of between 10% and 20%.
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[Treatment of acrylate wastewater by electrocatalytic reduction process].
Yu, Li-Na; Song, Yu-Dong; Zhou, Yue-Xi; Zhu, Shu-Quan; Zheng, Sheng-Zhi; Ll, Si-Min
2011-10-01
High-concentration acrylate wastewater was treated by an electrocatalytic reduction process. The effects of the cation exchange membrane (CEM) and cathode materials on acrylate reduction were investigated. It indicated that the acrylate could be reduced to propionate acid efficiently by the electrocatalytic reduction process. The addition of CEM to separator with the cathode and anode could significantly improve current efficiency. The cathode materials had significant effect on the reduction of acrylate. The current efficiency by Pd/Nickel foam, was greater than 90%, while those by nickel foam, the carbon fibers and the stainless steel decreased successively. Toxicity of the wastewater decreased considerably and methane production rate in the biochemical methane potential (BMP) test increased greatly after the electrocatalytic reduction process.
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Energy Technology Data Exchange (ETDEWEB)
Schierbaum, Klaus; El Achhab, Mhamed [Department of Materials Science, Institute for Experimental Condensed Matter Physics, Heinrich-Heine University, 40225 Duesseldorf, Universitaetsstrasse 1 (Germany)
2011-12-15
We show that chemically induced current densities up to 20 mA cm{sup -2} and an electromotive force (EMF) up to 465 mV are generated during the hydrogen-to-water-oxidation over Pt/TiO{sub 2}/Ti devices. We prepare the samples by plasma electrolytic oxidation (PEO) of titanium foils and deposition of Pt contact paste. This process yields porous structures and, depending on the anodization voltage, Schottky diode-type current-voltage curves of various ideality parameters. Our experiments demonstrate that Pt coated anodized titanium can also be utilized as hydrogen sensor; the system offers a number of advantages such as a wide temperature range of operation from -40 to 80 C, quick response and decay times of signals, and good electrical stability. Idealized sketch of the Pt coated anodized Ti foil and application as hydrogen sensor and electric generator. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
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Enzyme-free hydrogen peroxide sensor based on Au@Ag@C core-double shell nanocomposites
Energy Technology Data Exchange (ETDEWEB)
Li, Yancai, E-mail: liyancai@mnnu.edu.cn [College of Chemistry & Environment, Minnan Normal University, Zhangzhou 363000 (China); Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou 363000 (China); Zhang, Yayun; Zhong, Yanmei [College of Chemistry & Environment, Minnan Normal University, Zhangzhou 363000 (China); Li, Shunxing [College of Chemistry & Environment, Minnan Normal University, Zhangzhou 363000 (China); Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou 363000 (China)
2015-08-30
Graphical abstract: - Highlights: • A facile method was designed to synthesize Au@Ag@C core-double shell nanocomposites. • Carbon nanomaterials at the outermost layer could protect Au and Ag nanoparticles from oxidation and aggregation. • The Au@Ag@C core-double shell nanocomposites showed high sensitivity and selectivity to electrocatalytic reduction of hydrogen peroxide. • The hydrogen peroxide sensor has a wide linear range of 5.0 μM to 4.75 mM and a limit of detection as low as 0.14 μM. - Abstract: The well-designed Au@Ag@C core-double shell nanocomposites were synthesized via a facile method, and were used to fabricate an enzyme-free amperometric hydrogen peroxide (H{sub 2}O{sub 2}) sensor. The size, shape, elementary composition and structure of the nanocomposites were characterized by transmission electron microscope (TEM), energy-dispersed spectrum (EDS) and X-ray diffraction (XRD). The outermost layer of the nanocomposites was amorphous carbon, the second layer was Ag and the core was Au. The Au@Ag@C core-double shell nanocomposites exhibit attractive activity for electrocatalytic reduction of H{sub 2}O{sub 2} according to the electrochemical experiments. It also demonstrates the H{sub 2}O{sub 2} sensor possess well performance with a wide linear range of 5.0 μM to 4.75 mM and a limit of detection (LOD) as low as 0.14 μM (S/N = 3). Furthermore, the interference from the common interfering species, such as glucose, ascorbic acid, dopamine and uric acid can be effectively avoided. In a word, the Au@Ag@C nanocomposites are promising candidates for enzyme-free H{sub 2}O{sub 2} sensor.
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Electrocatalytic Activity of Electropolymerized Cobalt ...
African Journals Online (AJOL)
Mercaptobenzimidazole (MBI) was studied. ... The poly-CoTAPc film exhibited efficiently electrocatalytic activity for 6MP and MBI with relatively high sensitivity, stability and long-life. ... HOW TO USE AJOL.
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International Nuclear Information System (INIS)
Conner, W.C. Jr.
1973-01-01
Hydrogenation of olefins has been studied over metals and metal oxides. Over metals the following observations generalize the characteristics of hydrogenation and isomerization. Metal hydrogenation catalysts are effective for H 2 -D 2 exchange (and para hydrogen conversion) under the same conditions as they effect olefin hydrogenation. This suggests that hydrogen ''activation'' involves formation of hydrogen atoms as a surface intermediate. Addition of deuterium to light ethylene leads to ethane products of the form C 2 H/sub 6-x/D/sub x/ (where 0 less than or equal to x less than or equal to 6). This is a result of the reversal of the alkyl (C 2 H 5 *) formation on the surface. Moreover, efficient isomerization of olefins require hydrogen as a co-catalyst. Both these observations suggest that alkyl formation and its reversal play a major role in hydrogenation and related reactions over metals. In this work it is found that zinc oxide catalyzes the deuteration of ethylene to dideuterioethane selectivity. Furthermore, the hydrogenation of ethylene using mixtures of hydrogen and deuterium indicate that hydrogenation occurs in such a manner as to reflect the molecular identity of the gas phase in the product ethane
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Li, Yanji; Wang, Zi; Li, Xiaoling; Yin, Tian; Bian, Kexin; Gao, Faming; Gao, Dawei
2017-02-01
Palladium nanomaterials have attracted great attention on the development of electrocatalysts for fuel cells. Herein, we depicted a novel strategy in the synthesis of palladium nanoparticles with superior electrocatalytic activity. The new approach, based on the self-assembly of bacitracin biotemplate and palladium salt for the preparation of bacitracin-palladium nanoparticles (Bac-PdNPs), was simple, low-cost, and green. The complex, composed by a series of spherical Bac-PdNPs with a diameter of 70 nm, exhibited a chain-liked morphology in TEM and a face-centered cubic crystal structure in X-Ray diffraction and selected area electron diffraction. The palladium nanoparticles were mono-dispersed and stable in aqueous solution as shown in TEM and zeta potential. Most importantly, compared to the commercial palladium on carbon (Pd/C) catalyst (8.02 m2 g-1), the Bac-PdNPs showed a larger electrochemically active surface area (47.57 m2 g-1), which endowed the products an excellent electrocatalytic activity for ethanol oxidation in alkaline medium. The strategy in synthesis of Bac-PdNPs via biotemplate approach might light up new ideas in anode catalysts for direct ethanol fuel cells.
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Energy Technology Data Exchange (ETDEWEB)
Dou, Yanpeng; Peng, Junjun, E-mail: john-peng@whu.edu.cn; Li, Wei; Li, Ming; Liu, Huihong; Zhang, Hanmin [Wuhan Textile University, College of Chemistry and Chemical Engineering (China)
2015-12-15
Silver nanoparticles/graphene oxide (AgNPs/GO) nanocomposites were prepared in a solution of AgNO{sub 3} and GO. The GO serves not only as a reductant but also as a substrate to support the as-reduced silver nanoparticles. The reducibility of GO was investigated by analyzing the influence factors such as pH, duration, the reaction temperature, and the weight ratio of AgNO{sub 3} and GO in the AgNP/GO nanocomposite mixture, which were evaluated by the UV–vis absorption spectroscopy. The results demonstrated that Ag nanoparticles with an average diameter of 5–10 nm were uniformly dispersed on the surface of GO nanosheets under the optimum synthesis conditions of pH between 8 and 11, weight ratio of AgNO{sub 3} and GO between 55 % and 60 %, and at 80 °C for 6 h. Moreover, the obtained AgNPs/GO nanocomposites exhibit good electrocatalytic activity for the reduction of p-nitrophenol to 4-(hydroxyamino) phenol.
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DEFF Research Database (Denmark)
Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.
2012-01-01
The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction...
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Partial oxidation of n-hexadecane through decomposition of hydrogen peroxide in supercritical water
Alshammari, Y.M.
2015-01-01
© 2014 The Institution of Chemical Engineers. This work reports the experimental analysis of partial oxidation of n-hexadecane under supercritical water conditions. A novel reactor flow system was developed which allows for total decomposition of hydrogen peroxide in a separate reactor followed partial oxidation of n-hexadecane in a gasification reactor instead of having both reactions in one reactor. The kinetics of hydrothermal decomposition of hydrogen peroxide was studied in order to confirm its full conversion into water and oxygen under the desired partial oxidation conditions, and the kinetic data were found in a good agreement with previously reported literature. The gas yield and gasification efficiency were investigated under different operating parameters. Furthermore, the profile of C-C/C=C ratio was studied which showed the favourable conditions for maximising yields of n-alkanes via hydrogenation of their corresponding 1-alkenes. Enhanced hydrogenation of 1-alkenes was observed at higher O/C ratios and higher residence times, shown by the increase in the C-C/C=C ratio to more than unity, while increasing the temperature has shown much less effect on the C-C/C=C ratio at the current experimental conditions. In addition, GC-MS analysis of liquid samples revealed the formation of heavy oxygenated compounds which may suggest a new addition reaction to account for their formation under the current experimental conditions. Results show new promising routes for hydrogen production with in situ hydrogenation of heavy hydrocarbons in a supercritical water reactor.
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Energy Technology Data Exchange (ETDEWEB)
Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon, E-mail: swjeon3380@naver.com
2017-06-01
Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H{sub 2}O{sub 2}. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H{sub 2}O{sub 2} yield.
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International Nuclear Information System (INIS)
Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon
2017-01-01
Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H_2O_2. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H_2O_2 yield.
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Indian Academy of Sciences (India)
Administrator
Titanium-catalysed dehydrocoupling of chiral carbosilanes.................................. . .... Copper(II) nickel(II), cobalt(II) and oxovanadium(IV) complexes of substituted .... Electrocatalytic oxidation of hydrogen peroxide by poly(NiII-teta) complex.
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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)
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Shinagawa, Tatsuya
2015-01-01
Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.
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Experimental and simulation analysis of hydrogen production by partial oxidation of methanol
Energy Technology Data Exchange (ETDEWEB)
Sikander, U. [National Univ. of Science and Technology, Islamabad (Pakistan)
2014-10-15
Partial oxidation of methanol is the only self-sustaining process for onboard production of hydrogen. For this a fixed bed catalytic reactor is designed, based on heterogeneous catalytic reaction. To develop an optimized process, simulation is carried out using ASPEN HYSYS v 7.1. Reaction kinetics is developed on the basis of Langmuir Hinshel wood model. 45:55:5 of CuO: ZnO: Al/sub 2/O/sub 3/ is used as a catalyst. Simulation results are studied in detail to understand the phenomenon of partial oxidation of methanol inside the reactor. An experimental rig is developed for hydrogen production through partial oxidation of methanol. Results obtained from process simulation and experimental work; are compared with each other. (author)
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International Nuclear Information System (INIS)
Oudart, Y.
2006-09-01
Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)
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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
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Materials design for electrocatalytic carbon capture
Directory of Open Access Journals (Sweden)
Xin Tan
2016-05-01
Full Text Available We discuss our philosophy for implementation of the Materials Genome Initiative through an integrated materials design strategy, exemplified here in the context of electrocatalytic capture and separation of CO2 gas. We identify for a group of 1:1 X–N graphene analogue materials that electro-responsive switchable CO2 binding behavior correlates with a change in the preferred binding site from N to the adjacent X atom as negative charge is introduced into the system. A reconsideration of conductive N-doped graphene yields the discovery that the N-dopant is able to induce electrocatalytic binding of multiple CO2 molecules at the adjacent carbon sites.
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International Nuclear Information System (INIS)
Choi, Ayoung; Jeong, Haesang; Kim, Songmi; Jo, Suhee; Jeon, Seungwon
2008-01-01
Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H 2 SO 4 solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O 2 -saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e - reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction
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Hydrogen bonding-mediated dehydrogenation in the ammonia borane combined graphene oxide systems
Kuang, Anlong; Liu, Taijuan; Kuang, Minquan; Yang, Ruifeng; Huang, Rui; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong; Yang, Xiaolan
2018-03-01
The dehydrogenation of ammonia borane (AB) adsorbed on three different graphene oxide (GO) sheets is investigated within the ab initio density functional theory. The energy barriers to direct combination the hydrogens of hydroxyl groups and the hydridic hydrogens of AB to release H2 are relatively high, indicating that the process is energetically unfavorable. Our theoretical study demonstrates that the dehydrogenation mechanism of the AB-GO systems has undergone two critical steps, first, there is the formation of the hydrogen bond (O-H-O) between two hydroxyl groups, and then, the hydrogen bond further react with the hydridic hydrogens of AB to release H2 with low reaction barriers.
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Nagaraju, Doddahalli H.; Devaraj, Sappani; Balaya, Palani
2014-01-01
nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient
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International Nuclear Information System (INIS)
Jalowiecki-Duhamel, L.; Carpentier, J.; Payen, E.; Heurtaux, F.
2006-01-01
Lacunar mixed oxides based on cerium nickel and aluminium or zirconium CeM 0.5 Ni x O y s (M = Zr or Al), able to store high quantities of hydrogen, have been analysed in the hydrogenation of toluene into methyl-cyclohexane (MCH). When these solids present very good toluene hydrogenation activity and selectivity towards MCH in presence of H 2 , in absence of gaseous hydrogen, the reactive hydrogen species stored in the solid can hydrogenate toluene into MCH. The hydrogenation activity under helium + toluene flow decreases as a function of time and becomes nil. The integration of the curve obtained allows to determine the extractable hydrogen content of the solid used, and a value of 1.2 wt % is obtained at 80 C on a CeAl 0.5 Ni 3 O y compound pre-treated in H 2 at 300 C. To optimise the system, different parameters have been analysed, such as the catalyst formulation, the metal content, the pre-reducing conditions as well as the reaction conditions under helium + toluene. (authors)
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Energy Technology Data Exchange (ETDEWEB)
Thirumalai, Kuppulingam; Balachandran, Subramanian [Department of Chemistry, Annamalai University, Annamalainagar, 608 002, Tamil Nadu (India); Swaminathan, Meenakshisundaram, E-mail: chemres50@gmail.com [Department of Chemistry, Annamalai University, Annamalainagar, 608 002, Tamil Nadu (India); Nanomaterials Laboratory, International Research Centre, Kalasalingam Universty, Krihnankoil, 626126 (India)
2016-11-01
Ever growing research on modified semiconductor oxides made a significant progress in catalytic functional materials. In this article, we report the modification of ZnO photocatalyst by a simple hydrothermal decomposition method utilizing the cheaply available industrial waste fly ash. This modified Fly ash-ZnO photocatalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), high resolution transmission electron microscopy (HR-TEM), Atomic force microscopy (AFM), photoluminescence spectroscopy (PL) and diffuse reflectance spectroscopy (DRS). The XRD pattern indicates the presence of fly ash components and the hexagonal wurtzite structured ZnO. TEM images reveal well defined nanorod like structure. Reduction of photoluminescence intensity of Fly ash-ZnO at 418 nm, when compared to, prepared ZnO, indicates the suppression of recombination of the photogenerated electron–hole pair by loaded Fly ash on ZnO. Fly ash-ZnO exhibits enhanced photocatalytic activity for the degradation of azo dyes Reactive Orange 4, Rhodamine-B and Trypan Blue. This catalyst shows higher electrocatalytic activity than ZnO in the oxidation of methanol. Significant hydrophobicity of Fly ash-ZnO reveals its self cleaning property. - Highlights: • The degradation efficiency of Fly ash-ZnO under UV and Solar irradiation is greater than prepared ZnO and TiO{sub 2}‒P25. • Electrocatalytic activity of Fly ash-ZnO exhibits enhanced current production by methanol oxidation. • Fly ash-ZnO shows the high hydrophobicity than ZnO, it can be used as a self cleaning material for industrial applications.
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Energy Technology Data Exchange (ETDEWEB)
Im, Ji Sun; Lee, Young-Seak [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, Daejeon 305-764 (Korea); Park, Soo-Jin [Department of Chemistry, Inha University, Incheon 402-751 (Korea); Kim, Taejin [Core Technology Research Center for Fuel Cell, Jeollabuk-do 561-844 (Korea)
2009-05-15
In order to investigate the catalytic capacity of metals and metal oxides based on electrospun carbon fibers for improving hydrogen storage, electrospinning and heat treatments were carried out to obtain metal/metal oxide-embedded carbon fibers. Although the fibers were treated with the same activation procedure, they had different pore structures, due to the nature of the metal oxide. When comparing the catalytic capacity of metal and metal oxide, metal exhibits better performance as a catalyst for the improvement of hydrogen storage, when considering the hydrogen storage system. When a metal oxide with an m.p. lower than the temperature of heat treatment was used, the metal oxide was changed to metal during the heat treatment, developing a micropore structure. The activation process produced a high specific surface area of up to 2900 m{sup 2}/g and a pore volume of up to 2.5 cc/g. The amount of hydrogen adsorption reached approximately 3 wt% at 100 bar and room temperature. (author)
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Preparation and electrocatalytic properties of Pt-SiO2 nanocatalysts for ethanol electrooxidation.
Liu, B; Chen, J H; Zhong, X X; Cui, K Z; Zhou, H H; Kuang, Y F
2007-03-01
Due to their high stability in general acidic solutions, SiO(2) nanoparticles were selected as the second catalyst for ethanol oxidation in sulfuric acid aqueous solution. Pt-SiO(2) nanocatalysts were prepared in this paper. The micrography and elemental composition of Pt-SiO(2) nanoparticles were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The electrocatalytic properties of Pt-SiO(2) nanocatalysts for ethanol oxidation were investigated by cyclic voltammetry. Under the same Pt loading mass and experimental conditions for ethanol oxidation, Pt-SiO(2) nanocatalysts show higher activity than PtRu/C (E-Tek), Pt/C (E-Tek), and Pt catalysts. Additionally, Pt-SiO(2) nanocatalysts possess good anti-poisoning ability. The results indicate that Pt-SiO(2) nanocatalysts may have good potential applications in direct ethanol fuel cells.
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Metal oxide/hydrogen secondary battery; Kinzoku sankabutsu/suiso niji denchi
Energy Technology Data Exchange (ETDEWEB)
Hosobuchi, H.; Ema, M.
