Asymmetrically Coordinated Mn-S1 N3 Configuration Induces Localized Electric Field-Driven Peroxymonosulfate Activation for Remarkably Efficient Generation of 1 O2

Abstract

Singlet oxygen (¹ O₂ ) 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 ¹ O₂ 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-S₁ N₃ ), 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 ¹ O₂ production. Strikingly, an enhanced the local electric field caused by the dynamic inter-transformation of the Mn coordination structure (Mn-S₁ N₃ ↔ Mn-N₃ ) can further downshift the ¹ O₂ production energy barrier. Mn-S₁ N₃ demonstrates 100% selective product ¹ O₂ 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 ¹ O₂ -AOPs catalysts for more selective and efficient decontamination applications.

Keywords: Mn-S1N3; peroxymonosulfate; selective oxidation; singlet oxygen; water treatment.