Post‐Synthesis Functionalization Enables Fine‐Tuning the Molecular‐Sieving Properties of Zeolites for Light Olefin/Paraffin Separations

Abstract Zeolite molecular sieves are widely used in gas separation and shape‐selective catalysis, but these applications often require discriminating differences as little as 0.1 Å. Molecular sieving with such size selectivity demands zeolites with highly tunable pore diameters and adsorption properties, which are technically challenging to prepare. Nevertheless, it is shown that a wide range of organic functional groups can be covalently functionalized onto the interior pore walls of the zeolites, MOR, LTL, FAU, and MFI, to systematically “tune” their effective pore diameters with respect to the size of organic groups. For organic functionalization, small and aggressive organic electrophiles are used (e.g., organo‐halide and ‐diazonium) as grafting agents, which are accessible to the intracrystalline void space, forming a C–O_zeolite bond in a reaction with a bridging oxygen as proved by multiple analysis data. It is demonstrated that the post‐functionalization can be used to tailor the molecular sieving action of a parent zeolite to give size‐selective adsorbents for light olefin/paraffin separations. 4‐Methoxybenzene‐functionalized MOR separates ethylene from ethane with an ideal‐adsorbed‐solution‐theory selectivity of ≈5873, whereas toluene‐grafted MOR completely separates propylene/propane mixtures. Therefore, tailoring the molecular‐sieving properties of zeolites by organic functionalization broadens their applications to challenging separations.