Behavior and Characterization of Kinetically Involved Chemisorbed Intermediates in Electrocatalysis of Gas Evolution Reactions

Publisher Summary This chapter discusses the role of chemisorbed intermediates in a number of well-known electrocatalytic reactions and how their behavior at electrode surfaces can be experimentally deduced by electrochemical and physicochemical means. The electrolytic gas evolution reactions are highlighted. The chapter describes the methods for the characterization of the adsorption behavior of the intermediates that are the kinetically involved species in the main pathway of the respective reactions rather than strongly adsorbed byproducts that may, in some cases, importantly inhibit the overall reaction. Several important features of electrode processes that differ from regular heterogeneously catalyzed reactions must be recognized, such as chemisorbed intermediates are often generated from a reactant in solution by an electron-charge-transfer event, for example, the adsorption of H from H3O+ ion, plus an electron, resulting in a direct potential dependence of the rate of the production of such an intermediate.

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