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Abstract

Progress in the development of proton exchange membrane (PEM) water electrolysis technology requires decreasing the anode overpotential, where the sluggish multistep oxygen evolution reaction (OER) occurs. This calls for an understanding of the nature of the active OER sites and reaction intermediates, which are still being debated. In this work, we apply synchrotron radiation-based near-ambient pressure X-ray photoelectron and absorption spectroscopies under operando conditions in order to unveil the nature of the reaction intermediates and shed light on the OER mechanism on electrocatalysts most widely used in PEM electrolyzers—electrochemical and thermal iridium oxides. Analysis of the O K-edge and Ir 4f spectra backed by density functional calculations reveals a universal oxygen anion red–ox mechanism regardless of the nature (electrochemical or thermal) of the iridium oxide. The formation of molecular oxygen is considered to occur through a chemical step from the electrophilic O_I– species, which itself is formed in an electrochemical step.