1995-12-12
Since the shape of powder produced by crushing the hydrogen storage alloy containing rare earth element varies widely, the density of the negative electrode made by packing the alloy powder is low. As a result, the secondary battery employing this negative electrode has a small discharge capacity. This invention solves the problem. Employing the hydrogen storage alloy containing rare earth element composed of particle shape of aspect ratio, A, of over 1.0 and below 3.0 gives rise to the negative electrode with high packing density, improving the discharge capacity of the metal oxide - hydrogen secondary battery. The more the shape of powder of hydrogen storage alloy containing rare earth element is near to sphere, the higher the packing density of negative electrode made of the hydrogen storage alloy containing rare earth element becomes. The preferable aspect ratio, A, of the powder is 1.0 {le} A {le} 2.0. Such alloy powder can be produced by mechanically grinding the rare-earth-element-containing hydrogen alloy ingot, or grinding by hydration, or grinding by atomizing followed by sieving. 1 fig., 1 tab.
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Journal of Chemical Sciences | Indian Academy of Sciences
Indian Academy of Sciences (India)
, cobalt(II) and oxovanadium(IV) complexes of substituted ∙ - ... Synthesis, structure and spectral and electrochemical properties of new mixed .... Electrocatalytic oxidation of hydrogen peroxide by poly(Ni-teta) complex modified electrodes.
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Dick, Jeffrey E; Bard, Allen J
2015-11-04
We report the electrodeposition of electrocatalytic clusters of platinum from femtomolar platinate solutions. An inert carbon fiber ultramicroelectrode (UME) was held at a potential where proton reduction was unfavorable on carbon but favorable on platinum in a 1 M sulfuric acid solution. Upon addition of femtomolar amounts of hexachloroplatinic acid, which will also reduce to Pt(0) at the applied potential on the carbon fiber UME, cathodic blips were observed in the amperometric i-t response. These blips correspond to the reduction of protons to molecular hydrogen at the small platinum clusters followed by a rapid deactivation likely due to hydrogen bubble formation. On average, these current spikes occur when five platinum atoms have been formed on the electrode, as determined by a comparative analysis of experimental cathodic blips and calculated hexachloroplatinate molecule collision frequencies.
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Energy Technology Data Exchange (ETDEWEB)
Oudart, Y
2006-09-15
Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)
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Energy Technology Data Exchange (ETDEWEB)
Morales G, P
2001-07-01
In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co{sub 3}O{sub 4} and the Ni O as the mixtures Ni O/Co{sub 3}O{sub 4} were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co{sub 3}O{sub 4} and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co{sub 3}O{sub 4} mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)
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Energy Technology Data Exchange (ETDEWEB)
Oudart, Y
2006-09-15
Hydrogenase enzymes reversibly catalyze the oxidation and production of hydrogen in a range close to the thermodynamic potential. The [NiFe] hydrogenase active site contains an iron-cyano-carbonyl moiety linked to a nickel atom which is in an all sulphur environment. Both the active site originality and the potential development of an hydrogen economy make the synthesis of functional and structural models worthy. To take up this challenge, we have synthesised mononuclear ruthenium models and more importantly, nickel-ruthenium complexes, mimicking some structural features of the [NiFe] hydrogenase active site. Ruthenium is indeed isoelectronic to iron and some of its complexes are well-known to bear hydrides. The compounds described in this study have been well characterised and their activity in proton reduction has been successfully tested. Most of them are able to catalyze this reaction though their electrocatalytic potentials remain much more negative compared to which of platinum. The studied parameters point out the importance of the complexes electron richness, especially of the nickel environment. Furthermore, the proton reduction activity is stable for several hours at good rates. The ruthenium environment seems important for this stability. Altogether, these compounds represent the very first catalytically active [NiFe] hydrogenase models. Important additional results of this study are the synergetic behaviour of the two metals in protons reduction and the evidence of a protonation step as the limiting step of the catalytic cycle. We have also shown that a basic site close to ruthenium improves the electrocatalytic potential of the complexes. (author)
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Charge transfer effects in electrocatalytic Ni-C revealed by x-ray photoelectron spectroscopy
Energy Technology Data Exchange (ETDEWEB)
Haslam, G. E.; Chin, X.-Y.; Burstein, G. T. [Department of Materials Science and Metallurgy, University of Cambridge, Pembroke St., Cambridge CB2 3QZ (United Kingdom); Sato, K.; Mizokawa, T. [Department of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8651 (Japan)
2012-06-04
Binary Ni-C thin-film alloys, which have been shown to be passive against corrosion in hot sulphuric acid solution whilst also being electrocatalytically active, were investigated by XPS to determine the oxidation state of the metal and carbon components. The Ni component produces a Ni 2p spectrum similar to that of metallic nickel (i.e., no oxidation occurs) but with a 0.3 eV shift to higher binding energy (BE) due to electron donation to the carbon matrix. The C 1s peak shows a shift to lower BE by accepting electrons from the Ni nanocrystals. A cluster-model analysis of the observed Ni 2p spectrum is consistent with the electron transfer from the nickel to the carbon.
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International Nuclear Information System (INIS)
Rutkowska, Iwona A.; Sek, Jakub P.; Mehdi, B. Layla; Kulesza, Pawel J.; Cox, James A.
2014-01-01
Electrochemical deposition of crosslinked oxo-cyanoruthenate, Ru-O/CN-O, from a mixture of RuCl 3 and K 4 Ru(CN) 6 is known to yield a film on glassy carbon that promotes oxidations by a combination of electron and oxygen transfer. Layer-by-layer (LbL) deposition of this species at a film formed by cycling of the electrode potential in a ZrO 2 solution systematically increases the number of catalytically active sites of the Ru-O/CN-O on the electrode. The evaluation of the electrocatalytic activity was by cyclic voltammetric oxidation of cysteine at pH 2. Plots of the anodic peak current vs. the square root of scan rate were indicative of linear diffusion control of this oxidation, even in the absence of ZrO 2 , but the slopes of these linear plots increased with bilayer number, n, of (ZrO 2 | Ru-O/CN-O) n . The latter observation is hypothesized to be due to an increased number of active sites for a given geometric electrode area, but proof requires further study. To optimize utilization of the catalyst and to provide a size-exclusion characteristic to the electrode, the study was extended to LbL deposition of the composite in 50-nm pores of an organically modified silica film deposited by electrochemically assisted sol-gel processing using surface-bound poly(styrene sulfonate) nanospheres as a templating agent
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Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J
2016-02-23
Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.
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International Nuclear Information System (INIS)
Zhang, Yajun; Zhao, Guohua; Shi, Huijie; Zhang, Ya-nan; Huang, Wenna; Huang, Xiaofeng; Wu, Zhongyi
2015-01-01
Highlights: • Solar-driven PEC glucose oxidation to promote hydrogen production was presented. • The excellent PEC activity of Pd QDs@TNTAs was investigated. • The rate of hydrogen production from glucose was about 15 times than water. • A low-cost and efficient method in renewables-to-hydrogen conversion was put forward. - Abstract: The development of highly efficient and low-cost approaches for catalytic hydrogen production from renewable energy is of tremendous importance for a truly sustainable hydrogen-based energy carrier in future life. Herein, the probability of utilizing solar light to product hydrogen from biomass derivative, glucose, was systematically demonstrated by using the periodically ordered TiO 2 nanotube arrays (TNTAs) assembled of Palladium quantum dots (Pd QDs), i.e. Pd QDs@ TNTAs as photoanode. The results showed that remarkably increased photocurrent density was obtained in the glucose solution compared to the pure KOH electrolyte over as-prepared photoelectrode, which indicated that the glucose could be faster oxidized than water oxidation, and thus could promote the hydrogen production on Pt cathode. The yield of hydrogen production from glucose oxidation reached as high as 164.8 μmol cm −1 over Pd QDs@TNTAs photoanode and Pt cathode system (denoted as Pd QDs@TNTAs/Pt) under the solar light irradiation for 6 h, which was about 15 times higher than that from pure water splitting. The superior hydrogen production performance could be attributed to the less endergonic process of the glucose oxidation than water, as well as the efficient synergistic photoelectrocatalytic (PEC) glucose oxidation over Pd QDs@TNTAs photoanode which possesses excellent photoelectrochemical performance and structure characteristics. Moreover, a probable mechanism for the PEC hydrogen production from biomass derivatives oxidation was proposed and discussed
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New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review
Directory of Open Access Journals (Sweden)
Georgiy B. Shul’pin
2016-03-01
Full Text Available This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst. Works of recent years (mainly 2010–2016 devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon–hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.
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Hydrogen Evolution on Supported Incomplete Cubane-type [Mo3S4](4+) Electrocatalysts
DEFF Research Database (Denmark)
Jaramillo, Thomas; Bonde, Jacob Lindner; Zhang, Jingdong
2008-01-01
Electrocatalytic properties of biomimetic supported incomplete cubane-type [Mo3S4](4+) clusters are investigated. The activity toward the hydrogen evolution reaction (HER) is evaluated on both a high surface area gas diffusion electrode in a membrane electrode assembly and on highly orientated...
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Karim Asadpour-Zeynali; Venus Baghalabadi
2017-01-01
In this work poly eriochrome black T (EBT) was electrochemically synthesized on the glassy carbon electrode as electrode modifier. On the modified electrode, voltammetric behavior of isoniazid (INH) was investigated. The poly (EBT)-modified glassy carbon electrode has excellent electrocatalytic ability for the electrooxidation of isoniazid. This fact was appeared as a reduced overpotential of INH oxidation in a wide operational pH range from 2 to 13. It has been found that the catalytic peak ...
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International Nuclear Information System (INIS)
Gu, Yingying; Liu, Yicheng; Yang, Haihong; Li, Benqiang; An, Yarui
2015-01-01
Highlights: • Multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles, Ni(OH) 2 /TNTs, was prepared and investigated as anode electro-catalysts for glucose oxidation. • Ni(OH) 2 -24.2%/TNTs obtains the best catalytic activity. • Compared with Ni(OH) 2, the current density of Ni(OH) 2 -24.2%/TNTs increased 5.9 times in 0.1 M NaOH solution. - Abstract: The novel hybrid nanomaterial catalyst of multi-wall TiO 2 nanotube supported Ni(OH) 2 nanoparticles (Ni(OH) 2 /TNTs) was prepared through hydrothermal method and investigated as anode electro-catalysts for glucose oxidation. The nanostructure was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetry-differential thermal analysis (TGA) and nitrogen adsorption-desorption (BET-BJH). The electrochemical performance was measured by a range of electrochemical measurements. Compared with Ni(OH) 2 , the current density of Ni(OH) 2 /TNTs modified GC electrode increased 5.9 times in 0.1 M NaOH solution. The results indicated that the synthesized nanoparticles exhibited good electro-catalytic activity and stability for glucose oxidation. Meanwhile, the hybrid nanomaterial of Ni(OH) 2 /TNTs may be a potential candidate catalyst for direct glucose fuel cell
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Shinagawa, Tatsuya
2015-04-24
To maintain local pH levels near the electrode during electrochemical reactions, the use of buffer solutions is effective. Nevertheless, the critical effects of the buffer concentration on electrocatalytic performances have not been discussed in detail. In this study, two fundamental electrochemical reactions, oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR), on a platinum rotating disk electrode are chosen as model gas-related aqueous electrochemical reactions at various phosphate concentrations. Our detailed investigations revealed that the kinetic and limiting diffusion current densities for both the ORR and HOR logarithmically decrease with increasing solute concentration (log|jORR|=-0.39c+0.92,log|jHOR|=-0.35c+0.73). To clarify the physical aspects of this phenomenon, the electrolyte characteristics are addressed: with increasing phosphate concentration, the gas solubility decrease, the kinematic viscosity of the solution increase and the diffusion coefficient of the dissolved gases decrease. The simulated limiting diffusion currents using the aforementioned parameters match the measured ones very well (log|jORR|=-0.43c+0.99,log|jHOR|=-0.40c+0.54), accurately describing the consequences of the electrolyte concentration. These alterations of the electrolyte properties associated with the solute concentration are universally applicable to other aqueous gas-related electrochemical reactions because the currents are purely determined by mass transfer of the dissolved gases. © 2015 The Authors.
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Energy Technology Data Exchange (ETDEWEB)
Gholivand, Mohammad Bagher, E-mail: mbgholivand@yahoo.com [Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Azadbakht, Azadeh [Department of Chemistry, Faculty of Basic Science, Khorramabad Branch, Islamic Azad University, Khorramabad (Iran, Islamic Republic of)
2012-10-01
A nano-structured Ni(II)-chelidamic acid (2,6-dicarboxy-4-hydroxypyridine) film was electrodeposited on a gold nanoparticle-cysteine-gold electrode. The morphology of Ni(II)-chelidamic acid gold nanoparticle self-assembled electrode was investigated by scanning electron microscopy (SEM). Electrocatalytic oxidation of methanol on the surface of modified electrode was studied by cyclic voltammetry and chronoamperometry methods. The hydrodynamic amperometry at a rotating modified electrode at constant potential versus reference electrode was used for detection of methanol. Under optimized conditions the calibration plots are linear in the concentration range 0-50 mM with a detection limit of 15 {mu}M. The formed matrix in our work possessed a 3D porous network structure with a large effective surface area, high catalytic activity and behaved like microelectrode ensembles. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for analytical purposes. - Highlights: Black-Right-Pointing-Pointer The Au electrode modified with thin Ni(II)/CHE-AuNP film shows stable and reproducible behavior. Black-Right-Pointing-Pointer Long stability and excellent electrochemical reversibility were observed. Black-Right-Pointing-Pointer This modified electrode shows excellent catalytic activity for methanol oxidation. Black-Right-Pointing-Pointer Combination of unique properties of AuNP and Ni(II)/CHE resulted in improvement of current responses.
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Directory of Open Access Journals (Sweden)
Santos Antonio S.
2002-01-01
Full Text Available The electrochemical behavior of toluidine blue (TB adsorbed on a silica surface modified with niobium oxide (SN was investigated using a modified carbon paste electrode. The presence of SN gave the electrode high stability, avoiding the leaching out of the mediator from the electrode surface. The formal potential (E0' of the adsorbed TB was --113 mV vs. SCE, indicating a shift of almost 100 mV towards more positive potential values, compared to TB dissolved in aqueous solution or adsorbed on carbon paste. The stability and formal potential remained constant upon changing the solution pH in the range 5 to 8. In these solution pH values the electrocatalytic activity remained almost constant with a sensitivity of 1.2 10-4 A L mol-1 cm-2 and a K Mapp of 4.9 10-5 mol L-1. A linear response range for NADH concentration between 2.0 10-4 and 4.0 10-3 mol L-1 at pH 7.0, with a detection limit of 3.4 10-5 mol L-1 was observed for the sensor. A response time of 2 s and a precision of 1.0 %, expressed as relative standard deviation for 10 replicates, were observed for the sensor developed.
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Yu, Xue; Kuai, Long; Geng, Baoyou
2012-09-21
Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.
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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)
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Directory of Open Access Journals (Sweden)
Daoming Zhang
2017-06-01
Full Text Available Electrochemically synthesized nanosphere, nanorod and nanotube Fe2(MoO43 at optimized temperature and current density are characterized with XRD, SEM, TEM, XPS. Crystal lattices of the three types Fe2(MoO43 detected by HRTEM are well matched with the simulation analysis results from Materials Studio 6.0 based on the inorganic crystal structure database (ICSD data and the modified XRD lattice parameters. The ratios of Fe/Mo on the surface resulted from XPS analysis are 1.47, 1.63 and 2.22 respectively for nanosphere, nanorod and nanotube. The mixture of Fe2(MoO43 with polytetrafluoroethylene dispersion are coated on glass carbon substrate as electrode for electrocatalytic performance test by cyclic voltammetries in 0.1 mol/L KOH and 1 mol/L methanol electrolyte. Methanol oxidation peak current density of the Nanotube- Fe2(MoO43/GCEs electrode is 3.27 mA/cm2 higher than 2.8 mA/cm2 of platinum foil electrode, which shows enhanced catalytic activity of Nanotube-Fe2(MoO43/GCEs. The cyclic stability in terms of peak current retention are 91%, 92% and 88% respectively for Nanosphere-Fe2(MoO43/GCE, Nanorod-Fe2(MoO43/GCE and Nanotube-Fe2(MoO43/GCE electrode after 220 cycles. It is concluded that nanosized Fe2(MoO43 could be promising alternative non-noble electro-catalysts for electro-oxidation of methanol in alkaline medium.
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Roles of texture in controlling oxidation, hydrogen ingress and hydride formation in Zr alloys
International Nuclear Information System (INIS)
Szpunar, Jerzy A.; Qin, Wen; Li, Hualong; Kumar, Kiran
2011-01-01
Experimental observations shows that the oxide formed on Zr alloys are strongly textured. The texture and grain-boundary characteristics of oxide are dependent on the texture of metal substrate. Computer simulation and thermodynamic modeling clarify the effect of metal substrate on structure of oxide film, and intrinsic factors affecting the microstructure. Models of diffusion process of hydrogen atoms and oxygen diffusion through oxide are presented. Both intra-granular and inter-granular hydrides were found following (0001) α-Zr //(111) δ-ZrH1.5 relationship. The through-thickness texture inhomogeneity in cladding tubes, the effects of hoop stress on the hydride orientation and the formation of interlinked hydride structure were studied. A thermodynamic model was developed to analyze the nucleation and the stress-induced reorientation of intergranular hydrides. These works provide a framework for understanding the oxidation, the hydrogen ingress and the hydride formation in Zr alloys. (author)
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Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.
2016-10-01
The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV-vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.
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International Nuclear Information System (INIS)
Zhang, Ming; Lv, Jing-Jing; Li, Fang-Fang; Bao, Ning; Wang, Ai-Jun; Feng, Jiu-Ju; Zhou, Dan-Ling
2014-01-01
Graphical abstract: A simple, facile, and controllable method was developed for preparation of well-defined flower-like Pt arrays via one-step electrodeposition, assisted with urea as a growth directing agent. The as-prepared Pt nanocrystals have a larger electroactive surface area and higher electrocatalytic activity toward ethylene glycol and methanol oxidation in acid media, compared with Pt nanoparticles and commercial Pt black catalysts. - Highlights: • Well-defined flower-like Pt arrays were prepared via one-step electrodeposition, assisted with urea as a growth directing agent. • This method is simple, facile, and controllable, without using any template, seed or surfactant. • The Pt arrays show an enhanced electrocatalytic activity toward ethylene glycol and methanol oxidation. - Abstract: In this paper, well-defined flower-like Pt arrays were prepared on the glassy carbon electrode by one-step electrodeposition at–0.3 V for 600 s in 0.5 M H 2 SO 4 containing 5 mM H 2 PtCl 6 and 150 mM urea. This method is simple, facile, and controllable, without using any template, seed or surfactant. The experimental parameters were investigated and found urea acted as a growth directing agent. The as-prepared Pt nanocrystals were preferentially growing along the (111) directions, which were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive X-ray (EDX). Moreover, the flower-like Pt nanoarrays exhibited a large effective surface area (EASA) and enhanced performance toward the oxidation of ethylene glycol and methanol in acid media, compared with Pt nanoparticles and commercial Pt black catalysts. This strategy can be extended to prepare other noble metal nanostructures as good electrocatalysts in fuel cells
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International Nuclear Information System (INIS)
Santos, Elizabeth; Schmickler, Wolfgang
2008-01-01
A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others
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Feasibility of solid oxide fuel cell dynamic hydrogen coproduction to meet building demand
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.
