Constructing Connected Paths between UiO‐66 and PIM‐1 to Improve Membrane CO2 Separation with Crystal‐Like Gas Selectivity

Abstract Most metal–organic‐framework‐ (MOF‐) based hybrid membranes face the challenge of low gas permeability in CO 2 separation. This study presents a new strategy of interweaving UiO‐66 and PIM‐1 to build freeways in UiO‐66‐CN@sPIM‐1 membranes for fast CO 2 transport. In this strategy, sPIM‐1 is rigidified via thermal treatment to make polymer voids permanent, and concurrently polymer chains are mutually linked onto UiO‐66‐CN crystals to minimize interfacial defects. The pore chemistry of UiO‐66‐CN is kept intact in hybrid membranes, allowing full utilization of MOF pores and selective adsorption for CO 2 . Separation results show that UiO‐66‐CN@sPIM‐1 membranes possess exceptionally high CO 2 permeability (15433.4–22665 Barrer), approaching to that of UiO‐66‐NH 2 crystal (65–75% of crystal‐derived permeability). Additionally, the CO 2 /N 2 permeation selectivity for a representative membrane (23.9–28.6) moves toward that of single crystal (24.6–29.6). The unique structure and superior CO 2 /N 2 separation performance make UiO‐66‐CN@sPIM‐1 membranes promising in practical CO 2 separations.