Sabatier‐Adjusted d‐Band Centers of Scalable Asymmetric Iron Sites toward Dynamic Nonradical Network for Fast Mineralization with Low‐Amount Oxidant

Asymmetric iron single‐atom catalysts with Sabatier‐adjusted d‐band centers overcome the inherent limitations of peroxymonosulfate (PMS) activation by establishing a synergistic nonradical pathway network, achieving exceptional pollutant mineralization (≈85%) at only one‐tenth conventional PMS dosage. The stability and scalability offer a transformative solution for sustainable wastewater treatment. Abstract Nonradicals relying on peroxymonosulfate (PMS) activation face inherent kinetic and thermodynamic limitations in pollutant mineralization. This is overcome using asymmetric iron single‐atom catalysts (Fe‐SACs) with Sabatier‐adjusted d‐band centers that establish a synergistic nonradical network of pathways, achieving exceptional mineralization (≈85%) with only one‐tenth conventional PMS dosage. Direct coordination of high‐loading Fe (≈10 wt.%) with controllable p‐block elements (S, P, B) simultaneously facilitates electron‐transfer pathways and selective generation of nonradicals (1O2, FeIV = O). Compared to symmetric Fe1‐N4, they enhance pollutant removal and mineralization by 4.2‐fold and 6.3‐fold, respectively. Atomic‐resolution characterization and theory reveal that the dopant's electronegativity governs the electronic perturbations of the Fe center, dictating PMS adsorption. Pollutant‐specific charge transfer and adsorption affinity critically determine nonradical activity. The asymmetric Fe SACs exhibit excellent stability and applicability in complex matrices and continuous‐flow wastewater treatment. This work provides a transformative strategy to overcome fundamental limitations in advanced oxidation processes and a design framework for sustainable environmental technologies. Asymmetric iron single-atom catalysts with Sabatier-adjusted d -band centers overcome the inherent limitations of peroxymonosulfate (PMS) activation by establishing a synergistic nonradical pathway network, achieving exceptional pollutant mineralization (≈85%) at only one-tenth conventional PMS dosage. The stability and scalability offer a transformative solution for sustainable wastewater treatment. Abstract Nonradicals relying on peroxymonosulfate (PMS) activation face inherent kinetic and thermodynamic limitations in pollutant mineralization. This is overcome using asymmetric iron single-atom catalysts (Fe-SACs) with Sabatier-adjusted d -band centers that establish a synergistic nonradical network of pathways, achieving exceptional mineralization (≈85%) with only one-tenth conventional PMS dosage. Direct coordination of high-loading Fe (≈10 wt.%) with controllable p -block elements (S, P, B) simultaneously facilitates electron-transfer pathways and selective generation of nonradicals ( 1 O 2, Fe IV = O). Compared to symmetric Fe 1 -N 4, they enhance pollutant removal and mineralization by 4.2-fold and 6.3-fold, respectively. Atomic-resolution characterization and theory reveal that the dopant's electronegativity governs the electronic perturbations of the Fe center, dictating PMS adsorption. Pollutant-specific charge transfer and adsorption affinity critically determine nonradical activity. The asymmetric Fe SACs exhibit excellent stability and applicability in complex matrices and continuous-flow wastewater treatment. This work provides a transformative strategy to overcome fundamental limitations in advanced oxidation processes and a design framework for sustainable environmental technologies. Advanced Science, EarlyView.