Binary-Cooperative Ultrathin Porous Membrane for Gas Separation.

The construction of ultrathin porous membranes with stable structures is critical for achieving efficient gas separation. Inspired by the binary-cooperative structural features of bones and teeth-composed of rigid hydroxyapatite and flexible collagen, which confer excellent mechanical strength-a binary-cooperative porous membrane constructed with gel-state zeolitic imidazolate frameworks (g-ZIFs), synthesized using a metal-gel-induced strategy, is proposed. The enlarged cavity size and flexible frameworks of the g-ZIF nanoparticles significantly improve gas adsorption and diffusion, respectively. After thermal treatment, the coordination structures forming rigid segments in the g-ZIF membranes appear at the stacked g-ZIF boundaries, exhibiting a higher Young's modulus than the g-ZIF nanoparticles, denoted as the flexible segments. The g-ZIF membranes demonstrate excellent tensile and compression resistances, attributed to the effective translation of binary-cooperative effects of rigidity and flexibility into the membranes. The resulting dual-aperture structure, composed of g-ZIF nanoparticles surrounded by nanoscale apertures at the boundaries, yields a membrane with a stable CO permeance of 4834 GPU and CO/CH selectivity of 90 within 3.0 MPa.