Surface Electron-Hole Rich Species Active in the Electrocatalytic Water Oxidation

Abstract

Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge <i>operando</i> surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and <i>ab initio</i> DFT calculations, we were able to reveal the electronic structure of the active IrO_<i>x</i> centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally Ir^V species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (μ₁-O and μ₁-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (μ₃-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a μ₁-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species.