CO₂/N₂ Separation Properties of Polyimide-Based Mixed-Matrix Membranes Comprising UiO-66 with Various Functionalities

Nanocrystalline UiO-66 and its derivatives (containing -NH₂, -Br, -(OH)₂) were developed via pre-synthetic functionalization and incorporated into a polyimide membrane to develop a mixed-matrix membrane (MMM) for CO₂/N₂ separation. Incorporation of the non-functionalized UiO-66 nanocrystals into the polyimide membrane successfully improved CO₂ permeability, with a slight decrease in CO₂/N₂ selectivity, owing to its large accessible surface area. The addition of other functional groups further improved the CO₂/N₂ selectivity of the polymeric membrane, with UiO-66-NH₂, UiO-66-Br, and UiO-66-(OH)₂ demonstrating improvements of 12%, 4%, and 17%, respectively. Further evaluation by solubility-diffusivity analysis revealed that the functionalized UiO-66 in MMMs can effectively increase CO₂ diffusivity while suppressing N₂ sorption, thus, resulting in improved CO₂/N₂ selectivity. Such results imply that the structural tuning of UiO-66 by the incorporation of various functional groups is an effective strategy to improve the CO₂ separation performance of MMMs.