Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

DEFF Research Database (Denmark)

Mysling, Simon; Salbo, Rune; Ploug, Michael

2014-01-01

Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

Electrochemical reduction of cerium oxide into metal

Energy Technology Data Exchange (ETDEWEB)

Claux, Benoit [CEA, Valduc, F-21120 Is-sur-Tille (France); Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France); Serp, Jerome, E-mail: jerome.serp@cea.f [CEA, Valduc, F-21120 Is-sur-Tille (France); Fouletier, Jacques [Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France)

2011-02-28

The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO{sub 2} reduction is considered in this study. Present work clarifies, by electro-analytical techniques, the reduction pathway leading to the metal. The reduction of CeO{sub 2} into metal was feasible via an indirect mechanism. Electrolyses on 10 g of CeO{sub 2} were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl{sub 2}-KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride.

Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

Energy Technology Data Exchange (ETDEWEB)

Domenech, Antonio, E-mail: antonio.domenech@uv.es [Departament de Quimica Analitica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain); Montoya, Noemi; Alarcon, Javier [Departament de Quimica Inorganica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain)

2011-08-01

Highlights: > Electrochemical characterization of Pr centers in praseodymia-doped zircon. > Study of the catalytic effect on the reduction of peroxide radical anion in nonaqueous solvents. > Assessment of non-uniform distribution of Pr centers in the zircon grains. - Abstract: The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4}; y + z = x; 0.02 < x < 0.10) specimens prepared via sol-gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.

Electrochemical carbon dioxide reduction on rough copper surfaces

NARCIS (Netherlands)

Kas, Recep

2016-01-01

Sustainable development and climate change is considered to be one of the top challenges of humanity. Electrochemical carbon dioxide (CO2) reduction to fuels or fuel precursor using renewable electricity is a very promising way to recycle CO2 and store the electricity. This would also provide

Surface-reconstructed Cu Electrode via a Facile Electrochemical Anodization-Reduction Process for Low Overpotential CO 2 reduction

KAUST Repository

Min, Shixiong

2017-03-21

A high-surface-area Cu electrode, fabricated by a simple electrochemical anodization-reduction method, exhibits high activity and selectivity for CO2 reduction at low overpotential in 0.1 M KHCO3 solution. A faradaic efficiency of 37% for HCOOH and 27% for CO production was achieved with the current density of 1.5 mA cm-2 at −0.64 V vs. RHE, much higher than that of polycrystalline Cu. The enhanced catalytic performance is a result of the formation of the high electrochemical active surface area and high density of preferred low-index facets.

Pyro-Electrochemical Reduction of a Mixture of Rare Earth Oxides and NiO in LiCl molten Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun [Department of Chemical Engineering, Chungbuk National University, Cheongju (Korea, Republic of)

2017-06-15

An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

Surface-reconstructed Cu Electrode via a Facile Electrochemical Anodization-Reduction Process for Low Overpotential CO 2 reduction

KAUST Repository

Min, Shixiong; Yang, Xiulin; Lu, Ang-Yu; Tseng, Chien-Chih; Hedhili, Mohamed N.; Lai, Zhiping; Li, Lain-Jong; Huang, Kuo-Wei

2017-01-01

A high-surface-area Cu electrode, fabricated by a simple electrochemical anodization-reduction method, exhibits high activity and selectivity for CO2 reduction at low overpotential in 0.1 M KHCO3 solution. A faradaic efficiency of 37% for HCOOH

The electrochemical reduction of biotin (vitamin B7) and conversion into its ester

International Nuclear Information System (INIS)

Lauw, Sherman J.L.; Ganguly, Rakesh; Webster, Richard D.

2013-01-01

Highlights: •Biotin can be reduced electrochemically, by one-electron, at a platinum electrode. •The reduction likely follows a direct discharge mechanism of the carboxyl group. •Electrochemically generated biotin carboxylate was reacted with iodomethane (91%). •ATR–FTIR characterization of biotin, its carboxylate anion, and its methyl ester. -- Abstract: An electrochemical study on biotin (vitamin B7), performed in aprotic solvents and at a platinum electrode, revealed that at approximately E f 0 =−1.6to−1.8 vs. (Fc/Fc + )/V (E f 0 =formal reduction potential and Fc=ferrocene), biotin is reduced by one-electron to form its carboxylate anion and dihydrogen via a direct discharge of the carboxylic acid at the platinum surface. The electrochemical reduction process appeared to be chemically reversible on the time-frame of cyclic voltammetry (CV) (t ≤ s), but not over the extended period of controlled potential electrolysis (CPE) (t ≥ min) where the conversion of biotin into its carboxylate anion was found to be chemically irreversible. A strategy to functionalize biotin's carboxyl group was established by performing a bulk reductive electrolysis, and then reacting the electrochemically generated carboxylate anion with iodomethane to afford biotin methyl ester in excellent yield (91%). Attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy was successful in identifying several distinct and characteristic carbonyl absorbance peaks associated with the analogous forms of biotin available before electrolysis, after electrolysis, and after methylation

Enhancement of Capacitive Performance in Titania Nanotubes Modified by an Electrochemical Reduction Method

Directory of Open Access Journals (Sweden)

Nurul Asma Samsudin

2018-01-01

Full Text Available Highly ordered titania nanotubes (TNTs were synthesised by an electrochemical anodization method for supercapacitor applications. However, the capacitive performance of the TNTs was relatively low and comparable to the conventional capacitor. Therefore, in order to improve the capacitive performance of the TNTs, a fast and facile electrochemical reduction method was applied to modify the TNTs (R-TNTs by introducing oxygen vacancies into the lattice. X-ray photoelectron spectroscopy (XPS data confirmed the presence of oxygen vacancies in the R-TNTs lattice upon the reduction of Ti4+ to Ti3+. Electrochemical reduction parameters such as applied voltage and reduction time were varied to optimize the best conditions for the modification process. The electrochemical performance of the samples was analyzed in a three-electrode configuration cell. The cyclic voltammogram recorded at 200 mV s−1 showed a perfect square-shaped voltammogram indicating the excellent electrochemical performance of R-TNTs prepared at 5 V for 30 s. The total area of the R-TNTs voltammogram was 3 times larger than the unmodified TNTs. A specific capacitance of 11.12 mF cm−2 at a current density of 20 μA cm−2 was obtained from constant current charge-discharge measurements, which was approximately 57 times higher than that of unmodified TNTs. R-TNTs also displayed outstanding cycle stability with 99% capacity retention after 1000 cycles.

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

Science.gov (United States)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes

Energy Technology Data Exchange (ETDEWEB)

Arellano-González, Miguel Ángel; González, Ignacio [Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Química, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico D.F. (Mexico); Texier, Anne-Claire, E-mail: actx@xanum.uam.mx [Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Biotecnología, Av. San Rafael Atlixco No. 186, Col. Vicentina, 09340 Mexico, D.F. (Mexico)

2016-08-15

Highlights: • Dechlorination of 2-chlorophenol to phenol was 100% efficient on Pd-Ni/Ti electrode. • An ECCOCEL reactor was efficient and selective to obtain phenol from 2-chlorophenol. • Phenol was totally mineralized in a coupled denitrifying biorreactor. • Global time of 2-chlorophenol mineralization in the combined system was 7.5 h. - Abstract: In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of −0.40 V vs Ag/AgCl{sub (s)}/KCl{sub (sat)}, achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO{sub 2} and N{sub 2} as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5 h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes.

Electrochemical characterization of glassy carbon electrode modified with 1,10-phenanthroline groups by two pathways: reduction of the corresponding diazonium ions and reduction of phenanthroline

International Nuclear Information System (INIS)

Shul, Galyna; Weissmann, Martin; Bélanger, Daniel

2015-01-01

The electrochemical behaviour of 1,10-phenanthroline molecules immobilized on a glassy carbon electrode surface by electrochemical reduction of the corresponding in-situ generated diazonium ions in an aqueous solution was investigated. Firstly, the derivatization of glassy carbon electrode was confirmed by the presence of the barrier effect in the solution of a redox probe. Secondly, atomic force microscopy measurements revealed the deposition of thin (< 2 nm) uniform 1,10-phenanthroline film on the surface of pyrolyzed photoresist film electrode. Thirdly, the initially electrochemically inactive grafted organic film became electroactive after being subjected to electrochemical reduction and oxidation. Fourthly, the electrochemical behaviour of phenanthroline modified electrode by electrochemical reduction of the corresponding diazonium cations was found to be similar to that of electrode modified by electrochemical reduction of only phenanthroline dissolved in an aqueous acid solution. Finally, cyclic voltammetry experiments using various methyl substituted phenanthroline derivatives provided direct evidence that functional groups responsible for the film electroactivity are formed at 5 or/and 6 positions of grafted phenanthroline molecules. On the other hand, a phenanthroline derivative having these positions blocked by methyl groups can also display electroactivity with position 7 being most likely involved in the observed redox process

Electrochemical reduction of NO{sub x}

Energy Technology Data Exchange (ETDEWEB)

Lund Traulsen, M.

2012-04-15

NO and NO{sub 2} (collectively referred to as NO{sub x}) are air pollutants, and the largest single contributor to NO{sub x} pollution is automotive exhaust. This study investigates electrochemical deNO{sub x}, a technology which aims to remove NO{sub x} from automotive diesel exhaust by electrochemical reduction of NO{sub x} to N{sub 2} and O{sub 2}. The focus in this study is on improving the activity and selectivity of solid oxide electrodes for electrochemical deNO{sub x} by addition of NO{sub x} storage compounds to the electrodes. Two different composite electrodes, La{sub 0.85}Sr{sub 0.15}MnO{sub 3-{delta}-}Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95} (LSM15-CGO10) and La{sub 0.85}Sr{sub 0.15}FeO{sub 3-{delta}-}Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95} (LSF15-CGO10), have been investigated in combination with three different NO{sub x} storage compounds: BaO, K{sub 2}O and MnO{sub x}. The main focus in the investigation has been on conversion measurements and electrochemical characterization, the latter by means of electrochemical impedance spectroscopy and cyclic voltammetry. In addition, infrared spectroscopy has been performed to study how NO{sub x} adsorption on the electrodes is affected by the presence of the aforementioned NO{sub x} storage compounds. Furthermore, non-tested and tested electrode microstructures have been thoroughly evaluated by scanning electron microscopy. The studies reveal addition of MnO{sub x} or K{sub 2}O to the electrodes cause severe degradation problems, and addition of these compounds is thus unsuitable for electrode improvement. In contrast, addition of BaO to LSM15-CGO10 electrodes is shown to have a very positive impact on the NO{sub x} conversion. The increased NO{sub x} conversion, following the BaO addition, is attributed to a combination of 1) a decreased electrode polarisation resistance and 2) an altered NO{sub x} adsorption. The NO{sub x} conversion is observed to increase strongly with polarisation, and during 9 V polarisation of an

Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

Science.gov (United States)

Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

2015-10-07

The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied.

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

International Nuclear Information System (INIS)

Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

2006-01-01

We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

Energy Technology Data Exchange (ETDEWEB)

Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

2006-11-12

We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

Electrochemical Reduction of Zinc Phosphate

International Nuclear Information System (INIS)

Kim, Chang Hwan; Lee, Jung Hyun; Shin, Woon Sup

2010-01-01

We demonstrated first that the electrochemical reduction of zinc phosphate in neutral phosphate buffer is possible and potentially applicable to bio-compatible rechargeable battery. The actual redox component is Zn(s)/Zn phosphate(s) and the future research about the control of crystal formation for the better cyclability is required. In lead-acid battery, the electrochemical redox reaction of Pb (s) /PbSO 4(s) is used by reducing Pb(II) and oxidizing Pb(0) in sulfate rich solution. Since both reduced form and oxidized form are insoluble, they cannot diffuse to the opposite electrodes and react. It is a very common strategy to make a stable battery electrode that a metal element is reduced and oxidized in solution containing an abundance of anion readily precipitating with the metal ion. For the application of this strategy to construction of rechargeable battery using bio-compatible electrode materials and electrolytes, the use of phosphate ion can be considered as anion readily precipitating with metal ions. If phosphate buffer with neutral pH is used as electrolyte, the better bio-compatibility will be achieved than most of rechargeable battery using strong acid, strong base or organic solvent as electrolyte solution. There are many metal ions readily precipitating with phos-phate ion, and zinc is one of them

Electrochemical reduction of oxygen catalyzed by a wide range of bacteria including Gram-positive

Energy Technology Data Exchange (ETDEWEB)

Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France); Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Delia, Marie-Line; Bergel, Alain [Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Roques, Christine; Berge, Mathieu [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France)

2010-04-15

Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research. (author)

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

Science.gov (United States)

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Electrochemical reduction of sulfur dioxide in sulfolane

Energy Technology Data Exchange (ETDEWEB)

Vorob' ev, A.S.; Gavrilova, A.A.; Kolosnitsyn, V.S.; Nikitin, Yu.E.

1985-09-01

Solutions of sulfur dioxide in aproptic media are promising electrolyte oxidizing agents for chemical current sources with anodes of active metals. This work describes the electrochemical reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte which was investigated by the methods of voltamperometry and chronopotentiometry. The dependence of the current of the cathodic peak on the concentration of the supporting electrolyte salts, sulfur dioxide and water, was studied. On the basis of the data obtained, a hypothesis was advanced on the nature of the limiting step. The investigation showed that at low polarizing current densities, a substantial influence on the reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte is exerted by blockage of the electrode surface by sparingly soluble reaction products.

Electrochemical reduction of dilute chromate solutions on carbon felt electrodes

NARCIS (Netherlands)

Frenzel, Ines; Frenzel, I.; Holdik, Hans; Barmashenko, Vladimir; Stamatialis, Dimitrios; Wessling, Matthias

2006-01-01

Carbon felt is a potential material for electrochemical reduction of chromates. Very dilute solutions may be efficiently treated due to its large specific surface area and high porosity. In this work, the up-scaling of this technology is investigated using a new type of separated cell and

Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

DEFF Research Database (Denmark)

Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus

2007-01-01

with participation of H+ or electrochemically produced hydrogen. When added, methane partially suppresses the electrochemical reduction of NO. Methane outlet concentration monitoring has shown the CH4 participation in the chemical catalytic reduction, i.e., methane co-adsorption with NO inhibited the electrochemical...... NO reduction and introduced a dominant chemical path of the NO reduction. The products of the NO reduction with methane were N2, C2H4, and water. The catalytic NO reduction by methane was promoted when the catalyst was negatively polarized (−0.2 V). Repeated negative polarization of the catalyst increased...

Densely Packed, Ultra Small SnO Nanoparticles for Enhanced Activity and Selectivity in Electrochemical CO2 Reduction.

Science.gov (United States)

Gu, Jun; Héroguel, Florent; Luterbacher, Jeremy; Hu, Xile

2018-03-05

Controlling the selectivity in electrochemical CO 2 reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non-precious catalyst for CO 2 electroreduction, most Sn-based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO 2 reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra-small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical reduction of metal ions in dilute solution using hydrogen

NARCIS (Netherlands)

Portegies Zwart, I.; Wijnbelt, E.C.W.; Janssen, L.J.J.

1995-01-01

Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. A new electrochemical cell has been introduced. This cell - a GBC-cell - is a combination of a gasdiffusion electrode in direct contact with a packed bed of carbon particles.

The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

International Nuclear Information System (INIS)

Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

2016-01-01

We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li2O Salt

International Nuclear Information System (INIS)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon; Sohn, Jung Min

2016-01-01

In this study, the electrochemical reduction of RE 2 O 3 (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li 2 O. The electrochemical reduction behavior of the mixed RE 2 O 3 -NiO oxide has been investigated and the reduction path of RE 2 O 3 has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl 3 in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li 2 O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE 2 O 3 on the produced Ni to form intermetallic RENi 5 . The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd 2 O 3 was successfully converted to the metal in the presence of NiO.

Electrochemical reduction of O2 and NO on Ni, Pt and Au

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2008-01-01

The electrochemical reduction of oxygen and nitric oxide was studied using cyclic voltammetry on point electrodes of Ni, Pt and Au in the temperature range 400-600 degrees C. All the materials were more active towards the reduction of oxygen than towards the reduction of nitric oxide, except Pt...... the reduction of oxygen. This implies that the triple-phase boundary (3PB) catalyses the reduction of oxygen but not the reduction of nitric oxide, as Au is a catalytic inactive metal. All the materials were more active towards oxidation than towards reduction that is evolution of oxygen or oxidation of nitric...

Perchlorate reduction during electrochemically induced pitting corrosion of zero-valent titanium (ZVT)

Energy Technology Data Exchange (ETDEWEB)

Lee, Chunwoo, E-mail: clee@doosanhydro.com [Department of Research and Development, Doosan Hydro Technology, Inc, Tampa, FL 33619 (United States); Batchelor, Bill [Zachry Department of Civil Engineering, Texas A and M University, College Station, TX 77840 (United States); Park, Sung Hyuk [Environmental and Engineering Research Team, GS Engineering and Construction Research Institute, Youngin, Kyunggi-do 449-831 (Korea, Republic of); Han, Dong Suk; Abdel-Wahab, Ahmed [Chemical Engineering Program, Texas A and M University at Qatar, Education City, Doha, PO Box 23874 (Qatar); Kramer, Timothy A.

2011-12-15

Highlights: Black-Right-Pointing-Pointer ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. Black-Right-Pointing-Pointer Perchlorate is effectively reduced to chloride by soluble titanium species. Black-Right-Pointing-Pointer Solution pH and surface area of ZVT showed negligible effects on rates of perchlorate reduction. - Abstract: Zero-valent metals and ionic metal species are a popular reagent for the abatement of contaminants in drinking water and groundwater and perchlorate is a contaminant of increasing concern. However, perchlorate degradation using commonly used reductants such as zero-valent metals and soluble reduced metal species is kinetically limited. Titanium in the zero-valent and soluble states has a high thermodynamic potential to reduce perchlorate. Here we show that perchlorate is effectively reduced to chloride by soluble titanium species in a system where the surface oxide film is removed from ZVT and ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. The pitting potential of ZVT was measured as 12.77 {+-} 0.04 V (SHE) for a 100 mM solution of perchlorate. The rate of perchlorate reduction was independent of the imposed potential as long as the potential was maintained above the pitting potential, but it was proportional to the applied current. Solution pH and surface area of ZVT electrodes showed negligible effects on rates of perchlorate reduction. Although perchlorate is effectively reduced during electrochemically induced corrosion of ZVT, this process may not be immediately applicable to perchlorate treatment due to the high potentials needed to produce active reductants, the amount of titanium consumed, the inhibition of perchlorate removal by chloride, and oxidation of chloride to chlorine.

Perchlorate reduction during electrochemically induced pitting corrosion of zero-valent titanium (ZVT)

International Nuclear Information System (INIS)

Lee, Chunwoo; Batchelor, Bill; Park, Sung Hyuk; Han, Dong Suk; Abdel-Wahab, Ahmed; Kramer, Timothy A.

2011-01-01

Highlights: ► ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. ► Perchlorate is effectively reduced to chloride by soluble titanium species. ► Solution pH and surface area of ZVT showed negligible effects on rates of perchlorate reduction. - Abstract: Zero-valent metals and ionic metal species are a popular reagent for the abatement of contaminants in drinking water and groundwater and perchlorate is a contaminant of increasing concern. However, perchlorate degradation using commonly used reductants such as zero-valent metals and soluble reduced metal species is kinetically limited. Titanium in the zero-valent and soluble states has a high thermodynamic potential to reduce perchlorate. Here we show that perchlorate is effectively reduced to chloride by soluble titanium species in a system where the surface oxide film is removed from ZVT and ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. The pitting potential of ZVT was measured as 12.77 ± 0.04 V (SHE) for a 100 mM solution of perchlorate. The rate of perchlorate reduction was independent of the imposed potential as long as the potential was maintained above the pitting potential, but it was proportional to the applied current. Solution pH and surface area of ZVT electrodes showed negligible effects on rates of perchlorate reduction. Although perchlorate is effectively reduced during electrochemically induced corrosion of ZVT, this process may not be immediately applicable to perchlorate treatment due to the high potentials needed to produce active reductants, the amount of titanium consumed, the inhibition of perchlorate removal by chloride, and oxidation of chloride to chlorine.

Electrochemical Reduction of Isatin-monohydrazone on Mercury Electrode

Directory of Open Access Journals (Sweden)

Ender Biçer

2015-07-01

Full Text Available Electrochemical behaviour of isatin monohydrazone (IM on a hanging mercury drop electrode in the Britton-Robinson (B-R buffer solution of pH = 2.00–9.00 has been investigated using square-wave voltammetry (SWV and cyclic voltammetry (CV techniques. In the pH range of 2.00–5.00, the voltammogram of IM exhibited a single cathodic irreversible peak. When the pH value exceeds 5.00, a new cathodic irreversible peak was also seen. According to the voltammetric data, a plausible electrode reaction mechanism of IM was proposed. The first reduction peak of IM is resulted from the reduction of =N–NH– group with consumption of 2e–/2H+. Also, its second cathodic peak is formed by the participation of 2e–/2H+ for the reduction of –N=N– group on its tautomeric form.

Electrochemical promotion of NO reduction by hydrogen on a platinum/polybenzimidazole catalyst

DEFF Research Database (Denmark)

Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm

2003-01-01

The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference and...... at the negative polarization can be attributed to the electrochemical production of the promoters. At low gas flow rates, a charge-induced change of the strength of chemisorptive bonds can take place.......The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference...... and counter gas at the other electrode. Products of NO reduction (N-2 and H2O) were analyzed by an on-line mass spectrometer. At high NO+H-2+Ar flow rate (17 mL/min; 17 and 354 mL/min, respectively, at atmospheric pressure) the maximum rate enhancement ratio was 4.65. At low NO+H-2+Ar flow rate (17 mL/min; 17...

Electrochemical reduction of hexavalent chromium in ground water

Energy Technology Data Exchange (ETDEWEB)

Bansal, S. [Lawrence Livermore National Lab., CA (United States)

1994-12-01

Electrochemical reduction of hexavalent chromium (Cr{sup +6}) to its trivalent state (Cr{sup +3}) is showing promising results in treating ground water at Lawrence Livermore National Laboratory`s (LLNL`s) Main Site. An electrolytic cell using stainless-steel and brass electrodes has been found to offer the most efficient reduction while yielding the least amount of precipitate. Trials have successfully lowered concentrations of Cr{sup +6} to below 11 parts per billion (micrograms/liter), the California state standard. We ran several trials to determine optimal voltage for running the cell; each trial consisted of applying a voltage between 6V and 48V for ten minutes through samples obtained at Treatment Facility C(TFC). No conclusive data has been obtained yet.

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction

International Nuclear Information System (INIS)

Lemaire, M.

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V SHE and between 0,5 V SHE and 1 V SHE . The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V SHE , products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

Science.gov (United States)

Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

2017-05-09

An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of composition of the micro porous layer and the substrate on performance in the electrochemical reduction of CO2 to CO

Science.gov (United States)

Kim, Byoungsu; Hillman, Febrian; Ariyoshi, Miho; Fujikawa, Shigenori; Kenis, Paul J. A.

2016-04-01

With the development of better catalysts, mass transport limitations are becoming a challenge to high throughput electrochemical reduction of CO2 to CO. In contrast to optimization of electrodes for fuel cells, optimization of gas diffusion electrodes (GDE) - consisting of a carbon fiber substrate (CFS), a micro porous layer (MPL), and a catalyst layer (CL) - for CO2 reduction has not received a lot of attention. Here, we studied the effect of the MPL and CFS composition on cathode performance in electroreduction of CO2 to CO. In a flow reactor, optimized GDEs exhibited a higher partial current density for CO production than Sigracet 35BC, a commercially available GDE. By performing electrochemical impedance spectroscopy in a CO2 flow reactor we determined that a loading of 20 wt% PTFE in the MPL resulted in the best performance. We also investigated the influence of the thickness and wet proof level of CFS with two different feeds, 100% CO2 and the mixture of 50% CO2 and N2, determining that thinner and lower wet proofing of the CFS yields better cathode performance than when using a thicker and higher wet proof level of CFS.

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li{sub 2}O Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon [Chungbook National University, Chungju (Korea, Republic of); Sohn, Jung Min [Chonbuk National University, Jeonju (Korea, Republic of)

2016-05-15

In this study, the electrochemical reduction of RE{sub 2}O{sub 3} (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li{sub 2}O. The electrochemical reduction behavior of the mixed RE{sub 2}O{sub 3}-NiO oxide has been investigated and the reduction path of RE{sub 2}O{sub 3} has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl{sub 3} in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li{sub 2}O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE{sub 2}O{sub 3} on the produced Ni to form intermetallic RENi{sub 5}. The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd{sub 2}O{sub 3} was successfully converted to the metal in the presence of NiO.

Electrochemical Reduction of Oxygen and Nitric Oxide at Low Temperature on La1−xSrxFeO3−δ Cathodes

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2014-01-01

A series of six strontium-substituted lanthanum ferrites (La1-xSrxFeO3-delta, x = 0.00, 0.05, 0.15, 0.25, 0.35, and 0.50) were synthesized using the glycine-nitrate process and evaluated as cathodes for the electrochemical reduction of oxygen and nitric oxide in the temperature range 200 to 400...... degrees C, using cone-shaped electrodes and cyclic voltammetry. It was shown that the ferrites had a higher activity towards the electrochemical reduction of nitric oxide than towards the electrochemical reduction of oxygen, in the investigated temperature range. The highest activity towards...... the electrochemical reduction of nitric oxide was found for La0.95Sr0.05FeO3-delta at 400 degrees C. This compound also showed the highest activity towards the electrochemical reduction of oxygen at 400 degrees C. The highest apparent selectivity was found for the compound LaFeO3 at 200 degrees C. The materials...

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid

International Nuclear Information System (INIS)

Lemaire, M.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V S HE and 0.3 V S HE and O.5 V S HE and 1 V S HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V S HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Partial-Order Reduction for GPU Model Checking

NARCIS (Netherlands)

Neele, T.; Wijs, A.; Bosnacki, D.; van de Pol, Jan Cornelis; Artho, C; Legay, A.; Peled, D.

2016-01-01

Model checking using GPUs has seen increased popularity over the last years. Because GPUs have a limited amount of memory, only small to medium-sized systems can be verified. For on-the-fly explicit-state model checking, we improve memory efficiency by applying partial-order reduction. We propose

Electrochemical reduction behavior of simplified simulants of vitrified radioactive waste in molten CaCl2

Science.gov (United States)

Katasho, Yumi; Yasuda, Kouji; Nohira, Toshiyuki

2018-05-01

The electrochemical reduction of two types of simplified simulants of vitrified radioactive waste, simulant 1 (glass component only: SiO2, B2O3, Na2O, Al2O3, CaO, Li2O, and ZnO) and simulant 2 (also containing long-lived fission product oxides, ZrO2, Cs2O, PdO, and SeO2), was investigated in molten CaCl2 at 1103 K. The behavior of each element was predicted from the potential-pO2- diagram constructed from thermodynamic data. After the immersion of simulant 1 into molten CaCl2 without electrolysis, the dissolution of Na, Li, and Cs was confirmed by inductively coupled plasma atomic emission spectrometry and mass spectrometry analysis of the samples. The scanning electron microscopy/energy dispersive X-ray and X-ray diffraction analyses of simulants 1 and 2 electrolyzed at 0.9 V vs. Ca2+/Ca confirmed that most of SiO2 had been reduced to Si. After the electrolysis of simulants 1 and 2, Al, Zr, and Pd remained in the solid phase. In addition, SeO2 was found to remain partially in the solid phase and partially evaporate, although a small quantity dissolved into the molten salt.

Electrochemical Reduction of Quinones in Different Media: A Review

Directory of Open Access Journals (Sweden)

Partha Sarathi Guin

2011-01-01

Full Text Available The electron transfer reactions involving quinones, hydroquinones, and catechols are very important in many areas of chemistry, especially in biological systems. The therapeutic efficiency as well as toxicity of anthracycline anticancer drugs, a class of anthraquinones, is governed by their electrochemical properties. Other quinones serve as important functional moiety in various biological systems like electron-proton carriers in the respiratory chain and their involvement in photosynthetic electron flow systems. The present paper summarizes literatures on the reduction of quinones in different solvents under various conditions using different electrochemical methods. The influence of different reaction conditions including pH of the media, nature of supporting electrolytes, nature of other additives, intramolecular or intermolecular hydrogen bonding, ion pair formation, polarity of the solvents, stabilization of the semiquinone and quinone dianion, catalytic property, and adsorption at the electrode surface, are discussed and relationships between reaction conditions and products formed have been presented.

Small-angle neutron scattering and cyclic voltammetry study on electrochemically oxidized and reduced pyrolytic carbon

International Nuclear Information System (INIS)

Braun, A.; Kohlbrecher, J.; Baertsch, M.; Schnyder, B.; Koetz, R.; Haas, O.; Wokaun, A.

2004-01-01

The electrochemical double layer capacitance and internal surface area of a pyrolytic carbon material after electrochemical oxidation and subsequent reduction was studied with cyclic voltammetry and small-angle neutron scattering. Oxidation yields an enhanced internal surface area (activation), and subsequent reduction causes a decrease of this internal surface area. The change of the Porod constant, as obtained from small-angle neutron scattering, reveals that the decrease in internal surface area is not caused merely by a closing or narrowing of the pores, but by a partial collapse of the pore network

Perturbed Partial Cavity Drag Reduction at High Reynolds Numbers

Science.gov (United States)

Makiharju, Simo; Elbing, Brian; Wiggins, Andrew; Dowling, David; Perlin, Marc; Ceccio, Steven

2010-11-01

Ventilated partial cavities were investigated at Reynolds numbers to 80 million. These cavities could be suitable for friction drag reduction on ocean going vessels and thereby lead to environmental and economical benefits. The test model was a 3.05 m wide by 12.9 m long flat plate, with a 0.18 m backward-facing step and a cavity-terminating beach, which had an adjustable slope, tilt and height. The step and beach trapped a ventilated partial cavity over the longitudinal mid-section of the model. Large-scale flow perturbations, mimicking the effect of ambient ocean waves were investigated. For the conditions tested a cavity could be maintained under perturbed flow conditions when the gas flux supplied was greater than the minimum required to maintain a cavity under steady conditions, with larger perturbations requiring more excess gas flux to maintain the cavity. High-speed video was used to observe the unsteady three dimensional cavity closure, the overall cavity shape, and the cavity oscillations. Cavities with friction drag reduction exceeding 95% were attained at optimal conditions. A simplified energy cost-benefit analysis of partial cavity drag reduction was also performed. The results suggest that PCDR could potentially lead to energy savings.

Spinels as cathodes for the electrochemical reduction of O2 and NO

DEFF Research Database (Denmark)

Simonsen, Vibe Louise Ernlund; Find, D.; Lilliedal, M.

2007-01-01

the largest difference in activity between reduction of oxygen and the reduction of nitric oxide, the activity being highest for the reduction of nitric oxide. The material is probably not stable when polarised cathodically. However it seems that the electrode material can be regenerated upon oxidation. NiFe2......Spinels were synthesised and investigated as electro-catalyst for the electrochemical reduction of oxygen and nitric oxide using cyclic voltammetry and cone shaped electrodes. The following four spinels were investigated; CoFe2O4, NiFe2O4, CuFe2O4 and Co3O4. The composition CuFe2O4 revealed......O4 is also more active for the reduction of nitric oxide than for the reduction of oxygen, whereas the cobalt containing spinels have a higher activity for the reduction of oxygen than for the reduction of nitric oxide....

Improvement on electrochemical performance by partial replacement of Ru@Pt core-shell nanocatalyst by temperature modification

International Nuclear Information System (INIS)

Chang, Chih-Juei; Lin, Liang-You; Tseng, Fan-Gang

2014-01-01

In this paper, the homemade open-loop reduction system (OLRS), and redox transmetalation method were utilized to produce the core-shell Ru (ruthenium)/Pt (platinum) catalysts on the carbon cloth (CC) for direct methanol fuel cell (DMFC) application. By adjusting pH value and heating to proper temperature of the ionized reduction environment, Pt 4+ can be first converted into Pt 2+ to allow partial Ru replacement with Pt by redox transmetalation and produce Ru@Pt core-shell nanostructures[1]. And we change the reduction temperature to see how it affects the efficiency of the DMFC. The scanning electron microscopic (SEM) top-view micrographs showing that the apparent Ru@Pt nanoparticles successfully deposited on both the inner and outer surfaces of the hydrophilically-treated CC. At high SEM magnification, the small size and high-density distribution of the Ru@Pt nanoparticles were clearly observed on the hydrophilically-treated CC, and much more Pt@Ru catalyst deposit on the CC surface with the sample of 80 °C. The electrosorption charges of hydrogen ion (Q H ) and the peak current density (I P ) of the samples in the cyclic voltammetry (CV) curves. The magnitude of peak current density is positive correlation to the temperature. However, the CO tolerance, indicated that the better CO tolerance contributed to the less Pt replace on Ru cluster, which allow the Ru oxidizing CO to CO 2 efficiently, is negative correlation-- to the temperature. The sample of 50 °C shows the better combination catalyst efficiency between the CO tolerance and the electrochemical performance

Formation of Hydrogen Peroxide by Electrochemical Reduction of Molecular Oxygen using Luminol Chemiluminescence

International Nuclear Information System (INIS)

Rana, Sohail

2005-01-01

Formation of hydrogen peroxide by electrochemical reduction of molecular oxygen was examined by measuring luminol chemiluminescence and absorption spectrum using flow-injection method. Ferryl porphyrin is widely accepted as responsible species to stimulate the emission in hydrogen peroxide/ iron porphyrin/ luminol system. Emission was observed under cathodic potentials (0.05V at pH2.0 and -0.3V at pH11.0) by the electrochemical reduction of aerated electrolytes solution but emission was observed at anodic potentials. Iron porphyrin solution was added at down stream of the working electrode and was essential for the emission. Removal of the dissolved molecular oxygen resulted in the decrease of emission intensity by more than 70%. In order to examine the life time of reduced active species, delay tubes were introduced between working electrode Fe TMPyP inlet. Experimental results suggested the active species were stable for quite a long period. The emission was quenched considerably (>90%) when hydroperoxy was added at the down stream of working electrode whereas the Superoxide dismutase (SOD) had little effect and mannitol had no effect. The spectra at reduction potential under aerated condition were shifted to the longer wavelength (>430nm) compared to the original spectrum of Fe TMPyP (422nm), indicating that the ferryl species were mixed to some extent. These observations lead to the conclusion that hydrogen peroxide was produced first by electrochemical reduction of molecular oxygen which then converted Fe TMPyP into O=FeTMPyP to activate luminol. Comparing emission intensities with the reference experiments, the current efficiencies for the formation of hydrogen peroxide were estimated as about 30-65% in all over the pH range used. (author)

Influence of BaO in perovskite electrodes for the electrochemical reduction of NOx

DEFF Research Database (Denmark)

Simonsen, Vibe Louise Ernlund; Johnsen, M.M.; Kammer Hansen, Kent

2007-01-01

Using the point electrode method, the effect of BaO on electrochemical reduction of NO (x) was investigated using the perovskites La0.85Sr0.15MnO3 (LSM15) and La0.85Sr0.15CoO3 (LSCo15) as electrode materials. The experiments were carried out in the temperature range 400-600 degrees C in 1% NO and...... favored oxygen reduction compared to reduction of nitric oxide. The LSCO15 electrode containing BaO reacted to form a K2NiF4-structure and was not tested further....

Electrochemical co-reduction synthesis of graphene/nano-gold composites and its application to electrochemical glucose biosensor

International Nuclear Information System (INIS)

Wang, Xiaolin; Zhang, Xiaoli

2013-01-01

Graphical abstract: - Highlights: • Graphene/nano-Au composite was synthesized by electrochemical co-reduction method in one step. • Glucose oxidase achieves direct electrochemistry on the graphene/nano-Au composite film. • The glucose biosensor shows a high sensitivity of 56.93 μA mM −1 cm −2 toward glucose. • Glucose was detected with a wide linear range and low detection limit. - Abstract: A simple, green and controllable approach was employed for electrochemical synthesize of the graphene/nano-Au composites. The process was that graphene oxide and HAuCl 4 was electrochemically co-reduced onto the glassy carbon electrode (GCE) by cyclic voltammetry in one step. The obtained graphene/nano-Au/GCE exhibited high electrocatalytic activity toward H 2 O 2 , which resulted in a remarkable decrease in the overpotential of H 2 O 2 electrochemical oxidation compared with bare GCE. Such electrocatalytic behavior of the graphene/nano-Au/GCE permitted effective low-potential amperometric biosensing of glucose via the incorporation of glucose oxidase (GOD) with graphene/nano-Au. An obvious advantage of this enzyme electrode (graphene/nano-Au/GOD/GCE) was that the graphene/nano-Au nanocomposites provided a favorable microenvironment for GOD and facilitated the electron transfer between the active center of GOD and electrode. The immobilized GOD showed a direct, reversible redox reaction. Furthermore, the graphene/nano-Au/GOD/GCE was used as a glucose biosensor, displaying a low detection limit of 17 μM (S/N = 3), a high sensitivity of 56.93 μA mM −1 cm −2 , acceptable reproducibility, very good stability, selectivity and anti-interference ability

Thickness- and Particle-Size-Dependent Electrochemical Reduction of Carbon Dioxide on Thin-Layer Porous Silver Electrodes.

Science.gov (United States)

Zhang, Lin; Wang, Zhiyong; Mehio, Nada; Jin, Xianbo; Dai, Sheng

2016-03-08

The electrochemical reduction of CO2 can not only convert it back into fuels, but is also an efficient manner to store forms of renewable energy. Catalysis with silver is a possible technology for CO2 reduction. We report that in the case of monolithic porous silver, the film thickness and primary particle size of the silver particles, which can be controlled by electrochemical growth/reduction of AgCl film on silver substrate, have a strong influence on the electrocatalytic activity towards CO2 reduction. A 6 μm thick silver film with particle sizes of 30-50 nm delivers a CO formation current of 10.5 mA cm(-2) and a mass activity of 4.38 A gAg (-1) at an overpotential of 0.39 V, comparable to levels achieved with state-of-the-art gold catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocomposite films containing Au nanoparticles formed by electrochemical reduction of metal ions in the multilayer films as electrocatalyst for dioxygen reduction

International Nuclear Information System (INIS)

Huang Minghua; Shen Yan; Cheng Wenlong; Shao Yong; Sun Xuping; Liu Baifeng; Dong Shaojun

2005-01-01

Through electrostatic layer-by-layer assembly, AuCl 4 - anions and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) cations were alternately deposited on indium tin oxide (ITO) substrates, and 4-aminobenzoic acid modified glassy carbon electrode. Electrochemical reduction of AuCl 4 - anions sandwiched between CoTMPyP layers leads to the in situ formation of Au nanoparticles in the multilayer films. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. UV-vis spectroscopy, X-ray photoelectron spectroscopy and cyclic voltammetry confirm the formation of Au nanoparticles in the multilayer films after electrochemical reduction of AuCl 4 - anions. Atomic force spectroscopy verifies that the as-prepared Au nanoparticles are uniformly distributed with average particles diameters of 20-25 nm. The resulting composite films containing Au nanoparticles with high stability exhibit high electrocatalytic activity for the reduction of dioxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry demonstrate the Au nanoparticles-containing films can catalyze two-electron reduction of O 2 to H 2 O 2 in O 2 -saturated 0.1 M H 2 SO 4 solution

A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

KAUST Repository

Rasul, Shahid; Anjum, Dalaver H.; Jedidi, Abdesslem; Minenkov, Yury; Cavallo, Luigi; Takanabe, Kazuhiro

2014-01-01

The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-06-30

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

Electrochemical preparation of iron cuboid nanoparticles and their catalytic properties for nitrite reduction

International Nuclear Information System (INIS)

Chen Yanxin; Chen Shengpei; Chen Qingsong; Zhou Zhiyou; Sun Shigang

2008-01-01

Iron cuboid nanoparticles supported on glassy carbon (denoted nm-Fe/GC) were prepared by electrochemical deposition under cyclic voltammetric (CV) conditions. The structure and composition of the Fe nanomaterials were characterized by scanning electron microscopy (SEM), selected area electron diffraction (SAED), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). The results demonstrated that the Fe cuboid nanoparticles are dispersed discretely on GC substrate with an average size ca. 171 nm, and confirmed that the electrochemical synthesized nanocubes are single crystals of pure Fe. The catalytic properties of the Fe cuboid nanoparticles towards nitrite electroreduction were investigated, and enhanced electrocatalytic activity of the Fe nanocubes has been determined. In comparison with the data obtained on a bulk-Fe electrode, the onset potential of nitrite reduction on nm-Fe/GC is positively sifted by 100 mV, and the steady reduction current density is enhanced about 2.4-3.2 times

Electrochemical reduction of carbon dioxide to formate with Fe-C electrodes in anaerobic sludge digestion process.

Science.gov (United States)

Zhao, Zisheng; Zhang, Yaobin; Li, Yang; Zhao, Huimin; Quan, Xie

2016-12-01

Electrochemical reduction of carbon dioxide (CO 2 ) to useful chemicals is an attractive strategy to cut its emission in atmosphere. However, high overpotential and energy consumption required in the electrochemical reduction are the major barriers of this process. In this study, a new CO 2 reduction technique for production of formic acid was proposed from waste activated sludge digestion in a microbial electrosynthesis system (MES) with iron plate and carbon pillar as the electrodes. Compared with other reactors, methane production of the Fe-C MES reactor was slightly lower and CO 2 was undetectable. Instead, considerable formate (672.3 mg/L) and H 2 (45.8 mL) were produced in this Fe-C MES reactor, but not found in the other reactors. It should be ascribed to the reduction of CO 2 and H + at cathode. The reduction of H + resulted in a weak alkaline pH (9.3), which made the methanogenesis slightly lower in Fe-C MES. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemical reduction of oxygen catalyzed by Pseudomonas aeruginosa

Energy Technology Data Exchange (ETDEWEB)

Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France)] [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Berge, Mathieu; Roques, Christine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France); Bergel, Alain [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Delia, Marie-Line, E-mail: marieline.delia@ensiacet.f [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France)

2010-07-01

Pseudomonas aeruginosa has already been shown to catalyze oxidation processes in the anode compartment of a microbial fuel cell. The present study focuses on the reverse capacity of the bacterium, i.e. reduction catalysis. Here we show that P. aeruginosa is able to catalyze the electrochemical reduction of oxygen. The use of cyclic voltammetry showed that, for a given range of potential values, the current generated in the presence of bacteria could reach up to four times the current obtained without bacteria. The adhesion of bacteria to the working electrode was necessary for the catalysis to be observed but was not sufficient. The electron transfer between the working electrode and the bacteria did not involve mediator metabolites like phenazines. The transfer was by direct contact. The catalysis required a certain contact duration between electrodes and live bacteria but after this delay, the metabolic activity of cells was no longer necessary. Membrane-bound proteins, like catalase, may be involved. Various strains of P. aeruginosa, including clinical isolates, were tested and all of them, even catalase-defective mutants, presented the same catalytic property. P. aeruginosa offers a new model for the analysis of reduction catalysis and the protocol designed here may provide a basis for developing an interesting tool in the field of bacterial adhesion.

Reductive dechlorination of trichloroacetic acid (TCAA) by electrochemical process over Pd-In/Al_2O_3 catalyst

International Nuclear Information System (INIS)

Liu, Yanzhen; Mao, Ran; Tong, Yating; Lan, Huachun; Zhang, Gong; Liu, Huijuan; Qu, Jiuhui

2017-01-01

Highlights: • TCAA was efficiently removed by Pd-In/Al_2O_3 based electro-reductive process. • The active species for TCAA electroreduction involved electron (e"−) and atomic H*. • The atomic H* played a major contribution to TCAA removal. - Abstract: Electrochemical reduction treatment was found to be a promising method for dechlorination of Trichloroacetic acid (TCAA), and acceleration of electron transfer or enhancement of the concentration of atomic H* significantly improve the electrochemical dechlorination process. Bimetallic Pd-based catalysts have the unique property of simultaneously catalyzing the production of atomic H* and reducing target pollutants. Herein, a bimetallic Pd–In electrocatalyst with atomic ratio of 1:1 was evenly deposited on an Al_2O_3 substrate, and the bimetallic Pd-In structure was confirmed via X-ray photoelectron spectroscopy (XPS). Electrochemical removal of trichloroacetic acid (TCAA) by the Pd-In/Al_2O_3 catalyst was performed in a three-dimensional reactor. 94% of TCAA with the initial concentration of 500 μg L"−"1 could be degraded within 30 min under a relatively low current density (0.9 mA cm"−"2). In contrast to the presence of refractory intermediates (dichloroacetic acid (DCAA)) found in the Pd/Al_2O_3 system, TCAA could be thoroughly reduced to monochloroacetic acid (MCAA) using Pd-In/Al_2O_3 catalysts. According to scavenger experiments, an electron transfer process and atomic H* formation function both existed in the TCAA reduction process, and the enhanced indirect atomic H* reduction process (confirmed by ESR signals) played a chief role in the TCAA removal. Moreover, the synergistic effects of Pd and In were proven to be able to enhance both direct electron transfer and indirect atomic H* formation, indicating a promising prospect for bimetallic electrochemical reduction treatment.

Partial Reduction of Esters to Aldehydes Using a Novel Modified Red-Al Reducing Agent

Energy Technology Data Exchange (ETDEWEB)

Shin, Won Kyu; Kang, Daehoon; An, Duk Keun [Kangwon National Univ., Chunchon (Korea, Republic of)

2014-07-15

We have developed a convenient alternative method for the synthesis of aldehydes from both aromatic and aliphatic esters in very good to excellent yields in the absence of any additives using a modified Red-Al that was easily prepared by reacting commercially available Red-Al with cis-2,6-dimethyl morpholine. The advantages of the present methodology are as follows: simple preparation procedure of the reducing agent, improved product yields, convenient reaction temperature, and short reaction times. Therefore, the new reagent has great potential to be a useful alternative partial reducing agent for the synthesis of aldehydes from esters in organic synthesis. Aldehydes are valuable building blocks and reactive intermediates in organic synthesis. The general and classical syntheses of aldehydes from esters involve reduction-oxidation and partial reduction using efficient partial reducing agents. Obviously, one-step partial reduction methods are more useful than two-step reduction-oxidation methods owing to their simplicity, and generality in organic synthesis.

Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

Science.gov (United States)

Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

2015-08-07

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was

Electrochemical procedures in the treatment of the spent nuclear fuel

International Nuclear Information System (INIS)

Oliveira Forbicini, Christina Aparecida L.G. de.

1994-01-01

Taking into account the advantages of the electrochemical technique and operational features of contactors, type mixer-settler, a new electrolytic extraction equipment is presented. Preliminary studies on electrochemical reduction behavior were carried out with a single stage prototype to set the reliable parameters for the final multistage mixer-settler design (MIRELE). Titanium was the housing material (cathode) and platinum the anode. MIRELE was designed and manufactured at IPEN workshop. After operational tests, the equipment was installed in a glove-box and U/Pu electrochemical partitioning studies were accomplished. The influences of parameters, as hydrazine as scavenger agent in nitric acid medium, current density control in each transference unit and organic and aqueous flow rate on the process efficiency were verified. An uranium separation higher than 99,5% has been achieved. Based on these studies, a flowsheet for spent nuclear fuel treatment was performed, including: an U-Pu co-extraction and scrubbing step, a partial partitioning, followed by final partitioning both using electrochemical Pu reduction, and an uranium reextraction as last step. The product with Pu/U ratio 2,2 times higher than the initial one, with suitable composition for the MOX fuel re-fabrication, has been achieved, showing an important application of the equipment in the new concept of fuel recycling. Also, waste volume reduction, one of the important aspects of the process, has been obtained. Concluding the works, an electrochemical procedure for residual hydrazine decomposition, present in the plutonium product solution, was used to provide a safety operation during the concentration step. (author). 94 refs., 44 figs., 15 tabs

Electrochemical reduction study of Eu3+ in perchlorid media by cyclic chronopotentiometry

International Nuclear Information System (INIS)

Brotto, M.E.; Rabockai, T.

1990-01-01

The electrochemical reduction of Eu 3+ in perchloric media was studied by means of cyclic chronopotentiometry. It is shown that the charge transfer reaction is followed by a chemical reaction in which Eu 2+ ion reoxydized to the trivalent ion (catalytic reaction scheme). The mean value of the homogeneous reaction rate constant is (2,43 +- 0,24) x 10 -2 dm 3 .mol -1 . (author)

Controlling formation of single-molecule junctions by electrochemical reduction of diazonium terminal groups.

Science.gov (United States)

Hines, Thomas; Díez-Pérez, Ismael; Nakamura, Hisao; Shimazaki, Tomomi; Asai, Yoshihiro; Tao, Nongjian

2013-03-06

We report controlling the formation of single-molecule junctions by means of electrochemically reducing two axialdiazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in situ between the molecule and gold electrodes. We report a yield enhancement in molecular junction formation as the electrochemical potential of both junction electrodes approach the reduction potential of the diazonium terminal groups. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond.

