Pyrolytic Depolymerization of Polyolefins Catalyzed by Zirconium‐based UiO‐66 Metal‐Organic Frameworks

Polyolefins such as polyethylenes and polypropylenes are the most‐produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large‐scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially‐relevant petrochemicals. Metal‐organic frameworks (MOFs), despite their tremendous utility in heterogenous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores. Herein, we demonstrate the viability of UiO‐66 MOFs containing coordinatively‐unsaturated zirconia nodes, as effective catalysts for pyrolysis that significantly enhances the yields of valuable liquid and gas hydrocarbons, whilst halving the amounts of residual solids produced. Reactions occur on the Lewis‐acidic UiO‐66 zirconia nodes, without the need for noble metals, and yields aliphatic product distributions distinctly different from the aromatic‐rich hydrocarbons from zeolite catalysis. We also demonstrate the first unambiguous characterization of polyolefin penetration into UiO‐66 pores at pyrolytic temperatures, allowing access to the abundant Zr‐oxo nodes within the MOF interior for efficient C‐C cleavage. Our work highlights the potential of MOFs as highly‐designable heterogeneous catalysts for depolymerization of plastics which can complement conventional catalysts in reactivity.