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CeO₂ significantly enhances the oxygen evolution reaction (OER) activity of CoOx, although the mechanism behind this synergy is still unclear. Here, operando hard X-ray absorption spectroscopy (hXAS) is applied to monitor the Co-K edge and Ce L3 edge in CoOx/CeO2 to shed light on the evolution of Co and Ce oxidation states during OER. In addition, ex situ soft XAS (sXAS) characterizations provide information on the irreversible surface-specific transformations of the Co L3 edge as well as the O K edge.

Our findings disclose that P-functionalization successfully enhances the oxygen evolution reaction (OER) activity of different cobalt-based catalysts (namely, La_0.2Sr_0.8CoO_3–δ, La_0.2Sr_0.8Co_0.8Fe_0.2O_3–δ, and CoO_x) at near-neutral pHs and that both phosphate ion assistance in the OER mechanism and catalyst Co oxidation state can play a role in the enhanced OER activity.

The evolution of O₂ occurring in polymer electrolyte water electrolyzer anodes is a very slow reaction that must be catalyzed using iridium (Ir-) based materials. However, Ir is an extremely scarce metal, and thus the extended commercialization of these electrolyzers will only be possible if the amount of Ir implemented in their anodes is drastically reduced. This requires an improved understanding of the individual steps through which these Ir-based materials catalyze the evolution of O₂.

We carried out in situ and ex situ ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments on a La0.2Sr0.8CoO3-δ perovskite oxygen evolution reaction (OER) catalyst. The study shows that Sr is leached into the electrolyte after immersion, leading to surface Co active site enrichment. Such a Co-enriched surface evolves into a new phase during operation. With the help of theoretical simulations, such a species is assigned to Co-oxyhydroxide, providing direct evidence of its formation during the OER.