Ionic Cross-Linked MOF-Polymer Mixed-Matrix Membranes for Suppressing Interfacial Defects and Plasticization Behavior

To address the plasticization phenomenon and MOF-polymer interfacial defects, we report the synthesis of ionic cross-linked MOF MMMs from a dual brominated polymer and MOF components by using N,N'-dimethylpiperazine as the cross-linker. We synthesized brominated MIL-101(Cr) nanoparticles by using mixed linkers and prepared brominated polyimide (6FDA-DAM-Br) to form ionic cross-linked MMMs. The gas permeation properties of the polyimide, ionic cross-linked MOF-polymer MMMs, and non-cross-linked MOF-polymer MMMs with various MOF weight loadings were investigated systematically to effectively understand the effects of MOF weight loading and ionic cross-linking. The ionic cross-linked 40 wt % MOF-polymer MMM exhibited significantly enhanced gas permeability with an H₂ permeability of 1640 Barrer and CO₂ permeability of 1981 Barrer and slightly decreased H₂/CH₄, H₂/N₂, CO₂/CH₄ and CO₂/N₂ selectivities of 16.9, 15.4, 20.5, and 18.6, respectively. The H₂ and CO₂ permeabilities are approximately 2-3 fold higher than those of the pure polyimide (6FDA-DAM) membrane. Moreover, the ionic cross-linked 40 wt % MOF-polymer MMM exhibited significantly increased resistance to plasticization. This is because the brominated MOF incorporation boosted molecular transport and polymer chain rigidity, and ionic cross-linking further reduced the number of interfacial defects and polymer chain mobility.