Disordered, Sub-Nanometer Ru Structures on CeO2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

Nondegradable polyolefin plastics pose severe environmental threats and thus demand efficient upcycling technologies. In this work, we discovered that low-loading (≤0.25 wt %) Ru/CeO2 exhibits remarkable catalytic performance in the hydrogenolysis of polypropylene (PP), polyethylene (PE), and n-C16H34 that is superior to high-loading (≥0.5 wt %) Ru/CeO2. They possess high PP conversion efficiency (sevenfold increase over current literature reports), low selectivity toward undesired CH4, and good isomerization ability. In the low-loading range, the intrinsic activity of Ru in PP hydrogenolysis increases as the particle size decreases, opposite of the trend in the high-loading range. Detailed characterization revealed that the abrupt changes in catalytic behaviors coincide with Ru species transitioning from well-defined to highly disordered structures in the low-loading domain. The disordered Ru species were shown to be sub-nanometer in size and cationic. Mechanistically, the regioselectivity and the rate dependence on hydrogen pressure of C–C bond cleavage are different on low- and high-loading Ru/CeO2, both explained by the higher coverage of adsorbed hydrogen (*H) on low-loading Ru/CeO2. This work reveals the remarkable catalytic performance of highly disordered, sub-nanometer, cationic Ru species in polyolefin hydrogenolysis, opening immense opportunities to develop effective, selective, and versatile catalysts for plastic upcycling.