Low-Loading Mixed Matrix Materials: Fractal-Like Structure and Peculiarly Enhanced Gas Permeability

Mixed matrix materials (MMMs) containing metal–organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model’s prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon. Herein, we design an ideal series of MMMs containing polyethers (one of the leading polymers for CO₂/N₂ separation) and discrete metal–organic polyhedra (MOPs) with cage sizes of 2–5 nm. Adding 3 mass % MOP-3 in a polyether increases the CO₂ permeability by 100% from 510 to 1000 Barrer at 35 °C because of the increased gas diffusivity. No discernible changes in typical physical properties governing gas transport properties are detected, such as glass transition temperature, fractional free volume, d-spacing, etc. We hypothesize that this behavior is attributed to fractal-like networks formed by highly porous MOPs, and for the first time, we validate this hypothesis using small-angle X-ray scattering analysis.