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Sample records for electrochemical reductive dehalogenation

  1. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, Flynn William [Univ. of Arizona, Tucson, AZ (United States)

    1992-01-01

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using 14C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  2. Enzymatic Reductive Dehalogenation Controls the Biosynthesis of Marine Bacterial Pyrroles.

    Science.gov (United States)

    El Gamal, Abrahim; Agarwal, Vinayak; Rahman, Imran; Moore, Bradley S

    2016-10-12

    Enzymes capable of performing dehalogenating reactions have attracted tremendous contemporary attention due to their potential application in the bioremediation of anthropogenic polyhalogenated persistent organic pollutants. Nature, in particular the marine environment, is also a prolific source of polyhalogenated organic natural products. The study of the biosynthesis of these natural products has furnished a diverse array of halogenation biocatalysts, but thus far no examples of dehalogenating enzymes have been reported from a secondary metabolic pathway. Here we show that the penultimate step in the biosynthesis of the highly brominated marine bacterial product pentabromopseudilin is catalyzed by an unusual debrominase Bmp8 that utilizes a redox thiol mechanism to remove the C-2 bromine atom of 2,3,4,5-tetrabromopyrrole to facilitate oxidative coupling to 2,4-dibromophenol. To the best of our knowledge, Bmp8 is first example of a dehalogenating enzyme from the established genetic and biochemical context of a natural product biosynthetic pathway.

  3. The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries.

    Science.gov (United States)

    Peijnenburg, W; Eriksson, L; de Groot, A; Sjöström, M; Verboom, H

    1998-01-01

    Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.

  4. Humic substances-mediated microbial reductive dehalogenation of triclosan

    Science.gov (United States)

    Wang, L.; Xu, S.; Yang, Y.

    2015-12-01

    The role of natural organic matter in regulating the redox reactions as an electron shuttle has received lots of attention, because it can significantly affect the environmental degradation of contaminants and biogeochemical cycles of major elements. However, up to date, limited studies examined the role of natural organic matter in affecting the microbial dehalogenation of emergent organohalides, a critical detoxification process. In this study, we investigated the humic substance (HS)-mediated microbial dehalogenation of triclosan, a widely used antimicrobial agent. We found that the presence of HS stimulated the microbial degradation of triclosan by Shewanella putrefaciens CN-32. In the absence of HS, the triclosan was degraded gradually, achieving 8.6% residual at 8 days. With HS, the residual triclosan was below 2% after 4 days. Cl- was confirmed by ion chromatography analysis, but the dehalogenation processes and other byproducts warrant further investigations. The impact of HS on the degradation of triclosan was highly dependent on the concentration of HS. When the HS was below 15 mg/L, the degradation rate constant for triclosan increased with the organic carbon concentration. Beyond that point, the increased organic carbon concentration decreased the degradation of triclosan. Microbially pre-reduced HS abiotically reduced triclosan, testifying the electron shuttling processes. These results indicate that dissolved organic matter plays a dual role in regulating the degradation of triclosan: it mediates electron transport and inhibits the bioavailability through complexation. Such novel organic matter-mediated reactions for organohalides are important for evaluating the natural attenuation of emergent contaminants and designing cost-effective engineering treatment.

  5. Mechanism of Cobalamin-Mediated Reductive Dehalogenation of Chloroethylenes

    DEFF Research Database (Denmark)

    Ji, Li; Wang, Chenchen; Ji, Shujing

    2017-01-01

    uses experimentally calibrated density functional theory on a realistic cobalamin model to resolve controversies of cobalamin-mediated reduction of chloroethylenes by exploring mechanisms of electron transfer, nucleophilic substitution, and nucleophilic addition. The computational results provide......-chlorinated ethylenes mainly react through an inner-spherenucleophilic-addition pathway. Especially, the quantitative comparison of standard reduction potentials between the formed chlorinated-cobalamin and cob(II)alamin/cob(I)alamin couple can be used to distinguish whether the inner-sphere pathway can proceed or not...

  6. The potential for reductive dehalogenation of chlorinated phenol in a ...

    African Journals Online (AJOL)

    2005-04-14

    Apr 14, 2005 ... The transformation of chlorinated aromatic compounds is thermodynamically favourable with sulphate as terminal elec- tron acceptor (Colberg, 1990). This coupled with studies which support the assumption that reductive dechlorinating bacte- ria and SRB often share biotopes that are contaminated with.

  7. Reductive dehalogenation of brominated phenolic compounds by microorganisms associated with the marine sponge Aplysina aerophoba.

    Science.gov (United States)

    Ahn, Young-Beom; Rhee, Sung-Keun; Fennell, Donna E; Kerkhof, Lee J; Hentschel, Ute; Häggblom, Max M

    2003-07-01

    Marine sponges are natural sources of brominated organic compounds, including bromoindoles, bromophenols, and bromopyrroles, that may comprise up to 12% of the sponge dry weight. Aplysina aerophoba sponges harbor large numbers of bacteria that can amount to 40% of the biomass of the animal. We postulated that there might be mechanisms for microbially mediated degradation of these halogenated chemicals within the sponges. The capability of anaerobic microorganisms associated with the marine sponge to transform haloaromatic compounds was tested under different electron-accepting conditions (i.e., denitrifying, sulfidogenic, and methanogenic). We observed dehalogenation activity of sponge-associated microorganisms with various haloaromatics. 2-Bromo-, 3-bromo-, 4-bromo-, 2,6-dibromo-, and 2,4,6-tribromophenol, and 3,5-dibromo-4-hydroxybenzoate were reductively debrominated under methanogenic and sulfidogenic conditions with no activity observed in the presence of nitrate. Monochlorinated phenols were not transformed over a period of 1 year. Debromination of 2,4,6-tribromophenol, and 2,6-dibromophenol to 2-bromophenol was more rapid than the debromination of the monobrominated phenols. Ampicillin and chloramphenicol inhibited activity, suggesting that dehalogenation was mediated by bacteria. Characterization of the debrominating methanogenic consortia by using terminal restriction fragment length polymorphism (TRFLP) and denaturing gradient gel electrophoresis analysis indicated that different 16S ribosomal DNA (rDNA) phylotypes were enriched on the different halogenated substrates. Sponge-associated microorganisms enriched on organobromine compounds had distinct 16S rDNA TRFLP patterns and were most closely related to the delta subgroup of the proteobacteria. The presence of homologous reductive dehalogenase gene motifs in the sponge-associated microorganisms suggested that reductive dehalogenation might be coupled to dehalorespiration.

  8. Reductive dehalogenation of endosulfan by cast iron: Kinetics, pathways and modeling.

    Science.gov (United States)

    Lama, Yangdup; Sinha, Alok; Singh, Gurdeep; Masto, Reginald E

    2016-05-01

    Cast iron has been a material of choice for in-situ remediation of groundwater. In this study interaction of endosulfan with High Carbon Iron Filings (HCIF) was studied in batch reactors. Decline in total concentration (Ct) could be related to aqueous concentration (Ca) by equation dCt/dt = k1.M.Ca(n), where reaction rate constant (k1) and order (n) were found to be 1.246 × 10(-4) L g(-1) iron h(-1) and 1.47, respectively. Partitioning of endosulfan to HCIF could be explained by Freundlich isotherm. The process of simultaneous reductive dehalogenation and adsorption/desorption was successfully modelled. The reductive dehalogenation of endosulfan resulted in by-products identified as [(3a, alpha,7beta,7a alpha,8s)-4,5,6,7,8 Pentachloro 3a,4,7,7a-tetrahydro] (C9H3Cl5O3) and Benzofuran,4,5,7-trichloro-2,3-dihydro-2-methyl (C9H7Cl3O). Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Copper increases reductive dehalogenation of haloacetamides by zero-valent iron in drinking water: Reduction efficiency and integrated toxicity risk.

    Science.gov (United States)

    Chu, Wenhai; Li, Xin; Bond, Tom; Gao, Naiyun; Bin, Xu; Wang, Qiongfang; Ding, Shunke

    2016-12-15

    The haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs), are highly cytotoxic and genotoxic, and typically occur in treated drinking waters at low μg/L concentrations. Since many drinking distribution and storage systems contain unlined cast iron and copper pipes, reactions of HAcAms with zero-valent iron (ZVI) and metallic copper (Cu) may play a role in determining their fate. Moreover, ZVI and/or Cu are potentially effective HAcAm treatment technologies in drinking water supply and storage systems. This study reports that ZVI alone reduces trichloroacetamide (TCAcAm) to sequentially form dichloroacetamide (DCAcAm) and then monochloroacetamide (MCAcAm), whereas Cu alone does not impact HAcAm concentrations. The addition of Cu to ZVI significantly improved the removal of HAcAms, relative to ZVI alone. TCAcAm and their reduction products (DCAcAm and MCAcAm) were all decreased to below detection limits at a molar ratio of ZVI/Cu of 1:1 after 24 h reaction (ZVI/TCAcAm = 0.18 M/5.30 μM). TCAcAm reduction increased with the decreasing pH from 8.0 to 5.0, but values from an integrated toxic risk assessment were minimised at pH 7.0, due to limited removal MCAcAm under weak acid conditions (pH = 5.0 and 6.0). Higher temperatures (40 °C) promoted the reductive dehalogenation of HAcAms. Bromine was preferentially removed over chlorine, thus brominated HAcAms were more easily reduced than chlorinated HAcAms by ZVI/Cu. Although tribromoacetamide was more easily reduced than TCAcAm during ZVI/Cu reduction, treatment of tribromoacetamide resulted in a higher integrated toxicity risk than TCAcAm, due to the formation of monobromoacetamide (MBAcAm). Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Dehalogenimonas lykanthroporepellens gen. nov., sp. nov., a reductively dehalogenating bacterium isolated from chlorinated solvent-contaminated groundwater.

    Science.gov (United States)

    Moe, William M; Yan, Jun; Nobre, M Fernanda; da Costa, Milton S; Rainey, Fred A

    2009-11-01

    Two recently reported bacterial strains that are able to reductively dehalogenate polychlorinated aliphatic alkanes, including 1,2,3-trichloropropane, 1,2-dichloropropane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane and 1,2-dichloroethane, were further characterized to clarify their taxonomic position. The two strains, designated BL-DC-8 and BL-DC-9(T), were mesophilic, non-spore-forming, non-motile, Gram-negative staining and strictly anaerobic. Cells were irregular cocci, 0.3-0.6 mum in diameter. The two strains were resistant to ampicillin and vancomycin. Hydrogen was utilized as an electron donor. The genomic DNA G+C content of strains BL-DC-8 and BL-DC-9(T) was 54.0 and 53.8 mol%, respectively. The major cellular fatty acids were C(18 : 1)omega9c, C(16 : 1)omega9c, C(16 : 0) and C(14 : 0). Phylogenetic analyses based on 16S rRNA gene sequences indicated that the strains cluster within the phylum Chloroflexi, but are related only distantly to all recognized taxa in the phylum. Morphological, physiological and chemotaxonomic traits as well as phylogenetic analysis support the conclusion that these two strains represent a novel species of a new genus in the phylum Chloroflexi, for which the name Dehalogenimonas lykanthroporepellens gen. nov., sp. nov. is proposed. The type strain of Dehalogenimonas lykanthroporepellens is BL-DC-9(T) (=ATCC BAA-1523(T) =JCM 15061(T)).

  11. Genome sequence of Desulfitobacterium hafniense DCB-2, a Gram-positive anaerobe capable of dehalogenation and metal reduction

    Directory of Open Access Journals (Sweden)

    Kim Sang-Hoon

    2012-02-01

    Full Text Available Abstract Background The genome of the Gram-positive, metal-reducing, dehalorespiring Desulfitobacterium hafniense DCB-2 was sequenced in order to gain insights into its metabolic capacities, adaptive physiology, and regulatory machineries, and to compare with that of Desulfitobacterium hafniense Y51, the phylogenetically closest strain among the species with a sequenced genome. Results The genome of Desulfitobacterium hafniense DCB-2 is composed of a 5,279,134-bp circular chromosome with 5,042 predicted genes. Genome content and parallel physiological studies support the cell's ability to fix N2 and CO2, form spores and biofilms, reduce metals, and use a variety of electron acceptors in respiration, including halogenated organic compounds. The genome contained seven reductive dehalogenase genes and four nitrogenase gene homologs but lacked the Nar respiratory nitrate reductase system. The D. hafniense DCB-2 genome contained genes for 43 RNA polymerase sigma factors including 27 sigma-24 subunits, 59 two-component signal transduction systems, and about 730 transporter proteins. In addition, it contained genes for 53 molybdopterin-binding oxidoreductases, 19 flavoprotein paralogs of the fumarate reductase, and many other FAD/FMN-binding oxidoreductases, proving the cell's versatility in both adaptive and reductive capacities. Together with the ability to form spores, the presence of the CO2-fixing Wood-Ljungdahl pathway and the genes associated with oxygen tolerance add flexibility to the cell's options for survival under stress. Conclusions D. hafniense DCB-2's genome contains genes consistent with its abilities for dehalogenation, metal reduction, N2 and CO2 fixation, anaerobic respiration, oxygen tolerance, spore formation, and biofilm formation which make this organism a potential candidate for bioremediation at contaminated sites.

  12. Reductive dehalogenation by layered iron(II)-iron(III) hydroxides and related iron(II) containing solids

    DEFF Research Database (Denmark)

    Yin, Weizhao

    In the present PhD project, novel synthesis and modifications of layered Fe(II)-Fe(III) hydroxides (green rusts, GRs) were investigated with focus on improved dehalogenation of carbon tetrachloride by using modified green rusts and/or altered reaction conditions. The Ph.D. project has comprised: ...

  13. Reactivity of Aryl Halides for Reductive Dehalogenation in (Seawater Using Polymer-Supported Terpyridine Palladium Catalyst

    Directory of Open Access Journals (Sweden)

    Toshimasa Suzuka

    2015-05-01

    Full Text Available A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl; however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

  14. 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

  15. Electrochemical and photoelectrochemical reduction of furfurals

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Kyoung-Shin; Roylance, John James; Kubota, Stephen R.

    2018-02-06

    Electrochemical cells and photoelectrochemical cells for the reduction of furfurals are provided. Also provided are methods of using the cells to carry out the reduction reactions. Using the cells and methods, furfurals can be converted into furan alcohols or linear ketones.

  16. 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

  17. A simple and efficient electrochemical reductive method for ...

    Indian Academy of Sciences (India)

    The electrochemical reduction of graphene oxide typically involves complicated procedures, such as modification of electrodes and preparation of electrolytes, which is often needed in previous reports. In this paper, a simple and efficient electrochemical process is described for the synthesis of high-quality reduced ...

  18. Influence of temperature and voltage on electrochemical reduction ...

    Indian Academy of Sciences (India)

    Administrator

    increases from 0⋅1 to 12⋅5 V, the reduction degree of graphene oxide increases gradually. However, above. 2⋅5 V, increasing voltage has little effect on the reduction degree of graphene oxide. Keywords. Graphene oxide; electrochemical reduction; voltage; temperature. 1. Introduction. Graphene, a single atomic layer of ...

  19. Dehalogenation of halogenated aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Griller, D.; Hawari, J.A.; McPhee, D.J.

    1992-03-03

    A process is disclosed for dehalogenating aromatic halogenated compounds, comprising reacting an alkali metal with the halogenated aromatic material in the presence of a liquid hydrosiloxane until substantially all of the halogen has reacted, leaving the aromatic moiety in non-halogenated form. Preferably a non-halogenated non-aqueous polar solvent or diluent is present during the reaction. The excess alkali metal can be reacted with added termination agent, and excess hydrosiloxane can be precipitated and the solids separated. According to a further aspect of the invention, a kit is provided for carrying out the above dehalogenation process. The kit comprises a container containing alkali metal, a container containing liquid hydrosiloxane, or one container containing both the alkali metal and the hydrosiloxane. The starting material to be dehalogenated, in most applications of the process, will be polychlorinated biphenyls alone or as mixtures with various oils such as transformer oils. The alkali metal may be Li, Na, or K, and the hydrosiloxane should be a liquid miscible with the starting material, preferably a polyorganohydrosiloxane of relatively low molecular weight. Experiments are described to illustrate the process of the invention. It is shown that the process of the invention provides significantly improved dehalogenations at ambient temperatures and may be used for destruction of polychlorinated biphenyls to the point where they can no longer be detected by gas chromatography.

  20. A simple and efficient electrochemical reductive method for ...

    Indian Academy of Sciences (India)

    Administrator

    graphene oxide. The main procedures involve the electrophoretic deposition of graphene oxide onto positive electrode and the subsequent in situ electrochemical negative reduction when the electrode changes from positive to negative. This approach opens up a new, practical and green reducing method to prepare large-.

  1. 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

  2. Influence of temperature and voltage on electrochemical reduction ...

    Indian Academy of Sciences (India)

    Administrator

    629. Influence of temperature and voltage on electrochemical reduction of graphene oxide. XIUQIANG LI, DONG ZHANG*, PEIYING ZHU and CHAO YANG. Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, College of Materials Science and Engineering, Tongji University, 4800 CaoAn Road, ...

  3. 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

  4. Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz Montoya, Mercedes, E-mail: mmontoya@uhu.e [Departamento de Ingenieria Quimica, Quimica Fisica y Quimica Organica, Universidad de Huelva, Campus El Carmen, Facultad de Ciencias Experimentales, E-21071 Huelva (Spain); Pintado, Sara; Rodriguez Mellado, Jose Miguel [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' , E-14014 Cordoba (Spain)

    2010-03-30

    This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H{sub 2}SO{sub 4}) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH < pK{sub a}), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK{sub a} the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.

  5. Electrochemical reduction of NOx

    DEFF Research Database (Denmark)

    Traulsen, Marie Lund

    NO and NO2 (collectively referred to as NOx) are air pollutants, and the largest single contributor to NOx pollution is automotive exhaust. This study investigates electrochemical deNOx, a technology which aims to remove NOx from automotive diesel exhaust by electrochemical reduction of NOx to N2...... and O2. The focus in this study is on improving the activity and selectivity of solid oxide electrodes for electrochemical deNOx by addition of NOx storage compounds to the electrodes. Two different composite electrodes, La0.85Sr0.15MnO3-δ-Ce0.9Gd0.1O1.95 (LSM15-CGO10) and La0.85Sr0.15FeO3-δ-Ce0.9Gd0.1O...

  6. Microfluidic platform for studying the electrochemical reduction of carbon dioxide

    Science.gov (United States)

    Whipple, Devin Talmage

    Diminishing supplies of conventional energy sources and growing concern over greenhouse gas emissions present significant challenges to supplying the world's rapidly increasing demand for energy. The electrochemical reduction of carbon dioxide has the potential to address many of these issues by providing a means of storing electricity in chemical form. Storing electrical energy as chemicals is beneficial for leveling the output of clean, but intermittent renewable energy sources such as wind and solar. Electrical energy stored as chemicals can also be used as carbon neutral fuels for portable applications allowing petroleum derived fuels in the transportation sector to be replaced by more environmentally friendly energy sources. However, to be a viable technology, the electrochemical reduction of carbon dioxide needs to have both high current densities and energetic efficiencies (Chapter 1). Although many researchers have studied the electrochemical reduction of CO2 including parameters such as catalysts, electrolytes and temperature, further investigation is needed to improve the understanding of this process and optimize the performance (Chapter 2). This dissertation reports the development and validation of a microfluidic reactor for the electrochemical reduction of CO2 (Chapter 3). The design uses a flowing liquid electrolyte instead of the typical polymer electrolyte membrane. In addition to other benefits, this flowing electrolyte gives the reactor great flexibility, allowing independent analysis of each electrode and the testing of a wide variety of conditions. In this work, the microfluidic reactor has been used in the following areas: • Comparison of different metal catalysts for the reduction of CO2 to formic acid and carbon monoxide (Chapter 4). • Investigation of the effects of the electrolyte pH on the reduction of CO2 to formic acid and carbon monoxide (Chapter 5). • Study of amine based electrolytes for lowering the overpotentials for CO2

  7. CO2 Reduction: From the Electrochemical to Photochemical Approach

    OpenAIRE

    Wu, Jinghua; Huang, Yang; Ye, Wen; Li, Yanguang

    2017-01-01

    Abstract Increasing CO2 concentration in the atmosphere is believed to have a profound impact on the global climate. To reverse the impact would necessitate not only curbing the reliance on fossil fuels but also developing effective strategies capture and utilize CO2 from the atmosphere. Among several available strategies, CO2 reduction via the electrochemical or photochemical approach is particularly attractive since the required energy input can be potentially supplied from renewable source...

  8. Electrochemical Reduction of solid UO2 in Molten Fluoride Salts

    International Nuclear Information System (INIS)

    Gibilaro, Mathieu; Cassayre, Laurent; Massot, Laurent; Chamelot, Pierre; Malmbeck, Rikard; Dugne, Olivier; Allegri, Patrick

    2010-01-01

    The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+ 2wt % Li 2 O) at 850 deg. C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, reduction of oxide ions yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets have been performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to its direct reduction have been observed at a potential 150 mV more positive in comparison with the solvent reduction. Then, galvano-static electrolyses runs have been realised and products were characterised by SEM-EDX, EPMA/WDS and XRD. In one of the runs, uranium oxide was partially reduced and three phases were observed: non reduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides. (authors)

  9. 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.

  10. 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.

  11. Electrochemical reduction of /Ru edta L/ compounds in aqueous solution

    International Nuclear Information System (INIS)

    Fernandes, J.R.; Santos, A.A.; Oliveira, L.A.A.; Benedetti, A.V.

    1988-01-01

    Electrochemical reduction of the complexes [Ru edta L], [L= 2,2' bipyridine (2,2' bipy) pyrazinamide (pz CONH 2 ); 4-cyanopyridine 4-cyanopyridine (4-CNpy); nicotinamide (NIC); hydroxil; 3-aminophenol (3-NH 2 φ OH) and 2-aminopyridine (2-NH 2 py)] in aqueous solution (acetate buffer, pH 4.65 or phosphate buffer, pH=8.2), μ=0,2 M p-cH 3 φSO 3 Li is investigated. The measurements have been made by cyclic voltammetry technique, using platinum, gold and mercury pool as working electrodes. (M.J.C.) [pt

  12. Gold(III) diazonium complexes for electrochemical reductive grafting.

    Science.gov (United States)

    Overton, Atiya T; Mohamed, Ahmed A

    2012-05-21

    Gold(III) diazonium complexes were synthesized for the first time and studied for electrochemical reductive grafting. The diazonium complex [CN-4-C(6)H(4)N≡N]AuCl(4) was synthesized by protonating CN-4-C(6)H(4)NH(2) with chloroauric acid H[AuCl(4)]·3H(2)O to form the ammonium salt [CN-4-C(6)H(4)NH(3)]AuCl(4), which was then oxidized by the one-electron oxidizing agent [NO]PF(6) in CH(3)CN. The highly irreversible reduction potential of 0.1 mM [CN-4-C(6)H(4)N≡N]AuCl(4) observed at -0.06 V versus Ag/AgCl in CH(3)CN/0.1 M [Bu(4)N]PF(6) encompasses both gold(0) deposition and diazonium reduction. Repeated scans showed the absence of the reduction peak on the second run, which indicates that surface modification with a blocking gold aryl film has occurred and is largely complete.

  13. Electrochemical processing of spent nuclear fuels: An overview of oxide reduction in pyroprocessing technology

    Directory of Open Access Journals (Sweden)

    Eun-Young Choi

    2015-12-01

    Full Text Available The electrochemical reduction process has been used to reduce spent oxide fuel to a metallic form using pyroprocessing technology for a closed fuel cycle in combination with a metal-fuel fast reactor. In the electrochemical reduction process, oxides fuels are loaded at the cathode basket in molten Li2O–LiCl salt and electrochemically reduced to the metal form. Various approaches based on thermodynamic calculations and experimental studies have been used to understand the electrode reaction and efficiently treat spent fuels. The factors that affect the speed of the electrochemical reduction have been determined to optimize the process and scale-up the electrolysis cell. In addition, demonstrations of the integrated series of processes (electrorefining and salt distillation with the electrochemical reduction have been conducted to realize the oxide fuel cycle. This overview provides insight into the current status of and issues related to the electrochemical processing of spent nuclear fuels.

  14. Dehalogenation of aromatic halides by polyaniline/zero-valent iron composite nanofiber: Kinetics and mechanisms

    CSIR Research Space (South Africa)

    Giri, S

    2016-03-01

    Full Text Available was characterized by various physico-chemical techniques: ATR-FTIR, FE-SEM, HR-TEM, XRD, XPS and VSM. A mild reductive dehalogenation process of a wide range of aromatic bromides was explored in the presence of PANI/Fe0 catalyst. The catalyst was active...

  15. Simple colorimetric assay for dehalogenation reactivity of nanoscale zero-valent iron using 4-chlorophenol

    DEFF Research Database (Denmark)

    Hwang, Yuhoon; Mines, Paul D.; Jakobsen, Mogens Havsteen

    2015-01-01

    Despite the wide application of nanoscale zero valent iron (nZVI) for the treatment of a plethora of pollutants through reductive reactions, reactivity evaluation of nZVI towards dehalogenation has not been standardized. In this light, it was desired to develop a simple colorimetric assay, for ve...

  16. Electrochemical reduction of nitrous oxide on La1-xSrxFeO3 perovskites

    DEFF Research Database (Denmark)

    Kammer Hansen, Kent

    2010-01-01

    The electrochemical reduction of nitrous oxide and oxygen has been studied on cone-shaped electrodes of La1-xSrxFeO3-delta perovskites in an all solid state cell, using cyclic voltammetry. It was shown that the activity of the La1-xSrxFeO3-delta perovskites for the electrochemical reduction...... of nitrous oxide mainly depends on the amount of Fe(III) and oxide ion vacancies. The activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of nitrous oxide is much lower than the activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of oxygen......, making the possibility of electrochemically reducing nitrous oxide selectively in an exhaust gas containing excess oxygen on this type of materials very doubtful....

  17. 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.

  18. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    Science.gov (United States)

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-04-26

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  19. Electrochemical reduction of carbon dioxide at copper - modified nickel electrode in water + methanol

    OpenAIRE

    Sakaguchi, Y; Kaneco, S; Katsumata, H; Suzuki, T; Ohta, K

    2005-01-01

    In the electrochemical reduction of carbon dioxide, in water, at most metal electrodes the major reaction products were carbon monoxide and formic acid. However, only copper has proven a suitable electrode for the formation of hydrocarbons such as methane and ethylene, which can be used as fuel gases. Recently, many investigators have actively studied the electrochemical reduction of carbon dioxide using various metal electrodes in organic solvents, given that organic aprotic solvents dissolv...

  20. Electrochemical reduction of graphene oxide in electrically conducting poly(3,4-ethylenedioxythiophene) composite films

    International Nuclear Information System (INIS)

    Lindfors, Tom; Österholm, Anna; Kauppila, Jussi; Pesonen, Markus

    2013-01-01

    Here we show that the graphene oxide (GO) can be electrochemically reduced in composite films of poly(3,4-ethylenedioxythiophene) (PEDOT) and GO. EDOT was electropolymerized in an aqueous GO dispersion at a constant potential resulting in the incorporation of GO in the PEDOT matrix. Scanning electron microscopy (SEM) images revealed that the formed PEDOT–GO films had a layered structure. X-ray photoelectron spectra measured after 10, 20 and 30 min of electrochemical reduction at −0.85 V, verified that the reduction efficiently removed the epoxy and hydroxyl groups from the GO surface. The number of oxygen-containing functional groups decreased considerably already after 10 min of electrochemical reduction and the C:O ratio of the composite films increased with increasing reduction time confirming that GO was successfully reduced in the polymer matrix. In contrast to chemical reduction in 0.15 M NaBH 4 , we show that the PEDOT matrix withstands the electrochemical reduction without any degradation in electroactivity. We also studied the effect of pH of the GO dispersion on the subsequent redox behavior of the PEDOT–GO films. Increasing the pH from 2.5 to 4.5 improved the electroactivity of the films and also facilitated film formation probably due to the presence of a higher amount of ionized carboxylic groups on the GO surface. Electrochemical impedance measurements showed that increasing the pH of the GO dispersion resulted in films with a higher redox capacitance. Atomic force microscopy measurements revealed that the electrochemical reduction slightly increased the surface roughness of the composite films. The simple and fully electrochemical synthesis and reduction procedure of the PEDOT–GO films are expected to be useful in the fabrication of interfacial materials for electrochemical all-solid-state devices where it is desirable to have reversible ion-to-electron transduction in combination with high redox capacitance

  1. A comparative study of electrochemical reduction of isatin and its ...

    Indian Academy of Sciences (India)

    Administrator

    search, Princeton, USA) with Power suite software was used for all electrochemical experiments. The working electrode was a Static Mercury Drop Elec- ..... 16. Nicholson R S and Shain I 1964 Anal. Chem. 36. 706. 17. Brett C M A, Oliveira Brett A M 1993 Electroche- mistry: Principles, methods and applications (Ox-.

  2. 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

  3. 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.

  4. 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.

  5. 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...... in current diesel after-treatment techniques. The electrochemical system consisted of an electrochemical cell modified with NOx adsorbents and a diesel oxidation catalyst placed upstream of the cell. The system offers highly selective NOx reduction and a strong resistance to oxygen interference with almost...

  6. 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

    2013-09-24

    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.

  7. Transition metal-depleted graphenes for electrochemical applications via reduction of CO₂ by lithium.

    Science.gov (United States)

    Poh, Hwee Ling; Sofer, Zdenek; Luxa, Jan; Pumera, Martin

    2014-04-24

    Graphene has immense potential for future applications in the electrochemical field, such as in supercapacitors, fuel cells, batteries, or sensors. Graphene materials for such applications are typically fabricated through a top-down approach towards oxidation of graphite to graphite oxide, with consequent exfoliation/reduction to yield reduced graphenes. Such a method allows the manufacture of graphenes in gram/kilogram quantities. However, graphenes prepared by this method can contain residual metallic impurities from graphite which dominate the electrochemical properties of the graphene formed. This dominance hampers their electrochemical application. The fabrication of transition metal-depleted graphene is described, using ultrapure CO₂ (with benefits of low cost and easy availability) and elemental lithium by means of reduction of CO₂ to graphene. This preparation method produces graphene of high purity with electrochemical behavior that is not dominated by any residual transition metal impurities which would dramatically alter its electrochemical properties. Wide application of such methodology in industry and research laboratories is foreseen, especially where graphene is used for electrochemical devices. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A comparative study of electrochemical reduction of isatin and its ...

    Indian Academy of Sciences (India)

    Administrator

    0⋅1 M LiCl using cyclic voltammetry at Hanging Mercury Drop Electrode. All synthesized Schiff bases ex- hibit a single irreversible two-electron reduction wave in contrast with the two discrete one-electron transfer reduction waves observed for isatin in this medium. Observation of a well-developed single re- duction wave ...

  9. 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

  10. Electrochemical reduction of hydrogen peroxide on stainless steel

    Indian Academy of Sciences (India)

    Administrator

    has two segments suggesting a change in the mechanism of H2O2 reduction at concentrations of H2O2 ≥. 2 mM. From the rotating disc electrode ... tion of H2O2 in acidic electrolyte.7 Somasundrum et al8 studied H2O2 reduction on Cu .... sweep at –0⋅7 V, no oxidation current peak is observed. The appearance of an ...

  11. Electrochemical reduction of hydrogen peroxide on stainless steel

    Indian Academy of Sciences (India)

    Administrator

    commercial 304 grade stainless steel (SS) foil. (thickness: 0⋅2 mm) was used as the substrate for. H2O2 reduction. A solution of 0⋅5 M NaClO4. (pH = 5⋅8) was .... oxide layers, unlike mediation of the reduction by. CuO present on Cu. A mechanism involving decomposition (or dis- proportionation) of H2O2 leading to the ...

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

    DEFF Research Database (Denmark)

    Kammer Hansen, Kent

    2008-01-01

    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......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...... at 400 degrees C. As a general trend it was observed that the activity of the materials towards the reduction of oxygen increases more than the activity of the materials towards the reduction of nitric oxide with increasing temperature. The Ni wire was covered with a layer of NiO. The NiO layer inhibits...

  13. Influence of structure on electrochemical reduction of isomeric mono- and di-, nitro- or nitrosocalix[4]arenes

    Czech Academy of Sciences Publication Activity Database

    Liška, Alan; Flídrová, K.; Lhoták, P.; Ludvík, Jiří

    2015-01-01

    Roč. 146, č. 5 (2015), s. 857-862 ISSN 0026-9247 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : Electrochemical reduction * Nitrocalix[4]arenes * Nitrosocalix[4]arenes Subject RIV: CG - Electrochemistry Impact factor: 1.131, year: 2015

  14. Electrochemical reduction of the UCL4 to UCL3 on aqueous solution

    International Nuclear Information System (INIS)

    Ordonez, E.; Quiroz, H.; Fernandez-Valverde, S.; Solorza, O.

    1991-01-01

    An electrochemical study of the UCL4 to UCL3 reduction reaction on lead electrodes is presented. Up to 95% conversion is obtained using a divided cell with Nafion membrane as separator. The variation of UCL4 and UCL3 concentrations was monitored by visible spectrophotometry. (author)

  15. 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.

  16. 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)

  17. 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)

  18. 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.

  19. 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

  20. Detection and characterization of a dehalogenating microorganism by terminal restriction fragment length polymorphism fingerprinting of 16S rRNA in a sulfidogenic, 2-bromophenol-utilizing enrichment.

    Science.gov (United States)

    Fennell, Donna E; Rhee, Sung-Keun; Ahn, Young-Beom; Häggblom, Max M; Kerkhof, Lee J

    2004-02-01

    Terminal restriction fragment length polymorphism analysis of reverse-transcribed 16S rRNA during periods of community flux was used as a tool to delineate the roles of the members of a 2-bromophenol-degrading, sulfate-reducing consortium. Starved, washed cultures were amended with 2-bromophenol plus sulfate, 2-bromophenol plus hydrogen, phenol plus sulfate, or phenol with no electron acceptor and were monitored for substrate use. In the presence of sulfate, 2-bromophenol and phenol were completely degraded. In the absence of sulfate, 2-bromophenol was dehalogenated and phenol accumulated. Direct terminal restriction fragment length polymorphism fingerprinting of the 16S rRNA in the various subcultures indicated that phylotype 2BP-48 (a Desulfovibrio-like sequence) was responsible for the dehalogenation of 2-bromophenol. A stable coculture was established which contained predominantly 2BP-48 and a second Desulfovibrio-like bacterium (designated BP212 based on terminal restriction fragment length polymorphism fingerprinting) that was capable of dehalogenating 2-bromophenol to phenol. Strain 2BP-48 in the coculture could couple reductive dehalogenation to growth with 2-bromophenol, 2,6-dibromophenol, or 2-iodophenol and lactate or formate as the electron donor. In addition to halophenols, strain 2BP-48 appears to use sulfate, sulfite, and thiosulfate as electron acceptors and is capable of simultaneous sulfidogenesis and reductive dehalogenation in the presence of sulfate.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen Yanxin; Chen Shengpei; Chen Qingsong; Zhou Zhiyou [State Key Lab of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Sun Shigang [State Key Lab of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)], E-mail: sgsun@xmu.edu.cn

    2008-10-01

    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.

  2. 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

  3. Electrochemical surface derivation of glassy carbon by the reduction of triaryl- and alkyldiphenylsulfonium salts

    DEFF Research Database (Denmark)

    Vase, K.H.; Holm, A.H.; Norrman, Kion

    2008-01-01

    The range of materials susceptible to electrochemically assisted grafting onto carbon materials has been expanded to include a new group of compounds. This new approach is based on the reduction of symmetrical or unsymmetrical triarylsulfonium salts and alkyldiphenylsulfonium salts. Our findings......, the alkyldiphenylsulfonium salts are found to cleave almost exclusively to an alkyl radical and diphenyl sulfide. As judged from the electrochemical blocking properties of the films made from such species, either relatively thick or compact films are formed. The mass spectrometric analysis indicates that the films are made...... of a combination of alkyl and aryl groups and possibly related structural derivatives. Importantly, our findings provide evidence that it is possible to graft electrode surfaces with reactive aryl radicals even using precursors reduced at potentials that are substantially more negative than the estimated reduction...

  4. Electrochemical reduction of trinitrotoluene on core-shell tin-carbon electrodes

    International Nuclear Information System (INIS)

    Grigoriants, Irena; Markovsky, Boris; Persky, Rachel; Perelshtein, Ilana; Gedanken, Aharon; Aurbach, Doron; Filanovsky, Boris; Bourenko, Tatiana; Felner, Israel

    2008-01-01

    In this work, we studied the electrochemical process of 2,4,6-trinitrotoluene (TNT) reduction on a new type of electrodes based on a core-shell tin-carbon Sn(C) structure. The Sn(C) composite was prepared from the precursor tetramethyl-tin Sn(CH 3 ) 4 , and the product contained a core of submicron-sized tin particles uniformly enveloped with carbon shells. Cyclic voltammograms of Sn(C) electrodes in aqueous sodium chloride solutions containing TNT show three well-pronounced reduction waves in the potential range of -0.50 to -0.80 V (vs. an Ag/AgCl/Cl - reference electrode) that correspond to the multistep process of TNT reduction. Electrodes containing Sn(C) particles annealed at 800 deg. C under argon develop higher voltammetric currents of TNT reduction (comparing to the as-prepared tin-carbon material) due to stabilization of the carbon shell. It is suggested that the reduction of TNT on core-shell tin-carbon electrodes is an electrochemically irreversible process. A partial oxidation of the TNT reduction products occurred at around -0.20 V. The electrochemical response of TNT reduction shows that it is not controlled by the diffusion of the active species to/from the electrodes but rather by interfacial charge transfer and possible adsorption phenomena. The tin-carbon electrodes demonstrate significantly stable behavior for TNT reduction in NaCl solutions and provide sufficient reproducibility with no surface fouling through prolonged voltammetric cycling. It is presumed that tin nanoparticles, which constitute the core, are electrochemically inactive towards TNT reduction, but Sn or SnO 2 formed on the electrodes during TNT reduction may participate in this reaction as catalysts or carbon-modifying agents. The nitro-groups of TNT can be reduced irreversibly (via two possible paths) by three six-electron transfers, to 2,4,6-triaminotoluene, as follows from mass-spectrometric studies. The tin-carbon electrodes described herein may serve as amperometric sensors

  5. 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

    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 the l...

  6. 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...

  7. 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.

  8. 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.

  9. Electrochemical modification of gold electrodes with azobenzene derivatives by diazonium reduction.

    Science.gov (United States)

    Kibena, Elo; Marandi, Margus; Mäeorg, Uno; Venarusso, Luna B; Maia, Gilberto; Matisen, Leonard; Kasikov, Aarne; Sammelselg, Väino; Tammeveski, Kaido

    2013-04-02

    An electrochemical study of Au electrodes electrografted with azobenzene (AB), Fast Garnet GBC (GBC) and Fast Black K (FBK) diazonium compounds is presented. Electrochemical quartz crystal microbalance, ellipsometry and atomic force microscopy investigations reveal the formation of multilayer films. The elemental composition of the aryl layers is examined by X-ray photoelectron spectroscopy. The electrochemical measurements reveal a quasi-reversible voltammogram of the Fe(CN)6 (3-/4-) redox couple on bare Au and a sigmoidal shape for the GBC- and FBK-modified Au electrodes, thus demonstrating that electron transfer is blocked due to the surface modification. The electrografted AB layer results in strongest inhibition of the Fe(CN)6 (3-/4-) response compared with other aryl layers. The same tendencies are observed for oxygen reduction; however, the blocking effect is not as strong as in the Fe(CN)6 (3-/4-) redox system. The electrochemical impedance spectroscopy measurements allowed the calculation of low charge-transfer rates to the Fe(CN)6 (3-) probe for the GBC- and FBK-modified Au electrodes in relation to bare Au. From these measurements it can be concluded that the FBK film is less compact or presents more pinholes than the electrografted GBC layer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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

  11. Investigations on the Electrochemical Reduction Behaviors of Cu-Se Compound in Sulfuric Acid Solutions

    Science.gov (United States)

    Li, Yuan-yuan; Yang, Meng-qian; Yang, Wei-fang; Liu, Xiao-qing; Shen, Zheng-wu; Yi, Yun; Wang, Wei

    2017-05-01

    The electrochemical reduction behaviors of a Cu unitary system, Se unitary system and Cu-Se binary system were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy in solutions containing H2SO4, K2SO4, CuSO4 (Cu unitary system) or H2SeO3 (Se unitary system) or both CuSO4 and H2SeO3 (Cu-Se binary system). The effects of CuSO4 concentration, H2SeO3 concentration, H2SO4 concentration and K2SO4 concentration were also considered. In the Cu unitary system, the electrochemical reduction of Cu2+ to Cu0 experiences a two-step reaction process. Cu2+ in the solutions was first reduced to Cu+ and then to Cu0 on the surface of the electrode. A four-step electrochemical reduction process takes place in the Se unitary system. Se4+ existing in the form of H2SeO3 is first reduced to Se2+ by a two-electron reaction step and then to Se0 at a more negative potential. With the potential moving negatively, the electrodeposited Se0 on the surface of the electrode is further reduced to Se2-. There is also a chemical reaction taking place between the reduced Se2- and H2SeO3 existing in the solution to form Se0. In the Cu-Se binary system, there are three major processes taking place which form CuSe, Cu3Se2 and Cu2Se. X-ray diffraction and energy-dispersive spectroscopy were used in combination to verify their formation.

