Enlarged CoO Covalency in Octahedral Sites Leading to Highly Efficient Spinel Oxides for Oxygen Evolution Reaction.

Cobalt-containing spinel oxides are promising electrocatalysts for the oxygen evolution reaction (OER) owing to their remarkable activity and durability. However, the activity still needs further improvement and related fundamentals remain untouched. The fact that spinel oxides tend to form cation deficiencies can differentiate their electrocatalysis from other oxide materials, for example, the most studied oxygen-deficient perovskites. Here, a systematic study of spinel ZnFex Co2-x O4 oxides (x = 0-2.0) toward the OER is presented and a highly active catalyst superior to benchmark IrO2 is developed. The distinctive OER activity is found to be dominated by the metal-oxygen covalency and an enlarged CoO covalency by 10-30 at% Fe substitution is responsible for the activity enhancement. While the pH-dependent OER activity of ZnFe0.4 Co1.6 O4 (the optimal one) indicates decoupled proton-electron transfers during the OER, the involvement of lattice oxygen is not considered as a favorable route because of the downshifted O p-band center relative to Fermi level governed by the spinel's cation deficient nature.