Thiol-ene photopolymerization of vinyl-functionalized metal-organic frameworks towards mixed-matrix membranes

Abstract

We developed a facile methodology for fabricating a free-standing mixed-matrix membrane (MMM) containing covalently incorporated metal-organic framework (MOF) particles up to 60 wt% by utilizing thiol-ene photopolymerization with the MOF consisting of vinyl functionality. Vinyl-functionalized UiO-66 (UiO-66-CH═CH2) was synthesized from 2-vinyl-1,4-dicarboxylic acid with ZrCl4, and a free-standing MMM was readily produced by irradiation of a polymerization mixture containing UiO-66-CH═CH2, poly(ethylene glycol) divinyl ether (PEO-250), pentaerythritol tetra(3-mercaptopropionate) (PETM), 2,2′-(ethylenedioxy)diethanethiol (EDDT), and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoradical initiator. Assorted analyses combining FTIR, thermogravimetric analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction strongly supported the fact that the desired MMM containing well-dispersed UiO-66-CH═CH2 particles was successfully produced by C-S bond formation, which provided strong union of the MOF with the polymer matrix without interfacial voids. The produced MMM was highly flexible and showed improved mechanical properties as compared to the pristine polymeric membrane, indicating that the covalently immobilized UiO-66-CH═CH2 particles were homogeneously distributed in the polymer matrix. Gas permeability across the MMM was significantly enhanced compared with the pristine polymeric membrane as diffusion of the gas molecules was facilitated in the porous space in the MOF.