Unravelling the effects of active site density and energetics on the water oxidation activity of iridium oxides

Understanding what controls the reaction rate on iridium-based catalysts is central to designing better electrocatalysts for the water oxidation reaction in proton exchange membrane electrolysers. Here we quantify the densities of redox-active centres and probe their binding strengths on amorphous IrOx and rutile IrO2 using operando time-resolved optical spectroscopy. We establish a quantitative experimental correlation between the intrinsic reaction rate and the active-state energetics. We find that adsorbed oxygen species, *O, formed at water oxidation potentials, exhibit repulsive adsorbate–adsorbate interactions. Increasing their coverage weakens their binding, thereby promoting O–O bond formation, which is the rate-determining step. These analyses suggest that although amorphous IrOx exhibits a higher geometric current density, the intrinsic reaction rates per active state on IrOx and IrO2 are comparable at given potentials. Finally, we present a modified volcano plot that elucidates how the intrinsic water oxidation kinetics can be increased by optimizing both the binding energy and the interaction strength between the catalytically active states. (Figure presented.)