The thermodynamically challenging step in natural and artificial photosynthesis is the oxidation of water to dioxygen. Towards this end, we have identified a dinuclear copper water oxidation electrocatalyst which achieves high Faradaic efficiencies and moderate turnover rates. The catalyst partially dissociates in solution into a mononuclear species. A large kinetic isotope effect was observed, suggestive that initial oxidation of the dinuclear copper catalyst is rate limiting despite being energetically competitive with oxidation of the mononuclear copper species. These calculations further imply that mononuclear high-valent oxo pathways are not energetically viable. This lecture will present recent experimental and computational results on the mechanism of water oxidation by this catalyst and factors that direct the reaction landscape.

Electrocatalytic water oxidation by a homogeneous copper catalyst disfavors single-site mechanisms

254th National Meeting (2017)

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