  12. Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

    Science.gov (United States)

    Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

    2011-07-01

    The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

  13. Efficient degradation of tetrabromobisphenol A via electrochemical sequential reduction-oxidation: Degradation efficiency, intermediates, and pathway.

    Science.gov (United States)

    Hou, Yanping; Peng, Zhenbo; Wang, Li; Yu, Zebin; Huang, Lirong; Sun, Lingfang; Huang, Jun

    2018-02-05

    Tetrabromobisphenol A (TBBPA), a toxic persistent pollutant, should be effectively removed from the environment. In this study, an electrochemical sequential reduction-oxidation system was proposed by controlling reaction atmosphere with Pd-Fe nanoparticles modified Ni foam (Pd-Fe/Ni) electrode as cathode for TBBPA degradation. To obtain an efficient Pd-Fe/Ni electrode for TBBPA degradation, various factors, like Pd loading, Fe 2+ adding amounts, were examined. The Pd-Fe/Ni electrode exhibited higher TBBPA conversion and debromination than the counterparts, due to the synergism of Fe 0 and electrochemical reduction. Similar TBBPA conversions and debromination ratios were observed for the cases of sparging N 2 only and sparging N 2 followed by air, which were higher than those of aeration. Reductive debromination occurred while first bubbling N 2 , forming tri-BBPA, di-BBPA, mono-BBPA and BPA; and these intermediates were likely to be further oxidized by OH generated from H 2 O 2 together with Pd-Fe/Ni electrode under aeration. Reductive and oxidative intermediates (including aromatic ring-opened product) were identified by HPLC and UPLC-QTOF-MS. Based on the intermediates, the possible TBBPA degradation mechanism and pathway were proposed. This study demonstrates that sequential reduction-oxidation process tuned by N 2 and air bubbling was favored for TBBPA degradation, thus, it should be a promising process for HOCs degradation. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. 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

  15. Electrochemical Reduction of Carbon Dioxide on Pyrite as a Pathway for Abiogenic Formation of Organic Molecules

    Science.gov (United States)

    Vladimirov, M. G.; Ryzhkov, Y. F.; Alekseev, V. A.; Bogdanovskaya, V. A.; Otroshchenko, V. A.; Kritsky, M. S.

    2004-08-01

    A wide spectrum of electrode potentials of minerals that compose sulfide ores enables the latter, when in contact with hydrothermal solutions, to form galvanic pairs with cathode potentials sufficient for electrochemical reduction of CO2. The experiments performed demonstrated the increase of cathode current on the rotating pyrite disc electrode in a range of potentials more negative than -800 mV in presence of CO2. In high-pressure experiments performed in a specially designed electrochemical cell equipped with a pyrite cathode and placed into autoclave, accumulation of formate was demonstrated after 24 hr passing of CO2 (50 atm, room temperature) through electrolyte solution. The formation of this product started on increasing the cathode potential to -800 mV (with respect to saturated silver chloride electrode). The yield grew exponentially upon cathode potential increase up to -1200 mV. The maximum current efficiency (0.12%) was registered at cathode potentials of about -1000 mV. No formate production was registered under normal atmospheric pressure and in the absence of imposed cathode potential. Neither in experiments, nor in control was formaldehyde found. It is proposed that the electrochemical reduction of CO2 takes part in the formation of organic molecules in hydrothermal solutions accompanying sulfide ore deposits and in `black smokers' on the ocean floor.

  16. 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.

  17. Preparation of Ferrotitanium Alloy from Ilmenite by Electrochemical Reduction in Chloride Molten Salts

    Science.gov (United States)

    Qi, Can-can; Hua, Yi-xin; Chen, Kong-hao; Jie, Ya-fei; Zhou, Zhong-ren; Ru, Juan-jian; Xiong, Li; Gong, Kai

    2016-02-01

    Ferrotitanium alloy is prepared by electrochemical reduction from ilmenite in LiCl-KCl and LiCl-KCl-CaCl2 molten salts, respectively. The products prepared are observed by x-ray diffraction (XRD). It is shown that Fe2Ti can be prepared from ilmenite in LiCl-KCl molten salt at 1073 K with a cell voltage of 3.2 V. Ilmenite can be electrochemically reduced to FeTi in LiCl-KCl-CaCl2 molten salt under the same condition. It is indicated that CaCl2 can promote the reaction and is favors the deoxidization of the FeTiO3.

  18. Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

    Science.gov (United States)

    Yang, Hong Bin; Hung, Sung-Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin-Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

    2018-02-01

    Electrochemical reduction of CO2 to chemical fuel offers a promising strategy for managing the global carbon balance, but presents challenges for chemistry due to the lack of effective electrocatalyst. Here we report atomically dispersed nickel on nitrogenated graphene as an efficient and durable electrocatalyst for CO2 reduction. Based on operando X-ray absorption and photoelectron spectroscopy measurements, the monovalent Ni(i) atomic center with a d9 electronic configuration was identified as the catalytically active site. The single-Ni-atom catalyst exhibits high intrinsic CO2 reduction activity, reaching a specific current of 350 A gcatalyst-1 and turnover frequency of 14,800 h-1 at a mild overpotential of 0.61 V for CO conversion with 97% Faradaic efficiency. The catalyst maintained 98% of its initial activity after 100 h of continuous reaction at CO formation current densities as high as 22 mA cm-2.

  19. Electrochemical promotion of catalysis over Pd nanoparticles for CO2reduction.

    Science.gov (United States)

    Cai, Fan; Gao, Dunfeng; Zhou, Hu; Wang, Guoxiong; He, Ting; Gong, Huimin; Miao, Shu; Yang, Fan; Wang, Jianguo; Bao, Xinhe

    2017-04-01

    Electrochemical promotion of catalysis (EPOC) has been shown to accelerate the rate of many heterogeneous catalytic reactions; however, it has rarely been reported in low-temperature aqueous electrochemical reactions. Herein, we report a significant EPOC effect for the CO 2 reduction to generate formate over Pd nanoparticles (NPs) in a 1 M KHCO 3 aqueous solution. By applying a negative potential over differently-sized Pd NPs, the rate of formate production is greatly improved as compared to that at an open-circuit voltage, with a rate enhancement ratio ranging from 10 to 143. The thermocatalytic and electrocatalytic reduction of CO 2 compete with each other and are promoted by the applied negative potential and H 2 in the feeds, respectively. Inspired by the EPOC effect, a composite electrode containing Pd/C and Pt/C catalysts on different sides of a carbon paper was constructed for catalyzing the CO 2 reduction without adding H 2 to the feeds. Water electrolysis over Pt NPs generates H 2 , which then effectively promotes formate production over Pd NPs.

  20. 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...... 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...

  1. Enhanced electrochemical reduction of hydrogen peroxide on silver paste electrodes modified with surfactant and salt

    OpenAIRE

    Gonzalez-Macia, L.; Smyth, M.; Morrin, A.; Killard, A.

    2011-01-01

    The modification of silver paste electrodes with a combination of dodecyl benzenesulphonic acid and KCl has been shown to lead to significant enhancements of the electrochemical reduction of hydrogen peroxide. The catalytic enhancement was shown to be dependent on the concentration of the surfactant/salt solution, which resulted in increases of some 80-fold in amperometric response to hydrogen peroxide at – 0.1 V vs. Ag/AgCl, pH 6.8 over unmodified silver paste. Physical analysis showed modif...

  2. 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.

  3. 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.

  4. 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.

  5. Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO2.

    Science.gov (United States)

    Apaydin, Dogukan Hazar; Schlager, Stefanie; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

    2017-11-17

    A broad review of homogeneous and heterogeneous catalytic approaches toward CO 2 reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobilization on electrodes is discussed and compared to homogeneous catalysts in solution. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. 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.

  7. Efficient Electrochemical Reduction of Carbon Dioxide to Acetate on Nitrogen-Doped Nanodiamond.

    Science.gov (United States)

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

    2015-09-16

    Electrochemical reduction of CO2 is an attractive technique for reducing CO2 emission and converting it into useful chemicals, but it suffers from high overpotential, low efficiency or poor product selectivity. Here, N-doped nanodiamond/Si rod array (NDD/Si RA) was proposed as an efficient nonmetallic electrocatalyst for CO2 reduction. It preferentially and rapidly converted CO2 to acetate over formate with an onset potential of -0.36 V (vs RHE), overcoming the usual limitation of low selectivity for C2 products. Moreover, faradic efficiency of 91.2-91.8% has been achieved for CO2 reduction at -0.8 to -1.0 V. Its superior performance for CO2 reduction can be attributed to its high overpotential for hydrogen evolution and N doping, where N-sp(3)C species was highly active for CO2 reduction. Electrokinetic data and in situ infrared spectrum revealed the main pathway for CO2 reduction might be CO2 → CO2(•-) → (COO)2(•) → CH3COO(-).

  8. 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.

  9. Reductieve dehalogenering van heterocyclische verbindingen, relatie tussen structuur en omzettingssnelheid

    NARCIS (Netherlands)

    de Beer KGM; Peijnenburg WJGM; Verboom JH

    1992-01-01

    A relationship was derived between the structure of halogenated heterocyclic aromatic compounds and their rate of dehalogenation in anaerobic sediment-water mixtures. Of all compounds selected, the pseudo-first order reaction rate constant was determined from the concentration-time profile, as

  10. 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.

  11. 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.

  12. Study on the Effect of Electrochemical Dechlorination Reduction of Hexachlorobenzene Using Different Cathodes

    Directory of Open Access Journals (Sweden)

    Yingru Wang

    2014-01-01

    Full Text Available Hexachlorobenzene (HCB is a persistent organic pollutant and poses great threat on ecosystem and human health. In order to investigate the degradation law of HCB, a RuO2/Ti material was used as the anode, meanwhile, zinc, stainless steel, graphite, and RuO2/Ti were used as the cathode, respectively. The gas chromatography (GC was used to analyze the electrochemical products of HCB on different cathodes. The results showed that the cathode materials significantly affected the dechlorination efficiency of HCB, and the degradation of HCB was reductive dechlorination which occurred only on the cathode. During the reductive process, chlorine atoms were replaced one by one on various intermediates such as pentachlorobenzene, tetrachlorobenzene, and trichlorobenzene occurred; the trichlorobenzene was obtained when zinc was used as cathode. The rapid dechlorination of HCB suggested that the electrochemical method using zinc or stainless steel as cathode could be used for remediation of polychlorinated aromatic compounds in the environment. The dechlorination approach of HCB by stainless steel cathode could be proposed.

  13. New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions

    Energy Technology Data Exchange (ETDEWEB)

    Hromadova, Magdalena [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic)], E-mail: hromadom@jh-inst.cas.cz; Pospisil, Lubomir [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic)], E-mail: Lubomir.Pospisil@jh-inst.cas.cz; Sokolova, Romana [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic); Fanelli, Nicolangelo [Istituto per i Processi Chimico-Fisici, C.N.R., via G. Moruzzi 1, I-56124 Pisa (Italy)

    2009-09-01

    Nitroaromatic compound bifenox (methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate) is used as a model system for a new NDR oscillator in the aprotic solvent acetonitrile. The reduction of bifenox yields the anion radical, which is further reduced by an overall addition of three electrons and four protons to the corresponding phenylhydroxylamine. The second reduction step is strongly influenced by the nature and concentration of the tetraalkylammonium salts used as the supporting electrolytes. At the low concentration of tetrahexylammonium hexafluorophosphate the anion radical reduction occurs at extremely negative potentials due to the double-layer effect on the negatively charged reactant. An addition of small amounts of the alkali metal cations (Li{sup +}, Na{sup +} and K{sup +}) to such a system has a remarkable acceleration effect on the electron transfer rate since these ions undergo pairing with in situ generated anion radicals and the double-layer effect on the resulting particles of a diminished charge is much weaker. At potentials where alkali metal cations are reduced to the corresponding amalgams the acceleration ceases. As a result the current-potential curves show a negative slope. Electrochemical impedance spectroscopy sensitively indicates the presence of the negative differential charge transfer resistance (NDR). The addition of a high external resistor in series with the electrochemical cell leads to the current oscillations at the stationary mercury electrode and to the current instabilities on the dropping mercury electrode. Described system is a new example of the NDR oscillator, in which the double-layer effect in connection with cationic catalysis rather than anionic catalysis plays a crucial role in the observation of NDR.

  14. A Comparison between Two Cell Designs for Electrochemical Neodymium Reduction Using Numerical Simulation

    Science.gov (United States)

    Haas, Tim; Hilgendorf, Simon; Vogel, Hanno; Friedrich, Bernd; Pfeifer, Herbert

    2017-08-01

    Nowadays, neodymium is almost solely produced by the electrochemical reduction of Neodymium oxide in fused fluoride salts. Thereby, the fluid flow distribution within the electrolysis cell is important for the productivity and efficiency of the process. In this work, the flow field within a conventional cell with vertical electrodes is compared to that of an innovative cell concept with horizontal electrodes by computational fluid dynamics. The numerical model uses the Eulerian volume of fluid approach to track phase boundaries between the continuous phases, while the Lagrangian discrete phase model is applied to compute the rising trajectories of emitted off-gas bubbles. The calculated results indicate that the new cell type is more suitable for the efficient, large-scale production of neodymium, since there is potential to decrease the cell voltage and enhance the current efficiency. By that, the specific energy consumption can be lowered significantly. However, an advanced level of automation is necessary to operate the new cell.

  15. 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

    2017-11-24

    Electrochemical CO 2 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 CO 2 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.

  16. 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.

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

    International Nuclear Information System (INIS)

    Koca, Atif; Kalkan, Ayfer; Bayir, Zehra Altuntas

    2011-01-01

    Highlights: → Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. → The presence of O 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 + 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 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 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 + 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 + reduction in aqueous solution.

  18. The potential for reductive dehalogenation of chlorinated phenol in a ...

    African Journals Online (AJOL)

    2005-04-14

    Apr 14, 2005 ... Acetonitrile–distilled water–acetic acid (79:20:1 v/v) was used as eluant at 1 mℓ· min-1. Sulphate levels were quantified by HPLC anion exchange chromatography using a Waters 501 HPLC pump, a Hamilton PRP-X100 anion exchange column (150x4.1 mm) and Waters conductivity detector (Model 430).

  19. The potential for reductive dehalogenation of chlorinated phenol in a ...

    African Journals Online (AJOL)

    TCP) under sulphate-reducing conditions was made. Sulphate-reducing and dechloro-respiring activities were studied in a mixed microbial population operated in batch-fed as well as continuous pine chip-packed fluidised bed reactors.

  20. 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

    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...

  1. 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,

  2. One-Pot Synthesis of Concave Platinum-Cobalt Nanocrystals and Their Superior Catalytic Performances for Methanol Electrochemical Oxidation and Oxygen Electrochemical Reduction.

    Science.gov (United States)

    Ma, Yanxia; Yin, Lisi; Yang, Tao; Huang, Qingli; He, Maoshuai; Zhao, Hong; Zhang, Dongen; Wang, Mingyan; Tong, Zhiwei

    2017-10-18

    Exploring highly efficient electro-catalysts is of significant urgency for the widespread uptake of the direct methanol fuel cells (DMFCs). Pt-Co nanocrystals have attracted considerable attentions because of their superior catalytic performance toward both methanol oxidation and oxygen reduction in the preliminary assessments. This Research Article presents a Pt-Co bimetal catalyst that is synthesized through a facile coreduction strategy. The Pt-Co nanocrystals have concave cubic shape with a high uniform size of 7-9 nm and Pt-rich surfaces. The catalysis of the concave cubic Pt-Co nanoparticles toward both methanol electrochemical oxidation reaction (MOR) and oxygen electrochemical reduction reaction (ORR) is evaluated. In comparison with the commercial Pt/C catalyst (Johnson Matthey), the present concave cubic Pt-Co catalyst displays superior performances in not only catalytic activity but also durability. The concave Pt-Co catalyst also shows higher activities than spherical and cubic Pt-Co nanoparticles. The dramatic enhancement is mainly attributed to its alloyed composition, Pt-rich surface and the concave nanostructure. The results of our research indicate that the concave Pt-Co nanocrystal could be a promising catalyst for both MOR and ORR. The present work might also raise more concerns on exploiting morphology and composition of nanocrystal catalysts, which are expected to provide high catalytic performance in electrochemical reactions.

  3. 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)

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

    OpenAIRE

    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, three-phase boundary for gas–liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduct...

  5. Electrochemical reduction of CO2on graphene supported transition metals - towards single atom catalysts.

    Science.gov (United States)

    He, Haiying; Jagvaral, Yesukhei

    2017-05-10

    In this study, we have investigated the use of single metal atoms supported on defective graphene as catalysts for the electrochemical reduction of CO 2 using the first-principles approach and the computational hydrogen electrode model. Reaction pathways to produce a variety of C 1 products CO, HCOOH, HCHO, CH 3 OH and CH 4 have been studied in detail for five representative transition metals Ag, Cu, Pd, Pt, and Co. Different pathways were revealed in contrast to those found for metallic crystalline surfaces and nanoparticles. These single atom catalysts have demonstrated a general improvement in rate limiting potentials to generate C 1 hydrocarbons. They also show distinct differences in terms of their efficiency and selectivity in CO 2 reduction, which can be correlated with their elemental properties as a function of their group number in the periodic table. Six best candidates for CH 4 production are identified by conducting computational screening of 28 d-block transition metals. Ag has the lowest overpotential (0.73 V), and is followed by Zn, Ni, Pd, Pt and Ru with overpotentials all below 1 V. Cu in the supported single atom form shows a strong preference towards producing CH 3 OH with an overpotential of 0.68 V well below the value of 1.04 V for producing CH 4 .

  6. Electrochemical Reduction of Dissolved Oxygen in Alkaline, Solid Polymer Electrolyte Films.

    Science.gov (United States)

    Novitski, David; Kosakian, Aslan; Weissbach, Thomas; Secanell, Marc; Holdcroft, Steven

    2016-11-30

    Mass transport of oxygen through an ionomer contained within the cathode catalyst layer in an anion exchange membrane fuel cell is critical for a functioning fuel cell, yet is relatively unexplored. Moreover, because water is a reactant in the oxygen reduction reaction (ORR) in alkaline media, an adequate supply of water is required. In this work, ORR mass transport behavior is reported for methylated hexamethyl-p-terphenyl polymethylbenzimidazoles (HMT-PMBI), charge balanced by hydroxide ions (IEC from 2.1 to 2.5 mequiv/g), and commercial Fumatec FAA-3 membranes. Electrochemical mass transport parameters are determined by potential step chronoamperometry using a Pt microdisk solid-state electrochemical cell, in air at 60 °C, with relative humidity controlled between 70% and 98%. The oxygen diffusion coefficient (D bO2 ), oxygen concentration (c bO2 ), and oxygen permeability (D bO2 ·c bO2 ) were obtained by nonlinear curve fitting of the current transients using the Shoup-Szabo equation. Mass transport parameters are correlated to water content of the ionomer membrane. It is found that the oxygen diffusion coefficients decreased by 2 orders of magnitude upon reducing the water content of the ionomer membrane by lowering the relative humidity. The limitation of the Shoup-Szabo equation for extracting ORR mass transport parameters using thin ionomer films was evaluated by numerical modeling of the current transients, which revealed that a significant discrepancy (up to 29% under present conditions) was evident for highly hydrated membranes for which the oxygen diffusion coefficient was largest, and in which the oxygen depletion region reached the ionomer/gas interface during the chronoamperometric analysis.

  7. 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.

  8. A method for de-halogenating a composition containing halides as impurities

    International Nuclear Information System (INIS)

    Grossman, L.N.; Brigham, D.A.

    1974-01-01

    A fast dehalogenation low-temperature method, consisting in heating the halide-containing composition up to a temperature of from 315 deg C to 870 deg C in a de-halogenating atmosphere containing a vaporized alcohol. That method can be applied to the generation of uranium dioxide [fr

  9. 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.

  10. Dehalogenation and decolorization of wheat straw- basedbleachery ...

    African Journals Online (AJOL)

    AJB SERVER

    2007-02-05

    Feb 5, 2007 ... efficiency was also in accord with gas chromatography analysis indicating drastic reductions at low molecular weight adsorbable organic halogen compounds. Key words: Straw, bleaching, adsorbable organic halogens, pulping, Penicillium camemberti. INTRODUCTION. Compared with wood; hemp, ramie ...

  11. A Study of Electrochemical Reduction of Ethylene and PropyleneCarbonate Electrolytes on Graphite Using ATR-FTIR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Guorong V.; Yang, Hui; Blizanac, Berislav; Ross Jr.,Philip N.

    2005-05-12

    We present results testing the hypothesis that there is a different reaction pathway for the electrochemical reduction of PC versus EC-based electrolytes at graphite electrodes with LiPF6 as the salt in common. We examined the reduction products formed using ex-situ Fourier Transform Infrared (FTIR) spectroscopy in attenuated total reflection (ATR) geometry. The results show the pathway for reduction of PC leads nearly entirely to lithium carbonate as the solid product (and presumably ethylene gas as the co-product) while EC follows a path producing a mixture of organic and inorganic compounds. Possible explanations for the difference in reaction pathway are discussed.

  12. Synthesis and Electrochemical Characterization of Ni Nanoparticles by Hydrazine Reduction using Hydroxyethyl cellulose as Capping Agent

    International Nuclear Information System (INIS)

    Ramírez-Meneses, E.; Torres-Huerta, A.M.; Domínguez-Crespo, M.A.; Ponce-Varela, M.G.; Hernández-Pérez, M.A.; Betancourt, I.; Palacios-González, E.

    2014-01-01

    The controlled-size synthesis of well-dispersed metal nanoparticles has been the aim of many research works during the last two decades. In this context, simple and controlled methods are the most suitable to obtain metal nanoparticles. The reduction of transition metal salts in solution is the most widely used method for generating colloidal suspensions of metals. In this work, nickel nanoparticles were synthesized from NiCl 2 ·6H 2 O in an ethanol solution with hydrazine hydrate and an appropriate amount of NaOH in the presence of hydroxyethyl cellulose (HEC) used as a capping agent to avoid the coalescence of the nanostructures. Size effects on the nickel nanostructures were studied by varying the concentration of the reducing agent and temperature. The obtained nickel nanostructures were characterized by X-ray diffraction (XRD), showing a face-centered cubic (fcc) structure. Particle sizes from 7 to 13 nm were determined by the Scherrer equation. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed spherical sponge-like nanostructures formed by thin laminar structures. Additionally, infrared spectroscopy showed the presence of HEC functional groups on the surface of the nickel nanostructures after the purification step. Finally, the obtained Ni nanostructures were also characterized by electrochemical techniques and magnetic measurements to determine their electrocatalytic properties and magnetic response, respectively

  13. Minimizing losses in bio-electrochemical systems: the road to applications.

    Science.gov (United States)

    Clauwaert, Peter; Aelterman, Peter; Pham, The Hai; De Schamphelaire, Liesje; Carballa, Marta; Rabaey, Korneel; Verstraete, Willy

    2008-07-01

    Bio-electrochemical systems (BESs) enable microbial catalysis of electrochemical reactions. Plain electrical power production combined with wastewater treatment by microbial fuel cells (MFCs) has been the primary application purpose for BESs. However, large-scale power production and a high chemical oxygen demand conversion rates must be achieved at a benchmark cost to make MFCs economical competitive in this context. Recently, a number of valuable oxidation or reduction reactions demonstrating the versatility of BESs have been described. Indeed, BESs can produce hydrogen, bring about denitrification, or reductive dehalogenation. Moreover, BESs also appear to be promising in the field of online biosensors. To effectively apply BESs in practice, both biological and electrochemical losses need to be further minimized. At present, the costs of reactor materials have to be decreased, and the volumetric biocatalyst activity in the systems has to be increased substantially. Furthermore, both the ohmic cell resistance and the pH gradients need to be minimized. In this review, these losses and constraints are discussed from an electrochemical viewpoint. Finally, an overview of potential applications and innovative research lines is given for BESs.

  14. 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

  15. 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]+.

  16. 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.

  17. Nitrogen doped holey graphene as an efficient metal-free multifunctional electrochemical catalyst for hydrazine oxidation and oxygen reduction

    Science.gov (United States)

    Yu, Dingshan; Wei, Li; Jiang, Wenchao; Wang, Hong; Sun, Bo; Zhang, Qiang; Goh, Kunli; Si, Rongmei; Chen, Yuan

    2013-03-01

    Electrocatalysts for anode or cathode reactions are at the heart of electrochemical energy conversion and storage devices. Molecular design of carbon based nanomaterials may create the next generation electrochemical catalysts for broad applications. Herein, we present the synthesis of a three-dimensional (3D) nanostructure with a large surface area (784 m2 g-1) composed of nitrogen doped (up to 8.6 at.%) holey graphene. The holey structure of graphene sheets (~25% of surface area is attributed to pores) engenders more exposed catalytic active edge sites. Nitrogen doping further improves catalytic activity, while the formation of the 3D porous nanostructure significantly reduces graphene nanosheet stacking and facilitates the diffusion of reactants/electrolytes. The three factors work together, leading to superb electrochemical catalytic activities for both hydrazine oxidation (its current generation ability is comparable to that of 10 wt% Pt-C catalyst) and oxygen reduction (its limiting current is comparable to that of 20 wt% Pt-C catalyst) with four-electron transfer processes and excellent durability.Electrocatalysts for anode or cathode reactions are at the heart of electrochemical energy conversion and storage devices. Molecular design of carbon based nanomaterials may create the next generation electrochemical catalysts for broad applications. Herein, we present the synthesis of a three-dimensional (3D) nanostructure with a large surface area (784 m2 g-1) composed of nitrogen doped (up to 8.6 at.%) holey graphene. The holey structure of graphene sheets (~25% of surface area is attributed to pores) engenders more exposed catalytic active edge sites. Nitrogen doping further improves catalytic activity, while the formation of the 3D porous nanostructure significantly reduces graphene nanosheet stacking and facilitates the diffusion of reactants/electrolytes. The three factors work together, leading to superb electrochemical catalytic activities for both

  18. 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.

  19. Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces.

    Science.gov (United States)

    Ullien, Daniela; Thüne, Peter C; Jager, Wolter F; Sudhölter, Ernst J R; de Smet, Louis C P M

    2014-09-28

    4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2-7 nm, which indicate multilayer formation. Decreasing the diazonium salt concentration and the reaction time resulted in a smaller layer thickness, but did not prevent the formation of multilayers. It was demonstrated, mainly by X-ray photoelectron spectroscopy (XPS), that the diazonium salts not only react with the H-terminated Si surface, but also with electrografted phenyl groups via azo-bond formation. These azo bonds can be electrochemically reduced at Ered = -1.5 V, leading to the corresponding amino groups. This reduction resulted in a modest decrease in layer thickness, and did not yield monolayers. This indicates that other coupling reactions, notably a biphenyl coupling, induced by electrochemically produced phenyl radicals, take place as well. In addition to the azo functionalities, the nitro functionalities in electrografted layers of 4-NBD were independently reduced to amino functionalities at a lower potential (Ered = -2.1 V). The presence of amino functionalities on fully reduced layers, both from 4-NBD- and 4-BBD-modified Si, was shown by the presence of fluorine after reaction with trifluoroacetic anhydride (TFAA). This study shows that the electrochemical reduction of azo bonds generates amino functionalities on layers produced by electrografting of aryldiazonium derivatives. In this way multifunctional layers can be formed by employing functional aryldiazonium salts, which is believed to be very practical in the fabrication of sensor platforms, including those made of multi-array silicon nanowires.

  20. Mechanistic Pathway in the Electrochemical Reduction of CO2 on RuO2

    DEFF Research Database (Denmark)

    Karamad, Mohammadreza; Hansen, Heine Anton; Rossmeisl, Jan

    2015-01-01

    RuO2 has been reported to reduce CO2 electrochemically to methanol at low overpotential. Herein, we have used density functional theory (DFT) to gain insight into the mechanism for CO2 reduction on RuO2(110). We have investigated the thermodynamic stability of various surface terminations...... in the electrochemical environment and found CO covered surfaces to be particularly stable, although their formation might be kinetically limited under mildly reducing conditions. We have identified the lowest free energy pathways for CO2 reduction to formic acid (HCOOH), methanol (CH3OH), and methane (CH4) on partially...... reduced RuO2(110) covered with 0.25 and 0.5 ML of CO*. We have found that CO2 is reduced to formic acid, which is further reduced to methanol and methane. At 0.25 ML of CO*, the reduction of formate (OCHO*) to formic acid is the thermodynamically most difficult step and becomes exergonic at potentials...

  1. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2 to CO.

    Science.gov (United States)

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

    2015-02-09

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Transition Metal-Based Catalysts Modified with p-Block Elements for the Electrochemical Reduction of CO2

    OpenAIRE

    Larrazábal, Gastón O.

    2018-01-01

    Avoiding the most serious effects of climate change is one of the greatest technical and socio-political challenges of our time. At the present rate of anthropogenic CO2 emissions, in less than two decades mankind will lose the opportunity to limit the global temperature increase to 2 °C (as stated in the Paris Agreement), a fact that makes carbon dioxide an urgent target for recycling efforts. In this context, the combination of the electrochemical reduction of CO2 (eCO2RR) with carbon-neutr...

  3. 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

    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......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...

  4. 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).

  5. 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.

  6. Novel Electrochemical Synthesis of Polypyrrole/Ag Nanocomposite and Its Electrocatalytic Performance towards Hydrogen Peroxide Reduction

    OpenAIRE

    Ruma Gupta; Kavitha Jayachandran; J. S. Gamare; B. Rajeshwari; Santosh K. Gupta; J. V. Kamat

    2015-01-01

    A simple electrochemical method of synthesis of polypyrrole/silver (PPy/Ag) nanocomposite is presented. The method is based on potentiodynamic polymerization of pyrrole followed by electrodeposition of silver employing a single potentiostatic pulse. The synthesized PPy film has embedded Ag nanocubes. The morphology and structure of the resulting nanocomposite were characterized by field emission scanning electron microscopy and X-ray diffraction. Electron paramagnetic resonance studies showed...

  7. 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

  8. Electrochemical processes of adsorbed chlorobenzene and fluorobenzene on a platinum polycrystalline electrode

    Czech Academy of Sciences Publication Activity Database

    Kebrlová, Natálie; Janderka, P.; Trnková, L.

    2009-01-01

    Roč. 74, č. 4 (2009), s. 611-625 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40500505 Keywords : electrochemical degradation * hydrogenation * dehalogenation Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.856, year: 2009

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

    Science.gov (United States)

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

    2016-02-01

    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, three-phase boundary for gas-liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduction up to 85% are obtained. Moreover, the carbon monoxide formation rate is at least one order of magnitude larger when compared with state-of-the-art nanocrystalline copper electrodes. Copper hollow fibre electrodes can be prepared via a facile method that is compatible with existing large-scale production processes. The results of this study may inspire the development of new types of microtubular electrodes for electrochemical processes in which at least one gas-phase reactant is involved, such as in fuel cell technology.

  10. 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.

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

    Science.gov (United States)

    Kas, Recep; Hummadi, Khalid Khazzal; Kortlever, Ruud; de Wit, Patrick; Milbrat, Alexander; Luiten-Olieman, Mieke W. J.; Benes, Nieck E.; 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, three-phase boundary for gas–liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduction up to 85% are obtained. Moreover, the carbon monoxide formation rate is at least one order of magnitude larger when compared with state-of-the-art nanocrystalline copper electrodes. Copper hollow fibre electrodes can be prepared via a facile method that is compatible with existing large-scale production processes. The results of this study may inspire the development of new types of microtubular electrodes for electrochemical processes in which at least one gas-phase reactant is involved, such as in fuel cell technology. PMID:26888578

  12. 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.

  13. Mechanistic insights into electrochemical reduction of CO2over Ag using density functional theory and transport models.

    Science.gov (United States)

    Singh, Meenesh R; Goodpaster, Jason D; Weber, Adam Z; Head-Gordon, Martin; Bell, Alexis T

    2017-10-17

    Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in the reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.

  14. Electrochemical co-reduction between aluminium and lanthanide ions in fluoride salts: application to nuclear wastes pyrochemical treatment

    International Nuclear Information System (INIS)

    Gibilaro, M.

    2008-01-01

    Nuclear reaction produces fission products such as lanthanides; these neutro-phage elements represent a poison for the nuclear chain reaction and have to be extracted. This thesis concerns lanthanides extraction (neodymium, cerium and samarium) by electrodeposition in the LiF-CaF 2 eutectic mixture at 840 C. The process used is an alloy formation with aluminium by electrochemical co-reduction on an inert tungsten electrode. This technique is based on the simultaneous reduction of Al(III) and Ln(III) ions to obtain an alloy at the cathode. A decrease of the lanthanide activity in the alloy is obtained due to Al-Ln formation and a shift of lanthanide reduction potential to more positive values is observed: the theoretical extraction efficiency is then approaching 100 %. When both Ln(III) and Al(III) ions are present in the molten salt, new reduction waves appear between Al and Ln pure metal depositions and are attributed to Al-Ln alloy formation by co-reduction. The alloy compositions have been characterised in function of electrolysis potential: the more the electrolysis potential is negative, higher is the Ln content in the alloy. Finally, extractions by potentiostatic electrolyses have been carried out and the extraction efficiencies for the different lanthanides are higher than 99.4 %. (author)

  15. 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

  16. Pyrolysis and dehalogenation of plastics from waste electrical and electronic equipment (WEEE): a review.

    Science.gov (United States)

    Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng

    2013-02-01

    Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of

  17. 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

    2017-01-01

    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...... significant shifts of half-wave potentials indicating that surface Fe coordinated sites in all cases. The G@Fe catalyst showed the weakest poisoning effect (the lowest shifts of half-wave potential) compared to the Fe/N/C and FePc catalysts in both electrolytes. These results could be explained...

  18. 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.

  19. Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

    Science.gov (United States)

    Quinn, Jacqueline; Geiger, Cherie; Clausen, Chris; Brooks, Kathleen; Coon, Christina; O'Hara, Suzanne; Krug, Thomas; Major, David; Yoon, Woong-Sang; Gavaskar, Arun; hide

    2005-01-01

    This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nanoscale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, nonaqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (VOCs) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

  20. Electrochemical assembly of organic molecules by the reduction of iodonium salts

    Science.gov (United States)

    Dirk, Shawn M [Albuquerque, NM; Howell, Stephen W [Albuquerque, NM; Wheeler, David R [Albuquerque, NM

    2009-06-23

    Methods are described for the electrochemical assembly of organic molecules on silicon, or other conducting or semiconducting substrates, using iodonium salt precursors. Iodonium molecules do not assemble on conducting surfaces without a negative bias. Accordingly, the iodonium salts are preferred for patterning applications that rely on direct writing with negative bias. The stability of the iodonium molecule to acidic conditions allows them to be used with standard silicon processing. As a directed assembly process, the use of iodonium salts provides for small features while maintaining the ability to work on a surface and create structures on a wafer level. Therefore, the process is amenable for mass production. Furthermore, the assembled monolayer (or multilayer) is chemically robust, allowing for subsequent chemical manipulations and the introduction of various molecular functionalities for various chemical and biological applications.

  1. Electrochemical reduction of UO2 in LiCl-Li2O molten salt using porous and nonporous anode shrouds

    Science.gov (United States)

    Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun; Park, Wooshin; Im, Hun Suk; Hong, Sun-Seok; Hur, Jin-Mok

    2014-01-01

    Electrochemical reductions of uranium oxide in a molten LiCl-Li2O electrolyte were carried out using porous and nonporous anode shrouds. The study focused on the effect of the type of anode shroud on the current density by running experiments with six anode shrouds. Dense ceramics, MgO, and MgO (3 wt%) stabilized ZrO2 (ZrO2-MgO) were used as nonporous shrouds. STS 20, 100, and 300 meshes and ZrO2-MgO coated STS 40 mesh were used as porous shrouds. The current densities (0.34-0.40 A cm-2) of the electrolysis runs using the nonporous anode shrouds were much lower than those (0.76-0.79 A cm-2) of the runs using the porous shrouds. The ZrO2-MgO shroud (600-700 MPa at 25 °C) showed better bending strength than that of MgO (170 MPa at 25 °C). The high current densities achieved in the electrolysis runs using the porous anode shrouds were attributed to the transport of O2- ions through the pores in meshes of the shroud wall. ZrO2-MgO coating on STS mesh was chemically unstable in a molten LiCl-Li2O electrolyte containing Li metal. The electrochemical reduction runs using STS 20, 100, and 300 meshes showed similar current densities in spite of their different opening sizes. The STS mesh shrouds which were immersed in a LiCl-Li2O electrolyte were stable without any damage or corrosion.

  2. 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

    requires a high concentration (>200 mM) of the chemical reducing agent Tris(2-carboxyethyl)phosphine (TCEP) as the reduction rate constant is decreased at low pH and temperature. Serious adverse effects on chromatographic and mass spectrometric performances have been reported when using high concentrations......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...

  3. Electrochemical Reduction of CO2 to Organic Acids by a Pd-MWNTs Gas-Diffusion Electrode in Aqueous Medium

    Science.gov (United States)

    Lu, Guang; Bian, Zhaoyong; Liu, Xin

    2013-01-01

    Pd-multiwalled carbon nanotubes (Pd-MWNTs) catalysts for the conversion of CO2 to organic acids were prepared by the ethylene glycol reduction and fully characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) technologies. The amorphous Pd particles with an average size of 5.7 nm were highly dispersed on the surface of carbon nanotubes. Functional groups of the MWNTs played a key role in the palladium deposition. The results indicated that Pd-MWNTs could transform CO2 into organic acid with high catalytic activity and CO2 could take part in the reduction reaction directly. Additionally, the electrochemical reduction of CO2 was investigated by a diaphragm electrolysis device, using a Pd-MWNTs gas-diffusion electrode as a cathode and a Ti/RuO2 net as an anode. The main products in present system were formic acid and acetic acid identified by ion chromatograph. The selectivity of the products could be achieved by reaction conditions changing. The optimum faraday efficiencies of formic and acetic acids formed on the Pd-MWNTs gas-diffusion electrode at 4 V electrode voltages under 1 atm CO2 were 34.5% and 52.3%, respectively. PMID:24453849

  4. Electrochemically deposited Pd-Pt and Pd-Au codeposits on graphite electrodes for electrocatalytic H2O2 reduction.

    Science.gov (United States)

    Nagaiah, Tharamani Chikka; Schäfer, Dominik; Schuhmann, Wolfgang; Dimcheva, Nina

    2013-08-20

    Improved electrocatalytic activity and selectivity for the reduction of H2O2 were obtained by electrodepositing Pd-Pt and Pd-Au on spectrographic graphite from solutions containing salts of the two metals at varying ratio. The electrocatalytic activity of the resulting binary codeposits for H2O2 reduction was evaluated by means of the redox-competition mode of scanning electrochemical microscopy (SECM) and voltammetric methods. In a potential range from 0 to -600 mV (vs. Ag/AgCl/3 M KCl) at pH 7.0 in 0.1 M phosphate citrate buffer, the electrocatalytic activity of both Pd-Pt and Pd-Au codeposits was substantially improved as compared with the identically deposited single metals suggesting an electrocatalytic synergy of the codeposits. Pd-Pt and Pd-Au codeposits were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Codepositing with Au caused a change of hedgehog-like shaped Pd nanoparticles into cauliflower-like nanoparticles with the particle size decreasing with increasing Au concentration. Codepositing Pd with Pt caused the formation of oblong structures with the size initially increasing with increasing Pt content. However, the particle size decreases with further increase in Pt concentration. The improved electrocatalytic capability for H2O2 reduction of the Pd-Pt electrodeposits on graphite was further demonstrated by immobilizing glucose oxidase as a basis for the development of an interference-free amperometric glucose biosensor.

  5. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2.

