Construction of Fluorenone‐Functionalized Porous Organic Polymers for Visible‐Light‐Driven Oxidative Cleavage of Polystyrene to Acid

ABSTRACT Polystyrene (PS) is one of the most widely used plastics worldwide, but its degradation rate is low, and the upcycling effect is not ideal. Herein, this study reports a novel metal‐free porous organic polymer photocatalyst, V‐POPs (synthesized based on 9‐fluorenone and vinyl‐POSS monomers), which can efficiently catalyze the aerobic oxidation degradation of PS under ambient temperature and pressure through blue light (455 nm) irradiation. After 12 h of reaction, PS was converted into formic acid (96%), benzoic acid (67%), and acetophenone (4%). Mechanism studies show that this catalyst can induce oxygen (O 2 ) to produce reactive oxygen species ( • O 2 − and 1 O 2 ) to dominate the oxidation process, break the PS backbone through a radical pathway to generate oxygen‐containing intermediates, and finally convert them into organic acid products. This strategy provides a new approach for the green chemical upcycling of waste PS.