Defect-Free MOF-Based Mixed-Matrix Membranes Obtained by Corona Cross-Linking

Functionalized UiO-66 metal-organic frameworks (MOF) particles were covalently grafted with hydride-terminated poly(dimethylsiloxane) (PDMS) via postsynthetic modification. These PDMS-coated MOF particles (termed here "corona-MOF") were used in the preparation of mixed-matrix membranes (MMMs). Defect-free MMMs with weight loadings of 50% were achieved with corona-MOF particles, attributed to the improved dispersibility of the corona-MOF particles and covalent linkages between the corona-MOF particles and the polymer matrix. The PDMS MMMs showed distinct separation features in single gas permeation tests, displaying much higher CO₂ gas permeation with no decrease in selectivity when compared to MMMs prepared with unmodified UiO-66 particles. Single gas separation tests with CO₂, N₂, and propane were performed to probe the separation mechanism of the corona-MOF MMMs, demonstrating that these MMMs avoid nonideal "sieve-in-a-cage" and "plugged sieves" scenarios. Additionally, due to covalent bond formation between both the MOF and the polymer matrix in corona-MOF MMMs, particle aggregation is negligible during film curing, allowing for the formation of flexible, self-standing MMMs of <1 μm in thickness. Low quantities of polymer covalently attached to the MOF surface (<5 wt %) are sufficient to fabricate thin, defect-free, high MOF-loading MMMs.