    Science.gov (United States)

    Ju, Wen; Bagger, Alexander; Hao, Guang-Ping; Varela, Ana Sofia; Sinev, Ilya; Bon, Volodymyr; Roldan Cuenya, Beatriz; Kaskel, Stefan; Rossmeisl, Jan; Strasser, Peter

    2017-10-16

    Direct electrochemical reduction of CO 2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO 2 -consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO 2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO 2 reduction catalysts.Inexpensive and selective electrocatalysts for CO 2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO 2 to CO conversion.

  6. 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.

  7. Pt/YSZ electrochemical catalysts prepared by electrostatic spray deposition for selective catalytic reduction of NO by C{sub 3}H{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Lintanf, A.; Djurado, E. [Laboratoire d' Electrochimie et de Physico-Chimie des Materiaux et des Interfaces (LEPMI), ENSEEG/INPG/UJF/CNRS Institut National Polytechnique de Grenoble Domaine Universitaire, BP 75, 1130 rue de la Piscine, 38402 St Martin d' Heres Cedex (France); Vernoux, P. [Universite de Lyon, Institut de Recherches sur la Catalyse et l' Environnement de Lyon, UMR 5256, CNRS, Universite Claude Bernard Lyon 1, 2 avenue A. Einstein, 69626 Villeurbanne (France)

    2008-03-15

    Due to the great importance of automotive exhaust gas treatment, the catalytic activity was investigated in selective catalytic reduction of NO by propene on Pt films - with controlled microstructure - deposited on YSZ (8 mol% Y{sub 2}O{sub 3}-doped ZrO{sub 2}) by electrostatic spray deposition. This technique requires low Pt loadings in order to reduce costs and also to achieve high Pt particles dispersion with good reproducibility. This kind of electrochemical catalysts was found to be effective for NO reduction by propene in the presence of oxygen. A dense Pt film was found to be the most suitable. Furthermore, we have demonstrated that these electrochemical catalysts can implement the concept of electrochemical promotion of catalysis (EPOC). (author)

  8. Modular cathode assemblies and methods of using the same for electrochemical reduction

    Energy Technology Data Exchange (ETDEWEB)

    Wiedmeyer, Stanley G.; Barnes, Laurel A.; Williamson, Mark A.; Willit, James L.

    2018-03-20

    Modular cathode assemblies are useable in electrolytic reduction systems and include a basket through which fluid electrolyte may pass and exchange charge with a material to be reduced in the basket. The basket can be divided into upper and lower sections to provide entry for the material. Example embodiment cathode assemblies may have any shape to permit modular placement at any position in reduction systems. Modular cathode assemblies include a cathode plate in the basket, to which unique and opposite electrical power may be supplied. Example embodiment modular cathode assemblies may have standardized electrical connectors. Modular cathode assemblies may be supported by a top plate of an electrolytic reduction system. Electrolytic oxide reduction systems are operated by positioning modular cathode and anode assemblies at desired positions, placing a material in the basket, and charging the modular assemblies to reduce the metal oxide.

  9. Role of the oxide layer on Sn electrode in electrochemical reduction of CO2 to formate

    Science.gov (United States)

    Zhang, Rui; Lv, Weixin; Lei, Lixu

    2015-11-01

    The importance of oxide layer on Sn electrode to the efficiency of CO2 reduction has been evaluated by comparing the activities of Sn electrodes treated via etching and annealing. In KHCO3 aqueous solution saturated with CO2, Sn electrode with a native oxide layer exhibits high catalytic activity for CO2 reduction, in contrast, Sn electrode which is etched in HCl solution to remove the oxide layer or treated by annealing exhibits lower activity for CO2 reduction. If the etched Sn electrode is exposed in the air over 24 h, its catalytic performance for CO2 reduction will restore, meanwhile, the electrolysis current density for this electrode is around 1.5-fold than that for a untreated Sn electrode because the etching treatment makes the electrode rough and behave a larger superficial area.

  10. 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...

  11. Electrochemical NOx reduction on an LSM/CGO symmetric cell modified by NOx adsorbents

    DEFF Research Database (Denmark)

    Shao, Jing; Kammer Hansen, Kent

    2013-01-01

    were prepared and tested: a blank cell, a cell impregnated with BaO, and a cell coated with a BaO/Pt/Al2O3 layer. The electrochemical reduction of NOx on the three cells was studied by conversion measurement, degradation testing, and microstructure characterization. The modification, either...

  12. 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

    Czech Academy of Sciences Publication Activity Database

    Liška, Alan; Rosenkranz, M.; Klíma, Jiří; Dunsch, L.; Lhoták, P.; Ludvík, Jiří

    2014-01-01

    Roč. 140, SEP 2014 (2014), s. 572-578 ISSN 0013-4686 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : cone-calix[4]arenes * electrochemical reduction * in-situ UV-vis and ESR spectroelectrochemistry Subject RIV: CG - Electrochemistry Impact factor: 4.504, year: 2014

  13. (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

  14. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    2016-11-01

    Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing

  15. 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

  16. 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 U.; Mysling, Simon

    2015-01-01

    Analysis of disulfide-bonded proteins by hydrogen/deuterium exchange mass spectrometry (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 solution (e.g., tris(2-carboxyethyl)phosphine (TCEP)). The chemical reduction, however, is severely limited under quenched conditions due to a narrow time window as well as low pH and temperature. Here, we demonstrate the real-world applicability of integrating...... electrochemical reduction into an online HDX-MS workflow. We have optimized 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...

  17. Modular anode assemblies and methods of using the same for electrochemical reduction

    Energy Technology Data Exchange (ETDEWEB)

    Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L

    2015-02-17

    Modular anode assemblies are used in electrolytic oxide reduction systems for scalable reduced metal production via electrolysis. Assemblies include a channel frame connected to several anode rods extending into an electrolyte. An electrical system powers the rods while being insulated from the channel frame. A cooling system removes heat from anode rods and the electrical system. An anode guard attaches to the channel frame to prevent accidental electrocution or damage during handling or repositioning. Each anode rod may be divided into upper and lower sections to permit easy repair and swapping out of lower sections. The modular assemblies may have standardized components to permit placement at multiple points within a reducing system. Example methods may operate an electrolytic oxide reduction system by positioning the modular anode assemblies in the reduction system and applying electrical power to the plurality of anode assemblies.

  18. 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)

  19. Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO2 Reduction

    DEFF Research Database (Denmark)

    Cavalca, Filippo Carlo; Ferragut, Rafael; Aghion, Stefano

    2017-01-01

    Oxide-derived copper (OD-Cu) electrodes exhibit higher activity than pristine copper during the carbon dioxide reduction reaction (CO2RR) and higher selectivity towards ethylene. The presence of residual subsurface oxygen in OD-Cu has been proposed to be responsible for such improvements, although...

  20. 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

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

    OpenAIRE

    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.

    2017-01-01

    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 UO2 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 UO2 working electrode b...

  2. High Performance Fe Porphyrin/Ionic Liquid Co-catalyst for Electrochemical CO2 Reduction.

    Science.gov (United States)

    Choi, Jaecheol; Benedetti, Tania M; Jalili, Rouhollah; Walker, Ashley; Wallace, Gordon G; Officer, David L

    2016-09-26

    The efficient and selective catalytic reduction of CO2 is a highly promising process for both of the storage of renewable energy as well as the production of valuable chemical feedstocks. In this work, we show that the addition of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, in an aprotic electrolyte containing a proton source and FeTPP, promotes the in situ formation of the [Fe(0) TPP](2-) homogeneous catalyst at a less negative potential, resulting in lower overpotentials for the CO2 reduction (670 mV) and increased kinetics of electron transfer. This co-catalysis exhibits high Faradaic efficiency for CO production (93 %) and turnover number (2 740 000 after 4 hour electrolysis), with a four-fold increase in turnover frequency (TOF) when compared with the standard system without the ionic liquid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen

    KAUST Repository

    Shinagawa, Tatsuya

    2015-01-01

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction. This journal is © the Owner Societies.

  4. Dehalogenimonas alkenigignens sp. nov., a chlorinated-alkane-dehalogenating bacterium isolated from groundwater.

    Science.gov (United States)

    Bowman, Kimberly S; Nobre, M Fernanda; da Costa, Milton S; Rainey, Fred A; Moe, William M

    2013-04-01

    Two strictly anaerobic bacterial strains, designated IP3-3(T) and SBP-1, were isolated from groundwater contaminated by chlorinated alkanes and alkenes at a Superfund Site located near Baton Rouge, Louisiana (USA). Both strains reductively dehalogenate a variety of polychlorinated aliphatic alkanes, including 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane and 1,2,3-trichloropropane, when provided with hydrogen as the electron donor. To clarify their taxonomic position, strains IP3-3(T) and SBP-1 were characterized using a polyphasic approach. Both IP3-3(T) and SBP-1 are mesophilic, non-spore-forming, non-motile and Gram-stain-negative. Cells of both strains are irregular cocci with diameters of 0.4-1.1 µm. Both are resistant to ampicillin and vancomycin. The genomic DNA G+C contents of strains IP3-3(T) and SBP-1 are 55.5±0.4 and 56.2±0.2 mol% (HPLC), respectively. Major cellular fatty acids include C18 : 1ω9c, C16 : 0, C14 : 0 and C16 : 1ω9c. 16S rRNA gene sequence based phylogenetic analyses indicated that the strains cluster within the phylum Chloroflexi most closely related to but distinct from the species Dehalogenimonas lykanthroporepellens (96.2 % pairwise similarity) and Dehalococcoides mccartyi (90.6 % pairwise similarity). Physiological and chemotaxonomic traits as well as phylogenetic analysis support the conclusion that these strains represent a novel species within the genus Dehalogenimonas for which the name Dehalogenimonas alkenigignens sp. nov. is proposed. The type strain is IP3-3(T) ( = JCM 17062(T) = NRRL B-59545(T)).

  5. Reduction of chromium volatilisation from stainless steel interconnector of solid oxide electrochemical devices by controlled preoxidation

    International Nuclear Information System (INIS)

    Wongpromrat, Wichitra; Berthomé, Grégory; Parry, Valérie; Chandra-ambhorn, Somrerk; Chandra-ambhorn, Walairat; Pascal, Céline; Galerie, Alain; Wouters, Yves

    2016-01-01

    Highlights: • Chromium volatilisation from AISI 441 at 800 °C in O 2 + 5%H 2 O was measured and was shown to depend on gas velocity. • Preoxidation of samples before volatilisation measurements could reduce volatilisation rate by a factor 10. • Preoxidation at 250 °C formed an iron oxide scale, making a physical barrier between the steel and the gas phase. • For preoxidation at 850 °C in CO 2 /CO, the reduction of the volatilisation rate was the result of the modification of chromia electronic properties from p to n.

  6. Efficient Indium-Mediated Dehalogenation of Aromatics in Ionic Liquid Media

    Directory of Open Access Journals (Sweden)

    Flavia C. Zacconi

    2012-12-01

    Full Text Available An efficient indium-mediated dehalogenation reaction of haloaromatics and haloheteroaromatics in ionic liquids has been studied. This method is simple and effective in the presence of [bmim]Br. Furthermore, this methodology is environmentally friendly compared with conventional ones.

  7. Electron-transfer rates govern product distribution in electrochemically-driven P450-catalyzed dioxygen reduction.

    Science.gov (United States)

    van der Felt, Clairisse; Hindoyan, Kevork; Choi, Kang; Javdan, Nazafarin; Goldman, Peter; Bustos, Rose; Star, Andrew G; Hunter, Bryan M; Hill, Michael G; Nersissian, Aram; Udit, Andrew K

    2011-10-01

    Developing electrode-driven biocatalytic systems utilizing the P450 cytochromes for selective oxidations depends not only on achieving electron transfer (ET) but also doing so at rates that favor native-like turnover. Herein we report studies that correlate rates of heme reduction with ET pathways and resulting product distributions. We utilized single-surface cysteine mutants of the heme domain of P450 from Bacillus megaterium and modified the thiols with N-(1-pyrene)-iodoacetamide, affording proteins that could bond to basal-plane graphite. Of the proteins examined, Cys mutants at position 62, 383, and 387 were able to form electroactive monolayers with similar E(1/2) values (-335 to -340mV vs AgCl/Ag). Respective ET rates (k(s)(o)) and heme-cysteine distances for 62, 383, and 387 are 50 s(-1) and 16Ǻ, 0.8 s(-1) and 25Ǻ, and 650 s(-1) and 19Ǻ. Experiments utilizing rotated-disk electrodes were conducted to determine the products of P450-catalyzed dioxygen reduction. We found good agreement between ET rates and product distributions for the various mutants, with larger k(s)(o) values correlating with more electrons transferred per dioxygen during catalysis. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Electrochemical doping of three-dimensional graphene networks used as efficient electrocatalysts for oxygen reduction reaction

    Science.gov (United States)

    Wang, Zhijuan; Cao, Xiehong; Ping, Jianfeng; Wang, Yixian; Lin, Tingting; Huang, Xiao; Ma, Qinglang; Wang, Fuke; He, Chaobin; Zhang, Hua

    2015-05-01

    Three-dimensional graphene networks (3DGNs) doped with a mono-heteroatom of N or B, or dual-heteroatoms of N and B were fabricated, which exhibit excellent oxygen reduction reaction (ORR) performance. Importantly, the onset potential and current density of N and B co-doped 3DGNs are comparable to those of the commercial Pt (30%)/C catalyst.Three-dimensional graphene networks (3DGNs) doped with a mono-heteroatom of N or B, or dual-heteroatoms of N and B were fabricated, which exhibit excellent oxygen reduction reaction (ORR) performance. Importantly, the onset potential and current density of N and B co-doped 3DGNs are comparable to those of the commercial Pt (30%)/C catalyst. Electronic supplementary information (ESI) available: Details of the N-3DGN, B-3DGN and NB-3DGN fabrication process. Description of characterization. Rotating disk electrode linear sweep voltammograms of 3DGN and Pt (30%)/C in O2-saturated 0.1 M KOH with various rotation rates at a scan rate of 5 mV s-1. Koutecky-Levich plots of 3DGN, Pt (30%)/C, N-3DGN, B-3DGN and NB-3DGN at different electrode potentials. See DOI: 10.1039/c4nr06631f

  9. Electrochemical Probing of in Vivo 5-Hydroxymethyl Furfural Reduction in Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Kostesha, Natalie; Almeida, J.R.M.; Heiskanen, Arto

    2009-01-01

    amperometric signal during real-time monitoring of the concentration dependent HMF reduction in living cells could be translated into the cellular enzyme kinetic parameters: K-M,cell(app), V-MAX, k(cat,cell), and k(cat,cell)/K-M,cell(app). The results indicated that the overexpression of the ADH6 gene gave...... a 68% decrease in K-M,cell(app), and 42% increase in V-MAX, resulting in a 4-fold increase in k(cat,cell)/K-M,cell(app). These results demonstrate that the mediated amperometric method is useful for monitoring the short-term dynamics of NAD(P)H variations and determining cellular enzyme kinetic...... with HMF, was probed using the menadione-ferricyanide double mediator system. A lower intracellular NADPH level as the consequence of more effective HMF reduction was observed for the ADH6 strain both with and without added glucose, which increases the overall cellular NADPH level. The mediated...

  10. Anode-cathode power distribution systems and methods of using the same for electrochemical reduction

    Science.gov (United States)

    Koehl, Eugene R; Barnes, Laurel A; Wiedmeyer, Stanley G; Williamson, Mark A; Willit, James L

    2014-01-28

    Power distribution systems are useable in electrolytic reduction systems and include several cathode and anode assembly electrical contacts that permit flexible modular assembly numbers and placement in standardized connection configurations. Electrical contacts may be arranged at any position where assembly contact is desired. Electrical power may be provided via power cables attached to seating assemblies of the electrical contacts. Cathode and anode assembly electrical contacts may provide electrical power at any desired levels. Pairs of anode and cathode assembly electrical contacts may provide equal and opposite electrical power; different cathode assembly electrical contacts may provide different levels of electrical power to a same or different modular cathode assembly. Electrical systems may be used with an electrolyte container into which the modular cathode and anode assemblies extend and are supported above, with the modular cathode and anode assemblies mechanically and electrically connecting to the respective contacts in power distribution systems.

  11. Electrochemical kinetics and X-ray absorption spectroscopy investigations of select chalcogenide electrocatalysts for oxygen reduction reaction applications

    International Nuclear Information System (INIS)

    Ziegelbauer, Joseph M.; Murthi, Vivek S.; O'Laoire, Cormac; Gulla, Andrea F.; Mukerjee, Sanjeev

    2008-01-01

    Transition metal-based chalcogenide electrocatalysts exhibit a promising level of performance for oxygen reduction reaction applications while offering significant economic benefits over the state of the art Pt/C systems. The most active materials are based on Ru x Se y clusters, but the toxicity of selenium will most likely limit their embrace by the marketplace. Sulfur-based analogues do not suffer from toxicity issues, but suffer from substantially less activity and stability than their selenium brethren. The structure/property relationships that result in these properties are not understood due to ambiguities regarding the specific morphologies of Ru x S y -based chalcogenides. To clarify these properties, an electrochemical kinetics study was interpreted in light of extensive X-ray diffraction, scanning electron microscopy, and in situ X-ray absorption spectroscopy evaluations. The performance characteristics of ternary M x Ru y S z /C (M = Mo, Rh, or Re) chalcogenide electrocatalysts synthesized by the now-standard low-temperature nonaqueous (NA) route are compared to commercially available (De Nora) Rh- and Ru-based systems. Interpretation of performance differences is made in regards to bulk and surface properties of these systems. In particular, the overall trends of the measured activation energies in respect to increasing overpotential and the gross energy values can be explained in regards to these differences

  12. 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)

  13. Electrochemical stimulation of microbial reductive dechlorination of pentachlorophenol using solid-state redox mediator (humin) immobilization.

    Science.gov (United States)

    Zhang, Dongdong; Zhang, Chunfang; Li, Zhiling; Suzuki, Daisuke; Komatsu, Daisuke D; Tsunogai, Urumu; Katayama, Arata

    2014-07-01

    Immobilized solid-phase humin on a graphite electrode set at -500 mV (vs. standard hydrogen electrode) significantly enhanced the microbial reductive dechlorination of pentachlorophenol as a stable solid-phase redox mediator in bioelectrochemical systems (BESs). Compared with the suspended system, the immobilized system dechlorinated PCP at a much higher efficiency, achieving 116 μmol Cl(-)g(-1) humin d(-1). Fluorescence microscopy showed a conspicuous growth of bacteria on the negatively poised immobilized humin. Electron balance analyses suggested that the electrons required for microbial dechlorination were supplied primarily from the humin-immobilized electrode. Microbial community analyses based on 16S rRNA genes showed that Dehalobacter and Desulfovibrio grew on the immobilized humin as potential dechlorinators. These findings extend the potential of BESs using immobilized solid-phase humin as the redox mediator for in situ bioremediation, given the wide distribution of humin and its efficiency and stability as a mediator. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. 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

  15. Influence of tributylphosphate (TBP) on the electrochemical reduction of uranium(6) on the mercury electrodes

    International Nuclear Information System (INIS)

    Wojdecka-Semkow, K.; Sobkowska, A.

    1979-01-01

    The influence of TBP on the reduction of uranium(6) in aqueous perchlorate solutions using D.C. polarography, cyclic voltammetry and square-wave polarography has been studied. It was found that the TBP concentration lower than 7 x 10 -5 M has no influence on the polarographic wave or voltammetric curve of uranium(6). The presence of TBP in the concentration range of 7 x 10 -5 to 2 x 10 -4 M has an influence on a height and potentials of waves and curves of uranium(6). At the concentration of TBP higher than 2 x 10 -4 M the parameters of the polarographic waves and the voltammetric curves of uranium(6) do not depend on the concentration of TBP. It can be useful in the determination of uranium in the presence of TBP. The square-wave polarography method cannot be used for determination of uranium in the presence of TBP because of the great influence of surface active agents on parameters of the uranium peaks. (author)

  16. 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.

  17. Poisoning the active site of electrochemical reduction of dioxygen on metal monolayer modified electrode surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Oh, I.; Biggin, M.E.; Gewirth, A.A.

    2000-02-08

    The four electron electroreduction of dioxygen to water on the (2 x 2) Bi upd adlattice on Au(111) has been studied by deliberately poisoning the adlattice with thiocyanate and ethanethiol during the course of electroreduction activity. The diminution in reduction activity was monitored using chronoamperometry. For SCN{sup {minus}}, the drop in current could be modeled using a Langmuir kinetic expression yielding an adsorption rate constant of 1.1 x 10{sup 4}s{sup {minus}1}M{sup {minus}1}. The rate for ethanethiol could not be measured exactly but is approximately the same. STM images of the surface obtained following introduction of SCN{sup {minus}} revealed a (4 x 4) adlattice, which was partially (6%) defected. The percentage of defects agreed well with the percentage of residual current found at long times (3%) leading the authors to associate these defects with sites of catalytic activity. STM images obtained from surfaces poisoned with ethanethiol revealed two lattices: a (8 x 8) structure which was unstable and a more stable ({radical}57 x 3) structure which is consistent with an overlayer of thiols lying flat on the surface. IR studies of the SCN{sup {minus}}-poisoned surface showed that the SCN{sup {minus}} was S-bound to the surface at almost the same energy as that expected from SCN{sup {minus}} bound to a bare Au(111) surface. XPS measurements on emersed samples showed that Bi and S were present on the surface. Analysis of these data suggests that the site of dioxygen association with the (2 x 2) Bi unpoisoned surface is the uncoordinated Au atom in the (2 x 2) unit cell.

  18. Mechanistic insights into the reduction of carbon dioxide on tin and bismuth electrodes using in situ infrared spectroscopy and differential electrochemical mass spectrometry

    Science.gov (United States)

    Baruch, Maor F.

    The factors that govern the electrochemical reduction of CO2 on Sn and Bi electrodes were studied. Chapter 1 discusses the relevant literature, the merits of reducing CO2 electrochemically, the ways in which CO2 reduction systems are characterized, and the outstanding challenges. Chapter 2 describes the design and construction of a differential electrochemical mass spectrometry (DEMS) system that can be used to probe the products of electrochemical reactions in situ and in real time. In Chapter 3, the role of surface oxides and hydroxides in the reduction of CO2 on Sn electrodes is discussed. in situ attenuated total reflectance infrared (ATR-IR) spectroscopy is the main analytical technique by which the system was studied. Peaks that are attributed to a surface-bound Sn carbonate are present under conditions that are suitable for CO2 reduction. A strong correlation between the presence of these peaks and catalytic activity exists with respect to the applied potential, the pH of the electrolyte, and the surface condition of the electrode. X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and electrochemical analysis were also used characterize the catalysts. Based on these data, a mechanism for the reduction of CO2 on Sn cathodes is proposed. The roles of morphology and surface oxide presence in the reduction of CO2 on Bi cathodes are discussed in Chapter 4. ATR-IR spectroscopy, XPS, EDX, SEM, cyclic voltammetry, and preparative electrolysis are used to demonstrate that, unlike Sn, Bi electrodes do not possess oxide-dependent catalytic behavior. Instead, it is shown that Bi electrodes are highly sensitive to morphological changes in surface structure, and that surface roughness is detrimental to HCOO-- production from CO2. Finally, it is shown that oxide-derived Bi, formed by the in situ reduction of Bi2O3 nanoparticles at cathodic potentials, can reduce CO2 to HCOO-- at near unit efficiencies at

  19. 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)

  20. Vertical distribution of dehalogenating bacteria in mangrove sediment and their potential to remove polybrominated diphenyl ether contamination.

    Science.gov (United States)

    Pan, Ying; Chen, Juan; Zhou, Haichao; Farzana, Shazia; Tam, Nora F Y

    2017-11-30

    The removal and degradation of polybrominated diphenyl ethers (PBDEs) in sediments are not clear. The vertical distribution of total and dehalogenating bacteria in sediment cores collected from a typical mangrove swamp in South China and their intrinsic degradation potential were investigated. These bacterial groups had the highest abundances in surface sediments (0-5cm). A 5-months microcosm experiment also showed that surface sediments had the highest rate to remove BDE-47 than deeper sediments (5-30cm) under anaerobic condition. The deeper sediments, being more anaerobic, had lower population of dehalogenating bacteria leading to a weaker BDE-47 removal potential than surface sediments. Stepwise multiple regression analysis indicated that Dehalococcoides spp. were the most important dehalogenating bacteria affecting the anaerobic removal of BDE-47 in mangrove sediments. This is the first study reporting that mangrove sediments harbored diverse groups of dehalogenating bacteria and had intrinsic potential to remove PBDE contamination. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. 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.

  2. Effect of the UO2 form on the electrochemical reduction rate in a LiCl-Li2O molten salt

    Science.gov (United States)

    Choi, Eun-Young; Kim, Jong-Kook; Im, Hun-Suk; Choi, In-Kyu; Na, Sang-Ho; Lee, Jae Won; Jeong, Sang Mun; Hur, Jin-Mok

    2013-06-01

    Electrochemical reductions of various UO2 forms were investigated in a molten LiCl-Li2O electrolyte. The study focused on the influence of their sizes and densities on the reduction rate by running experiments with eight UO2 forms. They can be classified into porous and dense forms. The porous forms are one granule and four porous pellets with different densities (55%, 60%, 70% and 80%), all of which were fabricated in our laboratory. The dense forms were prepared by crushing dense pellets, and these were similar in size to the porous pellets and the granules. Systematic comparisons of the reduction rate among the tested UO2 forms revealed that a lower density and smaller size of UO2 led to a faster reduction rate. Particularly, attention was focused on the observation that the size of the UO2 provides more dominant effect on the reduction rate than the density.

  3. 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.

  4. Fungal Strains as Catalysts for the Biotransformation of Halolactones by Hydrolytic Dehalogenation with the Dimethylcyclohexane System

    Directory of Open Access Journals (Sweden)

    Małgorzata Grabarczyk

    2012-08-01

    Full Text Available Bicyclic chloro-, bromo- and iodo-γ-lactones with dimethylcyclohexane rings were used as substrates for bioconversion by several fungal strains (Fusarium, Botrytis and Beauveria. Most of the selected microorganisms transformed these lactones by hydrolytic dehalogenation into the new compound cis-2-hydroxy-4,6-dimethyl-9-oxabicyclo[4.3.0]- nonan-8-one, mainly the (−-isomer. When iodo-γ-lactone was used as the substrate, two products were observed: a hydroxy-γ-lactone and an unsaturated lactone. The structures of all substrates and products were established on the basis of their spectral data. The mechanism of dehalogenation of three halolactones was also studied.

  5. Indirect Evidence Link PCB Dehalogenation with Geobacteraceae in Anaerobic Sediment-Free Microcosms.

    Science.gov (United States)

    Praveckova, Martina; Brennerova, Maria V; Holliger, Christof; De Alencastro, Felippe; Rossi, Pierre

    2016-01-01

    Although polychlorinated biphenyls (PCBs) production was brought to a halt 30 years ago, recalcitrance to degradation makes them a major environmental pollutant at a global scale. Previous studies confirmed that organohalide-respiring bacteria (OHRB) were capable of utilizing chlorinated congeners as electron acceptor. OHRB belonging to the Phyla Chloroflexi and Firmicutes are nowadays considered as the main PCB-dechlorinating organisms. In this study, we aimed at exploring the involvement of other taxa in PCB dechlorination using sediment-free microcosms (SFMs) and the Delor PCB mixture. High rates of congener dehalogenation (up to 96%) were attained in long-term incubations of up to 692 days. Bacterial communities were dominated by Chloroflexi, Proteobacteria, and Firmicutes, among strictly simplified community structures composed of 12 major phyla only. In a first batch of SFMs, Dehalococcoides mccartyi closely affiliated with strains CG4 and CBDB1 was considered as the main actor associated with congener dehalogenation. Addition of 2-bromoethanesulfonate (BES), a known inhibitor of methanogenic activity in a second batch of SFMs had an adverse effect on the abundance of Dehalococcoides sp. Only two sequences affiliated to this Genus could be detected in two (out of six) BES-treated SFMs, contributing to a mere 0.04% of the communities. BES-treated SFMs showed very different community structures, especially in the contributions of organisms involved in fermentation and syntrophic activities. Indirect evidence provided by both statistical and phylogenetic analysis validated the implication of a new cluster of actors, distantly affiliated with the Family Geobacteraceae (Phylum δ-Proteobacteria), in the dehalogenation of low chlorinated PCB congeners. Members of this Family are known already for their dehalogenation capacity of chlorinated solvents. As a result, the present study widens the knowledge for the phylogenetic reservoir of indigenous PCB dechlorinating

  6. Characterization of anaerobic chloroethene-dehalogenating activity in several subsurface sediments

    Energy Technology Data Exchange (ETDEWEB)

    Skeen, R.S.; Gao, J.; Hooker, B.S.; Quesenberry, R.D.

    1996-11-01

    Anaerobic microcosms of subsurface soils from four locations were used to investigate the separate effects of several electron donors on tetrachloroethylene (PCE) dechlorination activity. The substrates tested were methanol, formate, lactate, acetate, and sucrose. Various levels of sulfate-reducing, acetogenic, fermentative, and methanogenic activity were observed in all sediments. PCE dechlorination was detected in all microcosms, but the amount of dehalogenation varied by several orders of magnitude. Trichloroethylene was the primary dehalogenation product; however, small amounts of cis-1,2-dichloroethylene, 1,1-dichloroethylene, and vinyl chloride were also detected in several microcosms. Lactate-amended microcosms showed large amounts of dehalogenation. in three of the four sediments. One of the two sediments which showed positive activity with lactate also had large amounts of delialogenation with methanol. Sucrose, formate, and acetate also stimulated large amounts of delialogenation in one sediment that showed activity with lactate. These results suggest that lactate may be an appropriate substrate for screening sediments for PCE or TCE delialogenation activity, but that the microbial response is not sufficient for complete in situ bioremediation. A detailed study of the Victoria activity revealed that delialogenation rates were more similar to the Cornell culture than to rates measured for methanogens, or a methanol-enriched sediment culture. This may suggest that these sediments contain a highly efficient delialogenation activity similar to the Cornell culture. This assertion is supported further by the fact that an average of 3% of added reducing equivalents could be diverted to dehalogenation in tests which were conducted using PCE-saturated hexadecane as a constant source of PCE during incubation. Further evidence is needed to confirm this premise. The application of these results to in situ bioremediation of highly contaminated areas are discussed.

  7. Polymer nanocomposite membranes with hierarchically structured catalysts for high throughput dehalogenation

    Science.gov (United States)

    Crock, Christopher A.

    Halogenated organics are categorized as primary pollutants by the Environmental Protection Agency. Trichloroethylene (TCE), which had broad industrial use in the past, shows persistence in the environment because of its chemical stability. The large scale use and poor control of TCE resulted in its prolonged release into the environment before the carcinogenic risk associated with TCE was fully understood. TCE pollution stemmed from industrial effluents and improper disposal of solvent waste. Membrane reactors are promising technology for treating TCE polluted groundwater because of the high throughput, relatively low cost of membrane fabrication and facile retrofitting of existing membrane based water treatment facilities with catalytic membrane reactors. Compared to catalytic fluidized or fixed bed reactors, catalytic membrane reactors feature minimal diffusional limitation. Additionally, embedding catalyst within the membrane avoids the need for catalyst recovery and can prevent aggregation of catalytic nanoparticles. In this work, Pd/xGnP, Pd-Au/xGnP, and commercial Pd/Al2O3 nanoparticles were employed in batch and flow-through membrane reactors to catalyze the dehalogenation of TCE in the presence of dissolved H2. Bimetallic Pd-Au/xGnP catalysts were shown to be more active than monometallic Pd/xGnP or commercial Pd/Al 2O3 catalysts. In addition to synthesizing nanocomposite membranes for high-throughput TCE dehalogenation, the membrane based dehalogenation process was designed to minimize the detrimental impact of common catalyst poisons (S2-, HS-, and H2S -) by concurrent oxidation of sulfide species to gypsum in the presence of Ca2+ and removal of gypsum through membrane filtration. The engineered membrane dehalogenation process demonstrated that bimetallic Pd-Au/xGnP catalysts resisted deactivation by residual sulfide species after oxidation, and showed complete removal of gypsum during membrane filtration.

  8. surface properties of electrochemically reduced viscose rayon ...

    African Journals Online (AJOL)

    DJFLEX

    A viscose rayon based activated carbon cloth (ACC) was electrochemically reduced under a wide ... Electrochemical reduction resulted in a loss of 28% BET surface .... electrodes. As shown in. Figure 1. Schematic of the electrochemical cell used for electrochemical reduction. Figure 1, the anodes were placed at equal.

  9. 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.

  10. 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.

  11. Controlled amino-functionalization by electrochemical reduction of bromo and nitro azobenzene layers bound to Si(111) surfaces

    NARCIS (Netherlands)

    Ullien, D.; Thüne, P.C.; Jager, W.F.; Sudhölter, E.J.R.; De Smet, L.C.P.M.

    2014-01-01

    4-Nitrobenzenediazonium (4-NBD) and 4-bromobenzenediazonium (4-BBD) salts were grafted electrochemically onto H-terminated, p-doped silicon (Si) surfaces. Atomic force microscopy (AFM) and ellipsometry experiments clearly showed layer thicknesses of 2–7 nm, which indicate multilayer formation.

  12. Structural analysis of an intact monoclonal antibody by online electrochemical reduction of disulfide bonds and Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Nicolardi, Simone; Deelder, André M; Palmblad, Magnus; van der Burgt, Yuri E M

    2014-06-03

    Structural confirmation and quality control of recombinant monoclonal antibodies (mAbs) by top-down mass spectrometry is still challenging due to the size of the proteins, disulfide content, and post-translational modifications such as glycosylation. In this study we have applied electrochemistry (EC) to overcome disulfide bridge complexity in top-down analysis of mAbs. To this end, an electrochemical cell was coupled directly to an electrospray ionization (ESI) source and a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer (MS) equipped with a 15 T magnet. By performing online EC-assisted reduction of interchain disulfide bonds in an intact mAb, the released light chains could be selected for tandem mass spectrometry (MS/MS) analysis without interference from heavy-chain fragments. Moreover, the acquisition of full MS scans under denaturing conditions allowed profiling of all abundant mAb glycoforms. Ultrahigh-resolution FTICR-MS measurements provided fully resolved isotopic distributions of intact mAb and enabled the identification of the most abundant adducts and other interfering species. Furthermore, it was found that reduction of interchain disulfide bonds occurs in the ESI source dependent on capillary voltage and solvent composition. This phenomenon was systematically evaluated and compared with the results obtained from reduction in the electrochemical cell.

  13. 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.

  14. Efficient Electrocatalytic Reduction of CO2by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes: A Step Towards the Electrochemical CO2Refinery.

    Science.gov (United States)

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

    2017-06-26

    Herein 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, dubbed "HNCM/CNT". The membrane is demonstrated to function as a binder-free, high-performance gas diffusion electrode for the electrocatalytic reduction of CO 2 to formate. The Faradaic efficiency (FE) for the production of formate is 81 %. Furthermore, the robust structural and electrochemical properties of the membrane endow it with excellent long-term stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid

    Directory of Open Access Journals (Sweden)

    Zongya Zhao

    2015-07-01

    Full Text Available In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO, HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM, electrochemical impedance spectroscopy (EIS and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR possessed the highest electrocatalytic activity toward dopamine (DA. As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA and uric acid (UA using the differential pulse voltammetry (DPV technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3. The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples.

  17. Amino acid assisted dehalogenation of carbon tetrachloride by green rust

    DEFF Research Database (Denmark)

    Yin, Weizhao; Strobel, Bjarne W.; Hansen, Hans Chr. Bruun

    2017-01-01

    Layered FeII-FeIII hydroxides (green rusts, GR) are promising reactants for reductive dechlorination of chlorinated solvents due to high reaction rates and the opportunity to inject reactive slurries of the compounds into contaminant plumes. However, it is necessary to develop strategies...

  18. NiCr (x) Fe2-x O-4 as cathode materials for electrochemical reduction of NO (x)

    DEFF Research Database (Denmark)

    Bræstrup, Frantz Radzik; Kammer Hansen, Kent

    2010-01-01

    the electrochemical behavior in 1% NO, 1% NO2, and 10% O2. NiCr2O4 shows high activity in NO and NO2 relative to O2 and can therefore be considered as a possible electrode material. Peaks were detected in the voltammograms recorded on NiCr2O4 in 1% NO. The origin of the peaks seems to be related to the oxidation...

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Direct electrochemistry and electrochemical catalysis of immobilized hemoglobin in an ethanol-water mixture.

    Science.gov (United States)

    Liu, Hui-Hong; Wan, Yong-Qing; Zou, Guo-Lin

    2006-08-01

    Hemoglobin (Hb) was immobilized on a glassy carbon electrode (GCE) surface by konjac glucomannan (KGM). KGM hydrogel films on GCE have relatively high stabilities in aqueous-ethanol mixtures. The entrapped hemoglobin undergoes fast direct electron transfer reactions in aqueous-organic solvent mixtures. The peak current is bigger, the peak-to-peak separation smaller and the formal potential observed in the cyclic voltammogram is more negative for Hb-KGM/GCE in ethanol-PBS compared to Hb-KGM/GCE in PBS. The electrochemical properties of the Hb in aqueous-organic solution are almost unchanged from with those observed for the purely aqueous solution, suggesting that water pools in the KGM hydrogel play an important role in preventing changes in conformation and making proteins unreactive with polar organic solvents. The immobilized Hb was able to catalyze the reduction of nitric oxide, peroxides (hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2-butanone peroxide), and the dehalogenation of haloethanes (hexachloroethane, pentachloroethane, tetrachloroethane, etc.). The stability and reproducibility of the modified electrode meant that it could be used to determine these substances.

  5. Genomic and Transcriptomic Analysis of Growth-Supporting Dehalogenation of Chlorinated Methanes in Methylobacterium

    Directory of Open Access Journals (Sweden)

    Pauline Chaignaud

    2017-09-01

    Full Text Available Bacterial adaptation to growth with toxic halogenated chemicals was explored in the context of methylotrophic metabolism of Methylobacterium extorquens, by comparing strains CM4 and DM4, which show robust growth with chloromethane and dichloromethane, respectively. Dehalogenation of chlorinated methanes initiates growth-supporting degradation, with intracellular release of protons and chloride ions in both cases. The core, variable and strain-specific genomes of strains CM4 and DM4 were defined by comparison with genomes of non-dechlorinating strains. In terms of gene content, adaptation toward dehalogenation appears limited, strains CM4 and DM4 sharing between 75 and 85% of their genome with other strains of M. extorquens. Transcript abundance in cultures of strain CM4 grown with chloromethane and of strain DM4 grown with dichloromethane was compared to growth with methanol as a reference C1 growth substrate. Previously identified strain-specific dehalogenase-encoding genes were the most transcribed with chlorinated methanes, alongside other genes encoded by genomic islands (GEIs and plasmids involved in growth with chlorinated compounds as carbon and energy source. None of the 163 genes shared by strains CM4 and DM4 but not by other strains of M. extorquens showed higher transcript abundance in cells grown with chlorinated methanes. Among the several thousand genes of the M. extorquens core genome, 12 genes were only differentially abundant in either strain CM4 or strain DM4. Of these, 2 genes of known function were detected, for the membrane-bound proton translocating pyrophosphatase HppA and the housekeeping molecular chaperone protein DegP. This indicates that the adaptive response common to chloromethane and dichloromethane is limited at the transcriptional level, and involves aspects of the general stress response as well as of a dehalogenation-specific response to intracellular hydrochloric acid production. Core genes only differentially

  6. Process for the solvent extraction for the radiolysis and dehalogenation of halogenated organic compounds in soils, sludges, sediments and slurries

    Science.gov (United States)

    Golden, Jeffry

    2007-02-13

    A process of extracting halogenated organic compounds, and particularly PCBs, from soil, sediment, slurry, sludge and dehalogenating the compounds contacts a contaminated soil sample with an extraction medium of a mixture of an alkane and a water miscible alcohol. The organic compounds dissolve in the extraction medium which is separated from the soil by passing water upwardly through the soil. The extraction medium floats to the surface of the water and is separated. Thereafter, the extraction medium containing the halogenated organic contaminants is subjected to ionizing radiation to radiolytically dehalogenate the compounds.

  7. 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.

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

    Science.gov (United States)

    Kugai, Junichiro; Kubota, Chihiro; Okazaki, Tomohisa; Seino, Satoshi; Nakagawa, Takashi; Nitani, Hiroaki; Yamamoto, Takao A.

    2015-06-01

    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.

  9. Catalytic reduction of 1,2-dihaloethanes by electrochemically generated C60n- (n=2 and 3)

    Science.gov (United States)

    D'Souza, F.; Choi, J.-P.; Hsieh, Y. Y.; Shriner, K.; Kutner, W.

