JACS Au. 2022 Oct 5;2(10):2259-2268. doi: 10.1021/jacsau.2c00402. eCollection 2022 Oct 24.
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.