Anchoring a Molecular Iron Catalyst to Solar-Responsive WO3 Improves the Rate and Selectivity of Photoelectrochemical Water Oxidation

Molecular catalysts help overcome the kinetic limitations of water oxidation and generally result in faster rates for water oxidation than do heterogeneous catalysts. However, molecular catalysts typically function in the dark and therefore require sacrificial oxidants such as Ce4+ or S2O82– to provide the driving force for the reaction. In this Communication, covalently anchoring a phosphonate-derivatized complex, Fe­(tebppmcn)­Cl2 (1), to WO3 removes the need for a sacrificial oxidant and increases the rate of photoelectrochemical water oxidation on WO3 by 60%. The dual-action catalyst, 1-WO3, also gives rise to increased selectivity for water oxidation in pH 3 Na2SO4 (56% on bare WO3, 79% on 1-WO3). This approach provides promising alternative routes for solar water oxidation.