Isoreticular Metal–Organic Frameworks Confined Mononuclear Ru-Hydrides Enable Highly Efficient Shape-Selective Hydrogenolysis of Polyolefins

Upcycling nonbiodegradable plastics such as polyolefins is paramount due to their ever-increasing demand and landfills after usage. Catalytic hydrogenolysis is highly appealing to convert polyolefins into targeted value-added products under mild reaction conditions compared with other methods, such as high-temperature incineration and pyrolysis. We have developed three isoreticular zirconium UiO-metal–organic frameworks (UiO-MOFs) node-supported ruthenium dihydrides (UiO-RuH₂), which are efficient heterogeneous catalysts for hydrogenolysis of polyethylene at 200 °C, affording liquid hydrocarbons with a narrow distribution and excellent selectivity via shape-selective catalysis. UiO-66-RuH₂ catalyzed hydrogenolysis of single-use low-density polyethylene (LDPE) produced a C12 centered narrow bell-shaped distribution of C8–C16 alkanes in >80% yield and 90% selectivity in the liquid phase. By tuning the pore sizes of the isoreticular UiO-RuH₂ MOF catalysts, the distribution of the products could be systematically altered, affording different fuel-grade liquid hydrocarbons from LDPE in high yields. Our spectroscopic and theoretical studies and control experiments reveal that UiO-RuH₂ catalysts enable highly efficient upcycling of plastic wastes under mild conditions owing to their unique combination of coordinatively unsaturated single-site Ru-active sites, uniform and tunable pores, well-defined porous structure, and superior stability. The kinetics and theoretical calculations also identify the C–C bond scission involving β-alkyl transfer as the turnover-limiting step.