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    Surface-bound molecular rulers for probing the electrical double layer

    Access Status
    Fulltext not available
    Authors
    Eggers, P.
    Darwish, Nadim
    Paddon-Row, M.
    Gooding, J.
    Date
    2012
    Type
    Journal Article
    
    Metadata
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    Citation
    Eggers, P. and Darwish, N. and Paddon-Row, M. and Gooding, J. 2012. Surface-bound molecular rulers for probing the electrical double layer. Journal of the American Chemical Society. 134 (17): pp. 7539-7544.
    Source Title
    Journal of the American Chemical Society
    DOI
    10.1021/ja301509h
    ISSN
    0002-7863
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/16913
    Collection
    • Curtin Research Publications
    Abstract

    Herein, we report the first experimental investigation on the effect of varying the position of redox-active moieties, within the electrical double layer, on the apparent formal potential and on the electron transfer rate constant. This was achieved using a rigid class of molecules, norbornylogous bridges, to place redox species (ferrocene) at a fixed position above the surface of the electrode. Cyclic voltammetry and alternating current voltammetry were used to calculate the apparent formal potential and the electron transfer rate constant for the electron transfer between the ferrocene and the gold electrode. We use the effect of electric field on the apparent formal potential measurement of the surface-bound redox species to calculate the potential drop from the initiation of the electrical double layer to different distances above it. It was found that self-assembled monolayers formed from ?- hydroxyalkanethiol have a potential profile very similar to that described by classical theories for bare metal electrodes. A steep drop in potential in the Stern layer was observed followed by a smaller potential drop in the Gouy-Chapman layer. The electron transfer rate constant was found to decrease as the distance between the ferrocene moiety and the initiation of the double layer is increased. Thus, the electron transfer rate constant appears to be dependent on ion concentration.

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