Atomically dispersed Mn atoms coordinated with N and O within an N-doped porous carbon framework for boosted oxygen reduction catalysis

Abstract

Developing efficient and robust catalysts to replace Pt group metals for the oxygen reduction reaction (ORR) is conducive to achieving highly efficient energy conversion. Here, we develop a general ion exchange strategy to construct highly efficient ORR catalysts consisting of various atomically dispersed metal atoms anchored on N-doped porous carbon (M–SAs/NC) to investigate the atomic structure–catalytic activity relationship. The structure characterization results demonstrated that the achieved atomic structure varied due to the presence of different metal centers. Mn–SAs/NC consists of MnN₃O₁ centers, in which the Mn single atoms are stabilized by 3 N and 1 O. In contrast, the center metals in Fe-/Co-/Cu single-atom catalysts are coordinated by merely N atoms. Mn–SAs/NC delivers superior performance for the ORR with a half-wave potential (E_1/2) of 0.91 V vs. RHE in 0.1 M KOH solution, outperforming that of the commercial Pt/C catalyst and the control Fe-/Co-/Cu single-atom catalysts. Furthermore, Mn–SAs/NC also shows excellent methanol tolerance and stability up to 5000 cycles. Density functional theory (DFT) calculations reveal that Mn single atom catalysts with MnN₃O₁ centers contributed to the superior ORR performance with lower energy barriers and optimized adsorption capacity of intermediates. These findings provide insights into the design and development of specific coordinated structures of atomically dispersed catalysts to facilitate the practical applications of energy conversion.