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

Energy Technology Data Exchange (ETDEWEB)

Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

2007-02-01

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

Reactivity study of silicon electrode modified by grafting using electrochemical reduction of diazonium salts

International Nuclear Information System (INIS)

Kaiber, A.; Cherkkaoui, M.; Chazalviel, J.N.

2015-01-01

The use of the hydrogenated surface of silicon is hampered by its chemical instability by surface oxidation. The researchers have attempted to modify this surface by direct grafting through the establishment of covalent silicon-carbon bonds from the reaction of chemical species on the surface. Different grafting methods can be implemented for the preparation of grafted surfaces. The choice of an electrochemical reaction allows fast grafting from the hydrogenated surface. We studied the formation of a phenyl layer by electrochemical reduction of aryl diazonium salts (BF4-,+N2-ph-OCH3) on a p-Si-H (111) electrode in an aqueous medium (0.05M H/sub 2/SO/sub 4/ + 0.05M HF). The grafting of an organic layer by reduction is confirmed by the observation of a cyclic voltammetry peak around -0.3V/SCE. In-situ infrared spectroscopy (IR) analysis allows to identify the chemical functions present on the grafted surface, allowing a direct monitoring of the grafting reaction. (author)

Rational Design of a Hierarchical Tin Dendrite Electrode for Efficient Electrochemical Reduction of CO2.

Science.gov (United States)

Won, Da Hye; Choi, Chang Hyuck; Chung, Jaehoon; Chung, Min Wook; Kim, Eun-Hee; Woo, Seong Ihl

2015-09-21

Catalysis is a key technology for the synthesis of renewable fuels through electrochemical reduction of CO2 . However, successful CO2 reduction still suffers from the lack of affordable catalyst design and understanding the factors governing catalysis. Herein, we demonstrate that the CO2 conversion selectivity on Sn (or SnOx /Sn) electrodes is correlated to the native oxygen content at the subsurface. Electrochemical analyses show that the reduced Sn electrode with abundant oxygen species effectively stabilizes a CO2 (.-) intermediate rather than the clean Sn surface, and consequently results in enhanced formate production in the CO2 reduction. Based on this design strategy, a hierarchical Sn dendrite electrode with high oxygen content, consisting of a multi-branched conifer-like structure with an enlarged surface area, was synthesized. The electrode exhibits a superior formate production rate (228.6 μmol h(-1)  cm(-2) ) at -1.36 VRHE without any considerable catalytic degradation over 18 h of operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

KAUST Repository

Rasul, Shahid

2014-12-23

The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous CO2 conversion. A non-noble metal electrocatalyst based on a copper-indium (Cu-In) alloy that selectively converts CO2 to CO with a low overpotential is reported. The electrochemical deposition of In on rough Cu surfaces led to Cu-In alloy surfaces. DFT calculations showed that the In preferentially located on the edge sites rather than on the corner or flat sites and that the d-electron nature of Cu remained almost intact, but adsorption properties of neighboring Cu was perturbed by the presence of In. This preparation of non-noble metal alloy electrodes for the reduction of CO2 provides guidelines for further improving electrocatalysis.

Beyond a complete failure : The impact of partial capacity reductions on public transport network vulnerability

NARCIS (Netherlands)

Cats, O.; Jenelius, E.

2015-01-01

Disruptions often result with partial capacity reduction without resulting with a complete breakdown. This study aims to move beyond the analysis of complete failure by investigating the impacts of partial capacity reduction on public transport network performance. We analyse the relation between

Correlation between Quantumchemically Calculated LUMO Energies and the Electrochemical Window of Ionic Liquids with Reduction-Resistant Anions

Directory of Open Access Journals (Sweden)

Wim Buijs

2012-01-01

Full Text Available Quantum chemical calculations showed to be an excellent method to predict the electrochemical window of ionic liquids with reduction-resistant anions. A good correlation between the LUMO energy and the electrochemical window is observed. Surprisingly simple but very fast semiempirical calculations are in full record with density functional theory calculations and are a very attractive tool in the design and optimization of ionic liquids for specific purposes.

Electrochemical reduction approach-based 3D graphene/Ni(OH)2 electrode for high-performance supercapacitors

International Nuclear Information System (INIS)

Yan, Huijun; Bai, Jianwei; Wang, Bin; Yu, Lei; Zhao, Lin; Wang, Jun; Liu, Qi; Liu, Jingyuan; Li, Zhanshuang

2015-01-01

Highlights: • 3D graphene foam is synthesized by a simple electrochemical reduction method. • The 3D graphene/Ni(OH) 2 composite is used as a monolithic free-standing electrode material. • The 3D conductive graphene network improves the contact between electrode and electrolyte. • Compositing graphene with Ni(OH) 2 sheets take full advantage of the synergistic effects. • Results show that the as-synthesized products have good electrochemical property. - Abstract: Using a simple electrochemical reduction approach, we have produced three-dimensional (3D) graphene foam having high conductivity and well-defined macroporous structure. Through a hydrothermal process, Ni(OH) 2 sheets are grown in-situ onto the graphene surface. This monolithic 3D graphene/Ni(OH) 2 composite is used as the free-standing electrode for supercapacitor application; it shows a high specific capacitance of 183.1 F g −1 (based on the total mass of the electrode), along with excellent rate capability and cycle performance. The asymmetric supercapacitor based on the 3D graphene/Ni(OH) 2 as a positive electrode and active carbon (AC) as a negative electrode is also assembled and it exhibits a specific capacitance of 148.3 F g −1 at 0.56 A g −1 and a high energy density of 52.7 W h kg −1 at a power density of 444.4 W kg −1 . Moreover, 3D graphene/Ni(OH) 2 //AC has a good cycle stability (87.9% capacitance retention after 1000 cycles), making it promising as one of the most attractive candidates for electrochemical energy storage. This excellent electrochemical performance results from the multiplexed 3D graphene network facilitating electron transport; the interlaced Ni(OH) 2 sheets shorten ion diffusion paths and facilitate the rapid migration of electrolyte ions

Conformational analysis of large and highly disulfide-stabilized proteins by integrating online electrochemical reduction into an optimized H/D exchange mass spectrometry workflow

DEFF Research Database (Denmark)

Trabjerg, Esben; Jakobsen, Rasmus Uffe; Mysling, Simon

2015-01-01

Analysis of disulfide-bonded proteins by HDX-MS requires effective and rapid reduction of disulfide bonds before enzymatic digestion in order to increase sequence coverage. In a conventional HDX-MS workflow, disulfide bonds are reduced chemically by addition of a reducing agent to the quench......-antibody, respectively. The presented results demonstrate the successful electrochemical reduction during HDX-MS analysis of both a small exceptional tightly disulfide-bonded protein (NGF) as well as the largest protein attempted to date (IgG1-antibody). We envision that online electrochemical reduction...... the electrochemical reduction efficiency during HDX-MS analysis of two particularly challenging disulfide stabilized proteins: a therapeutic IgG1-antibody and Nerve Growth Factor-β (NGF). Several different parameters (flow rate, applied square wave potential as well as the type of labeling- and quench buffer) were...

Synthesis of fully and partially sulfonated polyanilines derived from ortanilic acid: An electrochemical and electromicrogravimetric study

International Nuclear Information System (INIS)

Cano Marquez, Abraham Guadalupe; Torres Rodriguez, Luz Maria; Montes Rojas, Antonio

2007-01-01

The electrochemical polymerization of 2-aminobenzene sulfonic acid, also called ortanilic acid (o-ASA), on a gold electrode precoated with polyaniline (PANI), has been carried out. We proved that the electropolymerization of o-ASA is enhanced on PANI electrodes, resulting in thicker films obtained in aqueous media at room temperature. The electrosynthesized film (P(o-ASA)) was characterized by cyclic voltammetry, FTIR and nuclear magnetic resonance. The compensation of P(o-ASA) charge was evaluated using electrochemical quartz crystal microbalance combined with cyclic voltammetry, which showed that the electroneutralization process mainly involves cations. Additionally, copolymers of aniline and o-ASA were electrosynthesized, using a metallic electrode modified with PANI also as a working electrode. The degree of sulfanation of copolymers has been modulated with the proportions of monomers in the electrosynthesis solution. The studies reveal a more important participation of cations in fully sulfonated polyaniline than in partially sulfonated polyaniline

Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

International Nuclear Information System (INIS)

Prayitno

2007-01-01

The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

Role of the adsorbed oxygen species in the selective electrochemical reduction of CO_2 to alcohols and carbonyls on copper electrodes

International Nuclear Information System (INIS)

Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi

2017-01-01

The electrochemical reduction of CO_2 into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO_2 to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO_2 on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO_2 reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Isostable reduction with applications to time-dependent partial differential equations.

Science.gov (United States)

Wilson, Dan; Moehlis, Jeff

2016-07-01

Isostables and isostable reduction, analogous to isochrons and phase reduction for oscillatory systems, are useful in the study of nonlinear equations which asymptotically approach a stationary solution. In this work, we present a general method for isostable reduction of partial differential equations, with the potential power to reduce the dimensionality of a nonlinear system from infinity to 1. We illustrate the utility of this reduction by applying it to two different models with biological relevance. In the first example, isostable reduction of the Fokker-Planck equation provides the necessary framework to design a simple control strategy to desynchronize a population of pathologically synchronized oscillatory neurons, as might be relevant to Parkinson's disease. Another example analyzes a nonlinear reaction-diffusion equation with relevance to action potential propagation in a cardiac system.

Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction

NARCIS (Netherlands)

Kas, Recep; Hummadi, Khalid Khazzal; Kortlever, Ruud; de Wit, Patrick; Milbrat, Alexander; Luiten-Olieman, Maria W.J.; Benes, Nieck Edwin; Koper, Marc T.M.; Mul, Guido

2016-01-01

Aqueous-phase electrochemical reduction of carbon dioxide requires an active, earth-abundant electrocatalyst, as well as highly efficient mass transport. Here we report the design of a porous hollow fibre copper electrode with a compact three-dimensional geometry, which provides a large area,

Role of the adsorbed oxygen species in the selective electrochemical reduction of CO{sub 2} to alcohols and carbonyls on copper electrodes

Energy Technology Data Exchange (ETDEWEB)

Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi [School of Chemistry, University of Birmingham, Edgbaston (United Kingdom)

2017-10-09

The electrochemical reduction of CO{sub 2} into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO{sub 2} to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO{sub 2} on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO{sub 2} reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Facile synthesis of reduced graphene oxide nanosheets by a sodium diphenylamine sulfonate reduction process and its electrochemical property

International Nuclear Information System (INIS)

Ji, Yunzhou; Liu, Qi; Cheng, Meiling; Lai, Lifang; Li, Zhanfeng; Peng, Yuxin; Yang, Yong

2013-01-01

We report a new method to convert graphene oxide (GO) to stable colloidal dispersion of reduced graphene oxide nanosheets (RGONS) using sodium diphenylamine sulfonate (SDAS) as a reductant, as well as itself and its redox product as the stabilizer. The as-prepared RGONS have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, thermo-gravimetric analysis, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy and Raman spectroscopy. The results indicate that the bulk of oxygen-containing functional groups from GO have been removed. Based on the cyclic voltammogram (CV) analyses, it is found that the RGONS-based material exhibits better electrochemical activity in sensing ascorbic acid than GO. The simple method provides a new efficient route for the synthesis of water-soluble RGONS on a large scale and novel composites. - Highlights: • We report a new environment-friendly reductant for the reduction of graphene oxide. • The reduction process needn't use other stabilizer except for using reductant. • The reduced graphene oxide nanosheet (RGONS) aqueous dispersion is stable. • The RGONS shows a high electrochemical activity in sensing ascorbic acid

Nitrogen-doped diamond electrode shows high performance for electrochemical reduction of nitrobenzene

International Nuclear Information System (INIS)

Zhang, Qing; Liu, Yanming; Chen, Shuo; Quan, Xie; Yu, Hongtao

2014-01-01

Highlights: • A metal-free nitrogen-doped diamond electrode was synthesized. • The electrode exhibits high electrocatalytic activity for nitrobenzene reduction. • The electrode exhibits high selectivity for reduction of nitrobenzene to aniline. • High energy efficiency was obtained compared with graphite electrode. -- Abstract: Effective electrode materials are critical to electrochemical reduction, which is a promising method to pre-treat anti-oxidative and bio-refractory wastewater. Herein, nitrogen-doped diamond (NDD) electrodes that possess superior electrocatalytic properties for reduction were fabricated by microwave-plasma-enhanced chemical vapor deposition technology. Nitrobenzene (NB) was chosen as the probe compound to investigate the material's electro-reduction activity. The effects of potential, electrolyte concentration and pH on NB reduction and aniline (AN) formation efficiencies were studied. NDD exhibited high electrocatalytic activity and selectivity for reduction of NB to AN. The NB removal efficiency and AN formation efficiency were 96.5% and 88.4% under optimal conditions, respectively; these values were 1.13 and 3.38 times higher than those of graphite electrodes. Coulombic efficiencies for NB removal and AN formation were 27.7% and 26.1%, respectively; these values were 4.70 and 16.6 times higher than those of graphite electrodes under identical conditions. LC–MS analysis revealed that the dominant reduction pathway on the NDD electrode was NB to phenylhydroxylamine (PHA) to AN

Electrochemical functionalization of glassy carbon electrode by reduction of diazonium cations in protic ionic liquid

International Nuclear Information System (INIS)

Shul, Galyna; Ruiz, Carlos Alberto Castro; Rochefort, Dominic; Brooksby, Paula A.; Bélanger, Daniel

2013-01-01

Protic ionic liquid based on 2-methoxypyridine and trifluoroacetic acid was used as electrolyte for the functionalization of a glassy carbon electrode surface by electrochemical reduction of in situ generated 4-chlorobenzene diazonium and 4-nitrobenzene diazonium cations. The diazonium cations were synthesized in an electrochemical cell by reaction of the corresponding amines with NaNO 2 dissolved in protic ionic liquid. The resulting electrografted organic layers exhibit similar properties to those layers obtained by the derivatization from isolated diazonium salts dissolved in protic ionic liquid. Functionalized glassy carbon electrode surfaces were characterized by cyclic voltammetry, Fourier transform infrared and X-ray photoelectron spectroscopies. Atomic force microscopy thickness measurements revealed that, in our experimental conditions, the use of protic ionic liquid led to the formation of film with a thickness of about 1.5 nm. It is also demonstrated that the nitrobenzene chemisorbed on glassy carbon electrode or dissolved in protic ionic liquid undergoes electrochemical conversion to hydroxyaminobenzene

Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid

DEFF Research Database (Denmark)

Yoo, J.S.; Christensen, Rune; Vegge, Tejs

2016-01-01

The electrochemical reduction (electroreduction) of CO2 to formic acid (HCOOH) and its competing reactions, that is, the electroreduction of CO2 to CO and the hydrogen evolution reaction (HER), on twenty-seven different metal surfaces have been investigated using density functional theory (DFT) c...

Detection of CO2•- in the Electrochemical Reduction of Carbon Dioxide in N,N-Dimethylformamide by Scanning Electrochemical Microscopy.

Science.gov (United States)

Kai, Tianhan; Zhou, Min; Duan, Zhiyao; Henkelman, Graeme A; Bard, Allen J

2017-12-27

The electrocatalytic reduction of CO 2 has been studied extensively and produces a number of products. The initial reaction in the CO 2 reduction is often taken to be the 1e formation of the radical anion, CO 2 •- . However, the electrochemical detection and characterization of CO 2 •- is challenging because of the short lifetime of CO 2 •- , which can dimerize and react with proton donors and even mild oxidants. Here, we report the generation and quantitative determination of CO 2 •- in N,N-dimethylformamide (DMF) with the tip generation/substrate collection (TG/SC) mode of scanning electrochemical microscopy (SECM). CO 2 was reduced at a hemisphere-shaped Hg/Pt ultramicroelectrode (UME) or a Hg/Au film UME, which were utilized as the SECM tips. The CO 2 •- produced can either dimerize to form oxalate within the nanogap between SECM tip and substrate or collected at SECM substrate (e.g., an Au UME). The collection efficiency (CE) for CO 2 •- depends on the distance (d) between the tip and substrate. The dimerization rate (6.0 × 10 8 M -1 s -1 ) and half-life (10 ns) of CO 2 •- can be evaluated by fitting the collection efficiency vs distance curve. The dimerized species of CO 2 •- , oxalate, can also be determined quantitatively. Furthermore, the formal potential (E 0 ') and heterogeneous rate constant (k 0 ) for CO 2 reduction were determined with different quaternary ammonium electrolytes. The significant difference in k 0 is due to a tunneling effect caused by the adsorption of the electrolytes on the electrode surface at negative potentials.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

Science.gov (United States)

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M.

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V{sub SHE} and between 0,5 V{sub SHE} and 1 V{sub SHE}. The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V{sub SHE}, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Highly conductive alumina/NCN composites electrodes fabricated by gelcasting and reduction-sintering-An electrochemical behavior study in aggressive environments

International Nuclear Information System (INIS)

Liu Jingjun; Menchavez, Ruben L.; Watanabe, Hideo; Fuji, Masayoshi; Takahashi, Minoru

2008-01-01

A novel highly conductive alumina/nano-carbon network composites (alumina/NCN composites) was fabricated by gelcasting and reduction-sintering method under argon atmosphere. The electrochemical behaviors of the alumina/NCN composites were studied systematically in some aggressive solutions (HCl, H 2 SO 4 , HNO 3 , NaOH, and KOH), using potentiodynamic polarization and chronoamperometry and X-ray diffraction and SEM observations. The results showed that the electrochemical stability and reproducibility of the composite electrodes in these diluted acids and alkalis were very good and had, in some extent, an electro-catalytic activity toward formation of hydrogen evolution and reduction of dissolved oxygen in aqueous solutions in comparison with a commercial graphite electrode. In addition, the pyrolyzed nano-carbon contents, size, and shape in the alumina matrix, have greatly effects on the electrochemical performances and electrode reactions in these solutions. It is found that the minimal residual carbon content of 0.62 wt.% in the matrix is enough to improve electrochemical performances and avoid to loss the ceramics physical properties at the same time. When the additional potential in all the tested electrolytes was at +1700 mV (vs. SCE), alumina particles at the electrode surface were not observed to dissolve into solution in this case, indicating the material being suitable for electrodes in aggressive solutions

Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

KAUST Repository

Wang, Riming; Sun, Xiaohui; Ould-Chikh, Samy; Osadchii, Dmitrii; Bai, Fan; Kapteijn, Freek; Gascon, Jorge

2018-01-01

A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

Metal-Organic-Framework-Mediated Nitrogen-Doped Carbon for CO2 Electrochemical Reduction

KAUST Repository

Wang, Riming

2018-04-11

A nitrogen-doped carbon was synthesized through the pyrolysis of the well-known metal-organic framework ZIF-8, followed by a subsequent acid treatment, and has been applied as a catalyst in the electrochemical reduction of carbon dioxide. The resulting electrode shows Faradaic efficiencies to carbon monoxide as high as ∼78%, with hydrogen being the only byproduct. The pyrolysis temperature determines the amount and the accessibility of N species in the carbon electrode, in which pyridinic-N and quaternary-N species play key roles in the selective formation of carbon monoxide.

Improved 64-bit Radix-16 Booth Multiplier Based on Partial Product Array Height Reduction

DEFF Research Database (Denmark)

Antelo, Elisardo; Montuschi, Paolo; Nannarelli, Alberto

2016-01-01

, a reduction of one unit in the maximum height is achieved. This reduction may add flexibility during the design of the pipelined multiplier to meet the design goals, it may allow further optimizations of the partial product array reduction stage in terms of area/delay/power and/or may allow additional addends...

Electrochemical and partial oxidation of methane

Science.gov (United States)

Singh, Rahul

2008-10-01

Hydrogen has been the most common fuel used for the fuel cell research but there remains challenging technological hurdles and storage issues with hydrogen fuel. The direct electrochemical oxidation of CH4 (a major component of natural gas) in a solid oxide fuel cell (SOFC) to generate electricity has a potential of commercialization in the area of auxiliary and portable power units and battery chargers. They offer significant advantages over an external reformer based SOFC, namely, (i) simplicity in the overall system architecture and balance of plant, (ii) more efficient and (iii) availability of constant concentration of fuel in the anode compartment of SOFC providing stability factor. The extreme operational temperature of a SOFC at 700-1000°C provides a thermodynamically favorable pathway to deposit carbon on the most commonly used Ni anode from CH4 according to the following reaction (CH4 = C + 2H2), thus deteriorating the cell performance, stability and durability. The coking problem on the anode has been a serious and challenging issue faced by the catalyst research community worldwide. This dissertation presents (i) a novel fabricated bi-metallic Cu-Ni anode by electroless plating of Cu on Ni anode demonstrating significantly reduced or negligible coke deposition on the anode for CH4 and natural gas fuel after long term exposure, (ii) a thorough microstructural examination of Ni and Cu-Ni anode exposed to H2, CH4 and natural gas after long term exposure at 750°C by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction and (iii) in situ electrochemical analysis of Ni and Cu-Ni for H2, CH4 and natural gas during long term exposure at 750°C by impedance spectroscopy. A careful investigation of variation in the microstructure and performance characteristics (voltage-current curve and impedance) of Ni and Cu-Ni anode before and after a long term exposure of CH4 and natural gas would allow us to test the validation of a

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Direction du Cycle du Combustible

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V{sub S}HE and 0.3 V{sub S}HE and O.5 V{sub S}HE and 1 V{sub S}HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V{sub S}HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Electrochemical reduction induced self-doping of Ti3+ for efficient water splitting performance on TiO2 based photoelectrodes

KAUST Repository

Zhang, Zhonghai

2013-01-01

Hetero-element doping (e.g., N, F, C) of TiO2 is inevitably accompanied by significantly increased structural defects due to the dopants\\' nature being foreign impurities. Very recently, in situ self-doping with homo-species (e.g., Ti3+) has been emerging as a rational solution to enhance TiO2 photoactivity within both UV and visible light regions. Herein we demonstrate that conventional electrochemical reduction is indeed a facile and effective strategy to induce in situ self-doping of Ti3+ into TiO2 and the self-doped TiO2 photoelectrodes showed remarkably improved and very stable water splitting performance. In this study, hierarchical TiO2 nanotube arrays (TiO2 NTs) were chosen as TiO2 substrates and then electrochemically reduced under varying conditions to produce Ti3+ self-doped TiO2 NTs (ECR-TiO2 NTs). The optimized saturation photocurrent density and photoconversion efficiency on the ECR-TiO2 NTs under simulated AM 1.5G illumination were identified to be 2.8 mA cm-2 at 1.23 V vs. RHE and 1.27% respectively, which are the highest values ever reported for TiO 2 based photoelectrodes. The electrochemical impedance spectra measurement confirms that the electrochemical induced Ti3+ self-doping improved the electrical conductivity of the ECR-TiO2 NTs. The versatility and effectiveness of the electrochemical reduction method for Ti3+ self-doping in P25 based TiO2 was also examined and confirmed. This journal is © 2013 the Owner Societies.

Application of Elimination Voltammetry to the Study of Electrochemical Reduction and Determination of the Herbicide Metribuzin

Czech Academy of Sciences Publication Activity Database

Skopalová, J.; Navrátil, Tomáš

2007-01-01

Roč. 52, č. 6 (2007), s. 961-977 ISSN 0009-2223 R&D Projects: GA ČR GA203/07/1195 Institutional research plan: CEZ:AV0Z40400503 Keywords : Elimination voltammetry with linear scan (EVLS) * metribuzin * electrochemical reduction * mercury electrodes Subject RIV: CG - Electrochemistry Impact factor: 0.529, year: 2007

Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

International Nuclear Information System (INIS)

Dilimon, V.S.; Venkata Narayanan, N.S.; Sampath, S.

2010-01-01

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH 3 CONH 2 ), urea (NH 2 CONH 2 ) and ammonium nitrate (NH 4 NO 3 ). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step, 2-electron pathways of O 2 to H 2 O 2 and further reduction of H 2 O 2 to H 2 O. The first 2-electron reduction of O 2 to H 2 O 2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO 2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and RDE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BDD) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide.

Electrochemical study of nitrobenzene reduction using novel Pt nanoparticles/macroporous carbon hybrid nanocomposites

International Nuclear Information System (INIS)

Zhang Yufan; Zeng Lijun; Bo Xiangjie; Wang Huan; Guo Liping

2012-01-01

Graphical abstract: A one-step microwave-assisted route for rapidly synthesizing Pt nanoparticles ensemble on macroporous carbon hybrid nanocomposites (PNMPC) has been reported. As a novel electrode material, the excellent electrochemical behavior of nitrobenzene was investigated thoroughly at the PNMPC modified glassy carbon electrode. And moreover, the modified electrode was successfully applied to the determination of nitrobenzene in real samples. Highlights: ► One-step microwave-assisted heating synthesis Pt nanoparticles/macroporous carbon hybrid nanocomposites (PNMPC). ► Catalytic rate constant being 3.14 × 10 4 M −1 s −1 for NB in pH 7.0. ► Sensitive electrochemical detection of NB at the PNMPC/Nafion/GC electrode. ► The electrode showing excellent anti-interference ability and good stability for NB. - Abstract: Novel Pt nanoparticles (PN) ensemble on macroporous carbon (MPC) hybrid nanocomposites (PNMPC) were prepared through a rapidly and simple one-step microwave-assisted heating procedure. The obtained PNMPC was characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electrochemical methods. The electrochemical reduction of nitrobenzene (NB) was thoroughly investigated at the PNMPC modified glassy carbon (GC) electrode, and the catalytic rate constant was calculated to be 3.14 × 10 4 M −1 s −1 for NB. A sensitive NB sensor was developed based on the PNMPC/GC electrode, which showed a wide linear range (1–200 μM), low detection limit (50 nM), high sensitivity (6.93 μA μM −1 ), excellent anti-interference ability and good stability. And moreover, the electrode was successfully applied to the determination of NB in real samples.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

Science.gov (United States)

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-11-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels.

Science.gov (United States)

Singh, Meenesh R; Clark, Ezra L; Bell, Alexis T

2015-11-10

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Comparing the performances of electrochemical sensors using p-aminophenol redox cycling by different reductants on gold electrodes modified with self-assembled monolayers

International Nuclear Information System (INIS)

Xia, Ning; Ma, Fengji; Zhao, Feng; He, Qige; Du, Jimin; Li, Sujuan; Chen, Jing; Liu, Lin

2013-01-01

Highlights: • Performances of p-AP redox cycling using different reductants on gold surface are compared. • Background current decreases in order of hydrazine, Na 2 SO 3 , NaBH 4 , NADH, cysteamine, and TCEP. • Chemical reaction rate with QI increases in order of NADH, TCEP, and cysteamine. • NADH, TCEP and cysteamine are suitable for p-AP redox cycling on gold electrode. -- Abstract: p-Aminophenol (p-AP) redox cycling using chemical reductants is one strategy for developing sensitive electrochemical sensors. However, most of the reported reductants are only used on indium-tin oxide (ITO) electrodes but not gold electrodes due to the high background current caused by the oxidation reaction of the reductants on the highly electrocatalytic gold electrodes. Therefore, new strategies and/or reductants are in demand for expanding the application of p-AP redox cycling on gold electrodes. In this work, we compared the performances of several reductants in p-AP redox cycling on self-assembled monolayers (SAMs)-modified gold electrodes. Among the tested reagents, nicotinamide adenine dinucleotide (NADH), tris(2-carboxyethyl)phosphine (TCEP) and cysteamine were demonstrated to be suitable for p-AP redox cycling on the alkanethiol-modified gold electrodes because of their low background current. The rate of chemical reaction between reductants and p-quinone imine (QI, the electrochemically oxidized product of p-AP) increases in the order of NADH −1 was achieved. We believe that our work will be valuable for the development of electrochemical sensors using p-AP redox cycling on gold electrodes

Electrochemical reduction behavior of U3O8 powder in a LiCl molten salt

International Nuclear Information System (INIS)

Jeong, Sang Mun; Shin, Ho-Sup; Hong, Sun-Seok; Hur, Jin-Mok; Do, Jae Bum; Lee, Han Soo

2010-01-01

The reduction path of the U 3 O 8 powder vol-oxidized at 1200 deg. C has been determined by a series of electrochemical experiments in a 1 wt.% Li 2 O/LiCl molten salt. Various reaction intermediates are observed by during electrolysis of U 3 O 8 . The formation of the metallic uranium is caused from two different reduction paths, a direct reduction of uranium oxide and an electro-lithiothermic reduction. As the uranium oxide is converted to the metallic uranium, the lithium metal is more actively formed in the cathode basket. The reducibility of the rare earth oxides with the U 3 O 8 powder has been tested by constant voltage electrolysis. The results suggest the advanced vol-oxidation could lead to the enhancement in the reducibility of the rare earth fission products.

Electrochemical analysis

International Nuclear Information System (INIS)

Hwang, Hun

2007-02-01

This book explains potentiometry, voltametry, amperometry and basic conception of conductometry with eleven chapters. It gives the specific descriptions on electrochemical cell and its mode, basic conception of electrochemical analysis on oxidation-reduction reaction, standard electrode potential, formal potential, faradaic current and faradaic process, mass transfer and overvoltage, potentiometry and indirect potentiometry, polarography with TAST, normal pulse and deferential pulse, voltammetry, conductometry and conductometric titration.

Electrochemical modification of carbon electrode with benzylphosphonic groups

International Nuclear Information System (INIS)

Benjamin, Ossonon Diby; Weissmann, Martin; Bélanger, Daniel

2014-01-01

Electrochemical modification of carbon electrodes by aryl groups bearing a phosphonate terminal functionality was carried out by both electrochemical reduction of diazonium ions (diazobenzylphosphonic acid) and electrochemical oxidation of an amine (aminobenzylphosphonic acid). The grafting by electrochemical reduction of aryl diazonium ions was found to be more efficient. The surface concentration of phosphonate groups, estimated by electrochemical reduction of electrostatically bound Pb(II) ions, was found to be about 25% higher for the layer formed by electrochemical reduction of diazonium ions than for the layer formed by oxidation of the amine. The acid–base properties of the grafted films were slightly influenced by the grafting procedure and the difference in the apparent pK a was most likely related to the presence of the substrate –NH-aryl linkage for the film generated by amine oxidation. X-ray photoelectron spectroscopy was used to get some insight on the chemical species present at the carbon electrode surface. For both procedures, the films consist in mixture of at least two different covalently grafted species

A new strategy for 2,4,6-Trinitrotoluene adsorption and electrochemical reduction on poly(melamine)/graphene oxide modified electrode

International Nuclear Information System (INIS)

Cotchim, Suparat; Thavarungkul, Panote; Kanatharana, Proespichaya; Limbut, Warakorn

2015-01-01

Highlights: • A new fabrication strategy of a poly(melamine)/graphene oxide (PM/GO) modified glassy carbon electrode (GCE) (PM/GO/GCE) for the detection of ultra-traces of TNT is proposed. • The PM/GO/GCE exhibits excellent adsorption and electrochemical reduction of TNT via the AdCSV technique. • The PM/GO/GCE provides for a high sensitivity, good repeatability and selectivity. • This strategy opens new opportunities for the sensitive detection of TNT aiming at protection of the environmental and homeland securities. - Abstract: A poly(melamine)/graphene oxide (PM/GO) layer modified on a glassy carbon electrode (GCE) was used for the adsorption and electrochemical detection of 2,4,6 trinitrotoluene (TNT). The surface morphology and electrochemical behaviour of the PM/GO/GCE were characterized by scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR), cyclic voltammetry (CV) and adsorptive cathodic stripping voltammetry (AdCSV). The PM/GO/GCE exhibited excellent adsorption and electrochemical reduction of TNT via the AdCSV technique with two linear ranges, 1–90 μg L −1 and 100–1000 μg L −1 , a detection limit of 0.34 μg L −1 and a quantitation limit of 1.14 μg L −1 . The PM/GO/GCE provided for a high sensitivity, good repeatability and selectivity. This modified electrode was successfully applied to detect TNT in soil samples with good recoveries that ranged from 93 to 99%.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

Science.gov (United States)

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-01-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices. PMID:26504215

New model reduction technique for a class of parabolic partial differential equations

NARCIS (Netherlands)

Vajta, Miklos

1991-01-01

A model reduction (or lumping) technique for a class of parabolic-type partial differential equations is given, and its application is discussed. The frequency response of the temperature distribution in any multilayer solid is developed and given by a matrix expression. The distributed transfer

Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

Science.gov (United States)

Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

2018-02-01

Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

Knorr-Rabe partial reduction of pyrroles: Application to the synthesis of indolizidine alkaloids

Directory of Open Access Journals (Sweden)

Ryan John H

2008-01-01

Full Text Available Abstract Background The Birch reduction of electron rich pyrroles does not occur readily. However, dissolving metal reduction with zinc under acidic conditions gives 3-pyrrolines (2,5-dihydropyrroles in reasonable yield. This dissolving metal reduction was first reported by Knorr and Rabe in 1901 but since then has only been reported for the reduction of electron rich pyrroles. Results The partial reduction of bicyclic α-ketopyrrole derivatives has been performed under dissolving metal conditions with zinc and hydrochloric acid to give excellent yields of hexahydroindolizidines. This reduction method has been utilised for the diastereoselective synthesis of 5-alkylindolizidines and the stereoselectivity obtained is opposite to that of catalytic hydrogenation. Conclusion An efficient stereoselective synthesis of indolizidine alkaloids has been developed from α-ketopyrrole intermediates using a modified version of Knorr and Rabe's pyrrole reduction.

A Nitrogen-Doped Carbon Catalyst for Electrochemical CO2 Conversion to CO with High Selectivity and Current Density.

Science.gov (United States)

Jhong, Huei-Ru Molly; Tornow, Claire E; Smid, Bretislav; Gewirth, Andrew A; Lyth, Stephen M; Kenis, Paul J A

2017-03-22

We report characterization of a non-precious metal-free catalyst for the electrochemical reduction of CO 2 to CO; namely, a pyrolyzed carbon nitride and multiwall carbon nanotube composite. This catalyst exhibits a high selectivity for production of CO over H 2 (approximately 98 % CO and 2 % H 2 ), as well as high activity in an electrochemical flow cell. The CO partial current density at intermediate cathode potentials (V=-1.46 V vs. Ag/AgCl) is up to 3.5× higher than state-of-the-art Ag nanoparticle-based catalysts, and the maximum current density is 90 mA cm -2 . The mass activity and energy efficiency (up to 48 %) were also higher than the Ag nanoparticle reference. Moving away from precious metal catalysts without sacrificing activity or selectivity may significantly enhance the prospects of electrochemical CO 2 reduction as an approach to reduce atmospheric CO 2 emissions or as a method for load-leveling in relation to the use of intermittent renewable energy sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

Energy Technology Data Exchange (ETDEWEB)

Singh, Meenesh R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Clark, Ezra L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical & Biomolecular Engineering; Bell, Alexis T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical & Biomolecular Engineering

2015-10-26

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO₂ reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H₂ and CO) and Hythane (H₂ and CH₄) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C₂H₄ have high profitability indices.

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

Science.gov (United States)

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

Determination of the extent of reduction of dense UO{sub 2} cathodes from direct electrochemical reduction studies in molten chloride medium

Energy Technology Data Exchange (ETDEWEB)

Sri Maha Vishnu, D.; Sanil, N. [Fuel Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Murugesan, N. [Materials Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Shakila, L. [Fuel Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Ramesh, C. [Materials Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Mohandas, K.S., E-mail: ksmd@igcar.gov.in [Fuel Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Nagarajan, K. [Fuel Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India)

2012-08-15

Electro-reduction of solid UO{sub 2} to U has been studied with molten CaCl{sub 2} or LiCl as the electrolyte medium. Electro-reduction of thick (>3 mm), powder compacted and sintered pellets of UO{sub 2} showed incomplete reduction resulting in a mixture of uranium metal and UO{sub 2}. The extent of reduction of UO{sub 2} to U was determined by employing a novel method called 'metal estimation by hydrogen sensor (MEHS)', in which the hydrogen evolved during the reaction of U metal in the reduced product with con. HBr was measured using an in-house developed polymer electrolyte based amperometric hydrogen sensor. The results of our investigations on incompletely reduced UO{sub 2} pellets in both CaCl{sub 2} and LiCl melts showed that the extent of reduction of different regions of the oxide pellet was different. It varied from 88.3% on the surface of the pellet as against 3.7% towards the centre bulk during electro-reduction in CaCl{sub 2} (at 1173 K). The metallisation was found restricted to the surface of the pellets reduced in LiCl melt (at 923 K). Electro-reduction of small chunks of UO{sub 2} pellet in CaCl{sub 2} melt resulted in products with lower extent of reduction. Based on the measurements, a probable mechanism on the propagation of reduction through the solid UO{sub 2} matrix during the electrochemical reduction process has been proposed.

Partial Tmem106b reduction does not correct abnormalities due to progranulin haploinsufficiency.

Science.gov (United States)

Arrant, Andrew E; Nicholson, Alexandra M; Zhou, Xiaolai; Rademakers, Rosa; Roberson, Erik D

2018-06-22

Loss of function mutations in progranulin (GRN) are a major cause of frontotemporal dementia (FTD). Progranulin is a secreted glycoprotein that localizes to lysosomes and is critical for proper lysosomal function. Heterozygous GRN mutation carriers develop FTD with TDP-43 pathology and exhibit signs of lysosomal dysfunction in the brain, with increased levels of lysosomal proteins and lipofuscin accumulation. Homozygous GRN mutation carriers develop neuronal ceroid lipofuscinosis (NCL), an earlier-onset lysosomal storage disorder caused by severe lysosomal dysfunction. Multiple genome-wide association studies have shown that risk of FTD in GRN mutation carriers is modified by polymorphisms in TMEM106B, which encodes a lysosomal membrane protein. Risk alleles of TMEM106B may increase TMEM106B levels through a variety of mechanisms. Brains from FTD patients with GRN mutations exhibit increased TMEM106B expression, and protective TMEM106B polymorphisms are associated with decreased TMEM106B expression. Together, these data raise the possibility that reduction of TMEM106B levels may protect against the pathogenic effects of progranulin haploinsufficiency. We crossed Tmem106b +/- mice with Grn +/- mice, which model the progranulin haploinsufficiency of GRN mutation carriers and develop age-dependent social deficits and lysosomal abnormalities in the brain. We tested whether partial Tmem106b reduction could normalize the social deficits and lysosomal abnormalities of Grn +/- mice. Partial reduction of Tmem106b levels did not correct the social deficits of Grn +/- mice. Tmem106b reduction also failed to normalize most lysosomal abnormalities of Grn +/- mice, except for β-glucuronidase activity, which was suppressed by Tmem106b reduction and increased by progranulin insufficiency. These data do not support the hypothesis that Tmem106b reduction protects against the pathogenic effects of progranulin haploinsufficiency, but do show that Tmem106b reduction normalizes some

Synthesis of graphene platelets by chemical and electrochemical route

Energy Technology Data Exchange (ETDEWEB)

Ramachandran, Rajendran; Felix, Sathiyanathan [Centre for Nanotechnology Research, VIT University, Vellore 632014, Tamil Nadu (India); Joshi, Girish M. [Materials Physics Division, School of Advanced Sciences, VIT University, Vellore 632014, Tamil Nadu (India); Raghupathy, Bala P.C., E-mail: balapraveen2000@yahoo.com [Centre for Nanotechnology Research, VIT University, Vellore 632014, Tamil Nadu (India); Research and Advanced Engineering Division (Materials), Renault Nissan Technology and Business Center India (P) Ltd., Chennai, Tamil Nadu (India); Jeong, Soon Kwan, E-mail: jeongsk@kier.re.kr [Climate Change Technology Research Division, Korea Institute of Energy Research, Yuseong-gu, Daejeon 305-343 (Korea, Republic of); Grace, Andrews Nirmala, E-mail: anirmalagrace@vit.ac.in [Centre for Nanotechnology Research, VIT University, Vellore 632014, Tamil Nadu (India); Climate Change Technology Research Division, Korea Institute of Energy Research, Yuseong-gu, Daejeon 305-343 (Korea, Republic of)

2013-10-15

Graphical abstract: A schematic showing the overall reduction process of graphite to reduced graphene platelets by chemical and electrochemical route. - Highlights: • Graphene was prepared by diverse routes viz. chemical and electrochemical methods. • NaBH{sub 4} was effective for removing oxygen functional groups from graphene oxide. • Sodium borohydride reduced graphene oxide (SRGO) showed high specific capacitance. • Electrochemical rendered a cheap route for production of graphene in powder form. - Abstract: Graphene platelets were synthesized from graphene oxide by chemical and electrochemical route. Under the chemical method, sodium borohydride and hydrazine chloride were used as reductants to produce graphene. In this paper, a novel and cost effective electrochemical method, which can simplify the process of reduction on a larger scale, is demonstrated. The electrochemical method proposed in this paper produces graphene in powder form with good yield. The atomic force microscopic images confirmed that the graphene samples prepared by all the routes have multilayers of graphene. The electrochemical process provided a new route to make relatively larger area graphene sheets, which will have interest for further patterning applications. Attempt was made to quantify the quantum of reduction using cyclic voltammetry and choronopotentiometry techniques on reduced graphene samples. As a measure in reading the specific capacitance values, a maximum specific capacitance value of 265.3 F/g was obtained in sodium borohydride reduced graphene oxide.

Synthesis of graphene platelets by chemical and electrochemical route

International Nuclear Information System (INIS)

Ramachandran, Rajendran; Felix, Sathiyanathan; Joshi, Girish M.; Raghupathy, Bala P.C.; Jeong, Soon Kwan; Grace, Andrews Nirmala

2013-01-01

Graphical abstract: A schematic showing the overall reduction process of graphite to reduced graphene platelets by chemical and electrochemical route. - Highlights: • Graphene was prepared by diverse routes viz. chemical and electrochemical methods. • NaBH 4 was effective for removing oxygen functional groups from graphene oxide. • Sodium borohydride reduced graphene oxide (SRGO) showed high specific capacitance. • Electrochemical rendered a cheap route for production of graphene in powder form. - Abstract: Graphene platelets were synthesized from graphene oxide by chemical and electrochemical route. Under the chemical method, sodium borohydride and hydrazine chloride were used as reductants to produce graphene. In this paper, a novel and cost effective electrochemical method, which can simplify the process of reduction on a larger scale, is demonstrated. The electrochemical method proposed in this paper produces graphene in powder form with good yield. The atomic force microscopic images confirmed that the graphene samples prepared by all the routes have multilayers of graphene. The electrochemical process provided a new route to make relatively larger area graphene sheets, which will have interest for further patterning applications. Attempt was made to quantify the quantum of reduction using cyclic voltammetry and choronopotentiometry techniques on reduced graphene samples. As a measure in reading the specific capacitance values, a maximum specific capacitance value of 265.3 F/g was obtained in sodium borohydride reduced graphene oxide

Clinical outcome of trans-sacral interbody fusion after partial reduction for high-grade l5-s1 spondylolisthesis.

Science.gov (United States)

Smith, J A; Deviren, V; Berven, S; Kleinstueck, F; Bradford, D S

2001-10-15

A clinical retrospective study was conducted. To evaluate the clinical and radiographic outcome of reduction followed by trans-sacral interbody fusion for high-grade spondylolisthesis. In situ posterior interbody fusion with fibula allograft has improved the fusion rates for patients with high-grade spondylolisthesis. The use of this technique in conjunction with partial reduction has not been reported. Nine consecutive patients underwent treatment of high-grade (Grade 3 or 4) spondylolisthesis with partial reduction followed by posterior interbody fusion using cortical allograft. The average age at the time of surgery was 27 years (range, 8-51 years), and the average follow-up period was 43 months (range, 24-72 months). Before surgery, eight patients had low back pain, seven patients had radiating leg pain, and five patients had hamstring tightness. The average grade of spondylolisthesis by Meyerding grading was 3.9 (range, 3-5). Charts and radiographs were evaluated, and outcomes were collected by use of the modified SRS outcomes instrument. Radiographic indexes demonstrated significant improvement with partial reduction and fusion. The slip angle, as measured from the inferior endplate of L5, improved from 41.2 degrees (range, 24-82 degrees ) before surgery to 21 degrees (range, 5-40 degrees ) after surgery. All the patients were extremely or somewhat satisfied with surgery. The two patients who underwent this operation without initial instrumentation experienced fractures of their interbody grafts. Both of these patients underwent repair of the pseudarthrosis with placement of trans-sacral pedicle screw instrumentation and subsequent fusion. Partial reduction followed by posterior interbody fusion is an effective technique for the management of high-grade spondylolisthesis in pediatric and adult patient populations, as assessed by radiographic and clinical criteria. Pedicle screw instrumentation with the sacral screws capturing L5 is recommended when this

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [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); Masud, Jahangir [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, E-mail: ohsaka@echem.titech.ac.j [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)

2010-12-15

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

2010-01-01

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

Science.gov (United States)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

Voltage equilibration for reactive atomistic simulations of electrochemical processes

International Nuclear Information System (INIS)

Onofrio, Nicolas; Strachan, Alejandro

2015-01-01

We introduce electrochemical dynamics with implicit degrees of freedom (EChemDID), a model to describe electrochemical driving force in reactive molecular dynamics simulations. The method describes the equilibration of external electrochemical potentials (voltage) within metallic structures and their effect on the self-consistent partial atomic charges used in reactive molecular dynamics. An additional variable assigned to each atom denotes the local potential in its vicinity and we use fictitious, but computationally convenient, dynamics to describe its equilibration within connected metallic structures on-the-fly during the molecular dynamics simulation. This local electrostatic potential is used to dynamically modify the atomic electronegativities used to compute partial atomic changes via charge equilibration. Validation tests show that the method provides an accurate description of the electric fields generated by the applied voltage and the driving force for electrochemical reactions. We demonstrate EChemDID via simulations of the operation of electrochemical metallization cells. The simulations predict the switching of the device between a high-resistance to a low-resistance state as a conductive metallic bridge is formed and resistive currents that can be compared with experimental measurements. In addition to applications in nanoelectronics, EChemDID could be useful to model electrochemical energy conversion devices

Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

Science.gov (United States)

Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

2006-05-04

The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

Science.gov (United States)

Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

2018-03-01

We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

Binding of carbon dioxide to metal macrocycles: Toward a mechanistic understanding of electrochemical and photochemical carbon dioxide reduction

Energy Technology Data Exchange (ETDEWEB)

Fujita, E.

1993-01-01

Efforts were made to find effective catalysts for photochemical and electrochemical reduction of CO[sub 2]. We are studying the factors controlling excited-state lifetimes, electron-transfer rates to mediators/catalysts, properties of reduced mediators, binding of small molecules to reduced mediators, and reactivity of the mediators to yield the desired products. This document describes some of the results of binding on CO[sub 2] to metal macrocycles. The electrocatalytic activity of cobalt macrocycle complexes in reduction of CO[sub 2] in CO[sub 2]-saturated water at the Hg electrode is being studied. We are ready to study the mechanism and kinetics of the photochemical CO[sub 2] reduction in order to design more efficient photo-energy conversion systems. 19 refs.

Binding of carbon dioxide to metal macrocycles: Toward a mechanistic understanding of electrochemical and photochemical carbon dioxide reduction

Energy Technology Data Exchange (ETDEWEB)

Fujita, E.

1993-07-01

Efforts were made to find effective catalysts for photochemical and electrochemical reduction of CO{sub 2}. We are studying the factors controlling excited-state lifetimes, electron-transfer rates to mediators/catalysts, properties of reduced mediators, binding of small molecules to reduced mediators, and reactivity of the mediators to yield the desired products. This document describes some of the results of binding on CO{sub 2} to metal macrocycles. The electrocatalytic activity of cobalt macrocycle complexes in reduction of CO{sub 2} in CO{sub 2}-saturated water at the Hg electrode is being studied. We are ready to study the mechanism and kinetics of the photochemical CO{sub 2} reduction in order to design more efficient photo-energy conversion systems. 19 refs.

NO_X Reduction Using an Electrochemical Cell with NO_X adsorbents

DEFF Research Database (Denmark)

Shao, Jing

, surface diffusion, and transfer of NOx and O2 species at/near the triple phase boundary region, and the formation of intermediate NO2. Severe degradation was observed on both electrodes following long-term operation, caused by the corrosion of the Ag electrode covered by a nitrate melt, or associated......This thesis studied the electrochemical cells modified by NOx adsorbents for the NOx reduction under O2-rich conditions. The structure of a multilayer electrochemical cell with a NOx adsorption layer was optimized by removing a yttria-stabilized zirconia (YSZ) cover layer coated on a Pt...

