Second‐Shell Coordination Environment Modulation for MnN₄ Active Sites by Oxygen Doping to Boost Oxygen Reduction Performance

As a category of transition metal-nitrogen-carbon (M-N-C) catalysts, Mn-based single-atom catalysts (SACs) are considered as promising non-precious metal catalysts for stable oxygen reduction reaction (ORR) due to their Fenton-inactive character (versus Fe) and more abundant earth reserves (versus Ni, Co). However, their ORR activity is unsatisfactory. Besides, the structure-activity relationship via tuning the coordination environment of the second coordination shell for transition metal single sites is still elusive. Here, a Mn SAC with O doping in the second-shell of atomically dispersed Mn centers (MnSAC-O/C) as highly efficient and stable ORR catalyst is developed. X-ray absorption spectroscopy combined with theoretical calculations verifies the O doping in the second-shell of Mn center, and reveals the distortion of local environment of Mn center in the MnSAC-O/C. The MnSAC-O/C exhibits high ORR performance with a half-wave potential of 0.898 V, superior to MnSAC-C, commercial Pt/C and most reported non-noble metal-based SACs. More importantly, MnSAC-O/C based zinc-air batteries (ZABs) deliver outstanding durability with stable operation exceeding 930 h. Theoretical calculations confirm that O doping breaks the symmetry of charge distribution of MnN₄ active center and facilitates OH* desorption, thus attributing to the promoted ORR activity.