Self‐optimizing mixed metal oxides represent a novel class of electrocatalysts for the advanced oxygen evolution reaction (OER). Here, we report self‐assembled cobalt tungsten oxide nanostructures on a lab‐synthesized copper oxide substrate through a single‐step deposition approach. The resulting composite exhibits remarkable self‐optimization behavior, shown by significantly reduced overpotentials and enhanced current densities, accompanied with substantial increase in OER kinetics, electrocatalytically active surface area, surface wettability, and electrical conductivity. Under operating conditions, interfacial restructuring of the electrocatalyst reveals the in situ formation of oxidized cobalt species as the true active site. Complementary density functional theory (DFT) calculations further demonstrate the formation of *OOH intermediate as the rate‐determining step of OER, and highlight the adaptive binding of oxygen intermediates, which transitions from tungsten to cobalt site during OER process. Our study provides a fundamental understanding of the self‐optimization mechanism and advances the knowledge‐driven design of efficient water‐splitting electrocatalysts.
Progressively enhanced oxygen evolution is achieved by self-optimization of cobalt tungsten oxide deposited on lab-synthesized copper oxide substrate. Experimental data proved dynamic compositional / structural evolution while theoretical calculation revealed active site adaptation. The strategic design concept could strengthen the emergence of self-improved electrocatalysts for a wide range of challenging energy conversion and storage reactions.
