Coordination Reconstruction Enhanced Synergistic Nonradical Oxidation Pathways in Cobalt Single‐Atom Catalysts for Sustained Pollutant Destruction

Abstract Limited synthetic efficiency and high costs constrain industrial production of single‐atom catalysts (SACs) despite their superior catalytic performance. We report a scalable and economical solid‐state pyrolysis strategy for cobalt single‐atom catalysts (Co‐SACs) costing ∼35 kg −1. Hydrothermal O‐substitution precisely engineers the coordination environment from Co‐N3O1 to Co‐N2O2. The upshifted d‐band center and enhanced electron delocalization of Co‐N2O2 decrease electron density at the Co site, strengthening peroxymonosulfate (PMS) adsorption. Electron paramagnetic resonance, probe experiments, and electrochemical tests synergistic confirmed that Co‐N2O2 significantly promotes nonradical processes, including the generation of singlet oxygen, high‐valent metal oxo species, and electron transfer processes. The resultant Co‐N2O2 catalyst achieved over 98% degradation of high‐concentration sulfamethoxazole (100 mg L −1) within 10 min. The kilogram‐scale Co‐N2O2 (kg‐Co‐N2O2) demonstrated outstanding efficiency in treating landfill leachate (2548 mg L −1 TOC removal) and preeminent stability in 14 cycles and 10 h membrane dynamic experiments. This work provides both fundamental elucidation into coordination engineering and a practical solution for large‐scale production of SACs in environmental remediation.