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Li, Yuanchao; Nguyen, Trung Van
2018-04-01
Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.
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Evaluation of catalytic properties of tungsten carbide for the anode of microbial fuel cells
Energy Technology Data Exchange (ETDEWEB)
Rosenbaum, Miriam; Zhao, Feng; Quaas, Marion; Wulff, Harm; Schroeder, Uwe; Scholz, Fritz [Universitaet Greifswald, Institut fuer Biochemie, Felix-Hausdorff-Strasse 4, 17487 Greifswald (Germany)
2007-07-31
In this communication we discuss the properties of tungsten carbide, WC, as anodic electrocatalyst for microbial fuel cell application. The electrocatalytic activity of tungsten carbide is evaluated in the light of its preparation procedure, its structural properties as well as the pH and the composition of the anolyte solution and the catalyst load. The activity of the noble-metal-free electrocatalyst towards the oxidation of several common microbial fermentation products (hydrogen, formate, lactate, ethanol) is studied for microbial fuel cell conditions (e.g., pH 5, room temperature and ambient pressure). Current densities of up to 8.8 mA cm{sup -2} are achieved for hydrogen (hydrogen saturated electrolyte solution), and up to 2 mA cm{sup -2} for formate and lactate, respectively. No activity was observed for ethanol electrooxidation. The electrocatalytic activity and chemical stability of tungsten carbide is excellent in acidic to pH neutral potassium chloride electrolyte solutions, whereas higher phosphate concentrations at neutral pH support an oxidative degradation. (author)
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Adsorption/oxidation of hydrogen sulfide on nitrogen-containing activated carbons
Energy Technology Data Exchange (ETDEWEB)
Adib, F.; Bagreev, A.; Bandosz, T.J.
2000-02-22
Wood-based activated carbon was modified by impregnation with urea and heat treatment at 450 and 950 C. The chemical and physical properties of materials were determined using acid/base titration, FTIR, thermal analysis, IGC, and sorption of nitrogen. The surface features were compared to those of a commercial urea-modified carbon. Then, the H{sub 2}S breakthrough capacity tests were carried out, and the sorption capacity was evaluated. The results showed that urea-modified sorbents have a capacity similar to that of the received material; however, the conversion of hydrogen sulfide to a water-soluble species is significantly higher. It happens due to a high dispersion of basic nitrogen compounds in the small pores of carbons, where oxidation of hydrogen sulfide ions to sulfur radicals followed by the creation of sulfur oxides and sulfuric acid occurs. It is proposed that the process proceeds gradually, from small pores to larger, and that the degree of microporosity is an important factor.
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Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts
International Nuclear Information System (INIS)
Britton, M.D.
1995-01-01
This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g
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Bai, Juan; Xing, Shi-Hui; Zhu, Ying-Ying; Jiang, Jia-Xing; Zeng, Jing-Hui; Chen, Yu
2018-05-01
Rationally tailoring the surface/interface structures of noble metal nanostructures emerges as a highly efficient method for improving their electrocatalytic activity, selectivity, and long-term stability. Recently, hydrogen evolution reaction is attracting more and more attention due to the energy crisis and environment pollution. Herein, we successfully synthesize polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids via a facile one-pot hydrothermal method. Three-dimensionally branched rhodium nanosheet nanoassemblies are consisted of two dimensionally atomically thick ultrathin rhodium nanosheets. The as-prepared polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids show the excellent electrocatalytic activity for the hydrogen evolution reaction in acidic media, with a low onset reduction potential of -1 mV, a small overpotential of 5 mV at 10 mA cm-2, which is much superior to commercial platinum nanocrystals. Two dimensionally ultrathin morphology of rhodium nanosheet, particular rhodium-polyallylamine interface, and three-dimensionally networks induced by carbon nanotube are the key factors for the excellent hydrogen evolution reaction activity in acidic media.
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Hydrogen generator, via catalytic partial oxidation of methane for fuel cells
Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano
It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.
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Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin
2015-12-01
Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.
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International Nuclear Information System (INIS)
Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin
2015-01-01
Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611}high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H_2PtCl_6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells. (paper)
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Electrocatalytic reduction of carbon dioxide on electrodeposited tin-based surfaces
Alba, Bianca Christina S.; Camayang, John Carl A.; Mopon, Marlon L.; del Rosario, Julie Anne D.
2017-08-01
The electrocatalytic reduction of carbon dioxide to small organic molecular compounds provides a means of generating alternative fuel source while suppressing climate change. Suitable catalysts, however, are necessary to optimize its reaction kinetics towards more valuable products. Consequently, in this study, electrodeposited Sn electrodes have been developed as catalysts for CO2 electroreduction. Deposition potential was varied to produce different Sn catalysts. SEM showed varying morphologies and increasing amount as the applied potential becomes more negative. Cyclic voltammetry and chronoamperometry showed that the activity and stability of the catalysts towards CO2 reduction depend on the morphology and presence of tin oxides. These results provide a better understanding on the performance of electrodeposited Sn-based surfaces as catalysts for CO2 reduction.
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Levine, Audrey D; Raymer, Blake J; Jahn, Johna
2004-01-01
Hydrogen sulfide in groundwater can be oxidized by aerobic bacteria to form elemental sulfur and biomass. While this treatment approach is effective for conversion of hydrogen sulfide, it is important to have adequate control of the biomass exiting the biological treatment system to prevent release of elemental sulfur into the distribution system. Pilot scale tests were conducted on a Florida groundwater to evaluate the use of two-stage upflow filtration downstream of biological sulfur oxidation. The combined biological and filtration process was capable of excellent removal of hydrogen sulfide and associated turbidity. Additional benefits of this treatment approach include elimination of odor generation, reduction of chlorine demand, and improved stability of the finished water.
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Deactivation of iron oxide used in the steam-iron process to produce hydrogen
Bleeker, M.F.; Veringa, H.J.; Kersten, Sascha R.A.
2009-01-01
In the steam-iron process pure hydrogen can be produced from any hydrocarbon feedstock by using a redox cycle of iron oxide. One of the main problems connected to the use of the iron oxide is the inherent structural changes that take place during oxygen loading and unloading leading to severe
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International Nuclear Information System (INIS)
Muthuraman, Govindan; Chung, Sang Joon; Moon, Il Shik
2011-01-01
Highlights: → Simultaneous removal of H 2 S and CH 3 SH was achieved at electro-reactor. → Active catalyst Ag(II) perpetually regenerated in HNO 3 medium by electrochemical cell. → CH 3 SH destruction follows two reaction pathways. → H 2 S induced destruction of CH 3 SH has identified. → Low concentration of active Ag(II) (12.5 x 10 -4 mol L -1 ) is enough for complete destruction. - Abstract: In this study, an electrocatalytic wet scrubbing process was developed for the simultaneous removal of synthetic odorous gases namely, methyl mercaptan (CH 3 SH) and hydrogen sulfide (H 2 S). The initial process consists of the absorption of CH 3 SH and H 2 S gases by an absorbing solution, followed by their mediated electrochemical oxidation using a low concentration of active Ag(II) in 6 M HNO 3 . Experiments were conducted under different reaction conditions, such as CH 3 SH and H 2 S loadings, active Ag(II) concentrations and molar flow rates. The cyclic voltammetry for the oxidation of CH 3 SH corroborated the electro-reactor results, in that the silver in the 6 M HNO 3 reaction solution significantly influences the oxidation of CH 3 SH. At a low active Ag(II) concentration of 0.0012 M, the CH 3 SH removal experiments demonstrated that the CH 3 SH degradation was steady, with 100% removal at a CH 3 SH loading of 5 g m -3 h -1 . The electro-reactor and cyclic voltammetry results indicated that the removal of H 2 S (100%) follows a mediated electrocatalytic oxidation reaction. The simultaneous removal of 100% of the CH 3 SH and H 2 S was achieved, even with a very low active Ag(II) concentration (0.0012 M), as a result of the high efficiency of the Ag(II). The parallel cyclic voltammetry results demonstrated that a process of simultaneous destruction of both CH 3 SH and H 2 S follows an H 2 S influenced mediated electrocatalytic oxidation. The use of a very low concentration of the Ag(II) mediator during the electro-reactor process is promising for the complete
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Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes
Energy Technology Data Exchange (ETDEWEB)
Smith, Kjell-Tore
1996-08-01
Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.
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Molecular beam studies of oxide reduction by atomic hydrogen
International Nuclear Information System (INIS)
Olander, D.R.
1978-01-01
The graphite and oxide internals of a CTR are susceptible to chemical corrosion as well as to physical degradation by high-energy particles. Reactions of thermal atomic hydrogen with oxides are being studied. The hydrogen used is at thermal energy (0.22 eV). Typical data are reported for the H/UO 2 system. The reaction probability is plotted as a function of solid temperature at fixed beam intensity and moculation frequency. The reaction probability increases from low temperature to a high-temperature plateau at about 1300 0 C. Here the reaction rate is limited solely by the sticking probability of H on the surface; about one in seven of the incident atoms is chemisorbed by the surface and ultimately returns to the gas phase as water vapor. A reaction model comprising sticking, recombination to H 2 , solution and diffusion of H in the bulk of the UO 2 , surface reaction of adsorbed H with lattice oxygen atoms to produce the hydroxyl radical, and production of water is constructed. The rate constants for the elementary steps in the mechanism are tabulated. 2 figures, 2 tables
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Optical and electro-catalytic properties of bundled ZnO nanowires grown on a ITO substrate
International Nuclear Information System (INIS)
Xia Cao; Wang Ning; Wang Long
2010-01-01
Bundled wurtzite zinc oxide (ZnO) nanowires were fabricated in a facile manner on an ITO-conducting substrate via a microemulsion route without using any hard template or external electric/magnetic field. Structure and properties of the as-prepared ZnO electrode were investigated using scanning electron microscopy, X-ray diffraction, photoluminescence, Raman spectroscopy, as well as electrochemical tests. The ZnO electrode shows excellent optical and electrocatalytic ability, which may find further applications such as optoelectronics or as sensors as well as other modern industrial areas.
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Enhancing Charge Carrier Lifetime in Metal Oxide Photoelectrodes through Mild Hydrogen Treatment
Jang, Ji-Wook
2017-08-25
Widespread application of solar water splitting for energy conversion is largely dependent on the progress in developing not only efficient but also cheap and scalable photoelectrodes. Metal oxides, which can be deposited with scalable techniques and are relatively cheap, are particularly interesting, but high efficiency is still hindered by the poor carrier transport properties (i.e., carrier mobility and lifetime). Here, a mild hydrogen treatment is introduced to bismuth vanadate (BiVO4), which is one of the most promising metal oxide photoelectrodes, as a method to overcome the carrier transport limitations. Time-resolved microwave and terahertz conductivity measurements reveal more than twofold enhancement of the carrier lifetime for the hydrogen-treated BiVO4, without significantly affecting the carrier mobility. This is in contrast to the case of tungsten-doped BiVO4, although hydrogen is also a donor type dopant in BiVO4. The enhancement in carrier lifetime is found to be caused by significant reduction of trap-assisted recombination, either via passivation or reduction of deep trap states related to vanadium antisite on bismuth or vanadium interstitials according to density functional theory calculations. Overall, these findings provide further insights on the interplay between defect modulation and carrier transport in metal oxides, which benefit the development of low-cost, highly-efficient solar energy conversion devices.
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Energy Technology Data Exchange (ETDEWEB)
Lee, Hyunjoo; Habas, Susan; Somorjai, Gabor; Yang, Peidong
2007-12-14
Single crystalline surface such as (100), (111), (110) has been studied as an idealized platform for electrocatalytic reactions since the atomic arrangement affects a catalytic property. The secondary metal deposition on these surfaces also alters the catalytic property often showing improvement such as poisoning decrease. On the other hand, electrocatalysts used for practical purpose usually have a size on the order of nanometers. Therefore, linking the knowledge from single crystalline studies to nanoparticle catalysts is of enormous importance. Recently, the Pt nanoparticles which surface structure was preferentially oriented was synthesized and used as electrocatalysts. Here, we demonstrate a rational design of a binary metallic nanocatalyst based on the single crystalline study.
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Hydrogen production through high-temperature electrolysis in a solid oxide cell
International Nuclear Information System (INIS)
Herring, J.St.; Lessing, P.; O'Brien, J.E.; Stoots, C.; Hartvigsen, J.; Elangovan, S.
2004-01-01
An experimental research programme is being conducted by the INEEL and Ceramatec, Inc., to test the high-temperature, electrolytic production of hydrogen from steam using a solid oxide cell. The research team is designing and testing solid oxide cells for operation in the electrolysis mode, producing hydrogen rising a high-temperature heat and electrical energy. The high-temperature heat and the electrical power would be supplied simultaneously by a high-temperature nuclear reactor. Operation at high temperature reduces the electrical energy requirement for electrolysis and also increases the thermal efficiency of the power-generating cycle. The high-temperature electrolysis process will utilize heat from a specialized secondary loop carrying a steam/hydrogen mixture. It is expected that, through the combination of a high-temperature reactor and high-temperature electrolysis, the process will achieve an overall thermal conversion efficiency of 40 to 50%o while avoiding the challenging chemistry and corrosion issues associated with the thermochemical processes. Planar solid oxide cell technology is being utilised because it has the best potential for high efficiency due to minimized voltage and current losses. These losses also decrease with increasing temperature. Initial testing has determined the performance of single 'button' cells. Subsequent testing will investigate the performance of multiple-cell stacks operating in the electrolysis mode. Testing is being performed both at Ceramatec and at INEEL. The first cells to be tested were single cells based on existing materials and fabrication technology developed at Ceramatec for production of solid oxide fuel cells. These cells use a relatively thick (∼ 175 μm) electrolyte of yttria- or scandia-stabilised zirconia, with nickel-zirconia cermet anodes and strontium-doped lanthanum manganite cathodes. Additional custom cells with lanthanum gallate electrolyte have been developed and tested. Results to date have
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Atomic layer deposition of high-mobility hydrogen-doped zinc oxide
Macco, B.; Knoops, H.C.M.; Verheijen, M.A.; Beyer, W.; Creatore, M.; Kessels, W.M.M.
2017-01-01
In this work, atomic layer deposition (ALD) has been employed to prepare high-mobility H-doped zinc oxide (ZnO:H) films. Hydrogen doping was achieved by interleaving the ZnO ALD cycles with H2 plasma treatments. It has been shown that doping with H2 plasma offers key advantages over traditional
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Stabilization of hydrogen peroxide using tartaric acids in Fenton and fenton-like oxidation
Energy Technology Data Exchange (ETDEWEB)
Oh, Hyung Suk; Kim, Jeong-Jin; Kim, Young-Hun [Andong National University, Andong (Korea, Republic of)
2016-03-15
The stabilization of hydrogen peroxide is a key factor in the efficiency of a Fenton reaction. The stability of hydrogen peroxide was evaluated in a Fenton reaction and Fenton-like reactions in the presence of tartaric acid as a stabilizer. The interactions between ferrous or ferric iron and tartaric acid were observed through spectroscopic monitoring at variable pH around pKa{sub 1} and pKa{sub 2} of the stabilizer. Ferric iron had a strong interaction with the stabilizer, and the strong interaction was dominant above pKa{sub 2}. At a low pH, below pKa{sub 1}, the stabilizing effect was at its maximum and the prolonged life-time of hydrogen peroxide gave a higher efficiency to the oxidative degradation of nitrobenzene. In Fenton-like reactions with hematite, the acidic conditions caused dissolution of iron from an iron oxide, and an increase in iron species was the result. Tartaric acid showed a stabilizing effect on hydrogen peroxide in the Fentonlike system. The stabilization by tartaric acid might be due to an inhibition of catalytic activity of dissolved iron, and the stabilization strongly depends on the ionization state of the stabilizer.
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Stabilization of hydrogen peroxide using tartaric acids in Fenton and fenton-like oxidation
International Nuclear Information System (INIS)
Oh, Hyung Suk; Kim, Jeong-Jin; Kim, Young-Hun
2016-01-01
The stabilization of hydrogen peroxide is a key factor in the efficiency of a Fenton reaction. The stability of hydrogen peroxide was evaluated in a Fenton reaction and Fenton-like reactions in the presence of tartaric acid as a stabilizer. The interactions between ferrous or ferric iron and tartaric acid were observed through spectroscopic monitoring at variable pH around pKa 1 and pKa 2 of the stabilizer. Ferric iron had a strong interaction with the stabilizer, and the strong interaction was dominant above pKa 2 . At a low pH, below pKa 1 , the stabilizing effect was at its maximum and the prolonged life-time of hydrogen peroxide gave a higher efficiency to the oxidative degradation of nitrobenzene. In Fenton-like reactions with hematite, the acidic conditions caused dissolution of iron from an iron oxide, and an increase in iron species was the result. Tartaric acid showed a stabilizing effect on hydrogen peroxide in the Fentonlike system. The stabilization by tartaric acid might be due to an inhibition of catalytic activity of dissolved iron, and the stabilization strongly depends on the ionization state of the stabilizer.
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Yttrium bismuth titanate pyrochlore mixed oxides for photocatalytic hydrogen production
Energy Technology Data Exchange (ETDEWEB)
Merka, Oliver
2012-10-18
In this work, the sol-gel synthesis of new non-stoichiometric pyrochlore titanates and their application in photocatalytic hydrogen production is reported. Visible light response is achieved by introducing bismuth on the A site or by doping the B site by transition metal cations featuring partially filled d orbitals. This work clearly focusses on atomic scale structural changes induced by the systematical introduction of non-stoichiometry in pyrochlore mixed oxides and the resulting influence on the activity in photocatalytic hydrogen production. The materials were characterized in detail regarding their optical properties and their atomic structure. The pyrochlore structure tolerates tremendous stoichiometry variations. The non-stoichiometry in A{sub 2}O{sub 3} rich compositions is compensated by distortions in the cationic sub-lattice for the smaller Y{sup 3+} cation and by evolution of a secondary phase for the larger Bi{sup 3+} cation on the A site. For TiO{sub 2} rich compositions, the non-stoichiometry leads to a special vacancy formation in the A and optionally O' sites. It is shown that pyrochlore mixed oxides in the yttrium bismuth titanate system represent very active and promising materials for photocatalytic hydrogen production, if precisely and carefully tuned. Whereas Y{sub 2}Ti{sub 2}O{sub 7} yields stable hydrogen production rates over time, the bismuth richer compounds of YBiTi{sub 2}O{sub 7} and Bi{sub 2}Ti{sub 2}O{sub 7} are found to be not stable under irradiation. This drawback is overcome by applying a special co-catalyst system consisting of a precious metal core and a Cr{sub 2}O{sub 3} shell on the photocatalysts.
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Review of theoretical conceptions on regimes of oxidation and hydrogen pickup in Zr-alloys
International Nuclear Information System (INIS)
Likhanskii, V.; Evdokimov, I.
