Synergistic Coordination in Cu Single‐Atom Catalysts Enhances High‐Valent Copper‐Oxo Species for Efficient PMS Activation

Abstract In the domain of heterogeneous catalytic activation of peroxymonosulfate (PMS), high‐valent metal‐oxo (HVMO) species are widely recognized as potent oxidants for the abatement of organic pollutants. However, the generation selectivity and efficiency of HVMO are often constrained by stringent requirements for catalyst adsorption sites and electron transfer efficiency. In this study, a single‐atom catalyst, Cu SA /CNP&S, is synthesized featuring multiple types (planar/axial) of heteroatom coordination via an H‐bond‐assisted self‐assembly strategy. It is confirmed that CuN 3 active centers with axial S coordination are uniformly distributed in a carbon matrix modified by planar P atoms. Cu SA /CNP&S activated PMS to selectively generate Cu (III) ═OH species as the primary reactive oxygen species (ROS). The pseudo‐first‐order kinetic rate for bisphenol A degradation reached 1.51 min −1 , a 17.57‐fold increase compared to the unmodified Cu SA /CN catalyst. Additionally, the Cu SA /CNP&S catalyst demonstrates high efficiency and durability in removing contaminants from various aqueous matrices. Theoretical calculations and experimental results indicate that the intrinsic electric field generated by distal planar P atoms enhances electron transfer efficiency within the carbon matrix. Meanwhile, axial S coordination elevates the d‐band center and tunes the e g * band broadening of Cu, thereby enhancing the adsorption selectivity for the terminal oxygen of PMS. This multitype coordination synergistically mitigates the issues of low selectivity and yield of HVMO species.