Metal–organic framework (MOF) glasses are promising candidates for membrane fabrication due to their significant porosity, the ease of processing, and most notably, the potential to eliminate the grain boundary that is unavoidable for polycrystalline MOF membranes. Herein, we developed a ZIF‐62 MOF glass membrane and exploited its intrinsic gas‐separation properties. The MOF glass membrane was fabricated by melt‐quenching treatment of an in situ solvothermally synthesized polycrystalline ZIF‐62 MOF membrane on a porous ceramic alumina support. The molten ZIF‐62 phase penetrated into the nanopores of the support and eliminated the formation of intercrystalline defects in the resultant glass membrane. The molecular sieving ability of the MOF membrane is remarkably enhanced via vitrification. The separation factors of the MOF glass membrane for H2/CH4, CO2/N2 and CO2/CH4 mixtures are 50.7, 34.5, and 36.6, respectively, far exceeding the Robeson upper bounds.

A novel multi-permselective mixed matrix membrane (MP-MMM) is developed by incorporating versatile fillers functionalized with ethylene oxide (EO) groups and an amine carrier into a polymer matrix. The as-prepared MP-MMMs can separate CO2 efficiently because of the simultaneous enhancement of diffusivity selectivity, solubility selectivity, and reactivity selectivity. To be specific, MP-MMMs were fabricated by incorporating polyethylene glycol- and polyethylenimine-functionalized graphene oxide nanosheets (PEG-PEI-GO) into a commercial low-cost Pebax matrix. The PEG-PEI-GO plays multiple roles in enhancing membrane performance. First, the high-aspect ratio GO nanosheets in a polymer matrix increase the length of the tortuous path of gas diffusion and generate a rigidified interface between the polymer matrix and fillers, enhancing the diffusivity selectivity. Second, PEG consisting of EO groups has excellent affinity for CO2 to enhance the solubility selectivity. Third, PEI with abundant primary, secondary, and tertiary amine groups reacts reversibly with CO2 to enhance reactivity selectivity. Thus, the as-prepared MP-MMMs exhibit excellent CO2 permeability and CO2/gas selectivity. The MP-MMM doped with 10 wt % PEG-PEI-GO displays optimal gas separation performance with a CO2 permeability of 1330 Barrer, a CO2/CH4 selectivity of 45, and a CO2/N2 selectivity of 120, surpassing the upper bound lines of the Robeson study of 2008 (1 Barrer = 10(-10) cm(3) (STP) cm(-2) s(-1) cm(-1) Hg).

Composite membranes comprising a continuous polymer phase and a dispersed filler phase have revealed appealing potential in selective transport of molecules and ions. The multiphase characteristics of composite membranes provide more degrees of freedom to manipulate multiple interactions, tailor multiscale structures, and integrate multiple functionalities, compared to pristine polymer membranes.In this feature article, we have reviewed the various methods for the fabrication of composite membranes. In particular, we have thoroughly discussed two typical methods: the physical blending method and the sol-gel method. For each method, the major advances and challenges have been summarized. We have also tentatively delineated the new generation of composite membranes.

To solve the tradeoff between permeability and selectivity of polymeric membranes, organic−inorganic hybrid membranes composed of poly(vinyl alcohol) (PVA) and γ-glycidyloxypropyltrimethoxysilane (GPTMS) were prepared by an in situ sol−gel approach for pervaporative separation of benzene/ cyclohexane mixtures. The structure of PVA-GPTMS hybrid membranes was characterized with FTIR, 29Si NMR, SEM, TEM, and XRD. Energy-dispersive X-ray Si-mapping analysis demonstrated homogeneous dispersion of silica in the PVA matrix. Compared with pure PVA membranes, the hybrid membranes exhibited high thermal stability and lower T g, and in particular improved pervaporation properties. Permeation flux increased from 20.3 g/(m2 h) for pure PVA membrane to 137.1 g/(m2 h) for PVA-GPTMS hybrid membrane with 28 wt % GPTMS content, and separation factor increased from 9.6 to 46.9 correspondingly. The pervaporation results of PVA-GPTMS hybrid membranes are all above the upper bound tradeoff curve (Lue, S. J.; Peng, S. H. J. Membr. Sci. 2003, 222, 203), while that of pure PVA membrane is obviously below the curve. Positron annihilation lifetime spectroscopy (PALS) was employed to elucidate the enhancement of permeation flux in polymer-based pervaporation membranes, and a size-selective mechanism was proposed to explain the enhancement of the separation factor.