This research aimed to develop new composite membranes using a polymer of intrinsic microporosity (PIM-1) and metal organic frameworks (MOFs) for use in gas separations. PIM-1 was successfully synthesised using the high temperature method (40 min, 160 oC) and the resulting polymer was cast into membranes. PIM-1 membranes were chemically modified by reacting hexamethylenediamine (HMDA) with the nitrile group of PIM-1 to form HMDA-modified PIM-1 membranes. Surfaces of PIM-1 membranes were also modified by basic hydrolysis to form amide-modified PIM-1 membranes. These polymer materials were characterized by different techniques (GPC, NMR, ATR-IR, TGA, Elemental analysis and nitrogen sorption analysis). In addition, eight MOF materials [MIL-101(Cr), ED-g-MIL-101(Cr), TEPA-g-MIL-101(Cr), MIL-101(Cr)-NH2, MIL-101(Al)-NH2, UiO-66(Zr), UiO-66-NH2 and UiO-66(COOH)2] were successfully synthesized. They were chosen due to having high surface areas and large porosity. These MOF compounds were characterized using PXRD, SEM, TGA, and low pressure N2.Successful PIM-1/MOF MMMs were fabricated utilising PIM-1 and the MOFs outlined above with various loadings. The highest MOF loading achieved was 28.6 wt. %, apart from MIL-101(Cr)-NH2, for which it was 23.1 wt. %, and MIL-101(Al)-NH2, for which it was 19.8 wt. %. The morphology of MMMs was characterized by scanning electron microscopy (SEM), proving the dispersion of MOF fillers. Novel PIM-1 supported MOF membranes were successfully prepared by depositing ZIF-8 and HKUST-1 layers on the surfaces of unmodified and modified PIM-1 membranes. These materials were characterized using PXRD, SEM, ATR-IR and SEM-EDX. Gas permeation properties of the MOF/PIM-1 MMMs and PIM-1 supported MOF membranes were determined using a time lag method. Most MMMs tested showed an increase in the permeability and stable selectivity as the MOF amount was increased. However, this was not true for MIL-101(Al)-NH2, where the permeability and selectivity decreased. In contrast, PIM-1 supported ZIF-8 and HKUST-1 membranes caused a sharp decrease in the permeability and increase in the selectivity.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:728212 |
| Date | January 2017 |
| Creators | Khdhayyer, Muhanned |
| Contributors | Budd, Peter |
| Publisher | University of Manchester |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://www.research.manchester.ac.uk/portal/en/theses/mixed-matrix-membranes-comprising-metal-organic-frameworks-and-high-free-volume-polymers-for-gas-separations(172f6a4f-a531-44ae-979c-bbbd170f33db).html |
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