Formation and proof of stable bi-, tri- and tetraradical polyanions during the electrochemical reduction of cone-polynitrocalix[4]arenes. An ESR-UV-vis spectroelectrochemical study

International Nuclear Information System (INIS)

Liška, Alan; Rosenkranz, Marco; Klíma, Jiří; Dunsch, Lothar; Lhoták, Pavel; Ludvík, Jiří

2014-01-01

Graphical abstract: - Abstract: The first intermediates of electrochemical reduction of nitro compounds in nonaqueous DMF are stable radical anions. In the series of mono-, di-, tri- and tetranitro calix[4]arenes each nitro group represents a reduction center, therefore the question about the spin state of intermediary anions arises. In this communication, the voltammetric and coulometric investigation of these compounds is performed together with the spectral measurements (ESR and UV-vis). The in-situ spectroelectrochemical approach proved that during reduction, in all polynitro radicalic intermediates the electrons remain unpaired and thus relatively stable mono-, di-, tri- and tetraradical mono-, di-, tri- and tetraanions, respectively, can be electrochemically generated in aprotic DMF from polynitrocalix[4]arenes. This finding confirms that the nitrophenyl units in polynitrocalix[4]arenes are completely independent and no mutual electronic communication takes place among them

EQCM Study of Influence of Anion Nature on Electrochemical Reduction of Bismuth Sulfide in Nickel Plating Solution

Directory of Open Access Journals (Sweden)

Loreta TAMAŠAUSKAITĖ-TAMAŠIŪNAITĖ

2011-03-01

Full Text Available The influence of anion nature on the reduction of bismuth sulfide film deposited on gold using the successive ionic layer adsorption and reaction method in solutions containing Ni2+ ions has been investigated by electrochemical quartz crystal microbalance combined with cyclic voltammetry and X-ray photoelectron spectroscopy. It has been determined that the reduction of bismuth sulfide film in the nickel plating solution depends on the anion nature: larger cathodic current and mass changes (Dƒ are observed in the solution containing acetate anion as compared to those in the solution containing sulfate anion. As the reduction of bismuth sulfide film in the background solutions depends on the nature of anion, it influences the cathodic reduction of Ni2+ ions prior to OPD of Ni. A greater current and mass change (Dƒ is conditioned by simultaneously occurring reduction of bismuth sulfide film when the film is reduced in the acetate nickel plating electrolyte in contrast to that in the sulfate one.http://dx.doi.org/10.5755/j01.ms.17.1.244

Partial synchronization of relaxation oscillators with repulsive coupling in autocatalytic integrate-and-fire model and electrochemical experiments

Science.gov (United States)

Kori, Hiroshi; Kiss, István Z.; Jain, Swati; Hudson, John L.

2018-04-01

Experiments and supporting theoretical analysis are presented to describe the synchronization patterns that can be observed with a population of globally coupled electrochemical oscillators close to a homoclinic, saddle-loop bifurcation, where the coupling is repulsive in the electrode potential. While attractive coupling generates phase clusters and desynchronized states, repulsive coupling results in synchronized oscillations. The experiments are interpreted with a phenomenological model that captures the waveform of the oscillations (exponential increase) followed by a refractory period. The globally coupled autocatalytic integrate-and-fire model predicts the development of partially synchronized states that occur through attracting heteroclinic cycles between out-of-phase two-cluster states. Similar behavior can be expected in many other systems where the oscillations occur close to a saddle-loop bifurcation, e.g., with Morris-Lecar neurons.

The sequential use of washing and an electrochemical reduction process for the remediation of lead-contaminated soils.

Science.gov (United States)

Demir, Aydeniz; Köleli, Nurcan

2013-01-01

A two-step method for the remediation of three different types of lead (Pb)-contaminated soil was evaluated. The first step included soil washing with ethylenediaminetetraacetic acid (EDTA) to remove Pb from soils. The washing experiments were performed with 0.05 M Na2EDTA at 1:10 soil to liquid ratio. Following the washing, Pb removal efficiency from soils ranged within 50-70%. After the soil washing process, Pb2+ ions in the washing solution were reduced electrochemically in a fixed-bed reactor. Lead removal efficiency with the electrochemical reduction at -2.0 V potential ranged within 57-76%. The overall results indicate that this two-step method is an environmentally-friendly and effective technology to remediate Pb-contaminated soils, as well as Pb-contaminated wastewater treatment due to the transformation of toxic Pb2+ ions into a non-hazardous metallic form (Pb(0)).

Reduction of deviation angle during occlusion therapy: in partially accommodative esotropia with moderate amblyopia.

Science.gov (United States)

Chun, Bo Young; Kwon, Soon Jae; Chae, Sun Hwa; Kwon, Jung Yoon

2007-09-01

To evaluate changes in ocular alignment in partially accommodative esotropic children age ranged from 3 to 8 years during occlusion therapy for amblyopia. Angle measurements of twenty-two partially accommodative esotropic patients with moderate amblyopia were evaluated before and at 2 years after occlusion therapy. Mean deviation angle with glasses at the start of occlusion treatment was 19.45+/-5.97 PD and decreased to 12.14+/-12.96 PD at 2 years after occlusion therapy (pocclusion therapy, 9 (41%) cases were indications of surgery for residual deviation but if we had planned surgery before occlusion treatment, 18 (82%) of patients would have had surgery. There was a statistical relationship between increase of visual acuity ratio and decrease of deviation angle (r=-0.479, p=0.024). There was a significant reduction of deviation angle of partially accommodative esotropic patients at 2 years after occlusion therapy. Our results suggest that occlusion therapy has an influence on ocular alignment in partially accommodative esotropic patients with amblyopia.

(Spectro) Electrochemical investigation of reduction mechanism of a new energetic molecule 2,2-dinitroethene-1,1-diamine (FOX-7) in aprotic solvents

Czech Academy of Sciences Publication Activity Database

Šimková, Ludmila; Dmitrieva, E.; Klíma, Jiří; Dunsch, L.; Ludvík, Jiří

2015-01-01

Roč. 19, č. 1 (2015), s. 103-112 ISSN 1432-8488 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : FOX -7 * electrochemical reduction * Autoprotonation mechanism Subject RIV: CG - Electrochemistry Impact factor: 2.327, year: 2015

Electrochemical depassivation of zero-valent iron for trichloroethene reduction

Energy Technology Data Exchange (ETDEWEB)

Chen, Liang [Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Jin, Song [Department of Civil and Architectural Engineering, University of Wyoming, Laramie, WY 82071 (United States); Advanced Environmental Technologies, LLC, Fort Collins, CO 80524 (United States); Fallgren, Paul H. [Department of Civil Engineering, University of Colorado Denver, Denver, CO 80217 (United States); Swoboda-Colberg, Norbert G. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States); Liu, Fei [Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Colberg, Patricia J.S., E-mail: pczoo@uwyo.edu [Department of Civil and Architectural Engineering, University of Wyoming, Laramie, WY 82071 (United States)

2012-11-15

Highlights: Black-Right-Pointing-Pointer Electrical current may depassivate ZVI and restore its capacity to reduce TCE. Black-Right-Pointing-Pointer Electrical current may defer or even prevent surface oxidation of ZVI. Black-Right-Pointing-Pointer Electrical current coupled with ZVI achieves greater TCE reduction than ZVI alone. - Abstract: Permeable reactive barriers (PRBs) composed of zero-valent iron (ZVI) are susceptible to passivation, resulting in substantially decreased rates of chlorinated solvent removal over time. In this study, the application of low electrical direct current (DC) to restore the reductive capacity of passivated ZVI was examined. Electrical current was applied to a laboratory column reactor filled with a mixture of pre-passivated ZVI and sand. Variable voltage settings (0-12 V) were applied through two stainless steel electrodes placed at the ends of the reactor. While only partial restoration of the reductive capacity of the passivated ZVI was observed, higher rates of trichloroethene (TCE) removal were always obtained when current was applied, and the rates of TCE removal were roughly proportional to the voltage level. Although differences were observed between the rates and extent of TCE removal within the column, it is noteworthy that TCE removal was not restricted to that region of the column where the electrons entered (i.e., at the cathode). While complete 'depassivation' of ZVI may be difficult to achieve in practice, the application of DC demonstrated observable restoration of reactivity of the passivated ZVI. This study provides evidence that this approach may significantly extend the life of a ZVI PRB.

Electrochemical depassivation of zero-valent iron for trichloroethene reduction

International Nuclear Information System (INIS)

Chen, Liang; Jin, Song; Fallgren, Paul H.; Swoboda-Colberg, Norbert G.; Liu, Fei; Colberg, Patricia J.S.

2012-01-01

Highlights: ► Electrical current may depassivate ZVI and restore its capacity to reduce TCE. ► Electrical current may defer or even prevent surface oxidation of ZVI. ► Electrical current coupled with ZVI achieves greater TCE reduction than ZVI alone. - Abstract: Permeable reactive barriers (PRBs) composed of zero-valent iron (ZVI) are susceptible to passivation, resulting in substantially decreased rates of chlorinated solvent removal over time. In this study, the application of low electrical direct current (DC) to restore the reductive capacity of passivated ZVI was examined. Electrical current was applied to a laboratory column reactor filled with a mixture of pre-passivated ZVI and sand. Variable voltage settings (0–12 V) were applied through two stainless steel electrodes placed at the ends of the reactor. While only partial restoration of the reductive capacity of the passivated ZVI was observed, higher rates of trichloroethene (TCE) removal were always obtained when current was applied, and the rates of TCE removal were roughly proportional to the voltage level. Although differences were observed between the rates and extent of TCE removal within the column, it is noteworthy that TCE removal was not restricted to that region of the column where the electrons entered (i.e., at the cathode). While complete “depassivation” of ZVI may be difficult to achieve in practice, the application of DC demonstrated observable restoration of reactivity of the passivated ZVI. This study provides evidence that this approach may significantly extend the life of a ZVI PRB.

The effect of electrochemical CO annealing on platinum–cobalt nanoparticles in acid medium and their correlation to the oxygen reduction reaction

International Nuclear Information System (INIS)

Ciapina, Eduardo G.; Ticianelli, Edson A.

2011-01-01

Highlights: ► Modification of the surface properties of Pt 3 Co/C electrocatalyst. ► Electrochemical CO annealing in acid media generated a Pt-rich surface. ► In situ XAS revealed modifications in the Pt 5d band occupancy after CO annealing. ► The CO-annealed sample exhibited stronger interaction with oxygenated species. ► Increased Pt utilization in the CO-annealed Pt 3 Co/C electrocatalyst. - Abstract: This paper describes a modification of the surface properties of a carbon-supported Pt 3 Co catalyst resulting from an electrochemical cycling treatment in a 0.1 M HClO 4 and in a CO-saturated 0.1 M HClO 4 solution (electrochemical CO-annealing). The procedure generated a Pt-rich surface with electrochemical properties different from that presented by the as-received (untreated) sample. This was evidenced by a shift in the CO stripping peak to more positive potentials in the CO stripping voltammetry, and by an increased charge of H upd region and a modification of the oxide reduction peak observed in the base cyclic voltammogram. In situ X-ray absorption spectroscopy experiments conducted in the dispersive mode revealed differences in the electronic 5d band occupancy after the CO annealing, whereas the behavior of the intensity of the white-line as function of the potential for this material approached that found for pure Pt/C nanoparticles, in contrast to the small potential dependence profile exhibited by the as-received Pt 3 Co nanoparticles. Mass activities towards the oxygen reduction reaction measured by rotating disk experiments carried out at 1600 rpm in a O 2 -saturated solution at 25 °C increased from 0.10 A/mg of Pt to 0.19 A/mg of Pt, evidencing the higher Pt utilization in the CO-annealed Pt 3 Co/C electrocatalyst. The origin of the different electrochemical behavior is discussed.

Effect of Amine Adlayer on Electrochemical Uric Acid Sensor Conducted on Electrochemically Reduced Graphene Oxide

Energy Technology Data Exchange (ETDEWEB)

Park, Sumi; Kim, Kyuwon [Incheon National University, Incheon (Korea, Republic of)

2016-03-15

The electrochemical biosensing efficiency of uric acid (UA) detection on an electrochemically reduced graphene oxide (ERGO)-decorated electrode surface was studied by using various amine linkers used to immobilize ERGO. The amine linkers aminoethylphenyldiazonium , 2,2'-(ethylenedioxy)bis(ethylamine), 3-aminopro-pyltriethoxysilane, and polyethyleneimine were coated on indium-tin-oxide electrode surfaces through chemical or electrochemical deposition methods. ERGO-decorated surfaces were prepared by the electrochemical reduction of graphene oxide (GO), which was immobilized on the amine-coated electrode surfaces through the electrostatic interaction between GO and the ammonium ion of the linker on the surface. We monitored the sensing results of electrochemical UA detection with differential pulse voltammetry. The ERGO-modified surface presented electrocatalytic oxidation of UA and ascorbic acid. Among the different amines tested, 3-aminopropyltriethoxysilane provided the best biosensing performance in terms of sensitivity and reproducibility.

Effect of Amine Adlayer on Electrochemical Uric Acid Sensor Conducted on Electrochemically Reduced Graphene Oxide

International Nuclear Information System (INIS)

Park, Sumi; Kim, Kyuwon

2016-01-01

The electrochemical biosensing efficiency of uric acid (UA) detection on an electrochemically reduced graphene oxide (ERGO)-decorated electrode surface was studied by using various amine linkers used to immobilize ERGO. The amine linkers aminoethylphenyldiazonium , 2,2'-(ethylenedioxy)bis(ethylamine), 3-aminopro-pyltriethoxysilane, and polyethyleneimine were coated on indium-tin-oxide electrode surfaces through chemical or electrochemical deposition methods. ERGO-decorated surfaces were prepared by the electrochemical reduction of graphene oxide (GO), which was immobilized on the amine-coated electrode surfaces through the electrostatic interaction between GO and the ammonium ion of the linker on the surface. We monitored the sensing results of electrochemical UA detection with differential pulse voltammetry. The ERGO-modified surface presented electrocatalytic oxidation of UA and ascorbic acid. Among the different amines tested, 3-aminopropyltriethoxysilane provided the best biosensing performance in terms of sensitivity and reproducibility.

Electrochemical Impedance Studies of SOFC Cathodes

DEFF Research Database (Denmark)

Hjelm, Johan; Søgaard, Martin; Wandel, Marie

2007-01-01

Mixed ion- and electron-conducting composite electrodes consisting of doped ceria and perovskite have been studied by electrochemical impedance spectroscopy (EIS) at different temperatures and oxygen partial pressures. This paper aims to describe the different contributions to the polarisation...

Electrochemical CO2 Reduction by Ni-containing Iron Sulfides: How Is CO2 Electrochemically Reduced at Bisulfide-Bearing Deep-sea Hydrothermal Precipitates?

International Nuclear Information System (INIS)

Yamaguchi, Akira; Yamamoto, Masahiro; Takai, Ken; Ishii, Takumi; Hashimoto, Kazuhito; Nakamura, Ryuhei

2014-01-01

The discovery of deep-sea hydrothermal vents on the late 1970's has led to many hypotheses concerning chemical evolution in the prebiotic ocean and the early evolution of energy metabolism in ancient Earth. Such studies stand on the quest for the bioenergetic evolution to utilize reducing chemicals such as H 2 for CO 2 reduction and carbon assimilation. In addition to the direct reaction of H 2 and CO 2 , the electrical current passing across a bisulfide-bearing chimney structure has pointed to the possible electrocatalytic CO 2 reduction at the cold ocean-vent interface (R. Nakamura, et al. Angew. Chem. Int. Ed. 2010, 49, 7692 − 7694). To confirm the validity of this hypothesis, here, we examined the energetics of electrocatalytic CO 2 reduction by iron sulfide (FeS) deposits at slightly acidic pH. Although FeS deposits inefficiently reduced CO 2 , the efficiency of the reaction was substantially improved by the substitution of Fe with Ni to form FeNi 2 S 4 (violarite), of which surface was further modified with amine compounds. The potential-dependent activity of CO 2 reduction demonstrated that CO 2 reduction by H 2 in hydrothermal fluids was involved in a strong endergonic electron transfer reaction, suggesting that a naturally occurring proton-motive force (PMF) as high as 200 mV would be established across the hydrothermal vent chimney wall. However, in the chimney structures, H 2 generation competes with CO 2 reduction for electrical current, resulting in rapid consumption of the PMF. Therefore, to maintain the PMF and the electrosynthesis of organic compounds in hydrothermal vent mineral deposits, we propose a homeostatic pH regulation mechanism of FeS deposits, in which elemental hydrogen stored in the hydrothermal mineral deposits is used to balance the consumption of the electrochemical gradient by H 2 generation

Improved in vivo performance of amperometric oxygen (PO2) sensing catheters via electrochemical nitric oxide generation/release.

Science.gov (United States)

Ren, Hang; Coughlin, Megan A; Major, Terry C; Aiello, Salvatore; Rojas Pena, Alvaro; Bartlett, Robert H; Meyerhoff, Mark E

2015-08-18

A novel electrochemically controlled release method for nitric oxide (NO) (based on electrochemical reduction of nitrite ions) is combined with an amperometric oxygen sensor within a dual lumen catheter configuration for the continuous in vivo sensing of the partial pressure of oxygen (PO2) in blood. The on-demand electrochemical NO generation/release method is shown to be fully compatible with amperometric PO2 sensing. The performance of the sensors is evaluated in rabbit veins and pig arteries for 7 and 21 h, respectively. Overall, the NO releasing sensors measure both venous and arterial PO2 values more accurately with an average deviation of -2 ± 11% and good correlation (R(2) = 0.97) with in vitro blood measurements, whereas the corresponding control sensors without NO release show an average deviation of -31 ± 28% and poor correlation (R(2) = 0.43) at time points >4 h after implantation in veins and >6 h in arteries. The NO releasing sensors induce less thrombus formation on the catheter surface in both veins and arteries (p < 0.05). This electrochemical NO generation/release method could offer a new and attractive means to improve the biocompatibility and performance of implantable chemical sensors.

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst.

Science.gov (United States)

Dai, Lei; Qin, Qing; Zhao, Xiaojing; Xu, Chaofa; Hu, Chengyi; Mo, Shiguang; Wang, Yu Olivia; Lin, Shuichao; Tang, Zichao; Zheng, Nanfeng

2016-08-24

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

Selective Electrochemical Reduction of Carbon Dioxide to Ethanol on a Boron- and Nitrogen-Co-doped Nanodiamond.

Science.gov (United States)

Liu, Yanming; Zhang, Yujing; Cheng, Kai; Quan, Xie; Fan, Xinfei; Su, Yan; Chen, Shuo; Zhao, Huimin; Zhang, Yaobin; Yu, Hongtao; Hoffmann, Michael R

2017-12-04

Electrochemical reduction of CO 2 to ethanol, a clean and renewable liquid fuel with high heating value, is an attractive strategy for global warming mitigation and resource utilization. However, converting CO 2 to ethanol remains great challenge due to the low activity, poor product selectivity and stability of electrocatalysts. Here, the B- and N-co-doped nanodiamond (BND) was reported as an efficient and stable electrode for selective reduction of CO 2 to ethanol. Good ethanol selectivity was achieved on the BND with high Faradaic efficiency of 93.2 % (-1.0 V vs. RHE), which overcame the limitation of low selectivity for multicarbon or high heating value fuels. Its superior performance was mainly originated from the synergistic effect of B and N co-doping, high N content and overpotential for hydrogen evolution. The possible pathway for CO 2 reduction revealed by DFT computation was CO 2 →*COOH→*CO→*COCO→*COCH 2 OH→*CH 2 OCH 2 OH→CH 3 CH 2 OH. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of reduction gases: partial oxidation of hydrocarbons and coal

Energy Technology Data Exchange (ETDEWEB)

Tippmer, K

1976-04-01

After some general remarks on reduction gas and quality demands, the Texaco process of partial oxidation with scrubbing is dealt with. A comparison of current iron-sponge techniques shows that a heat demand below 3 M kcal/t Fe should be envisaged, which means that heavy fuel oil or coal should be used. The special features of oxygen generation, coal processing, demands made on fuel oil, gasoline, and natural gas, gas generation, soot recovery, hydrogen sulphide-carbon dioxide scrubbing, system Benfield HP process, recycle-carbon dioxide scrubbing, auxiliary steam system, gas preheating, recycle gas cooling and compression, process data and heat balances for natural gas (one-heat system) and heating fuel oil or naphtha (two-heat system) are given.

High temperature and pressure electrochemical test station

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos; Allebrod, Frank; Mogensen, Mogens Bjerg

2013-01-01

An electrochemical test station capable of operating at pressures up to 100 bars and temperatures up to 400 ◦C has been established. It enables control of the partial pressures and mass flow of O2, N2, H2, CO2, and H2O in a single or dual environment arrangement, measurements with highly corrosive...... media, as well as localized sampling of gas evolved at the electrodes for gas analysis. A number of safety and engineering design challenges have been addressed. Furthermore, we present a series of electrochemical cell holders that have been constructed in order to accommodate different types of cells...... and facilitate different types of electrochemical measurements. Selected examples of materials and electrochemical cells examined in the test station are provided, ranging from the evaluation of the ionic conductivity of liquid electrolytic solutions immobilized in mesoporous ceramic structures...

Solid State Electrochemical DeNOx

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2010-01-01

The literature on direct electrochemical reduction of NOx in a solid state cell has been reviewed. It is shown that that the reduction of nitric oxide either occurs on the electrode or on the electrolyte if F-centers are formed. It is also shown that some oxide based electrodes has a high apparent...

Electrochemical Reduction of Oxygen on Anthraquinone/Carbon Nanotubes Nanohybrid Modified Glassy Carbon Electrode in Neutral Medium

Directory of Open Access Journals (Sweden)

Zheng Gong

2013-01-01

Full Text Available The electrochemical behaviors of monohydroxy-anthraquinone/multiwall carbon nanotubes (MHAQ/MWCNTs nanohybrid modified glassy carbon (MHAQ/MWCNTs/GC electrodes in neutral medium were investigated; also reported was their application in the electrocatalysis of oxygen reduction reaction (ORR. The resulting MHAQ/MWCNTs nanohybrid was characterized by scanning electron microscope (SEM and transmission electron microscope (TEM. It was found that the ORR at the MHAQ/MWCNTs/GC electrode occurs irreversibly at a potential about 214 mV less negative than at a bare GC electrode in pH 7.0 buffer solution. Cyclic voltammetric and rotating disk electrode (RDE techniques indicated that the MHAQ/MWCNTs nanohybrid has high electrocatalytic activity for the two-electron reduction of oxygen in the studied potential range. The kinetic parameters of ORR at the MHAQ/MWCNTs nanohybrid modified GC electrode were also determined by RDE and EIS techniques.

Synthesis and electrochemical properties of olivine LiFePO{sub 4} prepared by a carbothermal reduction method

Energy Technology Data Exchange (ETDEWEB)

Liu, Hui-ping; Wang, Zhi-xing; Li, Xin-hai; Guo, Hua-jun; Peng, Wen-jie; Zhang, Yun-he; Hu, Qi-yang [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China)

2008-10-01

LiFePO{sub 4}/C composite cathode material was prepared by carbothermal reduction method, which uses NH{sub 4}H{sub 2}PO{sub 4}, Li{sub 2}CO{sub 3} and cheap Fe{sub 2}O{sub 3} as starting materials, acetylene black and glucose as carbon sources. The precursor of LiFePO{sub 4}/C was characterized by differential thermal analysis and thermogravimetry. X-ray diffraction (XRD), scanning electron microscopy (SEM) micrographs showed that the LiFePO{sub 4}/C is olivine-type phase, and the addition of the carbon reduced the LiFePO{sub 4} grain size. The carbon is dispersed between the grains, ensuring a good electronic contact. The products sintered at 700 C for 8 h with glucose as carbon source possessed excellent electrochemical performance. The synthesized LiFePO{sub 4} composites showed a high electrochemical capacity of 159.3 mAh g{sup -1} at 0.1C rate, and the capacity fading is only 2.2% after 30 cycles. (author)

Efficient electrochemical reduction of nitrate to nitrogen using Ti/IrO2-Pt anode and different cathodes

International Nuclear Information System (INIS)

Li Miao; Feng Chuanping; Zhang Zhenya; Sugiura, Norio

2009-01-01

Electrochemical reduction of nitrate using Fe, Cu, and Ti as cathodes and Ti/IrO 2 -Pt as anode in an undivided and unbuffered cell was studied. In the presence of appropriate amount of NaCl, both cathodic reduction of nitrate and anodic oxidation of the by-products of ammonia and nitrite were achieved by all cathodes under a proper condition. Both in the absence and presence of NaCl, the order of nitrate removal rate was Fe > Cu > Ti. The nitrate removal was 87% and selectivity to nitrogen was 100% in 3 h with Fe cathode in the presence of NaCl. Ti/IrO 2 -Pt anode played an important role during nitrate reduction, especially in the presence of NaCl, at which by-products could efficiently be oxidized. Moreover, atomic force microscopy (AFM) investigation shown Ti/IrO 2 -Pt anode was suitable for nitration reduction and the surface roughness of all cathodes increased. The concentrations of Fe, Cu, and Ti in the electrolyte were less than 0.15, 0.12 and 0.09 mg/L after 3 h electrolysis, respectively.

Electrochemical reduction of NO with propene in the presence of oxygen on LSCoM/CGO porous cell stacks impregnated with BaO

DEFF Research Database (Denmark)

Friedberg, Anja Zarah; Kammer Hansen, Kent

2015-01-01

of up to 30 % was achieved. In the presence of propene, the electrochemical promotion on the NOx conversion decreased and only 13 % was removed. A propene oxidation of 35 % was achieved as the highest at 400 °C. The propene acted as a reducing agent on the barium nitrates and caused a greater reduction...

Biomass derived porous nitrogen doped carbon for electrochemical devices

Directory of Open Access Journals (Sweden)

Litao Yan

2017-04-01

Full Text Available Biomass derived porous nanostructured nitrogen doped carbon (PNC has been extensively investigated as the electrode material for electrochemical catalytic reactions and rechargeable batteries. Biomass with and without containing nitrogen could be designed and optimized to prepare PNC via hydrothermal carbonization, pyrolysis, and other methods. The presence of nitrogen in carbon can provide more active sites for ion absorption, improve the electronic conductivity, increase the bonding between carbon and sulfur, and enhance the electrochemical catalytic reaction. The synthetic methods of natural biomass derived PNC, heteroatomic co- or tri-doping into biomass derived carbon and the application of biomass derived PNC in rechargeable Li/Na batteries, high energy density Li–S batteries, supercapacitors, metal-air batteries and electrochemical catalytic reaction (oxygen reduction and evolution reactions, hydrogen evolution reaction are summarized and discussed in this review. Biomass derived PNCs deliver high performance electrochemical storage properties for rechargeable batteries/supercapacitors and superior electrochemical catalytic performance toward hydrogen evolution, oxygen reduction and evolution, as promising electrodes for electrochemical devices including battery technologies, fuel cell and electrolyzer. Keywords: Biomass, Nitrogen doped carbon, Batteries, Fuel cell, Electrolyzer

Design of a Sensitive and Selective Electrochemical Aptasensor for the Determination of the Complementary cDNA of miRNA-145 Based on the Intercalation and Electrochemical Reduction of Doxorubicin.

Science.gov (United States)

Mohamadi, Maryam; Mostafavi, Ali; Torkzadeh-Mahani, Masoud

2017-11-01

The aim of this research was the determination of a microRNA (miRNA) using a DNA electrochemical aptasensor. In this biosensor, the complementary complementary DNA (cDNA) of miRNA-145 (a sense RNA transcript) was the target strand and the cDNA of miRNA-145 was the probe strand. Both cDNAs can be the product of the reverse transcriptase-polymerase chain reaction of miRNA. The proposed aptasensor's function was based on the hybridization of target strands with probes immobilized on the surface of a working electrode and the subsequent intercalation of doxorubicin (DOX) molecules functioning as the electroactive indicators of any double strands that formed. Electrochemical transduction was performed by measuring the cathodic current resulting from the electrochemical reduction of the intercalated molecules at the electrode surface. In the experiment, because many DOX molecules accumulated on each target strand on the electrode surface, amplification was inherently easy, without a need for enzymatic or complicated amplification strategies. The proposed aptasensor also had the excellent ability to regenerate as a result of the melting of the DNA duplex. Moreover, the use of DNA probe strands obviated the challenges of working with an RNA probe, such as sensitivity to RNase enzyme. In addition to the linear relationship between the electrochemical signal and the concentration of the target strands that ranged from 2.0 to 80.0 nM with an LOD of 0.27 nM, the proposed biosensor was clearly capable of distinguishing between complementary (target strand) and noncomplementary sequences. The presented biosensor was successfully applied for the quantification of DNA strands corresponding to miRNA-145 in human serum samples.

Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction

DEFF Research Database (Denmark)

Bagger, Alexander; Ju, Wen; Varela, Ana Sofia

2017-01-01

Currently, no catalysts are completely selective for the electrochemical CO2 Reduction Reaction (CO2RR). Based on trends in density functional theory calculations of reaction intermediates we find that the single metal site in a porphyrine-like structure has a simple advantage of limiting...... the competing Hydrogen Evolution Reaction (HER). The single metal site in a porphyrine-like structure requires an ontop site binding of hydrogen, compared to the hollow site binding of hydrogen on a metal catalyst surface. The difference in binding site structure gives a fundamental energy-shift in the scaling...... relation of ∼0.3eV between the COOH* vs. H* intermediate (CO2RR vs. HER). As a result, porphyrine-like catalysts have the advantage over metal catalyst of suppressing HER and enhancing CO2RR selectivity....

Silver-coated ion exchange membrane electrode applied to electrochemical reduction of carbon dioxide

International Nuclear Information System (INIS)

Hori, Y.; Ito, H.; Okano, K.; Nagasu, K.; Sato, S.

2003-01-01

Silver-coated ion exchange membrane electrodes (solid polymer electrolyte, SPE) were prepared by electroless deposition of silver onto ion exchange membranes. The SPE electrodes were used for carbon dioxide (CO 2 ) reduction with 0.2 M K 2 SO 4 as the electrolyte with a platinum plate (Pt) for the counterelectrode. In an SPE electrode system prepared from a cation exchange membrane (CEM), the surface of the SPE was partly ruptured during CO 2 reduction, and the reaction was rapidly suppressed. SPE electrodes made of an anion exchange membrane (SPE/AEM) sustained reduction of CO 2 to CO for more than 2 h, whereas, the electrode potential shifted negatively during the electrolysis. The reaction is controlled by the diffusion of CO 2 through the metal layer of the SPE electrode at high current density. Ultrasonic radiation, applied to the preparation of SPE/AEM, was effective to improve the electrode properties, enhancing the electrolysis current of CO 2 reduction. Observation by a scanning electron microscope (SEM) showed that the electrode metal layer became more porous by the ultrasonic radiation treatment. The partial current density of CO 2 reduction by SPE/AEM amounted to 60 mA cm -2 , i.e. three times the upper limit of the conventional electrolysis by a plate electrode. Application of SPE device may contribute to an advancement of CO 2 fixation at ambient temperature and pressure

Electrochemical reduction of oxygen on lead-silver alloys in an alkaline medium

International Nuclear Information System (INIS)

Seliverstov, S.D.; Arkhangel'skaya, Z.P.; Lyzlov, N.Y.

1986-01-01

The use of lead-silver alloys as materials for the gas-absorbing electrode in sealed silver-cadmium alkaline storage batteries is desirable primarily from the stanpoint of saving the costly silver. The authors studied reduction of oxygen with the aim of optimizing the composition of the Pb-Ag alloy and of the porous structure of the electrodes. The alloys were made in a muffle furnace in corundum crucibles under a layer of VI-2 flux. Curves are shown which represent the dependence of the ionization current of molecular oxygen on smooth partially immersed electrodes made from alloys differing in composition on the length of the part of the electrode withdrawn from the solution. It is shown that decrease of the corrosion resistance of the alloy in the porous electrode causes partial loss of its mechanical strength. Worsening of the electric contact between the particles of active material is also possible. An alloy of the composition (mass %) 60 Pb-40 Ag is the most suitable from the practical standpoint

Forecasting approach of electrochemical valorisation of CO2 in alkali molten carbonates

International Nuclear Information System (INIS)

Chery, Deborah

2015-01-01

Carbon Dioxide is a greenhouse which can be valorised by means of electrochemical valorisation into carbon monoxide. The main goals of the thesis consist in the theoretical determination of the conductive conditions leading to this electrochemical valorisation in alkali molten carbonates along with the study of the feasibility of this electrochemical reduction in binary and ternary eutectics under experimental condition. CO 2 solubility has been determined by manometric measure and increase along with the temperature. CO 2 electrochemical experimental feasibility into CO in eutectics on gold plate electrode and graphite carbon has been proved by cyclic volt-amperometry for temperatures exceeding 550 C, without gold plate electrode pretreatment and with gold plate pretreatment by an pre-electrolysis at potential slightly negative as the CO 2 reduction potential. A global approach of reactional mechanisms implied in CO 2 reduction is proposed. (author)

Electrochemical impedance spectroscopy of fully hydrated Nafion membranes at high and low hydrogen partial pressures

International Nuclear Information System (INIS)

Tsampas, M.N.; Brosda, S.; Vayenas, C.G.

2011-01-01

The proton transport mechanism in fully hydrated Nafion 117 membranes was examined via electrochemical impedance spectroscopy (EIS) and steady-state current–potential measurements both in a symmetric H 2 , Pt|Nafion|Pt, H 2 cell and in a H 2 , Pt|Nafion|Pt, air PEM fuel cell with hydrogen partial pressure values, P H 2 , varied between 0.5 kPa and 100 kPa. In agreement with recent studies it is found that for low P H 2 values the steady-state current–potential curves exhibit bistability and regions of positive slope. In these regions the Nyquist plots are found to exhibit negative real part impedance with a large imaginary component, while the Bode plots show a pronounced negative phase shift. These observations are consistent with the mechanism involving two parallel routes of proton conduction in fully hydrated Nafion membranes, one due to proton migration in the aqueous phase, the other due to proton transfer, probably involving tunneling, between adjacent sulfonate groups in narrow pores. The former mechanism dominates at high P H 2 values and the latter dominates in the low P H 2 region where the real part of the impedance is negative.

Cathodic Potential Dependence of Electrochemical Reduction of SiO2 Granules in Molten CaCl2

Science.gov (United States)

Yang, Xiao; Yasuda, Kouji; Nohira, Toshiyuki; Hagiwara, Rika; Homma, Takayuki

2016-09-01

As part of an ongoing fundamental study to develop a new process for producing solar-grade silicon, this paper examines the effects of cathodic potential on reduction kinetics, current efficiency, morphology, and purity of Si product during electrolysis of SiO2 granules in molten CaCl2 at 1123 K (850 °C). SiO2 granules were electrolyzed potentiostatically at different cathodic potentials (0.6, 0.8, 1.0, and 1.2 V vs Ca2+/Ca). The reduction kinetics was evaluated based on the growth of the reduced Si layer and the current behavior during electrolysis. The results suggest that a more negative cathodic potential is favorable for faster reduction. Current efficiencies in 60 minutes are greater than 65 pct at all the potentials examined. Si wires with sub-micron diameters are formed, and their morphologies show little dependence on the cathodic potential. The impurities in the Si product can be controlled at low level. The rate-determining step for the electrochemical reduction of SiO2 granules in molten CaCl2 changes with time. At the initial stage of electrolysis, the electron transfer is the rate-determining step. At the later stage, the diffusion of O2- ions is the rate-determining step. The major cause of the decrease in reduction rate with increasing electrolysis time is the potential drop from the current collector to the reaction front due to the increased contact resistance among the reduced Si particles.

Process for electrochemically gasifying coal using electromagnetism

Science.gov (United States)

Botts, Thomas E.; Powell, James R.

1987-01-01

A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

A novel molten-salt electrochemical cell for investigating the reduction of uranium dioxide to uranium metal by lithium using in situ synchrotron radiation.

Science.gov (United States)

Brown, Leon D; Abdulaziz, Rema; Jervis, Rhodri; Bharath, Vidal; Mason, Thomas J; Atwood, Robert C; Reinhard, Christina; Connor, Leigh D; Inman, Douglas; Brett, Daniel J L; Shearing, Paul R

2017-03-01

A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO 2 to U metal in LiCl-KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO 2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl-KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO 2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems.

Effect of flavin compounds on uranium(VI) reduction- kinetic study using electrochemical methods with UV-vis spectroscopy

International Nuclear Information System (INIS)

Yamasaki, Shinya; Tanaka, Kazuya; Kozai, Naofumi; Ohnuki, Toshihiko

2017-01-01

The reduction of uranium hexavalent (U(VI)) to tetravalent (U(IV)) is an important reaction because of the change in its mobility in the natural environment. Although the flavin mononucleotide (FMN) has acted as an electron shuttle for the U(VI) reduction in vivo system, which is called an electron mediator, only the rate constant for the electron transfer from FMN to U(VI) has been determined. This study examined the rate constant for the U(VI) reduction process by three flavin analogues (riboflavin, flavin mononucleotide, flavin adenine dinucleotide) to elucidate their substituent group effect on the U(VI) reduction rate by electrochemical methods. The formation of the U(IV) was monitored by UV-vis spectrometry at 660 nm during the constant potential electrolysis of the U(VI) solution in the presence of the mediator. The cyclic voltammograms indicated that the three flavin analogues behaved as electron mediator to reduce U(VI). The logarithmic rate constant for the U(VI) reduction was related to the standard redox potential of the mediators. This linear relationship indicated that the redox-active group of the mediator and the substituent group of the mediator dominate capability of the U(VI) reduction and its rate, respectively. The apparent reduction potential of U(VI) increased about 0.2 V in the presence of the mediators, which strongly suggests that the biological electron mediator makes the U(VI) reduction possible even under more oxidative conditions. - Highlights: • The rate constant for the U(VI) reduction by flavin analogues was determined. • The flavins showed a mediator effect on the U(VI) reduction. • The logarithmic rate constants for the U(VI) reduction was proportional to redox potential of the mediator. • The presence of the mediator increased about 0.2 V apparent redox potential of U(VI) to U(IV).

Electrochemical reduction of oxygen on small platinum particles supported on carbon in concentrated phosphoric acid. 2. Effects of teflon content in the catalyst layer and baking temperature of the electrode

Energy Technology Data Exchange (ETDEWEB)

Maoka, T.

1988-03-01

A relation between hydrophobicity (or wettability) of a porous gas diffusion electrode for use in a phosphoric acid fuel cell and its cathode performance (activity toward electrochemical oxygen reduction) was examined. The hydrophobicity of the gas diffusion electrode was regulated by changing either the amount of Teflon (PTFE) content in the catalyst layer or baking temperature of the electrode. The Tafel slope or electrochemical oxygen reduction became twice as high as that of the ordinary electrode when the wettability of electrode toward phosphoric acid was high. This fact supports a flooded agglomerate model as the mode of this type of porous gas diffusion electrode.

Electrochemically enhanced reduction of hexavalent chromium in contaminated clay: Kinetics, energy consumption, and application of pulse current

DEFF Research Database (Denmark)

Sun, Tian Ran; Pamukcu, Sibel; Ottosen, Lisbeth M.

2015-01-01

the dependency of reaction rate on energy consumption. A modified electrophoresis cell with platinum wires as working electrodes was used to run experiments. Results showed that the reduction rate of Cr(VI) was significantly increased by application of current with the pseudo-first-order rate constant kpse from......,Fe)(OH)3] precipitates. XRD analysis suggested that the [(Cr,Fe)(OH)3] formed at the clay surface and grew into the pore fluid. SEM-EDX results indicated that the overall Fe(III):Cr(III) ratio of the precipitates was approximately 1.26:1. Application of pulse current decreased the non-productive energy......Electrochemically enhanced reduction of Cr(VI) in clay medium is a technique based on inputting extra energy into the clay to drive the favorable redox reaction. In this study, the reducing reagent Fe(II) was transported into Cr(VI) spiked kaolinite clay by direct current to investigate...

New Method for Super Hydrophobic Treatment of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells Using Electrochemical Reduction of Diazonium Salts.

Science.gov (United States)

Thomas, Yohann R J; Benayad, Anass; Schroder, Maxime; Morin, Arnaud; Pauchet, Joël

2015-07-15

The purpose of this article is to report a new method for the surface functionalization of commercially available gas diffusion layers (GDLs) by the electrochemical reduction of diazonium salt containing hydrophobic functional groups. The method results in superhydrophobic GDLs, over a large area, without pore blocking. An X-ray photoelectron spectroscopy study based on core level spectra and chemical mapping has demonstrated the successful grafting route, resulting in a homogeneous distribution of the covalently bonded hydrophobic molecules on the surface of the GDL fibers. The result was corroborated by contact angle measurement, showing similar hydrophobicity between the grafted and PTFE-modified GDLs. The electrochemically modified GDLs were tested in proton exchange membrane fuel cells under automotive, wet, and dry conditions and demonstrated improved performance over traditional GDLs.

Fabrication of Electrochemically Reduced Graphene Oxide Modified Gas Diffusion Electrode for In-situ Electrochemical Advanced Oxidation Process under Mild Conditions

International Nuclear Information System (INIS)

Dong, Heng; Su, Huimin; Chen, Ze; Yu, Han; Yu, Hongbing

2016-01-01

With aim to develop an efficient heterogeneous metal-free cathodic electrochemical advance oxidation process (CEAOP) for persistent organic pollutants (POPs) removal from wastewater under mild conditions, electrochemically reduced graphene oxide (ERGO)-modified gas diffusion electrode (GDE) was prepared for oxygen-containing radicals production via electrochemical oxygen reduction reaction (ORR). A detailed physical characterization was carried out by SEM, Raman spectroscopy, XRD and XPS. The electrocatalytic behavior for ORR was investigated by electrochemical measurements and electrolysis experiments under constant current density. Bisphenol A (BPA) of 20 mg L −1 was used as a model of POPs to evaluate the performance of the CEAOP with ERGO-modified GDE. The results showed that the defects concentration and electrochemical active sites of the ERGO was increased as the reduction time (30 min, 60 min and 120 min), leading to different catalysis on ORR. ·O 2 generation via one-electron ORR was found under the electrocatalysis of ERGO (60 min and 120 min), contributing to a complete degradation of BPA within 20 min and a mineralization current efficiency (MCE) of 74.60%. An alternative metal-free CEAOP independent of Fenton reaction was established based on ERGO-modified GDE for POPs removal from wastewater under mild conditions.

A model and variance reduction method for computing statistical outputs of stochastic elliptic partial differential equations

International Nuclear Information System (INIS)

Vidal-Codina, F.; Nguyen, N.C.; Giles, M.B.; Peraire, J.

2015-01-01

We present a model and variance reduction method for the fast and reliable computation of statistical outputs of stochastic elliptic partial differential equations. Our method consists of three main ingredients: (1) the hybridizable discontinuous Galerkin (HDG) discretization of elliptic partial differential equations (PDEs), which allows us to obtain high-order accurate solutions of the governing PDE; (2) the reduced basis method for a new HDG discretization of the underlying PDE to enable real-time solution of the parameterized PDE in the presence of stochastic parameters; and (3) a multilevel variance reduction method that exploits the statistical correlation among the different reduced basis approximations and the high-fidelity HDG discretization to accelerate the convergence of the Monte Carlo simulations. The multilevel variance reduction method provides efficient computation of the statistical outputs by shifting most of the computational burden from the high-fidelity HDG approximation to the reduced basis approximations. Furthermore, we develop a posteriori error estimates for our approximations of the statistical outputs. Based on these error estimates, we propose an algorithm for optimally choosing both the dimensions of the reduced basis approximations and the sizes of Monte Carlo samples to achieve a given error tolerance. We provide numerical examples to demonstrate the performance of the proposed method

Metal Oxide Materials and Collector Efficiency in Electrochemical Supercapacitors

Science.gov (United States)

2010-12-01

However, even if thick tita - nium films and/or nanostructured layers were obtained using these methods, they were composed of non-conducting titanium...following electrochemical reduction in LiClO4/acetonitrile. Table 1 reports the electrochemical parameters and the atomic composition of the tita - nium

Electrochemical reduction of oxygen and nitric oxide at low temperature on Ce1−xPrxO2−δ cathodes

DEFF Research Database (Denmark)

Werchmeister, Rebecka Maria Larsen; Kammer Hansen, Kent

2013-01-01

The ability of praseodymium doped cerium oxide materials to electrochemically reduce NO and O2 was studied using cone-shaped electrodes in conjunction with cyclic voltammetry, in the temperature range 200–400 °C. Four samples were studied; Ce1−xPrxO2−δ (x = 0.1, 0.2, 0.3 and 0.4). It was shown...... the highest ratio of maximum cathodic current density (iNO/iO2iNO/iO2), which is used as an indication of a higher activity toward reduction of NO compared to reduction of O2. The apparent selectivity generally decreased with increasing temperature for all the compositions....

In-Situ Electrochemical Corrosion Behavior of Nickel-Base 718 Alloy Under Various CO2 Partial Pressures at 150 and 205 °C in NaCl Solution

Science.gov (United States)

Zhang, Yubi; Zhao, Yongtao; Tang, An; Yang, Wenjie; Li, Enzuo

2018-03-01

The electrochemical corrosion behavior of nickel-base alloy 718 was investigated using electrochemical impedance spectroscopy and potentiodynamic polarization techniques at various partial pressures of CO2 (P_{{{CO}2 }} s) in a 25 wt% NaCl solution at 150 and 205 °C. The passive films composed of FeCO3 exhibit good corrosion resistance with a feature of Warburg impedance, Tafel plots show a complete passivation and the anodic reactions was dominated by a diffusion process at low P_{{{CO}2 }} s (1.8-9.8 MPa) at 150 °C. While numerous dented corrosion areas appeared on the sample surface for the P_{{{CO}2 }} of 11.6 MPa at 205 °C, the Tafel plot with three anodic peaks and the Nyquist diagram with an atrophied impedance arc were present. This dented corrosion attribute to the synergistic effects of stress, temperature, P_{{{CO}2 }} and Cl-, the temperature and stress could play crucial roles on the corrosion of the alloy 718.

Preliminary results of the comparison of the electrochemical behavior of a thioether and biphenyl

Science.gov (United States)

Morales, W.; Jones, W. R.

1983-01-01

An electrochemical cell was constructed to explore the feasibility of using electrochemical techniques to simulate the tribochemistry of various substances. The electrochemical cell was used to study and compare the behavior of a thioether 1,3-bis(phenylthio) benzene and biphenyl. It is found that under controlled conditions biphenyl undergoes a reversible reduction to a radical anion whereas the thioether undergoes an irreversible reduction yielding several products. The results are discussed in relationship to boundary lubrication.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

Science.gov (United States)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

Electrochemical oxidation of ethanol using PtRh/C electrocatalysts in alkaline medium and synthesized by sodium borohydride and alcohol reduction

International Nuclear Information System (INIS)

Fontes, Eric Hossein

2017-01-01

PtRh/C were prepared by the following atomic proportions: (100,0), (0,100), (90,10), (70,30) and (50,50). The methods employed in the synthesis of these materials were reduction by sodium borohydride and reduction by alcohol. The metal salts used were H 2 PtCl 6 3•6H 2 0 and (RhNO 3 ) 3 , the support used was Carbon black XC72 and the bulk metal composition was 20% and 80% of support. The electrocatalysts were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction and Transmission electron microscopy. The ethanol electrochemical oxidation mechanism was investigated by in situ Fourier Transform Infrared Spectroscopy couple to an Attenuated Total Reflection technique. The electrocatalytic activity were evaluated by Cyclic Voltammetry, Linear Sweep Voltammetry and Chronoamperometry techniques. The Fuel Cells tests were made in a single direct alcohol fuel cell with alkaline membrane. The working electrodes were prepared by a thin porous coating technique. X-ray diffraction allowed to verify metallic alloys, segregate phases and to calculate the percentage of metallic alloys. It was else possible to identify crystallographic phases. Infrared Spectroscopy allowed to verify that the electrochemical oxidation of ethanol was carried out by an incomplete mechanism. PtRh(70:30)/C prepared by sodium borohydride produced large amounts of carbon dioxide and acetaldehyde. Rh/C showed electrocatalytic activity when compared with other materials studied.

Electrochemical system for the control of oxigen atmospheres in UO2 sintering

International Nuclear Information System (INIS)

Caneiro, Alberto; Abriata, J.P.

1980-01-01

The behaviour of an electrochemical pump and of an oxygen sensor, allowing a precise control of the UO 2 stoichiometry in the preparation and analysis of gaseous mixtures of low oxygen contents is described. The correct functioning of the system can be tested by applying Faraday's law. The oxygen partial pressures can be continuously controlled by the sole varation of the current applied to the electrochemical pump. The partial pressure of the system is within the range between x 10 -1 atm and 10 -27 atm at 800 deg C. This system may be utilized for sintering experiments at a laboratory scale. (M.E.L) [es

Superhydrophobic surfaces by electrochemical processes.

