Unveiling the Activity Origin of Electrochemical Oxygen Evolution on Heteroatom‐Decorated Carbon Matrix

Abstract Chemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure‐performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high‐electronegative F and N co‐doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic‐N (P y −N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential‐limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential‐limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER.