Ni/SiO₂ catalysts for polyolefin deconstruction via the divergent hydrogenolysis mechanism

Noble metal-based hydrogenolysis is emerging as a key chemical deconstruction technology of polyolefins into valuable products. Still, the catalyst cost and availability are significant barriers to handling the large volume of plastics. Cheap earth-abundant metals have been deemed inactive for polyolefin hydrogenolysis. Herein, we report that Ni/SiO₂ is active in deconstructing low-density polyethylene to n-alkanes (C₆-C₃₅) at mild conditions (300 °C, 30 bar H₂) with maximum liquid yields of 65 wt%. We expose a new mechanism of long-alkane hydrogenolysis that encompasses chain location-dependent single and multiple C-C bond cracking events and rationalizes product selectivity and molecular weight dependence. Ni/SiO₂ catalysts are reusable and can handle multiple plastics producing feedstock-dependent products (i.e., n-alkanes, iso-alkanes, cyclics, aromatics, etc.). The findings broaden the scope of viable catalysts polyolefin hydrogenolysis and unleash the potential to manage the volume of plastic waste.