The Catalytic Mechanism of a Highly Active Cobalt Chlorin Complex for Photocatalytic Water Oxidation.

Highly active catalysts for electrocatalytic and photocatalytic water oxidation are strongly demanded to realize artificial photosynthesis. A cobalt complex with a chlorin derivative ligand (Co(Ch)) exhibited high activity for electrocatalytic water oxidation with an overpotential of 0.45 V at pH 9.0. Spectroelectrochemistry (UV-vis) unveiled the formation of two intermediates by successive one-electron oxidations. Also, the Pourbaix diagram depicted by the pH dependence of redox potentials indicated that the water oxidation proceeded after the oxidation of both the central cobalt ion and chlorin ligand with proton-coupled electron transfer (PCET). Then, the photocatalytic activity of Co(Ch) was examined for water oxidation using [Ru(bpy)] (bpy: 2,2'-bipyridine) and SO as a photosensitizer and a sacrificial electron acceptor, respectively. The turnover number, turnover frequency, and oxygen yield reached as high as 980, 5.2 s, and 98%, respectively, under optimized conditions. The O-evolution rates increased in proportion to the square of the catalyst concentration in the reaction solution, suggesting that the formation of the O-O bond regarded as the rate-determining step of water oxidation proceeded by the interaction of two metal centers (I2M) mechanism in which two molecules of high-valent metal oxo or oxyl radical species react with each other.