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• W2037334564 endingPage "3918" @default.
• W2037334564 startingPage "3911" @default.
• W2037334564 abstract "Oxidation waves in cyclic voltammograms (CVs) observed during repeated potential cyclings of polypyrrole-as-deposited Pt/poly-1 electrodes (poly-1: poly[tris(4-vinyl-4′-methyl-2,2′-bipyridine)ruthenium(II) perchlorate]) in 0.1 M TBAP/acetonitrile, that lead to the bilayer (BL) electrochemistry, have been quantitatively analyzed. As the potential cycling is repeated, the CV change occurs, i.e., decrease of the peak current and positive shift of the peak potential. This is shown to be the result of logarithmic decrease in the complementary charge transfer coefficient β in the totally irreversible thin-layer (TITL) electrochemistry. kTL° (standard rate constant for polypyrrole oxidation) and CTL° (initial concentration of the reduced sites in polypyrrole) have been determined to be 5.50×10−9 cm mol−1 s−1 and 3.15×10−3 mol cm−3, respectively, by fitting CV data to the theory of the TITL model. The subsequent onset and growth of the CV waves in the higher potential region are explained as being due to progressive partitioning of polypyrrole sites from the TITL mode to the BL mode in which polypyrrole sites are oxidized. The partition coefficient θ, defined as the ratio of polypyrrole sites oxidized in the BL mode to all the polypyrrole sites, has been found to approximately depend on the logarithm of β. In the BL mode, a linear relationship is found between peak current and peak potential. Simulation of the CV waves has been performed based on the theoretical models of TITL and BL electrochemistry, and has revealed that a model assuming separation of polypyrrole sites into the TITL and BL modes prior to each cyclic sweep explains the occurrence of the significantly separated current peaks in both modes. These results are discussed in terms of Electrochemically driven Phase Separation (ECPS), in which the decrease in β is directly related to the separation of the mixed poly-1 and polypyrrole phase." @default.
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• W2037334564 date "1989-12-01" @default.
• W2037334564 modified "2023-09-25" @default.
• W2037334564 title "Analysis of Cyclic Voltammograms for Polypyrrole-as-Deposited Pt/poly[tris(4-vinyl-4′-methyl-2,2′-bipyridine)ruthenium(II) perchlorate] Electrodes" @default.
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• W2037334564 doi "https://doi.org/10.1246/bcsj.62.3911" @default.
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