Asymmetric Coordination Engineering of MXene‐Based Metal Arrays for Oriented Generation of High‐Valent Metal‐Oxo Species from Peroxymonosulfate for Fast Water Decontamination

Abstract High‐valent metal‐oxo species (HVMOS) are appealing for water purification because they break the activity‐selectivity trade‐off of conventional radical‐based advanced oxidation processes. However, oriented HVMOS generation via heterogeneous reactions has been challenging because of the difficulty in the precise design of favourable and high‐loading active sites. Herein, a facile asymmetric oxygen‐containing coordination strategy was developed to activate inert metal arrays in V 2 C MXene, which could effectively activate peroxymonosulfate (PMS) to selectively generate HVMOS. The unique ultrashort‐range distance between neighboring V sites (2.36 Å) in MXene with asymmetric coordination generated a distinctive topological sympathetic electric field (TSEF), which enabled efficient PMS activation and ultrafast oxidation of water pollutants ( k obs = 1498.33 min −1 M −1 ). Mechanistic studies revealed a new single‐electron‐transfer pathway from PMS to V 2 C through short‐range bimetallic oxygen bridges, significantly reducing the energy barrier of HVMOS generation promoted by TSEF. The nonradical system exhibited robust anti‐interference capacity and excellent stability in different real water matrices and long‐term operations.