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Published March 1, 1980 | public
Journal Article Open

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

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.

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.

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August 22, 2023
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October 16, 2023