Science.gov (United States)

Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

2013-03-13

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-equivalent electrochemical reduction of a cyano-complex [TlIII(CN)2]+ and the novel di-nuclear compound [(CN)5PtII-TlIII]0

International Nuclear Information System (INIS)

Dolidze, Tina D.; Khoshtariya, Dimitri E.; Behm, Martin; Lindbergh, Goeran; Glaser, Julius

2005-01-01

Extending our recent insights in two-electron transfer microscopic mechanisms for a Tl III /Tl I redox system [D.E. Khoshtariya, et al., Inorg. Chem. 41 (2002) 1728], the electrochemical response of glassy carbon electrode in acidified solutions of Tl III (ClO 4 ) 3 containing different concentrations of sodium cyanide has been extensively studied for the first time by use of cyclic voltammetry and the CVSIM curve simulation PC program. The complex [Tl III (CN) 2 ] + has been thoroughly identified electrochemically and shown to display a single well-defined reduction wave (which has no anodic counterpart), ascribed to the two-equivalent process yielding [Tl I (aq)] + . This behavior is similar to that of [Tl III (aq)] 3+ ion in the absence of sodium cyanide, disclosed in the previous work, and is compatible with the quasi-simultaneous yet sequential two-electron transfer pattern (with two reduction waves merged in one), implying the rate-determining first electron transfer step (resulting in the formation of a covalently interacting di-thallium complex as a metastable intermediate), and the fast second electron transfer step. Some preliminary studies of the two-equivalent reduction of directly metal-metal bonded stable compound [(CN) 5 Pt II -Tl III ] 0 has been also performed displaying two reduction waves compatible with a true sequential pattern

Reduction of multipartite qubit density matrixes to bipartite qubit density matrixes and criteria of partial separability of multipartite qubit density matrixes

OpenAIRE

Zhong, Zai-Zhe

2004-01-01

The partial separability of multipartite qubit density matrixes is strictly defined. We give a reduction way from N-partite qubit density matrixes to bipartite qubit density matrixes, and prove a necessary condition that a N-partite qubit density matrix to be partially separable is its reduced density matrix to satisfy PPT condition.

Single-Molecule Electrochemical Gating in Ionic Liquids

DEFF Research Database (Denmark)

Kay, Nicola J.; Higgins, Simon J.; Jeppesen, Jan O.

2012-01-01

The single-molecular conductance of a redox active molecular bridge has been studied in an electrochemical single-molecule transistor configuration in a room-temperature ionic liquid (RTIL). The redox active pyrrolo-tetrathiafulvalene (pTTF) moiety was attached to gold contacts at both ends through...... −(CH2)6S– groups, and gating of the redox state was achieved with the electrochemical potential. The water-free, room-temperature, ionic liquid environment enabled both the monocationic and the previously inaccessible dicationic redox states of the pTTF moiety to be studied in the in situ scanning...... and decreases again as the second redox process is passed. This is described as an “off–on–off–on–off” conductance switching behavior. This molecular conductance vs electrochemical potential relation could be modeled well as a sequential two-step charge transfer process with full or partial vibrational...

Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

International Nuclear Information System (INIS)

Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo

2013-01-01

We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K 2 SO 4 electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO 4 ) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium

Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

Energy Technology Data Exchange (ETDEWEB)

Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo [Korea Univ., Seoul (Korea, Republic of)

2013-08-15

We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K{sub 2}SO{sub 4} electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO{sub 4}) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium.

Towards high throughput screening of electrochemical stability of battery electrolytes

International Nuclear Information System (INIS)

Borodin, Oleg; Olguin, Marco; Spear, Carrie E; Leiter, Kenneth W; Knap, Jaroslaw

2015-01-01

High throughput screening of solvents and additives with potential applications in lithium batteries is reported. The initial test set is limited to carbonate and phosphate-based compounds and focused on their electrochemical properties. Solvent stability towards first and second reduction and oxidation is reported from density functional theory (DFT) calculations performed on isolated solvents surrounded by implicit solvent. The reorganization energy is estimated from the difference between vertical and adiabatic redox energies and found to be especially important for the accurate prediction of reduction stability. A majority of tested compounds had the second reduction potential higher than the first reduction potential indicating that the second reduction reaction might play an important role in the passivation layer formation. Similarly, the second oxidation potential was smaller for a significant subset of tested molecules than the first oxidation potential. A number of potential sources of errors introduced during screening of the electrolyte electrochemical properties were examined. The formation of lithium fluoride during reduction of semifluorinated solvents such as fluoroethylene carbonate and the H-transfer during oxidation of solvents were found to shift the electrochemical potential by 1.5–2 V and could shrink the electrochemical stability window by as much as 3.5 V when such reactions are included in the screening procedure. The initial oxidation reaction of ethylene carbonate and dimethyl carbonate at the surface of the completely de-lithiated LiNi 0.5 Mn 1.5 O 4 high voltage spinel cathode was examined using DFT. Depending on the molecular orientation at the cathode surface, a carbonate molecule either exhibited deprotonation or was found bound to the transition metal via its carbonyl oxygen. (paper)

Investigation of electrochemical reduction of GeO2 to Ge in molten CaCl2-NaCl

International Nuclear Information System (INIS)

Rong, Liangbin; He, Rui; Wang, Zhiyong; Peng, Junjun; Jin, Xianbo; Chen, George Z.

2014-01-01

Electrochemical reduction of solid GeO 2 has been investigated in the mixed CaCl 2 -NaCl melt at 1023 K for developing a more efficient process for preparation of Ge. Cyclic voltammetry and potentiostatic electrolysis were applied to study the GeO 2 -loaded metallic cavity electrode. In addition, porous GeO 2 pellets were reduced by potentiostatic and constant cell voltage electrolysis with a graphite anode, and the electrolysis products were analyzed by powder X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectrometry, focusing on understanding the reduction mechanism and the impact of electrode potential on the product purity. It was found that the reduction of GeO 2 to Ge occurred at a potential of about -0.50 V (vs. Ag/Ag + ), but generating various calcium germanates simultaneously, whose reduction was a little more difficult and needed a potential more negative than -1.00 V. However, if the cathode potential exceeded -1.60 V, Ca (or Na) - Ge intermetallic compounds might form. These results gave an appropriate potential range between -1.10 and -1.40 V for the production of pure germanium. Rapid electrolysis of GeO 2 to pure Ge has been realized at a cell voltage of 2.5 V with a current efficiency of about 92%

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

International Nuclear Information System (INIS)

Verma, Pallavi; Maire, Pascal; Novak, Petr

2011-01-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH 2 ) 3 OCO 2 Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C 6 H 4 NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C 6 H 4 CH 2 OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

Energy Technology Data Exchange (ETDEWEB)

Verma, Pallavi; Maire, Pascal [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland); Novak, Petr, E-mail: petr.novak@psi.c [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland)

2011-04-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH{sub 2}){sub 3}OCO{sub 2}Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C{sub 6}H{sub 4}NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C{sub 6}H{sub 4}CH{sub 2}OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Effect of reduction enhancer on a radiolytic synthesis of carbon-supported Pt–Cu nanoparticles and their structural and electrochemical properties

Energy Technology Data Exchange (ETDEWEB)

Kugai, Junichiro, E-mail: jkugai@kobe-kosen.ac.jp [Kobe City College of Technology, Department of Applied Chemistry (Japan); Kubota, Chihiro; Okazaki, Tomohisa; Seino, Satoshi; Nakagawa, Takashi [Osaka University, Graduate School of Engineering (Japan); Nitani, Hiroaki [High Energy Accelerator Research Organization, Institute of Materials Structure Science (IMSS) (Japan); Yamamoto, Takao A. [Osaka University, Graduate School of Engineering (Japan)

2015-06-15

In order to clarify the effect of reduction enhancer on the nanoparticle formation process and their structural and catalytic properties, carbon-supported Pt–Cu nanoparticles were synthesized by electron beam irradiation on an aqueous precursor solution in the presence/absence of reduction enhancer. In the absence of reduction enhancer, tetravalent platinum oxide particles of approximately 1 nm in diameter were formed on carbon support with copper barely precipitated, while in the presence of 2-propanol or ethylene glycol or glucose both platinum and copper precipitated as few-nanometer-sized alloy particles together with copper oxides. It was suggested that the metal nuclei produced upon electron beam irradiation do not have enough lifetime without reduction enhancer due to fast oxidation of the nuclei by oxidizing radicals, while the reduction enhancer scavenges these oxidizing radicals preventing oxidation of metallic clusters and prolonging their lifetime. Ethylene glycol gave smaller and better alloyed particles with less copper oxides compared to 2-propanol since the carbonyl compounds derived from oxidation of ethylene glycol protect metallic clusters from oxidation further prolonging their lifetime. In the electrochemical measurements, the methanol oxidation activities of Pt–Cu/C catalysts were well explained by their structural characteristics.

Application of electrochemical techniques in fuel reprocessing- an overview

Energy Technology Data Exchange (ETDEWEB)

Rao, M K; Bajpai, D D; Singh, R K [Power Reactor Fuel Reprocessing Plant, Tarapur (India)

1994-06-01

The operating experience and development work over the past several years have considerably improved the wet chemical fuel reprocessing PUREX process and have brought the reprocessing to a stage where it is ready to adopt the introduction of electrochemical technology. Electrochemical processes offer advantages like simplification of reprocessing operation, improved performance of the plant and reduction in waste volume. At Power Reactor Fuel Reprocessing plant, Tarapur, work on development and application of electrochemical processes has been carried out in stages. To achieve plant scale application of these developments, a new electrochemical cycle is being added to PUREX process at PREFRE. This paper describes the electrochemical and membrane cell development activities carried out at PREFRE and their current status. (author). 5 refs., 4 tabs.

Study for electrochemical behavior of uranium oxide in a molten LiCl-Li2O system

International Nuclear Information System (INIS)

Park, Sung Bin; Park, Byung Heung; Seo, Chung Seok; Jung, Ki Jung; Park, Seong Won

2005-01-01

Interest in the electrolytic reduction of uranium oxide is increasing in the treatment of spent fuel oxides. With complicated and expensive procedures many reactive metals can be prepared in a pure metal form, the electrochemical reduction of a metal oxide has been recently proposed in metallurgy. The electrochemical reduction process is simple and rapid when compared to the conventional processes. The process can reduce the production costs and be applicable to a wide range of metal oxides. Chen et al. proposed the direct electrochemical reduction of titanium dioxide to titanium in a molten calcium chloride. Argonne National Laboratory (ANL) has reported the experimental results of an electrochemical reduction of the uranium oxide fuel in a bench-scale apparatus with a cyclic voltammetry, and has designed high-capacity reduction (HCR) cells and conducted three kg-scale UO 2 reduction runs. Gourishankar et al. classified the mechanisms of the electrolytic reduction of the metal oxides in a LiCl-Li 2 O molten salt system into two types; the simultaneous reduction and the direct electrochemical reduction. The uranium oxide in LiCl-Li 2 O molten salt was converted to uranium metal according to two mechanisms. Korea Atomic Energy Research Institute (KAERI) has developed the Advanced Spent Fuel Conditioning Process (ACP) to be an innovative technology in handling the PWR spent fuel. As part of ACP, the electrolytic reduction process (ER process) is the electrochemical reduction process of uranium oxide to uranium metal in molten salt. The ER process has advantages in a technical stability, an economic potential and a good proliferation resistance. KAERI has reported on the good experimental results of an electrochemical reduction of the uranium oxide in a 20 kg HM/batch lab-scale. In this work, cyclic voltammograms for a LiCl-3 wt% Li 2 O system and an U 3 O 8 -LiCl-3 wt% Li 2 O system with the integrated cathode assembly have been obtained. From the cyclic

Electrochemical treatment of wastewater: A case study of reduction of DNT and oxidation of chlorinated phenols

Energy Technology Data Exchange (ETDEWEB)

Rodgers, J.D.; Bunce, N.J.; Jedral, W.

1999-07-01

Electrochemical treatment is under consideration as a treatment option for several recalcitrant compounds. In this work the authors investigate the oxidation of chlorophenols and the reduction of nitroaromatics. In the case of chlorinated phenols, they explore the problem of anode fouling which has hampered electrolytic treatment of phenolic compounds by examining phenols differing in the extent of chlorination, according to the mechanism of oxidation at different electrode types. Linear sweep voltammograms at a Pt anode were interpreted in terms of deposition of oligomers on the anode surface. Passivation increased in parallel with the uncompensated resistance of the solution and occurred only at potentials at which water is oxidized, suggesting that the formation of the oligomer film involves attack of hydroxyl radicals on electrochemically oxidized substrate. Relative reactivities of congeners were anode-dependent, due to different mechanisms of oxidation: direct electron transfer oxidation at PbO{sub 2} and hydroxyl radical attack at SnO{sub 2} and IrO{sub 2}. Voltammetry of 2,6-dinitrotoluene (DNT) was consistent with literature values. DNT was reduced at several cathodes with the most promising result at Ni-plated Ni wire. At current densities {lt} 0.1 mA cm{sup {minus}2}, current efficiencies {gt} 50% could be achieved with 4-chlorophenol at all three anodes and for 2,6-DNT at Ni-plated Ni wire.

Electrochemical pretreatment of amino-carbon nanotubes on graphene support as a novel platform for bilirubin oxidase with improved bioelectrocatalytic activity towards oxygen reduction.

Science.gov (United States)

Navaee, Aso; Salimi, Abdollah; Jafari, Fereydoon

2015-03-23

The electrochemical conditioning of amino-carbon nanotubes (CNTs) on a graphene support in an alkaline solution is used to produce -NHOH as hydrophilic functional groups for the efficient immobilization of bilirubin oxidase enzyme. The application of the immobilized enzyme for the direct electrocatalytic reduction of O2 is investigated. The onset potential of 0.81 V versus NHE and peak current density of 2.3 mA cm(-2) for rotating modified electrode at 1250 rpm, indicate improved biocatalytic activity of the proposed system for O2 reduction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superconducting Nb{sub 3}Sn intermetallics made by electrochemical reduction of Nb{sub 2}O{sub 5}-SnO{sub 2} oxides

Energy Technology Data Exchange (ETDEWEB)

Glowacki, B A; Fray, D J; Yan, X-Y; Chen, G

2003-05-01

The article is focused on low temperature superconducting Nb{sub 3}Sn material manufactured by novel electrodeoxidizing method developed in Cambridge whereby the range of alloys and intermetallics are produced cheaply making potential superconducting wires more cost effective. The process of direct electrochemical reduction of Nb{sub 2}O{sub 5}-SnO{sub 2} mixtures and in situ formation of the Nb{sub 3}Sn is discussed in details.

Preparation of porous lead from shape-controlled PbO bulk by in situ electrochemical reduction in ChCl-EG deep eutectic solvent

Science.gov (United States)

Ru, Juanjian; Hua, Yixin; Xu, Cunying; Li, Jian; Li, Yan; Wang, Ding; Zhou, Zhongren; Gong, Kai

2015-12-01

Porous lead with different shapes was firstly prepared from controlled geometries of solid PbO bulk by in situ electrochemical reduction in choline chloride-ethylene glycol deep eutectic solvents at cell voltage 2.5 V and 353 K. The electrochemical behavior of PbO powders on cavity microelectrode was investigated by cyclic voltammetry. It is indicated that solid PbO can be directly reduced to metal in the solvent and a nucleation loop is apparent. Constant voltage electrolysis demonstrates that PbO pellet can be completely converted to metal for 13 h, and the current efficiency and specific energy consumption are about 87.79% and 736.82 kWh t-1, respectively. With the electro-deoxidation progress on the pellet surface, the reduction rate reaches the fastest and decreases along the distance from surface to inner center. The morphologies of metallic products are porous and mainly consisted of uniform particles which connect with each other by finer strip-shaped grains to remain the geometry and macro size constant perfectly. In addition, an empirical model of the electro-deoxidation process from spherical PbO bulk to porous lead is also proposed. These findings provide a novel and simple route for the preparation of porous metals from oxide precursors in deep eutectic solvents at room temperature.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

Science.gov (United States)

Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

2016-06-01

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Partial scan artifact reduction (PSAR) for the assessment of cardiac perfusion in dynamic phase-correlated CT.

Science.gov (United States)

Stenner, Philip; Schmidt, Bernhard; Bruder, Herbert; Allmendinger, Thomas; Haberland, Ulrike; Flohr, Thomas; Kachelriess, Marc

2009-12-01

Cardiac CT achieves its high temporal resolution by lowering the scan range from 2pi to pi plus fan angle (partial scan). This, however, introduces CT-value variations, depending on the angular position of the pi range. These partial scan artifacts are of the order of a few HU and prevent the quantitative evaluation of perfusion measurements. The authors present the new algorithm partial scan artifact reduction (PSAR) that corrects a dynamic phase-correlated scan without a priori information. In general, a full scan does not suffer from partial scan artifacts since all projections in [0, 2pi] contribute to the data. To maintain the optimum temporal resolution and the phase correlation, PSAR creates an artificial full scan pn(AF) by projectionwise averaging a set of neighboring partial scans pn(P) from the same perfusion examination (typically N approximately 30 phase-correlated partial scans distributed over 20 s and n = 1, ..., N). Corresponding to the angular range of each partial scan, the authors extract virtual partial scans pn(V) from the artificial full scan pn(AF). A standard reconstruction yields the corresponding images fn(P), fn(AF), and fn(V). Subtracting the virtual partial scan image fn(V) from the artificial full scan image fn(AF) yields an artifact image that can be used to correct the original partial scan image: fn(C) = fn(P) - fn(V) + fn(AF), where fn(C) is the corrected image. The authors evaluated the effects of scattered radiation on the partial scan artifacts using simulated and measured water phantoms and found a strong correlation. The PSAR algorithm has been validated with a simulated semianthropomorphic heart phantom and with measurements of a dynamic biological perfusion phantom. For the stationary phantoms, real full scans have been performed to provide theoretical reference values. The improvement in the root mean square errors between the full and the partial scans with respect to the errors between the full and the corrected scans is

Partial scan artifact reduction (PSAR) for the assessment of cardiac perfusion in dynamic phase-correlated CT

International Nuclear Information System (INIS)

Stenner, Philip; Schmidt, Bernhard; Bruder, Herbert; Allmendinger, Thomas; Haberland, Ulrike; Flohr, Thomas; Kachelriess, Marc

2009-01-01

Purpose: Cardiac CT achieves its high temporal resolution by lowering the scan range from 2π to π plus fan angle (partial scan). This, however, introduces CT-value variations, depending on the angular position of the π range. These partial scan artifacts are of the order of a few HU and prevent the quantitative evaluation of perfusion measurements. The authors present the new algorithm partial scan artifact reduction (PSAR) that corrects a dynamic phase-correlated scan without a priori information. Methods: In general, a full scan does not suffer from partial scan artifacts since all projections in [0, 2π] contribute to the data. To maintain the optimum temporal resolution and the phase correlation, PSAR creates an artificial full scan p n AF by projectionwise averaging a set of neighboring partial scans p n P from the same perfusion examination (typically N≅30 phase-correlated partial scans distributed over 20 s and n=1,...,N). Corresponding to the angular range of each partial scan, the authors extract virtual partial scans p n V from the artificial full scan p n AF . A standard reconstruction yields the corresponding images f n P , f n AF , and f n V . Subtracting the virtual partial scan image f n V from the artificial full scan image f n AF yields an artifact image that can be used to correct the original partial scan image: f n C =f n P -f n V +f n AF , where f n C is the corrected image. Results: The authors evaluated the effects of scattered radiation on the partial scan artifacts using simulated and measured water phantoms and found a strong correlation. The PSAR algorithm has been validated with a simulated semianthropomorphic heart phantom and with measurements of a dynamic biological perfusion phantom. For the stationary phantoms, real full scans have been performed to provide theoretical reference values. The improvement in the root mean square errors between the full and the partial scans with respect to the errors between the full and the

Oxygen Vacancies and Stacking Faults Introduced by Low-Temperature Reduction Improve the Electrochemical Properties of Li2MnO3 Nanobelts as Lithium-Ion Battery Cathodes.

Science.gov (United States)

Sun, Ya; Cong, Hengjiang; Zan, Ling; Zhang, Youxiang

2017-11-08

Among the Li-rich layered oxides Li 2 MnO 3 has significant theoretical capacity as a cathode material for Li-ion batteries. Pristine Li 2 MnO 3 generally has to be electrochemically activated in the first charge-discharge cycle which causes very low Coulombic efficiency and thus deteriorates its electrochemical properties. In this work, we show that low-temperature reduction can produce a large amount of structural defects such as oxygen vacancies, stacking faults, and orthorhombic LiMnO 2 in Li 2 MnO 3 . The Rietveld refinement analysis shows that, after a reduction reaction with stearic acid at 340 °C for 8 h, pristine Li 2 MnO 3 changes into a Li 2 MnO 3 -LiMnO 2 (0.71/0.29) composite, and the monoclinic Li 2 MnO 3 changes from Li 2.04 Mn 0.96 O 3 in the pristine Li 2 MnO 3 (P-Li 2 MnO 3 ) to Li 2.1 Mn 0.9 O 2.79 in the reduced Li 2 MnO 3 (R-Li 2 MnO 3 ), indicating the production of a large amount of oxygen vacancies in the R-Li 2 MnO 3 . High-resolution transmission electron microscope images show that a high density of stacking faults is also introduced by the low-temperature reduction. When measured as a cathode material for Li-ion batteries, R-Li 2 MnO 3 shows much better electrochemical properties than P-Li 2 MnO 3 . For example, when charged-discharged galvanostatically at 20 mA·g -1 in a voltage window of 2.0-4.8 V, R-Li 2 MnO 3 has Coulombic efficiency of 77.1% in the first charge-discharge cycle, with discharge capacities of 213.8 and 200.5 mA·h·g -1 in the 20th and 30th cycles, respectively. In contrast, under the same charge-discharge conditions, P-Li 2 MnO 3 has Coulombic efficiency of 33.6% in the first charge-discharge cycle, with small discharge capacities of 80.5 and 69.8 mA·h·g -1 in the 20th and 30th cycles, respectively. These materials characterizations, and electrochemical measurements show that low-temperature reduction is one of the effective ways to enhance the performances of Li 2 MnO 3 as a cathode material for Li-ion batteries.

Electrochemical characterization of single-walled carbon nanotubes for electrochemical double layer capacitors using non-aqueous electrolyte

International Nuclear Information System (INIS)

Ruch, P.W.; Koetz, R.; Wokaun, A.

2009-01-01

Single-walled carbon nanotubes (SWCNTs) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy in a non-aqueous electrolyte, 1 M Et 4 NBF 4 in acetonitrile, suitable for supercapacitors. Further, in situ dilatometry and in situ conductance measurements were performed on single electrodes and the results compared to an activated carbon, YP17. Both materials show capacitive behavior characteristic of high surface area electrodes for supercapacitors, with the maximum full cell gravimetric capacitance being 34 F/g for YP17 and 20 F/g for SWCNTs at 2.5 V with respect to the total active electrode mass. The electronic resistance of SWCNTs and activated carbon decreases significantly during charging, showing similarities of the two materials during electrochemical doping. The SWCNT electrode expands irreversibly during the first electrochemical potential sweep as verified by in situ dilatometry, indicative of at least partial debundling of the SWCNTs. A reversible periodic swelling and shrinking during cycling is observed for both materials, with the magnitude of expansion depending on the type of ions forming the double layer.

Electrochemical processes for the environmental remediation of toxic Cr(VI): A review

International Nuclear Information System (INIS)

Jin, Wei; Du, Hao; Zheng, Shili; Zhang, Yi

2016-01-01

Highlights: • Recent advances in electrochemical technologies for practical Cr(VI) treatment applications was reviewed. • The mechanism and performance of electrocoagulation, electrochemical reduction, electrodialysis, electro-electrodialysis and electrodeionization were discussed and compared. • The remained challenges and future perspectives were commented. - Abstract: Hexavalent chromium Cr(VI) is extremely toxic and classified as one of the 17 chemicals posing the greatest threat to humans. Large amounts of Cr(VI) compounds are directly or indirectly discharged into the environment, therefore considerable efforts have been made to control the Cr(VI) concentration below the recommended level. It has been demonstrated that electrochemical technique is one of the most efficient and environmental benign approach for the Cr(VI) removal. This review aims at recent advances in electrochemical technology for practical Cr(VI) treatment applications. By using the “clean reagent” of electron, Cr(VI) can be completely eliminated or separated via different electrochemical techniques such as electrocoagulation, electrochemical reduction, electrodialysis, electro-electrodialysis and electrodeionization. Besides, the mechanism and performance of different strategies are commented and compared. The treatment process is largely dependent on variables such as pH, electrode materials, cell configuration and techniques integration. Furthermore, the remained limitation and challenges for the electrochemical Cr(VI) remediation are also discussed.

Electrochemical extraction of oxygen using PEM electrolysis technology

Directory of Open Access Journals (Sweden)

BOULBABA ELADEB

2012-11-01

Full Text Available Electrochemical extraction of oxygen from air can be carried out by chemical reduction of oxygen at the cathode and simultaneous oxygen evolution by water anode oxidation. The present investigation deals with the use of an electrolysis cell of PEM technology for this purpose. A dedicated 25 cm2 cell provided with a commercial water electrolysis MEA and titanium grooved plates has been designed for continuous operation at pressures close to the ambient level. The MEA consisted of a Nafion 117 membrane sandwiched between a Pt/C cathode and a non-supported Pt-Ir anode. Oxygen partial consumption in long-term runs was evaluated by analysis of the outlet air by gas chromatography, depending on the cell voltage - or the current density - and the excess in air oxygen fed to the cathode. Runs over more 50 hours indicated the relative stability of the components used for current densities ranging from 0.1 to 0.2 A cm-2 with high efficiency of oxygen reduction. Higher current density could be envisaged with more efficient MEA’s, exhibiting lower overpotentials for oxygen evolution to avoid too significant degradation of the anode material and the membrane. Interpretation of the data has been carried out by calculation of the cathode current efficiency.

Electrochemical Impedance Study of Reduction Kinetics of the Pesticide Vinclozoline

Czech Academy of Sciences Publication Activity Database

Pospíšil, Lubomír; Sokolová, Romana; Colombini, M. P.; Giannarelli, S.; Fuoco, R.

2000-01-01

Roč. 67, - (2000), s. 305-312 ISSN 0026-265X R&D Projects: GA MŠk OC D15.10; GA ČR GA203/97/1048 Institutional research plan: CEZ:AV0Z4040901 Keywords : electrochemical impedance * pesticide s * vinclozoline Subject RIV: CG - Electrochemistry Impact factor: 0.884, year: 2000

Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid.

Science.gov (United States)

Yoo, Jong Suk; Christensen, Rune; Vegge, Tejs; Nørskov, Jens K; Studt, Felix

2016-02-19

The electrochemical reduction (electroreduction) of CO2 to formic acid (HCOOH) and its competing reactions, that is, the electroreduction of CO2 to CO and the hydrogen evolution reaction (HER), on twenty-seven different metal surfaces have been investigated using density functional theory (DFT) calculations. Owing to a strong linear correlation between the free energies of COOH* and H*, it seems highly unlikely that the electroreduction of CO2 to HCOOH via the COOH* intermediate occurs without a large fraction of the current going to HER. On the other hand, the selective electroreduction of CO2 to HCOOH seems plausible if the reaction occurs via the HCOO* intermediate, as there is little correlation between the free energies of HCOO* and H*. Lead and silver surfaces are found to be the most promising monometallic catalysts showing high faradaic efficiencies for the electroreduction of CO2 to HCOOH with small overpotentials. Our methodology is widely applicable, not only to metal surfaces, but also to other classes of materials enabling the computational search for electrocatalysts for CO2 reduction to HCOOH. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical surface nitriding of pure iron by molten salt electrochemical process

Energy Technology Data Exchange (ETDEWEB)

Tsujimura, Hiroyuki; Goto, Takuya; Ito, Yasuhiko

2004-08-11

Electrochemical surface nitriding of pure iron was investigated in molten LiCl-KCl-Li{sub 3}N systems at 773 K. An outer compound layer and an inner diffusion layer were obtained by means of potentiostatic electrolysis at 1.00 V (versus Li{sup +}/Li). From XRD and SEM analyses, it was confirmed that the obtained compound layer consisted of {epsilon}-Fe{sub 2-3}N and {gamma}'-Fe{sub 4}N; the free energies of formation of the two nitrides are positive and the equilibrium nitrogen partial pressure of those are of the order of 10{sup 4} atm at 773 K. This result suggests that an apparent nitrogen partial pressure of at least the order of 10{sup 4} atm was imposed by the adsorbed nitrogen atoms (N{sub ads}) formed by anodic oxidation of nitride ion (N{sup 3-}) at the iron electrode surface.

A simple model of the batch electrochemical reduction of nitrate/nitrite waste

International Nuclear Information System (INIS)

Wingard, D.A.; Weidner, J.W.; Van Zee, J.W.

1994-01-01

A model of a divided parallel plate electrochemical cell operated in a batch mode for the destruction of NO 3 - /NO 2 - in alkaline waste streams is presented. The model uses boundary layer approximations at each electrode and at the separator to minimize computation time. Five competing electrochemical reactions are included at the cathode. The model uses either an explicit Runge-Kutta routine with empirically determined current efficiencies or an implicit stepping routine for each electrode if the current efficiencies are to be predicted. Tim dependent changes of the concentration, temperature, and cell voltage are predicted for constant current operation. Model predictions are compared with experimental data

Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

Science.gov (United States)

Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

2010-11-01

In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum

International Nuclear Information System (INIS)

Cames, B.

1997-01-01

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media (≤ 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 ≤ E ≤ 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

Binder-free carbon nanotube electrode for electrochemical removal of chromium.

Science.gov (United States)

Wang, Haitao; Na, Chongzheng

2014-11-26

Electrochemical treatment of chromium-containing wastewater has the advantage of simultaneously reducing hexavalent chromium (CrVI) and reversibly adsorbing the trivalent product (CrIII), thereby minimizing the generation of waste for disposal and providing an opportunity for resource reuse. The application of electrochemical treatment of chromium is often limited by the available electrochemical surface area (ESA) of conventional electrodes with flat surfaces. Here, we report the preparation and evaluation of carbon nanotube (CNT) electrodes consisting of vertically aligned CNT arrays directly grown on stainless steel mesh (SSM). We show that the 3-D organization of CNT arrays increases ESA up to 13 times compared to SSM. The increase of ESA is correlated with the length of CNTs, consistent with a mechanism of roughness-induced ESA enhancement. The increase of ESA directly benefits CrVI reduction by proportionally accelerating reduction without compromising the electrode's ability to adsorb CrIII. Our results suggest that the rational design of electrodes with hierarchical structures represents a feasible approach to improve the performance of electrochemical treatment of contaminated water.

Magnetic field effects on electrochemical metal depositions

Directory of Open Access Journals (Sweden)

Andreas Bund, Adriana Ispas and Gerd Mutschke

2008-01-01

Full Text Available This paper discusses recent experimental and numerical results from the authors' labs on the effects of moderate magnetic (B fields in electrochemical reactions. The probably best understood effect of B fields during electrochemical reactions is the magnetohydrodynamic (MHD effect. In the majority of cases it manifests itself in increased mass transport rates which are a direct consequence of Lorentz forces in the bulk of the electrolyte. This enhanced mass transport can directly affect the electrocrystallization. The partial currents for the nucleation of nickel in magnetic fields were determined using an in situ micro-gravimetric technique and are discussed on the basis of the nucleation model of Heerman and Tarallo. Another focus of the paper is the numerical simulation of MHD effects on electrochemical metal depositions. A careful analysis of the governing equations shows that many MHD problems must be treated in a 3D geometry. In most cases there is a complex interplay of natural and magnetically driven convection.

A novel method for identification of lithium-ion battery equivalent circuit model parameters considering electrochemical properties

Science.gov (United States)

Zhang, Xi; Lu, Jinling; Yuan, Shifei; Yang, Jun; Zhou, Xuan

2017-03-01

This paper proposes a novel parameter identification method for the lithium-ion (Li-ion) battery equivalent circuit model (ECM) considering the electrochemical properties. An improved pseudo two-dimension (P2D) model is established on basis of partial differential equations (PDEs), since the electrolyte potential is simplified from the nonlinear to linear expression while terminal voltage can be divided into the electrolyte potential, open circuit voltage (OCV), overpotential of electrodes, internal resistance drop, and so on. The model order reduction process is implemented by the simplification of the PDEs using the Laplace transform, inverse Laplace transform, Pade approximation, etc. A unified second order transfer function between cell voltage and current is obtained for the comparability with that of ECM. The final objective is to obtain the relationship between the ECM resistances/capacitances and electrochemical parameters such that in various conditions, ECM precision could be improved regarding integration of battery interior properties for further applications, e.g., SOC estimation. Finally simulation and experimental results prove the correctness and validity of the proposed methodology.

Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

International Nuclear Information System (INIS)

Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

2014-01-01

This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

Electrochemical formation of uranium-zirconium alloy in LiCl-KCl melts

Energy Technology Data Exchange (ETDEWEB)

Murakami, Tsuyoshi, E-mail: m-tsuyo@criepi.denken.or.j [Central Research Institute of Electric Power Industry (CRIEPI), Komae-shi, Tokyo 201-8511 (Japan); Kato, Tetsuya; Kurata, Masaki [Central Research Institute of Electric Power Industry (CRIEPI), Komae-shi, Tokyo 201-8511 (Japan); Yamana, Hajimu [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)

2009-11-15

Since zirconium is considered an electrochemically active species under practical conditions of the electrorefining process, it is crucial to understand the electrochemical behavior of zirconium in LiCl-KCl melts containing actinide ions. In this study, the electrochemical codeposition of uranium and zirconium on a solid cathode was performed. It was found that the delta-(U, Zr) phase, which is the only intermediate phase of the uranium-zirconium binary alloy system, was deposited on a tantalum substrate by potentiostatic electrolysis at -1.60 V (vs. Ag{sup +}/Ag) in LiCl-KCl melts containing 0.13 in mol% UCl{sub 3} and 0.23 in mol% ZrCl{sub 4} at 773 K. To our knowledge, this is the first report on the electrochemical formation of the delta-(U, Zr) phase. The relative partial molar properties of uranium in the delta-(U, Zr) phase were evaluated by measuring the open-circuit-potentials of the electrochemically prepared delta-phase electrode.

Electrochemical formation of uranium-zirconium alloy in LiCl-KCl melts

International Nuclear Information System (INIS)

Murakami, Tsuyoshi; Kato, Tetsuya; Kurata, Masaki; Yamana, Hajimu

2009-01-01

Since zirconium is considered an electrochemically active species under practical conditions of the electrorefining process, it is crucial to understand the electrochemical behavior of zirconium in LiCl-KCl melts containing actinide ions. In this study, the electrochemical codeposition of uranium and zirconium on a solid cathode was performed. It was found that the δ-(U, Zr) phase, which is the only intermediate phase of the uranium-zirconium binary alloy system, was deposited on a tantalum substrate by potentiostatic electrolysis at -1.60 V (vs. Ag + /Ag) in LiCl-KCl melts containing 0.13 in mol% UCl 3 and 0.23 in mol% ZrCl 4 at 773 K. To our knowledge, this is the first report on the electrochemical formation of the δ-(U, Zr) phase. The relative partial molar properties of uranium in the δ-(U, Zr) phase were evaluated by measuring the open-circuit-potentials of the electrochemically prepared δ-phase electrode.

Electrochemical Techniques in Textile Processes and Wastewater Treatment

Directory of Open Access Journals (Sweden)

Mireia Sala

2012-01-01

Full Text Available The textile industry uses the electrochemical techniques both in textile processes (such as manufacturing fibers, dyeing processes, and decolorizing fabrics and in wastewaters treatments (color removal. Electrochemical reduction reactions are mostly used in sulfur and vat dyeing, but in some cases, they are applied to effluents discoloration. However, the main applications of electrochemical treatments in the textile sector are based on oxidation reactions. Most of electrochemical oxidation processes involve indirect reactions which imply the generation of hypochlorite or hydroxyl radical in situ. These electrogenerated species are able to bleach indigo-dyed denim fabrics and to degrade dyes in wastewater in order to achieve the effluent color removal. The aim of this paper is to review the electrochemical techniques applied to textile industry. In particular, they are an efficient method to remove color of textile effluents. The reuse of the discolored effluent is possible, which implies an important saving of salt and water (i.e., by means of the “UVEC Cell”.

Electrochemical degradation of the chloramphenicol at flow reactor

International Nuclear Information System (INIS)

Rezende, Luis Gustavo P.; Prado, Vania M. do; Rocha, Robson S.; Beati, Andre A.G.F.; Sotomayor, Maria del Pilar T.; Lanza, Marcos R.V.

2010-01-01

This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the electrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L -1 ), nitrate ions (6 mg L -1 ) and nitrite ions (4.5 mg L -1 ). (author)

Electrochemical and structural characterization of carbon-supported Pt-Pd bimetallic electrocatalysts prepared by electroless deposition

Energy Technology Data Exchange (ETDEWEB)

Ohashi, Masato; Beard, Kevin D.; Ma Shuguo; Blom, Douglas A.; St-Pierre, Jean; Van Zee, John W. [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Monnier, John R., E-mail: monnier@cec.sc.ed [Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States)

2010-10-01

Electrochemical and structural characteristics of various Pt-Pd/C bimetallic catalysts prepared by electroless deposition (ED) methods have been investigated. Structural analysis was conducted by X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy (EDS). Monometallic Pt or Pd particles were not detected by EDS, indicating the ED methodology formed only bimetallic particles. The size of the Pt-Pd bimetallic particles was smaller than those of a commercially available Pt/C catalyst. The morphology of the Pt on Pd/C catalysts was identified and corresponded to Pd particles partially encapsulated by Pt. The electrochemical characteristics of the lowest Pd loading catalyst (7.0% Pt on 0.5% Pd/C) for the oxygen reduction reaction (ORR) have been investigated by the rotating ring disk electrode technique. The electrochemical activity was equal or lower than the commercially available Pt/C catalyst; however, the amount of hydrogen peroxide observed at the ring was reduced by the Pd, suggesting that such a catalyst has the potential to decrease ionomer degradation in applications. The Pt on Pd/C catalysts also show a higher tolerance to ripening induced by potential cycling. Therefore, catalyst suitability cannot be judged solely by its initial performance; information related to specific degradation mechanisms is also needed for a more complete assessment.

Reduction of CO2 by nickel (II) macrocycle catalyst at HMDE

Indian Academy of Sciences (India)

Unknown

CO is the major product in the gaseous phase and. HCOOH the sole product formed in the solution phase. Keywords. Nickel (II) azamacrocycle; electrocatalytic reduction of CO2; electrochemical reduction. 1. Introduction. Electrochemical processes for the conversion of carbon dioxide (CO2) to organic substances have ...

Catholyte-Free Electrocatalytic CO2 Reduction to Formate.

Science.gov (United States)

Lee, Wonhee; Kim, Young Eun; Youn, Min Hye; Jeong, Soon Kwan; Park, Ki Tae

2018-04-16

Electrochemical reduction of carbon dioxide (CO 2 ) into value-added chemicals is a promising strategy to reduce CO 2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO 2 reduction (CO 2 R) is the low solubility of CO 2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte-free electrocatalytic CO 2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm -2 , despite the decrease in CO 2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L -1 is obtained as a one-path product at 343 K with high PCD (51.7 mA cm -2 ) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Dynamics and Evolution of Bismuth Electrodes during Electrochemical Reduction of CO ₂ in Imidazolium-Based Ionic Liquid Solutions

Energy Technology Data Exchange (ETDEWEB)

Medina-Ramos, Jonnathan [Chemical; Lee, Sang Soo [Chemical; Fister, Timothy T. [Chemical; Hubaud, Aude A. [Chemical; Sacci, Robert L.; Mullins, David R.; DiMeglio, John L. [Department; Pupillo, Rachel C. [Department; Velardo, Stephanie M. [Department; Lutterman, Daniel A.; Rosenthal, Joel [Department; Fenter, Paul [Chemical

2017-09-14

Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near -1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM

Electrochemical production of hydrocarbons from carbon dioxide and water

NARCIS (Netherlands)

Ros, C.H.

2016-01-01

Electrocatalytic reduction of CO2 is one possibility to solve the electrical energy storage problem and decrease the amount of CO2. Copper is the only metal that has been reported to produce hydrocarbons in the electrochemical CO2 reduction at ambient pressure and temperature. External parameters

Partial scan artifact reduction (PSAR) for the assessment of cardiac perfusion in dynamic phase-correlated CT

Energy Technology Data Exchange (ETDEWEB)

Stenner, Philip; Schmidt, Bernhard; Bruder, Herbert; Allmendinger, Thomas; Haberland, Ulrike; Flohr, Thomas; Kachelriess, Marc [Institute of Medical Physics, Henkestrasse 91, 91052 Erlangen (Germany); Siemens AG, Healthcare Sector, Siemensstrasse 1, 91301 Forchheim (Germany); Institute of Medical Physics, Henkestrasse. 91, 91052 Erlangen (Germany)

2009-12-15

Purpose: Cardiac CT achieves its high temporal resolution by lowering the scan range from 2{pi} to {pi} plus fan angle (partial scan). This, however, introduces CT-value variations, depending on the angular position of the {pi} range. These partial scan artifacts are of the order of a few HU and prevent the quantitative evaluation of perfusion measurements. The authors present the new algorithm partial scan artifact reduction (PSAR) that corrects a dynamic phase-correlated scan without a priori information. Methods: In general, a full scan does not suffer from partial scan artifacts since all projections in [0, 2{pi}] contribute to the data. To maintain the optimum temporal resolution and the phase correlation, PSAR creates an artificial full scan p{sub n}{sup AF} by projectionwise averaging a set of neighboring partial scans p{sub n}{sup P} from the same perfusion examination (typically N{approx_equal}30 phase-correlated partial scans distributed over 20 s and n=1,...,N). Corresponding to the angular range of each partial scan, the authors extract virtual partial scans p{sub n}{sup V} from the artificial full scan p{sub n}{sup AF}. A standard reconstruction yields the corresponding images f{sub n}{sup P}, f{sub n}{sup AF}, and f{sub n}{sup V}. Subtracting the virtual partial scan image f{sub n}{sup V} from the artificial full scan image f{sub n}{sup AF} yields an artifact image that can be used to correct the original partial scan image: f{sub n}{sup C}=f{sub n}{sup P}-f{sub n}{sup V}+f{sub n}{sup AF}, where f{sub n}{sup C} is the corrected image. Results: The authors evaluated the effects of scattered radiation on the partial scan artifacts using simulated and measured water phantoms and found a strong correlation. The PSAR algorithm has been validated with a simulated semianthropomorphic heart phantom and with measurements of a dynamic biological perfusion phantom. For the stationary phantoms, real full scans have been performed to provide theoretical reference

The electrochemical impedance of metal hydride electrodes

DEFF Research Database (Denmark)

Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

2002-01-01

The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

Electrochemical destruction of nitrosamines

Energy Technology Data Exchange (ETDEWEB)

Lejen, T; Volchek, K; Ladanowski, C; Velicogna, D; Whittaker, H [Environment Canada, Ottawa, ON (Canada). Emergencies Engineering Div.

1996-09-01

Treatment conditions for the electrolytic destruction of nitrosamines were studied. The joint investigation between Canada and the Ukraine was part of an assessment of hazardous contaminants at former Soviet ICBM missile sites. The electrochemical destruction of N-dimethylnitrosamines (NDMA) on carbon/platinum electrodes was studied under basic and acidic conditions by UV spectroscopy, gas chromatography, mass spectroscopy, and colorimetry. Experiments with a 100 ppm NDMA solution showed that electrolytic-reduction was pH sensitive within a range of pH 0.5 to 4.0. Electrolysis was effective for the reduction of NDMA in strong acidic conditions. 30 refs., 1 tab., 4 figs.

Effect of CaO addition on preparation of ferrotitanium from ilmenite by electrochemical reduction in CaCl_2−NaCl molten salt

International Nuclear Information System (INIS)

Xiong, Li; Hua, Yixin; Xu, Cunying; Li, Jian; Li, Yan; Zhang, Qibo; Zhou, Zhongren; Zhang, Yadong; Ru, Juanjian

2016-01-01

Ferro-titanium (FeTi) alloy was prepared successfully from synthesized ilmenite through electrochemical reduction method in equal-molar CaCl_2−NaCl molten salt at 973 K and a cell voltage of 3.2 V under inert atmosphere, where molybdenum rod and graphite were used as cathode and anode respectively. It is indicated that the CaO content in the molten salt has an appreciable effect on the phase transformation of reactants occurring in the electrolytic process. The optimized CaO content in the molten salt is 1 mol% and this suitable content of CaO can significantly improve the reduction rate of ilmenite. The micromorphology of the ferrotitanium product is porous with the amount of 1 mol%CaO addition. It is observed that the particles of ferrotitanium had a uniform size in the initial period of time. Along with the electrolysis time extension, however, the particles connected with each other to generate strips and then form a honeycomb structure. These findings provide a basis for scientifically discussion on the optimization of CaO addition amount during the electrochemical reduction of ilmenite and other oxides in molten salts. - Highlights: • Ferro-titanium was prepared from synthesized ilmenite in CaCl_2−NaCl molten salt. • CaO content has appreciable effect on the phase transformation of ilmenite reactant. • The optimized CaO content is 1 mol% which can significantly improve reaction rate. • The products are connected with each other to form strips as electrolysis time.

Electrochemical remediation technologies for soil and groundwater

Energy Technology Data Exchange (ETDEWEB)

Doering, F. [Electrochemical Processes I.I. c. Valley Forge, PA (United States)]|[P2 Soil Remediation, Inc. Stuttgart (Germany); Doering, N. [P2 Soil Remediation, Inc. Stuttgart (Germany)

2001-07-01

In Direct Current Technologies (DCTs) a direct current electricity is passed between at least two subsurface electrodes in order to effect the remediation of the groundwater and/or the soil. DCTs in line with the U.S.-terminology comprise of the ElectroChemical Remediation Technologies (ECRTs), and GeoKinetics. The primary distinction between ECRTs and ElectroKinetics are the power input, and the mode of operation, which are electrochemical reactions vs. mass transport. ECRTs combine phenomena of colloid (surface) electrochemistry with the phenomena of Induced Polarization (IP). This report focuses on ECRTs, comprising of the ElectroChemical GeoOxidation (ECGO) for the mineralization of organic pollutants to finally carbon dioxide and water, and Induced Complexation (IC), related to the electrochemical conversion of metals enhancing the mobilization and precipitation of heavy metals on both electrodes. Both technologies are based on reduction-oxidation (redox) reactions at the scale of the individual soil particles. (orig.)

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

Energy Technology Data Exchange (ETDEWEB)

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp [International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan)

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Reduction of uranyl carbonate and hydroxyl complexes and neptunyl carbonate complexes studied with chemical-electrochemical methods and rixs spectroscopy

International Nuclear Information System (INIS)

Butorin, Sergei; Nordgren, Joseph; Ollila, Kaija; Albinsson, Yngve; Werme, Lars

2003-10-01

actinides have been mobilised through oxidation, they can migrate away from this potentially oxidising region and will encounter an oxygen free, reducing environment caused by the anaerobic corrosion of the cast iron insert. The actinyl species are no longer thermodynamically stable and reduction to the tetravalent state will be possible. There is, however, an open question whether the reduction kinetics will be sufficiently high to cause reduction in solution and if sorption onto the corroding iron surface will be accompanied by an electron transfer sufficiently rapid to reduce the actinide back to the tetravalent state. This report contains the results of experimental studies of uranium reduction-depletion from water solutions in the presence of corroding iron and spectroscopic studies of the oxidation state of uranium and neptunium sorbed/precipitated onto iron under oxygen free conditions using resonant inelastic soft x-ray scattering (RIXS) spectroscopy. The RIXS measurements show that at least partial reduction of both uranyl carbonate complexes and neptunyl carbonate complexes take place on the corroding iron surface. The chemical/electrochemical measurements indicate that reduction of uranyl carbonate complexes also take place in solution in a system containing corroding iron, i.e. sorption onto the iron/iron oxide surface may not be necessary in order for reduction to take place. Reduction of uranyl hydroxyl complexes was also found to take place in solution, but at a rate that was noticeably lower than for the uranyl carbonate complexes

Preparation and Electrochemical Properties of Silver Doped Hollow Carbon Nanofibers

Directory of Open Access Journals (Sweden)

LI Fu

2016-11-01

Full Text Available Silver doped PAN-based hollow carbon nanofibers were prepared combining co-electrospinning with in situ reduction technique subsequently heat treatment to improve the electrochemical performances of carbon based supercapacitor electrodes. The morphology, structure and electrochemical performances of the resulted nanofiber were studied. The results show that the silver nanoparticles can be doped on the surface of hollow carbon nanofibers and the addition of silver favors the improvement of the electrochemical performances, exhibiting the enhanced reversibility of electrode reaction and the capacitance and the reduced charge transfer impedance.

Graphene hydrogels deposited in nickel foams for high-rate electrochemical capacitors.

Science.gov (United States)

Chen, Ji; Sheng, Kaixuan; Luo, Peihui; Li, Chun; Shi, Gaoquan

2012-08-28

Graphene hydrogel/nickel foam composite electrodes for high-rate electrochemical capacitors are produced by reduction of an aqueous dispersion of graphene oxide in a nickel foam (upper half of figure). The micropores of the hydrogel are exposed to the electrolyte so that ions can enter and form electrochemical double-layers. The nickel framework shortens the distances of charge transfer. Therefore, the electrochemical capacitor exhibits highrate performance (see plots). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of potential extreme load reduction for a two-bladed upwind turbine with partial pitch

DEFF Research Database (Denmark)

Kim, Taeseong; Larsen, Torben J.; Yde, Anders

2015-01-01

This paper presents a wind turbine concept with an innovative design combining partial pitch with a two-bladed (PP-2B) turbine configuration. Special emphasis is on extreme load reduction during storm situations at standstill, but operational loads are also investigated. In order to compare...... loads are reduced by approximately 20% for the PP-2B and 18% for the PP-3B compared with the 3B turbine for the parked condition in a storm situation. Moreover, a huge potential of 60% is observed for the reduction of the extreme tower bottom bending moment for the PP-2B turbine, when the wind direction...... is from ±90° to the turbine, but this also requires that the turbine is parked in a T-configuration. © 2014 The Authors. Wind Energy published by John Wiley & Sons, Ltd....

