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    Silicon (100) electrodes resistant to oxidation in aqueous solutions: An unexpected benefit of surface acetylene moieties

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    Fulltext not available
    Authors
    Ciampi, Simone
    Eggers, P.
    Le Saux, G.
    James, M.
    Harper, J.
    Gooding, J.
    Date
    2009
    Type
    Journal Article
    
    Metadata
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    Citation
    Ciampi, S. and Eggers, P. and Le Saux, G. and James, M. and Harper, J. and Gooding, J. 2009. Silicon (100) electrodes resistant to oxidation in aqueous solutions: An unexpected benefit of surface acetylene moieties. Langmuir. 25 (4): pp. 2530-2539.
    Source Title
    Langmuir
    DOI
    10.1021/la803710d
    ISSN
    0743-7463
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/6817
    Collection
    • Curtin Research Publications
    Abstract

    Here we report on the functionalization of alkyne-terminated alkyl monolayers on highly doped Si(100) using "click" reactions to immobilize ferrocene derivatives. The reaction of hydrogen-terminated silicon surfaces with a diyne species was shown to afford very robust functional surfaces where the oxidation of the underlying substrate was negligible. Detailed characterization using X-ray photoelectron spectroscopy, X-ray reflectometry, and cyclic voltammetry demonstrated that the surface acetylenes had reacted in moderate yield to give surfaces exposing ferrocene moieties. Upon extensive exposure of the redox-active architecture to oxidative environments during preparative and characterization steps, no evidence of SiOx contaminants was shown for derivatized SAMs prepared from single-component 1,8-nonadiyne, fully acetylenylated, monolayers. An analysis of the redox behavior of the prepared Si(100) electrodes based on relevant parameters such as peak splitting and position and shape of the reduction/oxidation waves depicted a well-behaved redox architecture whose spectroscopic and electrochemical properties were not significantly altered even after prolonged cycling in aqueous media between -100 and 800 mV versus AglAgCl. The reported strategy represents an experimentally simple approach for the preparation of silicon-based electrodes where, in addition to close-to-ideal redox behavior, remarkable electrode stability can be achieved. Both the presence of a distal alkyne moiety and temperatures of formation above 100 °C were required to achieve this surface stabilization. © Copyright 2009 American Chemical Society.

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