Investigation of the kinetics of electron transfer processes involving fullerenes at liquid-liquid interfaces using scanning electrochemical microscopy: Evidence for Marcus inverted region behaviour

Jie Zhang, P. R. Unwin

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Abstract

Electron transfer (ET) reactions between the anions of fullerenes (C60 and C70) in chlorobenzene (PhCl) and Fe(CN)63- in an aqueous phase have been investigated using scanning electrochemical microscopy (SECM). Salts of the anion ClO4- were added to each phase to control the interfacial potential drop and maintain charge neutrality during the ET process. The rate constants of ET between C60- and Fe(CN)63- were similar to those between C70- and Fe(CN)63-. Although the measured ET kinetics were found to depend on the interfacial potential drop, the rate constant for the oxidation of the fulleride anion (reduction of aqueous Fe(CN)63-) decreased when the ClO4- concentration in the aqueous phase increased, even though this corresponds to an increase in driving force. It is suggested that this could be due to inverted region behaviour predicted by Marcus theory.

Original languageEnglish
Pages (from-to)1608-1612
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number9
Publication statusPublished - 2001
Externally publishedYes

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