Higher-Order Rewriting and Partial Evaluation

DEFF Research Database (Denmark)

Danvy, Olivier; Rose, Kristoffer H.

1997-01-01

transformations as meta-reductions, i.e., reductions in the internal “substitution calculus.” For partial-evaluation problems, this means that instead of having to prove on a case-by-case basis that one's “two-level functions” operate properly, one can concisely formalize them as a combinatory reduction system...... and obtain as a corollary that static reduction does not go wrong and yields a well-formed residual program. We have found that the CRS substitution calculus provides an adequate expressive power to formalize partial evaluation: it provides sufficient termination strength while avoiding the need...

Emerging electrochemical energy conversion and storage technologies

Science.gov (United States)

Badwal, Sukhvinder P. S.; Giddey, Sarbjit S.; Munnings, Christopher; Bhatt, Anand I.; Hollenkamp, Anthony F.

2014-01-01

Electrochemical cells and systems play a key role in a wide range of industry sectors. These devices are critical enabling technologies for renewable energy; energy management, conservation, and storage; pollution control/monitoring; and greenhouse gas reduction. A large number of electrochemical energy technologies have been developed in the past. These systems continue to be optimized in terms of cost, life time, and performance, leading to their continued expansion into existing and emerging market sectors. The more established technologies such as deep-cycle batteries and sensors are being joined by emerging technologies such as fuel cells, large format lithium-ion batteries, electrochemical reactors; ion transport membranes and supercapacitors. This growing demand (multi billion dollars) for electrochemical energy systems along with the increasing maturity of a number of technologies is having a significant effect on the global research and development effort which is increasing in both in size and depth. A number of new technologies, which will have substantial impact on the environment and the way we produce and utilize energy, are under development. This paper presents an overview of several emerging electrochemical energy technologies along with a discussion some of the key technical challenges. PMID:25309898

Preliminary comparison of different reduction methods of graphene

Indian Academy of Sciences (India)

The reduction of graphene oxide (GO) is a promising route to bulk produce graphene-based sheets. Different reduction processes result in reduced graphene oxide (RGO) with different properties. In this paper three reduction methods, chemical, thermal and electrochemical reduction, were compared on three aspects ...

Electrochemical stability of ionic clathrate hydrates and their structural consideration

International Nuclear Information System (INIS)

Lee, Wonhee; Lim, Dongwook; Lee, Huen

2013-01-01

Although electrochemical stability is an essential factor in relation to the potential applications of ionic clathrate hydrates to solid electrolytes, most studies regarding the proton conductors have focused on their ionic conductivity and thermal stability. Solid electrolytes in various electrochemical devices have to endure the applied potentials; thus, we examined the linear sweep voltammograms of various tetraalkylammonium hydroxide hydrates in order to shed light on the trend of electrochemical stability depending on the hydrate structure. We revealed that the electrochemical stability of Me 4 NOH hydrates is mainly affected by both their ionic concentration and cage occupancy. In particular, the true clathrate structures of β-Me 4 NOH hydrates are more electrochemically stable than their α-forms that possess partially broken hydrogen bonds. We also observed that the binary THF–Pr 4 NOH and pure Bu 4 NOH clathrate hydrates exhibit greater electrochemical stability than those of pure Me 4 NOH hydrates having lower or similar ionic concentrations. These results are considered to arise from the fact that each of the Pr 4 N + and Bu 4 N + ions occupies an extended space comprising four cages, which leads to stabilization of the larger unit, whereas a Me 4 N + ion is completely included only in one cage

Thermodynamic and kinetic modelling of the reduction of concentrated nitric acid

International Nuclear Information System (INIS)

Sicsic, David

2011-01-01

This research thesis aimed at determining and quantifying the different stages of the reduction mechanism in the case of concentrated nitric acid. After having reported the results of a bibliographical study on the chemical and electrochemical behaviour of concentrated nitric media (generalities, chemical equilibriums, NOx reactivity, electrochemical reduction of nitric acid), the author reports the development and discusses the results of a thermodynamic simulation of a nitric environment at 25 C. This allowed the main species to be identified in the liquid and gaseous phases of nitric acid solutions. The author reports an experimental electrochemical investigation coupled with analytic techniques (infrared and UV-visible spectroscopy) and shows that the reduction process depends on the cathodic overvoltage, and identifies three potential areas. A kinetic modelling of the stationary state and of the impedance is then developed in order to better determine, discuss and quantify the reduction process. The application of this kinetic model to the preliminary results of an electrochemical study performed on 304 L steel is then discussed [fr

Graphene-based materials via benzidine-assisted exfoliation and reduction of graphite oxide and their electrochemical properties

Science.gov (United States)

Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Boukos, N.; Psycharis, V.; Lei, C.; Lekakou, C.; Petridis, D.; Trapalis, C.

2017-01-01

Benzidine, a compound bearing aromatic rings and terminal amino groups, was employed for the intercalation and simultaneous reduction of graphite oxide (GO). The aromatic diamine can be intercalated into GO as follows: (1) by grafting with the epoxy groups of GO, (2) by hydrogen bonding with the oxygen containing groups of GO. Stacking between benzidine aromatic rings and unoxidized domains of GO may occur through π-π interaction. The role of benzidine is influenced by pH conditions and the weight ratio GO/benzidine. Two weight ratios were tested i.e. 1:2 and 1:3. Under strong alkaline conditions through K2CO3 addition (pH ∼10.4-10.6) both intercalation and reduction of GO via amino groups occur, while under strong acidic conditions through HCl addition (pH ∼1.4-2.2) π-π stacking is preferred. When no base or acid is added (pH ∼5.2) and the weight ratio is 1:2, there are indications that reduction and π-π stacking occur, while at a GO/benzidine weight ratio 1:3 intercalation via amino groups and reduction seem to dominate. The aforementioned remarks render benzidine a multifunctional tool towards production of reduced graphene oxide. The effect of pH conditions and the GO/benzidine weight ratio on the quality and the electrochemical properties of the produced graphene-based materials were investigated. Cyclic voltammetry measurements using three-electrode cell and KCl aqueous solution as an electrolyte gave specific capacitance values up to ∼178 F/g. When electric double-layer capacitors (EDLC) were fabricated from these materials, the maximum capacitance in organic electrolyte i.e., tetraethyl ammonium tetrafluoroborate (TEABF4) in polycarbonate (PC) was ∼29 F/g.

Transparent Electrochemical Gratings from a Patterned Bistable Silver Mirror.

Science.gov (United States)

Park, Chihyun; Na, Jongbeom; Han, Minsu; Kim, Eunkyoung

2017-07-25

Silver mirror patterns were formed reversibly on a polystyrene (PS)-patterned electrode to produce gratings through the electrochemical reduction of silver ions. The electrochemical gratings exhibited high transparency (T > 95%), similar to a see-through window, by matching the refractive index of the grating pattern with the surrounding medium. The gratings switch to a diffractive state upon the formation of a mirror pattern (T modulation, NIR light reflection, and on-demand heat transfer.

Highly Active, Carbon-supported, PdSn Nano-core, Partially ...

African Journals Online (AJOL)

Carbon-supported, Pt partially covered, PdSn alloy nanoparticles (Pt-PdSn/C) were synthesized via a metathetical reaction of PdSn alloy nanoparticles, and a platinum precursor. The electrochemical activity was evaluated by methanol oxidation. The Pt-PdSn/C catalysts were characterized by transmission electron ...

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

OpenAIRE

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in th...

Electrochemical extraction of samarium from molten chlorides in pyrochemical processes

International Nuclear Information System (INIS)

Castrillejo, Y.; Fernandez, P.; Medina, J.; Hernandez, P.; Barrado, E.

2011-01-01

This work concerns the electrochemical extraction of samarium from molten chlorides. In this way, the electrochemical behaviour of samarium ions has been investigated in the eutectic LiCl-KCl at the surface of tungsten, aluminium and aluminium coated tungsten electrodes. On a W inert electrode the electro-reduction of Sm(III) takes place in only one soluble-soluble electrochemical step Sm(III)/Sm(II). The electrochemical system Sm(II)/Sm(0) has not been observed within the electrochemical window, because of the prior reduction of Li(I) ions from the solvent, which inhibits the electro-extraction of Sm species from the salt on such a substrate. Sm metal in contact with the melt react to give Li(0) according to the reaction: Sm(0) + 2Li(I) ↔ Sm(II) + 2Li(0). On the contrary, on reactive Al electrodes the electrochemical system Sm(II)/Sm(0) was observed within the electroactive range. The potential shift of the redox couple is caused by the decrease of Sm activity in the metal phase due to the formation of Sm-Al alloys at the interface. The formation mechanism of the intermetallic compounds was studied in a melt containing: (i) both Sm(III) and Al(III) ions, using W and Al coated tungsten electrodes, and (ii) Sm(III) ions using an Al electrode. Analysis of the samples after potentiostatic electrolysis by X-ray diffraction and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), allowed the identification of Al 3 Sm and Al 2 Sm.

Electrochemical extraction of samarium from molten chlorides in pyrochemical processes

Energy Technology Data Exchange (ETDEWEB)

Castrillejo, Y., E-mail: ycastril@qa.uva.es [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Fernandez, P. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Medina, J. [Dept Fisica Materia Condensada Cristalografia y Mineralogia, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Hernandez, P. [Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Hidalgo, Carr. Pachuca-Tulancingo Km. 4.5, C.P. 42076 Pachuca, Hidalgo (Mexico); Barrado, E. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain)

2011-10-01

This work concerns the electrochemical extraction of samarium from molten chlorides. In this way, the electrochemical behaviour of samarium ions has been investigated in the eutectic LiCl-KCl at the surface of tungsten, aluminium and aluminium coated tungsten electrodes. On a W inert electrode the electro-reduction of Sm(III) takes place in only one soluble-soluble electrochemical step Sm(III)/Sm(II). The electrochemical system Sm(II)/Sm(0) has not been observed within the electrochemical window, because of the prior reduction of Li(I) ions from the solvent, which inhibits the electro-extraction of Sm species from the salt on such a substrate. Sm metal in contact with the melt react to give Li(0) according to the reaction: Sm(0) + 2Li(I) {r_reversible} Sm(II) + 2Li(0). On the contrary, on reactive Al electrodes the electrochemical system Sm(II)/Sm(0) was observed within the electroactive range. The potential shift of the redox couple is caused by the decrease of Sm activity in the metal phase due to the formation of Sm-Al alloys at the interface. The formation mechanism of the intermetallic compounds was studied in a melt containing: (i) both Sm(III) and Al(III) ions, using W and Al coated tungsten electrodes, and (ii) Sm(III) ions using an Al electrode. Analysis of the samples after potentiostatic electrolysis by X-ray diffraction and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), allowed the identification of Al{sub 3}Sm and Al{sub 2}Sm.

Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes - A Step Towards the Electrochemical CO2 Refinery

KAUST Repository

Wang, Hong; Jia, Jia; Song, Pengfei; Wang, Qiang; Li, Debao; Min, Shixiong; Qian, Chenxi; Wang, Lu; Li, Young Feng; Ma, Chun; Wu, Tao; Yuan, Jiayin; Antonietti, Markus; Ozin, Geoffrey A.

2017-01-01

The search for earth abundant, efficient and stable electrocatalysts that can enable the chemical reduction of CO2 to value-added chemicals and fuels at an industrially relevant scale, is a high priority for the development of a global network of renewable energy conversion and storage systems that can meaningfully impact greenhouse gas induced climate change. Here we introduce a straightforward, low cost, scalable and technologically relevant method to manufacture an all-carbon, electroactive, nitrogen-doped nanoporous carbon-carbon nanotube composite membrane. The membrane is demonstrated to function as a binder-free, high-performance electrode for the electrocatalytic reduction of CO2 to formate. The Faradaic efficiency for the production of formate is 81%. Furthermore, the robust structural and electrochemical properties of the membrane endow it with excellent long-term stability.

Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes - A Step Towards the Electrochemical CO2 Refinery

KAUST Repository

Wang, Hong

2017-05-12

The search for earth abundant, efficient and stable electrocatalysts that can enable the chemical reduction of CO2 to value-added chemicals and fuels at an industrially relevant scale, is a high priority for the development of a global network of renewable energy conversion and storage systems that can meaningfully impact greenhouse gas induced climate change. Here we introduce a straightforward, low cost, scalable and technologically relevant method to manufacture an all-carbon, electroactive, nitrogen-doped nanoporous carbon-carbon nanotube composite membrane. The membrane is demonstrated to function as a binder-free, high-performance electrode for the electrocatalytic reduction of CO2 to formate. The Faradaic efficiency for the production of formate is 81%. Furthermore, the robust structural and electrochemical properties of the membrane endow it with excellent long-term stability.

Oxygen reduction kinetics on mixed conducting SOFC model cathodes

Energy Technology Data Exchange (ETDEWEB)

Baumann, F.S.

2006-07-01

The kinetics of the oxygen reduction reaction at the surface of mixed conducting solid oxide fuel cell (SOFC) cathodes is one of the main limiting factors to the performance of these promising systems. For ''realistic'' porous electrodes, however, it is usually very difficult to separate the influence of different resistive processes. Therefore, a suitable, geometrically well-defined model system was used in this work to enable an unambiguous distinction of individual electrochemical processes by means of impedance spectroscopy. The electrochemical measurements were performed on dense thin film microelectrodes, prepared by PLD and photolithography, of mixed conducting perovskite-type materials. The first part of the thesis consists of an extensive impedance spectroscopic investigation of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) microelectrodes. An equivalent circuit was identified that describes the electrochemical properties of the model electrodes appropriately and enables an unambiguous interpretation of the measured impedance spectra. Hence, the dependencies of individual electrochemical processes such as the surface exchange reaction on a wide range of experimental parameters including temperature, dc bias and oxygen partial pressure could be studied. As a result, a comprehensive set of experimental data has been obtained, which was previously not available for a mixed conducting model system. In the course of the experiments on the dc bias dependence of the electrochemical processes a new and surprising effect was discovered: It could be shown that a short but strong dc polarisation of a LSCF microelectrode at high temperature improves its electrochemical performance with respect to the oxygen reduction reaction drastically. The electrochemical resistance associated with the oxygen surface exchange reaction, initially the dominant contribution to the total electrode resistance, can be reduced by two orders of magnitude. This &apos

Effect of CaO addition on preparation of ferrotitanium from ilmenite by electrochemical reduction in CaCl{sub 2}−NaCl molten salt

Energy Technology Data Exchange (ETDEWEB)

Xiong, Li [Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093 (China); State Key Lab of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093 (China); Hua, Yixin, E-mail: yxhua@kmust.edu.cn [Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093 (China); State Key Lab of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093 (China); Xu, Cunying; Li, Jian; Li, Yan; Zhang, Qibo; Zhou, Zhongren; Zhang, Yadong [Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093 (China); State Key Lab of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093 (China); Ru, Juanjian [Faculty of Material Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China)

2016-08-15

Ferro-titanium (FeTi) alloy was prepared successfully from synthesized ilmenite through electrochemical reduction method in equal-molar CaCl{sub 2}−NaCl molten salt at 973 K and a cell voltage of 3.2 V under inert atmosphere, where molybdenum rod and graphite were used as cathode and anode respectively. It is indicated that the CaO content in the molten salt has an appreciable effect on the phase transformation of reactants occurring in the electrolytic process. The optimized CaO content in the molten salt is 1 mol% and this suitable content of CaO can significantly improve the reduction rate of ilmenite. The micromorphology of the ferrotitanium product is porous with the amount of 1 mol%CaO addition. It is observed that the particles of ferrotitanium had a uniform size in the initial period of time. Along with the electrolysis time extension, however, the particles connected with each other to generate strips and then form a honeycomb structure. These findings provide a basis for scientifically discussion on the optimization of CaO addition amount during the electrochemical reduction of ilmenite and other oxides in molten salts. - Highlights: • Ferro-titanium was prepared from synthesized ilmenite in CaCl{sub 2}−NaCl molten salt. • CaO content has appreciable effect on the phase transformation of ilmenite reactant. • The optimized CaO content is 1 mol% which can significantly improve reaction rate. • The products are connected with each other to form strips as electrolysis time.

Influence of humic substances on electrochemical degradation of trichloroethylene in limestone aquifers

International Nuclear Information System (INIS)

Rajic, Ljiljana; Fallahpour, Noushin; Nazari, Roya; Alshawabkeh, Akram N.

2015-01-01

Highlights: • Humic substances (HS) adversely affect TCE electrochemical reduction. • The inverse correlation between HS content and TCE removal is linear. • HS interfere with the hydrodechlorination of TCE at the cathode. • The impact of HS on TCE removal was reduced in the presence of limestone gravel. - Abstract: In this study we investigate the influence of humic substances (HS) on electrochemical transformation of trichloroethylene (TCE) in groundwater from limestone aquifers. A laboratory flow-through column with an electrochemical reactor that consists of a palladized iron foam cathode followed by a MMO anode was used to induce TCE electro-reduction in groundwater. Up to 82.9% TCE removal was achieved in the absence of HS. Presence of 1, 2, 5, and 10 mgTOC L −1 reduced TCE removal to 70.9%, 61.4%, 51.8% and 19.5%, respectively. The inverse correlation between HS content and TCE removal was linear. Total organic carbon (TOC), dissolved organic carbon (DOC) and absorption properties (A = 254 nm, 365 nm and 436 nm) normalized to DOC, were monitored during treatment to understand the behavior and impacts of HS under electrochemical processes. Changes in all parameters occurred mainly after contact with the cathode, which implies that the HS are reacting either directly with electrons from the cathode or with H 2 formed at the cathode surface. Since hydrodechlorination is the primary TCE reduction mechanism in this setup, reactions of the HS with the cathode limit transformation of TCE. The presence of limestone gravel reduced the impact of HS on TCE removal. The study concludes that presence of humic substances adversely affects TCE removal from contaminated groundwater by electrochemical reduction using palladized cathodes.

The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

International Nuclear Information System (INIS)

Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

2010-01-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

Electrochemical treatment of liquid wastes

Energy Technology Data Exchange (ETDEWEB)

Hobbs, D.T. [Savannah River Technology Center, Aiken, SC (United States)

1997-10-01

Under this task, electrochemical treatment processes are being evaluated and developed for the destruction of organic compounds and nitrates/nitrites and the removal of other hazardous species from liquid wastes stored throughout the DOE complex. This technology targets the (1) destruction of nitrates, nitrites and organic compounds; (2) removal of radionuclides; and (3) removal of RCRA metals. The development program consists of five major tasks: (1) evaluation of electrochemical reactors for the destruction and removal of hazardous waste components, (2) development and validation of engineering process models, (3) radioactive laboratory-scale tests, (4) demonstration of the technology in an engineering-scale reactor, and (5) analysis and evaluation of test data. The development program team is comprised of individuals from national laboratories, academic institutions, and private industry. Possible benefits of this technology include: (1) improved radionuclide separation as a result of the removal of organic complexants, (2) reduction in the concentrations of hazardous and radioactive species in the waste (e.g., removal of nitrate, mercury, chromium, cadmium, {sup 99}Tc, and {sup 106}Ru), (3) reduction in the size of the off-gas handling equipment for the vitrification of low-level waste (LLW) by reducing the source of NO{sub x} emissions, (4) recovery of chemicals of value (e.g. sodium hydroxide), and (5) reduction in the volume of waste requiring disposal.

Quantum chemical analysis of Со2+ aqua complexes electrochemical reduction

Directory of Open Access Journals (Sweden)

Viktor F. Vargalyuk

2017-11-01

Full Text Available Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method as to [Co(H2On]z(H2O6–n clusters for z = 0, 1, 2 and n=1÷6, it has been demonstrated that electrochemical reduction of [Co(H2O6]2+ aqua complexes runs stage-wise. At the first stage, an electron injected into the [Co(H2O6]2+ complex is entirely located in the orbital of the central atom, as z(Co herewith changes from +1.714 е to +0.777 е. The weakening of Со–ОН2 bonds leads to decomposition of resulting [Co(H2O6]+ particles into two energetically related forms – [Co(H2O4]+ and [Co(H2O3]+. Further reduction of these intermediates runs differently. Electron injection into the [Co(H2O3]+ intermediate terminatesthe transition of Со2+-ions to Со0 z(Co= –0.264 е. This process is accompanied by rapid decomposition of [Co(H2O3]0 product into monohydrate atom of cobalt Со(Н2О. On the contrary, electron injection into the [Co(H2O4]+ intermediate leads to emergence of a specific structure – [Co+(H2O–(Н2О3]¹0, whereby the electron is located in the atoms of cobalt only by 28%, and by 72% in cobalt-coordinated water molecules, clearly focusing on one of the. In this molecule, z(H2O changes from +0.148 е to –0.347 е. There is an assumption that a non-equilibrium [Co+(H2O–(Н2О3]0¹ form transits to [Co(ОH(Н2О3]0 hydroxo-form, which further disproportionates turning into Co(ОH2 hydroxide. In order to reduce the impact of this unfavorable reaction pathway on the overall reaction rate Со2+ + 2ē = Со0, we suggest raising the temperature to ensure complete dissociation of [Co(H2O4]+ to [Co(H2O3]+.

Electrochemical and spectroscopic study on thiolation of polyaniline

International Nuclear Information System (INIS)

Blomquist, Maija; Bobacka, Johan; Ivaska, Ari; Levon, Kalle

2013-01-01

Highlights: ► We have thiolated and characterized polyaniline films in order to verify that the thiolation process has taken place. ► Such extensive characterization of thiolation of polyaniline has not previously been reported. ► Thiolation alters the electrochemical properties of polyaniline and the process should be understood. ► Through thiolation many reactive groups may covalently be bound to the polymer backbone. ► Possibility of covalent binding makes polyaniline films an attractive substrate for, e.g., biosensors. -- Abstract: Polyaniline (PANI) is a conducting polymer, easily synthesized and lucrative for many electrochemical applications like ion-selective sensors and biosensors. Thiolated molecules, including biological ones, can be bound by nucleophilic attachment to the polyaniline backbone. These covalently bound thiols add functionality to PANI, but also cause changes in the electrochemical properties of PANI. Polyaniline studied in this work was electropolymerized on glassy carbon electrodes. 2-Mercaptoethanol (MCE) and 6-(ferrocenyl)hexanethiol (FCHT) were used as the thiols to form functionalized films. The films were characterized by cyclic voltammetry (CV), ex situ FTIR and Raman spectroscopies, electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The goal of this work was to confirm the thiolation by spectroscopic methods and to study the impact of thiolation on the electrochemical properties of PANI. Our study showed that thiolated PANI has different electrochemical properties than PANI. Although the thiolation partially reduced the PANI backbone it still remained conductive after the thiolation. Detailed understanding of the thiolation process can be very useful for future applications of PANI

Synthesis and characterization of electrochemically-reduced graphene

Indian Academy of Sciences (India)

Graphene has superior electrical conductivity than graphite and other allotropes of carbon because of its high surface area and chemical tolerance. Electrochemically processed graphene sheets were obtained through the reduction of graphene oxide from hydrazine hydrate. The prepared samples were heated to different ...

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

Science.gov (United States)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

Energy Technology Data Exchange (ETDEWEB)

Chhina, H. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada); Campbell, S. [Automotive fuel cell corporation, 9000 Glenlyon Parkway, Burnaby, BC (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, 5 King' s College Road, University of Toronto, Toronto, Ontario (Canada)

2008-04-15

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 C and compared to that of HiSpec 4000 trademark Pt/Vulcan XC-72R in 0.5 M H{sub 2}SO{sub 4}. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000 trademark. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization. (author)

Ultramicroelectrode studies of oxygen reduction in polyelectrolyte membranes

Energy Technology Data Exchange (ETDEWEB)

Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

1997-12-31

A study on the oxygen reduction reaction in a solid state electrochemical cell was presented. The oxygen reduction reaction is a rate limiting reaction in the operation of solid polymer electrolyte fuel cells which use H{sub 2} and O{sub 2}. Interest in the oxygen reduction reaction of platinum electrodes in contact with Nafion electrolytes stems from its role in fuel cell technology. The kinetics of the oxygen reduction reaction in different polyelectrolyte membranes, such as Nafion and non-Nafion membranes, were compared. The electrode kinetics and mass transport parameters of the oxygen reduction reaction in polyelectrolyte membranes were measured by ultramicroelectrode techniques. The major difference found between these two classes of membrane was the percentage of water, which is suggestive of superior electrochemical mass transport properties of the non-Nafion membranes. 2 refs. 1 fig.

Effect of chemical functionalization on the electrochemical properties of conducting polymers. Modification of polyaniline by diazonium ion coupling and subsequent reductive degradation

Energy Technology Data Exchange (ETDEWEB)

Acevedo, Diego F.; Rivarola, Claudia R.; Miras, Maria C. [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina); Barbero, Cesar A., E-mail: cbarbero@exa.unrc.edu.a [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina)

2011-04-01

The electrochemical properties of polyaniline (PANI) can be altered by coupling the polymer with aryldiazonium ions. The ions are synthesized by diazotization of aromatic primary amines (1-aminoanthraquinone, sulphadiazine and 4-cyanoaniline) bearing functional groups which are then linked to the polyaniline backbone. All materials produced are electroactive, suggesting that the reaction involves coupling of the diazonium ion with the aromatic rings and not nucleophilic substitution by the aminic nitrogen of PANI on the aryl cations. The electrochemical properties of the modified polymers are different to those of PANI, likely due to electronic and steric effects of the attached groups. Reductive degradation of the azo linkages, using dithionite ion, removes the attached moieties leaving primary amino groups attached to the polyaniline backbone. In that way, the effect of the attached groups on the electrochemical properties of PANI is eliminated. FTIR spectroscopy measurement of the different polymers supports the proposed mechanism. Using the method a polymer containing redox (anthraquinone) groups, which could be used for charge storage, is obtained. Additionally a material containing sulphadiazine moieties, which can be released in vivo by bacterial activity, is also produced. The molecule is a well-known sulfa drug with bacteriostatic activity. The reaction sequence seems to be of general application to modify polyanilines, by attaching functional groups, and then to produce a PANI backbone bearing primary amino groups. Evidence is presented on the kinetic control of attached group removal.

Effect of chemical functionalization on the electrochemical properties of conducting polymers. Modification of polyaniline by diazonium ion coupling and subsequent reductive degradation

International Nuclear Information System (INIS)

Acevedo, Diego F.; Rivarola, Claudia R.; Miras, Maria C.; Barbero, Cesar A.

2011-01-01

The electrochemical properties of polyaniline (PANI) can be altered by coupling the polymer with aryldiazonium ions. The ions are synthesized by diazotization of aromatic primary amines (1-aminoanthraquinone, sulphadiazine and 4-cyanoaniline) bearing functional groups which are then linked to the polyaniline backbone. All materials produced are electroactive, suggesting that the reaction involves coupling of the diazonium ion with the aromatic rings and not nucleophilic substitution by the aminic nitrogen of PANI on the aryl cations. The electrochemical properties of the modified polymers are different to those of PANI, likely due to electronic and steric effects of the attached groups. Reductive degradation of the azo linkages, using dithionite ion, removes the attached moieties leaving primary amino groups attached to the polyaniline backbone. In that way, the effect of the attached groups on the electrochemical properties of PANI is eliminated. FTIR spectroscopy measurement of the different polymers supports the proposed mechanism. Using the method a polymer containing redox (anthraquinone) groups, which could be used for charge storage, is obtained. Additionally a material containing sulphadiazine moieties, which can be released in vivo by bacterial activity, is also produced. The molecule is a well-known sulfa drug with bacteriostatic activity. The reaction sequence seems to be of general application to modify polyanilines, by attaching functional groups, and then to produce a PANI backbone bearing primary amino groups. Evidence is presented on the kinetic control of attached group removal.

Electrochemical Reduction of CO2 on IrxRu(1–x)O2(110) Surfaces 

DEFF Research Database (Denmark)

Bhowmik, Arghya; Hansen, Heine Anton; Vegge, Tejs

2017-01-01

with oxygen-coordinated intermediates that can circumvent the limitations imposed by the scaling relations on metal catalysts. Here, we introduce an innovative concept of ligand effects in oxide catalysts. Both IrO2 and RuO2 binds OH* and other intermediates from the electrochemical reduction of CO2 (CO2RR......High overpotentials and low faradic efficiencies plague metal catalysts for direct conversion of CO2 to methanol and other liquid fuels. RuO2-based electrocatalysts have been observed to evolve methanol at low overpotentials, which has been attributed to an alternative reaction mechanism......) strongly, but the stable and miscible system IrxRu(1-x)O2 exhibits anomalous weaker binding energy in the presence of CO* spectators, because of Ru–Ir ligand effects. The weakened adsorbate binding leads to a very low CO2RR onset potential (methanol evolution at −0.2 V RHE). An Ir atom at the bridge site...

Electrochemically induced nuclear fusion of deuterium

International Nuclear Information System (INIS)

Jorne, J.

1990-01-01

In this paper cold fusion of deuterium by electrolysis of heavy water onto a palladium (or titanium) cathode is reported. Contrary to the assumption of Fleishmann and Pons that electrochemically compressed D + exists inside the palladium cathode, the observations of Jones et al. can be partially explained by the simultaneous presence of deuteride D - and the highly mobile positive deuterium ion D + . The opposite charges reduce the intranuclear distance and enhance the tunneling fusion rate. Furthermore, alloying of lithium with palladium can stabilize a negatively charged deuteride ion due to the salinelike character of lithium deuteride. The enormous pressure (or fugacity), achieved by the applied electrochemical potential (10 30 atm), is a virtual pressure that would have existed in equilibrium with palladium deuteride (PdD x ). It is speculated that nuclear fusion occurs at the surface, and the PdD x serves as a reservoir for the supply of deuteride ions

Improved variable reduction in partial least squares modelling based on predictive-property-ranked variables and adaptation of partial least squares complexity.

Science.gov (United States)

Andries, Jan P M; Vander Heyden, Yvan; Buydens, Lutgarde M C

2011-10-31

The calibration performance of partial least squares for one response variable (PLS1) can be improved by elimination of uninformative variables. Many methods are based on so-called predictive variable properties, which are functions of various PLS-model parameters, and which may change during the variable reduction process. In these methods variable reduction is made on the variables ranked in descending order for a given variable property. The methods start with full spectrum modelling. Iteratively, until a specified number of remaining variables is reached, the variable with the smallest property value is eliminated; a new PLS model is calculated, followed by a renewed ranking of the variables. The Stepwise Variable Reduction methods using Predictive-Property-Ranked Variables are denoted as SVR-PPRV. In the existing SVR-PPRV methods the PLS model complexity is kept constant during the variable reduction process. In this study, three new SVR-PPRV methods are proposed, in which a possibility for decreasing the PLS model complexity during the variable reduction process is build in. Therefore we denote our methods as PPRVR-CAM methods (Predictive-Property-Ranked Variable Reduction with Complexity Adapted Models). The selective and predictive abilities of the new methods are investigated and tested, using the absolute PLS regression coefficients as predictive property. They were compared with two modifications of existing SVR-PPRV methods (with constant PLS model complexity) and with two reference methods: uninformative variable elimination followed by either a genetic algorithm for PLS (UVE-GA-PLS) or an interval PLS (UVE-iPLS). The performance of the methods is investigated in conjunction with two data sets from near-infrared sources (NIR) and one simulated set. The selective and predictive performances of the variable reduction methods are compared statistically using the Wilcoxon signed rank test. The three newly developed PPRVR-CAM methods were able to retain

Application of non-reductive partial partitioning in FBR fuel reprocessing: a simulation study

International Nuclear Information System (INIS)

Shekhar Kumar; Koganti, S.B.

2002-06-01

The observed performance of conventional partitioning contactor in the Purex process in the Purex process is seldom satisfactory due to over-consumption of reductant and poor U-Pu decontamination factors. Contemporary trends indicate gradually move-over to MOX fuels for FBRs. In this scenario, it is not necessary to separate uranium and plutonium completely. By controlling the acid concentration and flow rates, it is possible to selectively strip essentially all the plutonium and part of the uranium in the aqueous stream. Therefore, a mixed product enriched in plutonium is obtained which can be precipitated and denitrated. Alternatively direct denitration by microwave heating can be used. The idea is particularly attractive for the flowsheet meant for the first core of FBTR where Pu/(U+Pu) ratio of 0.7 (in the discharged fuel) is diluted by addition of uranium to 0.3. By partial partitioning in the 2B contactor, a product enriched in plutonium (Pu/(U+Pu) ratio ∼0.6) can be obtained. After a minor uranium addition, this product will be suitable for the direct fabrication of II core of FBTR where a Pu/(U+Pu) ratio of 0.55 will be required. In a similar fashion, the enriched product can be used for multiple core zones of proposed PFBR by selective additions of uranium for each zone. To explore the feasibility of such partial partitioning step, an exhaustive simulation study was made using the in-house developed computer code SIMPSEX. 1300 simulations runs were completed for different combinations of parameters and results were analyzed. In this report, the results of this study and a possible flowsheet step have been discussed. Simultaneous variation in the flow rates has been considered and safe operating limits for the partial partitioning step have been established. (author)

Electrochemical Behaviour of a PPy(DBS)/Polyacrylonitrile (PAN):LITF:EC:PC/ Li Cell

DEFF Research Database (Denmark)

Vidanapathirana, K.; Careem, M.A.; Skaarup, Steen

2006-01-01

The electrochemical behaviour of Li rechargeable cells with Polypyrrole (PPy) as the cathode material was investigated using cyclic voltammetry. The PPy used was doped with the large surfactant anion dodecyl benzenesulphonate (DBS-). The cells were constructed with PAN:LiTF:EC:PC gel electrolyte...... with Li as anode. The results indicate that during the first reduction, cations are inserted into the PPy film forming LiDBS neutral salt. During the next oxidation/reduction cycles, the mechanism then switches to anion movement. Cyclic voltammetry studies also verified that complete electrochemical...

Method and apparatus for monitoring oxygen partial pressure in air masks

Science.gov (United States)

Kelly, Mark E. (Inventor); Pettit, Donald R. (Inventor)

2006-01-01

Method and apparatus are disclosed for monitoring an oxygen partial pressure in an air mask and providing a tactile warning to the user. The oxygen partial pressure in the air mask is detected using an electrochemical sensor, the output signal from which is provided to a comparator. The comparator compares the output signal with a preset reference value or range of values representing acceptable oxygen partial pressures. If the output signal is different than the reference value or outside the range of values, the air mask is vibrated by a vibrating motor to alert the user to a potentially hypoxic condition.

Destructive impact of molecular noise on nanoscale electrochemical oscillators

Science.gov (United States)

Cosi, Filippo G.; Krischer, Katharina

2017-06-01

We study the loss of coherence of electrochemical oscillations on meso- and nanosized electrodes with numeric simulations of the electrochemical master equation for a prototypical electrochemical oscillator, the hydrogen peroxide reduction on Pt electrodes in the presence of halides. On nanoelectrodes, the electrode potential changes whenever a stochastic electron-transfer event takes place. Electrochemical reaction rate coefficients depend exponentially on the electrode potential and become thus fluctuating quantities as well. Therefore, also the transition rates between system states become time-dependent which constitutes a fundamental difference to purely chemical nanoscale oscillators. Three implications are demonstrated: (a) oscillations and steady states shift in phase space with decreasing system size, thereby also decreasing considerably the oscillating parameter regions; (b) the minimal number of molecules necessary to support correlated oscillations is more than 10 times as large as for nanoscale chemical oscillators; (c) the relation between correlation time and variance of the period of the oscillations predicted for chemical oscillators in the weak noise limit is only fulfilled in a very restricted parameter range for the electrochemical nano-oscillator.

Pressure and partial wetting effects on superhydrophobic friction reduction in microchannel flow

Science.gov (United States)

Kim, Tae Jin; Hidrovo, Carlos

2012-11-01

Friction reduction in microchannel flows can help alleviate the inherently taxing pumping power requirements associated with the dimensions involved. One possible way of achieving friction reduction is through the introduction of surface microtexturing that can lead to a superhydrophobic Cassie-Baxter state. The Cassie-Baxter state is characterized by the presence of air pockets within the surface microtexturing believed to act as an effective "shear free" (or at least shear reduced) layer, decreasing the overall friction characteristics of the surface. Most work in this area has concentrated on optimizing the surface microtexturing geometry to maximize the friction reduction effects and overall stability of the Cassie-Baxter state. However, less attention has been paid to the effects of partially wetted conditions induced by pressure and the correlation between the liquid-gas interface location within the surface microtexturing and the microchannel flow characteristics. This is mainly attributed to the difficulty in tracking the interface shape and location within the microtexturing in the typical top-down view arrangements used in most studies. In this paper, a rectangular microchannel with regular microtexturing on the sidewalls is used to visualize and track the location of the air-water interface within the roughness elements. While visually tracking the wetting conditions in the microtextures, pressure drops versus flow rates for each microchannel are measured and analyzed in terms of the non-dimensional friction coefficient. The frictional behavior of the Poiseuille flow suggests that (1) the air-water interface more closely resembles a no-slip boundary rather than a shear-free one, (2) the friction is rather insensitive to the degree of microtexturing wetting, and (3) the fully wetted (Wenzel state) microtexturing provides lower friction than the non-wetted one (Cassie state), in corroboration with observations (1) and (2).

Electrochemical behaviour of gamma hydroxybutyric acid at a platinum electrode in acidic medium

International Nuclear Information System (INIS)

Jiménez-Pérez, R.; Sevilla, J.M.; Pineda, T.; Blázquez, M.; González-Rodríguez, J.

2013-01-01

Highlights: • This is the first reported electrochemical study of the behaviour of GHB. • The first study of the interaction of GHB on solid electrodes. • The GHB oxidation process in platinum electrodes is a complex process. • Re-dissolution and reduction of Pt oxides and oxidation of the GHB OH group. • The oxidation process is also influenced by pH and GHB concentration. -- Abstract: The electrooxidation of gamma hydroxybutyric acid (GHB) on a polycrystalline platinum electrode is studied by cyclic voltammetry in acidic medium. Two oxidation peaks, A and B, are obtained in the positive scan within the potential range of the double layer region and of the platinum oxide region, respectively. In the negative going potential sweep an inverted oxidation peak with an onset partially overlapping with the tail of the cathodic peak for the reduction of the platinum oxide formed during the anodic scan is obtained (peak C). This inverted peak can be observed at a potential close to +0.2 V (vs Ag/AgCl at pH 2) and separated 0.4 and 0.8 V from the two other oxidation peaks obtained during the anodic scan and in such conditions that the surface is particularly activated to favour this electrochemical process. The response obtained in the electronic current for the different peaks when GHB concentration and scan rate were changed to allows inferring that these are the result of a potential dependent mechanism. The behaviour observed is according with the oxidation of the alcohol group to the corresponding aldehyde and carboxylic acid (succinic acid) as main products

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

International Nuclear Information System (INIS)

Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

2016-01-01

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Soo, Li Ting, E-mail: nicolesoo90@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Loh, Kee Shyuan, E-mail: ksloh@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Mohamad, Abu Bakar, E-mail: drab@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Daud, Wan Ramli Wan, E-mail: wramli@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Wong, Wai Yin, E-mail: waiyin.wwy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); School of Engineering, Taylor' s University' s Lakeside Campus, No. 1, Jalan Taylor' s, 46500 Subang Jaya, Selangor (Malaysia)

2016-08-25

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

Science.gov (United States)

Luca, Oana R; Fenwick, Aidan Q

2015-11-01

The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination. Copyright © 2015 Elsevier B.V. All rights reserved.

Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

International Nuclear Information System (INIS)

Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J.; Gonzalez, Ignacio; Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos; Ribeiro, Rogerio Tavares; Longo, Ricardo L.; Navarro, Marcelo; Frontana, Carlos

2010-01-01

The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A 2- + A → 2A· - ). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

Evaluation of Nitrate and Nitrite Reduction Kinetics Related to Liquid-Air-Interface Corrosion

International Nuclear Information System (INIS)

Li, Xiaoji; Gui, F.; Cong, Hongbo; Brossia, C.S.; Frankel, G.S.

2014-01-01

Liquid-air interface (LAI) corrosion has been a concern for causing leaks in the carbon steel tanks used for holding high-level radioactive liquid waste. To assist in understanding the mechanism of LAI corrosion, the kinetics of nitrate and nitrite reduction reactions were investigated electrochemically. Cyclic voltammetry and cathodic polarization measurements indicated that the nitrite reduction reaction exhibited faster kinetics than the nitrate reduction reaction at higher cathodic overpotential. However, the primary reduction reaction at the open circuit potential under aerated conditions was the oxygen reduction reaction. The reduction of residual oxygen was also the dominant cathodic reaction at open circuit potential in deaerated conditions. Moreover, the kinetics of oxygen reduction on steel electrodes were significantly influenced by the sample immersion conditions (partial vs. full) for aerated liquid nuclear waste simulants, but not for deaerated conditions. Lastly, the gaseous products formed during LAI corrosion were analyzed using the gas detector tube method and gas chromatography-mass spectrometry and found to contain NH 3 , NO 2 and NO. However, the results suggested that these products were caused by the local acidification generated by the hydrolysis of cations after LAI corrosion underwent extensive propagation, instead of being directly reduced in alkaline conditions. Thus, the results in this work showed that the kinetics of nitrate and nitrite reduction could not generate a salt concentration cell in the meniscus region to cause LAI corrosion

Highly selective NOx reduction for diesel engine exhaust via an electrochemical system

DEFF Research Database (Denmark)

Shao, Jing; Tao, Youkun; Kammer Hansen, Kent

2016-01-01

It is challenging to reduce the nitrogen oxides (NOx) in diesel engine exhaust due to the inhibiting effect of excess oxygen. In this study, a novel electrochemical deNOx system was developed, which eliminated the need for additional reducing materials or a sophisticated controlling system as used...

Efficient electrochemical degradation of multiwall carbon nanotubes.

Science.gov (United States)

Reipa, Vytas; Hanna, Shannon K; Urbas, Aaron; Sander, Lane; Elliott, John; Conny, Joseph; Petersen, Elijah J

2018-07-15

As the production mass of multiwall carbon nanotubes (MWCNT) increases, the potential for human and environmental exposure to MWCNTs may also increase. We have shown that exposing an aqueous suspension of pristine MWCNTs to an intense oxidative treatment in an electrochemical reactor, equipped with an efficient hydroxyl radical generating Boron Doped Diamond (BDD) anode, leads to their almost complete mineralization. Thermal optical transmittance analysis showed a total carbon mass loss of over two orders of magnitude due to the electrochemical treatment, a result consistent with measurements of the degraded MWCNT suspensions using UV-vis absorbance. Liquid chromatography data excludes substantial accumulation of the low molecular weight reaction products. Therefore, up to 99% of the initially suspended MWCNT mass is completely mineralized into gaseous products such as CO 2 and volatile organic carbon. Scanning electron microscopy (SEM) images show sporadic opaque carbon clusters suggesting the remaining nanotubes are transformed into structure-less carbon during their electrochemical mineralization. Environmental toxicity of pristine and degraded MWCNTs was assessed using Caenorhabditis elegans nematodes and revealed a major reduction in the MWCNT toxicity after treatment in the electrochemical flow-by reactor. Published by Elsevier B.V.

Novel quasi-symmetric solid oxide fuel cells with enhanced electrochemical performance

KAUST Repository

Chen, Yonghong

2016-02-16

Symmetrical solid oxide fuel cell (SSOFC) using same materials as both anode and cathode simultaneously has gained extensively attentions, which can simplify fabrication process, minimize inter-diffusion between components, enhance sulfur and coking tolerance by operating the anode as the cathode in turn. With keeping the SSOFC\\'s advantages, a novel quasi-symmetrical solid oxide fuel cell (Q-SSOFC) is proposed to further improve the performance, which optimally combines two different SSOFC electrode materials as both anode and cathode simultaneously. PrBaFe2O5+δ (PBFO) and PrBaFe1.6Ni0.4O5+δ (PBFNO, Fe is partially substituted by Ni.) are prepared and applied as both cathode and anode for SSOFC, which exhibit desirable chemical and thermal compatibility with Sm0.8Ce0.2O1.9 (SDC) electrolyte. PBFO cathode exhibits higher oxygen reduction reaction (ORR) activity than PBFNO cathode in air, whereas PBFNO anode exhibits higher hydrogen oxidation reaction (HOR) activity than PBFO anode in H2. The as-designed Q-SSOFC of PBFNO/SDC/PBFO exhibits higher electrochemical performance than the conventional SSOFCs of both PBFO/SDC/PBFO and PBFNO/SDC/PBFNO. The superior performance of Q-SSOFC is attributed to the lowest polarization resistance (Rp). The newly developed Q-SSOFCs open doors for further improvement of electrochemical performance in SSOFC, which hold more promise for various potential applications. © 2016 Elsevier B.V. All rights reserved.

Partial order infinitary term rewriting

DEFF Research Database (Denmark)

Bahr, Patrick

2014-01-01

We study an alternative model of infinitary term rewriting. Instead of a metric on terms, a partial order on partial terms is employed to formalise convergence of reductions. We consider both a weak and a strong notion of convergence and show that the metric model of convergence coincides with th...... to the metric setting -- orthogonal systems are both infinitarily confluent and infinitarily normalising in the partial order setting. The unique infinitary normal forms that the partial order model admits are Böhm trees....

Water-mediated electrochemical nano-writing on thin ceria films

International Nuclear Information System (INIS)

Yang, Nan; Doria, Sandra; Tebano, Antonello; Licoccia, Silvia; Balestrino, Giuseppe; Kumar, Amit; Arruda, Thomas M; Jesse, Stephen; Ivanov, Ilia N; Baddorf, Arthur P; Strelcov, Evgheni; Kalinin, Sergei V; Jang, Jae Hyuck; Borisevich, Albina Y

2014-01-01

Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO 2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing. (paper)

Electrochemical flue gas desulfurization: Reactions in a pyrosulfate-based electrolyte

International Nuclear Information System (INIS)

Scott, K.; Fannon, T.; Winnick, J.

1988-01-01

A new electrolyte has been found suitable for use in an electrochemical membrane cell for flue gas desulfurization (FGD). The electrolyte is primarily K/sub 2/S/sub 2/O/sub 7/ and K/sub 2/SO/sub 4/ with V/sub 2/O/sub 5/ as oxidation enhancer. This electrolyte has a melting point near 300/sup 0/C which is compatible with flue gas exiting the economizer of coal-burning power plants. Standard electrochemical tests have revealed high exchange current densities around 30 mA/cm/sup 2/, in the free electrolyte. Sulfur dioxide is found to be removed from simulated flue gas in a multiple-step process, the first of which is electrochemical reduction of pyrosulfate

Textbook Error: Short Circuiting on Electrochemical Cell

Science.gov (United States)

Bonicamp, Judith M.; Clark, Roy W.

2007-01-01

Short circuiting an electrochemical cell is an unreported but persistent error in the electrochemistry textbooks. It is suggested that diagrams depicting a cell delivering usable current to a load be postponed, the theory of open-circuit galvanic cells is explained, the voltages from the tables of standard reduction potentials is calculated and…

Nitrogen-Doped Three Dimensional Graphene for Electrochemical Sensing.

Science.gov (United States)

Yan, Jing; Chen, Ruwen; Liang, Qionglin; Li, Jinghong

2015-07-01

The rational assembly and doping of graphene play an crucial role in the improvement of electrochemical performance for analytical applications. Covalent assembly of graphene into ordered hierarchical structure provides an interconnected three dimensional conductive network and large specific area beneficial to electrolyte transfer on the electrode surface. Chemical doping with heteroatom is a powerful tool to intrinsically modify the electronic properties of graphene due to the increased free charge-carrier densities. By incorporating covalent assembly and nitrogen doping strategy, a novel nitrogen doped three dimensional reduced graphene oxide nanostructure (3D-N-RGO) was developed with synergetic enhancement in electrochemical behaviors. The as prepared 3D-N-RGO was further applied for catechol detection by differential pulse voltammetry. It exhibits much higher electrocatalytic activity towards catechol with increased peak current and decreased potential difference between the oxidation and reduction peaks. Owing to the improved electro-chemical properties, the response of the electrochemical sensor varies linearly with the catechol concentrations ranging from 5 µM to 100 µM with a detection limit of 2 µM (S/N = 3). This work is promising to open new possibilities in the study of novel graphene nanostructure and promote its potential electrochemical applications.

Electrochemical behavior of boron in LiF-NaF-KF- melts

DEFF Research Database (Denmark)

Polyakova, L.P.; Bukatova, G.A.; Polyakova, E.G.

