Gravity induced deposition of MOFs to construct mixed-matrix substrate for defect-free and flexible MOFs membrane

Polymer-supported MOFs membranes with high separation performances show great potentials in industrial purification of H 2 . The key to growing defect-free and adherent MOFs layers on polymer substrates is the abundant and uniformly distributed nucleation sites on the surface of polymer substrates. Therefore, in this work, a mixed-matrix polyacrylonitrile (PAN) substrate with ZIF-8-rich seed layer (ZS-PAN) was constructed by gravity induced deposition and gradient distribution of ZIF-8 before phase inversion, then under the assistance of Tannic acid (TA), the dense and defect-free ZIF-8 membrane on flexible polymer substrate was fabricated followed by the secondary growth of ZIF-8. The EDS and SEM results of the membrane cross-section confirm the gradient distribution of ZIF-8 seeds, and the resultant membranes are defect-free. The H 2 permeance of TA-ZIF-8/ZS-PAN membrane is 953.66 GPU, and the H 2 /CO 2 selectivity is 12.09, which is 80.17 % higher than that of ZIF-8/ZS-PAN membrane without TA, exceeding the Robeson upper bound in 2008. This improved H 2 separation performance is derived from the following reasons. First, gravity-induced ZIF-8 seed deposition constructs a ZIF-8-rich seed layer on the mixed-matrix polymer substrate, which increases the nucleation sites. Second, the introduction of TA during the secondary growth process further increases the nucleation sites by hydroxyl-chelated zinc ions, both of which contribute to the dense ZIF-8 membrane. At the same time, the hydroxyl group in TA is CO 2 -philic, which can delay CO 2 permeation and improve the H 2 /CO 2 separation performance by physically adsorbing CO 2 . The proposed mixed-matrix substrate by gravity induced deposition of MOFs provides a novel strategy for constructing defect-free and flexible MOFs membrane.