Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO Capture.

Processable molecular-sieving membranes are important materials for realizing energy-efficient precombustion CO capture during industrial-scale hydrogen production. However, the promising design of mixed matrix membranes (MMMs) that aims to integrate the molecular-sieving properties of nanoporous architectures with industrial processable polymers still faces performance and fabrication issues due to the formation of segregated nanofiller domains in their polymer matrices. Here, an unconventional nanocomposite membrane design is proposed using soluble organic macrocyclic cavitands (OMCs) with tunable open cavity sizes that not only mitigate the formation the discrete nanofiller phases but also deliver distinct molecular-sieving separations. The versatile organic-solvent solubility coupled with highly interactive functionalities of OMCs allows them to obtain molecularly homogeneous mixing with matrix polymers and form only one integral continuous phase crucial to the robust processability of polymers. A series of polybenzimidazole-based molecularly mixed composite membranes (MMCMs) are fabricated via the incorporation of a soluble and thermally stable OMC choice, sulfocalixarenes, with various cavity sizes. These membranes achieve outstanding high-temperature mixed-gas H /CO separation performances comparable with several state-of-the-art molecular-sieving membranes owing to effective size-sieving gas passages through the open or partially-intruded supramolecular cavities. The broadly tunable structures and functionalities of OMCs would make their MMCMs attractive for other energy-intensive molecular separations.