Structural and Electronic Descriptors of Catalytic Activity of Graphene‐Based Materials: First‐Principles Theoretical Analysis

Abstract Characteristic features of the d‐band in electronic structure of transition metals are quite effective as descriptors of their catalytic activity toward oxygen reduction reaction (ORR). With the promise of graphene‐based materials to replace precious metal catalysts, descriptors of their chemical activity are much needed. Here, a site‐specific electronic descriptor is proposed based on the p z (π) orbital occupancy and its contribution to electronic states at the Fermi level. Simple structural descriptors are identified, and a linear predictive model is developed to precisely estimate adsorption free energies of OH (Δ G OH ) at various sites of doped graphene, and it is demonstrated through prediction of the most optimal site for catalysis of ORR. These structural descriptors, essentially the number of ortho, meta, and para sites of N/B‐doped graphene sheet, can be extended to other doped sp 2 hybridized systems, and greatly reduce the computational effort in estimating Δ G OH and site‐specific catalytic activity.