Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling

Abstract Chemical upcycling that catalyzes waste plastics back to high‐purity chemicals holds great promise in end‐of‐life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state. This approach involves the synthesis of p‐Ru/SBA catalysts, in which Ru nanoparticles are uniformly distributed within the channels of an SBA‐15 support, using a precise impregnation method. The unique design of the p‐Ru/SBA catalyst has demonstrated significant improvements in catalytic performance for the conversion of polyethylene into high‐value liquid fuels, particularly diesel. The catalyst achieved a high solid conversion rate of 1106 g ⋅ g Ru −1 ⋅ h −1 at 230 °C. Comparatively, this catalytic activity is 4.9 times higher than that of a control catalyst, Ru/SiO 2 , and 14.0 times higher than that of a commercial catalyst, Ru/C, at 240 °C. This remarkable catalytic activity opens up immense opportunities for the chemical upcycling of waste plastics.