Asymmetrically Coordinated Mn‐S1N3 Configuration Induces Localized Electric Field‐Driven Peroxymonosulfate Activation for Remarkably Efficient Generation of 1O2

Abstract Singlet oxygen ( 1 O 2 ) 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 O 2 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‐S 1 N 3 ), 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 O 2 production. Strikingly, an enhanced the local electric field caused by the dynamic inter‐transformation of the Mn coordination structure (Mn‐S 1 N 3 ↔ Mn‐N 3 ) can further downshift the 1 O 2 production energy barrier. Mn‐S 1 N 3 demonstrates 100% selective product 1 O 2 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 O 2 ‐AOPs catalysts for more selective and efficient decontamination applications.