    1998-08-01

    1,2-Dihaloethanes were catalytically reduced by electrochemically generated C60n- (n=2 or 3) anions in 0.1 M tetrabutlammonium hexafluorophosphate in benzonitrile under cyclic voltammetry and rotating disk electrode (RDE) voltammetry conditions at platinum electrodes. The second-order catalytic rate constants, determined by the RDE voltammetry under pseudo-first-order conditions against the 1,2-dihaloethanes, largely increase in the order: 1,2-dichloroethane1,2-dibromoethane<1,2-diiodoethane. Alkanes, alkenes and monohalogenated alkanes were products of the electrocatalyses.

  10. pH control for enhanced reductive bioremediation of chlorinated solvent source zones

    International Nuclear Information System (INIS)

    Robinson, Clare; Barry, D.A.; McCarty, Perry L.; Gerhard, Jason I.; Kouznetsova, Irina

    2009-01-01

    Enhanced reductive dehalogenation is an attractive treatment technology for in situ remediation of chlorinated solvent DNAPL source areas. Reductive dehalogenation is an acid-forming process with hydrochloric acid and also organic acids from fermentation of the electron donors typically building up in the source zone during remediation. This can lead to groundwater acidification thereby inhibiting the activity of dehalogenating microorganisms. Where the soils' natural buffering capacity is likely to be exceeded, the addition of an external source of alkalinity is needed to ensure sustained dehalogenation. To assist in the design of bioremediation systems, an abiotic geochemical model was developed to provide insight into the processes influencing the groundwater acidity as dehalogenation proceeds, and to predict the amount of bicarbonate required to maintain the pH at a suitable level for dehalogenating bacteria (i.e., > 6.5). The model accounts for the amount of chlorinated solvent degraded, site water chemistry, electron donor, alternative terminal electron-accepting processes, gas release and soil mineralogy. While calcite and iron oxides were shown to be the key minerals influencing the soil's buffering capacity, for the extensive dehalogenation likely to occur in a DNAPL source zone, significant bicarbonate addition may be necessary even in soils that are naturally well buffered. Results indicated that the bicarbonate requirement strongly depends on the electron donor used and availability of competing electron acceptors (e.g., sulfate, iron (III)). Based on understanding gained from this model, a simplified model was developed for calculating a preliminary design estimate of the bicarbonate addition required to control the pH for user-specified operating conditions.

  11. Dehalogenation, degradation and mineralization of diuron by peroxone (peroxide/ozone) treatment.

    Science.gov (United States)

    Catalkaya, Ebru Cokay; Kargi, Fikret

    2009-05-01

    Removal of diuron from aqueous solution by peroxone (hydrogen peroxide/ozone) oxidation was investigated using Box-Behnken statistical experiment design and the response surface methodology (RSM). Effects of diuron, H(2)O(2) concentrations and initial pH on the extent of diuron, total organic carbon (TOC) and adsorbable organic halogen (AOX) removals were investigated. Ozone dose was kept constant at 45 mg min(-1). Optimum reagent doses yielding the highest diuron, TOC and AOX removals were also determined. Hydrogen peroxide dose and pH were the most effective parameters for pesticide removal while hydrogen peroxide dose had the most significant effect on AOX removal (dehalogenation). All parameters affected mineralization (TOC removal) of diuron. Nearly complete removal of diuron was achieved within 5 minutes, while complete mineralization and dehalogenation were not achieved even within 60 minutes at high diuron doses indicating formation of some intermediate products. The optimal H(2)O(2)/pH/diuron ratio resulting in the maximum pesticide (100%), TOC (82%) and AOX (95%) removal was found to be 340/8/10.

  12. Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide.

    Science.gov (United States)

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

    2015-07-15

    Solar-driven electrochemical cells can be used to convert carbon dioxide, water, and sunlight into transportation fuels or into precursors to such fuels. The voltage efficiency of such devices depends on the (i) physical properties of its components (catalysts, electrolyte, and membrane); (ii) operating conditions (carbon dioxide flowrate and pressure, current density); and (iii) physical dimensions of the cell. The sources of energy loss in a carbon dioxide reduction (CO2R) cell are the anode and cathode overpotentials, the difference in pH between the anode and cathode, the difference in the partial pressure of carbon dioxide between the bulk electrolyte and the cathode, the ohmic loss across the electrolyte and the diffusional resistances across the boundary layers near the electrodes. In this study, we analyze the effects of these losses and propose optimal device configurations for the efficient operation of a CO2R electrochemical cell operating at a current density of 10 mA cm(-2). Cell operation at near-neutral bulk pH offers not only lower polarization losses but also better selectivity to CO2R versus hydrogen evolution. Addition of supporting electrolyte to increase its conductivity has a negative impact on cell performance because it reduces the electric field and the solubility of CO2. Addition of a pH buffer reduces the polarization losses but may affect catalyst selectivity. The carbon dioxide flowrate and partial pressure can have severe effects on the cell efficiency if the carbon dioxide supply rate falls below the consumption rate. The overall potential losses can be reduced by use of an anion, rather than a cation, exchange membrane. We also show that the maximum polarization losses occur for the electrochemical synthesis of CO and that such losses are lower for the synthesis of products requiring a larger number of electrons per molecule, assuming a fixed current density. We also find that the reported electrocatalytic activity of copper below -1

  13. Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

    International Nuclear Information System (INIS)

    Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

    2015-01-01

    Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

  14. Electrochemical impedance spectroscopy study of a surface confined redox reaction: The reduction of azobenzene on mercury in the absence of diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Prieto, Francisco, E-mail: dapena@us.es [Department of Physical Chemistry, University of Seville, c/Profesor Garcia Gonzalez no 2, 41012 Seville (Spain); Rueda, Manuela; Hidalgo, Jose; Martinez, Elisa; Navarro, Inmaculada [Department of Physical Chemistry, University of Seville, c/Profesor Garcia Gonzalez no 2, 41012 Seville (Spain)

    2011-09-30

    The kinetics of azobenzene reduction on mercury electrodes in the absence of diffussional mass transport is studied by electrochemical impedance spectroscopy (EIS) in acetic acid/acetate buffered solutions at different pH values. Cyclic voltammetry experiments confirm the absence of diffusion effects and provide the values of the surface equilibrium potential. The analysis of the impedance frequency spectrums at every potential within the faradaic region conforms well the model and provides the global rate constant of the process, k{sub f}. The potential dependence of k{sub f} suggests the existence of an EE mechanism, with two electron transfers controlling the overall rate. The kinetic parameters of every step are obtained and their pH dependences clarify the role played by the protonation steps.

  15. Effects of size reduction on the structure and magnetic properties of core–shell Ni3Si/silica nanoparticles prepared by electrochemical synthesis

    International Nuclear Information System (INIS)

    Pigozzi, Giancarlo; Mukherji, Debashis; Elerman, Yalçin; Strunz, Pavel; Gilles, Ralph; Hoelzel, Markus; Barbier, Bruno; Schmutz, Patrik

    2014-01-01

    Highlights: • β 1 -Ni 3 Si nanoparticles were produced by electrochemical selective phase dissolution. • A core–shell structure with ordered Ni 3 Si core and silica shell is obtained. • The ordered L1 2 crystal structure is maintained upon size reduction down to 20 nm. • Bulk Ni 3 Si is ferromagnetic below 260 K with low saturation magnetization (2 emu/g). • Nanoparticles are superparamagnetic (T B ∼ 9–11 K) with magnetization >20 emu/g. -- Abstract: Nanostructured nickel silicides find application in electronics, high-temperature alloys, electrode materials and catalysis. In this work, the effect of size reduction on the structure and magnetic properties of β 1 -Ni 3 Si intermetallic phase nanoparticles is studied. Electrochemical selective phase dissolution (ESPD) was used to produce the β 1 -Ni 3 Si nanoparticles of different sizes (from 20 to 215 nm) by extracting β 1 nano-size precipitates from two-phase Ni–Si and Ni–Si–Al precursor alloys. The extracted nanoparticles have a core–shell structure with β 1 -Ni 3 Si core and an amorphous silica shell. Particles size and shape are controlled by the composition and thermal treatment of the precursor alloys. Precipitates size is scaled without modifying the ordered L1 2 lattice structure. The bulk β 1 -Ni 3 Si is ferromagnetic below 260 K with low saturation magnetization (2 emu/g), while the core–shell Ni 3 Si/silica nanoparticles are superparamagnetic at low temperatures ( 20 emu/g at 5 T. It is suggested that weak particle magnetic moments and low magnetic anisotropy of the L1 2 structure are responsible for these properties. The shell on one hand protects the core from degradation; however the oxidation of the core/shell interface region can influence the magnetic behavior of the nano-powders

  16. 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.

  17. Effect of Si Addition on the Electrochemical Reduction Rate of SiO2 Granules in Molten CaCl2

    Science.gov (United States)

    Zhong, Ming; Yang, Xiao; Yasuda, Kouji; Homma, Takayuki; Nohira, Toshiyuki

    2018-02-01

    The effect of adding Si powder/granules on the electrochemical reduction rate of SiO2 granules in molten CaCl2 was investigated. Various starting materials were prepared by mixing different amounts (up to 80 mass pct) of Si powder/granules (four different sizes: temperature of 1123 K (850 °C). The effects of the size and amount of Si added on the reaction rates were then studied. When the size of the Si powder added is less than 5 µm, the reaction rate decreases as more Si is added. When Si with a size of 20 to 100 or 100 to 250 µm is used, the reaction rate does not change substantially with the amount added. When 0.5 to 1.0 mm Si is used, the reduction rate is the largest when 40 mass pct Si is added. The reduction rate is influenced by the reaction surface and the diffusion of O2- ions in the mixture.

  18. 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

  19. ELECTROCHEMICAL PROPERTIES AND ELECTROCHEMICAL ...

    African Journals Online (AJOL)

    Rct is about five times higher in acetonitrile relative to water. All these EIS results of the different types of PPy suggest a relation with the wettability of the polymer. KEY WORDS: Conducting polymers, Polypyrrole, Electrochemical impedance spectroscopy, Equivalent- electrical circuit, Micellar media. INTRODUCTION.

  20. Electrochemical reduction of oligo-nitrocalix[4]arenes - Molecules with multiple redox centers. different conformations and variable shape

    Czech Academy of Sciences Publication Activity Database

    Ludvík, Jiří; Liška, Alan; Lhoták, P.

    2015-01-01

    Roč. 66, č. 26 (2015), s. 23-31 ISSN 1938-5862 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : Aromatic compounds * Electrochemistry * Electrolytic reduction Subject RIV: CG - Electrochemistry

  1. Study of Pyridine-Mediated Electrochemical Reduction of CO2 to Methanol at High CO2 Pressure.

    Science.gov (United States)

    Rybchenko, Sergey I; Touhami, Dalila; Wadhawan, Jay D; Haywood, Stephanie K

    2016-07-07

    The recently proposed highly efficient route of pyridine-catalyzed CO2 reduction to methanol was explored on platinum electrodes at high CO2 pressure. At 55 bar (5.5 MPa) of CO2 , the bulk electrolysis in both potentiostatic and galvanostatic regimes resulted in methanol production with Faradaic yields of up to 10 % for the first 5-10 C cm(-2) of charge passed. For longer electrolysis, the methanol concentration failed to increase proportionally and was limited to sub-ppm levels irrespective of biasing conditions and pyridine concentration. This limitation cannot be removed by electrode reactivation and/or pre-electrolysis and appears to be an inherent feature of the reduction process. In agreement with bulk electrolysis findings, the CV analysis supported by simulation indicated that hydrogen evolution is still the dominant electrode reaction in pyridine-containing electrolyte solution, even with an excess CO2 concentration in the solution. No prominent contribution from either a direct or coupled CO2 reduction was found. The results obtained suggest that the reduction of CO2 to methanol is a transient process that is largely decoupled from the electrode charge transfer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. NOx reduction on ag electrochemical cells with a K-Pt-Al 2O3 adsorption layer

    DEFF Research Database (Denmark)

    Shao, Jing; Kammer Hansen, Kent

    2013-01-01

    and a microstructure characterization. The blank Ag cell was incapable of converting NOx to N2 under any of the investigated conditions. In contrast, the Ag cell with an adsorption layer showed good NOx reduction activity. An 82% NOx conversion with 100% N2 selectivity and 7.7% current efficiency was achieved at -1...

  3. 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.

  4. 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)

  5. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

  6. Electrochemical dissolution of fresh and passivated chalcopyrite electrodes. Effect of pyrite on the reduction of Fe3+ ions and transport processes within the passive film

    International Nuclear Information System (INIS)

    Olvera, O.G.; Quiroz, L.; Dixon, D.G.; Asselin, E.

    2014-01-01

    Graphical abstract: - Highlights: • FeS 2 increased the dissolution rate of fresh and passivated CuFeS 2 electrodes. • Fe 3+ reduction was the rate controlling step in the dissolution of fresh CuFeS 2 . • Diffusion within the passive film controlled the dissolution rate of passivated CuFeS 2 . - Abstract: The effect of pyrite (FeS 2 ) on the electrochemical dissolution of fresh and passivated chalcopyrite (CuFeS 2 ) electrodes has been studied. Current density values for the dissolution of CuFeS 2 were calculated from EIS measurements. FeS 2 increased the dissolution rate of fresh and passivated CuFeS 2 electrodes indicating that the galvanic effect continued even after the electrode was chemically passivated. The dissolution rate of CuFeS 2 decreased by a factor of 3 after the passivation treatment. Due to the low diffusion rates of ions within the CuFeS 2 passive film and due to an increase in the resistance to the transfer of electrons at the electrode/film interface, the activity of FeS 2 for the reduction of Fe 3+ ions was also reduced by a factor of 2.3 even though FeS 2 was not exposed to any chemical treatment. The results in this work indicate that the dissolution rate of the fresh CuFeS 2 electrode was controlled by the reduction of Fe 3+ ions whereas for the passivated CuFeS 2 electrode the dissolution rate was controlled by diffusion within the passive film

  7. Selectivity on Etching: Creation of High-Energy Facets on Copper Nanocrystals for CO2 Electrochemical Reduction.

    Science.gov (United States)

    Wang, Zhenni; Yang, Guang; Zhang, Zhaorui; Jin, Mingshang; Yin, Yadong

    2016-04-26

    Creating high-energy facets on the surface of catalyst nanocrystals represents a promising method for enhancing their catalytic activity. Herein we show that crystal etching as the reverse process of crystal growth can directly endow nanocrystal surfaces with high-energy facets. The key is to avoid significant modification of the surface energies of the nanocrystal facets by capping effects from solvents, ions, and ligands. Using Cu nanocubes as the starting material, we have successfully demonstrated the creation of high-energy facets in metal nanocrystals by controlled chemical etching. The etched Cu nanocrystals with enriched high-energy {110} facets showed significantly enhanced activity toward CO2 reduction. We believe the etching-based strategy could be extended to the synthesis of nanocrystals of many other catalysts with more active high-energy facets.

  8. Electrochemical CO2reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products.

    Science.gov (United States)

    Cave, Etosha R; Montoya, Joseph H; Kuhl, Kendra P; Abram, David N; Hatsukade, Toru; Shi, Chuan; Hahn, Christopher; Nørskov, Jens K; Jaramillo, Thomas F

    2017-06-21

    In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. We explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction on Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.

  9. Scanning electrochemical microscopy. 47. Imaging electrocatalytic activity for oxygen reduction in an acidic medium by the tip generation-substrate collection mode.

    Science.gov (United States)

    Fernández, José L; Bard, Allen J

    2003-07-01

    The oxygen reduction reaction (ORR) in acidic medium was studied on different electrode materials by scanning electrochemical microscopy (SECM) operating in a new variation of the tip generation-substrate collection mode. An ultramicroelectrode tip placed close to the substrate electrode oxidizes water to oxygen at a constant current. The substrate is held at a potential where the tip-generated oxygen is reduced and the resulting substrate current is measured. By changing the substrate potential, it is possible to obtain a polarization (current-potential) curve, which depends on the electrocatalytic activity of the substrate material. The main difference between this mode and the classical feedback SECM mode of operation is that the feedback diffusion process is not required for the measurement, allowing its application for studying the ORR in acidic solutions. Activity-sensitive images of heterogeneous surfaces, e.g., with Pt and Au electrodes, were obtained from the substrate current when the x-y plane was scanned with the tip. The usefulness of this technique for imaging electrocatalytic activity of smooth metallic electrodes and of highly dispersed fuel cell-type electrocatalysts was demonstrated. The application of this method to the combinatorial chemical analysis of electrode materials and electrocatalysts is discussed.

  10. Electrochemical properties and electrochemical impedance ...

    African Journals Online (AJOL)

    Polypyrrole (PPy) films of different thickness were characterized by electrochemical impedance spectroscopy (EIS) measurements in acetonitrile and aqueous solutions, containing 0.1 M NaClO4 or sodium dodecylsulfate as the dopant. The PPy films were electrochemically deposited on Pt, and their electrochemical ...

  11. Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza

    2013-01-01

    Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center of the po...... from CO, featuring an overpotential of 0.22 V. Additionally, we have also examined the hydrogen evolution and oxidation reaction, and in their case, too, Rh-porphyrin turned out to be the best catalyst with an overpotential of 0.15 V. © 2013 American Chemical Society....... of the porphyrin ring. A clear difference in catalytic properties compared to extended metal surfaces was observed owing to a different electronic nature of the active site. The preference to bind hydrogen, however, becomes a major obstacle in the reaction path. A possible solution to this problem is to reduce CO...... instead of CO2. Volcano plots were constructed on the basis of scaling relations of reaction intermediates, and from these plots the reaction steps with the highest overpotentials were deduced. The Rh-porphyrin-like functionalized graphene was identified as the most active catalyst for producing methanol...

  12. Durability of template-free Fe-N-C foams for electrochemical oxygen reduction in alkaline solution

    Science.gov (United States)

    Mufundirwa, Albert; Harrington, George F.; Smid, Břetislav; Cunning, Benjamin V.; Sasaki, Kazunari; Lyth, Stephen M.

    2018-01-01

    Due to the high cost and limited availability of platinum, the development of non-platinum-group metals (non-PGM) catalysts is of paramount importance. A promising alternative to Pt are Fe-N-C-based materials. Here we present the synthesis, characterization and electrochemistry of a template-free nitrogen-doped carbon foam, impregnated with iron. This low-cost and gram-scale method results in materials with micron-scale pore size and large surface area (1600 m2g-1). When applied as an oxygen reduction reaction (ORR) electrocatalyst in alkaline solution, the Fe-N-C foams display extremely high initial activity, slightly out-performing commercially available non-PGM catalysts (NCP-2000, Pajarito Powder). The load-cycle durability in alkaline solution is investigated, and the performance steadily degrades over 60,000 potential cycles, whilst the commercial catalyst is remarkably stable. The post-operation catalyst microstructure is elucidated by transmission electron microscopy (TEM), to provide insight into the degradation processes. The resulting images suggest that potential cycling leads to leaching of atomically dispersed Fe-N2/4 sites in all the catalysts, whereas encapsulated iron nanoparticles are protected.

  13. Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Le, Minh [Louisiana State Univ., Baton Rouge, LA (United States); Ren, Maoming [Louisiana State Univ., Baton Rouge, LA (United States); Zhang, Ziyu [Louisiana State Univ., Baton Rouge, LA (United States); Sprunger, Phillip T. [Louisiana State Univ., Baton Rouge, LA (United States); Kurtz, Richard L. [Louisiana State Univ., Baton Rouge, LA (United States); Flake, John C. [Louisiana State Univ., Baton Rouge, LA (United States)

    2011-03-05

    The direct reduction of CO2 to CH3OH is known to occur at several types of electrocatalysts including oxidized Cu electrodes. In this work, we examine the yield behavior of an electrodeposited cuprous oxide thin film and explore relationships between surface chemistry and reaction behavior relative to air-oxidized and anodized Cu electrodes. CH3OH yields (43 μmol cm-2 h-1) and Faradaic efficiencies (38%) observed at cuprous oxide electrodes were remarkably higher than air-oxidized or anodized Cu electrodes suggesting Cu(I) species may play a critical role in selectivity to CH3OH. Experimental results also show CH3OH yields are dynamic and the copper oxides are reduced to metallic Cu in a simultaneous process. Yield behavior is discussed in comparison with photoelectrochemical and hydrogenation reactions where the improved stability of Cu(I) species may allow continuous CH3OH generation.

  14. Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

    2017-04-15

    Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

  15. Structure-property relationship of bifunctional MnO2 nanostructures: highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media.

    Science.gov (United States)

    Meng, Yongtao; Song, Wenqiao; Huang, Hui; Ren, Zheng; Chen, Sheng-Yu; Suib, Steven L

    2014-08-13

    Manganese oxides of various structures (α-, β-, and δ-MnO2 and amorphous) were synthesized by facile methods. The electrocatalytic properties of these materials were systematically investigated for catalyzing both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in alkaline media. Extensive characterization was correlated with the activity study by investigating the crystal structures (XRD, HRTEM), morphologies (SEM), porosities (BET), surfaces (XPS, O2-TPD/MS), and electrochemical properties (Tafel analysis, Koutechy-Levich plots, and constant-current electrolysis). These combined results show that the electrocatalytic activities are strongly dependent on the crystallographic structures, and follow an order of α-MnO2 > AMO > β-MnO2 > δ-MnO2. Both OER studies and ORR studies reveal similar structure-determined activity trends in alkaline media. In the OER studies, α-MnO2 displays an overpotential of 490 mV compared to 380 mV shown by an Ir/C catalyst in reaching 10 mA cm(-2). Meanwhile, α-MnO2 also exhibits stability for 3 h when supplying a constant current density of 5 mA cm(-2). This was further improved by adding Ni(2+) dopants (ca. 8 h). The superior OER activity was attributed to several factors, including abundant di-μ-oxo bridges existing in α-MnO2 as the protonation sites, analogous to the OEC in PS-II of the natural water oxidation system; the mixed valencies (AOS = 3.7); and the lowest charge transfer resistances (91.8 Ω, η = 430 mV) as revealed from in situ electrochemical impedance spectroscopy (EIS). In the ORR studies, when reaching 3 mA cm(-2), α-MnO2 shows 760 mV close to 860 mV for the best ORR catalyst (20% Pt/C). The outstanding ORR activity was due to the strongest O2 adsorption capability of α-MnO2 suggested by temperature-programmed desorption. As a result, this discovery of the structure-related electrocatalytic activities could provide guidance in the further development of easily prepared, scalable, and low

  16. Bimetallic Pt-Au nanocatalysts electrochemically deposited on graphene and their electrocatalytic characteristics towards oxygen reduction and methanol oxidation.

    Science.gov (United States)

    Hu, Yaojuan; Zhang, Hua; Wu, Ping; Zhang, Hui; Zhou, Bo; Cai, Chenxin

    2011-03-07

    The burgeoning demand for clean and energy-efficient fuel cell system requires electrocatalysts to deliver greater activity and selectivity. Bimetallic catalysts have proven superior to single metal catalysts in this respect. This work reports the preparation, characterization, and electrocatalytic characteristics of a new bimetallic nanocatalyst. The catalyst, Pt-Au-graphene, was synthesized by electrodeposition of Pt-Au nanostructures on the surface of graphene sheets, and characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), and voltammetry. The morphology and composition of the nanocatalyst can be easily controlled by adjusting the molar ratio between Pt and Au precursors. The electrocatalytic characteristics of the nanocatalysts for the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) were systematically investigated by cyclic voltammetry. The Pt-Au-graphene catalysts exhibits higher catalytic activity than Au-graphene and Pt-graphene catalysts for both the ORR and the MOR, and the highest activity is obtained at a Pt/Au molar ratio of 2:1. Moreover, graphene can significantly enhance the long-term stability of the nanocatalyst toward the MOR by effectively removing the accumulated carbonaceous species formed in the oxidation of methanol from the surface of the catalyst. Therefore, this work has demonstrated that a higher performance of ORR and the MOR could be realized at the Pt-Au-graphene electrocatalyst while Pt utilization also could be greatly diminished. This method may open a general approach for the morphology-controlled synthesis of bimetallic Pt-M nanocatalysts, which can be expected to have promising applications in fuel cells.

  17. 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 d...

  18. The electrochemical reduction of PdCl42- and PdCl62- in polyaniline: Influence of Pd deposit morphology on methanol oxidation in alkaline solution

    International Nuclear Information System (INIS)

    Hatchett, David W.; Millick, Nicole M.; Kinyanjui, John M.; Pookpanratana, Sujitra; Baer, Marcus; Hofmann, Timo; Luinetti, Alessio; Heske, Clemens

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → The synthesis of PANI/Pd composites using PdCl 4 2- and PdCl 6 2- is achieved. → Conductivity of PANI/Pd composites is observed in alkaline solution (pH ∼ 14). → Oxidation of methanol at PANI/Pd is influenced to be the Pd surface morphology. → Surface poisoning is minimized for PANI/Pd produced using PdCl 4 2- . → The Pd metal acts as a solid state dopant in PANI. - Abstract: The controlled uptake and electrochemical reduction of metal precursors PdCl 4 2- and PdCl 6 2- in polyaniline (PANI) is demonstrated. The formation of PANI/Pd composites is achieved with a reduction in proton doping and an increase in the oxidation of the polymer with Pd deposits physically blocking the nitrogen groups. High surface area filaments (PdCl 4 2- ) or a rough encapsulation (PdCl 6 2- ) of Pd metal on PANI are obtained. The structural differences highlight the influence of the metal precursor oxidation state on the morphology of the Pd deposits in PANI. Thermal gravimetric analysis provides an estimate of the Pd content for each composite of ∼40%. X-ray Photoelectron Spectroscopy and X-ray-excited Auger Electron Spectroscopy analyses confirm the deposition of Pd metal. The catalytic oxidation of methanol was demonstrated for both PANI/Pd composites in alkaline solutions that prohibit proton doping of the polymer. The data indicates that Pd metal acts as a solid-state dopant that may delocalize the charge on the polymer backbone to maintain conductivity. Methanol oxidation at PANI/Pd composites produced using PdCl 4 2- was enhanced relative to the composite produced using PdCl 6 2- and a planar Pd electrode. Comparison of PANI/Pd composite produced using PdCl 4 2- with other Pd catalysts from the literature indicates surface poisoning is reduced when Pd is coupled with the polymer. The composite is robust and stable in alkaline solution with the charge density decreasing by 5% on the positive scan and 13% on the

  19. Solvent-dependent formation of Os(0) complexes by electrochemical reduction of [Os(CO)(2,2'-bipyridine)(L)Cl2]; L = Cl(-), PrCN.

    Science.gov (United States)

    Tory, Joanne; King, Lisa; Maroulis, Antonios; Haukka, Matti; Calhorda, Maria José; Hartl, František

    2014-02-03

    Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer-[Os(III)(CO) (bpy)Cl3] (bpy = 2,2'-bipyridine) and trans(Cl)-[Os(II)(CO) (PrCN)(bpy)Cl2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os(II)(CO) (bpy(•-))Cl3](2-) and trans(Cl)-[Os(II)(CO)(PrCN) (bpy(•-))Cl2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os(III)(CO) (bpy)Cl3] is reduced in THF to give ultimately an Os-Os-bonded polymer, probably [Os(0)(CO) (THF)(bpy)]n, whereas in PrCN the well-soluble, probably mononuclear [Os(0)(CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[Os(II)(CO)(PrCN) (bpy)Cl2] in both solvents. In MeCN, similar to THF, the [Os(0)(CO) (MeCN)(bpy)]n polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os(0)(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os(0)(CO) (THF)(bpy)]n: ΔE1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad ν(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic ν(Pr-CN) band below 2200 cm(-1) in addition to the intense and narrow ν(CO) absorption band. For the first time, in this work the M(0)-bpy (M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os(0)(CO) (PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os(0)(CO

  20. Enhanced photocatalytic, electrochemical and photoelectrochemical properties of TiO{sub 2} nanotubes arrays modified with Cu, AgCu and Bi nanoparticles obtained via radiolytic reduction

    Energy Technology Data Exchange (ETDEWEB)

    Nischk, Michał [Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, 11/12 G. Narutowicza 11/12 St., 80-233 Gdansk (Poland); Department of Environmental Technology, Faculty of Chemistry, University of Gdansk, 63 Wita Stwosza St., 80-308 Gdansk (Poland); Mazierski, Paweł [Department of Environmental Technology, Faculty of Chemistry, University of Gdansk, 63 Wita Stwosza St., 80-308 Gdansk (Poland); Wei, Zhishun [Institute for Catalysis, Hokkaido University, N21, W10, 001-0021, Sapporo (Japan); Siuzdak, Katarzyna [Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, 14 Fiszera St., 80-231 Gdansk (Poland); Kouame, Natalie Amoin [Laboratoire de Chimie Physique, CNRS—UMR 8000,Université Paris-Sud, Université Paris-Saclay, Bâtiment 349, 91405 Orsay (France); Kowalska, Ewa [Institute for Catalysis, Hokkaido University, N21, W10, 001-0021, Sapporo (Japan); Remita, Hynd [Laboratoire de Chimie Physique, CNRS—UMR 8000,Université Paris-Sud, Université Paris-Saclay, Bâtiment 349, 91405 Orsay (France); Zaleska-Medynska, Adriana, E-mail: adriana.zaleska@ug.edu.pl [Department of Environmental Technology, Faculty of Chemistry, University of Gdansk, 63 Wita Stwosza St., 80-308 Gdansk (Poland)

    2016-11-30

    Highlights: • TiO{sub 2} nanotubes were modified with Cu, AgCu, Bi nanoparticles via gamma radiolysis. • Excessive amount of deposited metal decreased photocatalytic activity. • AgCu-modified samples were more active than Cu-modified (with the same Cu content). • AgCu nanoparticles exist in a core{sub (Ag)}-shell{sub (Cu)} form. • Examined photocatalysts were resistant towards photocorrosion processes. - Abstract: TiO{sub 2} nanotubes arrays (NTs), obtained via electrochemical anodization of Ti foil, were modified with monometallic (Cu, Bi) and bimetallic (AgCu) nanoparticles. Different amounts of metals’ precursors were deposited on the surface of NTs by the spin-coating technique, and the reduction of metals was performed via gamma radiolysis. Surface modification of titania was studied by EDS and XPS analysis. The results show that AgCu nanoparticles exist in a Ag{sub core}-Cu{sub shell} form. Photocatalytic activity was examined under UV irradiation and phenol was used as a model pollutant of water. Over 95% of phenol degradation was achieved after 60 min of irradiation for almost all examined samples, but only slight difference in degradation efficiency (about 3%) between modified and bare NTs was observed. However, the initial phenol degradation rate and TOC removal efficiency was significantly enhanced for the samples modified with 0.31 and 0.63 mol% of Bi as well as for all the samples modified with Cu and AgCu nanoparticles in comparison with bare titania nanotubes. The saturated photocurrent, under the influence of simulated solar light irradiation, for the most active Bi- and AgCu-modified samples, was over two times higher than for pristine NTs. All the examined materials were resistant towards photocorrosion processes that enables their application for long term processes induced by light.

  1. Enhanced photocatalytic, electrochemical and photoelectrochemical properties of TiO2 nanotubes arrays modified with Cu, AgCu and Bi nanoparticles obtained via radiolytic reduction

    International Nuclear Information System (INIS)

    Nischk, Michał; Mazierski, Paweł; Wei, Zhishun; Siuzdak, Katarzyna; Kouame, Natalie Amoin; Kowalska, Ewa; Remita, Hynd; Zaleska-Medynska, Adriana

    2016-01-01

    Highlights: • TiO 2 nanotubes were modified with Cu, AgCu, Bi nanoparticles via gamma radiolysis. • Excessive amount of deposited metal decreased photocatalytic activity. • AgCu-modified samples were more active than Cu-modified (with the same Cu content). • AgCu nanoparticles exist in a core (Ag) -shell (Cu) form. • Examined photocatalysts were resistant towards photocorrosion processes. - Abstract: TiO 2 nanotubes arrays (NTs), obtained via electrochemical anodization of Ti foil, were modified with monometallic (Cu, Bi) and bimetallic (AgCu) nanoparticles. Different amounts of metals’ precursors were deposited on the surface of NTs by the spin-coating technique, and the reduction of metals was performed via gamma radiolysis. Surface modification of titania was studied by EDS and XPS analysis. The results show that AgCu nanoparticles exist in a Ag core -Cu shell form. Photocatalytic activity was examined under UV irradiation and phenol was used as a model pollutant of water. Over 95% of phenol degradation was achieved after 60 min of irradiation for almost all examined samples, but only slight difference in degradation efficiency (about 3%) between modified and bare NTs was observed. However, the initial phenol degradation rate and TOC removal efficiency was significantly enhanced for the samples modified with 0.31 and 0.63 mol% of Bi as well as for all the samples modified with Cu and AgCu nanoparticles in comparison with bare titania nanotubes. The saturated photocurrent, under the influence of simulated solar light irradiation, for the most active Bi- and AgCu-modified samples, was over two times higher than for pristine NTs. All the examined materials were resistant towards photocorrosion processes that enables their application for long term processes induced by light.

  2. Preparation of catalysts PtSb2O5.SnO2 supported on carbon and ATO using the alcohol reduction method for electrochemical oxidation of ethanol

    International Nuclear Information System (INIS)

    Ayoub, Jamil Mahmoud Said

    2013-01-01

    Pt Sn/C-ATO electrocatalysts with different Pt:Sn atomic ratios (90:10, 70:30 and 50:50) were prepared in a single step by an alcohol-reduction process using H 2 PtCl 6 .6H 2 O and SnCl 2 .2H 2 O as metal sources and ethylene glycol as solvent and reducing agent and a physical mixture of carbon Vulcan XC72 (85 wt%) and Sb 2 O 5 .SnO 2 (15 wt%) as support (C-ATO). The obtained materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The catalytic activity for ethanol electro-oxidation in acid medium was investigated by cyclic voltammetry and chronoamperometry and in single direct ethanol fuel cell (DEFC). XRD analyses showed that Pt(FCC), SnO 2 , carbon and ATO phases coexist in the obtained materials. The electrochemical studies showed that PtSn/C-ATO electrocatalysts were more active for ethanol electro-oxidation than PtSn/C electrocatalyst. The experiments at 100 deg C on a single DEFC showed that the power density of the cell using Pt Sn/C-ATO (90:10) was nearly 100% higher than the one obtained using Pt Sn/C (50:50). FTIR measurements showed that the addition of ATO to Pt Sn/C favors the formation of acetic acid as a product while for PtSn/C acetaldehyde was the principal product formed. (author)

  3. ELECTROCHEMICAL BEHAVIOUR AND VOLTAMMETRIC ...

    African Journals Online (AJOL)

    The electrochemical behaviour of Geshoidin was investigated at a glassy carbon electrode in mixtures of citric acid and di-sodium hydrogen orthophosphate aqueous buffer system over a wide pH range (pH 2-11) using cyclic voltammetry. Chemically irreversible single oxidation and reduction peaks were obtained in the ...

  4. Application of Electrochemical Impedance Spectroscopy for Fuel Cell Characterization: Polymer Electrolyte Fuel Cell (PEFC) and Oxygen Reduction Reaction in Alkaline Solution

    OpenAIRE

    Wagner, Norbert

    2012-01-01

    Separation of different electrochemical and ohmic contributions to the current/voltage U(i) characteristics requires additional experimental techniques like Electrochemical Impedance Spectroscopy (EIS). The application of EIS is an approach to determine parameters which have proved to be indispensable for the characterization and development of fuel cell electrodes and electrolyte electrode assemblies. By varying the operating conditions of the fuel cell and by simulation of the measured ...

  5. 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...

  6. Effect of temperature and pH on dehalogenation of total organic chlorine, bromine and iodine in drinking water.

    Science.gov (United States)

    Abusallout, Ibrahim; Rahman, Shamimur; Hua, Guanghui

    2017-11-01

    Disinfection byproduct (DBP) concentrations in drinking water distribution systems and indoor water uses depend on competitive formation and degradation reactions. This study investigated the dehalogenation kinetics of total organic chlorine (TOCl), bromine (TOBr) and iodine (TOI) produced by fulvic acid under different pH and temperature conditions, and total organic halogen (TOX) variations in a treated drinking water under simulated distribution system and heating scenarios. TOX dehalogenation rates were generally in the order of TOI ≅ TOCl(NH 2 Cl) > TOBr > TOCl(Cl 2 ). The half-lives of different groups of TOX compounds formed by fulvic acid varied between 27 and 139 days during incubation at 20 °C and 0.98-2.17 days during heating at 55 °C. Base-catalyzed reactions played a major role in TOX degradation as evidenced by enhanced dehalogenation under high pH conditions. The results of heating of a treated water in the presence of residuals showed that TOX concentrations of chlorinated samples increased rapidly when chlorine residuals were present and then gradually decreased after chlorine residuals were exhausted. The final TOX concentrations of chlorinated samples after heating showed moderate decreases with increasing ambient water ages. Chloraminated samples with different ambient water ages exhibited similar final TOX concentrations during simulated distribution system and heating experiments. This study reinforces the importance of understanding DBP variations in indoor water uses as wells as in distribution systems to provide more accurate DBP information for exposure assessment and regulatory determination. Published by Elsevier Ltd.

  7. Electrochemical Processes

    DEFF Research Database (Denmark)

    Bech-Nielsen, Gregers

    1997-01-01

    The notes describe in detail primary and secondary galvanic cells, fuel cells, electrochemical synthesis and electroplating processes, corrosion: measurments, inhibitors, cathodic and anodic protection, details of metal dissolution reactions, Pourbaix diagrams and purification of waste water from...... galvanic industries....

  8. Effects of size reduction on the structure and magnetic properties of core-shell Ni3Si/silica nanoparticles prepared by electrochemical synthesis

    Czech Academy of Sciences Publication Activity Database

    Pigozzi, G.; Mukherji, D.; Elerman, Y.; Strunz, Pavel; Gilles, R.; Hoelzel, M.; Barbier, B.; Schmutz, P.

    2014-01-01

    Roč. 584, JAN (2014), s. 119-127 ISSN 0925-8388 Institutional support: RVO:61389005 Keywords : intermetallics * nanostructured materials * transition metal alloys and compounds * electrochemical synthesis * crystal structure * magnetic measurements Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.999, year: 2014

  9. Electrochemical Cell

    DEFF Research Database (Denmark)

    1999-01-01

    The invention relates to a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode in which the positive electrode structure comprises a lithium cobalt manganese oxide of the composition Li¿2?Co¿y?Mn¿2-y?O¿4? where 0 ... for capacity losses in lithium ion cells and lithium-alloy cells....

  10. Electrochemical capacitor

    Science.gov (United States)

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  11. Reductive dehalogenation of aryl halides over palladium catalysts deposited on SBA-15 type molecular sieve modified with amine donor groups

    Czech Academy of Sciences Publication Activity Database

    Štěpnička, P.; Semler, M.; Demel, J.; Zukal, Arnošt; Čejka, Jiří

    2011-01-01

    Roč. 341, č. 1-2 (2011), s. 97-102 ISSN 1381-1169 R&D Projects: GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous catalysts * supported catalysts * palladium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.947, year: 2011

  12. Cyclopalladated complexes containing 2-C6R4PPh2 ligands (R = H, F): one-electron electrochemical reduction leading to metal-carbon σ-bond cleavage via palladium(I).

    Science.gov (United States)

    Kar, Gopa; Privér, Steven H; Jones, Lathe A; Guo, Si-Xuan; Torriero, Angel A J; Bond, Alan M; Bennett, Martin A; Bhargava, Suresh K

    2015-02-21

    Three new ortho-metallated palladium complexes, [Pd(O,O'-hfacac)(κ(2)-2-C6F4PPh2)] (), [Pd2(O,O'-hfacac)2(μ-2-C6F4PPh2)2] () and [Pd(O,O'-hfacac)(κC-2-C6F4PPh2)(PPh3)] () (hfacac = hexafluoroacetylacetonate), have been prepared and fully characterised. The electrochemical reductions of complexes , together with those of other cyclopalladated complexes containing 2-C6R4PPh2 ligands (R = H, F) were studied by cyclic, rotating disk and microelectrode voltammetry. Evidence for the one-electron reduction of [PdI(κ(2)-2-C6F4PPh2)(PPh2Fc)] () was obtained from coulometric analysis, although the product is unstable and undergoes further chemical processes. Preparative electro-reduction of [Pd2(μ-Br)2(κ(2)-2-C6F4PPh2)2] () in CH2Cl2 causes reductive cleavage of its Pd-C σ-bonds and formation of the complex [PdBr2{PPh2(2-C6F4H)}2] (); possible mechanisms are discussed.

  13. Electrochemical cell

    Science.gov (United States)

    Redey, L.I.; Myles, K.M.; Vissers, D.R.; Prakash, J.

