Sp‐Hybridized Nitrogen as New Anchoring Sites of Iron Single Atoms to Boost the Oxygen Reduction Reaction

Abstract Carbon supported single‐atom catalysts with metal‐N x configuration are considered as one of the most efficient catalysts for the oxygen reduction reaction (ORR). However, most of the metal‐N x active sites are composed by pyridinic N at the defect locations of graphene‐like supports. Here, we employ graphdiyne (GDY) as a new carbon substrate to synthesize an iron (Fe) single atom catalyst (Fe−N−GDY), showing excellent catalytic performance. Benefitting from the abundant acetylenic bonds in GDY, sp‐N anchored metal atoms are created without forming defects. The sp‐N and OH ligands regulate the electronic structure of Fe atoms and optimize the adsorption energy of ORR intermediates on the active sites by reducing the electron local density of Fe atoms, which accelerates the reaction kinetics and promotes the ORR activity of Fe−N−GDY. Furthermore, the practical application of Fe−N−GDY is corroborated by its high power density and long‐term performance via assembling a zinc–air battery.