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Factors Affecting the Electrochemical Responses of Metal Complexes at Pyrolytic Graphite Electrodes Coated with Films of Poly(4-Vinylpyridine)

Oyama, Noboru and Anson, Fred C. (1980) Factors Affecting the Electrochemical Responses of Metal Complexes at Pyrolytic Graphite Electrodes Coated with Films of Poly(4-Vinylpyridine). Journal of the Electrochemical Society, 127 (3). pp. 640-647. ISSN 0013-4651. http://resolver.caltech.edu/CaltechAUTHORS:OYAjes80c

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Abstract

Electrochemical responses from the reduction of RuIII (edta) coordinatedto films of high molecular weight poly(4-vinylpyridine) on pyrolytic graphiteelectrodes were studied as functions of film thickness, temperature, supportingelectrolyte composition, and solvent. Responses at filmed electrodes from metalcomplexes that do not coordinate to the films were also examined. With filmsthicker than ca. 1000Å, the current responses are limited by the rates of molecularmotions within the films. Penetration of counterions, segmental motion ofsections of the polymer chains, and juxtapositioning of pairs of attached metalcomplexes to facilitate intercomplex electron transfer within the film or combinationsof the three are suggested as likely current limiting processes.


Item Type:Article
Additional Information:©1980 The Electrochemical Society, Inc. Manuscript submitted July 23, 1979; revised manuscript received Oct. 15, 1979. The assistance of Prof. J. P. Revel and Pat Cohen in obtaining electron micrographs is acknowledged gratefully. Drs. Alan Rembaum and Roger Williams kindly provided the samples of fractionated PVP that were used to obtain the data for Fig. 2. Several perceptive comments and criticisms by the reviewers of an earlier version of this manuscript helped us to formulate our speculations more clearly. This work was supported by the National Science Foundation and the U.S. Army Research Office. Publication costs oS this article were assisted by the California Institute of Technology.
Subject Keywords:electrochemical electrodes; polymer films; graphite; electrochemistry; metals
Record Number:CaltechAUTHORS:OYAjes80c
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:OYAjes80c
Alternative URL:http://dx.doi.org/10.1149/1.2129725
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5671
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:27 Oct 2006
Last Modified:26 Dec 2012 09:14

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