The development of technologies to recycle polyethylene (PE) and polypropylene (PP), globally the two most produced polymers, is critical to increase plastic circularity. Here, we show that 5 wt % cobalt supported on ZSM-5 zeolite catalyzes the solvent-free hydrogenolysis of PE and PP into propane with weight-based selectivity in the gas phase over 80 wt % after 20 h at 523 K and 40 bar H2. This catalyst significantly reduces the formation of undesired CH4 (≤5 wt %), a product which is favored when using bulk cobalt oxide or cobalt nanoparticles supported on other carriers (selectivity ≤95 wt %). The superior performance of Co/ZSM-5 is attributed to the stabilization of dispersed oxidic cobalt nanoparticles by the zeolite support, preventing further reduction to metallic species that appear to catalyze CH4 generation. While ZSM-5 is also active for propane formation at 523 K, the presence of Co promotes stability and selectivity. After optimizing the metal loading, it was demonstrated that 10 wt % Co/ZSM-5 can selectively catalyze the hydrogenolysis of low-density PE (LDPE), mixtures of LDPE and PP, as well as postconsumer PE, showcasing the effectiveness of this technology to upcycle realistic plastic waste. Cobalt supported on zeolites FAU, MOR, and BEA were also effective catalysts for C2–C4 hydrocarbon formation and revealed that the framework topology provides a handle to tune gas-phase selectivity.

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste to liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal C–C bond scission. In this study, a variety of catalysts were investigated for the reductive deconstruction of polyethylene (PE) and polypropylene (PP) to identify supports that promote nonterminal C–C bond scission. We found that Ru nanoparticles supported on Brønsted-acidic zeolites with the faujasite (FAU) and Beta (BEA) topologies were highly active for the cleavage of C–C bonds in PE and PP, exhibiting improved liquid yields and suppressed methane formation. For the deconstruction of PE, supporting ruthenium nanoparticles (5 wt %) on FAU increased the yields of liquid alkanes to 67% compared to 33% over an inert silica support (5 wt % Ru/SiO2) at 200 °C, 16 h, under 30 bar of H2. A dramatic selectivity enhancement toward liquid hydrocarbons was also observed for PP over Ru/FAU and Ru/BEA compared to Ru/SiO2. To understand the origin of this selectivity improvement, a combination of ex situ and operando characterization techniques were used to reveal that both catalyst structure and acidity play key roles in PE and PP conversion. Operando X-ray absorption spectroscopy studies with model polyolefins over Ru-supported catalysts with varying acidity levels revealed that the local chemical environment of Ru[0] during the reaction is consistent across multiple acidic supports, although the onset of reduction during synthesis of the nanoparticles varies across different supports. These results, combined with reactivity data, demonstrate the importance of the acid-noble metal cooperativity in promoting selective C–C bond scission toward liquid alkanes that shifts the mechanism from hydrogenolysis to ideal hydrocracking.