1996-01-01

The electrochemical reduction of B(III) to B(0) in KBF4-LiF-NaF-KF melts has been studied by voltammetric and chronopotentiometric methods, Glassy carbon, Pt, and Ag were used as working electrode materials. Only in the case of Ag was the reduction not complicated by interaction between boron...

Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

Energy Technology Data Exchange (ETDEWEB)

Leung, Kevin; Hudak, Nicholas S.; Liu, Yang; Liu, Xiaohua H.; Fan, Hongyou; Subramanian, Arunkumar; Shaw, Michael J.; Sullivan, John Patrick; Huang, Jian Yu

2012-01-01

We report the development of new experimental capabilities and ab initio modeling for real-time studies of Li-ion battery electrochemical reactions. We developed three capabilities for in-situ transmission electron microscopy (TEM) studies: a capability that uses a nanomanipulator inside the TEM to assemble electrochemical cells with ionic liquid or solid state electrolytes, a capability that uses on-chip assembly of battery components on to TEM-compatible multi-electrode arrays, and a capability that uses a TEM-compatible sealed electrochemical cell that we developed for performing in-situ TEM using volatile battery electrolytes. These capabilities were used to understand lithiation mechanisms in nanoscale battery materials, including SnO{sub 2}, Si, Ge, Al, ZnO, and MnO{sub 2}. The modeling approaches used ab initio molecular dynamics to understand early stages of ethylene carbonate reduction on lithiated-graphite and lithium surfaces and constrained density functional theory to understand ethylene carbonate reduction on passivated electrode surfaces.

Progress in the electrochemical modification of graphene-based materials and their applications

International Nuclear Information System (INIS)

Chakrabarti, M.H.; Low, C.T.J.; Brandon, N.P.; Yufit, V.; Hashim, M.A.; Irfan, M.F.; Akhtar, J.; Ruiz-Trejo, E.; Hussain, M.A.

2013-01-01

Highlights: • Six means of functionalizing graphene electrochemically is reviewed. • Electrochemical functionalization is relatively new to other standard methods. • The technique is expected to improve graphene's application range considerably. -- Abstract: Graphene is a 2D allotrope of carbon with exciting properties such as extremely high electronic conductivity and superior mechanical strength. It has considerable potential for applications in fields such as bio-sensors, electrochemical energy storage and electronics. In most cases, graphene has been functionalized and modified with other materials to prepare composites. This work reviews the electrochemical modification of graphene. Commencing with a brief history, a summary of several different means of modifying graphene to effect diverse applications is provided. This is followed by a discussion on different composite materials that have been prepared with reduced graphene oxide prior to moving onto a detailed consideration of six different methods of electrochemically modifying graphene to prepare composite materials. These methods involve cathodic reduction of graphene oxide, electrophoretic deposition, electro-deposition techniques, electrospinning, electrochemical doping and electrochemical polymerization. Finally a consideration on the applications of electrochemically modified graphene composite materials in various fields is presented prior to discussing some prospects in enhancing the electrochemical process to realize excellent and economic composite materials in bulk

Electrochemical degradation and toxicity reduction of C.I. Basic Red 29 solution and textile wastewater by using diamond anode

International Nuclear Information System (INIS)

Koparal, A. Savas; Yavuz, Yusuf; Guerel, Canan; Oguetveren, Ulker Bakir

2007-01-01

Electrochemical oxidation of Basic Red 29 (BR29) was studied in a bipolar trickle tower (BTT) reactor by using Raschig ring shaped boron-doped diamond (BDD) electrodes, which were originally employed by the present researchers, in a recirculated batch mode. The model solution was prepared with BR29 using distilled water. The effects of initial dye concentration, Na 2 SO 4 concentration as supporting electrolyte, current density, flow rate and initial pH on the removal efficiency were investigated, and practically, complete BR29 removal (over 99%) was obtained in all the studies. After optimum experimental conditions were determined, textile wastewater has also studied by monitoring the destruction of color and COD. With the textile wastewater, 97.2% of color and 91% of COD removal were, respectively, achieved at the current density of 1 mA/cm 2 . Microtox toxicity tests were performed in both BR29 solution and textile wastewater under optimum experimental conditions, and relatively good toxicity reductions were obtained with respect to the initial values. According to the results, BDD anode was seen to be a unique material for the degradation of BR29 and COD and also the reduction of toxicity simultaneously

Electrochemical degradation and toxicity reduction of C.I. Basic Red 29 solution and textile wastewater by using diamond anode

Energy Technology Data Exchange (ETDEWEB)

Koparal, A. Savas [Anadolu Universitesi, Cevre Sor.Uyg. ve Aras, Merkezi, Eskisehir (Turkey)]. E-mail: askopara@anadolu.edu.tr; Yavuz, Yusuf [Anadolu Universitesi, Cevre Sor.Uyg. ve Aras, Merkezi, Eskisehir (Turkey); Guerel, Canan [Anadolu Universitesi, Cevre Sor.Uyg. ve Aras, Merkezi, Eskisehir (Turkey); Oguetveren, Ulker Bakir [Anadolu Universitesi, Cevre Sor.Uyg. ve Aras, Merkezi, Eskisehir (Turkey)

2007-06-25

Electrochemical oxidation of Basic Red 29 (BR29) was studied in a bipolar trickle tower (BTT) reactor by using Raschig ring shaped boron-doped diamond (BDD) electrodes, which were originally employed by the present researchers, in a recirculated batch mode. The model solution was prepared with BR29 using distilled water. The effects of initial dye concentration, Na{sub 2}SO{sub 4} concentration as supporting electrolyte, current density, flow rate and initial pH on the removal efficiency were investigated, and practically, complete BR29 removal (over 99%) was obtained in all the studies. After optimum experimental conditions were determined, textile wastewater has also studied by monitoring the destruction of color and COD. With the textile wastewater, 97.2% of color and 91% of COD removal were, respectively, achieved at the current density of 1 mA/cm{sup 2}. Microtox toxicity tests were performed in both BR29 solution and textile wastewater under optimum experimental conditions, and relatively good toxicity reductions were obtained with respect to the initial values. According to the results, BDD anode was seen to be a unique material for the degradation of BR29 and COD and also the reduction of toxicity simultaneously.

30-day hospital readmission after robotic partial nephrectomy--are we prepared for Medicare readmission reduction program?

Science.gov (United States)

Brandao, Luis Felipe; Zargar, Homayoun; Laydner, Humberto; Akca, Oktay; Autorino, Riccardo; Ko, Oliver; Samarasekera, Dinesh; Li, Jianbo; Rabets, John; Krishnan, Jayram; Haber, Georges-Pascal; Kaouk, Jihad; Stein, Robert J

2014-09-01

After CMS introduced the concept of the Hospital Readmissions Reduction Program, hospitals and health care centers became financially penalized for exceeding specific readmission rates. We retrospectively reviewed our institutional review board approved database of patients undergoing robotic partial nephrectomy at our institution and included in our analysis patients who were readmitted to any hospital as an inpatient stay within 30 days from discharge home after robotic partial nephrectomy. From March 2006 to March 2013 a total of 627 patients underwent robotic partial nephrectomy at our center and 28 (4.46%) were readmitted within 30 days of surgery. Postoperative bleeding was responsible for 8 (28.5%) readmissions. Pulmonary embolism was reported in 3 cases and retroperitoneal abscess was diagnosed in 2. Urinary leak requiring surgical intervention developed in 2 patients, pneumonia was diagnosed in 2 and 2 patients were readmitted for chest pain. Overall 9 (32.1%) patients presented with major complications requiring intervention. On multivariable analysis Charlson comorbidity index score was the only factor significantly associated with a higher 30-day readmission rate (p = 0.03). If the Charlson score was 5 or greater the chance of hospital readmission would be 2.7 times higher. Increased comorbidity, specifically a Charlson score of 5 or greater, was the only significant predictor of a higher incidence of 30-day readmission. This information can be useful in counseling patients regarding robotic partial nephrectomy and in determining baseline rates if CMS expands the number of conditions they evaluate for excess 30-day readmissions. Copyright © 2014 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Electrochemical removal of nickel ions from industrial wastewater

NARCIS (Netherlands)

Njau, K.N.; Woude, van der M.E.; Visser, G.J.; Janssen, L.J.J.

2000-01-01

The electrochemical reduction of nickel ions in dilute industrial wastewater from a galvanic nickel plating plant was carried out on a three-dimensional electrode in a gas diffusion electrode packed bed electrode cell (GBC) and also on a rotating disc electrode. To explain the experimental results,

Electrobiorefineries: Unlocking the Synergy of Electrochemical and Microbial Conversions.

Science.gov (United States)

Harnisch, Falk; Urban, Carolin

2017-12-13

An integrated biobased economy urges an alliance of the two realms of "chemical production" and "electric power". The concept of electrobiorefineries provides a blueprint for such an alliance. Joining the forces of microbial and electrochemical conversions in electrobiorefineries allows interfacing the production, storage, and exploitation of electricity as well as biobased chemicals. Electrobiorefineries are a technological evolution of biorefineries by the addition of (bio)electrochemical transformations. This interfacing of microbial and electrochemical conversions will result in synergies affecting the entire process line, like enlarging the product portfolio, increasing the productivity, or exploiting new feedstock. A special emphasis is given to the utilization of oxidative and reductive electroorganic reactions of microbially produced intermediates that may serve as privileged building blocks. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced catalytic and dopamine sensing properties of electrochemically reduced conducting polymer nanocomposite doped with pure graphene oxide.

Science.gov (United States)

Wang, Wenting; Xu, Guiyun; Cui, Xinyan Tracy; Sheng, Ge; Luo, Xiliang

2014-08-15

Significantly enhanced catalytic activity of a nanocomposite composed of conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) doped with graphene oxide (GO) was achieved through a simple electrochemical reduction process. The nanocomposite (PEDOT/GO) was electrodeposited on an electrode and followed by electrochemical reduction, and the obtained reduced nanocomposite (PEDOT/RGO) modified electrode exhibited lowered electrochemical impedance and excellent electrocatalytic activity towards the oxidation of dopamine. Based on the excellent catalytic property of PEDOT/RGO, an electrochemical sensor capable of sensitive and selective detection of DA was developed. The fabricated sensor can detect DA in a wide linear range from 0.1 to 175μM, with a detection limit of 39nM, and it is free from common interferences such as uric acid and ascorbic acid. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen embrittlement, revisited by in situ electrochemical nanoindentation

Energy Technology Data Exchange (ETDEWEB)

Barnoush, Afrooz

2007-07-01

The fine scale mechanical probing capability of NI-AFM was used to examine hydrogen interaction with plasticity. To realize this, an electrochemical three electrode setup was incorporated into the NI-AFM. The developed ECNI-AFM is capable of performing nanoindentation as well as imaging surfaces inside electrolytes. The developed ECNI-AFM setup was used to examine the effect of cathodically charged hydrogen on dislocation nucleation in pure metals and alloys. It was shown that hydrogen reduces the pop-in load in all of the tested materials except Cu. The reduced pop-in load can be interpreted as the HELP mechanism. Classical dislocation theory was used to model the homogeneous dislocation nucleation and it was shown that H reduces the activation energy for dislocation nucleation in H sensitive metals which are not undergoing a phase transformation. The activation energy for dislocation nucleation is related to the material specific parameters; shear modulus {mu}, dislocation core radius {rho} and in the case of partial dislocation nucleation, stacking fault energy {gamma}. These material properties can be influenced by H resulting in a reduced activation energy for dislocation nucleation. The universality of cohesion in bulk metals relates the reduction of the shear modulus to the reduction of the cohesion, meaning HEDE mechanism. The increase in the core radius of a dislocation due to H is a direct evidence of decrease in dislocation line energy and H segregation on the dislocation line. In the case of partial dislocations, the H can segregate on to the stacking fault ribbon and decrease {gamma}. This inhibits the cross slip process and enhances the slip planarity. Thus, HELP and HEDE are the two sides of a coin resulting in H embrittlement. However depending on the experimental approach utilized to probe the H effect, either HELP or HEDE can be observed. In this study, however, by utilizing a proper experimental approach, it was possible to resolve the

Investigation of Electrochemically Deposited and Chemically Reduced Platinum Nanostructured Thin Films as Counter Electrodes in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Chih-Hung Tsai

2018-02-01

Full Text Available In this paper, we demonstrated that platinum (Pt counter electrodes (CEs fabricated using electrochemical deposition and chemical reduction can replace conventional high-temperature thermally decomposed Pt electrodes. In this study, Pt electrodes were fabricated using thermal decomposition, electrochemical deposition, and chemical reduction, and the influence of the different Pt counter electrodes on the efficiency of the dye-sensitized solar cells (DSSCs was analyzed. The properties of the various Pt CEs were analyzed using scanning electron microscopy (SEM, surface area analysis, X-ray diffraction (XRD, electrochemical impedance spectroscopy (EIS, and cyclic voltammetry (CV. DSSCs with various Pt CEs were characterized using current density-voltage (J-V, incident photo-current conversion efficiency (IPCE, and EIS measurements. The results show that the power conversion efficiencies of these three types of DSSC devices were between 7.43% and 7.72%. The DSSCs based on the Pt electrode fabricated through electrochemical deposition exhibited the optimal power conversion efficiency. Because the processes of electrochemical deposition and chemical reduction do not require high-temperature sintering, these two methods are suitable for the fabrication of Pt on flexible plastic substrates.

Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

Energy Technology Data Exchange (ETDEWEB)

Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J. [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico); Gonzalez, Ignacio [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, Area de Electroquimica, Apartado Postal 55-534, 09340, D.F. (Mexico); Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, Tabuleiro do Martins, Maceio, AL, 57072-970 (Brazil); Ribeiro, Rogerio Tavares; Longo, Ricardo L. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Navarro, Marcelo, E-mail: navarro@ufpe.b [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico)

2010-11-30

The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A{sup 2-} + A {yields} 2A{center_dot}{sup -}). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

Electrochemical reductive dehalogenation of iodine-containing contrast agent pharmaceuticals: Examination of reactions of diatrizoate and iopamidol using the method of rotating ring-disc electrode (RRDE).

Science.gov (United States)

Yan, Mingquan; Chen, Zhanghao; Li, Na; Zhou, Yuxuan; Zhang, Chenyang; Korshin, Gregory

2018-06-01

This study examined the electrochemical (EC) reduction of iodinated contrast media (ICM) exemplified by iopamidol and diatrizoate. The method of rotating ring-disc electrode (RRDE) was used to elucidate rates and mechanisms of the EC reactions of the selected ICMs. Experiments were carried at varying hydrodynamic conditions, concentrations of iopamidol, diatrizoate, natural organic matter (NOM) and model compounds (resorcinol, catechol, guaiacol) which were used to examine interactions between products of the EC reduction of ICMs and halogenation-active species. The data showed that iopamidol and diatrizoate were EC-reduced at potentials < -0.45 V vs. s.c.e. In the range of potentials -0.65 to -0.85 V their reduction was mass transfer-controlled. The presence of NOM and model compounds did not affect the EC reduction of iopamidol and diatrizoate but active iodine species formed as a result of the EC-induced transformations of these ICMs reacted readily with NOM and model compounds. These data provide more insight into the nature of generation of iodine-containing by-products in the case of reductive degradation of ICMs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of graphene/nile blue nanocomposite: Application for oxygen reduction reaction and biosensing

International Nuclear Information System (INIS)

Shervedani, Reza Karimi; Amini, Akbar

2015-01-01

Highlights: •New nanocomposite is synthesized by electrochemical polymerization of Nile blue and reduction of GO on GCE. •The nanocomposite is characterized by SEM, UV–vis and electrochemical methods. •High electrocatalytic activity was observed for O 2 reduction on GNs-NB nanocomposite. •GCE-GNs-NB poly was tested successfully for immobilization of GOx and detection of glucose. -- Abstract: Nile blue/graphene (NB-GNs) nanocomposite was synthesized for the first time via a green and effective one-step electrochemical method, allowing to reduce graphene oxide (GO) and NB on the glassy carbon electrode (GCE) simultaneously and construct GCE-GNs-NB poly composite. The composite was characterized by scanning electron microscopy (SEM), UV–Vis spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrochemical results obtained in the absence of any redox probe, where NB was active, allowed to trace step-by-step addition of the NB-GNs nanocomposite onto the GCE electrode surface, supporting formation of the GCE-GNs-NB poly composite. The electrocatalytic activity of the as-prepared GCE-GNs-NB poly towards O 2 reduction was studied in neutral medium. The results revealed excellent electrocatalytic performance for two-electron reduction of oxygen, suggesting its potential application as metal-free electrocatalysts for O 2 reduction reaction. Application of the GCE-GNs-NB poly in electrochemical biosensing was demonstrated by immobilization of glucose oxidase (GOx) on the surface of GCE-GNs-NB poly , and then, using it for sensing of glucose. The biosensor exhibited a linear response, from 0.2 to 2.0 mM glucose, with a low detection limit, 2.1 μM, and high sensitivity, 67.0 μA mM −1 cm −2 , obtained by cyclic voltammetry method. The proposed biosensor was successfully tested for determination of glucose in blood serum samples

Electrochemical extraction of neodymium by co-reduction with aluminum in LiCl–KCl molten salt

International Nuclear Information System (INIS)

Yan, Yong-De; Xu, Yan-Lu; Zhang, Mi-Lin; Xue, Yun; Han, Wei; Huang, Ying; Chen, Qiong; Zhang, Zhi-Jian

2013-01-01

The electrochemical behavior of Nd(III) ions in LiCl–KCl and LiCl–KCl–AlCl 3 melts on a Mo electrode at 723 K was studied by various electrochemical techniques. The results showed that Nd(III) ions are reduced to Nd(0) through two consecutive steps, and the underpotential deposition of neodymium on pre-deposited Al electrode formed two kinds of Al–Nd intermetallic compounds in LiCl–KCl–AlCl 3 solutions. The electrochemical extraction of neodymium was carried out in LiCl–KCl–AlCl 3 melts on a Mo electrode at 873 K by potentiostatic and galvanostatic electrolysis. The extraction efficiency was 99.25% after potentiostatic electrolysis for 30 h. Al–Li–Nd bulk alloy was obtained by galvanostatic electrolysis. X-ray diffraction (XRD) suggested that Al 2 Nd and Al 3 Nd phases were formed in Al–Li–Nd alloy. The microstructure and micro-zone chemical analysis of Al–Li–Nd alloy were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), respectively

Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

Science.gov (United States)

He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

2016-06-08

Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

Science.gov (United States)

Bhattacharya, Sandeep

This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt microscopic information to the electrochemical performance, novel Li2CO3-coated electrodes were fabricated that were durable. The SEI formed on pre-treated electrodes reduced

Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

Energy Technology Data Exchange (ETDEWEB)

Calfuman, Karla [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile); Aguirre, Maria Jesus [Facultad de Quimica y Biologia, Departamento de Quimica de los Materiales, Universidad de Santiago de Chile, Santiago (Chile); Canete-Rosales, Paulina; Bollo, Soledad [Facultad de Ciencias Quimicas y Farmaceuticas, Departamento de Quimica Farmacologica y Toxicologica, Universidad de Chile, Santiago (Chile); Llusar, Rosa [Departamento de Quimica Fisica y Analitica, Universidad de Jaume I, Castellon (Spain); Isaacs, Mauricio, E-mail: misaacs@uchile.cl [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile)

2011-10-01

Highlights: > Preparation and characterization of modified electrodes with M(II) Tetraruthenated porphyrins onto a Nafion film. > The electrodes were characterized by SEM, TEM, AFM and SECM techniques. > The modified electrodes are active in the electrochemical reduction of nitrite at -660 mV vs Ag/AgCl. > GC/Nf/CoTRP modified electrode is more electrochemically active than their Ni and Zn analogues. - Abstract: This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues. These modified electrodes are able to reduce nitrite at -660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.

In situ electrochemical-mass spectroscopic investigation of solid electrolyte interphase formation on the surface of a carbon electrode

International Nuclear Information System (INIS)

Gourdin, Gerald; Zheng, Dong; Smith, Patricia H.; Qu, Deyang

2013-01-01

The energy density of an electrochemical capacitor can be significantly improved by utilizing a lithiated negative electrode and a high surface area positive electrode. During lithiation of the negative carbon electrode, the electrolyte reacts with the electrode surface and undergoes decomposition to form a solid electrolyte interphase (SEI) layer that passivates the surface of the carbon electrode from further reactions between Li and the electrolyte. The reduction reactions that the solvent undergoes also form insoluble and gaseous by-products. In this work, those gaseous by-products generated by reductive decomposition of a carbonate-based electrolyte, 1.2 M LiPF 6 in EC/PC/DEC (3:1:4), were analyzed at different stages during the lithiation process of an amorphous carbon electrode. The stages in the generation of gaseous by-products were determined to come as a result of two, 1-electron reduction steps of the cyclic carbonate components of the electrolyte. Electrochemical impedance spectroscopy was also used to investigate the two distinct electrochemical processes and the development of the two phases of the SEI structure. This is the first time that the state of an electrochemical cell during the formation of the SEI layer has been systematically correlated with theoretical reaction mechanisms through the use of in situ electrochemical-MS and impedance spectroscopy analyses

Reduced graphene oxide supported gold nanoparticles for electrocatalytic reduction of carbon dioxide

Science.gov (United States)

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.

Electrochemical properties of quaternary ammonium salts for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Ue, Makoto; Takeda, Masayuki; Takehara, Masahiro; Mori, Shoichiro [Mitsubishi Chemical Corp., Inashiki, Ibaraki (Japan). Tsukuba Research Center

1997-08-01

The limiting reduction and oxidation potentials and electrolytic conductivities of new quaternary ammonium salts were examined for electrochemical capacitor applications, whose anions have already been tested as lithium salts for lithium battery applications. The anodic stability was in the following order BR{sub 4}{sup {minus}} < ClO{sub 4}{sup {minus}} {le} CF{sub 3}SO{sub 3}{sup {minus}} < (CF{sub 3}SO{sub 2}){sub 2}N{sup {minus}} {le} C{sub 4}F{sub 9}SO{sub 3}{sup {minus}} < BF{sub 4}{sup {minus}} < PF{sub 6}{sup {minus}} {le} AsF{sub 6}{sup {minus}} < SbF{sub 6}{sup {minus}}. The electrolytic conductivities of Me{sub 4{minus}n}Et{sub n}N(CF{sub 3}SO{sub 2}){sub 2}N (n = 0--4) were examined in comparison with Me{sub 4{minus}n}Et{sub n}NBF{sub 4} counterparts. These imide salts showed good solubility, relatively high conductivity, and anodic stability in propylene carbonate. Et{sub 4}N(CF{sub 3}SO{sub 2}){sub 2}N was found to be a good supporting salt for low permittivity organic solvents, and it afforded a highly conductive electrolyte system based on the ethylene carbonate-dimethyl carbonate mixed solvent, which is useful for electrochemical capacitor applications.

Electrochemical hydrogen Storage Systems

International Nuclear Information System (INIS)

Macdonald, Digby

2010-01-01

As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not described in the

Electrochemical hydrogen Storage Systems

Energy Technology Data Exchange (ETDEWEB)

Dr. Digby Macdonald

2010-08-09

As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not

The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

2010-11-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualisation of local catalytic activity.

Science.gov (United States)

Eckhard, Kathrin; Chen, Xingxing; Turcu, Florin; Schuhmann, Wolfgang

2006-12-07

In order to locally analyse catalytic activity on modified surfaces a transient redox competition mode of scanning electrochemical microscopy (SECM) has been developed. In a bi-potentiostatic experiment the SECM tip competes with the sample for the very same analyte. This leads to a current decrease at the SECM tip, if it is positioned in close proximity to an active catalyst site on the surface. Specifically, local catalytic activity of a Pt-catalyst modified sample with respect to the catalytic reduction of molecular oxygen was investigated. At higher local catalytic activity the local 02 partial pressure within the gap between accurately positioned SECM tip and sample is depleted, leading to a noticeable tip current decrease over active sites. A flexible software module has been implemented into the SECM to adapt the competition conditions by proper definition of tip and sample potentials. A potential pulse profile enables the localised electrochemically induced generation of molecular oxygen prior to the competition detection. The current decay curves are recorded over the entire duration of the applied reduction pulse. Hence, a time resolved processing of the acquired current values provides movies of the local oxygen concentration against x,y-position. The SECM redox competition mode was verified with a macroscopic Pt-disk electrode as a test sample to demonstrate the feasibility of the approach. Moreover, highly dispersed electro-deposited spots of gold and platinum on glassy carbon were visualised using the redox competition mode of SECM. Catalyst spots of different nature as well as activity inhomogeneities within one spot caused by local variations in Pt-loading were visualised successfully.

Chip cleaning and regeneration for electrochemical sensor arrays

Energy Technology Data Exchange (ETDEWEB)

Bhalla, Vijayender [Biochemistry Department ' G.Moruzzi' , University of Bologna, Via Irnerio 48, 40126 Bologna (Italy); Carrara, Sandro, E-mail: sandro.carrara@epfl.c [Biochemistry Department ' G.Moruzzi' , University of Bologna, Via Irnerio 48, 40126 Bologna (Italy); Stagni, Claudio [Department DEIS, University of Bologna, viale Risorgimento 2, 40136 Bologna (Italy); Samori, Bruno [Biochemistry Department ' G.Moruzzi' , University of Bologna, Via Irnerio 48, 40126 Bologna (Italy)

2010-04-02

Sensing systems based on electrochemical detection have generated great interest because electronic readout may replace conventional optical readout in microarray. Moreover, they offer the possibility to avoid labelling for target molecules. A typical electrochemical array consists of many sensing sites. An ideal micro-fabricated sensor-chip should have the same measured values for all the equivalent sensing sites (or spots). To achieve high reliability in electrochemical measurements, high quality in functionalization of the electrodes surface is essential. Molecular probes are often immobilized by using alkanethiols onto gold electrodes. Applying effective cleaning methods on the chip is a fundamental requirement for the formation of densely-packed and stable self-assembly monolayers. However, the available well-known techniques for chip cleaning may not be so reliable. Furthermore, it could be necessary to recycle the chip for reuse. Also in this case, an effective recycling technique is required to re-obtain well cleaned sensing surfaces on the chip. This paper presents experimental results on the efficacy and efficiency of the available techniques for initial cleaning and further recycling of micro-fabricated chips. Piranha, plasma, reductive and oxidative cleaning methods were applied and the obtained results were critically compared. Some interesting results were attained by using commonly considered cleaning methodologies. This study outlines oxidative electrochemical cleaning and recycling as the more efficient cleaning procedure for electrochemical based sensor arrays.

An electrochemical study of U(VI) and Cr(VI) in molten borates

International Nuclear Information System (INIS)

Brigaudeau, M.; Gregori de Pinochet, I. de

1977-01-01

The electrochemical reduction of U(VI) and Cr(VI), in molten Na 2 B 4 O 7 at 800 deg C was studied by means of linear sweep voltammetry, and chronopotentiometry. The reduction of U(VI) to U(V) proceeded reversibly at a platinum electrode. The diffusion coefficient for the U(VI) species at 800 deg C was 4.10 -7 cm 2 .s -1 . The activation energy of diffusion was (34,8 +- 0,8) kcal. mole -1 . Electrochemical studies of Cr(VI) at 800 0 C reveal a two-step reduction process at a platinum electrode. Only the voltammogram for the first step charge transfer process was studied. Analysis indicated that Cr(VI) is reversibly reduced to Cr(III) at a platinum electrode. The diffusion coefficient for Cr(VI) at 800 0 C is 1,9.10 -7 cm 2 .s -1 [fr

Preparation and electrochemical characterization of MnOOH nanowire-graphene oxide

International Nuclear Information System (INIS)

Wang Lin; Wang Dianlong

2011-01-01

Highlights: → MnOOH nanowire-graphene oxide composites are prepared by hydrothermal reaction in distilled water or 5% ammonia aqueous solution at 130 deg. C, with MnO 2 -graphene oxide composites which are synthesized by a redox reaction between KMnO 4 and graphene oxide. → MnO 2 is deoxidized to MnOOH on graphene oxide through hydrothermal reaction without any extra reductants. → It is found that the electrochemical resistance of MnOOH nanowire-graphene oxide composites decreases and the capacitance increases to 76 F g -1 when hydrothermal reaction is conducted in ammonia aqueous solution. → MnOOH nanowire-graphene oxide composites prepared by hydrothermal reaction in 5% ammonia aqueous solution have excellent capacitance retention ratio at scan rate from 5 mV s -1 to 40 mV s -1 . - Abstract: MnOOH nanowire-graphene oxide composites are prepared by hydrothermal reaction in distilled water or 5% ammonia aqueous solution at 130 deg. C with MnO 2 -graphene oxide composites which are synthesized by a redox reaction between KMnO 4 and graphene oxide. Powder X-ray diffraction (XRD) analyses and energy dispersive X-ray analyses (EDAX) show MnO 2 is deoxidized to MnOOH on graphene oxide through hydrothermal reaction without any extra reductants. The electrochemical capacitance of MnOOH nanowire-graphene oxide composites prepared in 5% ammonia aqueous solution is 76 F g -1 at current density of 0.1 A g -1 . Moreover, electrochemical impedance spectroscopy (EIS) suggests the electrochemical resistance of MnOOH nanowire-graphene oxide composites is reduced when hydrothermal reaction is conducted in ammonia aqueous solution. The relationship between the electrochemical capacitance and the structure of MnOOH nanowire-graphene oxide composites is characterized by cyclic voltammetry (CV) and field emission scanning electron microscopy (FESEM). The results indicate the electrochemical performance of MnOOH nanowire-graphene oxide composites strongly depends on their

Electrochemical, interfacial, and surface studies of the conversion of carbon dioxide to liquid fuels on tin electrodes

Science.gov (United States)

Wu, Jingjie

The electrochemical reduction of carbon dioxide (CO2) into liquid fuels especially coupling with the intermittent renewable electricity offers a promising means of storing electricity in chemical form, which reduces the dependence on fossil fuels and mitigates the negative impact of anthropogenic CO2 emissions on the planet. Although converting CO2 to fuels is not in itself a new concept, the field has not substantially advanced in the last 30 years primarily because of the challenge of discovery of structural electrocatalysts and the development of membrane architectures for efficient collection of reactants and separation of products. An efficient catalyst for the electrochemical conversion of CO2 to fuels must be capable of mediating a proton-coupled electron transfer reaction at low overpotentials, reducing CO2 in the presence of water, selectively converting CO 2 to desirable chemicals, and sustaining long-term operations (Chapter 1). My Ph.D. research was an investigation of the electroreduction of CO2 on tin-based electrodes and development of an electrochemical cell to convert CO2 to liquid fuels. The initial study focused on understanding the CO2 reduction reaction chemistry in the electrical double layer with an emphasis on the effects of electrostatic adsorption of cations, specific adsorption of anion and electrolyte concentration on the potential and proton concentration at outer Helmholtz plane at which reduction reaction occurs. The variation of potential and proton concentration at outer Helmholtz plane accounts for the difference in activity and selectivity towards CO2 reduction when using different electrolytes (Chapter 2). Central to the highly efficient CO2 reduction is an optimum microstructure of catalyst layer in the Sn gas diffusion electrode (GDE) consisting of 100 nm Sn nanoparticles to facilitate gas diffusion and charge transfer. This microstructure in terms of the proton conductor fraction and catalyst layer thickness was optimized to

Morphological image processing operators. Reduction of partial volume effects to improve 3D visualization based on CT data

International Nuclear Information System (INIS)

Beier, J.; Bittner, R.C.; Hosten, N.; Troeger, J.; Felix, R.

1998-01-01

Aim: The quality of segmentation and three-dimensional reconstruction of anatomical structures in tomographic slices is often impaired by disturbances due to partial volume effects (PVE). The potential for artefact reduction by use of the morphological image processing operators (MO) erosion and dilation is investigated. Results: For all patients under review, the artefacts caused by PVE were significantly reduced by erosion (lung: Mean SBR pre =1.67, SBR post =4.83; brain: SBR pre =1.06, SBR post =1.29) even with only a small number of iterations. Region dilation was applied to integrate further structures (e.g. at tumor borders) into a configurable neighbourhood for segmentation and quantitative analysis. Conclusions: The MO represent an efficient approach for the reduction of PVE artefacts in 3D-CT reconstructions and allow optimised visualization of individual objects. (orig./AJ) [de

Reductions in Corpus Callosum Volume Partially Mediate Effects of Prenatal Alcohol Exposure on IQ

Directory of Open Access Journals (Sweden)

Stevie C. Biffen

2018-01-01

Full Text Available Disproportionate volume reductions in the basal ganglia, corpus callosum (CC and hippocampus have been reported in children with prenatal alcohol exposure (PAE. However, few studies have investigated these reductions in high prevalence communities, such as the Western Cape Province of South Africa, and only one study made use of manual tracing, the gold standard of volumetric analysis. The present study examined the effects of PAE on subcortical neuroanatomy using manual tracing and the relation of volumetric reductions in these regions to IQ and performance on the California Verbal Learning Test-Children's Version (CVLT-C, a list learning task sensitive to PAE. High-resolution T1-weighted images were acquired, using a sequence optimized for morphometric neuroanatomical analysis, on a Siemens 3T Allegra MRI scanner from 71 right-handed, 9- to 11-year-old children [9 fetal alcohol syndrome (FAS, 19 partial FAS (PFAS, 24 non-syndromal heavily exposed (HE and 19 non-exposed controls]. Frequency of maternal drinking was ascertained prospectively during pregnancy using timeline follow-back interviews. PAE was examined in relation to volumes of the CC and left and right caudate nuclei, nucleus accumbens and hippocampi. All structures were manually traced using Multitracer. Higher levels of PAE were associated with reductions in CC volume after adjustment for TIV. Although the effect of PAE on CC was confounded with smoking and lead exposure, additional analyses showed that it was not accounted for by these exposures. Amongst dysmorphic children, smaller CC was associated with poorer IQ and CVLT-C scores and statistically mediated the effect of PAE on IQ. In addition, higher levels of PAE were associated with bilateral volume reductions in caudate nuclei and hippocampi, effects that remained significant after control for TIV, child sex and age, socioeconomic status, maternal smoking during pregnancy, and childhood lead exposure. These data confirm

A study on the reduction of uranium oxide to uranium metal in LiCl molten salt

International Nuclear Information System (INIS)

Seo, J. S.; Hur, J. M.; Lee, W. K.; Hong, S. S.; Kang, D. S.; Park, S. W.

2002-01-01

Research for the analysis on a metallization process of uranium oxide in LiCl-Li molten salt was carried out. Effect of a concentration of Li 2 O on the metallization process was also studied. The new concept, electrochemical reduction of uranium oxide in LiCl-Li 2 O molten salt was proposed. The concept is based on the integrated process of metallization of UO 2 with simultaneous electrochemical reduction of Li 2 O which is recycled in a closed system. In a LiCl-Li molten salt system, U 3 O 8 whose conversion ratio to U turns out to be 97.1%, showed a better metallization characteristic than UO 2 . It is verified that electrochemically reduced Li is well deposited on the UO 2 powder cathode through a porous magnesia filter in LiCl-Li 2 O molten salt. In that process Li 2 O was from by the reduction process of UO 2 to U. This electrochemical reduction process showed good results to covert UO 2 to U

Electrochemical properties of copper-based compounds with polyanion frameworks

Energy Technology Data Exchange (ETDEWEB)

Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji, E-mail: kanno@echem.titech.ac.jp

2016-03-15

The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed based on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.

A Graphene-Based Electrochemical Sensor for Rapid Determination of Phenols in Water

OpenAIRE

Chen, Kun; Zhang, Zai-Li; Liang, Yong-Mei; Liu, Wei

2013-01-01

A glassy carbon electrode (GCE) coated with a graphene/polymer film was fabricated for rapid determination of phenols in aqueous solutions. The electrochemical behavior of different phenols at the graphene/polymer-coated GCE was also investigated. In PBS buffer solution with a pH of 6.5, hydroquinone exhibits a well-defined reduction peak at the modified GCE. Based on this, an electrochemical method for the direct determination of phenols is proposed. Investigating different parameters reveal...

The influnece of the partial single reduction on mechanical properties wires made from trip steel with 0,43 % C

Directory of Open Access Journals (Sweden)

S. Wiewiórowska

2015-01-01

Full Text Available Large strain inhomogeneity is caused by the shape of deformation zone of die and by the friction between tool and deformed wire for multistage wire drawing processes. The influence on the value of the redundant strain by the use of different partial single reductions during all wire drawing process was observed. This problem is particularly important for TRIP steel wires drawing processes because the strain intensity influences on the speed of retained austenite transformation into martensite.

Electrochemical and spectroscopic investigations of the K2SO4-V2O5 molten electrolyte

DEFF Research Database (Denmark)

Schmidt, Douglas S.; Winnick, Jack; Boghosian, Soghomon

1999-01-01

A 60 mol % K(2)SO(4)J/40 mol % V2O5 molten salt mixture was tested for electrochemical activity to determine its propensity for sulfate transport. Results of cyclic voltammetry showed a high electrochemical activity due likely to the reduction and oxidation of bulk, as opposed to minor, species...

3,5-Diamino-1,2,4-triazole@electrochemically reduced graphene oxide film modified electrode for the electrochemical determination of 4-nitrophenol

International Nuclear Information System (INIS)

Kumar, Deivasigamani Ranjith; Kesavan, Srinivasan; Baynosa, Marjorie Lara; Shim, Jae-Jin

2017-01-01

Highlights: •Triazole film was formed on electrochemically reduced graphene oxide. •pDAT@ERGO/GC was utilized for the electrochemical determination of 4-nitrophenol. •pDAT@ERGO/GC electrode offered wide concentration and nanomolar detection limit. •The fabricated electrode was employed in water sample analyses. -- Abstract: In this study, an eco-friendly benign method for the modification of electrochemically reduced graphene oxide (ERGO) on glassy carbon (GC) surface and electrochemical polymerized 3,5-diamino-1,2,4-triazole (DAT) film composite (pDAT@ERGO/GC) electrode was developed. The surface morphologies of the pDAT@ERGO/GC modified electrode were analyzed by field emission scanning electron microscopy (FESEM). FESEM images indicated that the ERGO supported pDAT has an almost homogeneous morphology structure with a size of 70 to 80 nm. It is due to the water oxidation reaction occurred while pDAT@ERGO/GC fabrication peak at +1.4 V leads to O 2 evolution and oxygen functional group functionalization on ERGO, which confirmed by X-ray photoelectron spectroscopy (XPS). In contrast, the bare GC modified with pDAT showed randomly arranged irregular bulky morphology structure compared to those of pDAT@ERGO/GC. Electrochemical reduction of graphene oxide was confirmed by Raman spectroscopy, XPS, and electrochemical impedance spectroscopy (EIS). The pDAT@ERGO/GC modified electrode was used for the electrochemical determination of 4-nitrophenol (4-NP). The 4-NP oxidation peak was observed at +0.25 V, and the differential pulse voltammetry demonstrated wide concentration range (5–1500 μM), high sensitivity (0.7113 μA μM −1 ), and low limit of detection (37 nM). Moreover, the pDAT@ERGO/GC electrode was applied to real water sample analysis by standard addition method, where in good recoveries (97.8% to 102.4%) were obtained.

Electrochemical Oxidation of Phenol using a Flow-through Micro ...

African Journals Online (AJOL)

The electrochemical oxidation of phenol to benzoquinone followed by the reduction to hydroquinone and catechol was demonstrated by constructing a three-dimensional porous micro-flow cell from lead dioxideand lead. The electrodes were made by using the principles of curing and formation of lead oxide material that ...

Oxygen Reduction on Platinum

DEFF Research Database (Denmark)

Nesselberger, Markus

. The influence of the ion adsorption strength, which is observed in the “particle size studies” on the oxygen reduction rate on Pt/C catalysts, is further investigated under similar reaction conditions by infrared spectroscopy. The designed in situ electrochemical ATR-FTIR setup features a high level...... of instrument automation and online data treatment, and provides welldefined mass transport conditions enabling kinetic measurements. A modified electrochemical / spectroscopic interface is presented allowing the exclusive investigation of the Pt/C catalyst layer. Three types of potential dependent adsorption...... adsorption on Pt does not block the ORR directly. Instead, the onset of oxide formation with the concomitant conversion of the anion adsorbate layer is the decisive blocking mechanism....

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

Science.gov (United States)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Characterization of electrochemically and chemically generated technetium diphosphonate radiopharmaceuticals

International Nuclear Information System (INIS)

Martin, J.L. Jr.

1987-01-01

Tc-Methylene diphosphonate, (MDP), the skeletal imaging ligand is most use in radiopharmacies, is the first metal-ligand complex prepared electrochemically in this work. A similar systematic evaluation of electrochemically reduced Tc-dimethylaminomethylene diphosphonate (DMAD) is presented. DMAD as well as MDP have been characterized by anion exchange HPLC following NaBH4 reduction. The goal is twofold. First, the effect of varying the applied potential on the resultant chromatographic distribution of complexes is investigated. Secondly, the combination(s) of applied potential and preparation pH which preferentially directs the formation of technetium diphosphonate complexes previously shown to be superior skeletal imaging agents is determined. EXAFS, extended x-ray absorption fine structure spectroscopy, is applied to the analysis of dilute solutions (10mM) of electrochemically and chemically reduced Tc-MDP complexes. Further characterizations of electrochemically and chemically generated complexes are performed using in-vitro and in-vivo physiological techniques of biodistribution and blood clearance studies on Sprague Dawley rats and beagle dogs respectively. Finally, in-vitro and in-vivo dilution studies were performed using water, human and dog urine, to determine the influence of the physiological environment on clinically prepared and injected radiopharmaceuticals

Selective electrochemical extraction of REEs from NdFeB magnet waste at room temperature

NARCIS (Netherlands)

Venkatesan, P.; Vander Hoogerstraete, Tom; Hennebel, Tom; Binnemans, Koen; Sietsma, J.; Yang, Y.

2018-01-01

NdFeB magnet waste is one of the important secondary resources from which rare-earth elements (REEs) can be recovered. Herein we present an electrochemical route to selectively extract REEs from the magnet waste at room temperature. First, the magnet waste was partially leached with HCl. The

Methods and systems for fuel production in electrochemical cells and reactors

Science.gov (United States)

Marina, Olga A.; Pederson, Larry R.

2018-01-30

Methods and systems for fuel, chemical, and/or electricity production from electrochemical cells are disclosed. A voltage is applied between an anode and a cathode of an electrochemical cell. The anode includes a metal or metal oxide electrocatalyst. Oxygen is supplied to the cathode, producing oxygen ions. The anode electrocatalyst is at least partially oxidized by the oxygen ions transported through an electrolyte from the cathode to the anode. A feed gas stream is supplied to the anode electrocatalyst, which is converted to a liquid fuel. The anode electrocatalyst is re-oxidized to higher valency oxides, or a mixture of oxide phases, by supplying the oxygen ions to the anode. The re-oxidation by the ions is controlled or regulated by the amount of voltage applied.

The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

International Nuclear Information System (INIS)

Zanoni, Maria Valnice Boldrin; Rogers, Emma I.; Hardacre, Christopher; Compton, Richard G.

2010-01-01

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium bis (trifluoromethanesulfonyl) imide [N 6,2,2,2 ][N(Tf) 2 ], 1-butyl-3-methylimidazolium hexafluorosphosphate [C 4 mim][PF 6 ], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C 4 mpyrr][N(Tf) 2 ], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C 4 mim][N(Tf) 2 ], N-butyl-N-methyl-pyrrolidinium dicyanamide [C 4 mpyrr][N(NC) 2 ] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P 14,6,6,6 ][FAP] on a platinum microelectrode. In [N 6,2,2,2 ][NTf 2 ] and [P 14,6,6,6 ][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion, which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P 14,6,6,6 ][FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N 6,2,2,2 ][NTf 2 ] and [P 14,6,6,6 ][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer

Ultrasensitive and simultaneous detection of hydroquinone, catechol and resorcinol based on the electrochemical co-reduction prepared Au-Pd nanoflower/reduced graphene oxide nanocomposite

International Nuclear Information System (INIS)

Chen, Yuan; Liu, Xiaoying; Zhang, Si; Yang, Liuqing; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

2017-01-01

A simple and efficient eletrochemical sensing platform for simultaneous detection of hydroquinone (HQ), catechol (CC) and resorcinol (RC) based on the Au-Pd bimetallic and graphene is described in this paper. The Au-Pd reduced graphene oxide (Au-Pd NF/rGO) was prepared by the electrochemical co-reduction deposition via cyclic voltammetry method (CV). The Au-Pd NF/rGO nanocomposite was examined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and electrochemical methods CV and differential pulse voltammety (DPV) study showed that the three dihydroxybenzene isomers can be catalytically oxidized and discriminated simultaneously on the Au-Pd NF/rGO/GCE. The presence of Pd makes the performance of the sensor superior to that of in the absence of it. Owing to the integrated superior conductivity and excellent catalytic property of Au-Pd NF/rGO, the sensitive and simultaneous detection of HQ, CC and RC was realized in the individual or triple-components solution based on the as proposed Au-Pd NF/rGO/GCE, which shows wide linear range and low detection limit. The detection of them in tap water, river water and lake water were also successfully performed and good recovery was obtained.

Electrochemical properties of SnO2/carbon composite materials as anode material for lithium-ion batteries

International Nuclear Information System (INIS)

Wang Jie; Zhao Hailei; Liu Xiaotong; Wang Jing; Wang Chunmei

2011-01-01

Highlights: → SnO 2 /carbon powders with a cauliflower-like particle structure were synthesized. → Post-annealing can improve the electrochemical properties of SnO 2 /C composite. → The 500 deg. C-annealed SnO 2 /C shows the best electrochemical performance. → The lithium ion diffusion coefficients of the SnO 2 /C electrodes were calculated. - Abstract: SnO 2 /carbon composite anode materials were synthesized from SnCl 4 .5H 2 O and sucrose via a hydrothermal route and a post heat-treatment. The synthesized spherical SnO 2 /carbon powders show a cauliflower-like micro-sized structure. High annealing temperature results in partial reduction of SnO 2 . Metallic Sn starts to emerge at 500 deg. C. High Sn content in SnO 2 /carbon composite is favorable for the increase of initial coulombic efficiency but not for the cycling stability. The SnO 2 /carbon annealed at 500 deg. C exhibits high specific capacity (∼400 mAh g -1 ), stable cycling performance and good rate capability. The generation of Li 2 O in the first lithiation process can prevent the aggregation of active Sn, while the carbon component can buffer the big volume change caused by lithiation/delithiation of active Sn. Both of them make contribution to the better cycle stability.

Electrochemical-metallothermic reduction of zirconium in molten salt solutions

International Nuclear Information System (INIS)

McLaughlin, D.F.; Talko, F.

1990-01-01

This patent describes a method for separating hafnium from zirconium of the type wherein a feed containing zirconium and hafnium chlorides is prepared from zirconium-hafnium chloride and the feed is introduced into a distillation column, which distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and wherein a hafnium chloride enriched stream is taken from the top of the column and a zirconium enriched chloride stream is taken from the bottom of the column. It comprises: reducing the zirconium enriched chloride stream taken from the distillation column to metal by electrochemically reducing an alkaline earth metal in a molten salt bath with the molten salt in the molten salt bath consisting essentially of a mixture of at least one alkali metal chloride and at least one alkaline earth metal chloride and zirconium chloride, with the reduced alkaline earth metal reacting with the zirconium chloride to produce zirconium metal and alkaline earth metal chloride

XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO_2 thin films to produce a new hybrid material coating

International Nuclear Information System (INIS)

Drevet, R.; Dragoé, D.; Barthés-Labrousse, M.G.; Chaussé, A.; Andrieux, M.

2016-01-01

Graphical abstract: An innovative hybrid material layer is synthesized by combining two processes. SnO_2 thin films are deposited by MOCVD on Si substrates and an organic layer made of carboxyphenyl moieties is electrochemically grafted by the reduction of a diazonium salt. XPS characterizations are carried out to assess the efficiency of the electrochemical grafting. Display Omitted - Highlights: • An innovative hybrid material layer is synthesized by combining two processes. • SnO_2 thin films are deposited by MOCVD on Si substrates. • An organic layer is electrochemically grafted by the reduction of a diazonium salt. • The efficiency of the grafting is accurately assessed by XPS. • Three electrochemical grafting models are proposed. - Abstract: This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO_2) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO_2 layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

International Nuclear Information System (INIS)

Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

2000-01-01

The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

Flexible graphene/carbon nanotube hybrid papers chemical-reduction-tailored by gallic acid for high-performance electrochemical capacitive energy storages

Science.gov (United States)

Yao, Lu; Zhou, Chao; Hu, Nantao; Hu, Jing; Hong, Min; Zhang, Liying; Zhang, Yafei

2018-03-01

Mechanically robust graphene papers with both high gravimetric and volumetric capacitances are desired for high-performance energy storages. However, it's still a challenge to tailor the structure of graphene papers in order to meet this requirement. In this work, a kind of chemical-reduction-tailored mechanically-robust reduced graphene oxide/carbon nanotube hybrid paper has been reported for high-performance electrochemical capacitive energy storages. Gallic acid (GA), as an excellent reducing agent, was used to reduce graphene oxide. Through vacuum filtration of gallic acid reduced graphene oxide (GA-rGO) and carboxylic multiwalled carbon nanotubes (MWCNTs) aqueous suspensions, mechanically robust GA-rGO/MWCNTs hybrid papers were obtained. The resultant hybrid papers showed high gravimetric capacitance of 337.6 F g-1 (0.5 A g-1) and volumetric capacitance of 151.2 F cm-3 (0.25 A cm-3). In addition, the assembled symmetric device based on the hybrid papers exhibited high gravimetric capacitance of 291.6 F g-1 (0.5 A g-1) and volumetric capacitance of 136.6 F cm-3 (0.25 A cm-3). Meanwhile, it exhibited excellent rate capability and cycling stability. Above all, this chemical reduction tailoring technique and the resultant high-performance GA-rGO/MWCNTs hybrid papers give an insight for designing high-performance electrodes and hold a great potential in the field of energy storages.

