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.