Assembling 99% MOFs into Bioinspired Rigid‐Flexible Coupled Membrane with Significant Permeability: The Impacts of Defects

Abstract Assembling metal‐organic frameworks (MOFs) into high‐performance macroscopic membranes is crucial but still challenging. MOF‐containing hybrid membranes can effectively integrate the advantages of flexible guest materials and MOFs. Nevertheless, the inherent limitations in fully harnessing the distinct characteristics of MOFs persist due to the substantial guest material content necessitated in membrane fabrication. Herein, inspired by the rigid and flexible structures in biological systems, rigid MIP‐202(Zr) and defective MIP‐202(Zr) (D‐MIP‐202(Zr)) modified flexible graphene oxide (GO) sheets are synthesized in situ and then assembled into a rigid‐flexible coupled MOF‐based membrane. The defects in D‐MIP‐202(Zr) are introduced by using acetic acid as the modulation agent. The obtained GO@MIP‐202(Zr) membrane possesses a hierarchical porous structure with a 99 wt% MOF proportion, which is higher than the GO@D‐MIP‐202(Zr) (75 wt%) membrane with a compact bulge‐structured surface. The water permeability of the GO@MIP‐202(Zr) membrane attains remarkedly 5762.92 L h −1 m −2 bar −1 , which is 960 and 2.6 times higher than that of the GO membrane and GO@D‐MIP‐202(Zr) membrane. Additionally, benefiting from the superhydrophilicity and underwater superoleophobicity, the resultant membrane not only demonstrates high rejection for oil‐water emulsions but also exhibits exceptional recyclability and anti‐fouling ability. These findings provide valuable insights into the assembly of MOFs into high‐performance membranes.