Yali Zhao,Xiayi Yang,Jiayu Luo,Yanying Wei,Haihui Wang
MOF membranes are very promising in molecular separation, but it is still a challenge for industrial applications due to the complex and time-consuming synthesis. We use the fast current-driven synthesis (FCDS) method to achieve controlled growth of ZIF-8 membranes on porous graphite-coated ceramic tubes by controlling the growth time and current density. Grown for 30 min at a current density of 0.74 mA/cm 2 , the ZIF-8 membrane exhibits selectivity for C 3 H 6 /C 3 H 8 up to 63 with C 3 H 6 permeance of 6 × 10 −9 mol/(m 2 s Pa). Furthermore, the ZIF-8 membrane exhibits a pressure resistance of up to 3 bar and good stability of ~96 h. This work realizes the breakthrough of the MOF membrane synthesis via FCDS method from the frequently-used expensive and fragile anodic aluminum oxide (AAO) disc substrate to the tough ceramic tubular substrate, which broadens the road for the industrialization of MOF membranes in gas separation fields.
Yali Zhao,Xitai Cai,Wufeng Wu,Libo Li,Yanying Wei,Haihui Wang
Metal-organic framework membranes have shown great potential for efficient separation applications. However, unavoidable grain boundary defects and the inconstant pore size due to framework flexibility hinder the application of MOF membranes for gas separation. Herein, low-crystallinity ZIF-8/dcIm-x membranes are synthesized via fast current-driven synthesis. The competitive coordination of 4,5-dichloroimidazole (dcIm) linker leads to the formation of a low-crystallinity MOF with reduced grain boundary defects for better gas separation performance. Meanwhile, the in-situ substitution of the mIm linker by dcIm narrows the pore size and transforms the ZIF-8 structure in the stiffened Cm polymorph, allowing precise CO 2 sieving. Consequently, the low-crystallinity ZIF-8/dcIm-14 membrane exhibits a promising CO 2 /CH 4 selectivity of 32.4 with a CO 2 permeance of 1.73 × 10 −8 mol m −2 s −1 Pa −1 , which surpasses other membranes. Furthermore, the membrane presents a remarkable pressure resistance up to 3 bar and stable temperature-swing operation between room temperature and 125 °C over 120 h.
Metal-organic framework (MOF) membranes show great promise for propene/propane separation, yet a sharp molecular sieving has not been achieved due to their inherent linker mobility. Here, zeolitic imidazolate framework ZIF-8–type membranes with suppressed linker mobility are prepared by a fast current–driven synthesis (FCDS) strategy within 20 min, showing sharpened molecular sieving for propene/propane separation with a separation factor above 300. During membrane synthesis, the direct current promotes the metal ions and ligands to assemble into inborn-distorted and stiffer frameworks with ZIF-8_Cm (a newly discovered polymorph of ZIF-8) accounting for 60 to 70% of the membrane composition. Molecular dynamics simulations further verify that ZIF-8_Cm is superior to ZIF-8_I 4 ¯ 3 m (the common cubic phase) for propene/propane separation. FCDS holds great potential to produce high-quality, ultrathin MOF membranes on a large scale.
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