Facile orientation control of MOF-303 hollow fiber membranes by a dual-source seeding method

Metal‒organic frameworks (MOFs) are nanoporous crystalline materials with enormous potential for further development into a new class of high-performance membranes. However, the preparation of defect-free and water-stable MOF membranes with high permselectivity and good structural integrity remains a challenge. Herein, we demonstrate a dual-source seeding (DS) approach to produce high-performance, water-stable MOF-303 membranes with hollow fiber (HF) geometry and preferentially tailored crystallographic orientation. By controlling the nucleation site density during secondary growth, MOF-303 membranes with a preferred crystallographic orientation (CPO) on the (011) plane were fabricated. The MOF-303 membrane with CPO on (011) provides straight one-dimensional permeation channels with a superior water flux of 18 kg m−2 h−1 in pervaporative water/ethanol separation, which is higher than that of most of the reported zeolite membranes and 1–2 orders of magnitude greater than that of previously reported MOF membranes. The straight water permeation channels also offer a promising water permeance of 15 L m−2 h−1 bar−1 and a molecular weight cut-off (MWCO ≈ 269) for dye nanofiltration. These results provide a concept for developing ultrapermeable MOF membranes with good selectivity and structural integrity for pervaporation and nanofiltration.