LAUSR

As the most promising alternative to platinum‐based catalysts for cathodic oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, further performance enhancement of Fe–N–C catalysts is highly expected to promote their wide application. In Fe–N–C catalysts, the single Fe atom forms a square‐planar configuration with four adjacent N atoms (D4h symmetry). Breaking the D4h symmetry of the FeN4 active center provides a new route to boost the activity of Fe–N–C catalysts. Herein, for the first time, the deformation of the square‐planar coordination of FeN4 moiety achieved by introducing chalcogen oxygen groups (XO2, X = S, Se, Te) as polar functional groups in the Fe–N–C catalyst is reported. The theoretical and experimental results demonstrate that breaking the D4h symmetry of FeN4 results in the rearrangement of Fe 3d electrons and increases spin moment of Fe centers. The efficient spin state manipulation optimizes the adsorption energetics of ORR intermediates, thereby significantly promoting the intrinsic ORR activity of Fe–N–C catalysts, among which the SeO2 modified catalyst lies around the peak of the ORR volcano plot. This work provides a new strategy to tune the local coordination and thus the electronic structure of single‐atom catalysts.