Generalizable Porous Aromatic Framework‐Included Polymer Membranes for Diffusion‐Enhanced Gas Separations

Abstract Industrial separation processes account for 10–15% of global energy consumption. Membrane‐based processes are less energy‐intensive than traditional gas separation technologies; however, enhanced material separation performance and stability for numerous gas mixtures are needed for widespread industrial adoption. This work presents a generalizable strategy for preparing mixed‐matrix gas separation membranes exceeding the performance upper bounds of existing polymer membranes for a wide variety of industrial gases. By incorporating robust porous aromatic framework (PAF) particles into various dense commercial polymer matrices, gas diffusivity and solubility can be enhanced. For diverse gas mixtures (e.g., CO 2 /N 2 , O 2 /N 2 , He/CH 4 , H 2 /N 2 , and C 2 H 4 /C 2 H 6 ), the resulting composite membranes exhibit enhanced gas permeabilities—by as much as 520%—and largely unchanged selectivities even after 6 years of aging under simulated flue gas conditions. These improvements arise from the ultrahigh porosity, excellent chemical compatibility, and unique physicochemical properties of the embedded PAF particles. Functionalizing the PAFs with polyamines also enables composite membranes that achieve among the highest reported performances against plasticization, a common obstacle in commercializing gas separation membranes. Significantly, the PAF‐1 particles are readily dispersible in various common membrane casting solvents, suggesting their broader utility as a filler for designing high‐performance membranes for many industrial gas separations.