SMSI-induced charge transfer for selective hydrogenolysis of polyolefins

The in-depth mechanism of the emerging Ru-catalyzed polyolefin hydrogenolysis remains unclear. Here, we overcome this challenge by constructing a strong metal-support interaction (SMSI) system based on Ru/TiO2 catalysts. With the increase of SMSI intensity, electrons are transferred from the TiOx capping layer to the Ru species. This effect facilitates the key steps of hydrogenation/desorption, while having little effect on the dehydrogenation and C-C cracking elementary reactions. As a result, the catalyst with higher hydrogenation capability prone to proceed hydrogenation and desorption step, thus suppressing cascade C-C cracking and avoiding the production of low value methane. The catalyst with the strongest SMSI effect exhibits a liquid fuel yield of 89.4% at similar to 100% solid conversion. The SMSI effect also enables the catalysts with superior stability, so it can also efficiently upcycle commercial polyolefins. This work provides an in-depth understanding of the effects of metal-support interactions on polyolefin hydrogenolysis and paves the way for catalyst design.