Precise Mo‐Fe Dual‐Atom Coordination Regulates the Selective Generation of Non‐Free Radicals in Peroxymoncosulfate Activation

Abstract Non‐radical species exhibit selective degradation of electron‐rich pollutants, yet their practical utility is hampered by low yields and uncontrolled speciation arising from competing radical formation. Herein, a novel FeMo─N─C catalyst is designed to simultaneously activate peroxymonosulfate and steer reaction pathways toward non‐radical oxidation by reducing the formation energy of non‐radical species, thus enabling selective degradation of electron‐donating organic contaminants. The catalyst achieves complete degradation of 50 mg L −1 2,4 dichlorophenol within 12 min, exhibiting a first‐order kinetic constant of 0.587 min −1 a 20.67 fold enhancement compared to the Fe─N─C/PMS system. Experimental results identified singlet oxygen ( 1 O 2 ) as the predominant reactive oxygen species. The incorporation of Mo not only promotes the generation of non‐radical species but also accelerates the Fe 3+ /Fe 2+ cycling, thereby improving both catalytic efficiency and reusability. Density functional theory calculations reveal that the introduction of Mo modulates the d‐band center of Fe sites and optimizes charge distribution, ultimately regulating non‐radical pathway formation. Thermodynamic analysis further demonstrates that the FeMo─N─C system possesses a lower energy barrier for 1 O 2 generation compared to Fe─N─C, favoring selective 1 O 2 production. These findings can guide the rational design of robust single‐atom catalysts toward the selective and controllable generation of non‐radical species with high yield.