2008-01-01
In this paper the following issues are presented: 1) Experimental observations published in the journals on corrosion regimes of zirconium alloys of various compositions both for ex-pile oxidation experiments and for in-pile operating conditions of the materials. Factors experimentally stated on the effect of alloying composition, microstructure and texture on the rate of uniform corrosion and susceptibility of alloys to nodular corrosion. 2) Phenomenological models existing in publications, which describe conditions of uniform and nodular corrosion for Zr-alloys of various composition and microstructures, effect of irradiation and oxidizing medium; 3) Experimental data and phenomenological models describing regimes of hydrogen absorption in zirconium alloys; 4) Examples of application of physical models in explaining regimes, peculiarities of oxidation and hydrogen pickup for zirconium claddings of various alloying composition and microstructure
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Directory of Open Access Journals (Sweden)
VLADIMIR V. PANIĆ
2010-10-01
Full Text Available The electrochemical characteristics of Ti0.6Ir0.4O2/Ti and Ti0.6Ru0.4O2/Ti anodes prepared by the sol–gel procedure from the corresponding oxide sols, obtained by force hydrolysis of the corresponding metal chlorides, were compared. The voltammetric properties in H2SO4 solution indicate that Ti0.6Ir0.4O2/Ti has more pronounced pseudocapacitive characteristics, caused by proton-assisted, solid state surface redox transitions of the oxide. At potentials negative to 0.0 VSCE, this electrode is of poor conductivity and activity, while the voltammetric behavior of the Ti0.6Ru0.4O2/Ti electrode is governed by proton injection/ejection into the oxide structure. The Ti0.6Ir0.4O2/Ti electrode had a higher electrocatalytical activity for oxygen evolution, while the investigated anodes were of similar activity for chlorine evolution. The potential dependence of the impedance characteristics showed that the Ti0.6Ru0.4O2/Ti electrode behaved like a capacitor over a wider potential range than the Ti0.6Ir0.4O2/Ti electrode, with fully-developed pseudocapacitive properties at potentials positive to 0.60 VSCE. However, the impedance characteristics of the Ti0.6Ir0.4O2/Ti electrode changed with increasing potential from resistor-like to capacitor-like behavior.
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UO{sub 2} surface oxidation by mixtures of water vapor and hydrogen as a function of temperature
Energy Technology Data Exchange (ETDEWEB)
Espriu-Gascon, A., E-mail: alexandra.espriu@upc.edu [Department of Chemical Engineering, Universitat Politècnica Catalunya-Barcelona Tech, Diagonal 647, E-08028 Barcelona (Spain); Llorca, J.; Domínguez, M. [Institut de Tècniques Energètiques (INTE), Universitat Politècnica Catalunya-Barcelona Tech, Diagonal 647, E-08028 Barcelona (Spain); Centre for Research in NanoEngineering (CRNE), Universitat Politècnica Catalunya-Barcelona Tech, Diagonal 647, E-08028 Barcelona (Spain); Giménez, J.; Casas, I. [Department of Chemical Engineering, Universitat Politècnica Catalunya-Barcelona Tech, Diagonal 647, E-08028 Barcelona (Spain); Pablo, J. de [Department of Chemical Engineering, Universitat Politècnica Catalunya-Barcelona Tech, Diagonal 647, E-08028 Barcelona (Spain); Fundació CTM Centre Tecnològic, Plaça de la Ciència 2, E-08243 Manresa (Spain)
2015-12-15
In the present work, X-Ray Photoelectron Spectroscopy (XPS) was used to study the effect of water vapor on the UO{sub 2} surface as a function of temperature. The experiments were performed in situ inside a high pressure chamber attached to the XPS instrument. UO{sub 2} samples were put in contact with either hydrogen or argon streams, saturated with water at room temperature, and the sample surface evolution was analyzed by XPS. In the case of the water vapor/argon experiments, one experiment at 350 °C was performed and, in the case of the water vapor/hydrogen experiments, the temperatures used inside the reactor were 60, 120, 200 and 350 °C. On one hand, in presence of argon, the results obtained showed that the water vapor in the argon stream oxidized 93% of the U(IV) in the sample surface. On the other hand, the degree of UO{sub 2} surface oxidation showed a different dependence on the temperature in the experiments performed in the presence of hydrogen: the maximum surface oxidation occurred at 120 °C, where 65.4% of U(IV) in the sample surface was oxidized, while at higher temperatures, the surface oxidation decreased. This observation is attributed to the increase of hydrogen reducing effect when temperature increases which prevents part of the oxidation of the UO{sub 2} surface by the water vapor. - Highlights: • UO{sub 2} surface has been oxidized by water vapor in an argon stream at 350 °C. • H{sub 2} reduced more uranium oxidation produced by water at 350 °C when compared to Ar. • In H{sub 2} presence, the uranium oxidation produced by water depends on the temperature.
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Charpy impact test of oxidized and hydrogenated zircaloy using a thin strip specimen
International Nuclear Information System (INIS)
Otsuka, Teppei; Hashizume, Kenichi; Sugisaki, Masayasu
2004-01-01
The impact properties of an oxidized and a hydrogenated Zircaloy have been studied with an instrumented Charpy machine by using a strip Charpy V-notch specimen (1 mm thick by 4mm wide). Fracture processes such as crack initiation and propagation were examined using load-displacement curves obtained in this study. In the case of the hydrogenated specimen containing preferentially oriented hydrides, an appreciable decrease in the absorbed energy was observed in the crack propagation rather than in the crack initiation. From results of fractographs of the specimen, it was suggested that the reduction of the crack propagation energy of hydrogenated specimen could be attributed to the change of the stress state in the Zircaloy matrix, which was caused by the fracture of hydride in the inner part of specimen. In the case of the specimen oxidized at 973k for 60 min, on which an oxide layer (4 μm in thickness) and oxygen incursion layer (4μm) were formed, the surface layers affected the crack initiation process. The growing oxygen incursion layer, in particular, resulted in the constraint of plastic deformation of the Zircaloy matrix not only in the crack initiation but also in the crack propagation as its thickness increased. (author)
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Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin
2015-11-16
Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Directory of Open Access Journals (Sweden)
Halimeh Rajabzade
2012-01-01
Full Text Available A highly sensitive electrode was prepared based on gold nanoparticles/nanotubes/ionic liquid for measurement of Hydrogen peroxide. Gold nanoparticles of 20–25 nm were synthesized on a nanotube carbon paste electrode by cyclic voltammetry technique while the coverage was controlled by applied potential and time. The gold nanoparticles were modified to form a monolayer on CNT, followed by decoration with ionic liquid for determination of hydrogen peroxide. The experimental conditions, applied potential and pH, for hydrogen peroxide monitoring were optimized, and hydrogen peroxide was determined amperometrically at 0.3 V vs. SCE at pH 7.0. Electrocatalytic effects of gold deposited CNT were observed with respect to unmodified one. The sensitivity obtained was 5 times higher for modified one. The presence of Au particles in the matrix of CNTs provides an environment for the enhanced electrocatalytic activities. The sensor has a high sensitivity, quickly response to H2O2 and good stability. The synergistic influence of MWNT, Au particles and IL contributes to the excellent performance for the sensor. The sensor responds to H2O2 in the linear range from 0.02 µM to 0.3 mM. The detection limit was down to 0.4 µM when the signal to noise ratio is 3.
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Enhanced Hydrogen Evolution Reactions on Nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS) Electrocatalyst
Energy Technology Data Exchange (ETDEWEB)
Digraskar, Renuka V.; Mulik, Balaji B. [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India); Walke, Pravin S. [National Centre for Nanosciences and Nanotechnology, University of Mumbai, Mumbai 400098, MH (India); Ghule, Anil V. [Department of Chemistry, Shivaji University, Kolhapur, 416004, MH (India); Sathe, Bhaskar R., E-mail: bhaskarsathe@gmail.com [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India)
2017-08-01
Graphical abstract: CZTS nano-electrocatalyst (2.6 ± 0.4 nm) for HER is synthesized by one step sonochemical method with uniform size distribution, which shows promisingly lower onset potential with higher current density and longer stability. - Highlights: • The nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS; ∼3 nm) based electrocatalytic systems were developed by facile sonochemical method. • The novel Cu{sub 2}ZnSnS{sub 4} based nanoclustered cathode improves the electrocatalytic performance toward hydrogen generation reaction (HER). • The electrocatalytic result exhibits lower Tafel slope, higher exchange current density, excellent current stability and lower charge transfer resistance. • The high activity due to synergetic effect of Cu, Zn, Sn and S from their internal cooperative supports. - Abstract: A novel and facile one-step sonochemical method is used to synthesize Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer−Emmett−Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density −130 mA/cm{sup 2}, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm{sup 2}, excellent
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Oxidation resistant organic hydrogen getters
Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA
2008-09-09
A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably Pt. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently removing hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.
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Fan, Jie-Ping; Zhang, Xiao-Min; Ying, Min
2010-01-01
The electrocatalytic activity of electropolymerized cobalt tetraaminophthalocyanine (poly-CoTAPc) film modified on the glassy carbon electrode (GCE) towards 6-mercaptopurine (6MP) and 2-Mercaptobenzimidazole (MBI) was studied. Comparing with the case at the unmodified GCE, the poly-CoTAPc film decreased the overpotential of oxidation of 6MP (1.0 x 10-3 mol L-1) and MBI (1.0 x 10-3 mol L-1) by 335 and 189 mV, respectively, and increased the peak current by about 3 and 2 times, respectively, wh...
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Czech Academy of Sciences Publication Activity Database
Eng, A.Y.S.; Poh, H. L.; Šaněk, F.; Maryško, Miroslav; Matějková, Stanislava; Šofer, Z.; Pumera, M.
2013-01-01
Roč. 7, č. 7 (2013), s. 5930-5939 ISSN 1936-0851 R&D Projects: GA ČR GA13-20507S Institutional support: RVO:68378271 ; RVO:61388963 Keywords : hydrogenated graphene * graphane * graphite oxide * ferromagnetism Subject RIV: BM - Solid Matter Physics ; Magnetism; CF - Physical ; Theoretical Chemistry (UOCHB-X) Impact factor: 12.033, year: 2013
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Solvent-dependent regioselective oxidation of trans-chalcones using aqueous hydrogen peroxide
Energy Technology Data Exchange (ETDEWEB)
Peng, Wang; Jiabin, Yang; Lushen, Li, E-mail: jimin@seu.edu.cn [Southeast University, Nanjing (China). School of Biological Science and Medical Engineering; Jin, Cai; Chunlong, Sun; Min, Ji [Southeast University, Nanjing (China). School of Chemistry and Chemical Engineering
2013-03-15
A novel method for regioselective oxidation of trans-chalcones with hydrogen peroxide in acetonitrile to afford cinnamic acids is reported. Only trans-b-arylacrylic acids were observed. A wide range of functionalized products can be effectively produced from various chalcones in good to excellent yields. (author)
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Life Time Performance Characterization of Solid Oxide Electrolysis Cells for Hydrogen Production
DEFF Research Database (Denmark)
Sun, Xiufu; Chen, Ming; Liu, Yi-Lin
2015-01-01
Solid oxide electrolysis cells (SOECs) offer a promising technological solution for efficient energy conversion and production of hydrogen or syngas. The commercialization of the SOEC technology can be promoted if SOECs can be operated at high current density with stable performance over ~5 years...... - 3 years (continuous operation, setting 1.5 V as the upper voltage defining “end of life”). The results provide technological input to future design of electrolysis plants for hydrogen production. © 2015 ECS - The Electrochemical Society...
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International Nuclear Information System (INIS)
Mahmudov, H.M.; Ismayilova, M.K.; Jafarova, N.A.; Azizova, K.V.
2017-01-01
The paper deals with hydrogen production using photocatalysis. In particular, we focus on the role of synergism on the reaction rate. For hydrogen production presented photocatalyst is composed of nanoAl_2O_3 and dispers TiO_2. Yet, the presence of the two mixed metal oxides together results in considerable enhancement of the reaction rate. The main reason for this is the increase of the charge carriers lifetime allowing for electron transfer to hydrogen ions and hole transfer to oxygen ions. It was investigated the mechanism of water splitting in presence of mixed nanocatalysed. It has been shown that the effect occurs during irradiation as a result of photooxidation of water with mixed metal oxides catalyst.
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Kos, Pavlo; Plenio, Herbert
2015-11-02
A Crabtree-type Ir(I) complex tagged with a fluorescent dye (bodipy) was synthesized. The oxidative addition of H2 converts the weakly fluorescent Ir(I) complex (Φ=0.038) into a highly fluorescent Ir(III) species (Φ=0.51). This fluorogenic reaction can be utilized for the detection of H2 and to probe the oxidative addition step in the catalytic hydrogenation of olefins. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Oxidation of methane and hydrogen on Ce1-xGdxO2-δ flourrites
DEFF Research Database (Denmark)
Kammer Hansen, K.; Mogensen, Mogens Bjerg
2005-01-01
The oxidation of methane and hydrogen was studied on cone shaped electrodes with the composition Ce1-xGdxO2-delta (x equals 0, 0.1, 0.2, 0.4). It was shown that the area specific resistance values measured at open-circuit voltage (OCV) for the oxidation of both methane and hydrogen is lowest...... for the composition Ce0.9Gd0.1O1.95. The OCV in wet methane was shown to depend on the material composition. It was shown that stable operation in wet methane could be achieved as long as the temperature was kept below 750degreesC. (C) 2004 The Electrochemical Society....
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Entringer, Anthony G.
The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting
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PALLADIUM DOPED TIN OXIDE BASED HYDROGEN GAS SENSORS FOR SAFETY APPLICATIONS
International Nuclear Information System (INIS)
Kasthurirengan, S.; Behera, Upendra; Nadig, D. S.
2010-01-01
Hydrogen is considered to be a hazardous gas since it forms a flammable mixture between 4 to 75% by volume in air. Hence, the safety aspects of handling hydrogen are quite important. For this, ideally, highly selective, fast response, small size, hydrogen sensors are needed. Although sensors based on different technologies may be used, thin-film sensors based on palladium (Pd) are preferred due to their compactness and fast response. They detect hydrogen by monitoring the changes to the electrical, mechanical or optical properties of the films. We report the development of Pd-doped tin-oxide based gas sensors prepared on thin ceramic substrates with screen printed platinum (Pt) contacts and integrated nicrome wire heaters. The sensors are tested for their performances using hydrogen-nitrogen gas mixtures to a maximum of 4%H 2 in N 2 . The sensors detect hydrogen and their response times are less than a few seconds. Also, the sensor performance is not altered by the presence of helium in the test gas mixtures. By the above desired performance characteristics, field trials of these sensors have been undertaken. The paper presents the details of the sensor fabrication, electronic circuits, experimental setup for evaluation and the test results.
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Zhang, Qian; Li, Pengsong; Zhou, Daojin; Chang, Zheng; Kuang, Yun; Sun, Xiaoming
2017-11-01
Hydrogen evolution reaction (HER) has prospect to becoming clean and renewable technology for hydrogen production and Ni-Mo alloy is among the best HER catalysts in alkaline electrolytes. Here, an in situ topotactic reduction method to synthesize ultrathin 2D Ni-Mo alloy nanosheets for electrocatalytic hydrogen evolution is reported. Due to its ultrathin structure and tailored composition, the as-synthesized Ni-Mo alloy shows an overpotential of 35 mV to reach a current density of 10 mA cm -2 , along with a Tafel slope of 45 mV decade -1 , demonstrating a comparable intrinsic activity to state-of-art commercial Pt/C catalyst. Besides, the vertically aligned assemble structure of the 2D NiMo nanosheets on conductive substrate makes the electrode "superaerophobic," thus leading to much faster bubble releasing during HER process and therefore shows faster mass transfer behavior at high current density as compared with drop drying Pt/C catalyst on the same substrate. Such in situ topotactic conversion finds a way to design and fabricate low-cost, earth-abundant non-noble metal based ultrathin 2D nanostructures for electrocatalytic issues. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Spray Pyrolyzed Polycrystalline Tin Oxide Thin Film as Hydrogen Sensor
Directory of Open Access Journals (Sweden)
Ganesh E. Patil
2010-09-01
Full Text Available Polycrystalline tin oxide (SnO2 thin film was prepared by using simple and inexpensive spray pyrolysis technique (SPT. The film was characterized for their phase and morphology by X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively. The crystallite size calculated from the XRD pattern is 84 nm. Conductance responses of the polycrystalline SnO2 were measured towards gases like hydrogen (H2, liquefied petroleum gas (LPG, ethanol vapors (C2H5OH, NH3, CO, CO2, Cl2 and O2. The gas sensing characteristics were obtained by measuring the sensor response as a function of various controlling factors like operating temperature, operating voltages (1 V, 5 V, 10 V 15 V, 20 V and 25 V and concentration of gases. The sensor response measurement showed that the SnO2 has maximum response to hydrogen. Furthermore; the SnO2 based sensor exhibited fast response and good recovery towards hydrogen at temperature 150 oC. The result of response towards H2 reveals that SnO2 thin film prepared by SPT would be a suitable material for the fabrication of the hydrogen sensor.
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Electrocatalytic cermet gas detector/sensor
Vogt, Michael C.; Shoemarker, Erika L.; Fraioli, deceased, Anthony V.
1995-01-01
An electrocatalytic device for sensing gases. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte.
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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).
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Hydrogen Production via Synthetic Gas by Biomass/Oil Partial Oxidation
Czech Academy of Sciences Publication Activity Database
Hanika, Jiří; Lederer, J.; Tukač, V.; Veselý, Václav; Kováč, D.
176-177, - (2011), s. 286-290 ISSN 1385-8947. [International Conference on Chemical Reactors CHEMREACTOR-19 /19./. Vienna, 05.09.2010-09.09.2010] R&D Projects: GA MPO 2A-2TP1/024 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrogen * biomass * partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.461, year: 2011
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Directory of Open Access Journals (Sweden)
Surin Saipanya
2014-01-01
Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.
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Pour, Ghobad Behzadi; Aval, Leila Fekri; Eslami, Shahnaz
2018-04-01
Hydrogen sensors are micro/nano-structure that are used to locate hydrogen leaks. They are considered to have fast response/recovery time and long lifetime as compared to conventional gas sensors. In this paper, fabrication of sensitive capacitive-type hydrogen gas sensor based on Ni thin film has been investigated. The C-V curves of the sensor in different hydrogen concentrations have been reported. Dry oxidation was done in thermal chemical vapor deposition furnace (TCVD). For oxidation time of 5 min, the oxide thickness was 15 nm and for oxidation time 10 min, it was 20 nm. The Ni thin film as a catalytic metal was deposited on the oxide film using electron gun deposition. Two MOS sensors were compared with different oxide film thickness and different hydrogen concentrations. The highest response of the two MOS sensors with 15 nm and 20 nm oxide film thickness in 4% hydrogen concentration was 87.5% and 65.4% respectively. The fast response times for MOS sensors with 15 nm and 20 nm oxide film thickness in 4% hydrogen concentration was 8 s and 21 s, respectively. By increasing the hydrogen concentration from 1% to 4%, the response time for MOS sensor (20nm oxide thickness), was decreased from 28s to 21s. The recovery time was inversely increased from 237s to 360s. The experimental results showed that the MOS sensor based on Ni thin film had a quick response and a high sensitivity.
