Insights into Correlation among Surface‐Structure‐Activity of Cobalt‐Derived Pre‐Catalyst for Oxygen Evolution Reaction

Rational design of unique pre‐catalysts for highly active catalysts toward catalyzing the oxygen evolution reaction (OER) is a great challenge. Herein, a Co‐derived pre‐catalyst that allows gradual exposure of CoOOH that acts as the active center for OER catalysis is obtained by both phosphate ion surface functionalization and Mo inner doping. The obtained catalyst reveals an excellent OER activity with a low overpotential of 265 mV at a current density of 10 mA cm−2 and good durability in alkaline electrolyte, which is comparable to the majority of Co‐based OER catalysts. Specifically, the surface functionalization produces lots of Co‐PO4 species with oxygen vacancies which can trigger the surface self‐reconstruction of pre‐catalyst for a favorable OER reaction. Density functional theory calculations reveal that the Mo doping optimizes adsorption‐free energy of *OOH formation and thus accelerates intrinsic electrocatalytic activity. Expanding on these explorations, a series of transition metal oxide pre‐catalysts are obtained using this general design strategy. The work offers a fundamental understanding toward the correlation among surface‐structure‐activity for the pre‐catalyst design. Unravelling the intrinsic mechanism, especially what the “true” catalyst for the oxygen evolution reaction (OER) is, is still highly challenging. Herein, a Co‐based pre‐catalyst is designed that enables rational control over exposure of true active CoOOH centers by in situ self‐reconstruction to deliver excellent electrocatalytic performance, representing one of the state‐of‐the‐art OER catalysts.