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

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 V₂C 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^-1M^-1). Mechanistic studies revealed a new single-electron-transfer pathway from PMS to V₂C 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.