PO₆ geometric configuration unit enhanced electrocatalytic performance of Co₃O₄ in acidic oxygen evolution

It is challenging to develop high-efficient and stable nonprecious metal-based electrocatalyst for oxygen evolution reaction (OER) in acid for proton exchange membrane (PEM) water splitting. Herein, P atoms were introduced into the lattice of spinel Co₃O₄ (P-Co₃O₄) to replace with octahedral coordinated Co³⁺ via a hydrothermal process following a thermal treatment. The formation of PO₆ geometric configuration unit in Co₃O₄ can trigger electron rearrangement around Co ions, which resulted in the high-active Co²⁺ site on the surface, significantly decreasing the energy barrier of rate-determining step for OER. Moreover, the weaker covalency of the Co 3d-O 2p bond and higher formation energy of oxygen vacancy around Co²⁺ in P-Co₃O₄ inhibited the participation of lattice oxygen during OER process, enabling that P-Co₃O₄ can work stably in acidic media. The obtained P-Co₃O₄ afforded satisfying stability over 30 h in a PEM electrolysis device with an overpotential of 400 mV@10 mA/cm² in 0.1 M HClO₄.