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Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; Song, Junhua; Xia, Haibing; Du, Dan; Lin, Yuehe
2016-10-01
To accelerate hydrogel formation and further simplify the synthetic procedure, a series of MCu (M = Pd, Pt, and Au) bimetallic aerogels is synthesized from the in situ reduction of metal precursors through enhancement of the gelation kinetics at elevated temperature. Moreover, the resultant PdCu aerogel with ultrathin nanowire networks exhibits excellent electrocatalytic performance toward ethanol oxidation, holding promise in fuel-cell applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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International Nuclear Information System (INIS)
Feng Yujie; Lv Jiangwei; Liu Junfeng; Gao Na; Peng Hongyan; Chen Yuqiang
2011-01-01
A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH 4 /H 2 /B(OCH 3 ) 3 gas mixture. A maximum growth rate of 0.65 mg cm -2 h -1 was obtained with CH 4 /H 2 /B(OCH 3 ) 3 radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH 3 ) 3 that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 10 20 cm -3 with CH 4 /H 2 /B(OCH 3 ) 3 ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/190/10 possessed the best phenol removal efficiency.
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Nagaraju, Doddahalli H.
2014-12-01
Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.
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Energy Technology Data Exchange (ETDEWEB)
Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Nanotechnology Research Center, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Hashemi, S. Hossein; Benvidi, Ali [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)
2010-06-04
For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 {mu}M and 268.3-417.3 {mu}M of hydrazine and for 4.0-33.8 {mu}M and 33.8-78.3 {mu}M of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 {mu}M and 0.45 {mu}M for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.
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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
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International Nuclear Information System (INIS)
Guo, Xiaolei; Li, Dong; Wan, Jiafeng; Yu, Xiujuan
2015-01-01
Titanium dioxide/Nano-graphite (TiO_2/Nano-G) composite was synthesized by a sol-gel method and TiO_2/Nano-G electrode was prepared in hot-press approach. The composite was characterized by X-ray photoelectron spectroscopy (XPS), fourier transform infrared (FT-IR), scanning electrons microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrochemical performance of the TiO_2/Nano-G anode electrode was investigated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electro-catalytic performance was evaluated by the yield of ·OH radicals, degradation of methyl orange and ceftriaxone sodium. The results demonstrated that TiO_2 nanoparticles were dispersed on the surface and interlamination of the Nano-G uniformly, TiO_2/Nano-G electrode owned higher electro-catalytic oxidation activity and stability than Nano-G electrode. Degradation rate of ceftriaxone sodium within 120 min by TiO_2(40)/Nano-G electrode was 97.7%. And ·OH radicals given by TiO_2/Nano-G electrode was higher than that of Nano-G electrode and DSA (Ti/IrO_2-RuO_2) electrode. The excellent electro-catalytic performance could be ascribed to the admirable conductive property of the Nano-G and more production of ·OH offered by TiO_2(40)/Nano-G electrode.
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International Nuclear Information System (INIS)
Zheng, Meixia; Gao, Feng; Wang, Qingxiang; Cai, Xili; Jiang, Shulian; Huang, Lizhang; Gao, Fei
2013-01-01
The electrochemical behaviors of acetaminophen (ACOP) on a graphene–chitosan (GR–CS) nanocomposite modified glassy carbon electrode (GCE) were investigated by cyclic voltammetry (CV), chronocoulometry (CC) and differential pulse voltammetry (DPV). Electrochemical characterization showed that the GR–CS nanocomposite had excellent electrocatalytic activity and surface area effect. As compared with bare GCE, the redox signal of ACOP on GR–CS/GCE was greatly enhanced. The values of electron transfer rate constant (k s ), diffusion coefficient (D) and the surface adsorption amount (Γ ⁎ ) of ACOP on GR–CS/GCE were determined to be 0.25 s −1 , 3.61 × 10 −5 cm 2 s −1 and 1.09 × 10 −9 mol cm −2 , respectively. Additionally, a 2e − /2H + electrochemical reaction mechanism of ACOP was deduced based on the acidity experiment. Under the optimized conditions, the ACOP could be quantified in the range from 1.0 × 10 −6 to 1.0 × 10 −4 M with a low detection limit of 3.0 × 10 −7 M based on 3S/N. The interference and recovery experiments further showed that the proposed method is acceptable for the determination of ACOP in real pharmaceutical preparations. Highlights: ► A chitosan–graphene nanocomposite modified glassy carbon electrode was prepared. ► The modified electrode was electrochemically characterized by CV and EIS. ► Electro-oxidation of acetaminophen was examined on the modified electrode. ► Sensing analysis of the modified electrode toward acetaminophen was studied
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Lin, Richen; Cheng, Jun; Ding, Lingkan; Song, Wenlu; Liu, Min; Zhou, Junhu; Cen, Kefa
2016-05-01
Ferric oxide nanoparticles (FONPs) were used to facilitate dark hydrogen fermentation using Enterobacter aerogenes. The hydrogen yield of glucose increased from 164.5±2.29 to 192.4±1.14mL/g when FONPs concentration increased from 0 to 200mg/L. SEM images of E. aerogenes demonstrated the existence of bacterial nanowire among cells, suggesting FONPs served as electron conduits to enhance electron transfer. TEM showed cellular internalization of FONPs, indicating hydrogenase synthesis and activity was potentially promoted due to the released iron element. When further increasing FONPs concentration to 400mg/L, the hydrogen yield of glucose decreased to 147.2±2.54mL/g. Soluble metabolic products revealed FONPs enhanced acetate pathway of hydrogen production, but weakened ethanol pathway. This shift of metabolic pathways allowed more nicotinamide adenine dinucleotide for reducing proton to hydrogen. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions
International Nuclear Information System (INIS)
Strozier, J.A.
1977-01-01
The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt
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Role of iron oxide impurities in electrocatalysis by multiwall carbon
Indian Academy of Sciences (India)
The role of iron oxide impurities in the electrocatalytic properties of multiwall carbon nanotubes (MWCNTs) prepared by catalytic chemical vapour decomposition method (CCVD) is studied in detail. A novel magnetically modified electrodes have been developed by which MWCNTs were immobilized on indium-tin oxide ...
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DEFF Research Database (Denmark)
Shao, Lidong; Huang, Xing; Teschner, Detre
2014-01-01
A constraint to industrial implementation of gold-catalyzed alkyne hydrogenation is that the catalytic activity was always inferior to those of other noble metals. In this work, gold was supported on graphene oxide (Au/GO) and used in a hydrogenation application. A 99% selectivity toward styrene...
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Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory
DEFF Research Database (Denmark)
Valdes, Alvaro; Brillet, Jeremie; Graetzel, Michael
2012-01-01
An overview of a collaborative experimental and theoretical effort toward efficient hydrogen production via photoelectrochemical splitting of water into di-hydrogen and di-oxygen is presented here. We present state-of-the-art experimental studies using hematite and TiO2 functionalized with gold n...... nanoparticles as photoanode materials, and theoretical studies on electro and photo-catalysis of water on a range of metal oxide semiconductor materials, including recently developed implementation of self-interaction corrected energy functionals....
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Directory of Open Access Journals (Sweden)
Ajda Podgoršek
2010-04-01
Full Text Available Oxidative chlorination with HCl/H2O2 in 1,1,1-trifluoroethanol was used to transform aryl iodides into aryliodine(III dihalides. In this instance 1,1,1-trifluoroethanol is not only the reaction medium, but is also an activator of hydrogen peroxide for the oxidation of hydrochloric acid to molecular chlorine. Aryliodine(III dichlorides were formed in 72–91% isolated yields in the reaction of aryl iodides with 30% aqueous hydrogen peroxide and hydrochloric acid at ambient temperature. A study of the effect that substituents on the aromatic ring have on the formation and stability of aryliodine(III dichlorides shows that the transformation is easier to achieve in the presence of the electron-donating groups (i.e. methoxy, but in this case the products rapidly decompose under the reported reaction conditions to form chlorinated arenes. The results suggest that oxidation of hydrogen chloride with hydrogen peroxide is the initial reaction step, while direct oxidation of aryl iodide with hydrogen peroxide is less likely to occur.
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Lu, Xiaojing; Song, Xinjie; Gu, Cuiping; Ren, Haibo; Sun, Yufeng; Huang, Jiarui
2018-05-01
Quick and efficient detection of low concentrations of hydrogen remains a challenge because of the stability of hydrogen. A sensor based on reduced oxide graphene functionalized with Pt nanoparticles is successfully fabricated using a freeze-drying method followed by heat treatment. The structure and morphology of the Pt@rGO nanocomposites are well analyzed by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The as-prepared Pt@rGO nanocomposites show excellent hydrogen gas sensing properties at a low working temperature of 50 °C. The sensitivity toward 0.5% hydrogen is 8%. The response and recovery times of the sensor exposed to 0.5% hydrogen are 63 and 104 s, respectively. The gas-sensing mechanism of Pt@rGO sensor is also discussed.
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Energy Technology Data Exchange (ETDEWEB)
Ahmed, Wael Ahmed Abou Taleb Sayed
2011-01-13
stability was reported for a reaction time of 10 hours. The results showed that the reaction route, the product distribution and hydrogen selectivity strongly depend on the iron oxide phase. The {alpha}-Fe{sub 2}O{sub 3} phase showed high hydrogen selectivity with the highest stability. Over {alpha}-Fe{sub 2}O{sub 3}/SiC supported catalysts acetaldehyde, water and CO{sub 2} were the main products. The product distributions strongly depended on the catalyst iron content. With increasing sample iron content, more CO{sub 2} and water was produced. The catalyst with an iron content of 1.9% showed the highest acetaldehyde yield. This is attributed to the low iron oxide content at active sites which lead to a dehydrogenation of ethanol to acetaldehyde. In contrast, at higher iron content more active sites were provided hence the acetaldehyde re-adsorbed and further oxidised to CO{sub 2}. All supported catalysts showed a good stability for 10 hours. In this time, the ethanol conversion was decreased by 9% with constant acetaldehyde yield. These results provide evidence that the reaction occurs over the iron oxide surface and iron oxide-support interface but not over the SiC particles. These results were supported by carrying out the ethanol oxidation over pure {alpha}-Fe{sub 2}O{sub 3} nanoparticles with different surface areas. Those surface areas were chosen depending on the surface areas measured for the pure {alpha}-Fe{sub 2}O{sub 3} and surface area calculated for iron oxide in the supported samples. The investigation showed that with a large catalyst surface areas hydrogen with a high selectivity may be produced, whereas with a small surface area only acetaldehyde, water and CO{sub 2} can be produced. The characterisation of the used catalyst showed a small variation of the iron oxide particle size and large surface area. This proved that the SiC support avoids a hot spot formation and prevents iron oxide particles from being sintered. (orig.)
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Hydrogen diffusion along grain boundaries in erbium oxide coatings
International Nuclear Information System (INIS)
Mao, Wei; Chikada, Takumi; Suzuki, Akihiro; Terai, Takayuki
2014-01-01
Diffusion of interstitial atomic hydrogen in erbium oxide (Er 2 O 3 ) was investigated using density functional theory (DFT) and molecular dynamics (MD) methods. Hydrogen diffusivity in bulk, on (0 0 1) surface, and along Σ13 (4–3–1)/[1 1 1] symmetric tilt grain boundaries (GBs) were evaluated in a temperature range of 673–1073 K, as well as hydrogen diffusion barriers. It was found that H diffusion shows the faster on (0 0 1) surface than along GBs and in bulk. Also, energy barrier of H diffusion in bulk estimated by DFT and MD methods is somewhat higher than that along GBs evaluated in the experiments. This suggests that H diffusion in Er 2 O 3 coatings depends on GBs rather than bulk. In addition, with a correction of GB density, the simulated diffusivity along GBs in MD simulations is in good agreement with the experimental data within one order of magnitude. The discrepancy of H diffusivity between the experiments and the simulations should be reduced by considering H concentration, H diffusion direction, deviations of the initial configuration, vacancy defects, etc
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Oxidation of hydrogen peroxide by [Ni (cyclam)] in aqueous acidic ...
Indian Academy of Sciences (India)
Oxidation of hydrogen peroxide by tris(2,2 -bipyridine) and tris(4,4 -dimethyl-2,2 - bipyridine) complexes of osmium(III), iron(III), ruthenium(III), and nickel(III) studied in acidic and neutral aqueous media, show an inverse acid depen- dence over the pH the range 6.0–8.5.12 Kinetic mea- surements with an excess of H2O2 ...
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International Nuclear Information System (INIS)
Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi
2014-01-01
Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs
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ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)
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...
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Microcontroller based instrumentation for heater control circuit of tin oxide based hydrogen sensor
International Nuclear Information System (INIS)
Premalatha, S.; Krithika, P.; Gunasekaran, G.; Ramakrishnan, R.; Ramanarayanan, R.R.; Prabhu, E.; Jayaraman, V.; Parthasarathy, R.
2015-01-01
A thin film sensor based on tin oxide developed in IGCAR is used to monitor very low levels of hydrogen (concentration ranging from 2 ppm to 80 ppm). The heater and the sensor patterns are integrated on a miniature alumina substrate and necessary electrical leads are taken out. For proper functioning of the sensor, the heater has to be maintained at a constant temperature of 350°C. The sensor output (voltage signal) varies with H 2 concentration. In fast breeder reactors, liquid sodium is used as coolant. The sensor is used to detect water/steam leak in secondary sodium circuit. During the start up of the reactor, steam leak into sodium circuit generates hydrogen gas as a product that doesn't dissolve in sodium, but escapes to the surge tank containing argon i.e. in cover gas plenum of sodium circuit. On-line monitoring of hydrogen in cover gas is done to detect an event of water/steam leakage. The focus of this project is on the instrumentation pertaining to the temperature control for the sensor heater. The tin oxide based hydrogen sensor is embedded in a substrate which consists of a platinum heater, essentially a resistor. There is no provision of embedding a temperature sensor on the heater surface due to the physical constraints, without which maintaining a constant heater temperature is a complex task
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International Nuclear Information System (INIS)
Sun, Mingjuan; Hu, Jiayue; Zhai, Chunyang; Zhu, Mingshan; Pan, Jianguo
2017-01-01
Highlights: •A p-n heterojunction of CuI/TiO 2 is constructed. •CuI/TiO 2 is used as the support for depositing Pt nanoparticles. •Enhanced catalytic activity of MOR by using Pt-CuI/TiO 2 under light irradiation. •Improved charger separation contributes to enhanced photoelectrocatalytic activity. -- Abstract: In this paper, a p-n heterojunction including p-type CuI and n-type TiO 2 is first time constructed to be the support for the deposition of Pt. The as-prepared Pt-CuI/TiO 2 modified electrode is studied for the electrocatalytic oxidation of methanol both in dark and under light illumination. Compare to traditional electrocatalytic oxidation, the electrocatalytic activity of Pt-CuI/TiO 2 for methanol oxidation is improved with 4.0 times upon light illumination. Moreover, compare to bare CuI and TiO 2 upon light illumination, the heterostructure of CuI/TiO 2 displays 4.3 and 9.1 times enhanced electrocatalytic activity for methanol oxidation, respectively. The synergistic effects of photocatalysis and electrocatalysis as well as the effective charge transport in the p-n heterojunction of Pt-CuI/TiO 2 contribute such big enhancement. The present studies indicate that the constructing of p-n heterojunction provides more insights in the fields of photoelectrochemical and photo–assisted fuel cell system.
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Hosseini, Mir Ghasem; Mahmoodi, Raana
2017-08-15
The Ni@Pt/C electrocatalysts were synthesized using two different methods: with sodium dodecyl sulfate (SDS) and without SDS. The metal loading in synthesized nanocatalysts was 20wt% and the molar ratio of Ni: Pt was 1:1. The structural characterizations of Ni@Pt/C electrocatalysts were investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HR-TEM). The electrocatalytic activity of Ni@Pt/C electrocatalysts toward BH 4 - oxidation in alkaline medium was studied by means of cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results showed that Ni@Pt/C electrocatalyst synthesized without SDS has superior catalytic activity toward borohydride oxidation (22016.92Ag Pt -1 ) in comparison with a catalyst prepared in the presence of SDS (17766.15Ag Pt -1 ) in NaBH 4 0.1M at 25°C. The Membrane Electrode Assembly (MEA) used in fuel cell set-up was fabricated with catalyst-coated membrane (CCM) technique. The effect of Ni@Pt/C catalysts prepared with two methods as anode catalyst on the performance of direct borohydride-hydrogen peroxide fuel cell was studied. The maximum power density was obtained using Ni@Pt/C catalyst synthesized without SDS at 60°C, 1M NaBH 4 and 2M H 2 O 2 (133.38mWcm -2 ). Copyright © 2017 Elsevier Inc. All rights reserved.
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Directory of Open Access Journals (Sweden)
Diab Hassan
2016-09-01
Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.
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International Nuclear Information System (INIS)
Luz, R.C.S.; Maroneze, C.M.; Tanaka, A.A.; Kubota, L.T.; Gushikem, Y.; Damos, F.S.
2010-01-01
The electrocatalytic activity of a supramolecular complex based on cobalt(II) phthalocyanine tetrasulfonate and iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin adsorbed on multi-walled carbon nanotubes for the oxidation of L-glutathione (GSH) was investigated at pH 7.4. Scanning electron microscopy and energy dispersive X-ray spectrometry were used to characterize the morphologies and composition of the materials. The modified electrode displayed efficient electrocatalytic activity in terms of oxidation of GSH at an oxidation potential of 0 V (versus Ag/AgCl). Cyclic voltammetry and amperometry indicated that the oxidation involves 2-electrons, with a heterogeneous rate constant of 4.9 x 10 5 mol -1 L s -1 . The response is linear from 2 to 210 μmol L -1 , the sensitivity is 1570 μA L mmol -1 , the detection limit is 0.03 μmol L -1 , and the relative standard deviation of 110 μmol L -1 GSH was 2.6% (n=10). The modified electrode was applied to the determination of GSH in erythrocytes and the results were in agreement with those obtained by a method reported in the literature. (author)
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De, Sandip Kumar; Mondal, Subrata; Sen, Pintu; Pal, Uttam; Pathak, Biswarup; Rawat, Kuber Singh; Bardhan, Munmun; Bhattacharya, Maireyee; Satpati, Biswarup; De, Amitabha; Senapati, Dulal
2018-06-14
Understanding and exploring the decisive factors responsible for superlative catalytic efficiency is necessary to formulate active electrode materials for improved electrocatalysis and high-throughput sensing. This research demonstrates the ability of bud-shaped gold nanoflowers (AuNFs), intermediates in the bud-to-blossom gold nanoflower synthesis, to offer remarkable electrocatalytic efficiency in the oxidation of ascorbic acid (AA) at nanomolar concentrations. Multicomponent sensing in a single potential sweep is measured using differential pulse voltammetry while the kinetic parameters are estimated using electrochemical impedance spectroscopy. The outstanding catalytic activity of bud-structured AuNF [iAuNFp(Bud)/iGCp ≅ 100] compared with other bud-to-blossom intermediate nanostructures is explained by studying their structural transitions, charge distributions, crystalline patterns, and intrinsic irregularities/defects. Detailed microscopic analysis shows that density of crystal defects, such as edges, terraces, steps, ledges, kinks, and dislocation, plays a major role in producing the high catalytic efficiency. An associated ab initio simulation provides necessary support for the projected role of different crystal facets as selective catalytic sites. Density functional theory corroborates the appearance of inter- and intra-molecular hydrogen bonding within AA molecules to control the resultant fingerprint peak potentials at variable concentrations. Bud-structured AuNF facilitates AA detection at nanomolar levels in a multicomponent pathological sample.