    1996-07-02

    An electrochemical cell is described with a positive electrode having an electrochemically active layer of at least one transition metal chloride. A negative electrode of an alkali metal and a compatible electrolyte including an alkali metal salt molten at cell operating temperature is included in the cell. The electrolyte is present at least partially as a corrugated {beta}{double_prime} alumina tube surrounding the negative electrode interior to the positive electrode. The ratio of the volume of liquid electrolyte to the volume of the positive electrode is in the range of from about 0.1 to about 3. A plurality of stacked electrochemical cells is disclosed each having a positive electrode, a negative electrode of an alkali metal molten at cell operating temperature, and a compatible electrolyte. The electrolyte is at least partially present as a corrugated {beta}{double_prime} alumina sheet separating the negative electrode and interior to the positive electrodes. The alkali metal is retained in a porous electrically conductive ceramic, and seals for sealing the junctures of the electrolyte and the adjacent electrodes at the peripheries thereof. 8 figs.

  14. 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.

  15. Pollution by s-triazine herbicides on waters. Electrochemical study on the simazine and propazone reductive deactivation; Contaminacion de aguas por herbicidas s-triazinicos. Estudio electroquimico de la desactivacion reductiva de simazina y propazina

    Energy Technology Data Exchange (ETDEWEB)

    Marin Galvin, R.; Rodriguez Mellado, J. M.; Higuera, M. J. [Universidad de Cordoba (Spain); Ruiz Montoya, M. [Universidad de Huelva (Spain)

    2000-07-01

    The s-Triazine herbicides are actually very used in the world's agricultural practices. Due to this they are widely found in soils and waters. In this sense, these herbicides can be deactivated by photooxidative way in that aquatic environments well sun-lighted and oxygenated. This paper deals on a electrochemical study al laboratory-scale on the reduction of simazine and propazine on mercury electrodes. According results, the global processes is irreversible and it is carried out at potentials of -1.000 mV and solutions with pH<4,0. The products then obtained are non aromatic and non chlorinated and must be reasonably of a lower toxicity than that of the primitive herbicides. The above implies that this reductive way could be applied to detoxify wastewaters herbicide-polluted by using another electrodes different of that mercury. On the other hand, the natural deactivation of natural waters containing simazine and propazine could theoretically act by this reductive way in acids, very poor oxygenated and rich in suspended materials waters (specially, carbonaceous). (Author) 23 refs.

  16. Chain reaction on de-halogenation of 1,2-dibromotetrafluoroethane and 1,1,2-trichlorotrifluoroethane induced by irradiation in alcohols

    International Nuclear Information System (INIS)

    Nakagawa, Seiko

    2015-01-01

    Methanol and 2-propanol solutions of 1,2-dibromotetrafluoroethane and 1,1,2-trichlorotrifluoroethane were irradiated with γ-rays after perfect de-oxygenation. The product, formed by the substitution of one of the bromine or chlorine atoms with a hydrogen atom, was observed by radiation-induced degradation and the product was also de-halogenated. The G-value of de-halogenation was more than a thousand times higher than G(e solv − ) and increased with the decreasing dose rate, meaning that a chain reaction is involved in the process. The efficiency of the degradation in 2-propanol was several times higher than that in methanol. It is concluded that the charge transfer from an alcohol radical will be the trigger of the chain reaction the same as in the degradation of hexachloroethane in alcohol solutions (Sawai et al., 1978). - Highlights: • Halone2402 and Furon113 were de-halogenated by radiation-induced chain reaction in pure alcohol. • The efficiency of the degradation in 2-propanol was several times higher than that in methanol. • The charge transfer from an alcohol radical will be the trigger of the chain reaction

  17. A view of aqueous electrochemical carbon dioxide reduction to formate at indium electrodes, and the reversible electrodeposition of silver in ionic liquids through the lens of fundamental surface science

    Science.gov (United States)

    Detweiler, Zachary M.

    Two systems were studied using in situ measurement techniques, demonstrating the importance of creative experimental design. The electroreduction of CO2 at heterogeneous indium electrodes in aqueous solution was analyzed by cyclic voltammetry. Bulk electrolyses showed that increased indium oxide presence prior to electrolysis improved the Faradaic efficiency of CO 2 reduction to formate in 0.5 M K2SO2 aqueous solutions at a pH of 4.4. In order to more accurately assign speciation at the electrode surface ex situ O2 and H2O dosing of metallic indium under UHV was studied with XPS, HREELS and TPD. Ambient pressure XPS showed that the ratio of oxide to hydroxide at the indium interface is strongly dependent on the partial pressure of water; decreasing as P(H2O) increases. Using this information, a qualitative picture of the indium interface could be generated. In situ ATR-FTIR with an indium thin film as the working electrode showed that bulk oxide quickly reduces with applied potential, but an interfacial oxide is still present at high reductive overpotential. Additionally, an adsorbed carbonate at the thin film interface was observed upon introducing CO 2 to the cell. The implication of a surface bound carbonate as the CO 2 reduction intermediate draws on a mechanism that has not previously been discussed in the electrochemical reduction of CO2. The previous study of this mechanism from Ficscher-Tropsch literature helps to predict the further reduced products found at more electropositive metals, such as copper or magnesium, the latter of which is described here. Additionaly described here is a series of ILs that were employed as electrolyte for reversible silver deposition. BMIM N(TfO)2 was found to be the most promising of those studied, intrinsically giving a more uniform deposit that was bright and reversible. Deposit formation was studied using SEM and EDX as a function of deposition potential and deposition time. In situ reflectometry was employed to get a

  18. Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

    Energy Technology Data Exchange (ETDEWEB)

    Billaud, D.; Naji, A.; Ghanbaja, J. [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P. [Centre National d`Etudes Spatiales (CNES), 31 - Toulouse (France)

    1996-12-31

    The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

  19. Electrochemical cell

    Science.gov (United States)

    Kaun, T.D.

    An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5 to 1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1 to 10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

  20. Microtiter plate based colorimetric assay for characterization of dehalogenation activity of GAC/Fe0 composite

    DEFF Research Database (Denmark)

    Hwang, Yuhoon; Salatas, Apostolos; Mines, Paul D.

    2015-01-01

    Even though nanoscale zero valent iron (nZVI) has been intensively studied for the treatment of a plethora of pollutants through reductive reaction, a quantification of nZVI reactivity has not been standardized. Here, we developed series of colorimetric assays for determining reductive activity o...

  1. 57Fe-Mössbauer spectroscopy and electrochemical activities of graphitic layer encapsulated iron electrocatalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Zhong, Lijie; Frandsen, Cathrine; Mørup, Steen

    2018-01-01

    Graphitic layer encapsulated iron based nanoparticles (G@FeNPs) have recently been disclosed as an interesting type of highly active electrocatalysts for the oxygen reduction reaction (ORR). However, the complex composition of the metal-containing components and their contributions in catalysis r...

  2. Platinum/nitrogen-doped carbon/carbon cloth: a bifunctional catalyst for the electrochemical reduction and carboxylation of CO2 with excellent efficiency.

    Science.gov (United States)

    Yang, Heng-Pan; Lin, Qing; Zhang, Han-Wen; Li, Guo-Dong; Fan, Liang-Dong; Chai, Xiao-Yan; Zhang, Qian-Ling; Liu, Jian-Hong; He, Chuan-Xin

    2018-03-14

    A novel Pt-NP@NCNF@CC composite was prepared by the electrospinning technique. It is a highly efficient and binder-free catalyst for the direct reduction and carboxylation of CO 2 with halides. Formate with 91% Faradaic efficiency and 2-phenylpropionic acid with 99% yield could be obtained, respectively. Moreover, this catalyst has excellent stability and reusability.

  3. Electrochemical behavior for a reduction of uranium oxide in a LiCl-Li2O molten salt with an integrated cathode assembly

    International Nuclear Information System (INIS)

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

    2005-01-01

    Electrolytic reduction of uranium oxide to uranium metal was studied in a LiCl-Li 2 O molten salt system. The reduction mechanism of the uranium oxide to a uranium metal has been studied by means of a cyclic voltammetry. Effects of the layer thickness of the uranium oxide and the thickness of the MgO on the overpotential of the cathode and the anode were investigated by means of a chronopotentiometry. From the cyclic voltamograms, the decomposition potentials of the metal oxides are the determining factors for the mechanism of the reduction of the uranium oxide in a Li Cl-3 wt% Li 2 O molten salt and the two mechanisms of the electrolytic reduction were considered with regards to the applied cathode potential. In the chronopotentiograms, the exchange current and the transfer coefficient based on the Tafel behavior were obtained with regard to the layer thickness of the uranium oxide which is loaded into the porous MgO membrane and the thickness of the porous MgO membrane. The maximum allowable currents for the changes of the layer thickness of the uranium oxide and the thickness of the MgO membrane were also obtained from the limiting potential which is the decomposition potential of LiCl

  4. Indirect Evidence Link PCB Dehalogenation with Geobacteraceae in Anaerobic Sediment-Free Microcosms

    Czech Academy of Sciences Publication Activity Database

    Pravečková, Martina; Brennerová, Mária; Holliger, Ch.; De Alencastro, F.; Rossi, P.

    2016-01-01

    Roč. 7, June (2016), s. 933 ISSN 1664-302X Institutional support: RVO:61388971 Keywords : polychlorinated biphenyl congeners * Delor 103 * reductive dechlorination Subject RIV: EE - Microbiology, Virology Impact factor: 4.076, year: 2016

  5. DISPOSAL OF POISONOUS ORGANIC HALIDES BY USING THE ELECTROCHEMICAL METHOD: DFT SIMULATION

    Directory of Open Access Journals (Sweden)

    Tudor Spataru

    2016-12-01

    Full Text Available Geometry optimizations at the UBP86/6-311++G** level of electronic structure theory have been performed for DDT, β-hexachlorocyclohexane, and heptachlor organic polychlorides as well for their positive and negative ions. The HOMO composition of these neutral molecules show no participation of the carbon-chlorine atomic orbitals, while LUMO of the calculated molecules include a major contribution of the anti-bonding character atomic orbitals from the two or three carbon-chloride bonds of each calculated molecule. Consequently, the negative ions were the most sensitive structure during the geometry optimization, showing the carbon-chloride bonds cleaving during the electronic structure calculations. Further geometry optimization of the obtained neutral intermediate molecules after the fi rst and second reducing by two electrons show that the electrochemical dehalogenation of the organic poychlorides is sequential.

  6. Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2 /NH3 Cycle.

    Science.gov (United States)

    Bao, Di; Zhang, Qi; Meng, Fan-Lu; Zhong, Hai-Xia; Shi, Miao-Miao; Zhang, Yu; Yan, Jun-Min; Jiang, Qing; Zhang, Xin-Bo

    2017-01-01

    Using tetrahexahedral gold nanorods as a heterogeneous electrocatalyst, an electrocatalytic N 2 reduction reaction is shown to be possible at room temperature and atmospheric pressure, with a high Faradic efficiency up to 4.02% at -0.2 V vs reversible hydrogen electrode (1.648 µg h -1 cm -2 and 0.102 µg h -1 cm -2 for NH 3 and N 2 H 4 ·H 2 O, respectively). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synergy of Cobalt and Silver Microparticles Electrodeposited on Glassy Carbon for the Electrocatalysis of the Oxygen Reduction Reaction: An Electrochemical Investigation

    Directory of Open Access Journals (Sweden)

    Claudio Zafferoni

    2015-08-01

    Full Text Available The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR, yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break the O–O bond of molecular oxygen, thus accelerating the first step of the reduction mechanism. At the same time, research is to further reduce the catalyst’s cost, reducing the amount of Ag, which, even though being much less expensive than Pt, is still a noble metal. From this point of view, using a small amount of Ag together with an inexpensive material, such as graphite, represents a good compromise. The aim of this work was to verify if the synergic effects are still operating when very small amounts of cobalt (2–10 μg·cm−2 are added to the microparticles of silver electrodeposited on glassy carbon, described in a preceding paper from us. To better stress the different behaviour observed when cobalt and silver are contemporarily present in the deposit, the catalytic properties of cobalt alone were investigated. The analysis was completed by the Levich plots to evaluate the number of electrons involved and by Tafel plots to show the effects on the reaction mechanism.

  8. NOX Reduction Using an Electrochemical Cell with NOadsorbents

    DEFF Research Database (Denmark)

    Shao, Jing

    connected adsorption layer with the electrode. Ag and (La0.85Sr0.15)0.99MnO3 (LSM) were investigated as electrode materials to substitute for Pt and Ni. Selective NOx reduction in the presence of excess O2 could be achieved for both Ag and LSM/Ce0.9Gd0.1O1.95 (CGO) electrodes by modifying the electrodes......, 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...

  9. Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

    Science.gov (United States)

    Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

    2017-10-01

    Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

  10. Synchrotron Based Structural Investigations of Mass-Selected PtxGd Nanoparticles and a Gd/Pt(111) Single Crystal for Electrochemical Oxygen Reduction

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Velazquez-Palenzuela, Amado Andres; Masini, Federico

    2015-01-01

    The sluggish kinetics of the oxygen reduction reaction (ORR) hinders the commercialization of proton exchange membrane fuel cells (PEMFC). The ORR activity is enhanced by alloying Pt with late transition 3d metals (i.e. Fe, Co, Ni, and Cu)1. However, these compounds tend to degrade in a fuel cell....... In this work, we present the experimental results of mass-selected PtxGd nanoparticles synthesized by gas aggregation after sputtering of an alloy target in an ultrahigh vacuum (UHV)3. PtxGd nanoparticles with nominal sizes of 3, 5, 7, and 9 nm were selected using time-of-flight mass filtering and deposited...... is separated from the Pt5Gd alloy, and the analysis of both diffraction patterns are presented. By investigating such well-defined structures, we gain valuable scientific insight into the relationship between their structure and functionality. On the basis of this insight, we can develop even better catalysts...

  11. 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.

  12. In situ reduction and functionalization of graphene oxide with l-cysteine for simultaneous electrochemical determination of cadmium(ii), lead(ii), copper(ii), and mercury(ii) ions

    KAUST Repository

    Muralikrishna, S. N.

    2014-01-01

    One pot reduction and functionalization of graphene oxide (GO) with l-cysteine (l-cys-rGO) at the edges and basal planes of the carbon layers are presented. The l-cys-rGO was characterized by X-ray diffraction studies (XRD), X-ray photoelectron spectroscopy (XPS), attenuated infrared spectroscopy (ATIR), and Raman spectroscopy. The surface morphology was studied by scanning electron microscopy (SEM) and transmittance electron microscopy (TEM). The l-cys-rGO was further utilized for the simultaneous electrochemical quantification of environmentally harmful metal ions such as, Cd2+, Pb2+, Cu2+ and Hg2+. Detection limits obtained for these metal ions were 0.366, 0.416, 0.261 and 1.113 μg L-1 respectively. The linear range obtained for Cd2+, Cu2+ and Hg2+ was 0.4 to 2.0 μM and for Pb2+ was 0.4 to 1.2 μM. The detection limits were found to be less than the World Health Organization (WHO) limits. The developed protocol was applied for the determination of the above metal ions in various environmental samples and the results obtained were validated by atomic absorption spectroscopy (AAS). This journal is

  13. 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...

  14. Complete Detoxification of Short Chain Chlorinated Aliphatic Compounds: Isolation of Halorespiring Organisms and Biochemical Studies of the Dehalogenating Enzyme Systems - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Tiedje, J.M.

    1999-10-01

    Work focused on the isolation and characterization of halorespiring populations, and the initial investigation of the dechlorinating enzyme systems. In addition, tools to evaluate the presence/activity to halorespiring populations in the environment were developed. The tools developed in this work (measurements of hydrogen consumption thresholds, molecular probes) are relevant for regulatory agencies in order to facilitate decisions on which bioremediation technology (biostimulation or bioaugmentation) is most promising at a particular site. In addition, a better understanding of the physiology of the halorespiring organisms as well as the biochemistry of the dehalogenating enzyme systems enhances our knowledge of how these organisms can successfully be employed in the bioremediation of contaminated sites.

  15. Impedance of electrochemically modified graphite.

    Science.gov (United States)

    Magdić, Katja; Kvastek, Krešimir; Horvat-Radošević, Višnja

    2014-01-01

    Electrochemical impedance spectroscopy, EIS, has been applied for characterization of electrochemically modified graphite electrodes in the sulphuric acid solution. Graphite modifications were performed by potential cyclization between potentials of graphite oxide formation/reduction, different number of cycles, and prolonged reduction steps after cyclization. Impedance spectra measured at two potential points within double-layer region of graphite have been successfully modeled using the concept of porous electrodes involving two different electrolyte diffusion paths, indicating existence of two classes of pores. The evaluated impedance parameter values show continuous changes with stages of graphite modification, indicating continuous structural changes of pores by number of potential cycles applied. Differences of impedance parameter values at two potential values indicate the potential induced changes of solution properties within the pores of modified graphite.

  16. ELECTROCHEMICAL BEHAVIOUR OF ENVIRONMENTALLY ...

    African Journals Online (AJOL)

    dell

    ABSTRACT. Electrochemical behaviour of Aloe secundiflora on carbon steel corrosion control in neutral and aerated soft water solutions have been investigated using electrochemical impedance spectroscopy and Tafel polarization techniques. The investigation was performed at different inhibitor concentrations under ...

  17. Separators for electrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

    2018-01-16

    Provided are separators for use in an electrochemical cell comprising (a) an inorganic oxide and (b) an organic polymer, wherein the inorganic oxide comprises organic substituents. Also provided are electrochemical cells comprising such separators.

  18. Electrochemical Hydrogen Refrigerator

    Data.gov (United States)

    National Aeronautics and Space Administration — The goal is to develop and test a 1 W at 20K Joule‐Thomson cryocooler using an electrochemical compressor. A Joule Thomson refrigerator based on electrochemical...

  19. 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.

  20. 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.

  1. Electrochemical study of oxygen reduction reaction in Pt/C catalysts synthesized by photo-deposition; Estudio electroquimico de la reaccion de reduccion de oxigeno en catalizadores de Pt/C sintetizados por fotodeposito

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Galindo, J. A.; Ruiz-Camacho, B.; Valenzuela-Zapata, M. A.; Gonzalez-Huerta, R. G. [IPN, ESIQIE, Mexico, D.F. (Mexico)]. E-mail: rosgonzalez_h@yahoo.com.mx

    2009-09-15

    Fuel batteries are considered one of the principal generators of energy for the immediate future, though their use is limited by their cost and useful lifetime. One of the main components of a fuel battery are electrodes made of a noble metal, such as Pt, dispersed in a support. The interaction between these two components has received a good deal of attention in recent years. It is considered to be responsible for structural growth effects and a decreased dispersion of metal particles on a support, causing the battery to have low overall performance and a reduced useful lifetime. The properties of the support are accentuated in cathode catalysts, where oxygen reduction reactions occur as a result of its operating conditions. Syntheses are currently being investigated to improve the metal-support interaction and thereby increase the lifetime of the fuel battery. This work presents the electrochemical study of nanometric-sized carbon-supported platinum (Pt/C) catalysts synthesized with chemical photo-deposition to determine its catalytic effect and stability for oxygen reduction reaction in an acid medium. C{sub 10}H{sub 14}O{sub 4}Pt (Pt(acac)2) was used as the platinum precursor. The electrochemical study was conducted with cyclic voltamperometry and rotary disc electrode (RDE) techniques, observing that the synthesized catalysts present a behavior similar to that of Pt (E-Tek). The kinetic study showed an open-circuit potential of de 0.96 V with a Tafel slope of 73 mV dec-1, and with a current of 0.1 mA cm-2 the potential is 0.91 V. The authors wish to thank the ICYTDF (project PICS08-37) and the IPN (project SIP-20090433). [Spanish] Las pilas de combustible se perfilan como uno de los principales generadores de energia en un futuro inmediato, pero su utilizacion esta limitada por su costo y tiempo de vida util. Uno de los componentes principales de la pila de combustible son los electrodos integrados por un metal noble, como el Pt, disperso en un soporte. La

  2. 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

  3. 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

  4. Electrochemical waste clean-up process for simultaneous removal of SO2 and NOx

    International Nuclear Information System (INIS)

    Juettner, K.; Kreysa, G.; Kleifges, K.H.; Rottmann, R.

    1994-01-01

    Based on the principles of electrochemical exhaust purification, a new process for electrochemical simultaneous removal of SO 2 and NO x is presented. It combines an ''cruter call'' process for NO x reduction with dithionite as homogeneous redox mediator with an ''inner cell'' process for direct oxidation of SO 2 in the anodic space of an electrochemical cell. Absorption experiments for NO x and SO 2 were carried out in separate laboratory scale electrochemical cells. Results are presented. (orig./BBR) [de

  5. The electrochemical synthesis of europium boride

    Directory of Open Access Journals (Sweden)

    Bukatova G.A.

    2003-01-01

    Full Text Available The electroreduction of boron, europium and the electrochemical synthesis of europium boride have been investigated in NaCl-KCl-NaF(10 wt. % melt on silver and molybdenum electrodes. The parameters of boron reduction in the chloride-fluoride melt have been obtained and the character of its joint deposition with europium has been studied.

  6. 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.

  7. 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

  8. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

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

    2002-01-01

    , 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...

  9. 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.

  10. Electrochemical Hydrogen Peroxide Generator

    Science.gov (United States)

    Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

    2010-01-01

    Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials

  11. 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...

  12. Electrochemical force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

    2017-01-10

    A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

  13. Emerging electrochemical energy conversion and storage technologies

    Science.gov (United States)

    Badwal, Sukhvinder; Giddey, Sarbjit; Munnings, Christopher; Bhatt, Anand; Hollenkamp, Tony

    2014-09-01

    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.

  14. 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

  15. Spectroscopic and electrochemical properties of di-2-thienyl ketone thiosemicarbazone (dtktsc): electrochemical reactions with electrophiles (H+ and CO2)

    International Nuclear Information System (INIS)

    Bakir, Mohammed; Lawrence, Mark A.W.; Nelson, Peter N.; Conry, Rebecca R.

    2016-01-01

    Graphical abstract: The preparation, spectroscopic, electrochemical, and solid state structural properties of the first thiosemicarbazone derivatives of di-2-thienyl ketone (dtktsc) are reported. Electrochemical measurements revealed electro-polymerization, proton and CO 2 mediated reduction, and electro-catalytic decomposition of dtktsc. - Highlights: • The first thiosemicarbazone derivative of di-2-thienyl ketone, di-2-thienyl ketone thiosemicarbazone (dtktsc) is reported. • Spectroscopic and electrochemical measurements on dtktsc revealed strong solvent-compound interaction. • Electrochemical reduction of dtktsc is imine based. • Electrophile (H + or CO 2 ) mediated multi-electron reactions occur on the imine reduction. • Voltammetric measurements revealed electrochemical decomposition, and electro-polymerization. - Abstract: The first di-2-thienyl ketone thiosemicarbazone (dtktsc) and its di-2-thienyl ketone (dtk) hybrid (dtktsc-dtk) were isolated and characterized from the results of their elemental analyses, spectroscopic measurements and X-ray structural analyses. Spectroscopic and electrochemical measurements disclosed sensitivity of dtktsc to changes in its surroundings. Electronic absorption measurements in protophilic solvents (dmso and dmf) in the presence and absence of a base disclosed deprotonation of the thioamide (NH) proton. Variable temperature 1 H NMR measurements divulged entropy driven exchange of NH and NH 2 protons with the residual water protons. X-ray structure analyses confirmed the identities of dtktsc and dtktsc-dtk. Electrochemical measurements on dtktsc in the presence and absence of an electrophile (CO 2 or H + ) revealed irreversible redox processes pointing to electrochemical decomposition, reactions with electrophiles and electro-polymerization. On GC-electrode electro-polymerization of dtktsc occurs in CH 3 CN on oxidative scans. On reductive scans at a Pt-electrode, electro-catalytic decomposition of dtktsc occurs

  16. Electrochemical oxidation of ethanol using PtRh/C electrocatalysts in alkaline medium and synthesized by sodium borohydride and alcohol reduction; Oxidação eletroquímica do etanol utilizando eletrocatalisadores PtRh/C em meio alcalino e sintetizados via borohidreto de sódio e redução por álcool

    Energy Technology Data Exchange (ETDEWEB)

    Fontes, Eric Hossein

    2017-07-01

    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{sub 2}PtCl{sub 6}3•6H{sub 2}0 and (RhNO{sub 3}){sub 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.

  17. 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.

  18. Combination of Advanced Oxidation and/or Reductive Dehalogenation and Biodegradation for the Decontamination of Waters Contaminated with Chlorinated Organic Compounds.

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, František; Maléterová, Ywetta; Kaštánek, P.

    2007-01-01

    Roč. 42, 7 (2007) , s. 1613-1625 ISSN 0149-6395 R&D Projects: GA MPO FI-IM3/050 Institutional research plan: CEZ:AV0Z40720504 Keywords : advanced oxidation * fenton reaction * consecutive aerobic biodegradation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.048, year: 2007

  19. Electrochemical Analysis of Neurotransmitters

    Science.gov (United States)

    Bucher, Elizabeth S.; Wightman, R. Mark

    2016-01-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements. PMID:25939038

  20. Electrochemical Sensors: Functionalized Silica

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Lin, Yuehe; Yantasee, Wassana

    2009-03-24

    This chapter summarizes recent devellopment of electrochemical sensors based on functionlized mesoporous silica materials. The nanomatrials based sensors have been developed for sensitive and selective enrironmental detection of toxic heavy metal and uranium ions.

  1. Electrochemical Analysis of Neurotransmitters

    Science.gov (United States)

    Bucher, Elizabeth S.; Wightman, R. Mark

    2015-07-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements.

  2. Fundamentals of electrochemical science

    CERN Document Server

    Oldham, Keith

    1993-01-01

    Key Features* Deals comprehensively with the basic science of electrochemistry* Treats electrochemistry as a discipline in its own right and not as a branch of physical or analytical chemistry* Provides a thorough and quantitative description of electrochemical fundamentals

  3. Amphitrite ornata Dehaloperoxidase (DHP): Investigations of Structural Factors That Influence the Mechanism of Halophenol Dehalogenation Using ;Peroxidase-like; Myoglobin Mutants and ;Myoglobin-like; DHP Mutants

    Energy Technology Data Exchange (ETDEWEB)

    Du, Jing; Huang, Xiao; Sun, Shengfang; Wang, Chunxue; Lebioda, Lukasz; Dawson, John H. (SC)

    2012-05-14

    Dehaloperoxidase (DHP), discovered in the marine terebellid polychaete Amphitrite ornata, is the first heme-containing globin with a peroxidase activity. The sequence and crystal structure of DHP argue that it evolved from an ancient O{sub 2} transport and storage globin. Thus, DHP retains an oxygen carrier function but also has the ability to degrade halophenol toxicants in its living environment. Sperm whale myoglobin (Mb) in the ferric state has a peroxidase activity {approx}10 times lower than that of DHP. The catalytic activity enhancement observed in DHP appears to have been generated mainly by subtle changes in the positions of the proximal and distal histidine residues that appeared during DHP evolution. Herein, we report investigations into the mechanism of action of DHP derived from examination of 'peroxidase-like' Mb mutants and 'Mb-like' DHP mutants. The dehalogenation ability of wild-type Mb is augmented in the peroxidase-like Mb mutants (F43H/H64L, G65T, and G65I Mb) but attenuated in the Mb-like T56G DHP variant. X-ray crystallographic data show that the distal His residues in G65T Mb and G65I are positioned {approx}0.3 and {approx}0.8 {angstrom}, respectively, farther from the heme iron compared to that in the wild-type protein. The H93K/T95H double mutant Mb with the proximal His shifted to the 'DHP-like' position has an increased peroxidase activity. In addition, a better dehaloperoxidase (M86E DHP) was generated by introducing a negative charge near His89 to enhance the imidazolate character of the proximal His. Finally, only minimal differences in dehalogenation activities are seen among the exogenous ligand-free DHP, the acetate-bound DHP, and the distal site blocker L100F DHP mutant. Thus, we conclude that binding of halophenols in the internal binding site (i.e., distal cavity) is not essential for catalysis. This work provides a foundation for a new structure-function paradigm for peroxidases and for the

  4. Solid state electrochemical composite

    Science.gov (United States)

    Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

    2009-06-30

    Provided is a composite electrochemical device fabricated from highly electronically conductive materials such as metals, metal alloys, or electronically conductive ceramics. The electronic conductivity of the electrode substrate is maximized. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in ionic (electrochemical) devices such as fuel cells and electrolytic gas separation systems including oxygen generation system.

  5. Electrochemical polymer electrolyte membranes

    CERN Document Server

    Fang, Jianhua; Wilkinson, David P

    2015-01-01

    Electrochemical Polymer Electrolyte Membranes covers PEMs from fundamentals to applications, describing their structure, properties, characterization, synthesis, and use in electrochemical energy storage and solar energy conversion technologies. Featuring chapters authored by leading experts from academia and industry, this authoritative text: Discusses cutting-edge methodologies in PEM material selection and fabricationPoints out important challenges in developing PEMs and recommends mitigation strategies to improve PEM performanceAnalyzes the cur

  6. 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.

  7. Oxygen Reduction on Platinum

    DEFF Research Database (Denmark)

    Nesselberger, Markus

    This thesis investigates the electro reduction of oxygen on platinum nanoparticles, which serve as catalyst in low temperature fuel cells. Kinetic studies on model catalysts as well as commercially used systems are presented in order to investigate the particle size effect, the particle proximity...... effect and anion adsorption on the performance of Pt based electrocatalysts. The anion adsorption is additionally studied by in situ electrochemical infrared spectroscopy during the oxygen reduction reaction (ORR). For this purpose an in situ FTIR setup in attenuated total refection (ATR) configuration....... 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...

  8. 19F NMR-, ESR-, and vis-NIR-spectroelectrochemical study of the unconventional reduction behaviour of a perfluoroalkylated fullerene: dimerization of the C70(CF3)10 – radical anion† †Electronic supplementary information (ESI) available: Additional electrochemical and spectroscopic results, mass spectrometry study, and DFT-optimized Cartesian coordinates. See DOI: 10.1039/c5an01129a Click here for additional data file.

    Science.gov (United States)

    Machata, Peter; Clikeman, Tyler T.; Rosenkranz, Marco

    2015-01-01

    The most abundant isomer of C70(CF3)10 (70-10-1) is a rare example of a perfluoroalkylated fullerene exhibiting electrochemically irreversible reduction. We show that electrochemical reversibility at the first reduction step is achieved at scan rates higher than 500 V s–1. Applying ESR-, vis-NIR-, and 19F NMR-spectroelectrochemistry, as well as mass spectrometry and DFT calculations, we show that the (70-10-1)– radical monoanion is in equilibrium with a singly-bonded diamagnetic dimeric dianion. This study is the first example of 19F NMR spectroelectrochemistry, which promises to be an important method for the elucidation of redox mechanisms of fluoroorganic compounds. Additionally, we demonstrate the importance of combining different spectroelectrochemical methods and quantitative analysis of the transferred charge and spin numbers in the determination of the redox mechanism. PMID:26359514

  9. 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.

  10. 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

  11. Electrochemical energy storage

    CERN Document Server

    Tarascon, Jean-Marie

    2015-01-01

    The electrochemical storage of energy has become essential in assisting the development of electrical transport and use of renewable energies. French researchers have played a key role in this domain but Asia is currently the market leader. Not wanting to see history repeat itself, France created the research network on electrochemical energy storage (RS2E) in 2011. This book discusses the launch of RS2E, its stakeholders, objectives, and integrated structure that assures a continuum between basic research, technological research and industries. Here, the authors will cover the technological

  12. Electrochemical nitridation of metal surfaces

    Science.gov (United States)

    Wang, Heli; Turner, John A.

    2015-06-30

    Electrochemical nitridation of metals and the produced metals are disclosed. An exemplary method of electrochemical nitridation of metals comprises providing an electrochemical solution at low temperature. The method also comprises providing a three-electrode potentiostat system. The method also comprises stabilizing the three-electrode potentiostat system at open circuit potential. The method also comprises applying a cathodic potential to a metal.

  13. Chemical and Electrochemical Properties of La0.58Sr0.4Fe0.8Co0.2O3-δ (LSCF) Thin Films upon Oxygen Reduction and Evolution Reactions

    DEFF Research Database (Denmark)

    Pitscheider, Simon; Machala, Michael; Guan, Zixuan

    2017-01-01

    The Oxygen Evolution and Oxygen Reduction Reactions (OER/ORR), occurring at the oxygen electrode of Solid Oxide Cells (SOCs) in the two possible ways of operation, require substantial overpotentials, therefore lowering the operating efficiency of the cells. The reaction mechanisms occurring...... deviates from the nominal bulk composition, and that secondary phases can segregate at the surfaces and interfaces during operation. Furthermore, the electrochemical properties such as Area Specific Resistance (ASR), oxygen exchange coefficient (kex), ASR activation energy (Ea) and pO2exponents for LSCF...... conditions. In particular, NAP-XPS studies of the surface chemistry evolution under operation, as well as the correlation between surface potential changes in relation to the applied overpotential are addressed, in an attempt to determine the real driving force for the oxygen reactions.For this purpose, thin...

  14. Enhancement of NOx removal performance for (La0.85Sr0.15)0.99MnO3/Ce0.9Gd0.1O1.95 electrochemical cells by NOx storage/reduction adsorption layers

    DEFF Research Database (Denmark)

    Shao, Jing; Kammer Hansen, Kent

    2013-01-01

    This study investigated the effect of adding a NOx adsorption layer to the cathode of an electrochemical cell on the removal of NOx from gaseous mixtures. The cathode was a composite of (La0.85Sr0.15)0.99MnO3 (LSM15) and Ce0.9Gd0.1O1.95 (CGO10). Two different kinds of adsorption layers, K–Pt–Al2O...... reaction path for NOx reduction. A stronger capability for oxidizing NO and/or trapping NOx under the test conditions may have contributed to the superior performance of the K–Pt–Al2O3 adsorption layer relative to the Ba–Pt–Al2O3 layer. © 2012 Elsevier Ltd. All rights reserved....

  15. SPECTROPHOTOMETRIC AND ELECTROCHEMICAL STUDIES ...

    African Journals Online (AJOL)

    ABSTRACT. Spectrophotometric and electrochemical studies concerning the interaction of cryptand 222 with DDQ and I2 have been performed in ethanol solution. In the case of DDQ, the results are indicative of the formation of C222+ and DDQ- through an equilibrium reaction. The results of I2 indicate the formation of ...

  16. Electrochemical Power Sources

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 7. Electrochemical Power Sources - Rechargeable Batteries. A K Shukla S K Martha. General Article Volume 6 Issue 7 July 2001 pp 52-63. Fulltext. Click here to view fulltext PDF. Permanent link:

  17. 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

  18. Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

    Science.gov (United States)

    Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hong; King, Glen C.; Watt, Gerald D.

    2007-01-01

    Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

  19. Current levels and composition profiles of emerging halogenated flame retardants and dehalogenated products in sewage sludge from municipal wastewater treatment plants in China.

    Science.gov (United States)

    Zeng, Lixi; Yang, Ruiqiang; Zhang, Qinghua; Zhang, Haidong; Xiao, Ke; Zhang, Haiyan; Wang, Yawei; Lam, Paul K S; Jiang, Guibin

    2014-11-04

    Occurrence of new toxic chemicals in sludge from wastewater treatment plants (WWTPs) is of concern for the environment and human health. Alternative halogenated flame retardants (HFRs) are a group of potentially harmful organic contaminants in the environment. In this study, a nationwide survey was carried out to identify the occurrence of HFRs and their potential dehalogenated products in sewage sludge from 62 WWTPs in China. Of all 20 target chemicals analyzed, decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD) and 1, 2-bis (2,4,6-tribromophenoxy)-ethane (BTBPE) were detected in all sludge samples, and the concentrations were in the range of 0.82-215, 0.09-65.8, and 0.10-2.26 ng g(-1) d.w., respectively. Dechlorane Plus (DP) was found in 60 of 62 samples, and the concentration ranged from nd-298 ng g(-1) with a mean of 18.9 ng g(-1) d.w. The anti-DP fractional abundance fanti (0.79) in the samples was much higher than the commercial DP composition (fanti=0.59), indicating a stereoselective degradation. Comparison with global sludge concentrations of HFRs indicate that China is at the medium pollution level in the world. Principal components analysis revealed that strong correlations existed between ln-transformed concentrations (natural logarithm) of the dominant BFRs and total organic carbon (TOC) as well as industrial wastewater proportion, influent volume and serving population. Significant linear relationships (R=0.360-0.893, pproducts, pentabromocyclododecane (PBCD) and undecachloropentacyclooctadecadiene (Cl11-DP), derived from HBCD and DP, were also identified in sewage sludge for the first time.

  20. Electrochemical Removal Of Selenate From Aqueous Solutions

    Science.gov (United States)

    Baek, Kitae; Kasem, Naji; Ciblak, Ali; Vesper, Dorothy; Padilla, Ingrid; Alshawabkeh, Akram N.

    2013-01-01

    Removal of selenate from solution is investigated in batch electrochemical systems using reactive iron anodes and copper plate cathode in a bicarbonate medium. Iron anodes produce ferrous hydroxide, which is a major factor in the removal of selenate from solution. Iron anodes also generate a significant decrease in the oxidation-reduction potential (ORP) of the solution because it prevents generation of oxygen gas at the anode by electrolysis. The removal rates varied from 45.1 to 97.4%, depending on current density and selenate concentration. The transformation of selenate by the process is modeled based on a heterogeneous reaction coupled with electrochemical generation of ferrous and hydroxide. The rates are optimized at lower initial concentrations, higher electrical currents, and the presence of anions. Presence of dissolved oxygen does not cause any significant effects the removal of selenate. PMID:23378820

  1. A study of the dissolution mechanism by chemical and electrochemical oxidation-reduction of actinide dioxides (UO2, NpO2, PuO2, and AmO2) in an acid aqueous medium

    International Nuclear Information System (INIS)

    Berger, P.

    1991-01-01

    The plan followed to describe our study will be as follows: In a first part, we will review the general properties of MO 2 oxides (M = U, Np, Pu, and Am), as well as the dissolution methods known so far. We will emphasize, in particular, the great similarities in their structures, properties, and methods of dissolution, which justifies a parallel study of these oxides using an electrochemical method. The second part will concern the experimental study of the dissolution under electrolysis. We will, first of all, investigate its thermodynamic aspect, with the calculation of the free enthalpies of dissolution; and we will next show the phenomena of oxidizing dissolution and reducing dissolution using carbon paste electrodes. In a third part, we will present the test results on oxidizing dissolution in solutions that are highly enriched with oxygen-18. The isotopic analysis of the oxygen in the actinyl ions formed, deduced from the Raman spectra of the solutions, will make it possible to demonstrate the existence of a first oxidation step involving the participation of the solid. In the fourth part, we will summarize the experimental observations that might contribute to a better understanding of the mechanisms of oxidizing dissolution. A fifth and last part will be devoted to the presentation of a simple model of the dissolution of oxides in a carbon paste electrode under a constant current

  2. Electrochemical Hydrogen Evolution

    DEFF Research Database (Denmark)

    Laursen, A.B.; Varela Gasque, Ana Sofia; Dionigi, F.

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment....... This exercise circumvents the complexity of traditional experiments while it still demonstrates the trends of the HER volcano known from literature....

  3. Electrochemical flow capacitors

    Science.gov (United States)

    Gogotsi, Yury; Presser, Volker; Kumbur, Emin Caglan

    2015-10-27

    The present invention generally relates to devices for energy storage technologies, and more particularly to electrochemical flow capacitor systems and applications. In some aspects, these flow capacitors have at least one electrode comprising a non-stationary solid or semi-solid composition comprising supercapacitive particles and an electrolytic solvent in electrical communication with at least one current collector, and energy is stored and/or released by charging and/or discharging the electrode(s).

  4. SnO2, IrO2, Ta2O5, Bi2O3, and TiO2 nanoparticle anodes: electrochemical oxidation coupled with the cathodic reduction of water to yield molecular H2

    International Nuclear Information System (INIS)

    Choi, Jina; Qu Yan; Hoffmann, Michael R.

