Geometry‐Controlled Cooperativity at Binuclear Fe 2 –N 6 Sites Enables Selective Fe IV ═OGeneration for Durable Fenton‐Like Oxidation

ABSTRACT Single atom catalysts (SACs) are emerging as a promising platform for Fenton‐like water purification; however, their practical deployment is often constrained by the trade‐off between high intrinsic activity and long‐term stability. Here, we construct an N‐bridged binuclear architecture that pairs isolated Fe–N 4 sites into a precisely defined Fe 2 ─N 6 configuration on N‐doped carbon (Fe 2 ─N 6 /NC). This Fe─N─Fe architecture induces charge delocalization and regional polarization, strengthening interfacial electronic coupling and enabling cooperative dual‐site adsorption of peroxymonosulfate (PMS). As a result, PMS activation becomes thermodynamically favored and proceeds selectively via a high‐valent Fe IV ═O pathway, fundamentally distinct from the singlet‐oxygen‐dominated regime of conventional single‐atom sites (Fe─N 4 ). The Fe IV ═O species generated over the proximity dual site simultaneously accelerate pollutant degradation while suppressing demetalation, thereby securing both catalytic activity and operational durability. In the continuous‐flow reactor, Fe 2 ─N 6 /NC maintains stable performance over 14 days of operation. Life cycle assessment and real‐world hospital wastewater treatment further demonstrate concurrent organic removal, reduced toxicity, and lower environmental impact. This work proposes binuclear site engineering as a general strategy to overcome the catalytic activity–stability dilemma in SAC‐based Fenton‐like systems, advancing their translation toward scalable, sustainable systems for real‐world water purification.