Unlocking the Transition of Electrochemical Water Oxidation Mechanism Induced by Heteroatom Doping

Abstract Heteroatom doping has emerged as a highly effective strategy to enhance the activity of metal‐based electrocatalysts toward the oxygen evolution reaction (OER). It is widely accepted that the doping does not switch the OER mechanism from the adsorbate evolution mechanism (AEM) to the lattice‐oxygen‐mediated mechanism (LOM), and the enhanced activity is attributed to the optimized binding energies toward oxygen intermediates. However, this seems inconsistent with the fact that the overpotential of doped OER electrocatalysts (<300 mV) is considerably smaller than the limit of AEM (>370 mV). To determine the origin of this inconsistency, we select phosphorus (P)‐doped nickel‐iron mixed oxides as…