Regulating the Electronic Synergy of Asymmetric Atomic Fe Sites with Adjacent Defects for Boosting Activity and Durability toward Oxygen Reduction

Abstract The oxygen reduction reaction (ORR) plays a fundamental role in sustainable energy technologies. However, the creation of non‐precious metal electrocatalysts with high ORR activity and durability under all pH conditions is of great significance but remains challenging. Herein, the aim is to overcome this challenge by creating a Fe single atom catalyst on a 2D defect‐containing nitrogen‐doped carbon support (Fe 1 /DNC) via a microenvironment engineering strategy. Microkinetic modeling reveals that FeN 4 (OH) moieties are the real active sites under reaction conditions. Due to the synergistic promotion effect of denser accessible FeN 4 (OH) moieties and defect‐induced electronic properties, Fe 1 /DNC catalyst achieves extraordinary ORR activity under alkaline, acidic, and neutral conditions, with half‐wave potentials of 0.95, 0.82, and 0.70 V, respectively. Moreover, a negligible performance decay is observed with this Fe catalyst in stability and methanol tolerance tests. Zn‐air battery employing Fe 1 /DNC delivers remarkable peak power density and long‐term operational durability. Theoretical analysis provides compelling evidence that the defects adjacent to FeN 4 (OH) moieties can endow an inductive effect to reshape electronic properties to balance the OOH* formation and OH* reduction. This work offers insight into the regulation of asymmetric coordination structure and electronic properties of metal sites for boosting electrocatalytic activity and stability.