Publication
840
Proc. Natl. Acad. Sci. U.S.A., 114 (43) ,11303-11308, 2017
DOI:10.1073/pnas.1711129114
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Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime
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Cyrille Costentin, Daniel G. Nocera, and Casey N. Brodsky
Laboratoire d’Electrochimie Moléculaire, Unité Mixte de Recherche Université–CNRS No.7591, Université Paris Diderot, Sorbonne Paris Cité, 75205 Paris Cedex 13, France
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138
Cyclic voltammetry responses are derived for two-electron, two-step homogeneous electrocatalytic reactions in the total catalysis regime. The models developed provide a framework for extracting kinetic information from cyclic voltammograms (CVs) obtained in conditions under which the substrate or cosubstrate is consumed in a multielectron redox process, as is particularly prevalent for very active catalysts that promote energy conversion reactions. Such determination of rate constants in the total catalysis regime is a prerequisite for the rational benchmarking of molecular electrocatalysts that promote multielectron conversions of small-molecule reactants. The present analysis is illustrated with experimental systems encompassing various limiting behaviors. |
