Insights into singlet oxygen generation and electron-transfer process induced by a single-atom Cu catalyst with saturated Cu-N4 sites

Persulfate-based nonradical oxidation processes are appealing in water treatment for the efficient and selective degradation of trace contaminants in complex water matrices. However, there is still lacking of systematic understanding of the relationship between multiple nonradical pathways and the active sites of catalyst. Herein, a single-atom Cu catalyst with saturated Cu-N₄ sites on a carbon substrate (SA-Cu-NC) was constructed to activate peroxymonosulfate (PMS), which exhibited high catalytic performance and selectivity for pollutant degradation in different water conditions. Combined with the results of density functional theory (DFT) calculations, the electron-rich area around Cu site and the electron-poor area around C site in the saturated Cu-N₄ configuration could efficiently adsorb and activate PMS, which promoted pollutant degradation through the oxidation of singlet oxygen (¹O₂) and electron transfer process, respectively. This study advances the understanding of the saturated coordination structure of metals and the superiority of multiple nonradical pathways in wastewater treatment.