title: Electron transfer kinetics at polarized nanoscopic liquid/liquid interfaces.
abstract: Rapid kinetics of electron transfer (ET) reactions across the interface between water and 1,2-dichloroethane were measured by steady-state voltammetry at nanopipet electrodes (50- to 400-nm orifice radius). The origins of previously reported imperfect voltammetric responses of ET reactions at micropipets were investigated. Several new experimental systems were explored, and two of them yielded high-quality voltammograms suitable for kinetic experiments. The determined standard rate constants were compared to those measured previously at polarized and nonpolarized liquid/liquid interfaces. The effect of the interfacial dimensions on the magnitude of the apparent ET rate constant is discussed. A new approach to ET kinetic measurements based on the use of the scanning electrochemical microscope with a nanopipet tip and a metallic substrate has been developed and employed to check the validity of determined kinetic parameters.
authors.affiliation: Department of Chemistry and Biochemistry, Queens College-CUNY, Flushing, NY 11367, USA.
authors.forename: Chenxin
authors.initials: C
authors.lastname: Cai
authors.forename: Michael V
authors.initials: MV
authors.lastname: Mirkin