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    Identification of surface heterogeneity effects in cyclic voltammograms derived from analysis of an individually Addressable Gold Array Electrode.

    Access Status
    Fulltext not available
    Authors
    Lee, C.
    Tan, Yong-jun
    Bond, A.
    Date
    2008
    Type
    Journal Article
    
    Metadata
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    Citation
    Lee, Chong-Yong and Tan, Yong and Bond, Alan M. 2008. Identification of surface heterogeneity effects in cyclic voltammograms derived from analysis of an individually Addressable Gold Array Electrode. Analytical Chemistry. 80: pp. 3873-3881.
    Source Title
    Analytical Chemistry
    DOI
    10.1021/ac8002227
    ISSN
    00032700
    Faculty
    School of Science
    Science and Engineering
    School
    Department of Applied Chemistry
    Remarks

    Copyright © 2008 American Chemical Society

    The website of Analitical Chemistry is available at: http://pubs.acs.org/journal/ancham

    Open access to this article will be available 12 months after publication via the website of the American Chemical Society. http://acswebcontent.acs.org/home.html

    URI
    http://hdl.handle.net/20.500.11937/43995
    Collection
    • Curtin Research Publications
    Abstract

    Voltammetric behavior at gold electrodes in aqueous media is known to be strongly dependent on electrode polishing and history. In this study, an electrode array consisting of 100 nominally identical and individually addressable gold disks electrodes, each with a radius of 127 m, has been fabricated. The ability to analyze both individual electrode and total array performance enables microscopic aspects of the overall voltammetric response arising from variable levels of inhomogeneity in each electrode to be identified. The array configuration was initially employed with the reversible and hence relatively surface insensitive [Ru(NH3)6]3+/2+ reaction and then with the more highly surface sensitive quasi-reversible [Fe(CN)6]3-/4- process. In both these cases, the reactants and products are solution soluble and, at a scan rate of 50 mV s-1, each electrode in the array is assumed to behave independently, since no evidence of overlapping of the diffusion layers was detected. As would be expected, the variability of the individual electrodes responses was significantly larger than found for the summed electrode behavior. In the case of cytochrome c voltammetry at a 4,4'-dipyridyl disulfide modified electrode, a far greater dependence on electrode history and electrode heterogeneity was detected. In this case, voltammograms derived from individual electrodes in the gold array electrode exhibit shape variations ranging from peak to sigmoidal. However, again the total response was always found to be well-defined. This voltammetry is consistent with a microscopic model of heterogeneity where some parts of each chemically modified electrode surface are electroactive while other parts are less active. The findings are consistent with the common existence of electrode heterogeneity in cyclic voltammetric responses at gold electrodes, that are normally difficult to detect, but fundamentally important, as electrode nonuniformity can give rise to subtle forms of kinetic and other forms of dispersion.

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