Partial oxidation of 2-propanol on perovskites

Energy Technology Data Exchange (ETDEWEB)

Sumathi, R.; Viswanathan, B.; Varadarajan, T.K. [Indian Inst. of Tech., Madras (India). Dept. of Chemistry

1998-12-31

Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)

Further Cost Reduction of Battery Manufacturing

Directory of Open Access Journals (Sweden)

Amir A. Asif

2017-06-01

Full Text Available The demand for batteries for energy storage is growing with the rapid increase in photovoltaics (PV and wind energy installation as well as electric vehicle (EV, hybrid electric vehicle (HEV and plug-in hybrid electric vehicle (PHEV. Electrochemical batteries have emerged as the preferred choice for most of the consumer product applications. Cost reduction of batteries will accelerate the growth in all of these sectors. Lithium-ion (Li-ion and solid-state batteries are showing promise through their downward price and upward performance trends. We may achieve further performance improvement and cost reduction for Li-ion and solid-state batteries through reduction of the variation in physical and electrical properties. These properties can be improved and made uniform by considering the electrical model of batteries and adopting novel manufacturing approaches. Using quantum-photo effect, the incorporation of ultra-violet (UV assisted photo-thermal processing can reduce metal surface roughness. Using in-situ measurements, advanced process control (APC can help ensure uniformity among the constituent electrochemical cells. Industrial internet of things (IIoT can streamline the production flow. In this article, we have examined the issue of electrochemical battery manufacturing of Li-ion and solid-state type from cell-level to battery-level process variability, and proposed potential areas where improvements in the manufacturing process can be made. By incorporating these practices in the manufacturing process we expect reduced cost of energy management system, improved reliability and yield gain with the net saving of manufacturing cost being at least 20%.

Structural and electrochemical properties of Cl-doped LiFePO{sub 4}/C

Energy Technology Data Exchange (ETDEWEB)

Sun, C.S.; Zhang, Y.; Zhang, X.J.; Zhou, Z. [Institute of New Energy Material Chemistry, Nankai University, Tianjin 300071 (China)

2010-06-01

Cl-doped LiFePO{sub 4}/C cathode materials were synthesized through a carbothermal reduction route, and the microstructure and electrochemical performances were systematically studied. Cl-doped LiFePO{sub 4}/C cathode materials presented a high discharge capacity of {proportional_to}90 mAh g{sup -1} at the rate of 20 C (3400 mA g{sup -1}) at room temperature. Electrochemical impedance spectroscopy and cyclic voltamperometry indicated the optimized electrochemical reaction and Li{sup +} diffusion in the bulk of LiFePO{sub 4} due to Cl-doping. The improved Li{sup +} diffusion capability is attributed to the microstructure modification of LiFePO{sub 4} via Cl-doping. (author)

Partial-order reduction for GPU model checking

NARCIS (Netherlands)

Neele, T.S.; Wijs, A.J.; Bošnački, D.; van de Pol, J.C.

2016-01-01

Model checking using GPUs has seen increased popularity over the last years. Because GPUs have a limited amount of memory, only small to medium-sized systems can be verified. For on-the-fly explicitstate model checking, we improve memory efficiency by applying partialorder reduction. We propose

Partial Transmit Sequence Optimization Using Improved Harmony Search Algorithm for PAPR Reduction in OFDM

Directory of Open Access Journals (Sweden)

Mangal Singh

2017-12-01

Full Text Available This paper considers the use of the Partial Transmit Sequence (PTS technique to reduce the Peak‐to‐Average Power Ratio (PAPR of an Orthogonal Frequency Division Multiplexing signal in wireless communication systems. Search complexity is very high in the traditional PTS scheme because it involves an extensive random search over all combinations of allowed phase vectors, and it increases exponentially with the number of phase vectors. In this paper, a suboptimal metaheuristic algorithm for phase optimization based on an improved harmony search (IHS is applied to explore the optimal combination of phase vectors that provides improved performance compared with existing evolutionary algorithms such as the harmony search algorithm and firefly algorithm. IHS enhances the accuracy and convergence rate of the conventional algorithms with very few parameters to adjust. Simulation results show that an improved harmony search‐based PTS algorithm can achieve a significant reduction in PAPR using a simple network structure compared with conventional algorithms.

Physicochemical characteristics and sensory acceptability of ready-to-eat sliced frozen roast beef with partial reduction of sodium chloride

Directory of Open Access Journals (Sweden)

Camila Vespúcio BIS

2016-01-01

Full Text Available Abstract Sodium chloride in meat products provides microbiological stability and desirable technological and sensory effects. Therefore, the reduction of this ingredient is a challenge for the meat industry. The objective of this study was to evaluate the physicochemical and sensory characteristics of ready-to-eat sliced frozen roast beef with partial replacement of sodium chloride by a commercial additive mostly composed of potassium chloride. The analyses performed were chemical composition, cooking yield and post defrosting loss, microbiological evaluation and sensory analysis. There was higher moisture content (p < 0.05 in the control treatment (without the presence of the replacement additive and all treatments were not different (p ≥ 0.05 in the cooking yield and in post-defrosting loss. The results of microbiological analysis are according to Brazilian Legislation. The sensory evaluation showed no difference between the control treatment and the T1 treatment (with the reduction of 35% of NaCl, while the T2 treatment (with reduction of 70% of NaCl had the lowest average values in all attributes. The study showed that the reduction of 35% NaCl for commercial additive, mostly composed of potassium chloride, in roast beef is feasible since no changes were observed in sensory and technological characteristics evaluated.

Synthesis, characterization and electrochemical investigation of hetaryl chromium(0) aminocarbene complexes

Czech Academy of Sciences Publication Activity Database

Metelková, R.; Tobrman, T.; Kvapilová, Hana; Hoskovcová, I.; Ludvík, Jiří

2012-01-01

Roč. 82, SI (2012), s. 470-477 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400813 Institutional support: RVO:61388955 Keywords : Fischer aminocarbene complexes * synthesis * Electrochemical oxidation and reduction Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

The electrochemical generation of useful chemical species from lunar materials

Science.gov (United States)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Comparative DEMS study on the electrochemical oxidation of carbon blacks

DEFF Research Database (Denmark)

Ashton, Sean James; Arenz, Matthias

2012-01-01

Publication year: 2012 Source:Journal of Power Sources, Volume 217 Sean J. Ashton, Matthias Arenz The intention of the study presented here is to compare the electrochemical oxidation tendencies of a pristine Ketjen Black EC300 high surface area (HSA) carbon black, and four graphitised counterparts...... heat-treated between 2100 and 3200 °C, such as those typically used as corrosion resistant carbon (CRC) supports for polymer electrolyte membrane fuel cell (PEMFC) catalysts. A methodology combining cyclic voltammetry (CV) and differential electrochemical mass spectrometry (DEMS) is used, which allows......; however, CRC samples graphitised =2800 °C did not exhibit this same behaviour. Highlights ¿ We quantitatively determine electrooxidation of carbon support materials. ¿ We can distinguish between the total and partial electrooxidation. ¿ Non or mildly heat treated carbon forms passivating layer. ¿ Heat...

Electrochemical biosensors

CERN Document Server

Cosnier, Serge

2015-01-01

"This is an excellent book on modern electrochemical biosensors, edited by Professor Cosnier and written by leading international experts. It covers state-of-the-art topics of this important field in a clear and timely manner."-Prof. Joseph Wang, UC San Diego, USA 　"This book covers, in 13 well-illustrated chapters, the potential of electrochemical methods intimately combined with a biological component for the assay of various analytes of biological and environmental interest. Particular attention is devoted to the description of electrochemical microtools in close contact with a biological cell for exocytosis monitoring and to the use of nanomaterials in the electrochemical biosensor architecture for signal improvement. Interestingly, one chapter describes the concept and design of self-powered biosensors derived from biofuel cells. Each topic is reviewed by experts very active in the field. This timely book is well suited for providing a good overview of current research trends devoted to electrochemical...

XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO{sub 2} thin films to produce a new hybrid material coating

Energy Technology Data Exchange (ETDEWEB)

Drevet, R., E-mail: richarddrevet@yahoo.fr [Univ. Paris Sud, SP2M-ICMMO, CNRS UMR 8182, Bât. 410, 91405 Orsay Cedex (France); Université d’Evry Val d’Essonne, LAMBE, CNRS-CEA UMR 8587, Boulevard François Mitterrand, 91025 Evry Cedex (France); Dragoé, D.; Barthés-Labrousse, M.G. [Univ. Paris Sud, SP2M-ICMMO, CNRS UMR 8182, Bât. 410, 91405 Orsay Cedex (France); Chaussé, A. [Université d’Evry Val d’Essonne, LAMBE, CNRS-CEA UMR 8587, Boulevard François Mitterrand, 91025 Evry Cedex (France); Andrieux, M. [Univ. Paris Sud, SP2M-ICMMO, CNRS UMR 8182, Bât. 410, 91405 Orsay Cedex (France)

2016-10-30

Graphical abstract: An innovative hybrid material layer is synthesized by combining two processes. SnO{sub 2} thin films are deposited by MOCVD on Si substrates and an organic layer made of carboxyphenyl moieties is electrochemically grafted by the reduction of a diazonium salt. XPS characterizations are carried out to assess the efficiency of the electrochemical grafting. Display Omitted - Highlights: • An innovative hybrid material layer is synthesized by combining two processes. • SnO{sub 2} thin films are deposited by MOCVD on Si substrates. • An organic layer is electrochemically grafted by the reduction of a diazonium salt. • The efficiency of the grafting is accurately assessed by XPS. • Three electrochemical grafting models are proposed. - Abstract: This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO{sub 2}) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO{sub 2} layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

Electrochemical cell and electrode designs for high-temperature/high-pressure kinetic measurements

International Nuclear Information System (INIS)

Nagy, Z.; Yonco, R.M.

1987-05-01

Many corrosion processes of interest to the nuclear power industry occur in high-temperature/high-pressure aqueous systems. The investigation of the kinetics of the appropriate electrode reactions is a serious experimental challenge, partially because of the high temperatures and pressures and partially because many of these reactions are very rapid, requiring fast relaxation measurements. An electrochemical measuring system is described which is suitable for measurements of the kinetics of fast electrode reactions at temperatures extending to at least 300 0 C and pressures to at least 10 MPa (100 atmospheres). The system includes solution preparation and handling equipment, the electrochemical cell, and several electrode designs. One of the new designs is a coaxial working electrode-counter electrode assembly; this electrode can be used with very fast-rising pulses, and it provides a well defined, repeatedly-polishable working surface. Low-impedance reference electrodes are also described, based on electrode concepts responding to the pH or the redox potential of the test solution. Additionally, a novel, long-life primary reference electrode design is reported, based on a modification of the external, pressure-balanced Ag/AgCl reference electrode

Electrochemical cell and electrode designs for high-temperature/high-pressure kinetic measurements

International Nuclear Information System (INIS)

Nagy, Z.; Yonco, R.M.

1988-01-01

Many corrosion processes of interest to the nuclear power industry occur in high-temperature/high-pressure aqueous systems. The investigation of the kinetics of the appropriate electrode reactions is a serious experimental challenge, partially because of the high temperatures and pressures and partially because many of these reactions are very rapid, requiring fast relaxation measurements. An electrochemical measuring system is described which is suitable for measurements of the kinetics of fast electrode reactions at temperatures extending to at least 300 0 C and pressures to at least 10 MPa (100 atmospheres). The system includes solution preparation and handling equipment, the electrochemical cell, and several electrode designs. One of the new designs is a coaxial working electrode-counter electrode assembly; this electrode can be used with very fast-rising pulses, and it provides a well defined, repeatedly-polishable working surface. Low-impedance reference electrodes are also described, based on electrode concepts responding to the pH or the redox potential of the test solution. Additionally, a novel, long-life primary reference electrode design is reported, based on a modification of the external, pressure-balanced Ag/AgCl reference electrode

Solar fuel processing efficiency for ceria redox cycling using alternative oxygen partial pressure reduction methods

International Nuclear Information System (INIS)

Lin, Meng; Haussener, Sophia

2015-01-01

Solar-driven non-stoichiometric thermochemical redox cycling of ceria for the conversion of solar energy into fuels shows promise in achieving high solar-to-fuel efficiency. This efficiency is significantly affected by the operating conditions, e.g. redox temperatures, reduction and oxidation pressures, solar irradiation concentration, or heat recovery effectiveness. We present a thermodynamic analysis of five redox cycle designs to investigate the effects of working conditions on the fuel production. We focused on the influence of approaches to reduce the partial pressure of oxygen in the reduction step, namely by mechanical approaches (sweep gassing or vacuum pumping), chemical approaches (chemical scavenger), and combinations thereof. The results indicated that the sweep gas schemes work more efficient at non-isothermal than isothermal conditions, and efficient gas phase heat recovery and sweep gas recycling was important to ensure efficient fuel processing. The vacuum pump scheme achieved best efficiencies at isothermal conditions, and at non-isothermal conditions heat recovery was less essential. The use of oxygen scavengers combined with sweep gas and vacuum pump schemes further increased the system efficiency. The present work can be used to predict the performance of solar-driven non-stoichiometric redox cycles and further offers quantifiable guidelines for system design and operation. - Highlights: • A thermodynamic analysis was conducted for ceria-based thermochemical cycles. • Five novel cycle designs and various operating conditions were proposed and investigated. • Pressure reduction method affects optimal operating conditions for maximized efficiency. • Chemical oxygen scavenger proves to be promising in further increasing efficiency. • Formulation of quantifiable design guidelines for economical competitive solar fuel processing

Synthesis and characterization of the WxRuySez from the electrochemical reduction of oxygen and their possible application as electrode in fuel cell

International Nuclear Information System (INIS)

Ramirez R, S.D.

1995-01-01

In this communication the synthesis of the W 0.03 RuSe 0.47 O 0.3 from the transition metal carbonyl compounds and the chalcogenide in m Xylene, the chemical characterization of the novel material was performed by neutron activation analysis (NAA), using the TRIGA Mark III Reactor from the Nuclear Center of Mexico. The oxygen present in the material was determined by Rutherford Backscattering Spectrometry (RBS). Also the RuSe 5.7 y WSe 2 were synthesized and characterized by NAA. The electro kinetic oxygen reduction behaviour of the W 0.03 RuSe 0.47 O 0.3 deposited in glassy carbon was investigated in aqueous H 2 SO 4 0.5M. The rotating disk electrode electrochemical technique was used for determining the kinetic parameters: The reaction was of first order which implied that the rate determining step is the transfer of one electron, the Tafel slope was 0.115 V/decade; the electron transfer coefficient found was of 0.5, and the activation energy in the oxygen reduction reaction was 0.47 eV. (Author)

Electrochemical properties of SnO{sub 2}/carbon composite materials as anode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Wang Jie [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Zhao Hailei, E-mail: hlzhao@ustb.edu.cn [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Lab of New Energy Materials and Technologies, Beijing 100083 (China); Liu Xiaotong; Wang Jing; Wang Chunmei [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China)

2011-07-15

Highlights: > SnO{sub 2}/carbon powders with a cauliflower-like particle structure were synthesized. > Post-annealing can improve the electrochemical properties of SnO{sub 2}/C composite. > The 500 deg. C-annealed SnO{sub 2}/C shows the best electrochemical performance. > The lithium ion diffusion coefficients of the SnO{sub 2}/C electrodes were calculated. - Abstract: SnO{sub 2}/carbon composite anode materials were synthesized from SnCl{sub 4}.5H{sub 2}O and sucrose via a hydrothermal route and a post heat-treatment. The synthesized spherical SnO{sub 2}/carbon powders show a cauliflower-like micro-sized structure. High annealing temperature results in partial reduction of SnO{sub 2}. Metallic Sn starts to emerge at 500 deg. C. High Sn content in SnO{sub 2}/carbon composite is favorable for the increase of initial coulombic efficiency but not for the cycling stability. The SnO{sub 2}/carbon annealed at 500 deg. C exhibits high specific capacity ({approx}400 mAh g{sup -1}), stable cycling performance and good rate capability. The generation of Li{sub 2}O in the first lithiation process can prevent the aggregation of active Sn, while the carbon component can buffer the big volume change caused by lithiation/delithiation of active Sn. Both of them make contribution to the better cycle stability.

Research factors of the electrochemical remediation clay soils from the nitrates

Energy Technology Data Exchange (ETDEWEB)

Korolev, V.A.; Babakina, O.A. [Moscow State Univ. (Russian Federation)

2001-07-01

The electrokinetic's methods are prevalent [1, 2], but abilities of the method for remediation nitrates contaminated soils are studied insufficiently. The investigations of effectiveness electrochemical remediation are complicated by processes of reduction nitrates to nitrites (that are more toxic) and then to nitrogen in soil under the constant electric current. Therefore, the objectives of the research was following: - Evaluate mechanism of electrokinetic's removing nitrates from soil; - Evaluate basic value of moisture and alkalinity influence for electrochemical remediation of soil from nitrates; - Determine flow-through regime effect on electrokinetic's treating. (orig.)

Carbon nanotube-polyamidoamine dendrimer hybrid-modified electrodes for highly sensitive electrochemical detection of microRNA24.

Science.gov (United States)

Li, Fengye; Peng, Jing; Zheng, Qiong; Guo, Xiang; Tang, Hao; Yao, Shouzhuo

2015-01-01

A simple and ultrasensitive microRNA (miRNA) electrochemical biosensor employing multiwalled carbon nanotube (MWCNT)-polyamidoamine (PAMAM) dendrimer and methylene blue (MB) redox indicator is reported in this work. The assay utilizes a glass carbon (GC) electrode modified with MWCNT-PAMAM, on which the oligonucleotide capture probes are immobilized. The electrochemical detection of miRNAs is completed by measuring the reduction signal change of MB before and after the probe hybridization with target miRNA (miRNA24 is used as a model case). The MWCNT-PAMAM/GC electrode shows greatly enhanced signal to MB reduction in contrast to bare GC electrode. The functionalization of MWCNT with PAMAM maintains the electrochemical property of MWCNT to MB reduction but minimizes the undesired adsorption of MB on the MWCNT surface. The effect of experimental variables on the miRNA detection is investigated and optimized. A detection limit of 0.5 fM and a linear peak current density-concentration relationship up to 100 nM are obtained following 60 min hybridization. The proposed assay is successfully used to detect miRNA24 in total RNA sample extracted from HeLa cells.

Graphene/VO2 hybrid material for high performance electrochemical capacitor

International Nuclear Information System (INIS)

Deng, Lingjuan; Zhang, Gaini; Kang, Liping; Lei, Zhibin; Liu, Chunling; Liu, Zong-Huai

2013-01-01

Graphical abstract: Graphene/VO 2 hybrid materials are prepared by one-step simultaneous hydrothermal reduction technology. The prepared graphene (1.0)/VO 2 hybrid material shows a specific capacitances of 225 F g −1 in 0.5 mol L −1 K 2 SO 4 solution. Furthermore, an asymmetric electrochemical capacitor with graphene (1.0)/VO 2 as a positive electrode and graphene as a negative electrode is assembled, and it can work in a cell voltage of 1.7 V and show excellent capacitive property. - Highlights: • Graphene/VO 2 hybrid material has been prepared by one-step hydrothermal reduction. • Graphene/VO 2 hybrid material exhibits high specific capacitance. • An asymmetric capacitor working at 1.7 V in aqueous solution is assembled based on graphene/VO 2 electrode. • The asymmetric capacitor exhibits high energy density. - Abstract: Vanadium oxides have attracted significant attention for electrochemical capacitor because of their extensive multifunctional properties. In the present work, graphene/VO 2 (RG/VO 2 ) hybrid materials with different RG amounts are prepared in a mixture of ammonium vanadate, formic acid and graphite oxide (GO) nanosheets by one-step simultaneous hydrothermal reduction technology. The hydrothermal treatment makes the reduction of GO into RG and the formation of VO 2 particles with starfruit morphology. The starfruit-like VO 2 particles are uniformly embedded in the hole constructed by RG nanosheets, which makes the electrode–electrolyte contact better. A high specific capacitance of 225 F g −1 has been achieved for RG(1.0)/VO 2 electrode with RG content of 26 wt% in 0.5 mol L −1 K 2 SO 4 electrolyte. An asymmetrical electrochemical capacitor is assembled by using RG(1.0)/VO 2 as positive electrode and RG as negative electrode, and it can be reversibly charged–discharged at a cell voltage of 1.7 V in 0.5 mol L −1 K 2 SO 4 electrolyte. The asymmetrical capacitor can deliver an energy density of 22.8 Wh kg −1 at a power density

Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

Directory of Open Access Journals (Sweden)

Milan Zimpl

2012-01-01

Full Text Available Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Electrochemical behavior of quinoxalin-2-one derivatives at mercury electrodes and its analytical use.

Science.gov (United States)

Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

2012-01-01

Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds.

Electrochemical Sensor for Explosives Precursors’ Detection in Water

Directory of Open Access Journals (Sweden)

Cloé Desmet

2017-03-01

Full Text Available Although all countries are intensifying their efforts against terrorism and increasing their mutual cooperation, terrorist bombing is still one of the greatest threats to society. The discovery of hidden bomb factories is of primary importance in the prevention of terrorism activities. Criminals preparing improvised explosives (IE use chemical substances called precursors. These compounds are released in the air and in the waste water during IE production. Tracking sources of precursors by analyzing air or wastewater can then be an important clue for bomb factories’ localization. We are reporting here a new multiplex electrochemical sensor dedicated to the on-site simultaneous detection of three explosive precursors, potentially used for improvised explosive device preparation (hereafter referenced as B01, B08, and B15, for security disclosure reasons and to avoid being detrimental to the security of the counter-explosive EU action. The electrochemical sensors were designed to be disposable and to combine ease of use and portability in a screen-printed eight-electrochemical cell array format. The working electrodes were modified with different electrodeposited metals: gold, palladium, and platinum. These different coatings giving selectivity to the multi-sensor through a “fingerprint”-like signal subsequently analyzed using partial least squares-discriminant analysis (PLS-DA. Results are given regarding the detection of the three compounds in a real environment and in the presence of potentially interfering species.

Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

International Nuclear Information System (INIS)

Yesildag, Ali; Ekinci, Duygu

2010-01-01

In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

Probing Electrochemical Reactions at a Plasma-Liquid Interface

Science.gov (United States)

2015-03-16

shift in the absorption spectrum. However, unlike conventional electrochemical systems with a solid cathode , the electrons enter the solution with...yields of the well-understood reduction of silver (Ag+) were measured. In electrochemistry, metals are electrodeposited on a substrate and the weight is...nanoparticles, which can disperse and in some cases dissolve. In order to measure the weight in a manner similar to electrodeposition experiments, we

New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions

Czech Academy of Sciences Publication Activity Database

Hromadová, Magdaléna; Pospíšil, Lubomír; Sokolová, Romana; Fanelli, N.

2009-01-01

Roč. 54, č. 22 (2009), s. 4991-4996 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400802; GA AV ČR IAA400400505; GA ČR GA203/08/1157; GA MŠk LC510; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : nitroaromatic radical * cationic catalysis * electrochemical impendance * oscillation Subject RIV: CG - Electrochemistry Impact factor: 3.325, year: 2009

Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

Science.gov (United States)

Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

2017-11-01

Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical energy generation

International Nuclear Information System (INIS)

Kreysa, G.; Juettner, K.

1993-01-01

The proceedings encompass 40 conference papers belonging to the following subject areas: Baseline and review papers; electrochemical fuel cells; batteries: Primary and secondary cells; electrochemical, regenerative systems for energy conversion; electrochemical hydrogen generation; electrochemistry for nuclear power plant; electrochemistry for spent nuclear fuel reprocessing; energy efficiency in electrochemical processes. There is an annex listing the authors and titles of the poster session, and compacts of the posters can be obtained from the office of the Gesellschaft Deutscher Chemiker, Abteilung Tagungen. (MM) [de

On the mechanism of electrochemical ammonia synthesis on the Ru catalyst.

Science.gov (United States)

Back, Seoin; Jung, Yousung

2016-04-07

We theoretically investigate the electrochemical N2 reduction reaction (NRR) mechanism to produce NH3 on the Ru catalyst. All possible N-N dissociation steps during the reduction processes were evaluated along with the conventional associative and dissociative pathways. Based on the calculated free energy diagrams, it is revealed that the kinetically facile intermediate dissociative pathways during the NRR require a thermodynamic limiting potential (-0.71 V) similar to the associative pathway (-0.68 V), although the initial dissociative pathway as in the Haber-Bosch process has a substantial kinetic barrier for the N-N bond dissociation. The competitive hydrogen evolution is found to be a major hurdle for achieving a high efficiency for the electrochemical nitrogen reduction. In the low overpotential region, the hydrogen adsorption is thermodynamically more favorable than the protonation of N2, thereby reducing the number of active sites for the N2 activation. A comparison of free energies in the presence of different H-coverages on the Ru further demonstrates that the H-coverage can significantly increase the energy barrier for the first protonation of N2, resulting in a change of the potential determining step and an increase in the overpotentials.

CHROMATE INHIBITION OF THE LOCALIZED CORROSION OF ALUMINUM: MEASUREMENTS OF ELECTROCHEMICAL TRANSIENTS

International Nuclear Information System (INIS)

SASAKI, K.; ISAACS, H.S.

2001-01-01

We investigated the inhibition by chromate ions of the localized corrosion of aluminum by electrochemical transient measurements. In agreement with other work, the measurements demonstrated that chromate is a cathodic inhibitor for aluminum in open circuit. The reduction of hexavalent chromium to trivalent chromium is assumed to take place on catalyzed sites of the surface. The resulting products inhibit oxygen reduction reactions at these sites, thereby retarding pitting corrosion

A comparative study of electrochemical reduction of isatin and its ...

Indian Academy of Sciences (India)

Administrator

hibit a single irreversible two-electron reduction wave in contrast with the two discrete one-electron transfer reduction ... experiments. The working electrode was a Static Mercury Drop Elec- ..... Women Scientist Scheme (WOS-A), is gratefully.

ELECTROCHEMICAL BEHAVIOR OF POLYCRYSTALLINE COPPER DURING THE ADSORPTION OF CO ABSTRACT

Directory of Open Access Journals (Sweden)

J. Salimon

2017-12-01

Full Text Available The electrochemical properties of electrode copper in carbon monoxide-saturated phosphate buffered solution were investigated. The electrochemistry of copper surface was sufficiently changed after the supporting electrolyte solution was saturated with CO. The hydrogen evolution region was depressed and shifted cathodically due to the adsorption process of CO on the copper surface in a linear or terminally bonded manner, Cu-CO . The oxidation and the reduction peaks of copper were significantly changed with two couple of redox peaks. This is due to the subsequent formation and the corresponding reduction of copper(I and the copper carbon monoxides species. Further changed in electrochemical properties occurred when the electrode surface was polarized at high cathodic potential (-1.4 V for a period of time (15 min. The hydrogen evolution region was further depressed due to the adsorption of CO process in multiple bonding sites as adsorbed bridge bonded CO, Cu-CO B L that occurred predominantly.

Technetium electrodeposition from aqueous formate solutions at graphite electrode: electrochemical study

International Nuclear Information System (INIS)

Maslennikov, A.; Peretroukhine, V.; Masson, M.; Lecomte, M.

1999-01-01

Recovery of technetium from aqueous formate buffer solutions of ionic strength μ = 1.0 was studied in the pH interval from 1.6 to 7.5 at graphite cathode in an electrolytic cell with separated compartments was studied, using cyclic voltammetry (CV) and inverse stripping voltammetry (ISV) techniques. It has been shown that Tc electrodeposition process becomes possible at the potentials of graphite cathode E cath. 1/2 = -0.72±0.02 V/SCE and was pH independent in the interval pH = 3.46-7.32. Mechanism of electrodeposition, including Tc(VII)/Tc(IV) reduction in the solution followed by Tc(IV) hydrolysis at the electrode surface with formation of hydrated Tc oxide cathodic deposit has been proposed. The further precision of the Tc(VII) electrochemical reduction mechanism in formate buffer media and optimization of the electrodeposition process seems to be possible using additional analytical facilities except electrochemical methods. (orig.)

Polycarbonate-based ordered arrays of electrochemical nanoelectrodes obtained by e-beam lithography

Energy Technology Data Exchange (ETDEWEB)

Moretto, L M; De Leo, M; Ugo, P [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy); Tormen, M; Carpentiero, A, E-mail: ugo@unive.it [CNR-IOM, TASC Laboratory, Basovizza S S 14 km 163.5, 34149 Trieste (Italy)

2011-05-06

Ordered arrays of nanoelectrodes for electrochemical use are prepared by electron beam lithography (EBL) using polycarbonate as a novel e-beam resist. The nanoelectrodes are fabricated by patterning arrays of holes in a thin film of polycarbonate spin-coated on a gold layer on Si/Si{sub 3}N{sub 4} substrate. Experimental parameters for the successful use of polycarbonate as high resolution EBL resist are optimized. The holes can be filled partially or completely by electrochemical deposition of gold. This enables the preparation of arrays of nanoelectrodes with different recession degree and geometrical characteristics. The polycarbonate is kept on-site and used as the insulator that separates the nanoelectrodes. The obtained nanoelectrode arrays (NEAs) exhibit steady state current controlled by pure radial diffusion in cyclic voltammetry for scan rates up to approximately 50 mV s{sup -1}. Electrochemical results showed satisfactory agreement between experimental voltammograms and suitable theoretical models. Finally, the peculiarities of NEAs versus ensembles of nanoelectrodes, obtained by membrane template synthesis, are critically evaluated.

One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

Science.gov (United States)

Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

2015-05-19

The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

Use of ion conductors in the pyrochemical reduction of oxides

International Nuclear Information System (INIS)

Miller, W.E.; Tomczuk, Z.

1994-01-01

An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO 2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a β-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca o used for reducing UO 2 and PuO 2 to U and Pu. 2 figures

Effect of uniaxial stress on the electrochemical properties of graphene with point defects

Science.gov (United States)

Szroeder, Paweł; Sagalianov, Igor Yu.; Radchenko, Taras M.; Tatarenko, Valentyn A.; Prylutskyy, Yuriy I.; Strupiński, Włodzimierz

2018-06-01

We report a calculational study of electron states and the resulting electrochemical properties of uniaxially strained graphene with point defects. For this study the reduction of ferricyanide to ferrocyanide serves as a benchmark electrochemical reaction. We find that the heterogeneous electron transfer activity of the perfect graphene electrode rises under uniaxial strain. However, evolution of the cathodic reaction rate depends on the direction of strain. For moderate lattice deformations, the zigzag strain improves electrochemical performance better than the armchair strain. Standard rate constant increases by 50% at the zigzag strain of 10%. Vacancies, covalently bonded moieties, charged adatoms and substitutional impurities in the zigzag strained graphene induce changes in the shape of the curve of the cathodic reaction rate. However, this changes do not translate into the electrocatalytic activity. Vacancies and covalently bonded moieties at concentration of 0.1% do not affect the electrochemical performance. Charged adatoms and substitutional impurities give a slight increase in the standard rate constant by, respectively, 2.2% and 3.4%.

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

Arenas, L.F.; Ponce de León, C.; Walsh, F.C.

2016-01-01

Highlights: • The relevance of cerium in laboratory and industrial electrochemistry is considered. • The history of fundamental electrochemical studies and applications is considered. • The chemistry, redox thermodynamics and electrode kinetics of cerium are summarised. • The uses of cerium ions in synthesis, energy storage, analysis and environmental treatment are illustrated. • Research needs and development perspectives are discussed. - Abstract: Anodic oxidation of cerous ions and cathodic reduction of ceric ions, in aqueous acidic solutions, play an important role in electrochemical processes at laboratory and industrial scale. Ceric ions, which have been used for oxidation of organic wastes and off-gases in environmental treatment, are a well-established oxidant for indirect organic synthesis and specialised cleaning processes, including oxide film removal from tanks and process pipework in nuclear decontamination. They also provide a classical reagent for chemical analysis in the laboratory. The reversible oxidation of cerous ions is an important reaction in the positive compartment of various redox flow batteries during charge and discharge cycling. A knowledge of the thermodynamics and kinetics of the redox reaction is critical to an understanding of the role of cerium redox species in these applications. Suitable choices of electrode material (metal or ceramic; coated or uncoated), geometry/structure (2-or 3-dimensional) and electrolyte flow conditions (hence an acceptable mass transport rate) are critical to achieving effective electrocatalysis, a high performance and a long lifetime. This review considers the electrochemistry of soluble cerium species and their diverse uses in electrochemical technology, especially for redox flow batteries and mediated electrochemical oxidation.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

Science.gov (United States)

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Disintegration of graphite matrix from the simulative high temperature gas-cooled reactor fuel element by electrochemical method

International Nuclear Information System (INIS)

Tian Lifang; Wen Mingfen; Li Linyan; Chen Jing

2009-01-01

Electrochemical method with salt as electrolyte has been studied to disintegrate the graphite matrix from the simulative high temperature gas-cooled reactor fuel elements. Ammonium nitrate was experimentally chosen as the appropriate electrolyte. The volume average diameter of disintegrated graphite fragments is about 100 μm and the maximal value is less than 900 μm. After disintegration, the weight of graphite is found to increase by about 20% without the release of a large amount of CO 2 probably owing to the partial oxidation to graphite in electrochemical process. The present work indicates that the improved electrochemical method has the potential to reduce the secondary nuclear waste and is a promising option to disintegrate graphite matrix from high temperature gas-cooled reactor spent fuel elements in the head-end of reprocessing.

Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts

DEFF Research Database (Denmark)

Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen

2018-01-01

is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...

A Central Composite Face-Centered Design for Parameters Estimation of PEM Fuel Cell Electrochemical Model

Directory of Open Access Journals (Sweden)

Khaled MAMMAR

2013-11-01

Full Text Available In this paper, a new approach based on Experimental of design methodology (DoE is used to estimate the optimal of unknown model parameters proton exchange membrane fuel cell (PEMFC. This proposed approach combines the central composite face-centered (CCF and numerical PEMFC electrochemical. Simulation results obtained using electrochemical model help to predict the cell voltage in terms of inlet partial pressures of hydrogen and oxygen, stack temperature, and operating current. The value of the previous model and (CCF design methodology is used for parametric analysis of electrochemical model. Thus it is possible to evaluate the relative importance of each parameter to the simulation accuracy. However this methodology is able to define the exact values of the parameters from the manufacture data. It was tested for the BCS 500-W stack PEM Generator, a stack rated at 500 W, manufactured by American Company BCS Technologies FC.

Electrocatalytic carbon dioxide reduction - a mechanistic study

NARCIS (Netherlands)

Schouten, Klaas Jan Schouten

2013-01-01

This thesis presents new insights into the reduction of carbon dioxide to methane and ethylene on copper electrodes. This electrochemical process has great potential for the storage of surplus renewable electrical energy in the form of hydrocarbons. The research described in this thesis focuses on

Electrochemical processing of nitrate waste solutions

International Nuclear Information System (INIS)

Genders, D.; Weinberg, N.; Hartsough, D.

1992-01-01

The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F - ions from the synthetic mix migrating across the cation exchange membrane and forming HF in the acid anolyte. Other possibilities for anode materials were explored. A membrane separation process was investigated which employs an anion and cation exchange membrane to remove nitrite and nitrate, recovering caustic and nitric acid. Present research has shown poor current efficiencies for nitrite and nitrate transport across the anion exchange membrane due to co-migration of hydroxide anions. Precipitates form within the anion exchange membranes which would eventually result in the failure of the membranes. Electrochemical processing offers a highly promising and viable method for the treatment of nitrate waste solutions

[Acrylic resin removable partial dentures].

Science.gov (United States)

de Baat, C; Witter, D J; Creugers, N H J

2011-01-01

An acrylic resin removable partial denture is distinguished from other types of removable partial dentures by an all-acrylic resin base which is, in principle, solely supported by the edentulous regions of the tooth arch and in the maxilla also by the hard palate. When compared to the other types of removable partial dentures, the acrylic resin removable partial denture has 3 favourable aspects: the economic aspect, its aesthetic quality and the ease with which it can be extended and adjusted. Disadvantages are an increased risk of caries developing, gingivitis, periodontal disease, denture stomatitis, alveolar bone reduction, tooth migration, triggering of the gag reflex and damage to the acrylic resin base. Present-day indications are ofa temporary or palliative nature or are motivated by economic factors. Special varieties of the acrylic resin removable partial denture are the spoon denture, the flexible denture fabricated of non-rigid acrylic resin, and the two-piece sectional denture. Furthermore, acrylic resin removable partial dentures can be supplied with clasps or reinforced by fibers or metal wires.

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

Energy Technology Data Exchange (ETDEWEB)

Barrera-Diaz, C. E-mail: cbarrera@uaemex.mx; Urena-Nunez, F. E-mail: fun@nuclear.inin.mx; Campos, E.; Palomar-Pardave, M. E-mail: mepp@correo.azc.uam.mx; Romero-Romo, M

2003-07-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus {gamma}-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ, that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a {gamma}-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC {gamma}-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms.

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

International Nuclear Information System (INIS)

Barrera-Diaz, C.; Urena-Nunez, F.; Campos, E.; Palomar-Pardave, M.; Romero-Romo, M.

2003-01-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus γ-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ, that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a γ-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC γ-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

Science.gov (United States)

Barrera-Díaz, C.; Ureña-Nuñez, F.; Campos, E.; Palomar-Pardavé, M.; Romero-Romo, M.

2003-07-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus γ-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ , that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a γ-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC γ-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms.

Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

Science.gov (United States)

Navaee, Aso; Salimi, Abdollah

2018-05-01

Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability.

Science.gov (United States)

Jackson, Ariel; Strickler, Alaina; Higgins, Drew; Jaramillo, Thomas Francisco

2018-01-12

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1 ), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

SnO{sub 2}/reduced graphene oxide composite films for electrochemical applications

Energy Technology Data Exchange (ETDEWEB)

Bondarenko, E.A. [Belarusian State University, Nezalezhnastsi Av. 4, Minsk 220030 (Belarus); Mazanik, A.V., E-mail: mazanikalexander@gmail.com [Belarusian State University, Nezalezhnastsi Av. 4, Minsk 220030 (Belarus); Streltsov, E.A. [Belarusian State University, Nezalezhnastsi Av. 4, Minsk 220030 (Belarus); Kulak, A.I., E-mail: kulak@igic.bas-net.by [Institute of General and Inorganic Chemistry, National Academy of Sciences of Belarus, Surganova str., 9/1, Minsk 220072 (Belarus); Korolik, O.V. [Belarusian State University, Nezalezhnastsi Av. 4, Minsk 220030 (Belarus)

2015-12-15

Highlights: • SnO{sub 2}/GO composites with mass fraction of carbon phase 0.01% ≤ w{sub C} ≤ 80% have been formed. • 400 °C annealing was applied for GO reduction in the composites. • SnO{sub 2}/rGO composites demonstrate a high electrocatalytic activity in anodic processes. • Exchange current density grows linearly with carbon phase concentration at w{sub C} ≤ 10%. - Abstract: SnO{sub 2}/GO (GO is graphene oxide) composite films with GO mass fraction w{sub C} ranging from 0.01 to 80% have been prepared using colloidal solutions. Heat treatment of SnO{sub 2}/GO films in Ar atmosphere at 400 °C leads to GO reduction accompanied by partial exfoliation and decreasing of the particle thickness. SnO{sub 2}/rGO (rGO is reduced GO) film electrodes demonstrate a high electrocatalytic activity in the anodic oxidation of inorganic (iodide-, chloride-, sulfite-anions) and organic (ascorbic acid) substances. The increase of the anodic current in these reactions is characterized by overpotential inherent to the individual rGO films and exchange current density grows linearly with rGO concentration at w{sub C} ≤ 10% indicating that the rGO particles in composites act as sites of electrochemical process. The SnO{sub 2}/rGO composite films, in which the chemically stable oxide matrix encapsulates the rGO inclusions, can be considered as a promising material for applied electrochemistry.

Electrochemical determination of xanthine oxidase inhibitor drug in urate lowering therapy using graphene nanosheets modified electrode

International Nuclear Information System (INIS)

Raj, M. Amal; John, S. Abraham

2014-01-01

We report the electrochemical determination of urate lowering therapeutic drug, allopurinol (AP) using the electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). The ERGO modified GCE was fabricated by self–assembling graphene oxide (GO) on 1,6-hexadiamine (HDA) modified GCE by the electrostatic interaction between the positively charged amine group and the negatively charged GO layers followed by the electrochemical reduction of GO layers at negative potential. XPS results confirmed the attachment of GO and its electrochemical reduction. The electrochemical behavior of AP was examined at ERGO modified electrode in the presence of ascorbic acid (AA) and uric acid (UA). It was found that ERGO modified electrode not only enhanced the oxidation currents of AP, AA and UA but also showed stable signals for them for repetitive potential cycles. The present modified electrode was successfully used to determine these analytes simultaneously in a mixture. Selective determination of AP in the presence of high concentrations of AA and UA was also demonstrated at ERGO modified GCE. Using amperometry, detections of 40 and 200 nM of UA and AP were achieved and the detection limits were found to be 9.0 × 10 −9 M and 1.1 × 10 −7 M, respectively (S/N = 3). Further, the practical application of the present modified electrode was demonstrated by simultaneously determining the concentrations of AA, UA and AP in human blood serum and urine samples

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

Science.gov (United States)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Electrochemical Insights into Platinum Catalysts for Fuel Cells

DEFF Research Database (Denmark)

Jensen, Kim Degn

. A preliminary electrochemical study of in-house synthesized Pt-Y nanoparticles have also been presented revealing specific mass actives of 0.3 ± 0.1A/mgPt in HClO4. The study revealed that extensive optimizations of the Pt-Y nanoparticles are required and their performance is severely impeded by poor......Development of sustainable energy production, conversion and storage technologies must be considered one of the major challenges of the 21st century. Insight and understanding of the oxygen reduction reaction is imperative in these pursuits. In this work electrochemical investigations and physical...... characterization of various model systems ranging from extended surfaces, to thin films and nanoparticle electrocatalysts have been presented and discussed. This have been done with a special focus on governing factors controlling the electroreduction of oxygen. Preparation of Cu/Pt(111) near-surface alloys...

Effects of hyperstoichiometry and fission products on the electrochemical reactivity of UO2 nuclear fuel

International Nuclear Information System (INIS)

Betteridge, J.S.; Scott, N.A.M.; Shoesmith, D.W.; Bahen, L.E.; Hocking, W.H.; Lucuta, P.G.

1997-03-01

The effects of hyperstoichiometry and fission products on the electrochemical reactivity Of UO 2 nuclear fuel have been systematically investigated using cyclic voltammetry and the O 2 reduction reaction. Significant constraints are placed on the active-site model for O 2 reduction by the modest impact of bulk hyperstoichiometry. Formation of the U 4 O 9 derivative phase was associated with a marked increase in transient surface oxidation/reduction processes, which probably involve localized attack and might be fostered by tensile stresses induced during oxidation. Electrocatalytic reduction Of O 2 on simulated nuclear fuel (SIMFUEL) has been determined to increase progressively with nominal burnup and pronounced enhancement of H 2 O reduction has been observed as well. Substitution of uranium by lower-valence (simulated) fission products, which was formerly considered the probable cause for this behaviour, has now been shown to merely provide good electrical conductivity. Instead, the enhanced reduction kinetics for O 2 and H 2 O on SIMFUEL can be fully accounted for by noble metals, which segregate to the UO 2 grain boundaries as micron-sized particles, despite their low effective surface area. Apparent convergence of the electrochemical properties Of UO 2 and SIMFUEL through natural corrosion likely reflects evolution toward a common active surface. (author)

Metallic oxide reduction in molten chlorides: electrochemical solvent regeneration

International Nuclear Information System (INIS)

Martin, A.

2005-11-01

We consider the reaction MeO 2 + 2 Ca → Me + 2 CaO in CaCl 2 at 850 C. We want to re-use the molten media, which is a CaO-CaCl 2 melt at the end of the reaction. For that we want to de-oxidize it. When we electrolyse CaO we obtain Ca and O 2 ; it presents three difficult points that we want to solve: (1) it is difficult to oxidize O 2 - without oxidizing Cl - because their oxidation potential are very closed, (2) the chemical or electrochemical anodic corrosion, (3) the anodically produced gas dissolution in the mell One way of avoiding chlorine gas evolution is to prevent chloride ions from reaching the anode, for example using a selective membrane. Furthermore, the best prevention of the anodically produced gas dissolution in the melt can be done with a compartment, physically separating the anode from the rest of the reactional media. Thus in this work we have used an yttria stabilized zirconia membrane as a selective membrane for the deoxidation of a CaO-CaCl 2 melt at 850 C. (author)

Electrochemical behavior of molten fluoride-water system

Energy Technology Data Exchange (ETDEWEB)

Takenaka, Toshihide; Ito, Yasuhiko; Ishikawa, Takayasu; Oishi, Jun

1984-11-01

The cathodic behavior of a molten fluoride-water system was investigated by the potential sweep method. LiF-KF-NaF eutectic melt was used as an electrolyte and HF-H/sub 2/O gas mixture with Ar as a carrier was bubbled into it. Gold wire was used as a working electrode. The peak currents due to the reduction of HF and H/sub 2/O were clearly observed. The relations between peak currents and the square roots of the scanning rates were linear, strongly suggesting that the reduction reactions of the HF and H/sub 2/O dissolved in the melt were diffusion controlled. From the linearity of the relations between peak currents and partial pressures of HF and H/sub 2/O in the low partial pressure region, it was concluded that the concentrations of HF and H/sub 2/O in a fluoride melt are proportional to the partial pressure of each gas. The peak current due to the reduction of OH/sup -/ ion could not be observed, though a clear peak current was observed when OH/sup -/ ion was added to the melt and a cathodic scan was applied immediately. This indicates that OH/sup -/ ion is unstable in a fluoride melt under HF-H/sub 2/O atmosphere.

Partial Cavity Flows at High Reynolds Numbers

Science.gov (United States)

Makiharju, Simo; Elbing, Brian; Wiggins, Andrew; Dowling, David; Perlin, Marc; Ceccio, Steven

2009-11-01

Partial cavity flows created for friction drag reduction were examined on a large-scale. Partial cavities were investigated at Reynolds numbers up to 120 million, and stable cavities with frictional drag reduction of more than 95% were attained at optimal conditions. The model used was a 3 m wide and 12 m long flat plate with a plenum on the bottom. To create the partial cavity, air was injected at the base of an 18 cm backwards-facing step 2.1 m from the leading edge. The geometry at the cavity closure was varied for different flow speeds to optimize the closure of the cavity. Cavity gas flux, thickness, frictional loads, and cavity pressures were measured over a range of flow speeds and air injection fluxes. High-speed video was used extensively to investigate the unsteady three dimensional cavity closure, the overall cavity shape and oscillations.

In-situ electrochemical coating of Ag nanoparticles onto graphite electrode with enhanced performance for Li-ion batteries

International Nuclear Information System (INIS)

Yun, Jiaojiao; Wang, Yan; Gao, Tian; Zheng, Huiyuan; Shen, Ming; Qu, Qunting; Zheng, Honghe

2015-01-01

The effects of silver hexafluorophosphate (AgPF 6 ) as an electrolyte additive on the electrochemical behaviors of graphite anode are systematically studied by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The surface structure and composition of graphite electrode after electrochemical cycles are investigated through scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. It is found that Ag nanoparticles derived from electrochemical reduction of Ag + are homogenously distributed on the graphite surface. Significant improvements on the discharge capacity, rate behavior, and low-temperature performance of graphite electrode are obtained. The reasons are associated with the decreased resistances of solid-electrolyte interface and charge-transfer process, which improve the electrode kinetics for Li + intercalation/deintercalation

Monitoring dynamic electrochemical processes with in situ ptychography

Science.gov (United States)

Kourousias, George; Bozzini, Benedetto; Jones, Michael W. M.; Van Riessen, Grant A.; Dal Zilio, Simone; Billè, Fulvio; Kiskinova, Maya; Gianoncelli, Alessandra

2018-03-01

The present work reports novel soft X-ray Fresnel CDI ptychography results, demonstrating the potential of this method for dynamic in situ studies. Specifically, in situ ptychography experiments explored the electrochemical fabrication of Co-doped Mn-oxide/polypyrrole nanocomposites for sustainable and cost-effective fuel-cell air-electrodes. Oxygen-reduction catalysts based on Mn-oxides exhibit relatively high activity, but poor durability: doping with Co has been shown to improve both reduction rate and stability. In this study, we examine the chemical state distribution of the catalytically crucial Co dopant to elucidate details of the Co dopant incorporation into the Mn/polymer matrix. The measurements were performed using a custom-made three-electrode thin-layer microcell, developed at the TwinMic beamline of Elettra Synchrotron during a series of experiments that were continued at the SXRI beamline of the Australian Synchrotron. Our time-resolved ptychography-based investigation was carried out in situ after two representative growth steps, controlled by electrochemical bias. In addition to the observation of morphological changes, we retrieved the spectroscopic information, provided by multiple ptychographic energy scans across Co L3-edge, shedding light on the doping mechanism and demonstrating a general approach for the molecular-level investigation complex multimaterial electrodeposition processes.

