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Electron transfer kinetics at polarized nanoscopic liquid/liquid interfaces

Journal of the American Chemical Society, ISSN: 0002-7863, Vol: 128, Issue: 1, Page: 171-179
2006
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Article Description

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. © 2006 American Chemical Society.

Bibliographic Details

Cai, Chenxin; Mirkin, Michael V

American Chemical Society (ACS)

Chemical Engineering; Chemistry; Biochemistry, Genetics and Molecular Biology

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