Tuning Fe Spin Moment in Fe–N–C Catalysts to Climb the Activity Volcano via a Local Geometric Distortion Strategy

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 ( D 4h symmetry). Breaking the D 4h symmetry of the FeN 4 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 FeN 4 moiety achieved by introducing chalcogen oxygen groups (XO 2 , 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 D 4h symmetry of FeN 4 results in the rearrangement of Fe 3 d 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 SeO 2 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.