    2012-01-01

    In recent years, the search for environmentally friendly alternative energy sources with reduced carbon footprints has increased. The coupling of photovoltaic power sources with advanced electrolysis systems for hydrogen production via water splitting using organic contaminants as sacrificial electron donors has been considered to a be viable alternative. In this report, we demonstrated the feasibility of a scaled-up rooftop prototype of the proposed hybrid photovoltaic-electrolysis system, which utilizes semiconductor nanoparticles coated on to metal substrates as electrodes for the generation of hydrogen coupled with the oxidation of wastewater. Application of an anodic bias of >2.0 V to bismuth-doped TiO 2 (BiO x –TiO 2 ) on Ti metal anodes with a sequential under-coatings of nanoparticulate SnO 2 , IrO 2 , Ta 2 O 5 , and Bi 2 O 3 results in the electrochemical degradation of a variety of organic chemical contaminants in water (i.e., rhodamine B (Rh.B), methylene blue (MB), salicylic acid, triclosan, and phenol) and actual wastewater from a chemical manufacturing plant, while at the same time, molecular hydrogen is produced at stainless steel (SS) cathodes. The kinetics of the anodic substrates oxidation is investigated as a function of the cell current (I cell ), substrate concentration, and background electrolyte composition (e.g., NaCl, Na 2 SO 4 , or seawater). Average current efficiencies were found to be in the range of 4–22 %, while the cathodic current and energy efficiencies for hydrogen production were found to be in the range of 50–70 % and 20–40 %, respectively.

  5. ELECTROCHEMICAL POWER FOR TRANSPORTATION

    Energy Technology Data Exchange (ETDEWEB)

    Cairns, Elton J.; Hietbrink, Earl H.

    1981-01-01

    This section includes some historical background of the rise and fall and subsequent rebirth of the electric vehicle; and a brief discussion of current transportation needs, and environmental and energy utilization issues that resulted in the renewed interest in applying electrochemical energy conversion technology to electric vehicle applications. Although energy utilization has evolved to be the most significant and important issue, the environmental issue will be discussed first in this section only because of its chronological occurrence. The next part of the chapter is a review of passenger and commercial electric vehicle technology with emphasis on vehicle design and demonstrated performance of vehicles with candidate power sources being developed. This is followed by a discussion of electrochemical power source requirements associated with future electric vehicles that can play a role in meeting modern transportation needs. The last part of the chapter includes first a discussion of how to identify candidate electrochemical systems that might be of interest in meeting electric vehicle power source requirements. This is then followed by a review of the current technological status of these systems and a discussion of the most significant problems that must be resolved before each candidate system can be a viable power source.

  6. Synthesis and characterization of technetium(III) complexes with nitrogen heterocycles by O atom transfer from oxotechnetium(V) cores. Crystal structures of mer-[Cl3(pic)3Tc] and mer-[Cl3(pic)(PMe2Ph)2Tc] (pic = 4-picoline). Electrochemical parameters fore the reduction of TcII, TcIII, and TcIV

    International Nuclear Information System (INIS)

    Lu, Jun; Yamano, Akahito; Clarke, M.J.

    1990-01-01

    The combination of pyridine ligands, (OCl 4 Tc) - , and O atom acceptors of different cone angles, such as PMe 2 Ph or PPh 3 , results in Tc III complexes that vary in the coordination of the phosphine ligand. The compounds mer[Cl 3 (4-picoline) 3 Tc] and mer-(Cl 3 (4-picoline)(PMe 2 Ph) 2 Tc) have been obtained in good yield and have been characterized spectroscopically and by single-crystal x-ray diffraction. The crystal structure data are reported. Linear correlations of technetium reduction potentials in DMF with electrochemical ligand additivity parameters (E L 's) have been obtained for the Tc II,I , Tc III,II , and Tc IV,III couples. The slope and intercept (S M , I M ) pairs for each technetium oxidation-reduction couple, respectively, are (1.39, -2.07), (1.29, -0.91), and (1.00, 0.65). 32 refs., 3 figs., 6 tabs

  7. Electrochemical Approaches to Renewable Energy

    Science.gov (United States)

    Lobaccaro, Peter

    chapters 4-6, the electrochemical reduction of carbon dioxide (CO2R) is investigated as this reaction can produce hydrocarbons and alcohols as opposed to just hydrogen. First in chapter 4, the electrochemical cell, which is used to test the activity of CO2R catalysts, is scrutinized. The electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. I show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences during CO2R, particularly as they relate to the bulk electrolyte CO2 concentration. By using the pH in the cell to measure the CO2 concentration, significant undersaturation of CO2 is observed in the bulk electrolyte, even at modest current densities of 10 mA cm-2. Undersaturation of CO2 produces large changes in the faradaic efficiency observed on copper electrodes, with hydrogen production becoming increasingly favored. Then in chapter 5, the use of selected-ion flow-tube mass spectrometry (SIFT-MS) as an analytical tool to detect the products of CO2R is investigated. The real-time analysis of the products of CO2R is especially of interest to enable the study of how and when the liquid products of the reaction are generated. This is currently only possible in some limited situations and an analytical tool that can do quantitative analysis of all the products of the CO2R reaction in real-time does not exist. I show that SIFT-MS is a promising technique which can uniquely detect the hydrocarbon, alcohols, and aldehydes produced during CO2R on copper. Furthermore, SIFT-MS should be able to provide quantitative results; however, further study is needed to rigorously prove this. Finally in chapter 6, a CO2R catalyst platform is developed based on templated electrochemically deposited nanowires. This platform is used to investigate the role of high surface area in catalyst

  8. Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction? ?Electronic supplementary information (ESI) available: Franck?Condon analysis; photochemical one-electron-reduced species formation and characterisation; photophysical, electrochemical and quenching properties of R(4?5) in DMA; photophysical and electrochemical properties of the catalysts; photocatalytic CO2 reduction experiments and additional data. See DOI: 10.1039/c6sc01913g Click here for additional data file.

    OpenAIRE

    Rohacova, Jana; Ishitani, Osamu

    2016-01-01

    We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl?bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO2 reduction in conjunction with vario...

  9. Isolation of novel bacteria within the Chloroflexi capable of reductive dechlorination of 1,2,3-trichloropropane.

    Science.gov (United States)

    Yan, J; Rash, B A; Rainey, F A; Moe, W M

    2009-04-01

    Two strictly anaerobic bacterial strains were isolated from contaminated groundwater at a Superfund site located near Baton Rouge, LA, USA. These strains represent the first isolates reported to reductively dehalogenate 1,2,3-trichloropropane. Allyl chloride (3-chloro-1-propene), which is chemically unstable, was produced from 1,2,3-trichloropropane, and it was hydrolysed abiotically to allyl alcohol and also reacted with the sulfide- and cysteine-reducing agents in the medium to form various allyl sulfides. Both isolates also dehalogenated a variety of other vicinally chlorinated alkanes (1,2-dichloropropane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2- tetrachloroethane) via dichloroelimination reactions. A quantitative real-time PCR (qPCR) approach targeting 16S rRNA genes indicated that both strains couple reductive dechlorination to cell growth. Growth was not observed in the absence of hydrogen (H2) as an electron donor and a polychlorinated alkane as an electron acceptor. Alkanes containing only a single chlorine substituent (1-chloropropane, 2-chloropropane), chlorinated alkenes (tetrachlorothene, trichlorothene, cisdichloroethene, trans-dichloroethene, vinyl chloride) and chlorinated benzenes (1-chlorobenzene and 1,2- dichlorobenzene) were not dechlorinated. Phylogenetic analysis based on 16S rRNA gene sequence data showed these isolates to represent a new lineage within the Chloroflexi. Their closest previously cultured relatives are 'Dehalococcoides' strains, with 16S rRNA gene sequence similarities of only 90%.

  10. Synthesis and characterization of electrochemically-reduced graphene

    Indian Academy of Sciences (India)

    Abstract. 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 ...

  11. 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 ...

  12. Electrochemical sensing and photocatalysis using Ag-TiO 2 ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 5. Electrochemical ... Anatase Ag-TiO2 microwires with high sensitivity and photocatalytic activity were synthesized via polyol synthesis route followed by a simple surface modification and chemical reduction approach for attachment of silver. The superior ...

  13. 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 ...

  14. Novel electrochemical process for coal conversion

    Energy Technology Data Exchange (ETDEWEB)

    Farooque, M.

    1989-07-01

    The feasibility of two distinctly different routes to coal conversion at low severity conditions was investigated. An electrochemical approach utilizing both the electro-oxidation and electro-reduction routes was employed. The electro-oxidation route consists of an electrochemical reaction involving H{sub 2}O and coal, leading to the breakup of coal molecules. The observed reaction rate has been explained as a combination of the coal and pyrite electro-oxidation currents. Organic sulfur has been identified as the contributing factor for the observation of more than 100% H{sub 2} production current efficiency with several coal samples. Also, an attractive coal pre-treatment process has been identified which results in production of useful products and simultaneous upgrading of the coal. Electrochemical oxidation of coal with H{sub 2}O leads to the production of hydrogen, CO{sub 2}, simultaneous removal of pyritic sulfur, and significant reduction of ash content. There is also indirect evidence that the organic sulfur may be removed in the process. A preliminary economic evaluation of this process has projected a cost advantage of > $8 per ton of Illinois {number sign}2 coal. A lab-scale cell has been successfully employed in this study for generating process data useful for future design calculations. This study also explored the electro-reduction route of coal conversion and has successfully demonstrated production of liquid products from different coal types at low severity conditions. A variety of aliphatic and aromatic compounds have been identified in the products. Coal type appeared to be the most important parameter affecting the product spectrum. 32 refs., 26 figs., 19 tabs.

  15. 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...

  16. Electrochemical studies on spent fuel corrosion processes

    International Nuclear Information System (INIS)

    Pablo, J. de; Casas, I.; Clarens, F.; Gimenez, J.; Rovira, M.

    2003-01-01

    This presentations is mainly based on the electrochemical studies carried out by the Canadian team and the research group of the Berlin University. Electrochemical studies allow to study separately both the anodic reaction which corresponds-sources on UO 2 -electrodes response is one of to the UO 2 dissolution and the cathodic reaction that is the reduction of the oxidants. By using intensity current-potential plots a mechanisms of UO 2 corrosion has been established. At-300 mV (vs SCE), irreversible oxidation of UO 2 takes place and dissolution begins. In the absence of complexing agents like carbonate, an oxidised layer is formed at 100 mV a stoichiometry close to UO 2 . In carbonate medium, the oxidized layer is not formed because the U(VI) formed is rapidly dissolved. Results in terms of dissolution rates obtained by electrochemical measurements are similar to the ones obtained in dissolution experiments by using flow through reactors and similar kinetic laws are obtained. The effect of external α and γ-sources on UO 2 -electrodes response is one of the few available data on the effects of radiolysis on the UO 2 dissolution rate and can offer a complementary knowledge to the spent fuel and α-doped pellets dissolution experiments. (Author)

  17. Pencil it in: pencil drawn electrochemical sensing platforms.

    Science.gov (United States)

    Foster, Christopher W; Brownson, Dale A C; Ruas de Souza, Ana P; Bernalte, Elena; Iniesta, Jesus; Bertotti, Mauro; Banks, Craig E

    2016-06-20

    Inspired by recent reports concerning the utilisation of hand drawn pencil macroelectrodes (PDEs), we report the fabrication, characterisation (physicochemical and electrochemical) and implementation (electrochemical sensing) of various PDEs drawn upon a flexible polyester substrate. Electrochemical characterisation reveals that there are no quantifiable electrochemical responses upon utilising these PDEs with an electroactive analyte that requires an electrochemical oxidation step first, therefore the PDEs have been examined towards the electroactive redox probes hexaammineruthenium(iii) chloride, potassium ferricyanide and ammonium iron(ii) sulfate. For the first time, characterisation of the number of drawn pencil layers and the grade of pencil are examined; these parameters are commonly overlooked when utilising PDEs. It is demonstrated that a PDE drawn ten times with a 6B pencil presented the most advantageous electrochemical platform, in terms of electrochemical reversibility and peak height/analytical signal. In consideration of the aforementioned limitation, analytes requiring an electrochemical reduction as the first process were solely analysed. We demonstrate the beneficial electroanalytical capabilities of these PDEs towards p-benzoquinone and the simultaneous detection of heavy metals, namely lead(ii) and cadmium(ii), all of which are explored for the first time utilising PDEs. Initially, the detection limits of this system were higher than desired for electroanalytical platforms, however upon implementation of the PDEs in a back-to-back configuration (in which two PDEs are placed back-to-back sharing a single connection to the potentiostat), the detection limits for lead(ii) and cadmium(ii) correspond to 10 μg L(-1) and 98 μg L(-1) respectively within model aqueous (0.1 M HCl) solutions.

  18. Remote electrochemical sensor

    Science.gov (United States)

    Wang, J.; Olsen, K.; Larson, D.

    1997-10-14

    An electrochemical sensor is described for remote detection, particularly useful for metal contaminants and organic or other compounds. The sensor circumvents technical difficulties that previously prevented in-situ remote operations. The microelectrode, connected to a long communications cable, allows convenient measurements of the element or compound at timed and frequent intervals and instrument/sample distances of ten feet to more than 100 feet. The sensor is useful for both downhole groundwater monitoring and in-situ water (e.g., shipboard seawater) analysis. 21 figs.

  19. Electrochemical Science and Technology

    CERN Document Server

    Oldham, Keith; Bond, Alan

    2011-01-01

    The book addresses the scientific principles underlying electrochemistry. Starting with the basic concepts of electricity, the early chapters discuss the physics and chemistry of the materials from which electrochemical cells are constructed and the properties that make these materials appropriate as cell components. Much of the importance of electrochemistry lies in the conversion of electrical energy into chemical energy and vice versa; the thermodynamics of these processes is described, in the context of a wide range of applications of these interconversions. An electrode is a surface at wh

  20. Preliminary comparison of different reduction methods of graphene ...

    Indian Academy of Sciences (India)

    Abstract. 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 ...

  1. 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 ...

  2. Alkaline Electrochemical Capacitor and Electrode Fabrication

    National Research Council Canada - National Science Library

    Finello, D

    1999-01-01

    .... The subject low cost alkaline electrochemical capacitor designs are based upon titanium nitride electrodes which exhibit 125 mF/sq cm surface capacitance density and remarkable electrochemical...

  3. Electrochemical bromination of germacrene D

    Energy Technology Data Exchange (ETDEWEB)

    Ogamino, Takahisa; Mori, Kazuki; Yamamura, Shosuke; Nishiyama, Shigeru [Keio University, Yokohama (Japan). Dept. of Chemistry

    2004-10-30

    Electrochemical bromination of germacrene D 1 and geraniol 2 carrying plural olefinic bonds provided the corresponding brominated products 3-10. The bicyclic derivative 6 was preferentially produced from 1, while chemical brominations provided no clear selectivity of its product distribution. Influence of the parameters of the electrochemical reaction conditions was evaluated, aiming at improvement of regioselectivity and yields of the brominated products. (author)

  4. Chemical Production of Graphene Catalysts for Electrochemical Energy Conversion

    DEFF Research Database (Denmark)

    Seselj, Nedjeljko

    by scanning tunneling microscopy (STM), to investigate the nature of L-cysteine bonds on Au. Synthesized electrocatalysts were characterized by spectroscopic, microscopic and electrochemical techniques. Electrocatalysis was examined by electrochemical oxidation of formic acid, methanol and ethanol, and oxygen...... reduction reaction experiments, for both anode and cathode catalyst applications respectively. Finally, the main goal was to investigate the electrocatalytic performance within the PEMFC systems. Direct formic acid, methanol and ethanol PEMFC station was established. As-synthesized grapheneimmobilized Au......@Pt NPs exhibited high electrocatalytic performance and long stability in direct formic acid, methanol and ethanol PEMFCs....

  5. Electrochemical biosensors for hormone analyses.

    Science.gov (United States)

    Bahadır, Elif Burcu; Sezgintürk, Mustafa Kemal

    2015-06-15

    Electrochemical biosensors have a unique place in determination of hormones due to simplicity, sensitivity, portability and ease of operation. Unlike chromatographic techniques, electrochemical techniques used do not require pre-treatment. Electrochemical biosensors are based on amperometric, potentiometric, impedimetric, and conductometric principle. Amperometric technique is a commonly used one. Although electrochemical biosensors offer a great selectivity and sensitivity for early clinical analysis, the poor reproducible results, difficult regeneration steps remain primary challenges to the commercialization of these biosensors. This review summarizes electrochemical (amperometric, potentiometric, impedimetric and conductometric) biosensors for hormone detection for the first time in the literature. After a brief description of the hormones, the immobilization steps and analytical performance of these biosensors are summarized. Linear ranges, LODs, reproducibilities, regenerations of developed biosensors are compared. Future outlooks in this area are also discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. 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)

  7. 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

  8. Synthesis of magnetite nanoparticles using electrochemical oxidation

    Directory of Open Access Journals (Sweden)

    Ye. Ya. Levitin

    2014-08-01

    Full Text Available The monodisperse magnetite nanoparticles are promising for use in the biomedical industry for targeted drug delivery, cell separation and biochemical products, Magnetic Resonance Imaging, immunological studies, etc. Classic method for the synthesis of magnetite is the chemical condensation Elmore’s, it is simple and cheap, but it is complicated by the formation of side compounds which impair the magnetic properties of the final product. Biological and medical purposes require high purity magnetite nanoparticles. Electrochemical methods of producing nanoparticles of magnetite acquire significant spread. The kinetics of electrochemical processes are a function of a larger number of parameters than the kinetics of conventional chemical reaction, thus electrochemical reactions can be thinner and more completely adjusted to give a predetermined size nanoparticles. In the kinetics of the electrochemical oxidation and reduction the important role is played by the nature of the electrode. In many industrial processes, it is advisable to use lead dioxide anodes with titanium current lead. Purpose of the work To determine the optimum conditions of electrochemical oxidation of Fe2+ Fe3+to produce magnetite with high purity and improved magnetic characteristics. Materials and methods Electrochemical studies were carried out in a glass cell ЯСЭ-2 using a potentiostat ПИ-50-1.1 and a recording device ПДА1. Reference electrode - silver chloride ЭВЛ1М 3.1, potentials listed on the hydrogen scale. The test solution contained 80 g/ l FeSO4×7H2O and H2SO4(to pH 1. The pH of the solution was measured with a pH–meter « рН–150». Concentration ratio of Fe3+/Fe2+in the solution was measured by permanganometric method. Magnetite particle sizes were measured by an electron microscope computer ЭВМ-100Л, an increasing is 2×105. Saturation magnetization was evaluated by the magnetization curve, for the measured sample in the field with strength

  9. Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

    Science.gov (United States)

    Kunz, Harold R.; Breault, Richard D.

    1993-01-01

    An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

  10. Rapid electrochemical phenotypic profiling of antibiotic-resistant bacteria.

    Science.gov (United States)

    Besant, Justin D; Sargent, Edward H; Kelley, Shana O

    2015-07-07

    Rapid phenotyping of bacteria to identify drug-resistant strains is an important capability for the treatment and management of infectious disease. At present, the rapid determination of antibiotic susceptibility is hindered by the requirement that, in existing devices, bacteria must be pre-cultured for 2-3 days to reach detectable levels. Here we report a novel electrochemical approach that achieves rapid readout of the antibiotic susceptibility profile of a bacterial infection within one hour. The electrochemical reduction of a redox-active molecule is monitored that reports on levels of metabolically-active bacteria. Bacteria are captured in miniaturized wells, incubated with antimicrobials and monitored for resistance. This electrochemical phenotyping approach is effective with clinically-relevant levels of bacteria, and provides results comparable to culture-based analysis. Results, however, are delivered on a much faster timescale, with resistance profiles available after a one hour incubation period.

  11. 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...... bands are observed on the Pt/C layer: bands arising from the functional groups of the carbon support, bands related to water and hydronium, and bands related to the sulfur anion interaction with the catalyst. The correlation of the anion absorption to the ORR current leads to the proposition that anion...

  12. Organic electrochemical transistors

    KAUST Repository

    Rivnay, Jonathan

    2018-01-16

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  13. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    Lipp, Ludwig [FuelCell Energy, Inc., Torrington, CT (United States)

    2016-01-21

    Conventional compressors have not been able to meet DOE targets for hydrogen refueling stations. They suffer from high capital cost, poor reliability and pose a risk of fuel contamination from lubricant oils. This project has significantly advanced the development of solid state hydrogen compressor technology for multiple applications. The project has achieved all of its major objectives. It has demonstrated capability of Electrochemical Hydrogen Compression (EHC) technology to potentially meet the DOE targets for small compressors for refueling sites. It has quantified EHC cell performance and durability, including single stage hydrogen compression from near-atmospheric pressure to 12,800 psi and operation of EHC for more than 22,000 hours. Capital cost of EHC was reduced by 60%, enabling a path to meeting the DOE cost targets for hydrogen compression, storage and delivery ($2.00-2.15/gge by 2020).

  14. Organic electrochemical transistors

    Science.gov (United States)

    Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Róisín M.; Berggren, Magnus; Malliaras, George G.

    2018-02-01

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  15. 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.

  16. 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.

  17. 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”.

  18. 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

  19. Preparation of electrochemically active silicon nanotubes in highly ordered arrays

    Directory of Open Access Journals (Sweden)

    Tobias Grünzel

    2013-10-01

    Full Text Available Silicon as the negative electrode material of lithium ion batteries has a very large capacity, the exploitation of which is impeded by the volume changes taking place upon electrochemical cycling. A Si electrode displaying a controlled porosity could circumvent the difficulty. In this perspective, we present a preparative method that yields ordered arrays of electrochemically competent silicon nanotubes. The method is based on the atomic layer deposition of silicon dioxide onto the pore walls of an anodic alumina template, followed by a thermal reduction with lithium vapor. This thermal reduction is quantitative, homogeneous over macroscopic samples, and it yields amorphous silicon and lithium oxide, at the exclusion of any lithium silicides. The reaction is characterized by spectroscopic ellipsometry for thin silica films, and by nuclear magnetic resonance and X-ray photoelectron spectroscopy for nanoporous samples. After removal of the lithium oxide byproduct, the silicon nanotubes can be contacted electrically. In a lithium ion electrolyte, they then display the electrochemical waves also observed for other bulk or nanostructured silicon systems. The method established here paves the way for systematic investigations of how the electrochemical properties (capacity, charge/discharge rates, cyclability of nanoporous silicon negative lithium ion battery electrode materials depend on the geometry.

  20. Electrochemical Hydrogen Compressor

    Energy Technology Data Exchange (ETDEWEB)

    David P. Bloomfield; Brian S. MacKenzie

    2006-05-01

    The Electrochemical Hydrogen Compressor EHC was evaluated against DOE applications for compressing hydrogen at automobile filling stations, in future hydrogen pipelines and as a commercial replacement for conventional diaphragm hydrogen compressors. It was also evaluated as a modular replacement for the compressors used in petrochemical refineries. If the EHC can be made inexpensive, reliable and long lived then it can satisfy all these applications save pipelines where the requirements for platinum catalyst exceeds the annual world production. The research performed did not completely investigate Molybdenum as a hydrogen anode or cathode, it did show that photoetched 316 stainless steel is inadequate for an EHC. It also showed that: molybdenum bipolar plates, photochemical etching processes, and Gortex Teflon seals are too costly for a commercial EHC. The use of carbon paper in combination with a perforated thin metal electrode demonstrated adequate anode support strength, but is suspect in promoting galvanic corrosion. The nature of the corrosion mechanisms are not well understood, but locally high potentials within the unit cell package are probably involved. The program produced a design with an extraordinary high cell pitch, and a very low part count. This is one of the promising aspects of the redesigned EHC. The development and successful demonstration of the hydraulic cathode is also important. The problem of corrosion resistant metal bipolar plates is vital to the development of an inexpensive, commercial PEM fuel cell. Our research suggests that there is more to the corrosion process in fuel cells and electrochemical compressors than simple, steady state, galvanic stability. It is an important area for scientific investigation. The experiments and analysis conducted lead to several recommended future research directions. First, we need a better understanding of the corrosion mechanisms involved. The diagnosis of experimental cells with titration to

  1. Characterization of Electrochemically Generated Silver

    Science.gov (United States)

    Adam, Niklas; Martinez, James; Carrier, Chris

    2014-01-01

    Silver biocide offers a potential advantage over iodine, the current state of the art in US spacecraft disinfection technology, in that silver can be safely consumed by the crew. Low concentrations of silver (Silver does not require hardware to remove it from a water system, and therefore can provide a simpler means for disinfecting water. The Russian segment of the International Space Station has utilized an electrochemically generated silver solution, which is colloidal in nature. To be able to reliably provide a silver biocide to drinking water by electrochemical means would reduce mass required for removing another biocide such as iodine from the water. This would also aid in crew time required to replace iodine removal cartridges. Future long term missions would benefit from electrochemically produced silver as the biocide could be produced on demand and requires only a small concentration to be effective. Since it can also be consumed safely, there is less mass in removal hardware and little consumables required for production. The goal of this project initially is to understand the nature of the electrochemically produced silver, the particle sizes produced by the electrochemical cell and the effect that voltage adjustment has on the particle size. In literature, it has been documented that dissolved oxygen and pH have an effect on the ionization of the electrochemical silver so those parameters would be measured and possibly adjusted to understand their effect on the silver.

  2. Electrochemical applications of CVD diamond

    International Nuclear Information System (INIS)

    Pastor-Moreno, Gustavo

    2002-01-01

    Diamond technology has claimed an important role in industry since non-expensive methods of synthesis such as chemical vapour deposition allow to elaborate cheap polycrystalline diamond. This fact has increased the interest in the scientific community due to the outstanding properties of diamond. Since Pleskov published in 1987 the first paper in electrochemistry, many researchers around the world have studied different aspects of diamond electrochemistry such as reactivity, electrical structure, etc. As part of this worldwide interest these studies reveal new information about diamond electrodes. These studies report investigation of diamond electrodes characterized using structural techniques like scanning electrode microscopy and Raman spectroscopy. A new electrochemical theory based on surface states is presented that explains the metal and the semiconductor behaviour in terms of the doping level of the diamond electrode. In an effort to characterise the properties of diamond electrodes the band edges for hydrogen and oxygen terminated surface are located in organic solvent, hence avoiding possible interference that are present in aqueous solution. The determination of the band edges is performed by Mott-Schottky studies. These allow the calculation of the flat band potential and therefore the band edges. Additional cyclic voltammetric studies are presented for both types of surface termination. Mott-Schottky data and cyclic voltammograms are compared and explained in terms of the band edge localisation. Non-degenerately p-type semiconductor behaviour is presented for hydrogen terminated boron doped diamond. Graphitic surface states on oxidised surface boron doped diamond are responsible for the electrochemistry of redox couples that posses similar energy. Using the simple redox couple 1,4-benzoquinone effect of surface termination on the chemical behaviour of diamond is presented. Hydrogen sublayers in diamond electrodes seem to play an important role for the

  3. 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

  4. New Photochemical and Electrochemical Methods for the Degradation of Pesticides in Aqueous media. Environmental Applications

    OpenAIRE

    AARON, Jean Jacques

    2014-01-01

    The development of new electrochemical and photochemical methods for the decontamination of natural water containing significant concentrations of aromatic pesticides is described. The electrochemical method is based on the electro-Fenton process, i.e. the simultaneous reduction of O2 and Fe3+ ions. Hydroxyl (OH.) radicals are electrosynthesized in aqueous solutions, followed by complete mineralization of the initial pollutants. The photochemical methods involve either a direct pho...

  5. Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

    Energy Technology Data Exchange (ETDEWEB)

    Yu Jiefei; Kupferle, Margaret J. [University of Cincinnati, Department of Civil and Environmental Engineering (United States)], E-mail: Margaret.Kupferle@uc.edu

    2008-08-15

    Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to 'active chlorine' species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite - essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate)

  6. Mechanism for reversible CO/CO2 electrochemical conversion on a patterned nickel electrode

    Science.gov (United States)

    Luo, Yu; Li, Wenying; Shi, Yixiang; Cai, Ningsheng

    2017-10-01

    The patterned Ni negative electrode on single-crystal YSZ in CO-CO2 atmosphere is investigated in both the solid oxide fuel cell (SOFC) and solid oxide electrolysis cell (SOEC) modes. The effects of the temperature T, partial pressure of CO and CO2 (pCO and pCO2) on the electrochemical performance are measured to obtain the intrinsic kinetic parameters by natural logarithm linear fitting. The strong dependency of surface diffusion resistance on pCO implies that surface diffusion could be related to CO(Ni). The electrochemical performance had an obviously positive correlation with T and pCO. The limitation of CO2 adsorption leads to a weak dependency of polarization on pCO2. The electrochemical performance of SOEC mode in the atmosphere without CO is 1.21 times higher than that in the atmosphere without CO2, which implies that CO electrochemical reduction could be more significant than CO2 electrochemical reduction in the patterned Ni electrode. An analytical calculation is performed for the speculation of rate-limiting steps. In the SOFC mode, CO oxidation into CO2 is speculated to be rate-determining, besides, adsorbed carbon oxidation into CO could be also non-ignorable. In the SOEC mode, CO reduction into carbon could be more probably the major electrochemical reaction on the pure Ni surface.

  7. 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-measurements ......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...

  8. Electrochemical Reductions of Methyl Azinyl Ketoximes on Mercury

    Czech Academy of Sciences Publication Activity Database

    Cibulka, R.; Liška, F.; Ludvík, Jiří

    2000-01-01

    Roč. 65, č. 10 (2000), s. 1630-1642 ISSN 0010-0765 R&D Projects: GA ČR GA203/99/0763 Institutional research plan: CEZ:AV0Z4040901; CEZ:A54/98:Z4-040-9-ii Subject RIV: CG - Electrochemistry Impact factor: 0.960, year: 2000

  9. Electrochemical reduction of Eu (III) in propionic media

    International Nuclear Information System (INIS)

    Brotto, M.E.; Rabockai, T.

    1988-01-01

    Some chronopotentiometric studies of Eu (III) electro-reducion in propionic media that suggests the presence of two parallel rections: Eu (III) → Eu (II) and Eu (III) → Eu (II) → Y are presented. Some experimental data, such Eu (III) reducion, electrolysis of solutions and ionic power of the system are discussed. (M.J.C.) [pt

  10. Electrochemical reduction of water. Development of a flat cell pile

    International Nuclear Information System (INIS)

    Viguie, J.C.

    1978-01-01

    The working conditions of an electrolyser are described. Great variations of water vapor concentrations through the battery makes us advocate for piling up flat cells working under a constant potential. A 50 cm 2 half cathodic cell has been fabricated. The solid electrolyte is made of zirconia (0,91 ZrO 2 , 0,09 Y 2 O 3 ) associated with an embedded layer of nickel powder as the cathode. The disc is supported by an honeycomb shaped ceramic which is covered by a layer of nickel. The most promising method for solid electrolyte fabrication is the powder compaction and sintering process. The plasma jet projection gave interesting results and can be considered as an alternative process. A test set working at 850 0 C is on the way. It will give informations on the stability of the prepared parts and allow us to measure the characteristics of the planar cell [fr

  11. Electrochemical oxidation of organic waste

    International Nuclear Information System (INIS)

    Almon, A.C.; Buchanan, B.R.

    1990-01-01

    Both silver catalyzed and direct electrochemical oxidation of organic species are examined in analytical detail. This paper describes the mechanisms, reaction rates, products, intermediates, capabilities, limitations, and optimal reaction conditions of the electrochemical destruction of organic waste. A small bench-top electrocell being tested for the treatment of small quantities of laboratory waste is described. The 200-mL electrochemical cell used has a processing capacity of 50 mL per day, and can treat both radioactive and nonradioactive waste. In the silver catalyzed process, Ag(I) is electrochemically oxidized to Ag(II), which attacks organic species such as tributylphosphate (TBP), tetraphenylborate (TPB), and benzene. In direct electrochemical oxidation, the organic species are destroyed at the surface of the working electrode without the use of silver as an electron transfer agent. This paper focuses on the destruction of tributylphosphate (TBP), although several organic species have been destroyed using this process. The organic species are converted to carbon dioxide, water, and inorganic acids

  12. Novel nanoarchitectures for electrochemical biosensing

    Science.gov (United States)

    Archibald, Michelle M.

    Sensitive, real-time detection of biomarkers is of critical importance for rapid and accurate diagnosis of disease for point-of-care (POC) technologies. Current methods, while sensitive, do not adequately allow for POC applications due to several limitations, including complex instrumentation, high reagent consumption, and cost. We have investigated two novel nanoarchitectures, the nanocoax and the nanodendrite, as electrochemical biosensors towards the POC detection of infectious disease biomarkers to overcome these limitations. The nanocoax architecture is composed of vertically-oriented, nanoscale coaxial electrodes, with coax cores and shields serving as integrated working and counter electrodes, respectively. The dendritic structure consists of metallic nanocrystals extending from the working electrode, increasing sensor surface area. Nanocoaxial- and nanodendritic-based electrochemical sensors were fabricated and developed for the detection of bacterial toxins using an electrochemical enzyme-linked immunosorbent assay (ELISA) and differential pulse voltammetry (DPV). Proof-of-concept was demonstrated for the detection of cholera toxin (CT). Both nanoarchitectures exhibited levels of sensitivity that are comparable to the standard optical ELISA used widely in clinical applications. In addition to matching the detection profile of the standard ELISA, these electrochemical nanosensors provide a simple electrochemical readout and a miniaturized platform with multiplexing capabilities toward POC implementation. Further development as suggested in this thesis may lead to increases in sensitivity, enhancing the attractiveness of the architectures for future POC devices.

  13. Electrochemically produced alumina as TL detector

    International Nuclear Information System (INIS)

    Osvay, M.

    1996-01-01

    The goal of this work was to compare the TL properties of various electrochemically produced alumina layers (E-AIO) in order to investigate the effect of the electrolyte and the Mg content on the alloys. It has been found that the TL sensitivity of oxidised layers is more influenced by the type of electrolyte, than by the composition of alloy. Hard oxide layer evolved in reduction electrolyte has rather different character compared to other alumina production investigated. The effect of reducing media seems to be very important during preparation of alumina layer. One of the advantages properties of E-AIO is, that it serve a promising method to increase the measuring range of TL method above 10 kGy as well. (author)

  14. Alkaline Electrochemical Capacitor and Electrode Fabrication

    National Research Council Canada - National Science Library

    Finello, D

    1999-01-01

    Highly capacitive (high surface area) electrodes that are electrochemically stable in strong alkaline electrolyte will form the basis for a new generation of electrical and electrochemical energy storage and conversion devices...

  15. Electrochemical processing of nitrate waste solutions

    Energy Technology Data Exchange (ETDEWEB)

    Genders, D.; Weinberg, N.; Hartsough, D. (Electrosynthesis Co., Inc., Cheektowaga, NY (United States))

    1992-10-07

    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[sup [minus

  16. 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

  17. Materials for electrochemical device safety

    Science.gov (United States)

    Vissers, Daniel R.; Amine, Khalil; Thackeray, Michael M.; Kahaian, Arthur J.; Johnson, Christopher S.

    2015-04-07

    An electrochemical device includes a thermally-triggered intumescent material or a gas-triggered intumescent material. Such devices prevent or minimize short circuits in a device that could lead to thermal run-away. Such devices may include batteries or supercapacitors.

  18. Electrochemical Machining Removes Deep Obstructions

    Science.gov (United States)

    Catania, Mark J.

    1987-01-01

    Electrochemical machining (ECM) is effective way of removing obstructing material between two deep holes supposed to intersect but do not because of misalignment of drilling tools. ECM makes it possible to rework costly castings otherwise scrapped. Method fast even for tough or hard alloys and complicated three-dimensional shapes.

  19. SUPPLEMENTARY INFORMATION A combined Electrochemical ...

    Indian Academy of Sciences (India)

    DELL

    A combined Electrochemical and Theoretical study of pyridine-based Schiff bases as novel corrosion inhibitors for mild steel in hydrochloric acid medium. PARUL DOHAREa, M A QURAISHIb* and I B OBOTb. aDepartment of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi, Uttar. Pradesh 221 ...

  20. Electrolytes for magnesium electrochemical cells

    Science.gov (United States)

    Burrell, Anthony K.; Sa, Niya; Proffit, Danielle Lee; Lipson, Albert; Liao, Chen; Vaughey, John T.; Ingram, Brian J.

    2017-07-04

    An electrochemical cell includes a high voltage cathode configured to operate at 1.5 volts or greater; an anode including Mg.sup.0; and an electrolyte including an ether solvent and a magnesium salt; wherein: a concentration of the magnesium salt in the ether is 1 M or greater.

  1. Electrochemical method for transferring graphene

    DEFF Research Database (Denmark)

    2015-01-01

    The present application discloses a method for separating a graphene-support layer laminate from a conducting substrate-graphene-support layer laminate, using a gentle, controllable electrochemical method. In this way, substrates which are fragile, expensive or difficult to manufacture can be used...... - and even re-used - without damage or destruction of the substrate or the graphene....

  2. Graphene-based electrochemical supercapacitors

    Indian Academy of Sciences (India)

    Graphenes prepared by three different methods have been investigated as electrode materials in electrochemical supercapacitors. The samples prepared by exfoliation of graphitic oxide and by the transformation of nanodiamond exhibit high specific capacitance in aq. H2SO4, the value reaching up to 117 F/g. By using an ...

  3. Electrochemical Genosensing of Circulating Biomarkers

    Science.gov (United States)

    Campuzano, Susana; Yáñez-Sedeño, Paloma; Pingarrón, José Manuel

    2017-01-01

    Management and prognosis of diseases requires the measurement in non- or minimally invasively collected samples of specific circulating biomarkers, consisting of any measurable or observable factors in patients that indicate normal or disease-related biological processes or responses to therapy. Therefore, on-site, fast and accurate determination of these low abundance circulating biomarkers in scarcely treated body fluids is of great interest for health monitoring and biological applications. In this field, electrochemical DNA sensors (or genosensors) have demonstrated to be interesting alternatives to more complex conventional strategies. Currently, electrochemical genosensors are considered very promising analytical tools for this purpose due to their fast response, low cost, high sensitivity, compatibility with microfabrication technology and simple operation mode which makes them compatible with point-of-care (POC) testing. In this review, the relevance and current challenges of the determination of circulating biomarkers related to relevant diseases (cancer, bacterial and viral infections and neurodegenerative diseases) are briefly discussed. An overview of the electrochemical nucleic acid–based strategies developed in the last five years for this purpose is given to show to both familiar and non-expert readers the great potential of these methodologies for circulating biomarker determination. After highlighting the main features of the reported electrochemical genosensing strategies through the critical discussion of selected examples, a conclusions section points out the still existing challenges and future directions in this field. PMID:28420103

  4. Electrochemical DNA biosensor for bovine papillomavirus detection using polymeric film on screen-printed electrode.

    Science.gov (United States)

    Nascimento, Gustavo A; Souza, Elaine V M; Campos-Ferreira, Danielly S; Arruda, Mariana S; Castelletti, Carlos H M; Wanderley, Marcela S O; Ekert, Marek H F; Bruneska, Danyelly; Lima-Filho, José L

    2012-01-01

    A new electrochemical DNA biosensor for bovine papillomavirus (BPV) detection that was based on screen-printed electrodes was comprehensively studied by electrochemical methods of cyclic voltammetry (CV) and differential pulse voltammetry (DPV). A BPV probe was immobilised on a working electrode (gold) modified with a polymeric film of poly-L-lysine (PLL) and chitosan. The experimental design was carried out to evaluate the influence of polymers, probe concentration (BPV probe) and immobilisation time on the electrochemical reduction of methylene blue (MB). The polymer poly-L-lysine (PLL), a probe concentration of 1 μM and an immobilisation time of 60 min showed the best result for the BPV probe immobilisation. With the hybridisation of a complementary target sequence (BPV target), the electrochemical signal decreased compared to a BPV probe immobilised on the modified PLL-gold electrode. Viral DNA that was extracted from cattle with papillomatosis also showed a decrease in the MB electrochemical reduction, which suggested that the decreased electrochemical signal corresponded to a bovine papillomavirus infection. The hybridisation specificity experiments further indicated that the biosensor could discriminate the complementary sequence from the non-complementary sequence. Thus, the results showed that the development of analytical devices, such as a biosensor, could assist in the rapid and efficient detection of bovine papillomavirus DNA and help in the prevention and treatment of papillomatosis in cattle. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. 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...

