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

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 pz (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 (ΔGOH) 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 sp2 hybridized systems, and greatly reduce the computational effort in estimating ΔGOH and site‐specific catalytic activity. Structural and electronic descriptors are identified to predict the site‐specific activity of doped graphene. Using the number of dopants that lie at ortho, para and meta positions relative to the active site, free energy of OH binding at that site can be estimated. Electronic origin of the activity of graphene‐based catalysts is traced to the site‐specific pz orbital occupancy.