Atomically dispersed Mn–Nx catalysts derived from Mn‐hexamine coordination frameworks for oxygen reduction reaction

Abstract Metal‐organic frameworks recently have been burgeoning and used as precursors to obtain various metal–nitrogen–carbon catalysts for oxygen reduction reaction (ORR). Although rarely studied, Mn–N–C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis. Here, we developed a facile strategy for anchoring the atomically dispersed nitrogen‐coordinated single Mn sites on carbon nanosheets (MnNCS) from an Mn‐hexamine coordination framework. The atomically dispersed Mn–N 4 sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure. The optimized MnNCS displayed an excellent ORR performance in half‐cells (0.89 V vs. reversible hydrogen electrode (RHE) in base and 0.76 V vs. RHE in acid in half‐wave potential) and Zn–air batteries (233 mW cm −2 in peak power density), along with significantly enhanced stability. Density functional theory calculations further corroborated that the Mn–N 4 –C 12 site has favorable adsorption of *OH as the rate‐determining step. These findings demonstrate that the metal‐hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.