Spontaneously self-assembled dual-layer mixed matrix membranes containing mass-produced mesoporous TiO2 for CO2 capture

• PVC-g-POEM graft copolymer was prepared for selective carbon dioxide separation.
• The reduction of solvent evaporation rate resulted in the dual-layer MMMs
• The increase of evaporation rate resulted in the single-layer MMMs.

Herein, a high performance mixed matrix membrane (MMM) is reported, through control of the solvent evaporation rate based on the spontaneous self-assembly of mesoporous TiO2 (m-TiO2) fillers in a poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer matrix. In particular, a facile, non-hydrothermal and mass-producible preparation method for m-TiO2 is described. Slow solvent evaporation resulted in the formation of dual-layer MMMs consisting of a top PVC-g-POEM rich layer over a bottom m-TiO2 rich layer, whereas fast evaporation led to the case of single-layer MMMs. Both CO2 permeability and CO2/N2 selectivity increased as the m-TiO2 content increased up to 20 wt% for single-layer as well as dual-layer MMMs, due to loose packing structures and increased chain flexibility. However, above 20 wt% loading, dual-layer MMMs exhibited much higher CO2 permeabilities and CO2/N2 selectivities than single-layer MMMs, resulting from self-assembled dual-layer architecture as well as better interfacial adhesion properties. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and density measurements revealed that the PVC-g-POEM graft copolymer chains penetrated into the m-TiO2 rich layer to generate web-like interconnected structures, forming proper pore sizes for selective CO2 transport. The dual-layer MMMs exhibited excellent improvements in CO2 permeability of over 3000% from 46.2 to 1430.9 Barrer (1 Barrer = 1×10−10 cm3 (STP) cm /cm2 s cmHg) with a CO2/N2 selectivity of 22.4, which was only slightly below the upper bound (2008).

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