Electron-transfer Mediation and Catalysis of Electropolymerized Polyanilinecoated Electrodes for the Redox Reaction of Dissolved Redox Species

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  • OHSAKA Takeo
    Department of Applied Chemistry for Resources, Tokyo University of Agriculture and Technology
  • CHIBA Kazuyuki
    Department of Applied Chemistry for Resources, Tokyo University of Agriculture and Technology
  • OYAMA Noboru
    Department of Applied Chemistry for Resources, Tokyo University of Agriculture and Technology

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Other Title
  • 溶存レドックス化学種の酸化還元反応に対する電解重合ポリアニリン膜被覆電極の電極触媒作用
  • ヨウゾン レドックス カガクシュ ノ サンカ カンゲン ハンノウ ニ タイスル

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Description

Electron-transfer mediation and catalysis of electroactive polyaniline(PA)-coated basal plane pyrolytic graphite(BPG) electrodes, which were prepared by electropolymerization of aniline in an acidic aqueous solution, for the oxidation or reduction of solution-phase redox species (i. e., Fe3+, [Fe(CN)6]4-, [Fe(CN)6]3- and [W(CN)8]4-) were examined by cyclic voltammetry, normal pulse voltammetry and hydrodynamic voltammetry using rotating disk electrodes.<BR>The electrode reaction of Fe3+/2+ couple at PA-coated BPG electrode was found to be much faster than that at uncoated BPG electrode, reflecting the fact that the standard rate constant of the electrode reaction of PA film on BPG electrode is about ten times larger than that of Fe3+/2+ couple at uncoated BPG electrode. From the dependence of the limiting current of hydrodynamic voltammograms for the reduction of Fe3+ ion at uncoated and PA-coated rotating disk BPG electrodes upon the rotation rate of electrode, the concentration of Fe3+ ion, and the thickness of PA film, it was found that Fe3+ ion could not penetrate into the PA film and thus the electron cross-exchange reaction between Fe3+ ion and the reduced form of PA film occurred substantially at the PA film/solution interface. In this case, the limiting current was controlled by the mass transport of Fes+ ion from the bulk of solution to the PA film/solution interface; it was not controlled both by the electron transfer reaction within the PA film and by the electron cross-exchange reaction between Fe3+ ion and the reduced form of PA film. As a result, almost same limiting current values were observed at uncoated and PA-coated BPG electrodes. The oxidation of [Fe(CN)6]4- and [W(CN)8]4-ions and the reduction of [Fe(CN)6]3- ion at PA-coated BPG electrodes occurred at the PA film/solution interface.<BR>In addition, on the basis of the results obtained, the usefulness of the PA-coated electrodes as electron-transfer catalyst and mediator was discussed.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1986 (3), 457-464, 1986-03-10

    The Chemical Society of Japan

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