The engine of metal-oxide oxidation catalysis is the oxyl active site–a species with unpaired electron density on O and a labile metal–oxygen bond. Dimensionally-reduced metallate clusters (M-OECs) are highly active OER catalysts that can be accessed via electrochemical oxidation of metal ion precursors of Mn, Co, and Ni in the presence of buffering anions such as borate and phosphate. The M-OECs, with their reactive metal-oxyl active sites, support both water oxidation (solar fuels applications) and the oxidation of organic substrates (biofuels cell applications). The mechanism involving the generation and reactivity of the oxyl radical of the M-OECs and its bifurcation along water and organic substrate oxidation pathways will be discussed.

Energy conversion mechanisms involving metal-oxyl radicals

2019 Spring National Meeting

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