Packing Engineering of Zirconium Metal-Organic Cages in Mixed Matrix Membranes for CO₂/CH₄ Separation

Metal-organic cages (MOCs) have been considered as emerging zero-dimensional (0D) porous fillers to generate molecularly homogeneous MOC-based membrane materials. However, the discontinuous pore connectivity and low filler concentrations limit the improvement of membrane separation performance. Herein, we propose the dimension augmentation of MOCs in membranes using three-dimensional (3D) supramolecular MOC networks as filler materials in mixed matrix membranes (MMMs). We further explore the packing engineering of MOC networks to produce distinct polymorphs (α and β phases) for tailoring membrane performance. Synchrotron X-ray absorption and positron annihilation lifetime spectroscopy were employed to differentiate distinct MOC polymorphous networks within membranes. Gas permeation tests revealed that the corresponding MMMs showed superior CO₂/CH₄ separation performance, exceeding the Robeson upper bound. Our proposed approach is expected to enrich the repertoire of reticular chemistry pertaining to molecular-based networks.