Confined Isomerization Enables Solar-Thermal Upcycling of Polyolefins into High-Octane Gasoline.

Upcycling polyolefin waste into liquid fuels through hydrogenolysis holds great promise for advancing a circular carbon economy. However, extensive skeletal isomerization crucial for high-octane gasoline production remains a fundamental and unresolved limitation. Herein, we introduce a self-confined adsorption-configuration strategy that enables isomerization during polyolefin hydrogenolysis. By enforcing single-point adsorption on isolated Ir sites, β-scission intermediates gain the geometric freedom necessary for carbocation rearrangements, ultimately enabling the direct production of high-octane gasoline under solar-thermal conditions. In addition to promoting internal C-C bond rearrangement, the confined adsorption mode suppresses terminal cracking pathways. The Ir SA/WO3 catalyst achieves 92% conversion of polyolefin waste to liquid hydrocarbons while nearly eliminating methane production. Overall, this work advances a practical route for upcycling waste plastics into valuable energy products, contributing to a more closed-loop and carbon-efficient anthropogenic carbon cycle.