Consequences of Kinetic Dispersion on the Electrochemistry of an Adsorbed Redox-Active Monolayer

摘要

Mixed monolayers of (ferrocenylcarboxy) -alkanethiol/n-alkanethiol have beeninvestigated electrochemically in 2:1 (v:v) chloroethane:butyronitrile solvent in the temperature range of 120K to 150K. Cyclic voltammetry of these monolayers shows large oxidation-reduction peak potential separations indicative of electron transfer rate control. The voltammetric waveshapes are also broadened; this and curved logI vs. time transients observed in potential step experiments are interpreted as a dispersion in the reaction rates of the ferrocene sites. This paper considers origins and three models for such kinetic dispersion. jg.