The synthesis of a polymer that combines the processability of plastics with the extreme rigidity of cross-linked organic networks is highly attractive for molecular sieving applications. However, cross-linked networks are typically insoluble or infusible, preventing them from being processed as plastics. Here, we report a solution-processable conjugated microporous thermoset with permanent pores of ~0.4 nm, prepared by a simple heating process. When employed as a two-dimensional molecular sieving membrane for hydrogen separation, the membrane exhibits ultrahigh permeability with good selectivity for H 2 over CO 2, O 2, N 2, CH 4, C 3H 6 and C 3H 8. The combined processability, structural rigidity and easy feasibility make this polymeric membrane promising for large-scale hydrogen separations of commercial and environmental relevance.
Rigidity, as seen in crosslinked polymers, and plastic processability are mutually exclusive properties. Here, the authors prepare a solution-processable conjugated microporous thermoset with permanent pores and demonstrate its application as a two-dimensional molecular sieving membrane for hydrogen separation.