Covalent‐Organic Framework‐Manipulated Multi‐Reactant Activation Enables Polystyrene Electrodegradation in Tandem With Over‐Oxidation Product Upgrading

ABSTRACT Polystyrene (PS) waste is exceptionally difficult to chemically degrade under environmental conditions, and the high‐value utilization of low‐value C 1 products generated during the process has never been achieved. Herein, we constructed a metalloporphyrin–anthracene sp 2 covalent‐organic framework (COF) electrocatalyst, TAPP‐Fe III ‐An , which displays high structural stability and outstanding capability in activating O 2 and multi‐reactants. This enables it to effectively electro‐degrade PS into high‐value benzoyl products (yield, 23.2%, M w residue 0.3%) and re‐convert 20% of C 1 products into high‐value 1‐formyl‐1,2,3,4‐tetrahydroquinoline (anticancer drug intermediate) with 9.4% yield, through a tandem quinoline carbonylation reaction. This breaks the traditional dilemma where PS degradation produces low‐value byproducts that are difficult to re‐utilize. Electrochemical experiments combined with theoretical calculations reveal that the valence tautomerism (Fe II –Fe III –Fe IV ) of metal center and active An ligand endow TAPP‐Fe III ‐An catalyst with the ability to activate O 2 (generating 1 O 2 , •O 2 − , and •OH) and multi‐reactants (PS and CO), thus enabling efficient PS electrodegradation (to benzoyl products) in tandem with low‐value C 1 products carbonylation (to anticancer drug intermediate). In this process, the generated C 1 products (HCOOH, CO) were re‐activated by TAPP‐Fe III centers, and then react with 1,2,3,4‐tetrahydroquinoline for high‐value conversion. This work pioneers a tandem conversion strategy for PS waste degradation and low‐value C 1 products upgrading.