Chemical and mechanical properties of redox polymer-modified electrodes. Part II. Redox thermodynamics of plasma-polymerized vinylferrocene electrodes

M. F. Dautartas, E. F. Bowden, J. F. Evans

Research output: Contribution to journalArticle

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Abstract

The thermodynamics of thin films (< 200 nm) of plasma-polymerized vinylferrocene (PPVF) deposited on various substrates have been examined in aqueous and non-aqueous electrolytes by controlled potential coulometry. The Nerst plots (E vs log[cFc+/cFc0]) of these data give slopes in the range of 120-150 mV/decade. Scanning electron microscopy of thicker films (> 400 nm) shows that significant physical damage can occur during electrolysis. These and related observations suggest that the super-Nersntian behavior may be related to stress induced by the forced incorporation of the anion of the supporting electrolyte, as is required to maintain electroneutrality within the films. A mechanical/electrochemical model is employed to explain the origin of the excess free energy required to convert ferrocene sites to ferrocenium sites within the PPVF films.

Original languageEnglish (US)
Pages (from-to)71-89
Number of pages19
JournalJournal of Electroanalytical Chemistry
Volume219
Issue number1-2
DOIs
StatePublished - Mar 10 1987

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