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Mechanistic Studies of Electrode-Assisted Catalytic Oxidation by Flavinium and Acridinium Cations

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Department of Chemistry, Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, United States
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, United States
Cite this: ACS Catal. 2014, 4, 8, 2635–2644
Publication Date (Web):June 30, 2014
https://doi.org/10.1021/cs5005135
Copyright © 2014 American Chemical Society
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Abstract

Electrochemical behavior of flavinium (Et-Fl+) and acridinium (Acr+) cations is presented, in order to investigate their activity toward catalytic water oxidation. Cyclic voltammograms of Acr+ and Et-Fl+ in acetonitrile are qualitatively similar, with oxidation peaks at highly positive potentials, and these oxidation peaks depend strongly on the type of the working electrode being used. However, the two model compounds exhibit different behaviors in the presence of water: while Et-Fl+ facilitates electrocatalytic water oxidation through an electrode-assisted mechanism, water oxidation is not accelerated in the presence of Acr+. A comparative study of variable scan-rate cyclic voltammetry, concentration dependence, and spectroelectrochemical behavior of two model compounds suggest that Et-Fl+ and Acr+ exhibit different reaction pathways with the electrode surface. On the basis of the experimental results, a mechanism is proposed to account for the observed differences in electrocatalysis.

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