  6. Alizarin Red S as an electrochemical indicator for saccharide recognition

    Energy Technology Data Exchange (ETDEWEB)

    Schumacher, Soeren, E-mail: soeren.schumacher@ibmt.fraunhofer.de [Fraunhofer Institute for Biomedical Engineering, Am Muehlenberg 13, 14476 Potsdam (Germany); Nagel, Thomas; Scheller, Frieder W.; Gajovic-Eichelmann, Nenad [Fraunhofer Institute for Biomedical Engineering, Am Muehlenberg 13, 14476 Potsdam (Germany)

    2011-07-30

    Graphical abstract: Display Omitted Highlights: > Transfer of the established Alizarin Red S (ARS) for saccharide-boronic acid interaction to electrochemistry. > Investigation of electrochemical behaviour of ARS and its interaction with phenylboronic acid at pH 7.4. > Through addition of fructose the ARS was displaced. > Displaced ARS could be monitored electrochemically corresponding to the used fructose concentration. - Abstract: In addition to the well-established spectroscopic Alizarin Red S (ARS) assay for the determination of binding constants between arylboronic acids and different saccharides, we report the use of ARS as a reporter in an electrochemical set-up. The electrochemical properties of ARS, the binding to phenyl boronic acid (PBA) and the competition with fructose in phosphate buffer at pH 7.4 were investigated by cyclic voltammetry (CV). By choosing a negative scan direction (starting at +0.2 V), a quasi-reversible process was detected at E{sup 0}' = -0.59V with {Delta}E{sub p} = 0.1V. An irreversible oxidation peak at +0.42 V could also be detected. These peaks are characterised both as a 2-proton-2-electron transfer and corresponds to the oxidation and reduction of the anthraquinone or the ortho-quinone moiety. After addition of phenylboronic acid a new oxidation peaks occurred at -0.42 V which correlates with the ARS-PBA interaction. The peak current increased with increasing phenylboronic acid concentration according to the release of BA and formation of the ARS-PBA ester. After addition of fructose the peak current decreases again, in proportion to the fructose concentration, enabling the use of ARS as an electrochemical reporter for fructose detection up to 50 mM. Also the interaction with other cis-diol containing compounds such as sorbitol, mannitol, glucose and mannose was investigated and a dependence based on already published binding constants to phenylboronic acid could be shown.

  7. 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.

  8. An accelerated electrochemical MIC test for stainless alloys

    International Nuclear Information System (INIS)

    Gendron, T.S.; Cleland, R.D.

    1994-01-01

    Previous work in our laboratory and elsewhere has suggested that MIC of stainless steels and nickel-base alloys occurs in locally anaerobic regions that support the growth of sulfate reducing bacteria (SRB). The cathodic reaction is provided by oxygen reduction at remote sites. Such a coupling between anode and cathode is difficult to reproduce in the laboratory, but can be simulated indirectly using a double electrochemical cell, as in previous work. A more realistic simulation using a single aerated electrochemical cell has now been developed, in which a second organism (P. aeruginosa) is used to provide an anoxic habitat for SRB growth and possibly a source of organic carbon, within a layer of silt. A bare alloy electrode is used as the oxygen cathode. Tests of this kind using rigorous microbiological procedures have generated pitting corrosion of several alloys in low chloride media simulating freshwater heat exchanger conditions. Similar test procedures are applicable to other environments of interest to this symposium

  9. Poverty Reduction

    OpenAIRE

    Ortiz, Isabel

    2007-01-01

    The paper reviews poverty trends and measurements, poverty reduction in historical perspective, the poverty-inequality-growth debate, national poverty reduction strategies, criticisms of the agenda and the need for redistribution, international policies for poverty reduction, and ultimately understanding poverty at a global scale. It belongs to a series of backgrounders developed at Joseph Stiglitz's Initiative for Policy Dialogue.

  10. Electrochemical corrosion of metallic biomaterials.

    Science.gov (United States)

    Pourbaix, M

    1984-05-01

    Methods of electrochemical thermodynamics (electrode potential-pH equilibrium diagrams) and electrochemical kinetics (polarization curves) may help to understand and predict the corrosion behaviour of metals and alloys in the presence of body fluids. A short review of the literature is given concerning some applications of such methods, both in vitro and in vivo, relating to surgical implants (stainless steels, chromium-cobalt-molybdenum alloys, titanium and titanium alloys) and to dental alloys (silver-tin-copper amalgams, silver-base and gold-base casting alloys, nickel-base casting alloys). Attention is drawn to the necessity of more basic research on crevice- and fretting-corrosion of surgical implant materials and dental alloys, and to the toxicity of corrosion products. A perfect understanding of the exact significance of electrode-potentials is essential for the success of such a task.

  11. Electrochemical treatment of liquid wastes

    International Nuclear Information System (INIS)

    Hobbs, D.

    1996-01-01

    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 activity consists of five major tasks: (1) evaluation of different 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 size reactor, and (5) analysis and evaluation of testing data. The development program team is comprised of individuals from federal, academic, and private industry. Work is being carried out in DOE, academic, and private industrial laboratories

  12. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  13. Electrochemical synthesis of multisegmented nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Kok, Kuan-Ying; Ng, Inn-Khuan; Saidin, Nur Ubaidah [Malaysian Nuclear Agency, Bangi, 43000 Kajang (Malaysia)

    2012-11-27

    Electrochemical deposition has emerged as a promising route for nanostructure fabrication in recent years due to the many inherent advantages it possesses. This study focuses on the synthesis of high-aspect-ratio multisegmented Au/Ni nanowires using template-directed sequential electrochemical deposition techniques. By selectively removing the Ni segments in the nanowires, high-yield of pure gold nanorods of predetermined lengths was obtained. Alternatively, the sacrificial Ni segments in the nanowires can be galvanically displaced with Bi and Te to form barbells structures with Bi{sub x}Te{sub y} nanotubes attached to neighbouring gold segments. Detailed studies on the nanostructures obtained were carried out using various microscopy, diffraction and probebased techniques for structural, morphological and chemical characterizations.

  14. Electrochemical sensing carcinogens in beverages

    CERN Document Server

    Zia, Asif Iqbal

    2016-01-01

    This book describes a robust, low-cost electrochemical sensing system that is able to detect hormones and phthalates – the most ubiquitous endocrine disruptor compounds – in beverages and is sufficiently flexible to be readily coupled with any existing chemical or biochemical sensing system. A novel type of silicon substrate-based smart interdigital transducer, developed using MEMS semiconductor fabrication technology, is employed in conjunction with electrochemical impedance spectroscopy to allow real-time detection and analysis. Furthermore, the presented interdigital capacitive sensor design offers a sufficient penetration depth of the fringing electric field to permit bulk sample testing. The authors address all aspects of the development of the system and fully explain its benefits. The book will be of wide interest to engineers, scientists, and researchers working in the fields of physical electrochemistry and biochemistry at the undergraduate, postgraduate, and research levels. It will also be high...

  15. Recent Advances in Electrochemical Glycobiosensing

    Directory of Open Access Journals (Sweden)

    Germarie Sánchez-Pomales

    2011-01-01

    Full Text Available Biosensors based on electrochemical transduction mechanisms have recently made advances into the field of glycan analysis. These glyco-biosensors offer simple, rapid, sensitive, and economical approaches to the measurement need for rapid glycan analysis for biomarker detection, cancer and disease diagnostics, and bioprocess monitoring of therapeutic glycoproteins. Although the prevalent methods of glycan analysis (high-performance liquid chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy provide detailed identification and structural analysis of glycan species, there are significantly few low-cost, rapid glycan assays available for diagnostic and screening applications. Here we review instances in which glyco-biosensors have been used for glycan analysis using a variety of electrochemical transduction mechanisms (e.g., amperometric, potentiometric, impedimetric, and voltammetric, selective binding agents (e.g., lectins and antibodies, and redox species (e.g., enzyme substrates, inorganic, and nanomaterial.

  16. Recent Advances in Electrochemical Glycobiosensing

    OpenAIRE

    Sánchez-Pomales, Germarie; Zangmeister, Rebecca A.

    2011-01-01

    Biosensors based on electrochemical transduction mechanisms have recently made advances into the field of glycan analysis. These glyco-biosensors offer simple, rapid, sensitive, and economical approaches to the measurement need for rapid glycan analysis for biomarker detection, cancer and disease diagnostics, and bioprocess monitoring of therapeutic glycoproteins. Although the prevalent methods of glycan analysis (high-performance liquid chromatography, mass spectrometry, and nuclear magnet...

  17. Electrochemical techniques for the removal of Reactofix Golden Yellow 3 RFN from industrial wastes.

    Science.gov (United States)

    Jain, Rajeev; Varshney, Shaily; Sikarwar, Shalini

    2007-09-01

    Electrochemical methods for pollution abatement have been shown to be viable alternatives or complementary to biological treatment in some instances, especially when pollutants are recalcitrant to biological processing. Electrochemical oxidation and reduction have been found successful in decomposing the most resilient compounds, and electrolysis is assigned an important role in the elucidation of the electrode process. Small well-defined cathodic and anodic peak were observed that on controlled-potential electrolysis (CPE) reduced substantially with a considerable decrease in color and absorbance. The rate of decrease of the current and absorbance was found to exhibit a first-order dependence. The COD of the solutions showed a decrease from 1416 to 352 mg/L. No peak could be observed in the voltammograms after CPE, indicating the absence of any electroactive substance left in the solutions. Results show that electrochemical reduction is a superior technology for treatment of dyes, as there is no simultaneous addition of anions, such as sulfate or chloride.

  18. Electrochemical studies of ruthenium compounds

    International Nuclear Information System (INIS)

    Kumar Ghosh, B.; Chakravorty, A.

    1989-01-01

    In many ways the chemistry of transition metals is the chemistry of multiple oxidation states and the associated redox phenomena. If a particular element were to be singeld out to illustrate this viewpoint, a model choice would be ruthenium - an element that is directly or indirectly the active centre of a plethora of redox phenomena encompassing ten different oxidation states and a breathtaking diversity of structure and bonding. In the present review the authors are primarily concerned with the oxidation states of certain ligands coordinated to ruthenium. This choice is deliberate since this is one area where the unique power of electrochemical methods is splendidly revealed. Without these methods, development in this area would have been greatly hampered. A brief summary of metal oxidation states is also included as a prelude to the main subject of this review. The authors have generally emphasize the information derived which is of chemical interest leaving the details of formal electrochemical arguments in the background. The authors have reviewed the pattern and systematics of ligand redox in ruthenium complexes. The synergistic combination of electrochemical and spectroscopic methods have vastly increased our understanding of ligand phenomena during the last 15 years or so. This in turn has led to better understanding and new developments in other fields. Photophysics and photochemistry could be cited as examples. (author). 176 refs.; 10 figs.; 10 tabs

  19. 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.

  20. Pencil it in: pencil drawn electrochemical sensing platforms

    OpenAIRE

    Foster, Christopher W.; Brownson, Dale A.C.; Ruas de Souza, Ana P.; Bernalte, Elena; Iniesta, Jesus; Bertotti, Mauro; Banks, Craig E.

    2016-01-01

    Inspired by recent reports concerning the utilisation of hand drawn pencil macroelectrodes (PDEs), we report the fabrication, characterisation (physicochemical and electrochemical) and implementation (electrochemical sensing) of various PDEs drawn upon a flexible polyester substrate. Electrochemical characterisation reveals that there are no quantifiable electrochemical responses upon utilising these PDEs with an electroactive analyte that requires an electrochemical oxidation step first, the...

  1. Characterization of surface electrochemical reactions used in electrochemical atomic layer epitaxy and digital etching

    Science.gov (United States)

    Sorenson, Thomas Allen

    Surface analytical techniques have been used to characterize electrochemical reactions to be used in semiconductor processing technologies. Studies have been performed using UHV-EC methodology to determine conditions for the surface limited dissolution of CdTe(100). Electrochemical conditions were identified which resulted in the reduction of the top layer of tellurium atoms, leaving behind a cadmium enriched surface. Attempts to find an electrochemical potential for the oxidative dissolution of the cadmium surface were complicated by the simultaneous oxidation of the compound CdTe. In situ scanning tunneling microscopy has also been used to characterize the formation of tellurium atomic layers formed on Au(111) and Au(100) by underpotential deposition. On Au(100), the following sequence of surface structures was observed prior to bulk electrodeposition: a p(2x2), a (2x✓10), a (2x4), and a (✓2x✓5). The transitions between these structures was observed by STM and mechanisms for the phase transitions are presented. The results are correlated to UHV-EC studies of tellurium UPD on Au(100). On Au(111), the following sequence of structures was observeḑ: a (✓3 x✓3), a (✓7x✓13), and a (3x3). The (✓3x✓3) was shown to exist with a network of domain walls, forming long range triangular and diamond shaped superstructures. Conversion of the (✓3x✓3) to higher coverage structure resulted in roughening of the underlying Au surface and a mechanism is hypothesized to explain this transition. The STM results are also correlated to low energy electron diffraction (LEED) results obtained by UHV-EC studies. The surface structures formed by reductive UPD of the chalcogenide elements and Se on both Au(100) and Au(111) are compared. Both elements initially resulted in structures consisting of isolated atoms separated by distances close to the reported van der Waals diameter. Higher coverage structures resulted in interatomic chalcogenide bonding and the structures

  2. 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...

  3. Electrochemical components employing polysiloxane-derived binders

    Science.gov (United States)

    Delnick, Frank M.

    2013-06-11

    A processed polysiloxane resin binder for use in electrochemical components and the method for fabricating components with the binder. The binder comprises processed polysiloxane resin that is partially oxidized and retains some of its methyl groups following partial oxidation. The binder is suitable for use in electrodes of various types, separators in electrochemical devices, primary lithium batteries, electrolytic capacitors, electrochemical capacitors, fuel cells and sensors.

  4. Electrochemical ion separation in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Spoerke, Erik David; Ihlefeld, Jon; Waldrip, Karen; Wheeler, Jill S.; Brown-Shaklee, Harlan James; Small, Leo J.; Wheeler, David R.

    2017-12-19

    A purification method that uses ion-selective ceramics to electrochemically filter waste products from a molten salt. The electrochemical method uses ion-conducting ceramics that are selective for the molten salt cations desired in the final purified melt, and selective against any contaminant ions. The method can be integrated into a slightly modified version of the electrochemical framework currently used in pyroprocessing of nuclear wastes.

  5. Management of processes of electrochemical dimensional processing

    Science.gov (United States)

    Akhmetov, I. D.; Zakirova, A. R.; Sadykov, Z. B.

    2017-09-01

    In different industries a lot high-precision parts are produced from hard-processed scarce materials. Forming such details can only be acting during non-contact processing, or a minimum of effort, and doable by the use, for example, of electro-chemical processing. At the present stage of development of metal working processes are important management issues electrochemical machining and its automation. This article provides some indicators and factors of electrochemical machining process.

  6. Applications of Nonlinear Electrochemical Impedance Spectroscopy (NLEIS)

    KAUST Repository

    Adler, S. B.

    2013-08-31

    This paper reviews the use of nonlinear electrochemical impedance spectroscopy (NLEIS) in the analysis of SOFC electrode reactions. By combining EIS and NLEIS, as well as other independent information about an electrode material, it becomes possible to establish quantitative links between electrochemical kinetics and materials properties, even when systems are unstable with time. After a brief review of the method, this paper summarizes recent results analyzing the effects of Sr segregation in thin-film LSC electrodes. © The Electrochemical Society.

  7. Method and system for the purification of exhaust gas with an electrochemical cell

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a method for electrochemical reduction of nitrogen oxides and concomitant oxidation of soot, as well as systems useful therefor. Such methods and systems in particular are useful in the context of exhaust gas purification, in particular for diesel engines....

  8. Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor

    2007-01-01

    The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt...

  9. 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

  10. Near-Wall Turbulence in Drag Reducing Flows Investigated by the Photolithography-Electrochemical Probes

    Czech Academy of Sciences Publication Activity Database

    Deslouis, C.; Tribollet, B.; Tihon, Jaroslav

    2004-01-01

    Roč. 123, 2-3 (2004), s. 141-150 ISSN 0377-0257 R&D Projects: GA MŠk OC F2.10 Institutional research plan: CEZ:AV0Z4072921 Keywords : drag reduction * near-wall turbulence * electrochemical technique Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.862, year: 2004

  11. 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

  12. Breast reduction

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/007405.htm Breast reduction To use the sharing features on this page, please enable ... discharge Images Mammoplasty References Fisher J, Higdon KK. Reduction mammaplasty. In: Neligan PC, ed. Plastic Surgery . 3rd ed. Philadelphia, PA: Elsevier Saunders; 2013: ...

  13. Rich Reduction

    DEFF Research Database (Denmark)

    Niebuhr, Oliver

    2016-01-01

    evidence on articulatory prosodies and the involvement of reduction in conveying communication functions both suggest the next steps along the line of argument opened up by Lindblom. Specifically, we need to supplement Lindblom's explanatory framework and revise the speaker-listener conflict that lies...... corresponding to the time domain of the reduction variation....

  14. Electrochemical Investigation of The Catalytical Processes During Sulfuric Acid Production

    DEFF Research Database (Denmark)

    Bjerrum, Niels; Petrushina, Irina; Berg, Rolf W.

    1995-01-01

    pyrosulfate was also investigated. The potential window for pureK2S2O7 was estimated as 2.1 V, being limited by the S2O72- oxidation and reduction. The oxidation of SO4-2 to oxygen isreversible in the basic melt. It is found that V(V) electroreduction proceeds in two steps. The first reduction stage [V(V) V......The electrochemical behavior of molten K2S2O7 and its mixtures with V2O5 [2–20 mole percent (m/o) V2O5] was studiedat 440°C in argon, by using cyclic voltammetry on a gold electrode. The effect of the addition of sulfate and lithium ions onthe electrochemical processes in the molten potassium......(IV)], starting at 0.7–0.8 V vs. Ag+/Ag, is reversible for V2O5 concentrations lower than 5 m/o and at potential scan ratesless than 200 mV/s. For all studied compositions, the first reduction stage is a one-electron reaction. The second reductionstage [V(IV) --> V(III)], starting at 0.1–0.2 V, is irreversible...

  15. ELECTROCHEMICAL BEHAVIOUR OF METHYLENE BLUE IN NON-AQUEOUS SOLVENTS

    International Nuclear Information System (INIS)

    Caram, J.A.; Suárez, J.F. Martínez; Gennaro, A.M.; Mirífico, M.V.

    2015-01-01

    Graphical abstract: Display Omitted - Highlights: • The dye is electro-reduced in two separated monoelectronic charge transfers. • Solvent/supporting electrolyte/acid/base modifies the electrochemical parameters. • A dissociation equilibrium of the dye in non-aqueous solvent is proposed. • The electro-generated and stable dye-radical is also chemically produced in EDA or KOH/DMF. • A new species is reversibly formed in KOH/EtOH or ACN. - Abstract: The electrochemical behaviour of methylene blue in solution of non-aqueous solvents with different supporting electrolytes was studied by cyclic voltammetry. Dye electro-reduction presents two well-defined processes of monoelectronic charge transfer yielding a free radical in the first process and an anion in the second electron transfer. Free radical and anion are long living species in some of the studied media. Effects of supporting electrolyte and solvent on the peak potentials, the peak current functions and the reversibility of the charge transfer processes are reported. A dissociation equilibrium of the dye in solution of non-aqueous solvents and the acid or base added determine markedly the electrochemical responses. In the particular cases of KOH/DMF or EDA basic media the chemical formation of the stable methylene blue radical was detected and it was characterized by EPR spectroscopy. A general reaction scheme is proposed

  16. New analytical portable instrument for microchip electrophoresis with electrochemical detection.

    Science.gov (United States)

    Fernández-la-Villa, Ana; Pozo-Ayuso, Diego F; Castaño-Alvarez, Mario

    2010-08-01

    A new portable instrument that includes a high voltage power supply, a bipotentiostat, and a chip holder has been especially developed for using microchips electrophoresis with electrochemical detection. The main unit of the instrument has dimensions of 150 x 165 x 70 mm (wxdxh) and consists of a four-outputs high voltage power supply with a maximum voltage of +/-3 KV and an acquisition system with two channels for dual amperometric (DC or pulsed amperometric detection) detection. Electrochemical detection has been selected as signal transduction method because it is relatively easily implemented, since nonoptical elements are required. The system uses a lithium-ion polymer battery and it is controlled from a desktop or laptop PC with a graphical user interface based on LabVIEW connected by serial RS232 or Bluetooth. The last part of the system consists of a reusable chip holder for housing the microchips, which contain all the electrical connections and reservoirs for making the work with microchips easy. The performance of the new instrument has been evaluated and compared with other commercially available apparatus using single- and dual-channel pyrex microchips for the separation of the neurotransmitters dopamine, epinephrine, and 3,4-dihydroxy-L-phenyl-alanine. The reduction of the size of the instrument has not affected the good performance of the separation and detection using microchips electrophoresis with electrochemical detection. Moreover, the new portable instrument paves the way for in situ analysis making the use of microchips electrophoresis easier.

  17. Electrochemical removal of pentachlorophenol in a lab-scale platinum electrolyzer.

    Science.gov (United States)

    Wu, Ting-Nien

    2010-01-01

    This study is focused on the removal of pentachlorophenol from its aqueous phase by electrochemically induced degradation with Pt electrodes. The objective of this study was to contrast the electrochemical removal of pentachlorophenol at the oxidative and the reductive potentials, and further to understand how to apply the electrochemical treatment on PCP degradation. Lab experiments were conducted in a Pt electrolyzer, and the voltage source was supplied and precisely controlled by an electrochemical analyzer. In these experiments, the variables including electrolyte species, pH, voltage supply, and reaction time were examined to compare the efficiency of pentachlorophenol removal. Experimental results showed that pentachlorophenol was completely degraded after being electrolyzed for 1 h at-1.5 V in a 0.5 M KCl solution, while the removal of pentachlorophenol is negligible under the similar condition when 0.5 M NaNO(3) or Na(2)CO(3) was used as the electrolyte. The electrolyte concentration below 0.5 M is unfavourable for the electrochemical removal of pentachlorophenol. The removal efficiency of pentachlorophenol is slightly affected by pH, and the strong basic environment might impede the degradation of pentachlorophenol. Comparing with those under positive potentials, the experiments conducted under negative potentials have shown a better removal of pentachlorophenol with a higher current efficiency. It implies that pentachlorophenol degradation followed the reductive pathway. Based on the analysis of GC/MS, the intermediates of pentachlorophenol degradation were identified as 1,2-dichlorocyclohexane and 2-chlorocyclohexanol.

  18. Electrochemical removal of NOx and hydrocarbons

    DEFF Research Database (Denmark)

    Friedberg, Anja Zarah

    , or to contribute with entirely new properties to the system. The LSM was also tested with cobalt doping in the structure.Two types of electrochemical cells were tested. The simplest one being the symmetrical cell and the other a cell stack of porous alternating layers of electrode and electrolyte. To evaluate...... that impregnation of the praseodymium doped ceria (CPO) in LSF/CGO electrode, enhanced the direct decomposition of NO in the presence of excess oxygen significantly.The study also demonstrated the possibility to enhance the NOx reduction with the application of a potential when propene was present in the gas...

  19. Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction† †Electronic supplementary information (ESI) available: Franck–Condon analysis; photochemical one-electron-reduced species formation and characterisation; photophysical, electrochemical and quenching properties of R(4·5) in DMA; photophysical and electrochemical properties of the catalysts; photocatalytic CO2 reduction experiments and additional data. See DOI: 10.1039/c6sc01913g Click here for additional data file.

    Science.gov (United States)

    Rohacova, Jana

    2016-01-01

    We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl–bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO2 reduction in conjunction with various mononuclear catalysts, such as Re(i), Ru(ii) and Mn(i) metal complexes, employing a relatively weak sacrificial electron donor, triethanolamine. Each system showed good product selectivity (CO or HCOOH) and an excellent quantum yield of product formation Φ CO = 0.60 to 0.74 using fac-[ReI(bpy)(CO)3(CH3CN)]+, Φ HCOOH = 0.58 using trans(Cl)–RuII(dtbb)(CO)2Cl2 and Φ HCOOH = 0.48 using a fac-[MnI(dtbb)(CO)3(CH3CN)]+ catalyst. The high photocatalytic efficiencies for CO2 reduction are attributed to efficient reductive quenching of the Re-ring by triethanolamine and fast electron transfer from the generated one-electron-reduced species of the ring to the catalyst. PMID:28451117

  20. Electrochemical Analysis of Antichemotherapeutic Drug Zanosar in Pharmaceutical and Biological Samples by Differential Pulse Polarography

    OpenAIRE

    Reddy, Chennupalle Nageswara; ReddyPrasad, Puthalapattu; Sreedhar, NeelamYughandhar

    2013-01-01

    The electrochemical reduction of zanosar was investigated systematically by direct current polarography, cyclic voltammetry, and differential pulse polarography (DPP). A simple DPP technique was proposed for the direct quantitative determination of anticancer drug zanosar in pharmaceutical formulation and spiked human urine samples for the first time. The reduction potential was −0.28 V versus Ag/AgCl with a hanging mercury drop electrode in Britton-Robinson buffer as supporting electrolyte. ...

  1. Mediated electrochemical hazardous waste destruction

    International Nuclear Information System (INIS)

    Hickman, R.G.; Farmer, J.C.; Wang, F.T.

    1992-03-01

    There are few permitted processes for mixed waste (radioactive plus chemically hazardous) treatment. We are developing an electrochemical process, based upon mediated electrochemical oxidation (MEO), that converts toxic organic components of mixed waste to water, carbon dioxide, and chloride or chloride precipitates. Aggressive oxidizer ions such as Ag 2+ , Co 3+ , or Fe 3+ are produced at an anode. These can attack organic molecules directly, and may also produce hydroxyl free radicals that promote destruction. Solid and liquid radioactive waste streams containing only inorganic radionuclide forms may be treated with existing technology and prepared for final disposal. The coulombic efficiency of the process has been determined, as well as the destruction efficiency for ethylene glycol, a surrogate waste. In addition, hazardous organic materials are becoming very expensive to dispose of and when they are combined with transuranic radioactive elements no processes are presently permitted. Mediated electrochemical oxidation is an ambient- temperature aqueous-phase process that can be used to oxidize organic components of mixed wastes. Problems associated with incineration, such as high-temperature volatilization of radionuclides, are avoided. Historically, Ag(II) has been used as a mediator in this process. Fe(III) and Co(III) are attractive alternatives to Ag(II) since they form soluble chlorides during the destruction of chlorinated solvents. Furthermore, silver itself is toxic heavy metal. Quantitative data have been obtained for the complete oxidation of ethylene glycol by Fe(III) and Co(III). Though ethylene glycol is a nonhalogenated organic, these data have enabled us to make direct comparisons of activities of Fe(III) and Co(III) with Ag(II). Very good quantitative data for the oxidation of ethylene glycol by Ag(II) had already been collected

  2. Electrochemical characterization of liquid resistors

    International Nuclear Information System (INIS)

    Wilson, J.M.; Whiteley, R.V.

    1983-01-01

    During the first two years of operation of Sandia's Particle Beam Fusion Accelerator (PBFA I) the reliability of the CuSO 4 solution resistors in the Marx Generator Energy Storage System has been unsatisfactory. Resistor failure, which is characterized by a large increase in resistance, has been attributed to materials, production techniques, and operating parameters. The problems associated with materials and production techniques have been identified and solutions are proposed. Non-ideal operating parameters are shown to cause polarization of the cathode in the resistor. This initiates electrochemical reactions in the resistor. These reactions often lead to resistance changes and to eventual resistor failure

  3. Nanoporous carbon for electrochemical capacitors.

    Energy Technology Data Exchange (ETDEWEB)

    Siegal, Michael P.; Bunker, Bruce Conrad; Limmer, Steven J.; Yelton, William Graham

    2010-05-01

    Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

  4. Nanoelectrode array for electrochemical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Yelton, William G [Sandia Park, NM; Siegal, Michael P [Albuquerque, NM

    2009-12-01

    A nanoelectrode array comprises a plurality of nanoelectrodes wherein the geometric dimensions of the electrode controls the electrochemical response, and the current density is independent of time. By combining a massive array of nanoelectrodes in parallel, the current signal can be amplified while still retaining the beneficial geometric advantages of nanoelectrodes. Such nanoelectrode arrays can be used in a sensor system for rapid, non-contaminating field analysis. For example, an array of suitably functionalized nanoelectrodes can be incorporated into a small, integrated sensor system that can identify many species rapidly and simultaneously under field conditions in high-resistivity water, without the need for chemical addition to increase conductivity.

  5. Nanoporous carbon for electrochemical capacitors.

    Energy Technology Data Exchange (ETDEWEB)

    Overmyer, Donald L.; Siegal, Michael P.; Bunker, Bruce Conrad; Limmer, Steven J.; Yelton, William Graham

    2010-04-01

    Nanoporous carbon (NPC) is a purely graphitic material with highly controlled densities ranging from less than 0.1 to 2.0 g/cm3, grown via pulsed-laser deposition. Decreasing the density of NPC increases the interplanar spacing between graphene-sheet fragments. This ability to tune the interplanar spacing makes NPC an ideal model system to study the behavior of carbon electrodes in electrochemical capacitors and batteries. We examine the capacitance of NPC films in alkaline and acidic electrolytes, and measure specific capacitances as high as 242 F/g.

  6. Lead-nickel electrochemical batteries

    CERN Document Server

    Glaize, Christian

    2012-01-01

    The lead-acid accumulator was introduced in the middle of the 19th Century, the diverse variants of nickel accumulators between the beginning and the end of the 20th Century. Although old, these technologies are always very present on numerous markets. Unfortunately they are still not used in optimal conditions, often because of the misunderstanding of the internal electrochemical phenomena.This book will show that batteries are complex systems, made commercially available thanks to considerable amounts of scientific research, empiricism and practical knowledge. However, the design of

  7. Printed-Compliant Electrochemical Systems

    Science.gov (United States)

    Gaikwad, Abhinav Machhindra

    Compliant electronic devices such as health monitoring tags, wearable electronics, fabricated using add-on printing techniques or by patterning traditional silicon based electronics in ultrathin format, enable them to flex, stretch and twist without any noticeable change in performance. These devices require a power source---a primary or secondary battery---to power the electronics. Traditional forms of batteries are bulky and negate the advantages of this new class of devices. Herein, I investigate various printing techniques and architectures that enable compliant batteries and study the performance of such batteries under mechanical deformations. Firstly, this dissertation investigates electrochemical-mechanical performance of a dispenser printed micro-battery using a microfluidic cell. Nanoparticulate silver ink was printed and cured to form silver electrodes, which was charged in-situ to form a silver-zinc battery. The electrochemical performance of the silver-zinc micro-battery was similar to macro-sized batteries. The shear stress generated by flow of electrolyte over the electrode was used to emulate the shear stress generated during flexing and was used as a tool to study the shear strength of the silver electrode at different state of charge. The dissertation then investigates supported architecture as a reinforcement to maintain the performance of the battery under strain. We demonstrate a highly flexible Zn-MnO2 alkalinebattery by embedding the electrochemically active particles in a mesh support. The mesh support absorbs the stresses generated during flexing. A Similar principle was used to make a stretchable battery. The backbone of the stretchable electrode was a stretchable fabric with silver-coated fibers weaved through a rubber network, which served as the current collector. The fabric was coated with Zn and MnO2 to form a stretchable electrode. Due to the weave architecture the electrode could stretch by 100% without any loss is contact between

  8. Size and ligand effects on the electrochemical and spectroelectrochemical responses of CdSe nanocrystals.

    Science.gov (United States)

    Querner, Claudia; Reiss, Peter; Sadki, Said; Zagorska, Malgorzata; Pron, Adam

    2005-09-07

    The electrochemical properties of CdSe quantum dots with electrochemically inactive surface ligands (TOPO) have been investigated in comparison with the analogous nanocrystals containing electrochemically active oligoaniline ligands. The TOPO-capped nanocrystals have been studied in a wide size range (from 3 to 6.5 nm) with the goal to amplify the influence of the quantum confinement effect on the electrochemical response. The determined HOMO and LUMO levels have been found in good agreement with the ones obtained from photoluminescence studies and those predicted theoretically. Ligand exchange with aniline tetramer significantly influences the voltammetric peaks associated with the HOMO oxidation and the LUMO reduction of the quantum dots, which are shifted to higher and lower potentials, respectively. These shifts are interpreted in terms of the positive ligand charging which precedes the oxidation of the nanocrystals and the insulating nature of the ligand in the case of the nanocrystal reduction. The ligand-nanocrystal interactions have also been studied by UV-Vis-NIR and Raman spectroelectrochemistry in comparison with a specially prepared model compound which, apart from the anchoring function is identical to the grafted oligoaniline ligand. Both spectroelectrochemical techniques clearly indicate the same nature of the oxidation/reduction pathway for both the model compound and the grafted ligand. The influence of the grafting is manifested by a shift in the onset of the ligand oxidation as compared to the case of the "free" model compound. Since both components (ligands and nanocrystals) mutually influence their electrochemical and spectroelectrochemical properties, the newly developed system can be considered as a true molecular hybrid. Such hybrids are of interest because the potential zone of the ligand electroactivity is well separated from that of the nanocrystals and, as a result, the organic part can be electrochemically switched between the

  9. Electrochemical synthesis and characterization of chloride doped ...

    Indian Academy of Sciences (India)

    Unknown

    (HCl) by potentiodynamic method in an electrochemical cell and studied by cyclic voltammetry and FTIR techniques. The FTIR spectra confirmed Cl– ion doping in the ... were not hygroscopic whereas chloride doped polyaniline films were found to be highly hygroscopic. Keywords. Conducting polymer; electrochemical ...

  10. Hydrogel membrane electrolyte for electrochemical capacitors

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 121; Issue 5. Hydrogel membrane electrolyte for electrochemical capacitors ... In the present study, the preparation and characterization of poly(vinyl alcohol)-based hydrogel membranes (PHMEs) as electrolytes for electrochemical capacitors have been reported.

  11. Method for making an electrochemical cell

    Science.gov (United States)

    Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.; Pal, Uday B.

    1996-01-01

    An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is provided.

  12. Electrochemical synthesis of alkyl nitroaromatic compounds.

    Science.gov (United States)

    Gallardo, Iluminada; Guirado, Gonzalo; Marquet, Jordi

    2003-01-24

    Alkyl nitroaromatic compounds were readily prepared via nucleophilic aromatic substitution for hydrogen or a heteroatom by electrochemical oxidation of the sigma-complex. Butyllithium and butylmagnesium chloride were used as nucleophiles, and several nitrocompounds were tested to explore the possibilities of the NASH and NASX reactions promoted electrochemically.

  13. Three dimensional electrochemical system for neurobiological studies

    DEFF Research Database (Denmark)

    Vazquez, Patricia; Dimaki, Maria; Svendsen, Winnie Edith

    2009-01-01

    In this work we report a novel three dimensional electrode array for electrochemical measurements in neuronal studies. The main advantage of working with these out-of-plane structures is the enhanced sensitivity of the system in terms of measuring electrochemical changes in the environment...

  14. ELECTROCHEMICAL STUDIES OF N'-FERROCENYLMETHYL-N ...

    African Journals Online (AJOL)

    2011-12-31

    Dec 31, 2011 ... All the freshly prepared solutions were degassed under argon gas flow before experiments. 3.2. Electrochemical studies. Electrochemical characterization was carried out on a potentiostat type voltalab 40 of radiometer, with a three-stand electrode cell. Cyclic voltammetric experiments were performed in ...

  15. Harm reduction

    OpenAIRE

    Normand, Jacques; Li, Jih-Heng; Thomson, Nicholas; Jarlais, Don Des

    2013-01-01

    The “Harm Reduction” session was chaired by Dr. Jacques Normand, Director of the AIDS Research Program of the U.S. National Institute on Drug Abuse. The three presenters (and their presentation topics) were: Dr. Don Des Jarlais (High Coverage Needle/Syringe Programs for People Who Inject Drugs in Low and Middle Income Countries: A Systematic Review), Dr. Nicholas Thomson (Harm Reduction History, Response, and Current Trends in Asia), and Dr. Jih-Heng Li (Harm Reduction Strategies in Taiwan).

  16. Direct synthesis of lithium-intercalated graphene for electrochemical energy storage application.

    Science.gov (United States)

    Kumar, Ashavani; Reddy, Arava Leela Mohana; Mukherjee, Arnab; Dubey, Madan; Zhan, Xiaobo; Singh, Neelam; Ci, Lijie; Billups, W Edward; Nagurny, John; Mital, Gandhi; Ajayan, Pulickel M

    2011-06-28

    A novel approach for bulk synthesis of lithium-intercalated graphene sheets through the reduction of exfoliated graphene oxide in liquid ammonia and lithium metal is reported. It is demonstrated here that as-synthesized lithiated graphite oxide sheets (Li-RGO) can be directly used as an electrode material in lithium batteries. The electrochemical studies on Li-RGO electrodes show a significant enhancement in the specific capacity of the lithium battery over commercially available graphite electrodes. Partial intercalation of lithium ions in between graphene layers makes this material a good candidate for electrochemical energy storage applications.

  17. Solid oxide electrochemical reactor science.

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, Neal P. (Colorado School of Mines, Golden, CO); Stechel, Ellen Beth; Moyer, Connor J. (Colorado School of Mines, Golden, CO); Ambrosini, Andrea; Key, Robert J. (Colorado School of Mines, Golden, CO)

    2010-09-01

    Solid-oxide electrochemical cells are an exciting new technology. Development of solid-oxide cells (SOCs) has advanced considerable in recent years and continues to progress rapidly. This thesis studies several aspects of SOCs and contributes useful information to their continued development. This LDRD involved a collaboration between Sandia and the Colorado School of Mines (CSM) ins solid-oxide electrochemical reactors targeted at solid oxide electrolyzer cells (SOEC), which are the reverse of solid-oxide fuel cells (SOFC). SOECs complement Sandia's efforts in thermochemical production of alternative fuels. An SOEC technology would co-electrolyze carbon dioxide (CO{sub 2}) with steam at temperatures around 800 C to form synthesis gas (H{sub 2} and CO), which forms the building blocks for a petrochemical substitutes that can be used to power vehicles or in distributed energy platforms. The effort described here concentrates on research concerning catalytic chemistry, charge-transfer chemistry, and optimal cell-architecture. technical scope included computational modeling, materials development, and experimental evaluation. The project engaged the Colorado Fuel Cell Center at CSM through the support of a graduate student (Connor Moyer) at CSM and his advisors (Profs. Robert Kee and Neal Sullivan) in collaboration with Sandia.

  18. Buffered Electrochemical Polishing of Niobium

    Energy Technology Data Exchange (ETDEWEB)

    Ciovati, Gianluigi [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Tian, Hui [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); College of William and Mary, Williamsburg, VA (United States); Corcoran, Sean [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

    2011-03-01

    The standard preparation of superconducting radio-frequency (SRF) cavities made of pure niobium include the removal of a 'damaged' surface layer, by buffered chemical polishing (BCP) or electropolishing (EP), after the cavities are formed. The performance of the cavities is characterized by a sharp degradation of the quality factor when the surface magnetic field exceeds about 90 mT, a phenomenon referred to as 'Q-drop.' In cavities made of polycrystalline fine grain (ASTM 5) niobium, the Q-drop can be significantly reduced by a low-temperature (? 120 °C) 'in-situ' baking of the cavity if the chemical treatment was EP rather than BCP. As part of the effort to understand this phenomenon, we investigated the effect of introducing a polarization potential during buffered chemical polishing, creating a process which is between the standard BCP and EP. While preliminary results on the application of this process to Nb cavities have been previously reported, in this contribution we focus on the characterization of this novel electrochemical process by measuring polarization curves, etching rates, surface finish, electrochemical impedance and the effects of temperature and electrolyte composition. In particular, it is shown that the anodic potential of Nb during BCP reduces the etching rate and improves the surface finish.

  19. Bussing Structure In An Electrochemical Cell

    Science.gov (United States)

    Romero, Antonio L.

    2001-06-12

    A bussing structure for bussing current within an electrochemical cell. The bussing structure includes a first plate and a second plate, each having a central aperture therein. Current collection tabs, extending from an electrode stack in the electrochemical cell, extend through the central aperture in the first plate, and are then sandwiched between the first plate and second plate. The second plate is then connected to a terminal on the outside of the case of the electrochemical cell. Each of the first and second plates includes a second aperture which is positioned beneath a safety vent in the case of the electrochemical cell to promote turbulent flow of gasses through the vent upon its opening. The second plate also includes protrusions for spacing the bussing structure from the case, as well as plateaus for connecting the bussing structure to the terminal on the case of the electrochemical cell.

  20. 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.

  1. Carbon catalysts for electrochemical hydrogen peroxide production in acidic media

    DEFF Research Database (Denmark)

    Čolić, Viktor; Yang, Sungeun; Révay, Zsolt

    2018-01-01

    Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run the reac......Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run...... the reaction in an acidic electrolyte with high performance is particularly important, as it would allow the use of polymer solid electrolytes and the production of pH-neutral hydrogen peroxide. Carbon catalysts, which are cheap, abundant, durable and can be highly selective show promise as potential catalysts...... to determine the cause of these differences, we employ prompt gamma ray/neutron activation analysis and XPS measurements to assess the contribution of heteroatoms and defects, as well as low temperature N2-adsorption and transmission electron microscopy to elucidate the particle size, shape, BET surface area...

