Mn Doping at High‐Activity Octahedral Vacancies of γ‐Fe₂O₃ for Oxygen Reduction Reaction Electrocatalysis in Metal‐Air Batteries

γ-Fe₂O₃ with the intrinsic cation vacancies is an ideal substrate for heteroatom doping into the highly active octahedral sites in spinel oxide catalysts. However, it is still a challenge to confirm the vacancy location of γ-Fe₂O₃ through experiments and obtain enhanced catalytic performance by preferential occupation of octahedral sites for heteroatom doping. Here, a Mn-doped γ-Fe₂O₃ incorporated with carbon nanotubes catalyst was developed to successfully achieve preferential doping into highly active octahedral sites by employing γ-Fe₂O₃ as the precursor. Further, the vacancy in γ-Fe₂O₃ was only located on octahedral sites rather than tetrahedral ones, which was first proved by direct experimental evidence through the clarification doping sites of Mn. Notably, the catalyst shows outstanding activity towards oxygen reduction reaction with the half-wave potential of 0.82 V and 0.64 V vs. reversible hydrogen electrode in alkaline and neutral electrolytes, respectively, as well as the maximum power density of 179 mWcm^-2 and 403 mWcm^-2 for Mg-air batteries and Al-air batteries, respectively. It could be attributed to the synergistic effect of the doping Mn on octahedral sites and the substrate γ-Fe₂O₃ along with the modification of the adsorption/desorption properties for oxygen-containing intermediates as well as the optimization of the reaction energy barriers.