Carefully assessing the energetics along the pathway of the oxygen evolution reaction (OER), our computational study reveals that the "classical" OER mechanism on the (110) surface of iridium dioxide (IrO2) must be reconsidered. We find that the OER follows a bi-nuclear mechanism with adjacent top surface oxygen atoms as fixed adsorption sites, whereas the iridium atoms underneath play an indirect role and maintain their saturated 6-fold oxygen coordination at all stages of the reaction. The oxygen molecule is formed, via an Ir-OOOO-Ir transition state, by association of the outer oxygen atoms of two adjacent Ir-OO surface entities, leaving two intact Ir-O entities at the surface behind. This is drastically different from the commonly considered mono-nuclear mechanism where the O2 molecule evolves by splitting of the Ir-O bond in an Ir-OO entity. We regard the rather weak reducibility of crystalline IrO2 as the reason for favoring the novel pathway, which allows the Ir-O bonds to remain stable and explains the outstanding stability of IrO2 under OER conditions. The establishment of surface oxygen atoms as fixed electrocatalytically active sites on a transition-metal oxide represents a paradigm shift for the understanding of water oxidation electrocatalysis, and it reconciles the theoretical understanding of the OER mechanism on iridium oxide with recently reported experimental results from operando X-ray spectroscopy. The novel mechanism provides an efficient OER pathway on a weakly reducible oxide, defining a new strategy towards the design of advanced OER catalysts with combined activity and stability.
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