Oxygen‐Vacancy‐Driven Electron Transfer Enables Synergistic Peroxymonosulfate Activation on Co 3 O 4 Hollow Nanocubes

ABSTRACT Conventional Co 3 O 4 catalysts are limited by sluggish electron transfer, dominant radical pathways that suffer from interference in complex water matrices; shifting toward non‐radical pathways via oxygen‐vacancy engineering and hollow nanocube (HNC) architecture offers a promising strategy that enhances selectivity, stability, and anti‐interference capability. Therefore, oxygen‐vacancy‐engineered Co 3 O 4 HNCs (V o ‐Co 3 O 4 HNCs) were designed via a ZIF‐67‐templated etching–oxidation–reduction route that couples structural precision with defect control. The optimized 38 %–V o sample exhibits a rare balance between activity and stability, achieving 98.7 % tetracycline removal within 5 min and maintaining over 96 % efficiency from pH 3–11 and real‐water matrices. Spectroscopic and electrochemical analyses reveal that moderate V o enrichment tunes the Co 2+ /Co 3+ valence equilibrium and accelerates charge transport, thereby promoting a synergistic radical (SO 4 •− , •OH, O 2 •− ) and non‐radical ( 1 O 2 , electron‐transfer) oxidation network. Predominant 1 O 2 and high‐valent Co (IV) = O species endow the system with exceptional anti‐interference capability, low charge‐transfer resistance (3.26 Ω), and long‐term stability with negligible Co leaching. This work reveals a clear defect–structure–activity correlation for PMS activation and demonstrates that coupling rational morphology with precise oxygen‐vacancy modulation enables fast, selective, and recyclable degradation of emerging organic pollutants, providing a general blueprint for defect‐orchestrated transition‐metal‐oxide catalysts in sustainable environmental remediation.