Controlling ¹ O ₂ Evolution by Mixed‐Spin‐Orbital Engineering With a Waste‐PET‐Derived‐MOF on Kevlar for Enhanced Water Decontamination

Peroxymonosulfate (PMS) is a versatile oxidant for wastewater treatment; however, achieving both high PMS utilization efficiency and controllable, selective activation toward singlet oxygen ( 1 O 2 ) in complex wastewater remains a challenge. Here, we fabricate a waste polyethylene terephthalate (PET)‐derived MOF‐on‐fiber heterostructure (W‐Co‐MOF@Kevlar) for PMS adsorption‐activation and 1 O 2 generation, which enables sustained, near‐complete pollutant removal with high mineralization efficiency and strong tolerance to common matrix interferences (ions and humic acid) in realistic waters. The composite catalysts markedly enhance the degradation performance of electron‐rich micropollutants by promoting 1 O 2 evolution (e.g., delivering a metal‐atom utilization rate (MAUR) of (1.6‐1.8) × 10 5 mg CIP mol metal −1 for ciprofloxacin (CIP) degradation, which is 50 times higher than that of LS‐only Co‐MOF). We demonstrate that spin‐orbital engineering within this PET‐derived heterostructure induces Co spin‐orbital level splitting, promoting a partial electronic population shift from low‐spin to high‐spin states. The resultant non‐degenerate orbitals shift the energy levels upward, activating additional 3D orbital electronic states. This electronic structure optimization redirects the PMS activation pathway, favoring efficient 1 O 2 generation. Furthermore, utilizing waste PET as a feedstock and securing it via covalent bonding to the fiber substrate endows the W‐Co‐MOF@Kevlar catalyst with enhanced environmental sustainability and significant potential for practical industrial application.