  2. Deep reduced PEDOT films support electrochemical applications: Biomimetic color front.

    Directory of Open Access Journals (Sweden)

    Toribio Fernandez OTERO

    2015-02-01

    Full Text Available Most of the literature accepts, despite many controversial results, that during oxidation/reduction films of conducting polymers move from electronic conductors to insulators. Thus, engineers and device’s designers are forced to use metallic supports to reoxidize the material for reversible device work. Electrochromic front experiments appear as main visual support of the claimed insulating nature of reduced conducting polymers. Here we present a different design of the biomimetic electrochromic front that corroborates the electronic and ionic conducting nature of deep reduced films. The direct contact PEDOT metal/electrolyte and film/electrolyte was prevented from electrolyte contact until 1cm far from the metal contact with protecting Parafilm®. The deep reduced PEDOT film supports the flow of high currents promoting reaction induced electrochromic color changes beginning 1 cm far from the metal-polymer electrical contact and advancing, through the reduced film, towards the metal contact. Reverse color changes during oxidation/reduction always are initiated at the film/electrolyte contact advancing, under the protecting film, towards the film/metal contact. Both reduced and oxidized states of the film demonstrate electronic and ionic conductivities high enough to be used for electronic applications or, as self-supported electrodes, for electrochemical devices. The electrochemically stimulated conformational relaxation (ESCR model explains those results.

  3. Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

    Science.gov (United States)

    Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

    2018-01-10

    Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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.

  5. Electrochemical sensor having suspended element counter electrode and deflection method for current sensing

    Science.gov (United States)

    Thundat, Thomas G.; Brown, Gilbert M.

    2010-05-18

    An electrochemical suspended element-based sensor system includes a solution cell for holding an electrolyte comprising solution including at least one electrochemically reducible or oxidizable species. A working electrode (WE), reference electrode (RE) and a counter electrode (CE) are disposed in the solution. The CE includes an asymmetric suspended element, wherein one side of the suspended element includes a metal or a highly doped semiconductor surface. The suspended element bends when current associated with reduction or oxidation of the electrochemically reducible or oxidizable species at the WE passes through the suspended element. At least one measurement system measures the bending of the suspended element or a parameter which is a function of the bending.

  6. Electrochemical Catalysis of Inorganic Complex K4[Fe(CN)6] by Shewanellaoneidensis MR-1

    DEFF Research Database (Denmark)

    Zheng, Zhiyong; Wu, Ranran; Xiao, Yong

    a pair of redox peaks on voltammetry on bare glassy carbon electrode (GCE), symmetric with ideal peak-peak separation of about 60 mV, indicating ofa reversible one-electron transfer process(blue curve, Figure 1). Surprisingly, the presence of S. oneidensis MR-1 on GCE results an asymmetric redox peak......The interaction between metal and bacteria is a universal and important biogeochemical processin environment. As a dissimilatory metal reduction bacterium, the electrochemically activebacteriium Shewanella oneidensis MR-1 can transfer intracellular electrons to minerals. This ability is attributed...... to the redox proteins localized on the outer-membrane, for example, the MtrC, MtrB, MtrA and CymA2. Here we investigate its electrochemical properties towards redoxinorganic redox compounds. It shows strong electrocatalysis toward electrochemical oxidation of K4[Fe(CN)6]. As a redox molecule, K4[Fe(CN)6] gives...

  7. Effect of Electrochemical Treatment on Electrical Conductivity of Conical Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    S. M. Khantimerov

    2016-01-01

    Full Text Available Interaction of conical carbon nanotubes (CNTs with hydrogen during electrochemical treatment and its effect on their electronic properties was studied. The temperature dependencies of electroconductivity of initial and electrochemically hydrogenated conical CNTs were investigated by using four-probe van der Pauw method. The studies revealed that the electrochemical hydrogen absorption leaded to a significant reduction in the electroconductivity of conical carbon nanotubes. We assume that these changes can be associated with a decrease in the concentration of charge carriers as a result of hydrogen localization on the carbon π-orbitals, the transition from sp2 to sp3 hybridization of conical CNTs band structure, and, therefore, a metal-semiconductor-insulator transition.

  8. Eco-Friendly Dyeing of Cotton with Indigo Dye By Electrochemical Method

    Science.gov (United States)

    Prabu, H. Gurumallesh; Sarala, K.; Babu, S. Ananda; Savitha, K. U.

    2011-07-01

    Eco-friendly dyeing of cotton was performed in two step process; (i) enzymatic pre-treatment of grey cotton fabric and (ii) Electrochemical dyeing of the pre-treated cotton fabric with indigo. The enzymatic pre-treatment was done in three methods; (i) amylase treatment only, (ii) amylase and hydrogen peroxide treatment and (iii) single bath method. The dyeing was carried out with the pre-treated cotton fabric. The reduction of indigo dye by electrochemical method was initiated by applying potential. Then the dyeing was carried out different concentrations of dye, glucose and NaOH. Conventional method of dyeing was also carried out and compared with the electrochemical method. Dyeability was measured by computer colour matching (CCM) GretagMacbeth colour eye 2180UV instrument.

  9. 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

  10. Electrochemical impedance spectroscopy of oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Mula, Guido, E-mail: guido.mula@unica.it [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Tiddia, Maria V. [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Ruffilli, Roberta [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Falqui, Andrea [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Palmas, Simonetta; Mascia, Michele [Dipartimento di Ingegneria Meccanica Chimica e dei Materiali, Università degli Studi di Cagliari, Piazza d' Armi, 09126 Cagliari (Italy)

    2014-04-01

    We present a study of the electrochemical oxidation process of porous silicon. We analyze the effect of the layer thickness (1.25–22 μm) and of the applied current density (1.1–11.1 mA/cm{sup 2}, values calculated with reference to the external samples surface) on the oxidation process by comparing the galvanostatic electrochemical impedance spectroscopy (EIS) measurements and the optical specular reflectivity of the samples. The results of EIS were interpreted using an equivalent circuit to separate the contribution of different sample parts. A different behavior of the electrochemical oxidation process has been found for thin and thick samples: whereas for thin samples the oxidation process is univocally related to current density and thickness, for thicker samples this is no more true. Measurements by Energy Dispersive Spectroscopy using a Scanning Electron Microscopy confirmed that the inhomogeneity of the electrochemical oxidation process is increased by higher thicknesses and higher currents. A possible explanation is proposed to justify the different behavior of thin and thick samples during the electrochemical process. - Highlights: • A multidisciplinary approach on porous Si electrochemical oxidation is proposed. • Electrochemical, optical, and structural characterizations are used. • Layer thickness and oxidation current effects are shown. • An explanation of the observed behavior is proposed.

  11. Nanoscale Electrochemical Sensing and Processing in Microreactors.

    Science.gov (United States)

    Odijk, Mathieu; van den Berg, Albert

    2018-03-08

    In this review, we summarize recent advances in nanoscale electrochemistry, including the use of nanoparticles, carbon nanomaterials, and nanowires. Exciting developments are reported for nanoscale redox cycling devices, which can chemically amplify signal readout. We also discuss promising high-frequency techniques such as nanocapacitive CMOS sensor arrays or heterodyning. In addition, we review electrochemical microreactors for use in (drug) synthesis, biocatalysis, water treatment, or to electrochemically degrade urea for use in a portable artificial kidney. Electrochemical microreactors are also used in combination with mass spectrometry, e.g., to study the mimicry of drug metabolism or to allow electrochemical protein digestion. The review concludes with an outlook on future perspectives in both nanoscale electrochemical sensing and electrochemical microreactors. For sensors, we see a future in wearables and the Internet of things. In microreactors, a future goal is to monitor the electrochemical conversions more precisely or ultimately in situ by combining other spectroscopic techniques. Expected final online publication date for the Annual Review of Analytical Chemistry Volume 11 is June 12, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  12. Electrochemical & Thermochemical Behavior of Cerium(IV) Oxide delta

    Science.gov (United States)

    Chueh, William C.

    The mixed-valent nature of nonstoichiometric ceria (CeO2-delta ) gives rise to a wide range of intriguing properties, such as mixed ionic and electronic conduction and oxygen storage. Surface and transport behavior in rare-earth (samaria) doped and undoped ceria were investigated, with particular emphasis on applications in electrochemical and thermochemical energy conversion processes such as fuel cells and solar fuel production. The electrochemical responses of bulk-processed ceria with porous Pt and Au electrodes were analyzed using 1-D and 2-D transport models to decouple surface reactions, near-surface transport and bulk transport. Combined experimental and numerical results indicate that hydrogen electro-oxidation and hydrolysis near open-circuit conditions occur preferentially over the ceria | gas interface rather than over the ceria | gas | metal interface, with the rate-limiting step likely to be either surface reaction or transport through the surface oxygen vacancy depletion layer. In addition, epitaxial thin films of ceria were grown on zirconia substrates using pulsed-laser deposition to examine electrocatalysis over well-defined microstructures. Physical models were derived to analyze the electrochemical impedance response. By varying the film thickness, interfacial and chemical capacitance were decoupled, with the latter shown to be proportional to the small polaron densities. The geometry of microfabricated metal current collectors (metal = Pt, Ni) was also systematically varied to investigate the relative activity of the ceria | gas and the ceria | metal | gas interfaces. The data suggests that the electrochemical activity of the metal-ceria composite is only weakly dependent on the metal due to the relatively high activity of the ceria | gas interface. In addition to electrochemical experiments, thermochemical reduction-oxidation studies were performed on ceria. It was shown that thermally-reduced ceria, upon exposure to H 2O and/or CO2, can be

  13. Numerical simulation of electrochemical desalination

    Science.gov (United States)

    Hlushkou, D.; Knust, K. N.; Crooks, R. M.; Tallarek, U.

    2016-05-01

    We present an effective numerical approach to simulate electrochemically mediated desalination of seawater. This new membraneless, energy efficient desalination method relies on the oxidation of chloride ions, which generates an ion depletion zone and local electric field gradient near the junction of a microchannel branch to redirect sea salt into the brine stream, consequently producing desalted water. The proposed numerical model is based on resolution of the 3D coupled Navier-Stokes, Nernst-Planck, and Poisson equations at non-uniform spatial grids. The model is implemented as a parallel code and can be employed to simulate mass-charge transport coupled with surface or volume reactions in 3D systems showing an arbitrarily complex geometrical configuration.

  14. Composite Electrodes for Electrochemical Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yang QuanMin

    2010-01-01

    Full Text Available Abstract Manganese dioxide nanofibers with length ranged from 0.1 to 1 μm and a diameter of about 4–6 nm were prepared by a chemical precipitation method. Composite electrodes for electrochemical supercapacitors were fabricated by impregnation of the manganese dioxide nanofibers and multiwalled carbon nanotubes (MWCNT into porous Ni plaque current collectors. Obtained composite electrodes, containing 85% of manganese dioxide and 15 mass% of MWCNT, as a conductive additive, with total mass loading of 7–15 mg cm−2, showed a capacitive behavior in 0.5-M Na2SO4 solutions. The decrease in stirring time during precipitation of the nanofibers resulted in reduced agglomeration and higher specific capacitance (SC. The highest SC of 185 F g−1 was obtained at a scan rate of 2 mV s−1 for mass loading of 7 mg cm−2. The SC decreased with increasing scan rate and increasing electrode mass.

  15. Scanning Electrochemical Microscopy in Neuroscience

    Science.gov (United States)

    Schulte, Albert; Nebel, Michaela; Schuhmann, Wolfgang

    2010-07-01

    This article reviews recent work involving the application of scanning electrochemical microscopy (SECM) to the study of individual cultured living cells, with an emphasis on topographical and functional imaging of neuronal and secretory cells of the nervous and endocrine system. The basic principles of biological SECM and associated negative amperometric-feedback and generator/collector-mode SECM imaging are discussed, and successful use of the methodology for screening soft and fragile membranous objects is outlined. The drawbacks of the constant-height mode of probe movement and the benefits of the constant-distance mode of SECM operation are described. Finally, representative examples of constant-height and constant-distance mode SECM on a variety of live cells are highlighted to demonstrate the current status of single-cell SECM in general and of SECM in neuroscience in particular.

  16. Electrochemical studies of corrosion inhibitors

    Science.gov (United States)

    Danford, M. D.

    1990-01-01

    The effect of single salts, as well as multicomponent mixtures, on corrosion inhibition was studied for type 1010 steel; for 5052, 1100, and 2219-T87 aluminum alloys; and for copper. Molybdate-containing inhibitors exhibit an immediate, positive effect for steel corrosion, but an incubation period may be required for aluminum before the effect of a given inhibitor can be determined. The absence of oxygen was found to provide a positive effect (smaller corrosion rate) for steel and copper, but a negative effect for aluminum. This is attributed to the two possible mechanisms by which aluminum can oxidize. Corrosion inhibition is generally similar for oxygen-rich and oxygen-free environments. The results show that the electrochemical method is an effective means of screening inhibitors for the corrosion of single metals, with caution to be exercised in the case of aluminum.

  17. All-Polymer Electrochemical Sensors

    DEFF Research Database (Denmark)

    Kafka, Jan Robert

    This thesis presents fabrication strategies to produce different types of all-polymer electrochemical sensors based on electrodes made of the highly conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT). Three different systems are presented, fabricated either by using microdrilling or by hot......-controlled microdrilling was applied to drill through an insulating polymer, covering a conductive layer of PEDOT. The sudden drop in electrical resistance between the metal drill and the PEDOT layer upon physical contact was employed as stop criterion for the drilling process. Arrays of 3x 3 microelectrodes of diameter...... electrode configurations showed that the conducting polymer electrodes approach the steady state currents predicted from modeling, but at a much slower rate than expected. This wasshown to be caused by the use of electro active PEDOT electrodes. Subtraction of the latter contribution gave an approach...

  18. Mediated electrochemical hazardous waste destruction

    International Nuclear Information System (INIS)

    Hickman, R.G.; Farmer, J.C.; Wang, F.T.

    1991-08-01

    There are few permitted processes for mixed waste (radioactive plus chemically hazardous) treatment. We are developing electrochemical processes that convert the toxic organic components of mixed waste to water, carbon dioxide, an innocuous anions such as chloride. Aggressive oxidizer ions such as Ag 2+ or Ce +4 are produced at an anode. These can attack the organic molecules directly. They can also attack water which yields hydroxyl free radicals that in turn attack the organic molecules. The condensed (i.e., solid and/or liquid) effluent streams contain the inorganic radionuclide forms. These may be treated with existing technology and prepared for final disposal. Kinetics and the extent of destruction of some toxic organics have been measured. Depending on how the process is operated, coulombic efficiency can be nearly 100%. In addition, hazardous organic materials are becoming very expensive to dispose of and when they are combined with transuranic radioactive elements no processes are presently permitted. Mediated electrochemical oxidation is an ambient-temperature aqueous-phase process that can be used to oxidize organic components of mixed wastes. Problems associated with incineration, such as high-temperature volatilization of radionuclides, are avoided. Historically, Ag (2) has been used as a mediator in this process. Fe(6) and Co(3) are attractive alternatives to Ag(2) since they form soluble chlorides during the destruction of chlorinated solvents. Furthermore, silver itself is a toxic heavy metal. Quantitative data has been obtained for the complete oxidation of ethylene glycol by Fe(6) and Co(3). Though ethylene glycol is a nonhalogenated organic, this data has enabled us to make direct comparisons of activities of Fe(6) and Co(3) with Ag(2). Very good quantitative data for the oxidation of ethylene glycol by Ag(2) had already been collected. 4 refs., 6 figs

  19. Electrochemical Measurement of Atmospheric Corrosion

    Science.gov (United States)

    DeArmond, Anna H.; Davis, Dennis D.; Beeson, Harold D.

    1999-01-01

    Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

  20. Performance and Electrochemical Characterisation of Thin Electrolyte SOFCs

    DEFF Research Database (Denmark)

    Ramos, Tania; Hjelm, Johan; Wandel, Marie Emilie

    2008-01-01

    The performance and electrochemical behavior of two anode-supported thin electrolyte cells, with different manufacturing parameters, is determined by polarization measurements and electrochemical impedance spectroscopy (EIS). In addition to characterization, a previously suggested equivalent......-depth electrochemical characterization can provide valuable guidelines for production/performance optimization. © 2008 ECS - The Electrochemical Society...

  1. Building micro and nanosystems with electrochemical discharges

    Energy Technology Data Exchange (ETDEWEB)

    Wuethrich, Rolf, E-mail: wuthrich@encs.concordia.c [Department of Mechanical and Industrial Engineering, Concordia University, 1455 de Maisonneuve Blvd. West, Montreal, QC (Canada); Allagui, Anis [Department of Mechanical and Industrial Engineering, Concordia University, 1455 de Maisonneuve Blvd. West, Montreal, QC (Canada)

    2010-11-30

    Since the discovery of the electrochemical discharge phenomenon by Fizeau and Foucault, several contributions have expanded the wide range of applications associated with this high current density electrochemical process. The complexity of the phenomenon, from the macroscopic to the microscopic scales, led since then to experimental and theoretical studies from different research fields. This contribution reviews the chemical and electrochemical perspectives where a mechanistic model based on results from radiation chemistry of aqueous solutions is proposed. In addition applications to micro-machining and fabrication of nanoparticles are discussed.

  2. Electrochemical cell structure including an ionomeric barrier

    Science.gov (United States)

    Lambert, Timothy N.; Hibbs, Michael

    2017-06-20

    An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

  3. Building micro and nanosystems with electrochemical discharges

    International Nuclear Information System (INIS)

    Wuethrich, Rolf; Allagui, Anis

    2010-01-01

    Since the discovery of the electrochemical discharge phenomenon by Fizeau and Foucault, several contributions have expanded the wide range of applications associated with this high current density electrochemical process. The complexity of the phenomenon, from the macroscopic to the microscopic scales, led since then to experimental and theoretical studies from different research fields. This contribution reviews the chemical and electrochemical perspectives where a mechanistic model based on results from radiation chemistry of aqueous solutions is proposed. In addition applications to micro-machining and fabrication of nanoparticles are discussed.

  4. 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......, to the electrochemical characterization of high temperature and pressure alkaline electrolysis cells and the use of pseudo-reference electrodes for the separation of each electrode contribution. A future perspective of various electrochemical processes and devices that can be developed with the use of the established...

  5. Electrochemical ammonia production on molybdenum nitride nanoclusters

    DEFF Research Database (Denmark)

    Howalt, Jakob Geelmuyden; Vegge, Tejs

    2013-01-01

    Theoretical investigations of electrochemical production of ammonia at ambient temperature and pressure on nitrogen covered molybdenum nanoparticles are presented. Density functional theory calculations are used in combination with the computational hydrogen electrode approach to calculate the free...... energy profile for electrochemical protonation of N2 and N adatoms on cuboctahedral Mo13 nanoparticles. Pathways for electrochemical ammonia production via direct protonation of N adatoms and N2 admolecules with an onset potential as low as -0.5 V and generally lower than -0.8 V on both a nitrogen...

  6. Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

    International Nuclear Information System (INIS)

    Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

    2001-01-01

    The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

  7. 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.

  8. Influence of ionic liquid on pseudocapacitance performance of electrochemically synthesized conductive polymer: Electrochemical and theoretical investigation.

    Science.gov (United States)

    Ehsani, A; Kowsari, E; Dashti Najafi, M; Safari, R; Mohammad Shiri, H

    2017-08-15

    This study demonstrates a method for improving supercapacitive performance of electrochemically synthesized conductive polymer. In this regards, 1-Butyl-3-methyl imidazolium hexafluorophosphate (BI) as a new high efficient ionic liquid was synthesized using chemical approach and then fabricated POAP/BI films by electro-polymerization of POAP in the presence of BI to serve as the active electrode for electrochemical supercapacitor. Theoretical study (AIM) and electrochemical analysis have been used for characterization of ionic liquid and POAP/BI composite film. Different electrochemical methods including galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. This work introduces new most efficient materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area and stability in an aqueous electrolyte. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Preparation of catalysts PtSb{sub 2}O{sub 5}.SnO{sub 2} supported on carbon and ATO using the alcohol reduction method for electrochemical oxidation of ethanol; Preparacao de eletrocatalisadores PtSb{sub 2}O{sub 5}.SnO{sub 2} suportados em carbono e ATO pelo metodo da reducao por alcool para oxidacao eletroquimica do etanol

    Energy Technology Data Exchange (ETDEWEB)

    Ayoub, Jamil Mahmoud Said

    2013-06-01

    Pt Sn/C-ATO electrocatalysts with different Pt:Sn atomic ratios (90:10, 70:30 and 50:50) were prepared in a single step by an alcohol-reduction process using H{sub 2}PtCl{sub 6}.6H{sub 2}O and SnCl{sub 2}.2H{sub 2}O as metal sources and ethylene glycol as solvent and reducing agent and a physical mixture of carbon Vulcan XC72 (85 wt%) and Sb{sub 2}O{sub 5}.SnO{sub 2} (15 wt%) as support (C-ATO). The obtained materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The catalytic activity for ethanol electro-oxidation in acid medium was investigated by cyclic voltammetry and chronoamperometry and in single direct ethanol fuel cell (DEFC). XRD analyses showed that Pt(FCC), SnO{sub 2}, carbon and ATO phases coexist in the obtained materials. The electrochemical studies showed that PtSn/C-ATO electrocatalysts were more active for ethanol electro-oxidation than PtSn/C electrocatalyst. The experiments at 100 deg C on a single DEFC showed that the power density of the cell using Pt Sn/C-ATO (90:10) was nearly 100% higher than the one obtained using Pt Sn/C (50:50). FTIR measurements showed that the addition of ATO to Pt Sn/C favors the formation of acetic acid as a product while for PtSn/C acetaldehyde was the principal product formed. (author)

  10. 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

  11. 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.

  12. Stimulation of reductive dechlorination of tetrachloroethane in anaerobic aquifer microcosms by addition of short-chain organic acids or alcohols

    International Nuclear Information System (INIS)

    Gibson, S.A.; Sewell, G.W.

    1992-01-01

    Although the ecological and public health risk associated with tetrachloroethene (PCE) contamination may be the most severe when spills affect groundwater, little is known about the environmental conditions necessary to initiate and sustain dehalogenation activity in contaminated aquifers. This study was done with core material collected from a site impacted by both aviation gasoline and chloroethenes at a Coast Guard Air Station at Traverse City, Michigan. The effect of the addition of common fermentation products on the dehalogenation of tetrachloroethene was studied in methanogenic slurries made with aquifer solids. Lactate, propionate, crotonate, butyrate, and ethanol stimulated dehalogenation activity, while acetate, methanol, and isopropanol did not

  13. 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)

  14. System and method for networking electrochemical devices

    Science.gov (United States)

    Williams, Mark C.; Wimer, John G.; Archer, David H.

    1995-01-01

    An improved electrochemically active system and method including a plurality of electrochemical devices, such as fuel cells and fluid separation devices, in which the anode and cathode process-fluid flow chambers are connected in fluid-flow arrangements so that the operating parameters of each of said plurality of electrochemical devices which are dependent upon process-fluid parameters may be individually controlled to provide improved operating efficiency. The improvements in operation include improved power efficiency and improved fuel utilization in fuel cell power generating systems and reduced power consumption in fluid separation devices and the like through interstage process fluid parameter control for series networked electrochemical devices. The improved networking method includes recycling of various process flows to enhance the overall control scheme.

  15. Alkaline Electrochemical Capacitor and Electrode Fabrication

    National Research Council Canada - National Science Library

    Finello, D

    1999-01-01

    .... With energy density in excess of 300 mJ/cc and the potential to exceed a power density of 100 W/cc, the alkaline electrochemical capacitor represents a significant advancement in technology for high power energy storage.

  16. ELECTROCHEMICAL STUDIES OF N'-FERROCENYLMETHYL-N ...

    African Journals Online (AJOL)

    2011-12-31

    Phenylbenzohydrazide. FcX was studied in acetonitrile with tetrabutylammonium hexafluorophosphate as the supporting electrolyte and aqueous ethanol using the electrochemical technique. This study using cyclic (CV) and rotating ...

  17. Electrochemical behaviour of alkaline copper complexes

    Indian Academy of Sciences (India)

    cyanide- plating bath for copper has been developed using alkaline trisodium citrate and triethanolamine solutions5. The present investigation presents cyclic voltammetric studies on the electrochemical behaviour of alkaline copper complexes, ...

  18. Synthesis, characterization and electrochemical performance of ...

    Indian Academy of Sciences (India)

    Scanning electron microscopy andFourier transform infrared spectroscopy investigations were carried out, which reveal the morphology and function groupsof the synthesized samples. Furthermore, electrochemical impedance spectra measurements are performed. The obtainedresults indicated that the highest conductivity ...

  19. Electrochemical supercapacitor behaviour of functionalized candle ...

    Indian Academy of Sciences (India)

    diamond) and G (graphite) phase of carbon present in the candle soots. The electrochemical characterization was performed by cyclic voltammetry, galvanostatic charge/discharge test and impedance spectroscopy in 1MH2SO4 electrolyte.

  20. Electrochemical conversion of micropollutants in gray water

    NARCIS (Netherlands)

    Butkovskyi, A.; Jeremiasse, A.W.; Hernandez Leal, L.; Zande, van der T.; Rijnaarts, H.; Zeeman, G.

    2014-01-01

    Electrochemical conversion of micropollutants in real gray water effluent was studied for the first time. Six compounds that are frequently found in personal care and household products, namely methylparaben, propylparaben, bisphenol A, triclosan, galaxolide, and 4- methylbenzilidene camphor

  1. Bismuth-based electrochemical stripping analysis

    Science.gov (United States)

    Wang, Joseph

    2004-01-27

    Method and apparatus for trace metal detection and analysis using bismuth-coated electrodes and electrochemical stripping analysis. Both anodic stripping voltammetry and adsorptive stripping analysis may be employed.

  2. Electrochemical Energy Storage Technical Team Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    None

    2013-06-01

    This U.S. DRIVE electrochemical energy storage roadmap describes ongoing and planned efforts to develop electrochemical energy storage technologies for plug-in electric vehicles (PEVs). The Energy Storage activity comprises a number of research areas (including advanced materials research, cell level research, battery development, and enabling R&D which includes analysis, testing and other activities) for advanced energy storage technologies (batteries and ultra-capacitors).

  3. Low temperature thermally regenerative electrochemical system

    Science.gov (United States)

    Loutfy, Raouf O.; Brown, Alan P.; Yao, Neng-Ping

    1983-01-01

    A thermally regenerative electrochemical system including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the complexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

  4. Low-temperature thermally regenerative electrochemical system

    Science.gov (United States)

    Loutfy, R.O.; Brown, A.P.; Yao, N.P.

    1982-04-21

    A thermally regenerative electrochemical system is described including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the ocmplexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

  5. Nanomaterials for electrochemical sensing and biosensing

    CERN Document Server

    Pumera, Martin

    2014-01-01

    Part 1: Nanomaterial-Based ElectrodesCarbon Nanotube-Based Electrochemical Sensors and Biosensors, Martin Pumera, National Institute for Materials Science, JapanElectrochemistry on Single Carbon Nanotube, Pat Collier, Caltech, USATheory of Voltammetry at Nanoparticle-Modified Electrodes, Richard G. Compton, Oxford University, UKMetal Oxide Nanoparticle-Modified Electrodes, Frank Marken, University of Bath, UKSemiconductor Quantum Dots for Electrochemical Bioanalysis, Eugenii Katz, Clarkson University, USAN

  6. Bacterial diversity and reductive dehalogenase redundancy in a 1,2-dichloroethane-degrading bacterial consortium enriched from a contaminated aquifer

    Directory of Open Access Journals (Sweden)

    Wittebolle Lieven

    2010-02-01

    Full Text Available Abstract Background Bacteria possess a reservoir of metabolic functionalities ready to be exploited for multiple purposes. The use of microorganisms to clean up xenobiotics from polluted ecosystems (e.g. soil and water represents an eco-sustainable and powerful alternative to traditional remediation processes. Recent developments in molecular-biology-based techniques have led to rapid and accurate strategies for monitoring and identification of bacteria and catabolic genes involved in the degradation of xenobiotics, key processes to follow up the activities in situ. Results We report the characterization of the response of an enriched bacterial community of a 1,2-dichloroethane (1,2-DCA contaminated aquifer to the spiking with 5 mM lactate as electron donor in microcosm studies. After 15 days of incubation, the microbial community structure was analyzed. The bacterial 16S rRNA gene clone library showed that the most represented phylogenetic group within the consortium was affiliated with the phylum Firmicutes. Among them, known degraders of chlorinated compounds were identified. A reductive dehalogenase genes clone library showed that the community held four phylogenetically-distinct catalytic enzymes, all conserving signature residues previously shown to be linked to 1,2-DCA dehalogenation. Conclusions The overall data indicate that the enriched bacterial consortium shares the metabolic functionality between different members of the microbial community and is characterized by a high functional redundancy. These are fundamental features for the maintenance of the community's functionality, especially under stress conditions and suggest the feasibility of a bioremediation treatment with a potential prompt dehalogenation and a process stability over time.

  7. High temperature and pressure electrochemical test station

    Science.gov (United States)

    Chatzichristodoulou, C.; Allebrod, F.; Mogensen, M.

    2013-05-01

    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, to the electrochemical characterization of high temperature and pressure alkaline electrolysis cells and the use of pseudo-reference electrodes for the separation of each electrode contribution. A future perspective of various electrochemical processes and devices that can be developed with the use of the established test station is provided.

  8. Electrochemical processing of nitrate waste solutions. Phase 2, Final report

    Energy Technology Data Exchange (ETDEWEB)

    Genders, D.; Weinberg, N.; Hartsough, D. [Electrosynthesis Co., Inc., Cheektowaga, NY (US)

    1992-10-07

    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{sup {minus}} 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.

  9. Isolation and characterization of Desulfitobacterium dehalogenans gen. nov., sp. nov., an anaerobic bacterium which reductively dechlorinates chlorophenolic compounds.

    Science.gov (United States)

    Utkin, I; Woese, C; Wiegel, J

    1994-10-01

    An organism that is able to reductively ortho-dechlorinate 2,4-dichlorophenol and 3-chloro-4-hydroxyphenylacetate (3-Cl-4-OHPA) was isolated from a methanogenic lake sediment. This organism, an anaerobic, motile, Gram-type-positive, rod-shaped bacterium, grew in the presence of 0.1% yeast extract when pyruvate, lactate, formate, or hydrogen was used as the electron donor for reductive dehalogenation of 3-Cl-4-OHPA. Sulfite, thiosulfate, and sulfur were reduced to sulfide, nitrate was reduced to nitrite, and fumarate was reduced to succinate. Dissimilatory reduction of sulfate could not be demonstrated, and no adenylylsulfate reductase was detected with an immunoassay. The organism fermented two pyruvate molecules to one lactate molecule, one acetate molecule, and one carbon dioxide molecule. The pH and temperature optima for both growth and dechlorination of 3-Cl-4-OHPA were 7.5 and 38 degrees C, respectively. The doubling time under these conditions was approximately 3.5 h. On the basis of the results of a 16S rRNA analysis and the inability of the organism to use sulfate as an electron acceptor, strain JW/IU-DC1 is described as the type strain of the new taxon Desulfitobacterium dehalogenans gen. nov., sp. nov.

  10. A combined UHV-STM-flow cell set-up for electrochemical/electrocatalytic studies of structurally well-defined UHV prepared model electrodes

    DEFF Research Database (Denmark)

    Schnaidt, J.; Beckord, S.; Engstfeld, Albert Kilian

    2017-01-01

    UHV conditions on the one hand and, after electrode transfer under clean conditions, electrochemical measurements under continuous, controlled electrolyte mass transport conditions on the other. Electrochemical measurements can be coupled with online product detection, either using an additional...... collector electrode or by differential electrochemical mass spectrometry (DEMS). The potential of the set-up will be illustrated in two electrocatalytic reactions on complex, but structurally well-defined bimetallic electrode surfaces, O-2 reduction on PtxAg1-x/Pt(111) monolayer surface alloys and bulk CO...

  11. Electrochemical Removal of NOx on Ceria-Based Catalyst-Electrodes

    Directory of Open Access Journals (Sweden)

    Xi Wang

    2017-02-01

    Full Text Available This study reports the electrochemical properties for NOx reduction of a ceria-based mixed ionic electronic conducting porous electrode promoted by Pt nanoparticles, as efficient catalyst for NO oxidation, and BaO, as sorbent to store NOx. This catalytic layer was deposited by screen-printing on a dense membrane of gadolinia-doped ceria, an O2− ionic conductor. The targeted Ba and Pt loadings were 150 and 5 μg/cm2, respectively. The NOx selective electrochemical reduction was performed between 400 °C and 500 °C with and without oxygen in the feed. Variations of the open-circuit voltage with time were found to be a good sensor of the NOx storage process on the ceria-based catalyst-electrode. However, no N2 production was observed in the presence of O2 phase in spite of nitrates formation.

  12. Photocatalytic and electrochemical combined treatment of textile wash water

    International Nuclear Information System (INIS)

    Neelavannan, M.G.; Revathi, M.; Ahmed Basha, C.

    2007-01-01

    Various chemical and physical processes for treatment of textile effluent are not destructive but they only transfer the contaminants from one form to another. The presence of high concentration of organic dye and total dissolved solids (TDS) in the effluent that are not removed by biological treatment must be eliminated by an alternative method to the conventional ones is the advanced oxidation process (AOP). A procion blue dye effluent was treated by photo and electrochemical oxidation process as well as by combining photocatalytic degradation using TiO 2 suspensions. Chemical oxygen demand (COD) and colour removal can be used to follow the degradation of the organic pollutant. The effects of pH, current density, flow rate of effluent that passes into the reactor and supporting electrolyte were studied. Comparative studies were carried out on photocatalytic and electrochemical process to degrade the procion blue. The maximum COD reduction and colour removal were 96 and 100%, respectively. Photodegradation efficiency of dye was high when photolysis was carried out in the presence of 40 mg/l of TiO 2

  13. Enhancing the electrochemical response of myoglobin with carbon nanotube electrodes.

    Science.gov (United States)

    Esplandiu, M J; Pacios, M; Cyganek, L; Bartroli, J; del Valle, M

    2009-09-02

    In this paper, the electrochemical behavior of different myoglobin-modified carbon electrodes is evaluated. In particular, the performance of voltammetric biosensors made of forest-like carbon nanotubes, carbon nanotube composites and graphite composites is compared by monitoring mainly the electrocatalytic reduction of H(2)O(2) by myoglobin and their corresponding electroanalytical characteristics. Graphite composites showed the worst electroanalytical performance, exhibiting a small linear range, a limit of detection (LOD) of 9 x 10(-5) M and low sensitivity. However, it was found that the electrochemical response was enhanced with the use of carbon nanotube-based electrodes with LOD up to 5 x 10(-8) M, higher sensitivities and wider linear range response. On the one hand, in the case of the CNT epoxy composite, the improvement in the response can be mainly attributed to its more porous surface which allows the immobilization of higher amounts of the electroactive protein. On the other hand, in the case of the forest-like CNT electrodes, the enhancement is due to an increase in the electron transfer kinetics. These findings encourage the use of myoglobin-modified carbon nanotube electrodes as potential (bio)sensors of H(2)O(2) or O(2) in biology, microbiology and environmental fields.

  14. An accelerated electrochemical MIC test for stainless alloys

    International Nuclear Information System (INIS)

    Gendron, T.S.; Cleland, R.D.

    1994-11-01

    Previous work in our laboratory and elsewhere has suggested that microbially influenced corrosion (MIC) of stainless steels and nickel-base alloys occurs in locally anaerobic regions that support the growth of sulfate-reducing bacteria (SRB). The cathodic reaction is provided by oxygen reduction at remote sites. Such a coupling between anode and cathode is difficult to reproduce in the laboratory, but can be simulated indirectly using a double electrochemical cell, as in previous work. A more realistic simulation using a single aerated electrochemical cell has now been developed, in which a second organism (P. aeruginosa) is used to provide an anoxic habitat for SRB growth and possible a source of organic carbon, within a layer of silt. A bare alloy electrode is used as the oxygen cathode. Tests of this kind using rigorous microbiological procedures have generated pitting corrosion of several alloys in low chloride media simulating freshwater heat exchanger conditions. This report discusses the adaption of these procedures to study corrosion of nuclear waste containers. (author). 20 refs., 2 tabs., 7 figs

  15. High performance electrochemical pseudocapacitors from ionic liquid assisted electrochemically synthesized p-type conductive polymer.

    Science.gov (United States)

    Ehsani, A; Mohammad Shiri, H; Kowsari, E; Safari, R; Torabian, J; Hajghani, S

    2017-03-15

    In this paper firstly, 1-methyl-3-methylimidazolium bromide (MB) as a new high efficient ionic liquid was synthesized using chemical approach and then fabricated POAP/MB films by electro-polymerization of POAP in the presence of MB to serve as the active electrode for electrochemical supercapacitor. Theoretical study (AIM) and electrochemical analysis have been used for characterization of ionic liquid and POAP/MB composite film. Different electrochemical methods including galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. This work introduces new most efficient materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area and stability in an aqueous electrolyte. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Evaluation of electrochemical oxidation techniques for degradation of dye effluents--a comparative approach.

    Science.gov (United States)

    Raghu, S; Lee, Chang Woo; Chellammal, S; Palanichamy, S; Basha, C Ahmed

    2009-11-15

    The high energy cost of an electrochemical method is the fatal drawback that hinders its large scale application in wastewater treatment. The traditional single-chamber electrochemical method used in the waste water treatment mainly focused on anodic oxidation, but hydrogen produced on the cathode and indirect electrochemical treatment involves application of an electrical current to the wastewater containing chloride to convert into chlorine/hypochlorite. The two-compartment electrolytic cell, separated by an anion exchange membrane, has been developed in this work. In the new reactor, indirect oxidation at anode, indirect oxidation by hydrogen peroxide and ultraviolet/hydrogen peroxide (UV/H(2)O(2)) at cathode can occur simultaneously. The electrochemically produced hydrogen peroxide at the cathode by reduction of oxygen is affected by passing atmospheric air. Therefore "dual electrochemical oxidation" in one electrochemical reactor was achieved successfully. Compared to a traditional one-cell reactor, this reactor reduces the energy cost approximately by 25-40%, and thus the present work becomes significant in wastewater treatment. Experiments were carried out at different current densities using Ti/RuO(2)/IrO(2) as anode and carbon felt gas diffusion electrode used as a cathode fed with oxygen containing gases to produce hydrogen peroxide. During the various stages of electrolysis, the parameters such as, effect of pH, chemical oxygen demand (COD), colour, energy consumption were monitored. UV-vis spectrometry, Fourier transform infrared spectroscopy (FTIR), high-performance liquid chromatography (HPLC) studies were carried out to assess efficiencies of dye degradation.

  17. Reduction of friction during wire drawing by electrode control

    Science.gov (United States)

    Su, Y.-Y.; Marek, M.

    1995-04-01

    In wire drawing, the wire is drawn through a series of dies sprayed with or immersed in an emulsion lubricant. The surface conditions of the wire play a vital part in the mechanism of lubrication, and the conditions can be affected by electrochemical parameters. The electrochemical behavior of copper in selected emulsions was studied, and laboratory friction as well as pilot plant tests were performed. Reduction of friction was detected at various potentials depending on the lubricant composition. Surface quality of the wire was improved by the electrode control.

  18. Written-in conductive patterns on robust graphene oxide biopaper by electrochemical microstamping.

    Science.gov (United States)

    Hu, Kesong; Tolentino, Lorenzo S; Kulkarni, Dhaval D; Ye, Chunhong; Kumar, Satish; Tsukruk, Vladimir V

    2013-12-16

    The silk road: By employing silk fibroin as a binder between graphene oxide films and aluminum foil for a facile, highly localized reduction process, conductive paper is reinvented. The flexible, robust biographene papers have high toughness and electrical conductivity. This electrochemical written-in approach is readily applicable for the fabrication of conductive patterned papers with complex circuitries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Radon reduction

    International Nuclear Information System (INIS)

    Hamilton, M.A.

    1990-01-01

    During a radon gas screening program, elevated levels of radon gas were detected in homes on Mackinac Island, Mich. Six homes on foundations with crawl spaces were selected for a research project aimed at reducing radon gas concentrations, which ranged from 12.9 to 82.3 pCi/l. Using isolation and ventilation techniques, and variations thereof, radon concentrations were reduced to less than 1 pCi/l. This paper reports that these reductions were achieved using 3.5 mil cross laminated or 10 mil high density polyethylene plastic as a barrier without sealing to the foundation or support piers, solid and/or perforated plastic pipe and mechanical fans. Wind turbines were found to be ineffective at reducing concentrations to acceptable levels. Homeowners themselves installed all materials

  20. 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.