INVESTIGATION OF ION AND SOLVENT TRANSPORT ACCOMPANYING REDOX REACTIONS OF POLYVINYLFERROCENE FILMS USING AN IN SITU ELECTROCHEMICAL QUARTZ CRYSTAL MICROBALANCE TECHNIQUE
INVESTIGATION OF ION AND SOLVENT TRANSPORT ACCOMPANYING REDOX REACTIONS OF POLYVINYLFERROCENE FILMS USING AN IN SITU ELECTROCHEMICAL QUARTZ CRYSTAL MICROBALANCE TECHNIQUE
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DOI：
10.1246/bcsj.64.2887
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发表时间：
1991-10-01
影响因子：
4
通讯作者：
OYAMA, N
中科院分区：
文献类型：
--
作者：
MIZUNUMA, M;OHSAKA, T;OYAMA, N
采用原位电化学石英晶体微天平（insituEQCM）技术研究了聚乙烯二茂铁（PVF）膜在石英晶体电极上氧化还原反应过程中的离子和溶剂输运。与溶液相二茂铁衍生物相比，考察了PVF膜中F（c）-度/F（c）+氧化还原电对（F（c）-度和F（c）+分别代表膜中的还原和氧化位点）的表观形式电位（E（f）poly）app对支持电解质浓度的依赖性. PVF膜在水溶液和乙腈介质中对ClO 4-阴离子都具有理想的选择透过性。PVF在水介质中的氧化（或聚乙烯铁离子的还原）伴随着每个氧化还原位点和一些溶剂（约100 μ g/ml）的一个ClO 4-离子的进入（或排出）。每个氧化还原位点一个H2O）。在LiClO_4乙腈介质中，在氧化过程中，ClO_4 ~-离子与某些溶剂一起插入膜中，在还原过程中出现相反的现象。结果表明，在原位EQCM测量和测量的依赖性（E（f）聚）app的支持电解质的浓度的组合，使得有可能定量阐明的离子和/或溶剂的传输过程中的聚合物膜/溶液界面的氧化还原反应。
The in situ electrochemical quartz crystal microbalance (in situ EQCM) technique has been applied to study ion and solvent transport accompanying the redox reaction of polyvinylferrocene (PVF) film coated on quartz crystal electrodes in aqueous and acetonitrile media. The dependence of apparent formal potentials (E(f)poly)app of the F(c)-degrees/F(c)+ redox couple (F(c)-degrees and F(c)+ represent the reduced and oxidized sites, respectively, in the PVF film) upon the concentration of supporting electrolyte has been also examined in comparison with those of solution-phase ferrocene derivatives. The PVF film is ideally permselective to ClO4- anion in both aqueous and acetonitrile media. The PVF oxidation (or reduction of polyvinylferricenium ion) in aqueous media is accompanied by the ingress (or egress) of one ClO4- ion per redox site and some solvent (ca. one H2O per redox site). In LiClO4 acetonitrile media, during the oxidation process ClO4- ion with some solvent inserts into the film and the reverse phenomenon occurs during the reduction process. The results demonstrate that a combination of the in situ EQCM measurement and the measurement of the dependence of (E(f)poly)app on the concentration of supporting electrolyte makes possible to elucidate quantitatively the ion and/or solvent transport process across the polymer film/solution interface during the redox reaction.