Water oxidation is the �other half reaction� in most solar fuels schemes in which the goal is to use sunlight to drive water splitting into hydrogen and oxygen or to use water to reduce CO2 to CO, other oxygenates, or hydrocarbons. Oxidizing water to oxygen, 2H2O ? O2 + 4e� + 4H+, presents a significant mechanistic challenge with requirements for both 4e-/4H+ loss and O---O bond formation. Significant advances have been made recently based on single site polypyridyl complexes in solution and on the surfaces of oxide electrodes. As illustrated below for Ru(Mebimpy)(bpy)(OH2)2+, water oxidation occurs by stepwise mechanisms based on Proton Coupled Electron Transfer (PCET), O---O bond formation, and peroxo intermediates. In more recent studies, new pathways for water oxidation have been identified and catalytic water oxidation has been extended to first row transition metals and complexes of Cu, Co, and Fe.  

Oxidizing water

243rd National Meeting (2012)

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