B‐N Co‐Doped Graphene: Stability and Catalytic Activity in Oxygen Reduction Reaction – A Theoretical Insight

Abstract We systematically investigated the stable configurations and catalytic activity in the Oxygen Reduction Reaction (ORR) of graphene co‐doped with boron and nitrogen (B‐N) using first‐principles methods. Compared to single B/N doping, co‐doping with BN is energetically favored. We found that intermediate species of ORR process adsorb on boron atoms, which act as catalytic sites. The presence of neighboring nitrogen atoms around boron plays a crucial role in modulating the catalytic activity of boron. For the same adsorption configuration, the adsorption energy of the adsorbate increases with the number of neighboring nitrogen atoms around boron and generally correlates positively with the number of electrons gained by the adsorbate. Regarding the catalytic activity of ORR, excessively strong adsorption of adsorbates impedes their hydrogenation. The best substrates for ORR catalytic activity are B‐N‐graphene and N‐B2‐graphene, with the rate‐determining step being the hydrogenation of *OO and overpotentials of 0.49 V and 0.54 V, respectively.