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Energy Technology Data Exchange (ETDEWEB)
Moradi, S. E. [Islamic Azad University, Sari (Iran, Islamic Republic of)
2014-09-15
Novel microporous activated carbon (MAC) with high surface area and pore volume has been synthesized by microwave heating. Iron oxide nanoparticles were loaded into MAC by using Fe(NO{sub 3}){sub 3}·9H{sub 2}O followed by microwave irradiation for up to five minutes. The surface modified microporous activated carbon was characterized by BET, XRD, SEM and thermogravimetric examinations. Adsorption data of H{sub 2} on the unmodified and modified MACs were collected with PCT method for a pressure range up to 120 bar at 303 K. Greater hydrogen adsorption was observed on the carbon adsorbents doped with 1.45 wt% of iron oxide nanoparticle loaded due to the joint properties of hydrogen adsorption on the carbon surface and the spill-over of hydrogen molecules into carbon structures.
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DEFF Research Database (Denmark)
Zhu, Nan; Han, Shuang; Gan, Shiyu
2013-01-01
applications in detection of hydrogen peroxide or/and other organic peroxides. The as‐prepared PBNPs–RGO papers are further capable of biocompatible accommodation of enzymes for development of free‐standing enzyme based biosensors. In this regard, glucose oxidase is used as an example for electrocatalytic...... oxidation and detection of glucose. The present work demonstrates a facile and highly reproducible way to construct free‐standing and flexible graphene paper doped with electroactive catalyst. Thanks to high stability, low‐cost and efficient electrocatalytic characteristics, this kind of nanohybrid material...
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Directory of Open Access Journals (Sweden)
P. P. Silva
2015-09-01
Full Text Available AbstractThe objective of this paper was to use a thermodynamic analysis to find operational conditions that favor the production of hydrogen from steam and oxidative reforming of liquefied petroleum gas (LPG. We also analyzed the performance of a catalyst precursor, LaNiO3, in order to compare the performance of the obtained catalyst with the thermodynamic equilibrium predictions. The results showed that it is possible to produce high concentrations of hydrogen from LPG reforming. The gradual increase of temperature and the use of high water concentrations decrease the production of coke and increase the formation of H2. The reaction of oxidative reforming of LPG was more suitable for the production of hydrogen and lower coke formation. Furthermore the use of an excess of water (H2O/LPG =7.0 and intermediate temperatures (973 K are the most suitable conditions for the process.
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Electrolytic Synthesis of Ni-W-MWCNT Composite Coating for Alkaline Hydrogen Evolution Reaction
Elias, Liju; Hegde, A. Chitharanjan
2018-03-01
Nickel-tungsten multi-walled carbon nanotube (Ni-W-MWCNT) composite films were fabricated by an electrodeposition technique, and their electrocatalytic activity toward hydrogen evolution reaction (HER) was studied. Ni-W-MWCNT composite films with a homogeneous dispersion of MWCNTs were deposited from an optimal Ni-W plating bath containing functionalized MWCNTs, under galvanostatic condition. The presence of functionalized MWCNT was found to enhance the induced codeposition of the reluctant metal W and resulted in a W-rich composite coating with improved properties. The electrocatalytic behaviors of Ni-W-MWCNT composite coating toward HER were studied by cyclic voltammetry (CV) and chronopotentiometry techniques in 1.0 M KOH medium. Further, Tafel polarization and electrochemical impedance spectroscopy (EIS) studies were carried out to establish the kinetics of HER on the alloy and composite electrodes. The experimental results revealed that the addition of MWCNTs (having a diameter of around 10-15 nm) into the alloy plating bath has a significant effect on the electrocatalytic behavior of Ni-W alloy deposit. The Ni-W-MWCNT composite coating was found to show better HER activity than the conventional Ni-W alloy coating. The enhanced electrocatalytic activity of Ni-W-MWCNT composite coating is attributed to the MWCNT intersticed in the deposit matrix, evidenced by surface morphology, composition and phase structure of the coating through SEM, EDS and XRD analyses, respectively.
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Reduction of nickel oxide particles by hydrogen studied in an environmental TEM
DEFF Research Database (Denmark)
Jeangros, Q.; Hansen, Thomas Willum; Wagner, Jakob Birkedal
2013-01-01
In situ reduction of nickel oxide (NiO) particles is performed under 1.3 mbar of hydrogen gas (H2) in an environmental transmission electron microscope (ETEM). Images, diffraction patterns and electron energy-loss spectra (EELS) are acquired to monitor the structural and chemical evolution of the...
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Merati, Zohreh; Basiri Parsa, Jalal
2018-03-01
Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.
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Directory of Open Access Journals (Sweden)
Lović Jelena D.
2012-01-01
Full Text Available The electrocatalytic activity of carbon supported PtRu/C catalysts, with different composition, toward the electrooxidation of methanol, CO and formic acid were examined in acid and alkaline solution at ambient temperature using thin-film rotating disk electrode (RDE method and compared with activity of Pt/C. The catalysts were characterized by XRD, AFM and STM techniques. XRD pattern revealed that PtRu-1/C catalyst is consisted of two structures e.g. Pt-Ru-fcc and Ru-hcp (the solid solution of Ru in Pt and the small amount of Ru or solid solution of Pt in Ru, as opposed to PtRu-2/C catalyst which is consisted of one structure mostly, Pt-Ru-fcc. According to STM images, PtRu as well as Pt, particles size were between 2 and 6 nm, which is in a good agreement with the mean particles size determined by XRD. To establish the activity and stability of the catalysts potentiodynamic and quasi steady-state measurements were performed. It was found that the activity of Pt and PtRu for CO and methanol oxidation is a strong function of pH of solution. The kinetics are much higher in alkaline than in acid solution and the difference between Pt/C and PtRu/C is much less pronounced in alkaline media. Results presented in this work indicate that activity of PtRu catalysts depends on catalyst composition, e.g. on Pt/Ru atomic ratio, as well as on alloying degree of catalysts. Comparison of CO, methanol and formic acid oxidation on PtRu-2/C, PtRu-1/C and Pt/C catalysts revealed that PtRu-2/C is the most active one. It was shown that the PtRu-2/C catalyst, due to fact that it is consisted of only one phase, with high alloying degree, through the bifunctional mechanism improved by electronic effect, achieve the activity two times higher related to PtRu-1/C in the oxidation of all organic molecules investigated, and about three times higher compared to Pt/C in the oxidation of methanol and CO, and five times higher in formic acid oxidation.
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Ethanol Electrooxidation on Pt with Lanthanum Oxide as Cocatalyst in a DAFC
Directory of Open Access Journals (Sweden)
T. A. B. Santoro
2012-01-01
Full Text Available Electrocatalytic activity toward ethanol electrooxidation of Pt particles in PtLa/C catalysts with different Pt : La ratios has been studied with different electrochemical and spectroscopic techniques, and the results were compared to those of Pt/C catalyst. Significant enhancement in the electrocatalytic activity has been achieved by depositing the Pt particles with lanthanum oxides/hydroxides using an alcohol reduction method. Compared to Pt/C catalyst, PtLa/C materials exhibit a lower onset potential and a higher electron-transfer rate constant for the investigated reaction. These studies illustrate the possibility of utilizing Pt/C with La oxides/hidroxides as electrocatalyst for direct alcohol fuel cells (DAFCs.
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Pd-Cu/poly(o-Anisidine) nanocomposite as an efficient catalyst for formaldehyde oxidation
Energy Technology Data Exchange (ETDEWEB)
Hosseini, Sayed Reza, E-mail: r.hosseini@umz.ac.ir [Nanochemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, 47416-95447 Babolsar (Iran, Islamic Republic of); Raoof, Jahan-Bakhsh [Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, 47416-95447 Babolsar (Iran, Islamic Republic of); Ghasemi, Shahram; Gholami, Zahra [Nanochemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, 47416-95447 Babolsar (Iran, Islamic Republic of)
2016-08-15
Highlights: • o-Anisidine monomer was electro-polymerized at the pCPE surface in acid medium. • Palladium/copper NPs were prepared by galvanic replacement method at the POA/pCPE. • Pd-Cu NPs showed excellent electrocatalytic activity towards formaldehyde oxidation. • The bimetallic Pd-Cu NPs/POA nanocomposite showed satisfactory long-term stability. - Abstract: In this work, for the first time, the electrocatalytic oxidation of formaldehyde in 0.5 M sulfuric acid solution at spherical bimetallic palladium-copper nanoparticles (Pd-Cu NPs) deposited on the poly (o-Anisidine) film modified electrochemically pretreated carbon paste electrode (POA/pCPE) has been investigated. Highly porous POA film prepared by electropolymerization onto the pCPE was used as a potent support for deposition of the Pd-Cu NPs. The Pd-Cu NPs were prepared through spontaneous and irreversible reaction via galvanic replacement between Pd{sup II} ions and the Cu{sup 0} particles. The prepared Pd-Cu NPs were characterized by scanning electron microscopy, energy dispersive spectroscopy and electrochemical methods. The obtained results showed that the utilization of Cu nanoparticles and pretreatment technique enhances the electrocatalytic activity of the modified electrode towards formaldehyde oxidation. The influence of several parameters on formaldehyde oxidation as well as stability of the Pd-Cu/POA/pCPE has been investigated.
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Liu, Zhongqing; Cao, Xiaohao; Wang, Bin; Xia, Min; Lin, Sidney; Guo, Zhanhu; Zhang, Xiaoming; Gao, Shiyuan
2017-02-01
PbTesbnd PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTesbnd PbS/TiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTesbnd PbS/TNAs, the two electrode system in which PbTesbnd PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 °C and 1.0 V bath voltage, the system registers 6.1 mL cm-2 h-1 rate of hydrogen generation, consuming electric power of 26.2 kW h kg-1 H2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling.
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International Nuclear Information System (INIS)
Rozenkevich, M.; Andreev, B.; Magomedbekov, E.; Park, Yu.; Sakharovsky, Yu.; Perevezentsev, A.
2005-01-01
Water detritiation facility based on CECE (Combined Electrolysis and Catalytic Exchange) technology needs an electrolyser for water conversion to hydrogen. Use of a conventional alkali electrolyser requires a very deep purification of hydrogen stream from alkali prior to injection to LPCE (Liquid Phase Catalytic Exchange) column. In some applications conversion of detritiated hydrogen back into water is required. This is usually performed via hydrogen catalytic oxidation in a recombiner. This paper presents results of study to improve hydrogen and oxygen purification for alkali electrolysers and develop a hydrogen recombiner based on use of hydrophobic catalyst
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Catalyst support effects on hydrogen spillover
Karim, Waiz; Spreafico, Clelia; Kleibert, Armin; Gobrecht, Jens; Vandevondele, Joost; Ekinci, Yasin; van Bokhoven, Jeroen A.
2017-01-01
Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.
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MAZLOUMARDAKANI, Mohammad; KARAMI, Payam EBRAHIMI
2014-01-01
The electrocatalytic behavior of hydroxylamine was studied on a glassy carbon electrode modified by electrodeposition of quinizarine, using cyclic voltammetry, chronoamperometry, and rotating disk voltammetry as diagnostic techniques. Cyclic voltammetry showed that the catalytic current of the system depends on the concentration of hydroxylamine. The magnitude of the peak current for quinizarine increased sharply in the presence of hydroxylamine and proportional to hydroxylamine conc...
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Role of iron oxide impurities in electrocatalysis by multiwall carbon ...
Indian Academy of Sciences (India)
The electro-catalytic oxidation of dopamine, and reduction of hydro- gen peroxide have ... herent ferromagnetic properties at room temperature, which have been used to ... tion of ferrocene in ethanol gave iron oxide nanoparticles. (Io-NPs) with an .... anism shows strong dependence on the nature of the elec- trode surface.
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Cyclic etching of tin-doped indium oxide using hydrogen-induced modified layer
Hirata, Akiko; Fukasawa, Masanaga; Nagahata, Kazunori; Li, Hu; Karahashi, Kazuhiro; Hamaguchi, Satoshi; Tatsumi, Tetsuya
2018-06-01
The rate of etching of tin-doped indium oxide (ITO) and the effects of a hydrogen-induced modified layer on cyclic, multistep thin-layer etching were investigated. It was found that ITO cyclic etching is possible by precisely controlling the hydrogen-induced modified layer. Highly selective etching of ITO/SiO2 was also investigated, and it was suggested that cyclic etching by selective surface adsorption of Si can precisely control the etch rates of ITO and SiO2, resulting in an almost infinite selectivity for ITO over SiO2 and in improved profile controllability.
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Exfoliated MoS2 nanosheets as efficient catalysts for electrochemical hydrogen evolution
International Nuclear Information System (INIS)
Ji, Shanshan; Yang, Zhe; Zhang, Chao; Liu, Zhenyan; Tjiu, Weng Weei; Phang, In Yee; Zhang, Zheng; Pan, Jisheng; Liu, Tianxi
2013-01-01
Graphical abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on exfoliation of bulk MoS 2 crystals via a direct dispersion and ultrasonication method. Drop-casting method is used to fabricate the exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings. The E-MoS 2 /GCE with electrode loading of 48 μg cm −1 exhibits high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV). -- Highlights: • Two-dimensional MoS 2 nanosheets have been obtained by exfoliation of bulk MoS 2 crystals. • Exfoliated MoS 2 nanosheets show high electrocatalytic activity for H 2 production. • This study provides a new approach for renewable and economic H 2 production. -- Abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on liquid exfoliation of bulk MoS 2 via a direct dispersion and ultrasonication method. Transmission electron microscopy and atomic force microscopy measurements show that the exfoliated MoS 2 consists of two-dimensional nanosheets. The exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings is fabricated via a drop-casting method. The electrocatalytic activity of E-MoS 2 /GCE toward hydrogen evolution reaction is examined using linear sweep voltammetry. It is shown that the E-MoS 2 /GCE with an electrode loading of 48 μg cm −2 exhibits a high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV)
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Wang, Beibei; Ji, Xueping; Ren, Jujie; Ni, Ruixing; Wang, Lin
2017-12-01
A simple, ultrasensitive peroxynitrite anion (ONOO - ) electrochemical sensing platform was developed by immobilizing hemin on a density controllable electrochemically reduced graphene oxide-Au nanoparticles (ERGO-AuNPs) nanohybrids. The ERGO-AuNPs in situ nanohybrids were produced onto a glass carbon electrode (GCE) by one-step electrodeposition, the density of which could be easily controlled by electrodeposited time. The morphology of ERGO-AuNPs nanohybrids was characterized by a scanning electron microscope (SEM). The ERGO-AuNPs nanohybrids showed a high electrocatalytic activity for immobilized-hemin, because the nanostructures hybrids could effectively promote electron transfer rate between hemin and the electrode. Due to nanohybrids-enhanced catalytic effect for hemin, they were firstly selected for use as a highly sensitive electrochemical platform for ONOO - detection. The resulted sensor showed a high electrocatalytic activity toward ONOO - oxidation, being free from the electroactive interferents, including nitrite, nitrate, dopamine and uric acid at an applied potential of 0.7V. The sensor exhibited a high sensitivity of 123.1nAμM -1 and a lower detection limit of 0.1μM, and a wide linear range of 2.4×10 -6 to 5.5×10 -5 M, which could be attributed to the synergy between ERGO and AuNPs in hybrids. The nanohybrids in situ preparation and ONOO - detection methods would be beneficial to developing other sensing interface and have promising applications in biological molecules analysis and clinical diagnostic. Copyright © 2017 Elsevier B.V. All rights reserved.
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International Nuclear Information System (INIS)
Chatraei, Fatemeh; Zare, Hamid R.
2013-01-01
In this study, a promising electrochemical sensor was fabricated by the electrodeposition of nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles, RuON) on a glassy carbon electrode (RuON–GCE). Then, the electrocatalytic oxidation of iodate and periodate was investigated on it, using cyclic voltammetry, chronoamperometry and amperometry as diagnostic techniques. The charge transfer coefficient, α, and the charge transfer rate constant, k s , for electron transfer between RuON and GCE were calculated as 0.5 ± 0.03 and 9.0 ± 0.7 s −1 respectively. A comparison of the data obtained from the electrocatalytic reduction of iodate and periodate at a bare GCE (BGCE) and RuON–GCE clearly shows that the unique electronic properties of nanoparticles definitely improve the characteristics of iodate and periodate electrocatalytic reduction. The kinetic parameters such as the electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the reduction of iodate and periodate at RuON–GCE surface were determined using cyclic voltammetry. Amperometry revealed a good linear relationship between the peak current and the concentration of iodate and periodate. The detection limits of 0.9 and 0.2 μM were calculated for iodate and periodate respectively. Highlights: ► Ruthenium oxide nanoparticles, RuON, were used for electrocatalytic reduction iodate and periodate. ► Formal potential, E 0 ′, of the surface redox couple of RuON is pH-dependent. ► The heterogeneous electron transfer rate constant values between both analytes and RuON were calculated.
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Facile Hydrogen Evolution Reaction on WO3Nanorods
Directory of Open Access Journals (Sweden)
Rajeswari Janarthanan
2007-01-01
Full Text Available AbstractTungsten trioxide nanorods have been generated by the thermal decomposition (450 °C of tetrabutylammonium decatungstate. The synthesized tungsten trioxide (WO3 nanorods have been characterized by XRD, Raman, SEM, TEM, HRTEM and cyclic voltammetry. High resolution transmission electron microscopy and X-ray diffraction analysis showed that the synthesized WO3nanorods are crystalline in nature with monoclinic structure. The electrochemical experiments showed that they constitute a better electrocatalytic system for hydrogen evolution reaction in acid medium compared to their bulk counterpart.
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Rosca, V.; Muresan, L.; Popescu, I.C.; Cristea, C.; Silberg, I.A.
