In Situ Synthesis of Multivariate Zeolitic Imidazolate Frameworks for C 2 H 4 /C 2 H 6 Kinetic Separation.

Herein, a new approach for the in situ synthesis of zeolitic imidazolate framework (ZIF) nanoparticles with triple ligands, referred to as Sogang ZIF-8 (SZIF-8), is reported for enhanced C 2 H 4 /C 2 H 6 kinetic separation. SZIF-8 consists of tetrahedral zinc metals coordinated with tri-butyl amine (TBA), 2,4-dimethylimidazole (DIm), and 2-methylimidazole (MIm). SZIF-8(x) with different DIm contents in x (up to 23.2 mol%) are synthesized in situ because TBA preferably deprotonates DIm ligands due to the much lower pK a of DIm over MIm, allowing for the Zn-DIm coordination. The Zn-DIm coordination reduces the window size of ZIF-8 with suppressed linker flipping motion due to bulky DIm ligands and simultaneously enhances the interfacial interaction between 6FDA-DAM polyimide (6FDA) and SZIF-8 via electron donor-acceptor interactions. Consequently, 6FDA/SZIF-8(13) mixed matrix membrane exhibits an excellent C 2 H 4 permeability of 60.3 Barrer and C 2 H 4 /C 2 H 6 selectivity of 4.5. The temperature-dependent transport characterization reveals that such excellent C 2 H 4 /C 2 H 6 kinetic separation is attained by the enhancement in size discrimination-based energetic selectivity. Our hybrid multi-ligand approach can offer a useful tool for the fine-tuning of molecular structures and textural properties of other metal organic frameworks.