Atomic‐Level Engineered Cobalt Catalysts for Fenton‐Like Reactions: Synergy of Single Atom Metal Sites and Nonmetal‐Bonded Functionalities

Abstract Single atom catalysts (SACs) are atomic‐level‐engineered materials with high intrinsic activity. Catalytic centers of SACs are typically the transition metal (TM)–nonmetal coordination sites, while the functions of coexisting non‐TM‐bonded functionalities are usually overlooked in catalysis. Herein, the scalable preparation of carbon‐supported cobalt‐anchored SACs (CoCN) with controlled Co─N sites and free functional N species is reported. The role of metal‐ and nonmetal‐bonded functionalities in the SACs for peroxymonosulfate (PMS)‐driven Fenton‐like reactions is first systematically studied, revealing their contribution to performance improvement and pathway steering. Experiments and computations demonstrate that the Co─N₃C coordination plays a vital role in the formation of a surface‐confined PMS* complex to trigger the electron transfer pathway and promote kinetics because of the optimized electronic state of Co centers, while the nonmetal‐coordinated graphitic N sites act as preferable pollutant adsorption sites and additional PMS activation sites to accelerate electron transfer. Synergistically, CoCN exhibits ultrahigh activity in PMS activation for p‐hydroxybenzoic acid oxidation, achieving complete degradation within 10 min with an ultrahigh turnover frequency of 0.38 min⁻¹, surpassing most reported materials. These findings offer new insights into the versatile functions of N species in SACs and inspire rational design of high‐performance catalysts in complicated heterogeneous systems.