2001-01-01
16H,18H-Dibenzo[c,l]-7,9-dithia-16,18-diazapentacene (DDDP), a new phenothiazine derivative containing two linearly condensed phenothiazine rings, strongly adsorbs on polyoriented gold resulting in a modified electrode with electrocatalytic activity for ß-nicotinamide adenine dinucleotide (NADH)
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International Nuclear Information System (INIS)
Kumar, Alam Venugopal Narendra; Joseph, James
2014-01-01
The electrochemical modification of solid electrodes with metal hexacyanoferrate thin films for enhancing the interfacial properties has created interest for over the past three decades. The preparation of Prussian blue (PB) Au nano composites for the enhancement in the electrocatalytic properties of PB on glassy carbon electrode has been reported by us. The incorporation of Au nano particles in Cobalt hexacyanoferrate (CoHCF) films on Glassy carbon by co-electrodeposition is expected to benefit its interfacial electron transfer properties. The present work describes the effect on the interfacial properties by incorporated Au particles in CoHCF (CoHCF(Au)) modified electrodes. The CoHCF(Au) modified electrodes were characterized by UV-Vis spectrophotometry, Cyclic Voltammetry, AC Impedance, FE-SEM etc., Influence on the electrocatalytic properties of CoHCF(Au) films have been explored by performing two important reactions i) Hydrazine elecrtro-oxidation ii) Oxygen evolution reaction. Our results reveal that CoHCF(Au) modified GC electrode perform better in terms of charge transport in the redox film and also for the electrooxidation of hydrazine in comparision with simple CoHCF modified electrodes. By using the current-transient technique (chrono method i vs t curve) the hydrazine diffusion coefficient (D 0 ) were calculated. Diffusion coefficient of hydrazine was approximately three times higher on CoHCF(Au) electrode, 9.5 × 10 −5 cm 2 s −1 compared with simple CoHCF modified electrode, 3.3× 10 −5 cm 2 s −1 . Similarly, we also discuss results which reveal that CoHCF(Au) electrodes enhances electrocatalytic activity in splitting water to oxygen in 0.1 M NaOH solution compared to simple CoHCF and Au deposited on GC electrodes
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Directory of Open Access Journals (Sweden)
Yousri M.A. Welaya
2012-06-01
Full Text Available Proton exchange membrane fuel cell (PEM generates electrical power from air and from hydrogen or hydrogen rich gas mixtures. Therefore, there is an increasing interest in converting current hydrocarbon based marine fuels such as natural gas, gasoline, and diesel into hydrogen rich gases acceptable to the PEM fuel cells on board ships. Using chemical flow sheeting software, the total system efficiency has been calculated. Natural gas appears to be the best fuel for hydrogen rich gas production due to its favorable composition of lower molecular weight compounds. This paper presents a study for a 250 kW net electrical power PEM fuel cell system utilizing a partial oxidation in one case study and steam reformers in the second. This study has shown that steam-reforming process is the most competitive fuel processing option in terms of fuel processing efficiency. Partial oxidation process has proved to posses the lowest fuel processing efficiency. Among the options studied, the highest fuel processing efficiency is achieved with natural gas steam reforming system.
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International Nuclear Information System (INIS)
Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa
2012-01-01
Graphical abstract: - Abstract: Pt/Au and Pd/Au surface interfaces show very high activity in electrocatalytic oxidation of alcohols in alkaline media. In this work, we present a method for preparation of such structures, which is based on galvanic displacement of the more noble gold with the less noble elements, and investigate their electrocatalytic properties. We propose that active states atoms on the surface of gold may be replaced with Pt and Pd. The generation of active sites on gold is achieved by cathodization in acidic solution. We show that depending on the cathodization time (active sites amount) gold surface electrochemistry changes from that resembling Au to the one typical for pure Pt. The Pt/Au structures prepared with a trace amount of platinum show extremely high electrocatalytic activity. The peak current of methanol oxidation on the Pt/Au electrode is more than an order of magnitude higher than that of the platinum film electrode and more than two orders of magnitude higher than that on the gold unactivated electrode. The difference in the peak current of ethanol oxidation between the Pt/Au and Pt electrodes is ca. 25 times. Moreover, similar deposition of Pt and Pd on active sites on high surface area gold prepared by hydrogen evolution assisted deposition and improved electrocatalytic properties of such structures toward alcohols oxidation is shown.
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Electrocatalytic Metal-Organic Frameworks for Energy Applications.
Downes, Courtney A; Marinescu, Smaranda C
2017-11-23
With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal-organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best-performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble-metal-based catalysts in commercial energy-converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy-related reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Yoneda, Toshiki; Tomofuji, Takaaki; Kunitomo, Muneyoshi; Ekuni, Daisuke; Irie, Koichiro; Azuma, Tetsuji; Machida, Tatsuya; Miyai, Hisataka; Fujimori, Kouhei; Morita, Manabu
2017-01-13
Obesity induces gingival oxidative stress, which is involved in the progression of alveolar bone resorption. The antioxidant effect of hydrogen-rich water may attenuate gingival oxidative stress and prevent alveolar bone resorption in cases of obesity. We examined whether hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption in obese rats fed a high-fat diet. Male Fischer 344 rats ( n = 18) were divided into three groups of six rats each: a control group (fed a regular diet and drinking distilled water) and two experimental groups (fed a high-fat diet and drinking distilled water or hydrogen-rich water). The level of 8-hydroxydeoxyguanosine was determined to evaluate oxidative stress. The bone mineral density of the alveolar bone was analyzed by micro-computerized tomography. Obese rats, induced by a high-fat diet, showed a higher gingival level of 8-hydroxydeoxyguanosine and a lower level of alveolar bone density compared to the control group. Drinking hydrogen-rich water suppressed body weight gain, lowered gingival level of 8-hydroxydeoxyguanosine, and reduced alveolar bone resorption in rats on a high-fat diet. The results indicate that hydrogen-rich water could suppress gingival oxidative stress and alveolar bone resorption by limiting obesity.
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Directory of Open Access Journals (Sweden)
Mukhamad Nurhadi
2018-01-01
How to Cite: Nurhadi, M., Kusumawardani, R., Nur, H. (2018. Negative Effect of Calcination to Catalytic Performance of Coal Char-loaded TiO2 Catalyst in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 113-118 (doi:10.9767/bcrec.13.1.1171.113-118
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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 .
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Gold-catalyzed oxidation of substituted phenols by hydrogen peroxide
Cheneviere, Yohan
2010-10-20
Gold nanoparticles deposited on inorganic supports are efficient catalysts for the oxidation of various substituted phenols (2,6-di-tert-butyl phenol and 2,3,6-trimethyl phenol) with aqueous hydrogen peroxide. By contrast to more conventional catalysts such as Ti-containing mesoporous silicas, which convert phenols to the corresponding benzoquinones, gold nanoparticles are very selective to biaryl compounds (3,3′,5,5′-tetra-tert-butyl diphenoquinone and 2,2′,3,3′,5,5′-hexamethyl-4,4′- biphenol, respectively). Products yields and selectivities depend on the solvent used, the best results being obtained in methanol with yields >98%. Au offers the possibility to completely change the selectivity in the oxidation of substituted phenols and opens interesting perspectives in the clean synthesis of biaryl compounds for pharmaceutical applications. © 2010 Elsevier B.V. All rights reserved.
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Hydrogen evolution on Au(111) covered with submonolayers of Pd
DEFF Research Database (Denmark)
Björketun, Mårten; Karlberg, Gustav; Rossmeisl, Jan
2011-01-01
A theoretical investigation of electrochemical hydrogen evolution on Au(111) covered with submonolayers of Pd is presented. The size and shape of monoatomically high Pd islands formed on the Au(111) surface are determined using Monte Carlo simulations, for Pd coverages varying from 0.02 to 0.95 ML....... The energetics of adsorption and desorption of hydrogen on/from different types of sites on the Pd-Au(111) surface are assessed by means of density functional theory calculations combined with thermodynamic modeling. Based on the density functional and Monte Carlo data, the hydrogen evolution activity...... is evaluated with a micro-kinetic model. The analysis reproduces measured Pd-coverage-dependent activities for Pd submonolayers exceeding similar to 0.15 ML and enables the relative contributions from different types of electrocatalytically active sites to be determined. Finally, the implications of surface...
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Examination of several pre-oxidation procedures and their effect as hydrogen permeation-barrier
International Nuclear Information System (INIS)
Heimes, E.
1986-03-01
Several pre-oxidation procedures have been tested with respect to their effect as a hydrogen permeation barrier at the high temperature alloys Hastelloy X and Inconel 617. By outside coating of Hastelloy X samples with alumina the determined impeding effects were very low. A surface aluminium enrichment by different procedures were accomplished before selective oxidation. The method of Aluminium-Hot-Dipping generated oxide layers with a four- to fivefold higher impeding effect compared to specimens fabricated by a standard procedure. With the aid of a metallographical follow-up examination it was shown that the higher impeding effects are due to an improved adhesion between the oxide layer and the high temperature material, whereby in the cooling period after manufacturing a smaller amount of oxide cracking is obtainable. (orig./PW) [de
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Ammonia, nitrous oxide and hydrogen cyanide emissions from five passenger vehicles
International Nuclear Information System (INIS)
Karlsson, Hua Lu
2004-01-01
In this paper, three unregulated components, ammonia, nitrous oxide and hydrogen cyanide, emitted from five passenger vehicles are investigated. With focus upon emission factors from existing production technology, vehicles produced between 1989 and 1998 with considerable mileage (7000 to 280,000) are chosen. Among the five vehicles, four were sold in the European market, whereas one was sold in the US market. The vehicles are tested on a chassis dynamometer. An EU2000 Driving Cycle (NEDC) and a US Urban Driving Cycle (UDC) of the Federal Test Procedure 75 (FTP-75) are used in the study. The regulated emissions are measured using a Horiba Mexa series. Unregulated emissions, ammonia (NH 3 ), nitrous oxide (N 2 O) and hydrogen cyanide (HCN) are analysed by mass spectrometer, gas chromatography and CNT-NA, TIM315-74W method, respectively. Both the unregulated emissions and the regulated emissions show driving cycle dependency; and they are also improved with newer vehicle and emission control technology. However, a gasoline direct injection vehicle (relatively new technology in this study) has rather high regulated emissions, whereas the NH 3 , N 2 O and HCN emissions are low
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Ammonia, nitrous oxide and hydrogen cyanide emissions from five passenger vehicles.
Karlsson, Hua Lu
2004-12-01
In this paper, three unregulated components, ammonia, nitrous oxide and hydrogen cyanide, emitted from five passenger vehicles are investigated. With focus upon emission factors from existing production technology, vehicles produced between 1989 and 1998 with considerable mileage (7000 to 280,000) are chosen. Among the five vehicles, four were sold in the European market, whereas one was sold in the US market. The vehicles are tested on a chassis dynamometer. An EU2000 Driving Cycle (NEDC) and a US Urban Driving Cycle (UDC) of the Federal Test Procedure 75 (FTP-75) are used in the study. The regulated emissions are measured using a Horiba Mexa series. Unregulated emissions, ammonia (NH(3)), nitrous oxide (N(2)O) and hydrogen cyanide (HCN) are analysed by mass spectrometer, gas chromatography and CNT-NA, TIM315-74W method, respectively. Both the unregulated emissions and the regulated emissions show driving cycle dependency; and they are also improved with newer vehicle and emission control technology. However, a gasoline direct injection vehicle (relatively new technology in this study) has rather high regulated emissions, whereas the NH(3), N(2)O and HCN emissions are low.
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International Nuclear Information System (INIS)
Guo, Mengmeng; Wu, Qikang; Yu, Miaomiao; Wang, Yinling; Li, Maoguo
2017-01-01
Two different kinds of carbon-based amorphous molybdenum sulfide composite catalysts (activated carbon supported amorphous molybdenum sulfide and acetylene black supported amorphous molybdenum sulfide) had been prepared in a facile and scalable one-step liquid phase chemical method. The morphological and structural information of catalysts was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and it’s electro-catalytic HER activity were evaluated by linear sweep voltammetry(LSV), amperometric i-t technology and AC impedance technology. The as-prepared carbon-based amorphous molybdenum sulfides showed greatly enhanced electro-catalytic activity for HER compared with pure amorphous molybdenum sulfides. Especially, the nano-sized acetylene black supported molybdenum sulfide exhibited excellent electro-catalytic HER performances with a low onset potential of −116 mV versus reverse hydrogen electrode (RHE) and a small Tafel slope of 51 mV per decade.
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International Nuclear Information System (INIS)
Tabassum, Rana; Gupta, Banshi D
2016-01-01
We present an experimental study on a surface plasmon resonance (SPR) based fiber optic hydrogen gas sensor employing a palladium doped zinc oxide nanocomposite (ZnO (1−x) Pd x , 0 ≤ x ≤ 0.85) layer over the silver coated unclad core of the fiber. Palladium doped zinc oxide nanocomposites (ZnO (1−x) Pd x ) are prepared by a chemical route for different composition ratios and their structural, morphological and hydrogen sensing properties are investigated experimentally. The sensing principle involves the absorption of hydrogen gas by ZnO (1−x) Pd x , altering its dielectric function. The change in the dielectric constant is analyzed in terms of the red shift of the resonance wavelength in the visible region of the electromagnetic spectrum. To check the sensing capability of sensing probes fabricated with varying composition ratio (x) of nanocomposite, the SPR curves are recorded typically for 0% H 2 and 4% H 2 in N 2 atmosphere for each fabricated probe. On changing the concentration of hydrogen gas from 0% to 4%, the red shift in the SPR spectrum confirms the change in dielectric constant of ZnO (1−x) Pd x on exposure to hydrogen gas. It is noted that the shift in the SPR spectrum increases monotonically up to a certain fraction of Pd in zinc oxide, beyond which it starts decreasing. SEM images and the photoluminescence (PL) spectra reveal that Pd dopant atoms substitutionally incorporated into the ZnO lattice profoundly affect its defect levels; this is responsible for the optimal composition of ZnO (1−x) Pd x to sense the hydrogen gas. The sensor is highly selective to hydrogen gas and possesses high sensitivity. Since optical fiber sensing technology is employed along with the SPR technique, the present sensor is capable of remote sensing and online monitoring of hydrogen gas. (paper)
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Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok
2013-09-01
Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.
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International Nuclear Information System (INIS)
Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok
2013-01-01
Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H 2 S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H 2 S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H 2 S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H 2 and CO 2 on H 2 S adsorption was also investigated. The presence of hydrogen in the H 2 S stream had a positive effect on the removal of H 2 S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn 2+ ) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO 2 ) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H 2 S and CO 2 .
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Method for absorbing hydrogen using an oxidation resisant organic hydrogen getter
Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA
2009-02-03
A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably platinum, is disclosed. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently remove hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.
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Bak, Jumi; Bae, Hyung Bin; Kim, Jaehoon; Oh, Jihun; Chung, Sung-Yoon
2017-05-10
Atomic-scale direct probing of active sites and subsequent elucidation of the structure-activity relationship are important issues involving oxide-based electrocatalysts to achieve better electrochemical conversion efficiency. By generating Ruddlesden-Popper (RP) two-dimensional homologous faults via simple control of the cation nonstoichiometry in LaNiO 3 thin films, we demonstrate that strong tetragonal distortion of [NiO 6 ] octahedra is induced by more than 20% elongation of Ni-O bonds in the faults. In addition to direct visualization of the elongation by scanning transmission electron microscopy, we identify that the distorted [NiO 6 ] octahedra in the faults show considerably higher electrocatalytic activities than other surface sites during the electrochemical oxygen evolution reaction. This unequivocal evidence of the octahedral distortion and its impact on electrocatalysis in LaNiO 3 suggests that the formation of RP-type faults can provide an efficient way to control the octahedral geometry and thereby remarkably enhance the oxygen catalytic performance of perovskite oxides.
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Siriviriyanun, Ampornphan; Imae, Toyoko
2013-04-14
Electrochemical sensors consisting of electrodes loaded with carbon nanotubes and Pt nanoparticles (PtNPs) protected by dendrimers have been developed using a facile method to fabricate them on two types of disposable electrochemical printed chips with a screen-printed circular gold or a screen-printed circular glassy carbon working electrode. The electrochemical performance of these sensors in the oxidation of methanol was investigated by cyclic voltammetry. It was revealed that such sensors possess stable durability and high electrocatalytic activity: the potential and the current density of an anodic peak in the oxidation of methanol increased with increasing content of PtNPs on the electrodes, indicating the promotion of electrocatalytic activity in relation to the amount of catalyst. The low anodic potential suggests the easy electrochemical reaction, and the high catalyst tolerance supports the almost complete oxidation of methanol to carbon dioxide. The significant performance of these sensors in the detection of methanol oxidation comes from the high electrocatalytic ability of PtNPs, excellent energy transfer of carbon nanotubes and the remarkable ability of dendrimers to act as binders. Thus these systems are effective for a wide range of applications as chemical, biomedical, energy and environmental sensors and as units of direct methanol fuel cells.
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International Nuclear Information System (INIS)
Tajabadi, M.T.; Sookhakian, M.; Zalnezhad, E.; Yoon, G.H.; Hamouda, A.M.S.; Azarang, Majid; Basirun, W.J.; Alias, Y.
2016-01-01
Highlights: • Nitrogen doped graphene with different thickness by electrophoretic deposition. • The conductivity of N-graphene layer depends on the tickness. • Support of platinum shows efficient electrocatalytic performance for biosensor. • CV curves and amperometric responses improved and optimized in the presence of N-graphene. - Abstract: An efficient non-enzymatic biosensor electrode consisting of nitrogen-doped graphene (N-graphene) and platinum nanoflower (Pt NF) with different N-graphene loadings were fabricated on indium tin oxide (ITO) glass using a simple layer-by-layer electrophoretic and electrochemical sequential deposition approach. N-graphene was synthesized by annealing graphene oxide with urea at 900 °C. The structure and morphology of the as-fabricated non-enzymatic biosensor electrodes were determined using X-ray diffraction, field emission electron microscopy, transmission electron microscopy, Raman and X-ray photoelectron spectra. The as-fabricated Pt NF-N-graphene-modified ITO electrodes with different N-graphene loadings were utilized as a non-enzymatic biosensor electrode for the detection of hydrogen peroxide (H_2O_2). The behaviors of the hybrid electrodes towards H_2O_2 reduction were assessed using chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy analysis. The Pt NF-N-graphene-modified ITO electrode with a 0.05 mg ml"−"1 N-graphene loading exhibited the lowest detection limit, fastest amperometric sensing, a wide linear response range, excellent stability and reproducibility for the non-enzymatic H_2O_2 detection, due to the synergistic effect between the electrocatalytic activity of the Pt NF and the high conductivity and large surface area of N-graphene.
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Durability of solid oxide electrolysis cells for hydrogen production
Energy Technology Data Exchange (ETDEWEB)
Hauch, A.; Hoejgaard Jensen, S.; Dalgaard Ebbesen, S.
