Carbonate Ions Induce Highly Efficient Electrocatalytic Water Oxidation by Cobalt Oxyhydroxide Nanoparticles

Synthetic models of oxygen evolving complex (OEC) are used not only to gain better understanding of the mechanism and the roles of cofactors for water oxidation in photosynthesis, but also as water oxidation catalysts to realize artificial photosynthesis, which is anticipated as a promising solar fuel production system. However, although much attention has been paid to the composition and structure of active sites for development of heterogeneous OEC models, the cofactors, which are essential for water oxidation by the photosynthetic OEC, remain little studied. The high activity of CoO(OH) nanoparticles for electrocatalytic water oxidation is shown to be induced by a CO₃^2- cofactor. The possibility of CO₃^2- ions acting as proton acceptors for O-O bond formation based on the proton-concerted oxygen atom transfer mechanism is proposed. The O-O bond formation is supposed to be accelerated due to effective proton acceptance by adjacent CO₃^2- ions coordinated on the Co^IV center in the intermediate, which is consistent with Michaelis-Menten-type kinetics and the significant H/D isotope effect observed in electrocatalysis.