Microenvironment Engineering of Conjugated Microporous Polymer Membranes Enabling Ultrahigh Solvent Permeability and Molecular Sieving

Mass transfer intensification in separation technologies requires membranes with precisely engineered pore architectures and chemistry, as well as scalable fabrication. Herein, the first large-scale conjugated microporous polymer (CMP) composite membranes have been fabricated via solution-processable superacid-catalyzed ketone condensation, exhibiting ultrahigh solvent permeability and exceptional chemical stability. Molecular microenvironment engineering of CMPs via incorporation of fluorinated moieties achieves hierarchical free-volume control and forms confined mass transfer nanochannels with low surface energy. The fluorinated CMP (F_<i>x</i>-CMP) membranes deliver the highest structural parameter (ε/τ) and a record <i>n</i>-hexane permeability of 2272 L m^-2 h^-1 bar^-1 nm, reported to date among polymer membranes. The inertness of C-F bonds, coupled with fluorine-induced reduction in aryl electrophilicity, confers exceptional resistance to 18 M H₂SO₄, surpassing all previously reported acid-resistant membranes. When applied to separate active pharmaceutical ingredients (APIs), the F_<i>x</i>-CMP membrane achieved a 50-fold enrichment of API within 2.2 h, with a 90% reduction in CO₂ emissions compared to conventional thermal separation processes.