Coordination-Engineered Fe Single Atoms Enable Synergistic PVC Upcycling into Fuel-Range Hydrocarbons via Fenton-Like Pathway.

Poly(vinyl chloride) (PVC) poses a persistent environmental challenge due to its high chlorine content and additive-mediated recalcitrance. Herein, we report an N,O-dual-coordinated iron single-atom catalyst (Fe-N2O2-hCN) integrated with palladium nanoparticles (Pd NPs) for efficient hydrothermal Fenton-like upcycling of PVC into fuel-range hydrocarbons. The asymmetric Fe-N2O2 configuration modulates the electronic structure of Fe centers, promoting H2O2 activation and hydroxyl radical generation for efficient C-Cl and C-C bond cleavage under mild conditions, outperforming the conventional Fe-N4 catalyst. The bifunctional Pd NPs/Fe-N2O2-hCN system achieves high PVC degradation efficiency (97.38%) and near-complete dechlorination, while selectively hydrogenating depolymerized intermediates into fuel-range alkanes (C3-C20) with a high selectivity (86.01%). Mechanistic studies reveal enhanced electron transfer and a lowered energy barrier for H2O2 dissociation, with Pd NPs generating reactive hydrogen species for olefin saturation. Life cycle assessment (LCA) demonstrates a 77% reduction in carbon emissions and significantly lower eco-costs than incineration. This work provides a coordination-engineered platform for converting hazardous plastic waste into valuable fuels, advancing a circular plastic economy.