Thin-film composite mixed-matrix membranes (TFC-MMMs) have potential applications in practical gas separation processes because of their high permeance (gas flux) and gas selectivity. In this study, we fabricated a high-performance TFC-MMM based on a rubbery comb copolymer, i.e., poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate)-co-poly(oxyethylene methacrylate) (PBE), and metal–organic framework MOF-808 nanoparticles. The rubbery copolymer penetrates through the pores of MOF-808, thereby tuning the pore size. In addition, the rubbery copolymer forms a defect-free interfacial morphology with polymer-infiltrated MOF-808 nanoparticles. Consequently, TFC-MMMs (thickness = 350 nm) can be successfully prepared even with a high loading of MOF-808. As polymer-infiltrated MOF is incorporated into the polymer matrix, the PBE/MOF-808 membrane exhibits a significantly higher CO₂ permeance (1069 GPU) and CO₂/N₂ selectivity (52.7) than that of the pristine PBE membrane (CO₂ permeance = 431 GPU and CO₂/N₂ selectivity = 36.2). Therefore, the approach considered in this study is suitable for fabricating high-performance thin-film composite membranes via polymer infiltration into MOF pores.

Thin-film composite (TFC) membranes containing various fillers and additives present an effective alternative to conventional dense polymer membranes, which often suffer from low permeance (flux) and the permeability–selectivity tradeoff. Alongside the development and utilization of numerous new polymers over the past few decades, diverse additives such as metal–organic frameworks (MOFs), graphene oxides (GOs), and ionic liquids (ILs) have been integrated into the polymer matrix to enhance performance. However, achieving desirable interfacial compatibility between these additives and the host polymer matrix, particularly in TFC structures, remains a significant challenge. This review discusses recent advancements in TFC membranes for CO₂/N₂ separation, focusing on material structure, polymer–additive interaction, interface and separation properties. Specifically, we examine membranes operating under dry conditions to clearly assess the impact of additives on membrane properties and performance. Additionally, we provide a perspective on future research directions for designing high-performance membrane materials.