title: Kinetics of electron-transfer reactions at nanoelectrodes.
abstract: The kinetics of several fast heterogeneous electron-transfer reactions were investigated by steady-state voltammetry at nanoelectrodes and scanning electrochemical microscopy (SECM). The disk-type, polished Pt nanoelectrodes (3.7-400-nm radius) were characterized by a combination of voltammetry, scanning electron microscopy, and SECM. A number of experimental curves were obtained at the same nanoelectrode to attain the accuracy and reproducibility similar to those reported previously for micrometer-sized probes. A new analytical approximation was developed and used for analysis of steady-state tip voltammograms. The self-consistent kinetic parameter values with the uncertainty margin of approximately 10% were obtained for electrodes of different radii and for a wide range of the SECM tip/substrate separation distances. The determined standard rate constants are compared to those previously measured at the electrodes of different dimensions, and the correlation between the heterogeneous and self-exchange rate constants is discussed.
authors.affiliation: Department of Chemistry and Biochemistry, Queens College-CUNY, Flushing, New York 11367, USA.
authors.forename: Peng
authors.initials: P
authors.lastname: Sun
authors.forename: Michael V
authors.initials: MV
authors.lastname: Mirkin