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Temporal Instabilities in Anodic Oxidation of Small Molecules/Ions at Solid Electrodes

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Self-Organization in Electrochemical Systems I

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Abstract

Dynamic instabilities associated with anodic oxidation of small molecules and ions: hydrogen, carbon monoxide, formaldehyde, formate ions, alcohols: methanol, ethanol, 2-propanol and 1-butanol, and sulfide ions at solid (mainly polycrystalline and single crystal Pt electrodes) are described. Electrooxidation of most of these molecules is of significant practical importance due to their application, e.g., in the fuel cells. Understanding of the reaction mechanism and control of associated instabilities can improve the efficiency of such cells. Also, their course can exhibit analogies with the characteristics of nerve excitation. In spite of simplicity of the structure of the above-mentioned molecules or ions, their electrocatalytic oxidation processes exhibit a rich variety of dynamic instabilities, corresponding to properties of N-NDR, S-NDR, and HN-NDR systems. These dynamic instabilities include also excitability and experimentally rarely reported phenomenon of tristability. In particular, the electrooxidation of CO constitutes an important subsystem in the anodic processes of other organic molecules, as CO is an intermediate which poisons the Pt surface. The reported dynamic instabilities are discussed in terms of relevant electrochemical mechanisms, supported by appropriate numerical modeling and bifurcation analysis. In addition, the oscillatory oxidations of hydrazine, ethylene, iodide ions and graphite are briefly characterized.

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  1. Faculty of Chemistry, University of Warsaw, Warsaw, Poland

    Marek Orlik

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Orlik, M. (2012). Temporal Instabilities in Anodic Oxidation of Small Molecules/Ions at Solid Electrodes. In: Self-Organization in Electrochemical Systems I. Monographs in Electrochemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-27673-6_5

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