Electrode kinetics of viologen polymers attached on graphite surfaces.
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概要
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A "heterogeneous" electron-transfer process of three kinds of viologen polymers, <I>i.e.</I>, <I>N</I>,<I>N</I>′-dimethyl-4,4′-bipyridinium (methylviologen, MV)–Nafion<SUP>R</SUP>, poly(xylylviologen) (PXV)-poly(<I>p</I>-styrenesulfonate) (PSS) and poly(methylviologen) (PMV), in which MV and PXV were electrostatically trapped in Nafion and PSS, respectively, on a basal-plane pyrolytic graphite (BPG) electrode and PMV was directly attached to the BPG electrode surface, was examined by normal pulse voltammetry. The relevant kinetic parameters (<I>i.e.</I>, the standard rate constant, <I>k</I><SUP>o</SUP><SUB>el</SUB> and the cathodic transfer coefficient, α) of the electrode reaction and the apparent diffusion coefficients, <I>D</I><SUB>app</SUB>, for the "homogeneous" charge transport within these polymer films were determined at the various surface concentrations (<I>Γ</I><SUB>MV<SUP>2+</SUP></SUB> in units of mol cm<SUP>−2</SUP>) of viologen dication site. With the PMV and PXV–PSS systems, both <I>k</I><SUP>o</SUP><SUB>el</SUB> and <I>D</I><SUB>app</SUB> were independent of <I>Γ</I><SUB>MV<SUP>2+</SUP></SUB>, while with the MV–Nafion system both <I>k</I><SUP>o</SUP><SUB>el</SUB> and <I>D</I><SUB>app</SUB> decreased with an increase in <I>Γ</I><SUB>MV<SUP>2+</SUP></SUB> under the constant concentration of Nafion. The values of α were independent of <I>Γ</I><SUB>MV<SUP>2+</SUP></SUB> and constant (<I>i.e.</I>, 0.56, 0.58, and 0.20 for the PMV, MV–Nafion and PXV–PSS systems, respectively).
- 公益社団法人 日本化学会の論文
著者
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Oyama Noboru
Department Of Applied Chemistry Faculty Of Technology Tokyo University Of Agriculture And Technology
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Kaneko Masao
The Institute Of Biophotochemonics Co. Ltd.
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Nakamura Setsuko
Department Of Chemistry And Materials Science Tokyo Institute Of Technology
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Ohsaka Takeo
Department Of Applied Chemistry Faculty Of Technology Tokyo University Of Agriculture And Technology
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YAMADA Akira
The Institute of Physical and Chemical Research
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Nakamura Michiko
Department Of Mathematics Faculty Of Science Science University Of Tokyo
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Yamamoto Hisao
Department of Applied Chemistry for Resources, Tokyo University of Agriculture and Technology
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Nakamura Setsuko
Department of Chemistry, Japan Women's University
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Nakamura Michiko
Department of Chemistry, Faculty of Science, Kobe University
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Nakamura Michiko
Department of Chemistry, Japan Women's University
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