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

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 & horbar;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 & horbar;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. A series of single-atom Co catalysts with different types of nitrogen species are synthesized to study the roles of metal- and nonmetal-bonded functionalities in Fenton-like reactions. Co & horbar;N coordination is optimal for peroxymonosulfate (PMS) adsorption to trigger electron transfer pathway, while graphitic N helps adsorb target micropollutant and acts as a secondary PMS adsorption site, synergistically promoting the degradation efficiency. image