How polymer infiltration affects metal-organic frameworks-based facilitated hybrid membrane performances for CO₂ separation

Membrane separation technology has been widely used in the separation and capture of CO₂ to reduce carbon emissions. The performances of facilitated hybrid membranes (FHMs) can be improved by properly adding metal-organic framework (MOF)-based nanoparticles (NPs) and modifying polymers to the polymer matrix. Grafting and blending methods are widely used to introduce modifying polymers to improve the compatibility between NPs and the polymer matrix, and the performance of FHMs for CO₂ separation. However, the separation performance of FHMs decreases significantly when the long chains of the polymer infiltrate into the pores of the MOF at the interface between the modifying polymer and MOF. To in-depth understand the nano-scale polymer-NPs interfacial interaction mechanism of the grafting and blending methods, we herein employed molecular dynamic (MD) simulation method combined with experiments to investigate the interface between NPs of Cu-MOF (Cu-BDC) and four commonly used modifying polymers (PEG, polyethylene glycol; PEI, polyethylenimine; PVA, polyvinyl alcohol; PPy, polypyrrole) with PVDF (polyvinylidene difluoride) as the polymer matrix. The results showed that the blending method for modification can effectively avoid the polymer blockage in Cu-BDC pores by using four modifying polymers, while the grafting method caused polymer infiltration for PEG and PEI. The relationship between the polymer diameter and the pore limiting diameter (PLD) of the Cu-BDC was evaluated to analyze the polymer infiltration effect. FHMs of Cu-BDC/PEG@PVDF were synthesized based on the MD simulation results, which showed excellent CO₂ separation performance due to the good compatibility between the Cu-BDC and the modified matrix polymer. This work offers an insight in nano-scale into the interface design between the MOF and the polymer for FHMs separating CO₂.