Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction

The ability to determine the electronic structure of catalysts during electrochemical reactions is highly important for identification of the active sites and the reaction mechanism. Here we successfully applied soft X-ray spectroscopy to follow in operando the valence and spin state of the Co ions in Li₂Co₂O₄ under oxygen evolution reaction (OER) conditions. We have observed that a substantial fraction of the Co ions undergo a voltage-dependent and time-dependent valence state transition from Co³⁺ to Co⁴⁺ accompanied by spontaneous delithiation, whereas the edge-shared Co-O network and spin state of the Co ions remain unchanged. Density functional theory calculations indicate that the highly oxidized Co⁴⁺ site, rather than the Co³⁺ site or the oxygen vacancy site, is mainly responsible for the high OER activity.