Asymmetrically Coordinated Mn-S₁N₃ Configuration Induces Localized Electric Field-Driven Peroxymonosulfate Activation...

Singlet oxygen (¹O₂) species generated in peroxymonosulfate (PMS)-based advanced oxidation processes offer opportunities to overcome the low efficiency and secondary pollution limitations of existing AOPs, but efficient production of ¹O₂ via tuning the coordination environment of metal active sites remains challenging due to insufficient understanding of their catalytic mechanisms. Herein, an asymmetrical configuration characterized by a manganese single atom coordinated is established with one S atom and three N atoms (denoted as Mn-S₁N₃), which offer a strong local electric field to promote the cleavage of O─H and S─O bonds, serving as the crucial driver of its high ¹O₂ production. Strikingly, an enhanced the local electric field caused by the dynamic inter-transformation of the Mn coordination structure (Mn-S₁N₃ ↔ Mn-N₃) can further downshift the ¹O₂ production energy barrier. Mn-S₁N₃ demonstrates 100% selective product ¹O₂ by activation of PMS at unprecedented utilization efficiency, and efficiently oxidize electron-rich pollutants. This work provides an atomic-level understanding of the catalytic selectivity and is expected to guide the design of smart ¹O₂-AOPs catalysts for more selective and efficient decontamination applications.