Corrosion of conductive polypyrrole: Effects of environmental factors, electrochemical stimulation, and doping anions

International Nuclear Information System (INIS)

Qi Kai; Qiu Yubing; Chen Zhenyu; Guo Xingpeng

2012-01-01

Highlights: ► Corrosive galvanic cells form on PPy film with the electrochemical reduction of O 2. ► Suitable electrochemical stimulation can inhibit the PPy’s corrosion. ► PPy film doped with larger sized anions has better corrosion resistance performance. - Abstract: The effects of environmental factors, electrochemical stimulation, and doping anions on the corrosion behaviour of conductive polypyrrole (PPy) films in alkaline aqueous media were studied with cyclic voltammetry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. High concentrations of electrolyte, low dissolved oxygen and low temperatures enhance the stability of PPy. Polarising PPy at a negative potential inhibits its corrosion obviously. PPy doped with large counter anions shows better corrosion resistance than PPy doped with small counter ions. The possible mechanism involved in PPy corrosion process is discussed.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

Science.gov (United States)

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

International Nuclear Information System (INIS)

Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia; Tavagnacco, Claudio; Borsari, Marco

2011-01-01

Highlights: → Denaturation involves intermediate and partially unfolded forms. → An unfolded species displaying the haem with Fe coordinated by two His is observed. → Under unfolding conditions the nature of the SAM influences conformation of protein. → Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E o ' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E o ' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

Energy Technology Data Exchange (ETDEWEB)

Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy); Tavagnacco, Claudio [Department of Chemistry, University of Trieste, via Giorgieri 1, 34127 Trieste (Italy); Borsari, Marco, E-mail: marco.borsari@unimore.it [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy)

2011-08-01

Highlights: > Denaturation involves intermediate and partially unfolded forms. > An unfolded species displaying the haem with Fe coordinated by two His is observed. > Under unfolding conditions the nature of the SAM influences conformation of protein. > Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E{sup o}' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E{sup o}' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

Development of Head-end Pyrochemical Reduction Process for Advanced Oxide Fuels

International Nuclear Information System (INIS)

Park, B. H.; Seo, C. S.; Hur, J. M.; Jeong, S. M.; Hong, S. S.; Choi, I. K.; Choung, W. M.; Kwon, K. C.; Lee, I. W.

2008-12-01

The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U 3 O 8 was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U 3 O 8 and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li 2 Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool

Electrochemical sensors for biofilm and biocorrosion

Energy Technology Data Exchange (ETDEWEB)

Tribollet, B. [UPR 15 du CNRS, Universite Paris 6, 4 Place Jussieu, 75252 Paris Cedex05 (France)

2003-07-01

The presence of biofilm modifies the electrochemical properties of the interface and the mass transport near the interface. Two biofilm effects are damageable: the reduction of heat and/or mass transfer and the biocorrosion or microbiologically influenced corrosion (MIC). Two kinds of electrochemical sensors were developed: the first kind for the biofilm detection and the second one to evaluate the MIC risk. The biofilm detection is obtained by considering either the potential modification of the interface or the mass transport modification. The mass transport modification is analysed by considering the limiting diffusion current measured on a gold electrode where the biofilm development occurs. The MIC risk is evaluated with a sensor composed of two concentric electrodes in the material under investigation (e.g. carbon steel): a small disk electrode in the centre and a large ring. In a first step, a pit is artificially initiated by applying a current through these electrodes. In a second step, the risk factors of MIC are investigated by analysing the free coupling current circulating between these two short-circuited electrodes. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

Electrochemical investigations of La, Nd and Am in molten chloride salts in view of Am/Ln partitioning

International Nuclear Information System (INIS)

Pernel, C.; Serp, J.; Ougier, M.; Malmbeck, R.; Glatz, J.P.

2001-01-01

The electrochemical behaviour of La, Nd and Am has been investigated in molten LiCl-KCl eutectic. La shows a reversible single reduction/oxidation step controlled by mass transfer. The electrochemical reduction of Nd and Am proceeds via a two steps process, i.e. the reduction of trivalent species (Nd(III) and Am(III)) leading to Nd(II) and Am(II) species which are reduced at more negative potentials to form metallic deposits. Diffusion coefficients of La, Nd and Am have been calculated and are in reasonable agreement with literature data. Electro-depositions of La and Nd have been carried out onto solid Ni and liquid Cd cathodes. Much higher deposition efficiency is obtained for La compared to Nd on a solid cathode. This is an effect of the multi-valent nature of Nd in the chloride melts. (author)

Electrochemical investigations of La, Nd and Am in molten chloride salts in view of Am/Ln partitioning

Energy Technology Data Exchange (ETDEWEB)

Pernel, C.; Serp, J.; Ougier, M.; Malmbeck, R.; Glatz, J.P. [European Commission, JRC, ITU, Karlsruhe (Germany)

2001-07-01

The electrochemical behaviour of La, Nd and Am has been investigated in molten LiCl-KCl eutectic. La shows a reversible single reduction/oxidation step controlled by mass transfer. The electrochemical reduction of Nd and Am proceeds via a two steps process, i.e. the reduction of trivalent species (Nd(III) and Am(III)) leading to Nd(II) and Am(II) species which are reduced at more negative potentials to form metallic deposits. Diffusion coefficients of La, Nd and Am have been calculated and are in reasonable agreement with literature data. Electro-depositions of La and Nd have been carried out onto solid Ni and liquid Cd cathodes. Much higher deposition efficiency is obtained for La compared to Nd on a solid cathode. This is an effect of the multi-valent nature of Nd in the chloride melts. (author)

Experimental Monitoring of Cr(VI) Bio-reduction Using Electrochemical Geophysics

International Nuclear Information System (INIS)

Birsen Canan; Gary R. Olhoeft; William A. Smith

2007-01-01

Many Department of Energy (DOE) sites are contaminated with highly carcinogenic hexavalent chromium (Cr(VI)). In this research, we explore the feasibility of applying complex resistivity to the detection and monitoring of microbially-induced reduction of hexavalent chromium (Cr(VI)) to a less toxic form (Cr(III)). We hope to measure the change in ionic concentration that occurs during this reduction reaction. This form of reduction promises to be an attractive alternative to more expensive remedial treatment methods. The specific goal of this research is to define the minimum and maximum concentration of the chemical and biological compounds in contaminated samples for which the Cr(VI) - Cr(III) reduction processes could be detected via complex resistivity. There are three sets of experiments, each comprised of three sample columns. The first experiment compares three concentrations of Cr(VI) at the same bacterial cell concentration. The second experiment establishes background samples with, and without, Cr(VI) and bacterial cells. The third experiment examines the influence of three different bacterial cell counts on the same concentration of Cr(VI). A polarization relaxation mechanism was observed between 10 and 50 Hz. The polarization mechanism, unfortunately, was not unique to bio-chemically active samples. Spectral analysis of complex resistivity data, however, showed that the frequency where the phase minimum occurred was not constant for bio-chemically active samples throughout the experiment. A significant shifts in phase minima occurred between 10 to 20 Hz from the initiation to completion of Cr(VI) reduction. This phenomena was quantified using the Cole-Cole model and the Marquardt-Levenberg nonlinear least square minimization method. The data suggests that the relaxation time and the time constant of this relaxation are the Cole-Cole parameters most sensitive to changes in biologically-induced reduction of Cr(VI)

LSFM perovskites as cathodes for the electrochemical reduction of NO

DEFF Research Database (Denmark)

Kammer Hansen, K.; Skou, E.M.

2005-01-01

Six La0.6Sr0.4Fe1-xMnO3-delta (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) perovskite compounds have been synthesised by the citric-acid route. The perovskites have been characterised by powder XRD and are shown to belong to the hexagonal crystal system. The perovskites are also evaluated by TG...... degrees C on a ceria based electrolyte. Only La0.6Sr0.4Fe0.8Mn0.2O3-delta (LSFM020) and La0.6Sr0.4FeO3-delta (LSFM000) show significant activity for the reduction of NO. This can probably be related to the high redox capacity of these compounds. The activity of the perovskites for the reduction of oxygen...... increases systematically with increasing iron content. The selectivity of the perovskites towards the reduction of NO with regard to the reduction of O-2 is highest at the lowest temperatures. (c) 2004 Published by Elsevier B.V....

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

Science.gov (United States)

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Influence of temperature and voltage on electrochemical reduction ...

Indian Academy of Sciences (India)

Administrator

Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, College of Materials Science ... not only waste energy sources, but also influence reduc- tion effect. Thus, the ... was 1⋅2 cm, typical concentrations and reduction time of. GO were 1 ..... Project (12JC1408600) and the National High Technology.

Green reduction of graphene oxide by ascorbic acid

Science.gov (United States)

Khosroshahi, Zahra; Kharaziha, Mahshid; Karimzadeh, Fathallah; Allafchian, Alireza

2018-01-01

Graphene, a single layer of sp2-hybridized carbon atoms in a hexagonal (two-dimensional honey-comb) lattice, has attracted strong scientific and technological interest due to its novel and excellent optical, chemical, electrical, mechanical and thermal properties. The solution-processable chemical reduction of Graphene oxide (GO is considered as the most favorable method regarding mass production of graphene. Generally, the reduction of GO is carried out by chemical approaches using different reductants such as hydrazine and sodium borohydride. These components are corrosive, combustible and highly toxic which may be dangerous for personnel health and the environment. Hence, these reducing agents are not promising choice for reducing of graphene oxide (GO). As a consequence, it is necessary for further development and optimization of eco-friendly, natural reducing agent for clean and effective reduction of GO. Ascorbic acid, an eco-friendly and natural reducing agents, having a mild reductive ability and nontoxic property. So, the aim of this research was to green synthesis of GO with ascorbic acid. For this purpose, the required amount of NaOH and ascorbic acid were added to GO solution (0.5 mg/ml) and were heated at 95 °C for 1 hour. According to the X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electrochemical results, GO were reduced with ascorbic acid like hydrazine with better electrochemical properties and ascorbic acid is an ideal substitute for hydrazine in the reduction of graphene oxide process.

Spectro-electrochemical and DFT study of tenoxicam metabolites formed by electrochemical oxidation

International Nuclear Information System (INIS)

Ramírez-Silva, M.T.; Guzmán-Hernández, D.S.; Galano, A.; Rojas-Hernández, A.; Corona-Avendaño, S.; Romero-Romo, M.; Palomar-Pardavé, M.

2013-01-01

Highlights: • Tenoxicam deprotonation and electrochemical oxidation were studied. • Both spectro-electrochemical and theoretical DFT studies were considered. • It was found that the ampholitic species of tenoxicam is a zwitterion. • Electrochemical oxidation of tenoxicam yields two non-electroactive products. • The nature of these fragments was further confirmed by a chromatography study. -- Abstract: From experimental (spectro-electrochemical) and theoretical (DFT) studies, the mechanisms of tenoxicam deprotonation and electrochemical oxidation were assessed. From these studies, new insights on the nature of the ampholitic species involved during tenoxicam's deprotonation in aqueous solution are presented; see scheme A. Moreover, it is shown that, after the analysis of two different reaction schemes that involve up to 10 different molecules and 12 reaction paths, the electrochemical oxidation of tenoxicam, yields two non-electroactive products that are predominately formed by its fragmentation, after the loss of two electrons. The nature of these fragments was further confirmed by a chromatography study

CORROSION RESISTANCE OF ORGANOMETALLIC COATING APLICATED IN FUEL TANKS USING ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IN BIOFUEL – PART I

Directory of Open Access Journals (Sweden)

Milene Adriane Luciano

2014-10-01

Full Text Available Nowadays, the industry has opted for more sustainable production processes, and the planet has also opted for new energy sources. From this perspective, automotive tanks with organometallic coatings as well as a partial substitution of fossil fuels by biofuels have been developed. These organometallic coated tanks have a zinc layer, deposited by a galvanizing process, formed between the steel and the organometallic coating. This work aims to characterize the organometallic coating used in metal automotive tanks and evaluate their corrosion resistance in contact with hydrated ethyl alcohol fuel (AEHC. For this purpose, the resistance of all layers formed between Zinc and EEP steel and also the tin coated steel, which has been used for over thirty years, were evaluated. The technique chosen was the Electrochemical Impedance Spectroscopy. The results indicated an increase on the corrosion resistance when organometallic coatings are used in AEHC medium. In addition to that, these coatings allow an estimated 25% reduction in tanks production costs.

AC impedance electrochemical modeling of lithium-ion positive electrodes

International Nuclear Information System (INIS)

Dees, D.; Gunen, E.; Abraham, D.; Jansen, A.; Prakash, J.

2004-01-01

numerically using a partial differential equation solver (FlexPDE) over the frequency range of interest. The electrochemical AC impedance model was used as a diagnostic tool to examine ageing effects associated with the positive electrode, and to investigate ways to reduce the impact of these effects on the overall cell performance

Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

Energy Technology Data Exchange (ETDEWEB)

Yesildag, Ali [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey); Ekinci, Duygu, E-mail: dekin@atauni.edu.t [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey)

2010-09-30

In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN){sub 6}{sup 3-} and Ru(NH{sub 3}){sub 6}{sup 3+} by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

Effects of oxygen partial pressure on Li-air battery performance

Science.gov (United States)

Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

2017-10-01

For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

Effect of the electrochemical passivation on the corrosion behaviour of austenitic stainless steel

International Nuclear Information System (INIS)

Barbucci, A.; Delucchi, M.; Panizza, M.; Farne, G.; Cerisola, G.

2004-01-01

Cold rolled SS is also fruitfully used in deep drawing however the presence of scales or oxides on the surface reduces the life of the tools and emphasises creep phenomena of the material. Then a cleaning of the SS surface from these impurities is necessary. Oxides can be formed during the hot rolling preceding the cold one, or during the annealing performed between the several steps of thickness reduction. The annealing helps to decrease the work hardening occurring during the process. Normally this heat treatment is performed in reducing atmosphere of pure hydrogen (bright annealing), but even in this conditions oxides are formed on the SS surface. To avoid this uncontrolled oxide growth one method recently applied is an electrochemical cleaning performed in an electrolytic solution containing chrome, generally called electrochemical passivation. The electrochemical passivation allows the dissolution of the contaminating hard particles on the strips. Few scientific contributions are available in literature, which explain in detail the process mechanism. The aim of this work is to investigate if the electrochemical passivated surface acts in a different way with regard to corrosion phenomena with respect to conventional SS. Electrochemical measurements like polarisation, chrono-amperometries and surface analysis were used to investigate the corrosion behaviour of electrochemically passivated AISI 304L and AISI 305. The effect of some process parameters were considered, too. (authors)

Effect of the electrochemical passivation on the corrosion behaviour of austenitic stainless steel

Energy Technology Data Exchange (ETDEWEB)

Barbucci, A.; Delucchi, M.; Panizza, M.; Farne, G.; Cerisola, G. [DICheP, University of Genova, P.le Kennedy 1, 16129 Genova (Italy)

2004-07-01

Cold rolled SS is also fruitfully used in deep drawing however the presence of scales or oxides on the surface reduces the life of the tools and emphasises creep phenomena of the material. Then a cleaning of the SS surface from these impurities is necessary. Oxides can be formed during the hot rolling preceding the cold one, or during the annealing performed between the several steps of thickness reduction. The annealing helps to decrease the work hardening occurring during the process. Normally this heat treatment is performed in reducing atmosphere of pure hydrogen (bright annealing), but even in this conditions oxides are formed on the SS surface. To avoid this uncontrolled oxide growth one method recently applied is an electrochemical cleaning performed in an electrolytic solution containing chrome, generally called electrochemical passivation. The electrochemical passivation allows the dissolution of the contaminating hard particles on the strips. Few scientific contributions are available in literature, which explain in detail the process mechanism. The aim of this work is to investigate if the electrochemical passivated surface acts in a different way with regard to corrosion phenomena with respect to conventional SS. Electrochemical measurements like polarisation, chrono-amperometries and surface analysis were used to investigate the corrosion behaviour of electrochemically passivated AISI 304L and AISI 305. The effect of some process parameters were considered, too. (authors)

Some aspects of the electrochemical behaviour of mild steel in carbonate/bicarbonate solutions

International Nuclear Information System (INIS)

Rangel, C.M.; Leitao, R.A.; Fonseca, I.T.

1986-01-01

The electrochemical behaviour of mild steel in aqueous solutions of sodium carbonate/sodium bicarbonate (600 ppm) has been investigated using potentiodynamic polarization. In the pre-passive region three well-defined peaks are observed associated to reduction peaks corresponding to Fe(II) and Fe(III) species. A transpassive anodic peak is also observed being attributed to Fe(VI) species showing, in sweep reversal experiments, an associated reduction peak and an increase in the peak associated to the reduction of Fe(III) species. The characterization of the transpassive peak will be subject of further publication. (author)

Electrochemical behavior of cysteine at a CuGeO3 nanowires modified glassy carbon electrode

International Nuclear Information System (INIS)

Dong Yongping; Pei Lizhai; Chu Xiangfeng; Zhang Wangbing; Zhang Qianfeng

2010-01-01

A CuGeO 3 nanowire modified glassy carbon electrode was fabricated and characterized by scanning electron microscopy. The results of electrochemical impedance spectroscopy reveal that electron transfer through nanowire film is facile compared with that of bare glassy carbon electrode. The modified electrode exhibited a novel electrocatalytic behavior to the electrochemical reactions of L-cysteine in neutral solution, which was not reported previously. Two pairs of semi-reversible electrochemical peaks were observed and assigned to the processes of oxidation/reduction and adsorption/desorption of cysteine at the modified electrode, respectively. The electrochemical response of cysteine is poor in alkaline condition and is enhanced greatly in acidic solution, suggesting that hydrogen ions participate in the electrochemical oxidation process of cysteine. The intensities of two anodic peaks varied linearly with the concentration of cysteine in the range of 1 x 10 -6 to 1 x 10 -3 mol L -1 , which make it possible to sensitive detection of cysteine with the CuGeO 3 nanowire modified electrode. Furthermore, the modified electrode exhibited good reproducibility and stability.

Nanoporous gold microelectrode prepared from potential modulated electrochemical alloying–dealloying in ionic liquid

International Nuclear Information System (INIS)

Jiang, Junhua; Wang, Xinying; Zhang, Lei

2013-01-01

Highlights: • A green chemistry method for producing nanoporous gold microelectrode was studied. • An ionic liquid plating bath was utilized for electrochemical alloying–dealloying. • Nanostructures of gold surface layers can be tuned by modulating potential. • Nanoporous gold microelectrode has high surface area and merit of a microelectrode. • Nitrite oxidation and reduction on nanoporous gold microelectrode were studied. -- Abstract: Nanoporous gold (NPG) microelectrodes with high surface area and open pore network were successfully prepared by applying modulated potential to a polycrystalline Au-disk microelectrode in ionic liquid electrolyte containing ZnCl 2 at elevated temperature. During cathodic process, Zn is electrodeposited and interacted with Au microdisk substrate to form a AuZn alloy phase. During subsequent anodic process, Zn is selectively dissolved from the alloy phase, leading to the formation of a NPG layer which can grow with repetitive potential modulation. Scanning-electron microscope and energy dispersive X-ray microscope measurements show that the NPG microelectrodes possessing nanoporous structures can be tuned via potential modulation, and chemically contain a small amount of Zn whose presence has no obvious influence on electrochemical responses of the electrodes. Steady-state and cyclic voltammetric studies suggest that the NPG microelectrodes have high surface area and keep diffusional properties of a microelectrode. Electrochemical nitrite reduction and oxidation are studied as model reactions to demonstrate potential applications of the NPG microelectrodes in electrocatalysis and electroanalysis. These facts suggest that the potential-modulated electrochemical alloying/dealloying in ionic liquid electrolyte offers a convenient green-chemistry method for the preparation of nanoporous microelectrodes

A model reduction approach to numerical inversion for a parabolic partial differential equation

International Nuclear Information System (INIS)

Borcea, Liliana; Druskin, Vladimir; Zaslavsky, Mikhail; Mamonov, Alexander V

2014-01-01

We propose a novel numerical inversion algorithm for the coefficients of parabolic partial differential equations, based on model reduction. The study is motivated by the application of controlled source electromagnetic exploration, where the unknown is the subsurface electrical resistivity and the data are time resolved surface measurements of the magnetic field. The algorithm presented in this paper considers inversion in one and two dimensions. The reduced model is obtained with rational interpolation in the frequency (Laplace) domain and a rational Krylov subspace projection method. It amounts to a nonlinear mapping from the function space of the unknown resistivity to the small dimensional space of the parameters of the reduced model. We use this mapping as a nonlinear preconditioner for the Gauss–Newton iterative solution of the inverse problem. The advantage of the inversion algorithm is twofold. First, the nonlinear preconditioner resolves most of the nonlinearity of the problem. Thus the iterations are less likely to get stuck in local minima and the convergence is fast. Second, the inversion is computationally efficient because it avoids repeated accurate simulations of the time-domain response. We study the stability of the inversion algorithm for various rational Krylov subspaces, and assess its performance with numerical experiments. (paper)

A model reduction approach to numerical inversion for a parabolic partial differential equation

Science.gov (United States)

Borcea, Liliana; Druskin, Vladimir; Mamonov, Alexander V.; Zaslavsky, Mikhail

2014-12-01

We propose a novel numerical inversion algorithm for the coefficients of parabolic partial differential equations, based on model reduction. The study is motivated by the application of controlled source electromagnetic exploration, where the unknown is the subsurface electrical resistivity and the data are time resolved surface measurements of the magnetic field. The algorithm presented in this paper considers inversion in one and two dimensions. The reduced model is obtained with rational interpolation in the frequency (Laplace) domain and a rational Krylov subspace projection method. It amounts to a nonlinear mapping from the function space of the unknown resistivity to the small dimensional space of the parameters of the reduced model. We use this mapping as a nonlinear preconditioner for the Gauss-Newton iterative solution of the inverse problem. The advantage of the inversion algorithm is twofold. First, the nonlinear preconditioner resolves most of the nonlinearity of the problem. Thus the iterations are less likely to get stuck in local minima and the convergence is fast. Second, the inversion is computationally efficient because it avoids repeated accurate simulations of the time-domain response. We study the stability of the inversion algorithm for various rational Krylov subspaces, and assess its performance with numerical experiments.

Electrochemical reduction of cerium oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.; Serp, J.; Fouletier, J.

2011-01-01

This brief article describes a pyrochemical process that is used by CEA to turn actinide oxides into metal actinides. This process is applied to Cerium oxides (CeO 2 ) that simulate actinide oxides well chemically as cerium belongs to the lanthanide family. The process is in fact an electrolysis of cerium oxide in a bath of molten calcium chloride salt whose temperature is between 800 and 900 Celsius degrees. At those temperatures calcium chloride becomes a ionic liquid (Ca 2+ and Cl - ) that is a good electrical conductor and is particularly well-adapted as solvent to an electrolytic process. The electrolysis current allows the transformation of solvent Ca 2+ ions into metal calcium which, in turn, can reduce cerium oxide into metal cerium through chromatically. Experimental data shows the reduction of up to 90% of 10 g samples of CeO 2 in a 6 hour long electrolysis while the best reduction rate ever known was 80% so far. This result is all the more promising that cerium oxides are more difficult to reduce than actinide oxides from the thermodynamical perspective

Electrochemical behavior of fission palladium in 1-butyl-3-methylimidazolium chloride

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A.; Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

2007-08-01

Electrochemical behavior of palladium (II) chloride in 1-butyl-3-methylimidazolium chloride has been investigated by various electrochemical transient techniques using glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram consisted of a prominent reduction wave at -0.61 V (vs. Pd) due to the reduction of Pd(II) to Pd, and two oxidation waves at -0.26 and 0.31 V. A nucleation loop is observed at -0.53 V. The diffusion coefficient of palladium (II) in bmimCl ({proportional_to}10{sup -7} cm{sup 2}/s) was determined and the energy of activation (63 kJ/mol) was deduced from the cyclic voltammograms at various temperatures. Nucleation and growth of palladium on glassy carbon working electrode has been investigated by chronoamperometry and chronopotentiometry. The growth and decay of chronocurrents measured for palladium deposition has been found to follow the instantaneous nucleation model with three-dimensional growth of nuclei. The surface morphology of the deposit obtained at various applied potentials revealed the formation of dendrites immediately after nucleation and spread in all the directions with time. (author)

Electrochemical Oxidation of Propene with a LSF15/CGO10 Electrochemical Reactor

DEFF Research Database (Denmark)

Ippolito, Davide; Kammer Hansen, Kent

2014-01-01

A porous electrochemical reactor, made of La0.85Sr0.15FeO3 (LSF) as electrode and Ce0.9Gd0.1O1.95 (CGO) as electrolyte, was studied for the electrochemical oxidation of propene over a wide range of temperatures. Polarization was found to enhance propene oxidation rate. Ce0.9Gd0.1O1.95 was used...... as infiltration material to enhance the effect of polarization on propene oxidation rate, especially at low temperatures. The influence of infiltrated material, as a function of heat treatment, on the reactor electrochemical behavior has been evaluated by using electrochemical impedance spectroscopy...... in suppressing the competing oxygen evolution reaction and promoting the oxidation of propene under polarization, with faradaic efficiencies above 70% at 250◦C. © 2014 The Electrochemical Society....

Structure, temperature and frequency dependent electrical conductivity of oxidized and reduced electrochemically exfoliated graphite

Science.gov (United States)

Radoń, Adrian; Włodarczyk, Patryk; Łukowiec, Dariusz

2018-05-01

The article presents the influence of reduction by hydrogen in statu nascendi and modification by hydrogen peroxide on the structure and electrical conductivity of electrochemically exfoliated graphite. It was confirmed that the electrochemical exfoliation can be used to produce oxidized nanographite with an average number of 25 graphene layers. The modified electrochemical exfoliated graphite and reduced electrochemical exfoliated graphite were characterized by high thermal stability, what was associated with removing of labile oxygen-containing groups. The presence of oxygen-containing groups was confirmed using Fourier-transform infrared spectroscopy. Influence of chemical modification by hydrogen and hydrogen peroxide on the electrical conductivity was determined in wide frequency (0.1 Hz-10 kHz) and temperature range (-50 °C-100 °C). Material modified by hydrogen peroxide (0.29 mS/cm at 0 °C) had the lowest electrical conductivity. This can be associated with oxidation of unstable functional groups and was also confirmed by analysis of Raman spectra. The removal of oxygen-containing functional groups by hydrogen in statu nascendi resulted in a 1000-fold increase in the electrical conductivity compared to the electrochemical exfoliated graphite.

Electrochemical noise measurements under pressurized water reactor conditions

International Nuclear Information System (INIS)

Van Nieuwenhove, R.

2000-01-01

Electrochemical potential noise measurements on sensitized stainless steel pressure tubes under pressurized water reactor (PWR) conditions were performed for the first time. Very short potential spikes, believed to be associated to crack initiation events, were detected when stressing the sample above the yield strength and increased in magnitude until the sample broke. Sudden increases of plastic deformation, as induced by an increased tube pressure, resulted in slower, high-amplitude potential transients, often accompanied by a reduction in noise level

Development of a Telemetric, Miniaturized Electrochemical Amperometric Analyzer

OpenAIRE

Jaehyo Jung; Jihoon Lee; Siho Shin; Youn Tae Kim

2017-01-01

In this research, we developed a portable, three-electrode electrochemical amperometric analyzer that can transmit data to a PC or a tablet via Bluetooth communication. We performed experiments using an indium tin oxide (ITO) glass electrode to confirm the performance and reliability of the analyzer. The proposed analyzer uses a current-to-voltage (I/V) converter to convert the current generated by the reduction-oxidation (redox) reaction of the buffer solution to a voltage signal. This signa...

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

Directory of Open Access Journals (Sweden)

Ariel Jackson

2018-01-01

Full Text Available Improving the performance of oxygen reduction reaction (ORR electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs. Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mgPt−1 at 0.9 V versus the reversible hydrogen electrode (RHE, which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mgPt−1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s−1, maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

Obtention of superconductivity by room temperature electrochemical oxidation of La2CuO4

International Nuclear Information System (INIS)

Casan-Pastor, N.; Fuertes, A.; Gomez-Romero, P.

1993-01-01

The undoped oxide La2CuO4 has required traditionally synthesis under high pressure of oxygen (and high temperatures) to incorporate excess oxygen into its structure and become a superconductor. The electrochemical oxidation of this same oxide at room temperature and pressure constitutes a striking example of the use of an alternative driving force for the oxidation of oxides to become superconductors. Electrochemical treatment of oxides has been frequently applied to their reduction with cationic intercalation. Oxidations of these solid with the concomitant intercalation of anions into their lattice shows also great promises. The paper reports recent results in the electrochemical oxidation of La2CuO4 and other cuprates, showing also the important role of post-oxidation thermal treatments on the properties of the resulting solids

The influence of oxide on the electrochemical processes in K2NbF7-NaCl-KCl melts

DEFF Research Database (Denmark)

Lantelme, F.; Berghoute, Y.; Barner, Jens H. Von

1995-01-01

Transient electrochemical techniques showed that in NaCl-KCl melts the reduction of K2NbF7 occurs through atwo-step reaction Nb(V) --> Nb(IV) --> Nb. When oxide ions were introduced, cyclic voltammetry indicated that the wavescorresponding to reduction of the complex NbF72- progressively...

Electrochemical and AFM Characterization of G-Quadruplex Electrochemical Biosensors and Applications

Science.gov (United States)

2018-01-01

Guanine-rich DNA sequences are able to form G-quadruplexes, being involved in important biological processes and representing smart self-assembling nanomaterials that are increasingly used in DNA nanotechnology and biosensor technology. G-quadruplex electrochemical biosensors have received particular attention, since the electrochemical response is particularly sensitive to the DNA structural changes from single-stranded, double-stranded, or hairpin into a G-quadruplex configuration. Furthermore, the development of an increased number of G-quadruplex aptamers that combine the G-quadruplex stiffness and self-assembling versatility with the aptamer high specificity of binding to a variety of molecular targets allowed the construction of biosensors with increased selectivity and sensitivity. This review discusses the recent advances on the electrochemical characterization, design, and applications of G-quadruplex electrochemical biosensors in the evaluation of metal ions, G-quadruplex ligands, and other small organic molecules, proteins, and cells. The electrochemical and atomic force microscopy characterization of G-quadruplexes is presented. The incubation time and cations concentration dependence in controlling the G-quadruplex folding, stability, and nanostructures formation at carbon electrodes are discussed. Different G-quadruplex electrochemical biosensors design strategies, based on the DNA folding into a G-quadruplex, the use of G-quadruplex aptamers, or the use of hemin/G-quadruplex DNAzymes, are revisited. PMID:29666699

Stable and highly efficient electrochemical production of formic acid from carbon dioxide using diamond electrodes

Energy Technology Data Exchange (ETDEWEB)

Natsui, Keisuke; Iwakawa, Hitomi; Ikemiya, Norihito [Department of Chemistry, Keio University, Yokohama (Japan); Nakata, Kazuya [Photocatalysis International Research Center, Tokyo University of Science, Chiba (Japan); Einaga, Yasuaki [Department of Chemistry, Keio University, Yokohama (Japan); JST-ACCEL, Yokohama (Japan)

2018-03-01

High faradaic efficiencies can be achieved in the production of formic acid (HCOOH) by metal electrodes, such as Sn or Pb, in the electrochemical reduction of carbon dioxide (CO{sub 2}). However, the stability and environmental load in using them are problematic. The electrochemical reduction of CO{sub 2} to HCOOH was investigated in a flow cell using boron-doped diamond (BDD) electrodes. BDD electrodes have superior electrochemical properties to metal electrodes, and, moreover, are highly durable. The faradaic efficiency for the production of HCOOH was as high as 94.7 %. Furthermore, the selectivity for the production of HCOOH was more than 99 %. The rate of the production was increased to 473 μmol m{sup -2} s{sup -1} at a current density of 15 mA cm{sup -2} with a faradaic efficiency of 61 %. The faradaic efficiency and the production rate are almost the same as or larger than those achieved using Sn and Pb electrodes. Furthermore, the stability of the BDD electrodes was confirmed by 24 h operation. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Stable and Highly Efficient Electrochemical Production of Formic Acid from Carbon Dioxide Using Diamond Electrodes.

Science.gov (United States)

Natsui, Keisuke; Iwakawa, Hitomi; Ikemiya, Norihito; Nakata, Kazuya; Einaga, Yasuaki

2018-03-01

High faradaic efficiencies can be achieved in the production of formic acid (HCOOH) by metal electrodes, such as Sn or Pb, in the electrochemical reduction of carbon dioxide (CO 2 ). However, the stability and environmental load in using them are problematic. The electrochemical reduction of CO 2 to HCOOH was investigated in a flow cell using boron-doped diamond (BDD) electrodes. BDD electrodes have superior electrochemical properties to metal electrodes, and, moreover, are highly durable. The faradaic efficiency for the production of HCOOH was as high as 94.7 %. Furthermore, the selectivity for the production of HCOOH was more than 99 %. The rate of the production was increased to 473 μmol m -2  s -1 at a current density of 15 mA cm -2 with a faradaic efficiency of 61 %. The faradaic efficiency and the production rate are almost the same as or larger than those achieved using Sn and Pb electrodes. Furthermore, the stability of the BDD electrodes was confirmed by 24 h operation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

Energy Technology Data Exchange (ETDEWEB)

Cames, B

1997-12-31

In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media ({<=} 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 {<=} E {<=} 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

Insight into the electroreduction of nitrate ions at a copper electrode, in neutral solution, after determination of their diffusion coefficient by electrochemical impedance spectroscopy

International Nuclear Information System (INIS)

Aouina, Nizar; Cachet, Hubert; Debiemme-chouvy, Catherine; Tran, Thi Tuyet Mai

2010-01-01

The electrochemical reduction of nitrate ions at a copper electrode in an unbuffered neutral aqueous solution is studied. Using a two compartment electrochemical cell, three stationary cathodic waves, noted P1, P2 and P3, were evidenced by cyclic voltammetry at -0.9, -1.2 and -1.3 V/SCE, respectively. By comparing the electrochemical response of nitrate and nitrite containing solutions, P1 was attributed to the reduction of nitrate to nitrite. In order to assign P2 and P3 features by determining the number of electrons involved at the corresponding potential, rotating disk electrode experiments at various rotation speeds, combined with linear sweep voltammetry, were performed. Current data analysis at a given potential was carried out using Koutecky-Levich treatment taking into account water reduction. Confident values of the diffusion coefficient D of nitrate ions were assessed by electrochemical impedance spectroscopy for nitrate concentrations of 10 -3 , 10 -2 and 10 -1 M. For a nitrate concentration of 10 -2 M, D was found to be 1.31 x 10 -5 cm 2 s -1 allowing the number of electrons to be determined as 6 for P2 and 8 for P3, in accordance with nitrate reduction into hydroxylamine and ammonia, respectively. The formation of hydroxylamine was confirmed by the observation of its reoxidation at a Pt microelectrode present at the Cu electrode/nitrate solution interface.

A multiscale approach to modelling electrochemical processes occurring across the cell membrane with application to transmission of action potentials.

Science.gov (United States)

Richardson, G

2009-09-01

By application of matched asymptotic expansions, a simplified partial differential equation (PDE) model for the dynamic electrochemical processes occurring in the vicinity of a membrane, as ions selectively permeate across it, is formally derived from the Poisson-Nernst-Planck equations of electrochemistry. It is demonstrated that this simplified model reduces itself, in the limit of a long thin axon, to the cable equation used by Hodgkin and Huxley to describe the propagation of action potentials in the unmyelinated squid giant axon. The asymptotic reduction from the simplified PDE model to the cable equation leads to insights that are not otherwise apparent; these include an explanation of why the squid giant axon attains a diameter in the region of 1 mm. The simplified PDE model has more general application than the Hodgkin-Huxley cable equation and can, e.g. be used to describe action potential propagation in myelinated axons and neuronal cell bodies.

Development of Head-end Pyrochemical Reduction Process for Advanced Oxide Fuels

Energy Technology Data Exchange (ETDEWEB)

Park, B. H.; Seo, C. S.; Hur, J. M.; Jeong, S. M.; Hong, S. S.; Choi, I. K.; Choung, W. M.; Kwon, K. C.; Lee, I. W. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2008-12-15

The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U{sub 3}O{sub 8} was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U{sub 3}O{sub 8} and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li{sub 2}Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool.

Improving corrosion resistance of magnesium-based alloys by surface modification with hydrogen by electrochemical ion reduction (EIR) and by plasma immersion ion implantation (PIII)

Energy Technology Data Exchange (ETDEWEB)

Bakkar, A. [Institut fuer Materialpruefung und Werkstofftechnik, Dr. Doelling und Dr. Neubert GmbH, Freiberger Strasse 1, 38678 Clausthal (Germany); Department of Metallurgy and Materials Engineering, Suez Canal University, P.O. Box 43721, Suez (Egypt); Neubert, V. [Institut fuer Materialpruefung und Werkstofftechnik, Dr. Doelling und Dr. Neubert GmbH, Freiberger Strasse 1, 38678 Clausthal (Germany)]. E-mail: volkmar.neubert@tu-clausthal.de

2005-05-01

Magnesium-based hydrides are well known that they have a high hydrogen-storage capacity. In this study, two different methods have been provided for hydrogen surface modification of high purity magnesium (hp Mg) and AZ91 magnesium alloy. One was electrochemical ion reduction (EIR) of hydrogen from an alkaline electrolyte on such Mg-based cathode. The other was plasma immersion ion implantation (PIII or PI{sup 3}) into Mg-based substrate. The depth profile of H-modified surfaces was described by Auger electron spectroscopy (AES) and by secondary ion mass spectrometry (SIMS) measurements. Corrosion testing was carried out in Avesta cell by potentiodynamic polarisation in chloride-containing aqueous solutions of pH 7 and pH 12. A greatly significant improvement in the corrosion resistance of H-modified surfaces was verified.

Improving corrosion resistance of magnesium-based alloys by surface modification with hydrogen by electrochemical ion reduction (EIR) and by plasma immersion ion implantation (PIII)

International Nuclear Information System (INIS)

Bakkar, A.; Neubert, V.

2005-01-01

Magnesium-based hydrides are well known that they have a high hydrogen-storage capacity. In this study, two different methods have been provided for hydrogen surface modification of high purity magnesium (hp Mg) and AZ91 magnesium alloy. One was electrochemical ion reduction (EIR) of hydrogen from an alkaline electrolyte on such Mg-based cathode. The other was plasma immersion ion implantation (PIII or PI 3 ) into Mg-based substrate. The depth profile of H-modified surfaces was described by Auger electron spectroscopy (AES) and by secondary ion mass spectrometry (SIMS) measurements. Corrosion testing was carried out in Avesta cell by potentiodynamic polarisation in chloride-containing aqueous solutions of pH 7 and pH 12. A greatly significant improvement in the corrosion resistance of H-modified surfaces was verified

Hybrid electronic tongue based on optical and electrochemical microsensors for quality control of wine.

Science.gov (United States)

Gutiérrez, Manuel; Llobera, Andreu; Vila-Planas, Jordi; Capdevila, Fina; Demming, Stefanie; Büttgenbach, Stephanus; Mínguez, Santiago; Jiménez-Jorquera, Cecilia

2010-07-01

A multiparametric system able to classify red and white wines according to the grape varieties and for analysing some specific parameters is presented. The system, known as hybrid electronic tongue, consists of an array of electrochemical microsensors and a colorimetric optofluidic system. The array of electrochemical sensors is composed of six ISFETs based sensors, a conductivity sensor, a redox potential sensor and two amperometric electrodes, an Au microelectrode and a microelectrode for sensing electrochemical oxygen demand. The optofluidic system is entirely fabricated in polymer technology and comprises a hollow structure, air mirrors, microlenses and self-alignment structures. The data obtained from these sensors has been treated with multivariate advanced tools; Principal Component Analysis (PCA), for the patterning recognition and classification of wine samples, and Partial-Least Squares (PLS) regression, for quantification of several chemical and optical parameters of interest in wine quality. The results have demonstrated the utility of this system for distinguishing the samples according to the grape variety and year vintage and for quantifying several sample parameters of interest in wine quality control.

Facile route to covalently-jointed graphene/polyaniline composite and it's enhanced electrochemical performances for supercapacitors

Science.gov (United States)

Qiu, Hanxun; Han, Xuebin; Qiu, Feilong; Yang, Junhe

2016-07-01

A polyaniline/graphene composite with covalently-bond is synthesized by a novel approach. In this way, graphene oxide is functionalized firstly by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of polyaniline (PANI) via in-situ polymerization. The composite material is characterized by electron microscopy, the resonant Raman spectra, X-ray diffraction, transform infrared spectroscopy and X-ray photoelectron spectroscopy. The electrochemical properties of the composite are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. With the functionalization process, the graphene/polyaniline composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F g-1 at 0.5 A g-1, which is superior to those of its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and polyaniline, suggesting promising potentials for supercapacitors.

Application of spectral analysis of the electrochemical noise to the investigation of aluminium alloy pitting corrosion

International Nuclear Information System (INIS)

Bataillon, Christian

1987-01-01

The objective of this research is to decode (at least partially) the nature of the information contained in the electrochemical noise associated with the pitting corrosion phenomenon in aluminium alloys. After a general presentation of aluminium and its alloys and a report of a bibliographical study on the electrochemical noise, the author gives an overview of a theoretical approach of stochastic phenomena, and of an experimental approach. Then, the experimental investigation of the electrochemical noise in the case of pitting corrosion leads to a noise control law, to a study of the structure of pitting growth, and to the elaboration of a procedure of assessment of spectral characteristics of this noise. The author reports a systematic study of the electrochemical noise with respect to the parameters of the control law. Results allow a quantitative characterization of pitting corrosion resistance of the studied alloys, notably by using the kinetic aspect of pitting growth and the structure of pitting corrosion. The author discusses the physicochemical nature of random fluctuations which build up the noise. He proposes a more precise explanation of phenomena related to initiation and propagation of pitting corrosion on aluminium alloys in marine environment [fr

Higher-order rewriting and partial evaluation

DEFF Research Database (Denmark)

Danvy, Olivier; Rose, Kristoffer H.

1998-01-01

We demonstrate the usefulness of higher-order rewriting techniques for specializing programs, i.e., for partial evaluation. More precisely, we demonstrate how casting program specializers as combinatory reduction systems (CRSs) makes it possible to formalize the corresponding program...

Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach.

Science.gov (United States)

Lee, Hiang Kwee; Koh, Charlynn Sher Lin; Lee, Yih Hong; Liu, Chong; Phang, In Yee; Han, Xuemei; Tsung, Chia-Kuang; Ling, Xing Yi

2018-03-01

Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF's water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor-abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries.

The mechanism and kinetics of the electrochemical cleavage of azo bond of 2-hydroxy-5-sulfophenyl-azo-benzoic acids

International Nuclear Information System (INIS)

Mandic, Zoran; Nigovic, Biljana; Simunic, Branimir

2004-01-01

The electrochemical reduction of 2-hydroxy-5-[(4-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(3-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(2-sulfophenyl)azo]benzoic acid and 2-hydroxy-5-azo-benzoic acid has been carried out in aqueous solutions at glassy carbon electrode using cyclic voltammetry and chronoamperometry. The position of sulfo substituent relative to azo bridge as well as pH of the solution have significant impact on the electrochemical behavior of these compounds. It has been proposed that these compounds are reduced predominantly as hydrazone tautomers resulting in corresponding hydrazo compounds. The overall electrochemical reduction follows DISP2 mechanism, ultimately leading to the 5-amino salicylic acid and sulfanilic acid. The rate determining step is the homogenous redox reaction between intermediate hydrazo compound and 5-amino salicylic acid quinoneimine. The mechanism is proposed in which activated complex of 5-amino salicylic acid quinoneimine and intermediate hydrazo compound is formed with the simultaneous loss of one proton

Structure and electrochemical performances of LiFe{sub 1−2x}Ti{sub x}PO{sub 4}/C cathode doped with high valence Ti{sup 4+} by carbothermal reduction method

Energy Technology Data Exchange (ETDEWEB)

Fan, Chang-ling, E-mail: clfanhd@yahoo.com.cn [College of Materials Science and Engineering, Hunan University, Changsha 410082 (China); Han, Shao-chang [College of Materials Science and Engineering, Hunan University, Changsha 410082 (China); Li, Ling-fang [College of Materials Science and Engineering, Hunan University, Changsha 410082 (China); College of Mechanical Engineering, Hunan University of Art and Science, Changde 415000 (China); Bai, Yong-mei [Equipment Manufacturing College, Hebei University of Engineering, Handan 056038 (China); Zhang, Ke-he; Chen, Jin; Zhang, Xiang [College of Materials Science and Engineering, Hunan University, Changsha 410082 (China)

2013-11-05

Highlights: •LiFePO{sub 4}/C and LiFe{sub 1−2x}Ti{sub x}PO{sub 4}/C are prepared by carbothermal reduction method. •Phenol–formaldehyde resin is used as reducing agent and carbon source. •Mechanism of carbothermal reduction reaction is presented on the basis of TG–DSC. •The electrochemical performances of samples are systematically investigated. -- Abstract: LiFePO{sub 4}/C (LFPC) and LiFe{sub 1−2x}Ti{sub x}PO{sub 4}/C (LFTPC) were prepared by carbothermal reduction method using FePO{sub 4}·2H{sub 2}O as iron source and phenol–formaldehyde resin as reducing agent and carbon source. Different ratios of TiO{sub 2} (IV) with high valence and small radius were applied to dope LiFePO{sub 4} to enhance its electrochemical performances. Results show that LFPC and LFTPC are synthesized successfully by carbothermal reduction method. The optimal carbon content in LFPC is 5 wt.% and its discharge capacity at 0.1 C is 150.8 mA h g{sup −1}. The crystallite structure of LFTPC becomes stable. They possess the smaller particle size compared with LiFePO{sub 4}. LFTPC-2 possesses the best C-rate and cycle performances among all the samples. Its discharge capacities at 0.1 C, 1 C and 3 C are 132.7 mA h g{sup −1}, 98.7 mA h g{sup −1} and 83.1 mA h g{sup −1}. The discharge curve can maintain its stable and flat platform of 3.3 V at 3 C. The electronic conductivity of LFTPC, which is coated with carbon and doped with Ti, can reach ∼10{sup −4} S cm{sup −1}. The charge transfer resistance of LFTPC-2 is 33.68 Ω, which is much lower than that of other samples.

The improvement of boron-doped diamond anode system in electrochemical degradation of p-nitrophenol by zero-valent iron

International Nuclear Information System (INIS)

Zhu Xiuping; Ni Jinren

2011-01-01

Boron-doped diamond (BDD) electrodes are promising anode materials in electrochemical treatment of wastewaters containing bio-refractory organic compounds due to their strong oxidation capability and remarkable corrosion stability. In order to further improve the performance of BDD anode system, electrochemical degradation of p-nitrophenol were initially investigated at the BDD anode in the presence of zero-valent iron (ZVI). The results showed that under acidic condition, the performance of BDD anode system containing zero-valent iron (BDD-ZVI system) could be improved with the joint actions of electrochemical oxidation at the BDD anode (39.1%), Fenton's reaction (28.5%), oxidation–reduction at zero-valent iron (17.8%) and coagulation of iron hydroxides (14.6%). Moreover, it was found that under alkaline condition the performance of BDD-ZVI system was significantly enhanced, mainly due to the accelerated release of Fe(II) ions from ZVI and the enhanced oxidation of Fe(II) ions. The dissolved oxygen concentration was significantly reduced by reduction at the cathode, and consequently zero-valent iron corroded to Fe(II) ions in anaerobic highly alkaline environments. Furthermore, the oxidation of released Fe(II) ions to Fe(III) ions and high-valent iron species (e.g., FeO 2+ , FeO 4 2− ) was enhanced by direct electrochemical oxidation at BDD anode.

Electrochemical thermodynamic measurement system

Science.gov (United States)

Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA

2009-09-29

The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

An accelerated electrochemical MIC test for stainless alloys

International Nuclear Information System (INIS)