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

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.