Non‐planar Nest‐like [Fe2S2] Cluster Sites for Efficient Oxygen Reduction Catalysis

Abstract Metal‐nitrogen‐carbon catalysts, as promising alternative to platinum‐based catalysts for oxygen reduction reaction (ORR), are still highly expected to achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed the non‐planar nest‐like [Fe 2 S 2 ] cluster sites in N‐doped carbon plane. Adjacent double Fe atoms effectively weaken the O−O bond by forming a peroxide bridge‐like adsorption configuration, and the introduction of S atoms breaks the planar coordination of Fe resulting in greater structural deformation tension, lower spin state, and downward shifted Fe d‐band center, which together facilitate the release of OH* intermediate. Hence, the non‐planar [Fe 2 S 2 ] cluster catalyst, with a half‐wave potential of 0.92 V, displays superior ORR activity than that of planar [FeN 4 ] or [Fe 2 N 6 ]. This work provides insights into the co‐regulation of atomic composition and spatial configuration for efficient oxygen reduction catalysis.