Operando Raman spectroscopy tracks oxidation-state changes in an amorphous Co oxide material for electrocatalysis of the oxygen evolution reaction

Transition metal oxides are of high interest in both energy storage (batteries) and production of non-fossil fuels by (photo)electrocatalysis. Their functionally crucial charge (oxidation state) changes and electrocatalytic properties are best investigated under electrochemical operation conditions. We established operando Raman spectroscopy for investigation of the atomic structure and oxidation state of a non-crystalline, hydrated, and phosphate-containing Co oxide material (CoCat), which is an electrocatalyst for the oxygen evolution reaction (OER) at neutral pH and is structurally similar to LiCoO2 of batteries. Raman spectra were collected at various sub-catalytic and catalytic electric potentials. 2H labeling suggests Co oxidation coupled to Co—OH deprotonation at catalytic potentials. 18O labeling supports O—O bond formation starting from terminally coordinated oxygen species. Two broad bands around 877 cm−1 and 1077 cm−1 are assigned to CoCat-internal H2PO4-. Raman peaks corresponding to terminal ...