Redox-Active Ligand Assisted Catalytic Water Oxidation by a Ru^IV =O Intermediate

Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understanding this process in depth and have received wide attention since the first Ru-based catalyst was reported in 1982. Ru^V =O is considered a key intermediate to initiate the O-O bond formation through either a water nucleophilic attack (WNA) pathway or a bimolecular coupling (I2M) pathway. Herein, we report a Ru-based catalyst that displays water oxidation reactivity with Ru^IV =(O) with the help of a redox-active ligand at pH 7.0. The results of electrochemical studies and DFT calculations disclose that ligand oxidation could significantly improve the reactivity of Ru^IV =O toward water oxidation. Under these conditions, sustained water oxidation catalysis occurs at reasonable rates with low overpotential (ca. 183 mV).