Spectroelectrochemistry of Water Oxidation Kinetics in Molecular versus Heterogeneous Oxide Iridium Electrocatalysts

Water oxidation is the step limiting the efficiency of electrocatalytic hydrogen production from water. Spectroelectrochemical analyses are employed to make a direct comparison of water oxidation reaction kinetics between a molecular catalyst, the dimeric iridium catalyst [Ir₂(pyalc)₂(H₂O)₄-(μ-O)]²⁺ (Ir, pyalc = 2-(2'pyridinyl)-2-propanolate) immobilized on a mesoporous indium tin oxide (ITO) substrate, with that of an heterogeneous electrocatalyst, an amorphous hydrous iridium (IrO) film. For both systems, four analogous redox states were detected, with the formation of Ir(4+)-Ir(5+) being the potential-determining step in both cases. However, the two systems exhibit distinct water oxidation reaction kinetics, with potential-independent first-order kinetics for Ir contrasting with potential-dependent kinetics for IrO. This is attributed to water oxidation on the heterogeneous catalyst requiring co-operative effects between neighboring oxidized Ir centers. The ability of Ir to drive water oxidation without such co-operative effects is explained by the specific coordination environment around its Ir centers. These distinctions between molecular and heterogeneous reaction kinetics are shown to explain the differences observed in their water oxidation electrocatalytic performance under different potential conditions.