Interface and Polarization Engineering of ZIF‐67(Co)‐Based Heterojunctions for Selective Non‐Radical PMS Activation: Simultaneous Generation of 1O2 and Co(IV)=O for Efficient and Safe Water Remediation

Abstract The activation of peroxymonosulfate (PMS) via non‐radical pathways offers promising routes for efficient and selective degradation of emerging contaminants. However, conventional transition metal–organic frameworks (MOFs) primarily induce radical‐based processes, limiting their stability and selectivity under complex water matrices. A series of KNbO 3 /ZIF‐67(Co) heterojunctions (K@Z‐ x ) with interfacial Co─O─Nb bonds is constructed via piezoelectric polarization engineering. This unique bonding microenvironment reconfigures the electron density of Co(II) sites and optimizes PMS adsorption configurations. Co─O─Nb bridging shifts PMS activation from radical ( • OH and SO4 •− ) to dual non‐radical pathways, enabling simultaneous generation of singlet oxygen ( 1 O 2 ) and high‐valent cobalt‐oxo (Co(IV)═O) species. Theoretical calculations reveal reduced energy barriers for *SO 5 ─H formation and enhance electron delocalization at the heterointerface. Visible light and ultrasound co‐irradiations accelerate Co(III)/Co(II) cycling via piezoelectric field‐enhanced carrier separation, sustaining Co(IV)═O generation. The optimized K@Z‐2/PMS/Vis/US system achieves near‐complete tetracycline degradation within 1 min, with excellent selectivity, stability, and environmental tolerance. Toxicity evaluation confirms its low ecotoxicity, while life cycle assessment highlights its reduced energy consumption and environmental burden. This work pioneers atomic‐level coordination engineering of MOFs to steer PMS activation toward selective non‐radical pathways, offering a robust strategy for designing interference‐resistant wastewater pretreatment catalysts.