Role of Defects in Reversible Surface Restructuring and Activity of Co₃O₄Oxygen Evolution Electrocatalysts

Overcoming the slow kinetics of the oxygen evolution reaction at the anode is a key challenge for the production of hydrogen via electrolysis. This reaction operates at very positive potentials, where the electrocatalyst is exposed to highly oxidative conditions and prone to potential-dependent transformation of the near-surface region. While substantial evidence for such surface restructuring exists, its extent and relevance for the catalyst’s activity are unclear. We address this topic for the case of Co₃O₄, one of the best-known electrocatalysts exhibiting surface restructuring, by studies of epitaxial (111)-ordered electrodeposited films with combined operando X-ray surface diffraction and absorption spectroscopy, electrochemical impedance spectroscopy, and electrochemical measurements on rotating disk electrodes. Comparison of the as-prepared and annealed state of the same samples, which both are stable even under long-term oxygen evolution conditions, provides clear insight into the role of surface defects. Our results show that defect-free annealed Co₃O₄(111) surfaces are structurally stable over a wide potential range and hydroxylate via adsorption at surface oxygen and Co sites. Potential-induced surface restructuring of the Co₃O₄ lattice occurs only in the presence of surface defects, leading to the formation of the well-known nanometer-thick oxyhydroxide skin layer. The presence of this skin layer promotes oxygen evolution at low overpotentials but results in higher Tafel slopes. As a result, highly ordered Co₃O₄(111) surfaces are more active at high current densities than defective Co₃O₄ surfaces that undergo surface restructuring. These results highlight that strategies for catalyst surface defect engineering need to be application-oriented.