2007-05-15
In the perspective of the increasing interest in renewable energy and hydrogen economy, the reversible solid oxide cells (SOCs) is a promising technology as it has the potential of providing efficient and cost effective hydrogen production by high temperature electrolysis of steam (HTES). Furthermore development of such electrolysis cells can gain from the results obtained within the R and D of SOFCs. For solid oxide electrolysis cells (SOEC) to become interesting from a technological point of view, cells that are reproducible, high performing and long-term stable need to be developed. In this paper we address some of the perspectives of the SOEC technology i.e. issues such as a potential H2 production price as low as 0.71 US dollar/kg H{sub 2} using SOECs for HTES; is there a possible market for the electrolysers? and what R and D steps are needed for the realisation of the SOEC technology? In the experimental part we present electrolysis test results on SOCs that have been optimized for fuel cell operation but applied for HTES. The SOCs are produced on a pre-pilot scale at Risoe National Laboratory. These cells have been shown to have excellent initial electrolysis performance, but the durability of such electrolysis cells are not optimal and examples of results from SOEC tests over several hundreds of hours are given here. The long-term tests have been run at current densities of -0.5 A/cm{sup 2} and -1 A/cm{sup 2}, temperatures of 850 deg. C and 950 deg. C and p(H{sub 2}O)/p(H{sub 2}) of 0.5/0.5 and 0.9/0.1. Long-term degradation rates are shown to be up to 5 times higher for SOECs compared to similar SOFC testing. Furthermore, hydrogen and synthetic fuel production prices are calculated using the experimental results from long-term electrolysis test as input and a short outlook for the future work on SOECs will be given as well. (au)
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Energy Technology Data Exchange (ETDEWEB)
Li, K.T.; Chi, Z.H. [Department of Chemical Engineering, Tunghai University, ROC Taichung (Taiwan)
2001-05-17
The effect of antimony oxide addition to MgV{sub 2}O{sub 6} and Mg{sub 3}V{sub 2}O{sub 8} was studied in the selective oxidation of hydrogen sulfide to sulfur. Significant improvements in sulfur selectivity and yield were observed for the uncalcined mechanical mixtures of magnesium vanadates with {alpha}-Sb{sub 2}O{sub 4}. Calcination of the mechanical mixtures resulted in the much stronger synergy in catalytic activity and sulfur selectivity. For the uncalcined samples, XRD, TPR and XPS studies indicated that antimony reduction behaviors in the mechanical mixtures differed very much from those in {alpha}-Sb{sub 2}O{sub 4} alone, suggested that their selectivity improvements might be due to the interactions (probably oxygen transfer) between {alpha}-Sb{sub 2}O{sub 4} and magnesium vanadates. For the calcined samples, XRD results indicated that their better catalytic performances in H{sub 2}S oxidation were primarily attributed to the formation of VSbO{sub 4} compound from antimony oxide and magnesium vanadates.
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Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.
Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P
2011-12-28
Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.
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Tao, Shasha; Yang, Florent; Schuch, Jona; Jaegermann, Wolfram; Kaiser, Bernhard
2018-03-09
Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH) 2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm -2 as well as a small Tafel slope of 88 mV dec -1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH) 2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni 0 , NiO, and Ni(OH) 2 into the less active Ni(OH) 2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Energy Technology Data Exchange (ETDEWEB)
Carugno, Sofía [INQUIMAE – DQIAQF, Facultad de Ciencias, Exactas y Naturales, Universidad de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, 1428 Buenos Aires (Argentina); Chassaing, Elisabeth [IRDEP (UMR7174), EDF R and D, 6 Quai Watier, 78401 Chatou (France); Rosso, Michel [LPMC (UMR7643), CNRS, Ecole Polytechnique, F91128 Palaiseau Cedex (France); González, Graciela A., E-mail: graciela@qi.fcen.uba.ar [INQUIMAE – DQIAQF, Facultad de Ciencias, Exactas y Naturales, Universidad de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, 1428 Buenos Aires (Argentina)
2014-02-14
In this paper, we report a study of electrocatalytic oxidation of methanol on copper electrodes subjected to different surface treatments, either electrocorrosion or electrodeposition in the absence of strong hydrogen co-deposition. The surface morphology of treated electrodes was examined by Field Emission Scanning Electron Microscopy (FE-SEM). The effect of different treatment conditions and the methanol concentration dependence were evaluated by cyclic voltammetric technique. The results indicate that the oxidation of methanol can be enhanced by a suitable micro and nano structure generated by these treatments. This enhanced electrode activity is related to an increase of the effective surface area and/or to an increase of the surface concentration of electroactive molecules or intermediates. - Highlights: • We presented simple treatments to increase the response of copper electrodes. • Copper electrodes were modified by electrocorrosion and electrodeposition. • Scanning Electron Microscopy images reveal the effects of the different treatments. • The response is enhanced by an area increase and/or intermediates concentration. • For each treatment the concentration range of the diffusion control is analyzed.
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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.
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Hydrogen storage behaviors of Ni-doped graphene Oxide/MIL-101 hybrid composites.
Lee, Seul-Yi; Park, Soo-Jin
2013-01-01
In this work, Ni-doped graphene oxide/MIL-101 hybrid composites (Ni--GO/MIL) were prepared to investigate their hydrogen storage behaviors. Ni--GO/MIL was synthesized by adding Ni--GO in situ during the synthesis of MIL-101 using a hydrothermal process, which was conducted by conventional convection heating with Cr(III) ion as a metal center and telephthalic acid as organic ligands. The crystalline structures and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The specific surface area and micropore volume were investigated by N2/77 K adsorption isotherms using the Brunauer-Emmett-Teller (BET) method and Dubinin-Radushkevic (D-R) equation, respectively. The hydrogen storage capacity was investigated by BEL-HP at 77 K and 1 bar. The obtained results show that Ni--GO/MIL presents new directions for achieving novel hybrid materials with higher hydrogen storage capacity.
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Directory of Open Access Journals (Sweden)
Mansur Ahmed
2008-01-01
Full Text Available Hydrogen peroxide oxidation of pentaamminecobalt(III complexes of α-hydroxy acids at 35°C in micellar medium has been attempted. In this reaction the rate of oxidation shows first order kinetics each in [cobalt(III] and [H2O2]. Hydrogen peroxide induced electron transfer in [(NH35 CoIII-L]2+ complexes of α-hydroxy acids readily yields 100% of cobalt(II with nearly 100% of C-C bond cleavage products suggesting that it behaves mainly as one equivalent oxidant in micellar medium. With unbound ligand also it behaves only as C-C cleavage agent rather than C-H cleavage agent. With increasing micellar concentration an increase in the rate is observed.
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Energy Technology Data Exchange (ETDEWEB)
Lee, Jihye; Jang, Ho Young; Jung, Insub; Yoon, Yeoheung; Jang, Heejeong; Lee, Hyoyoung; Park, Sungho [Sungkyunkwan Univ., Suwon (Korea, Republic of)
2014-07-15
Here, we present a facile method to synthesize Pt nanoparticles (NPs) and graphene composite materials (Pt/G) via vacuum filtration. Anodic aluminum oxide (AAO) templates were used to separate Pt/G composite and liquid phase. This method can be used to easily tune the mass ratio of Pt NPs and graphene. Pt NPs, graphene, and carbon nanotubes (CNTs) as building blocks were characterized by a variety of techniques such as scanning electron microscopy, UV-Vis spectroscopy, and Raman spectroscopy. We compared the electrocatalytic activities of Pt/G with Pt NP and CNT films (Pt/CNT) by cyclic voltammetry (CV), CO oxidation, and methanol oxidation. Pt/G was much more stable than pure Pt films. Also, Pt/G had better electrochemical activity, CO tolerance and methanol oxidation than Pt/CNT loaded with the same amount of Pt NPs due to the better dispersion of Pt NPs on graphene flakes without aggregation. We further synthesized Au Pt disk/G and Pt nanorods/G to determine if our synthetic method can be applied to other NP shapes such as nanodisks and nanorods, for further electrocatalysis studies.
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Fabrication of Te@Au core-shell hybrids for efficient ethanol oxidation
Jin, Huile; Wang, Demeng; Zhao, Yuewu; Zhou, Huan; Wang, Shun; Wang, Jichang
2012-10-01
Using Au nanoparticles to catalyze the oxidation of alcohols has garnered increasing attention due to its potential application in direct alcohol fuel cells. In this research Te@Au core-shell hybrids were fabricated for the catalytic oxidation of ethanol, where the preparation procedure involved the initial production of Te crystals with different microstructures and the subsequent utilization of the Te crystal as a template and reducing agent for the production of Te@Au hybrids. The as-prepared core-shell hybrids were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction techniques. Electrochemical measurements illustrate that the hybrids have great electrocatalytic activity and stability toward ethanol oxidation in alkaline media. The enhanced electrocatalytic property may be attributed to the cooperative effects between the metal and semiconductor and the presence of a large number of active sites on the hybrids surface.
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Horng, Rong-Fang; Chou, Huann-Ming; Lee, Chiou-Hwang; Tsai, Hsien-Te
This paper investigates experimentally, the transient characteristics of a small methanol reformer using partial oxidation (POX) and auto-thermal reforming (ATR) for fuel cell applications. The parameters varied were heating temperature, methanol supply rate, steady mode shifting temperature, O 2/C (O 2/CH 3OH) and S/C (H 2O/CH 3OH) molar ratios with the main aim of promoting a rapid response and a high flow rate of hydrogen. The experiments showed that a high steady mode shifting temperature resulted in a faster temperature rise at the catalyst outlet and vice versa and that a low steady mode shifting temperature resulted in a lower final hydrogen concentration. However, when the mode shifting temperature was too high, the hydrogen production response was not necessarily improved. It was subsequently shown that the optimum steady mode shifting temperature for this experimental set-up was approximately 75 °C. Further, the hydrogen concentration produced by the auto-thermal process was as high as 49.12% and the volume flow rate up to 23.0 L min -1 compared to 40.0% and 20.5 L min -1 produced by partial oxidation.
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Zhang, Ke; Xu, Hui; Yan, Bo; Wang, Jin; Gu, Zhulan; Du, Yukou
2017-12-01
This article reports a rapid synthetic method for the preparation of dendritic platinum-lead bimetallic catalysts by using an oil bath for 5 min in the presence of hexadecyltrimethylammonium chloride (CTAC) and ascorbic acid (AA). CTAC acts as a shape-direction agent, and AA acts as a reducing agent during the reaction process. A series of physical techniques are used to characterize the morphology, structure and electronic properties of the dendritic Pt/Pb nanoparticles, indicating the Pt/Pb dendrites are porous, highly alloying, and self-supported nanostructures. Various electrochemical techniques were also investigated the catalytic performance of the Pt/Pb catalysts toward the ethanol electrooxidation reaction. Cyclic voltammetry and chronoamperometry indicated that the synthesized dendritic Pt/Pb nanoparticles possessed much higher electrocatalytic performance than bulk Pt catalyst. This study may inspire the engineering of dendritic bimetallic catalysts, which are expected to have great potential applications in fuel cells.
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International Nuclear Information System (INIS)
Ensafi, Ali A.; Jafari-Asl, Mehdi; Nabiyan, Afshin; Rezaei, Behzad; Dinari, Mohammad
2016-01-01
New efficient hydrogen storage hybrids were fabricated based on hydrogen spillover mechanism, including chemisorptions and dissociation of H_2 on the surface of LDH (layered double hydroxides) and diffusion of H to rGO (reduced graphene oxide). The structures and compositions of all of the hybrids (LDHs/rGO) have been verified using different methods including transmission electron microscopy, X ray diffraction spectroscopy, infrared spectroscopy and Brunauer–Emmett–Teller analysis. Then, the abilities of the LDHs/rGOs, as hydrogen spillover, were investigated by electrochemical methods. In addition, the LDHs/rGOs were decorated with palladium, using redox replacement process, and their hydrogen spillover properties were studied. The results showed that the hydrogen adsorption/desorption kinetics, hydrogen storage capacities and stabilities of Pd"#LDH/rGOs are better than Pd/rGO. Finally presence of different polymers (synthesis with monomers, 4–aminophenol, 4–aminothiophenol, o-phenylenediamine and p-phenylenediamine) at the surface of the Pd#LDH/rGOs on hydrogen storage were studied. The results showed that presence of o-phenylenediamine and p-phenylenediamine improves the kinetics of the hydrogen adsorption/desorption and increase the capacity of the hydrogen storage. - Highlights: • Efficient hydrogen storage sorbents are introduced. • The sorbents are synthesized based on hybrids of layered double hydroxide. • The compositions of all of the hybrids are verified using different methods. • Pd nanoparticles modified nanohybrids are investigated for hydrogen storage. • Presence of different polymers beside the hydrogen sorbents are investigated.
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Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun
2018-01-31
The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.
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International Nuclear Information System (INIS)
Zheng Jie; Zhang Yaohua; Song Xubo; Li Xingguo
2011-01-01
Ceria nanoparticles with well defined facets are prepared in argon–hydrogen thermal plasma followed by controlled oxidation. With increasing hydrogen fraction in the plasma, a clear sphere-to-polyhedron shape transition is observed. The heat released during the hydrogenation of cerium, which significantly enhances the species mobility on the surface, favors the growth of well defined facets. The polyhedron ceria nanoparticles, though lower in specific surface area, exhibit superior catalytic performance for CO oxidation over the round particles, which is attributed to the higher density of the reactive {200} and {220} facets on the surface. The hydrogen mediated shape control mechanism provides new insights into the shape control of nanoparticles during thermal plasma processing.
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Energy Technology Data Exchange (ETDEWEB)
Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)
2006-07-01
The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.
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International Nuclear Information System (INIS)
Jiang, Liu-Ying; Lin, Xiao-Xiao; Wang, Ai-Jun; Yuan, Junhua; Feng, Jiu-Ju; Li, Xin-Sheng
2017-01-01
Highlights: • Uniform Pt 2.6 Co 1 nanoflowers were prepared by a simple solvothermal method. • Glucose and CTAC were used as the green reductant and structure director, respectively. • The architectures had the enlarged ECSA. • The architectures exhibited excellent catalytic performances for HER in acid and alkaline media. • The architectures showed highly catalytic performances for ORR in acid media. - Abstract: Herein, uniform Pt 2.6 Co 1 nanoflowers (NFs) were synthesized in oleylamine by a one-pot solvothermal method, using cetyltrimethylammonium chloride (CTAC) and glucose as the capping agent and green reducing agent. The samples were mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The architectures had larger electrochemically active surface area (ECSA) of 23.84 m 2 g −1 Pt than Pt 1.2 Co 1 nanocrystals (NCs, 14.96 m 2 g −1 Pt ), Pt 3.7 Co 1 NCs (16.96 m 2 g −1 Pt ) and commercial Pt black (20.35 m 2 g −1 Pt ). And the as-obtained Pt 2.6 Co 1 catalyst displayed superior catalytic performance and better durability for hydrogen evolution reaction (HER) as compared to Pt 1.2 Co 1 NCs, Pt 3.7 Co 1 NCs, commercial 50% Pt/C and Pt black catalysts in acid and alkaline media. Meanwhile, the electrocatalytic performance of Pt 2.6 Co 1 NFs for oxygen reduction reaction (ORR) is better in acid media as compared with that in alkaline media. It indicates the great potential applications of the as-prepared catalyst in fuel cells.
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International Nuclear Information System (INIS)
Hu Zhongai; Shang Xiuli; Yang Yuying; Kong Chao; Wu Hongying
2006-01-01
Polyaniline (PANI)/polysulfone (PSF) composite films with asymmetric porous structure were successfully prepared by electropolymerization. The back face (in contact with the electrode) of the freestanding composite film is green while the outer face is white. The chemical component and the morphology of the surfaces were characterized by FTIR spectra and scanning electron microscopy, respectively. It was shown that replicate films gave reproducible voltammetry in 0.5 M H 2 SO 4 . The influence of the electrolyte and the acidic concentration on the redox peak currents of polyaniline were investigated in detail. The composite film electrode showed good electrocatalytic activity for ascorbic acid, which the anodic overpotential was evidently reduced compared with that obtained at bare Pt electrode. The diffusion coefficient of ascorbic acid was 1.38 x 10 -6 cm 2 s -1
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Energy Technology Data Exchange (ETDEWEB)
Song, Hoon Sub [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Park, Moon Gyu [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of); Croiset, Eric, E-mail: ecroiset@uwaterloo.ca [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Chen, Zhongwei [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Nam, Sung Chan; Ryu, Ho-Jung [Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Yi, Kwang Bok, E-mail: cosy32@cnu.ac.kr [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of)
2013-09-01
Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H{sub 2}S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H{sub 2}S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H{sub 2}S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H{sub 2} and CO{sub 2} on H{sub 2}S adsorption was also investigated. The presence of hydrogen in the H{sub 2}S stream had a positive effect on the removal of H{sub 2}S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn{sup 2+}) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO{sub 2}) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H{sub 2}S and CO{sub 2}.
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Effect of nitrogen doping of graphene oxide on hydrogen and hydroxyl adsorption
Energy Technology Data Exchange (ETDEWEB)
Min, Byeong June; Jeong, Hae Kyung [Daegu University, Kyungsan (Korea, Republic of)
2014-05-15
We investigate how nitrogen-doping affects the hydrogen (H) and the hydroxyl (OH) adsorption on graphene oxide (GO) and on nitrogen-doped GO (NGO) via pseudopotential plane wave density functional calculations within the local spin density approximation. We find that the nitrogen doping brings about drastic changes in the hydrogen and the hydroxyl adsorption energetics, but its effects depend sensitively on the nitrogen configuration in NGO. The H and the OH adsorption energies are comparable only for pyrrolic NGO. In GO and quarternary NGO, the H adsorption energy is greater than the OH adsorption energy while the trend is reversed in pyridinic NGO. Also, the OH adsorption process is less affected by nitrogen-doping than the H adsorption is.
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Langmuir hydrogen dissociation approach in radiolabeling carbon nanotubes and graphene oxide
International Nuclear Information System (INIS)
Badun, Gennadii A.; Chernysheva, Maria G.; Eremina, Elena A.; Egorov, Alexander V.; Grigorieva, Anastasia V.
2016-01-01
Carbon-based nanomaterials have piqued the interest of several researchers. At the same time, radioactive labeling is a powerful tool for studying processes in different systems, including biological and organic; however, the introduction of radioactive isotopes into carbon-based nanomaterial remains a great challenge. We have used the Langmuir hydrogen dissociation method to introduce tritium in single-walled carbon nanotubes and graphene oxide. The technique allows us to achieve a specific radioactivity of 107 and 27 Ci/g for single-layer graphene oxide and single-walled carbon nanotubes, respectively. Based on the analysis of characteristic Raman modes at 1350 and 1580 cm -1 , a minimal amount of structural changes to the nanomaterials due to radiolabeling was observed. The availability of a simple, nondestructive, and economic technique for the introduction of radiolabels to single-walled carbon nanotubes and graphene oxide will ultimately expand the applicability of these materials.
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Langmuir hydrogen dissociation approach in radiolabeling carbon nanotubes and graphene oxide
Energy Technology Data Exchange (ETDEWEB)
Badun, Gennadii A.; Chernysheva, Maria G.; Eremina, Elena A.; Egorov, Alexander V. [Lomonosov Moscow State Univ. (Russian Federation). Dept. of Chemistry; Grigorieva, Anastasia V. [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Materials Science
2016-11-01
Carbon-based nanomaterials have piqued the interest of several researchers. At the same time, radioactive labeling is a powerful tool for studying processes in different systems, including biological and organic; however, the introduction of radioactive isotopes into carbon-based nanomaterial remains a great challenge. We have used the Langmuir hydrogen dissociation method to introduce tritium in single-walled carbon nanotubes and graphene oxide. The technique allows us to achieve a specific radioactivity of 107 and 27 Ci/g for single-layer graphene oxide and single-walled carbon nanotubes, respectively. Based on the analysis of characteristic Raman modes at 1350 and 1580 cm{sup -1}, a minimal amount of structural changes to the nanomaterials due to radiolabeling was observed. The availability of a simple, nondestructive, and economic technique for the introduction of radiolabels to single-walled carbon nanotubes and graphene oxide will ultimately expand the applicability of these materials.
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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)