Partial pore blockage and polymer chain rigidification phenomena in PEO/ZIF-8 mixed matrix membranes synthesized by in situ polymerization

Nanostructured zeolitic imidazolate frameworks(ZIF-8) was incorporated into the mixture of poly(ethylene glycol) methyl ether acrylate(PEGMEA) and pentaerythritol triacrylate(PETA) to synthesize mixed matrix membranes(MMMs) by in situ polymerization for CO_2/CH_4 separation. The solvent-free polymerization between PEGMEA and PETA was induced by UV light with 1-hydroxylcyclohexyl phenyl ketone as initiator. The chemical structural characterization was performed by Fourier transform infrared spectroscopy. The morphology was characterized by scanning electron microscope. The average chain-to-chain distance of the polymer chains in MMMs was investigated by X-ray diffraction. The thermal property was evaluated by differential scanning calorimetry. The CH_4 and CO_2 gas transport properties of MMMs are reported. The relationship between gas permeation–separation performances or physical properties and ZIF-8 loading is also discussed. However, the permeation–separation performance was not improved in Robeson upper bound plot compared with original polymer membrane as predicted. The significant partial pore blockage and polymer rigidification effect around the ZIFs confirmed by the increase in glass temperature and the decrease in the d-spacing, were mainly responsible for the failure in performance improvement, which offset the high diffusion induced by porous ZIF-8.

Ultrapermeable membranes based on connected cluster of hollow polydimethylsiloxane nanoparticles for gas separation

Mixed matrix membranes(MMMs)with the performance between the matrix and the filler is a promising strategy for membranes with excellent gas permeability-selectivity.In this study,the hollow polydimethylsiloxane nanoparticles were synthesized and then incorporated with the poly(oxide ethylene)monomer and tri-functional cross-linker to form mixed matrix membranes by in situ poly-merization.The hollow nanoparticles formed the independent closed nanocavities in membranes,which enhanced the gas permeability contributed by both the improved diffusivity and solubility.At high loading,the hollow polydimethylsiloxane nanoparticle was converted into the continuous phase with the cross-linked poly(oxide ethylene)as the dispersed phase.Gases preferred to permeate through the connected cluster of hollow polydimethylsiloxane nanoparticles,finally leading to ultrahigh gas per-meabilities far going beyond the instinct values of polydimethylsiloxane and the cross-linked poly(oxide ethylene).The optimized membrane with 34 wt%hollow nanoparticles loadings exhibited ultrahigh permeabilities with the values of 44186 Barrer for CO_(2) and 11506 Barrer for O_(2),accompanied with a CO_(2)/N_(2) selectivity of 9.9 and an O_(2)/N_(2) selectivity of 2.6,which exceeded the 2008 Robeson upper bound for O_(2)/N_(2) and located at the 2008 Robeson upper bound for CO_(2)/N_(2).

H_2/CO_2 Gas Transport Performance in Poly(Ethylene Oxide) Reverse-selective Membrane with Star-like Structures

A series of poly(ethylene oxide)(PEO) membranes with star-like structures for CO_2/H_2 separation were prepared by the photo-polymerization method. The structure of PEO membrane was characterized by Fourier transform infrared spectroscopy(FTIR). The thermal property and inter-segmental distance of polymer chain were investigated by differential scanning calorimetry and wide-angle X-ray diffraction, respectively. The density was determined by hydrostatic weighing method. The gas permeability, solubility and diffusivity of CO_2 and H_2 were investigated in the star-like PEO membranes. The relationship between gas permeation performances and physical properties was also discussed. The membrane exhibits outstanding CO_2 permeability(about 9.7×10^(-11) cm^3(STP) cm/cm^2/s/Pa) and CO_2/H_2 selectivity(about 11) compared with other membranes.