Membrane-based gas separation has been recognized as one of the mostpromising and energy-efficient processes for CO2 capture from industrialgas streams. Remarkably, commercial gas separation membranes typicallycontain conventional polymers with sub-optimal performance,necessitating the search for better-performing materials. In this work,we developed novel mixed matrix membranes (MMMs) based on the benchmarkpolyimide Matrimid (R) 9725 and a soluble poly (ether ether ketone)PEEK-WC. The addition of a zinc-based metalorganic cage (MOC) featuringtwo calixsalen macrocyclic units significantly improved the transportproperties for various gas pairs with an up to 100 \% increase inpermeability and up to 10 \% increase in selectivity at 30 \% MOC. SEMand DSC analyses offered valuable insights into the compatibilitybetween the polymer and MOC, revealing excellent dispersion of up to 30\% of MOC with almost complete phase separation from the matrix. Thethermal properties and transport properties were successfully describedusing the Fox equation and the Maxwell model, respectively. Mostinterestingly, thin film composites (TFCs) performed much better at 3times higher cage concentrations than the corresponding self-standingthick films because the faster solvent evaporation limited crystalgrowth to sub-micron size, favouring a fine homogeneous distribution ofthe MOC in the polymer matrix. Based on their pure and mixed gaspermeation, the TFC-MMMs show promise for the future development ofnew-generation gas separation membranes.

Metal-organic cages in polyimide and polyetheretherketone thin film composite mixed matrix membranes for gas separation

Longo Mariagiulia
Primo
;
Monteleone Marcello;Fuoco Alessio;Esposito Elisa;Hajivand Pegah;Jansen Johannes C.
2025

Abstract

Membrane-based gas separation has been recognized as one of the mostpromising and energy-efficient processes for CO2 capture from industrialgas streams. Remarkably, commercial gas separation membranes typicallycontain conventional polymers with sub-optimal performance,necessitating the search for better-performing materials. In this work,we developed novel mixed matrix membranes (MMMs) based on the benchmarkpolyimide Matrimid (R) 9725 and a soluble poly (ether ether ketone)PEEK-WC. The addition of a zinc-based metalorganic cage (MOC) featuringtwo calixsalen macrocyclic units significantly improved the transportproperties for various gas pairs with an up to 100 \% increase inpermeability and up to 10 \% increase in selectivity at 30 \% MOC. SEMand DSC analyses offered valuable insights into the compatibilitybetween the polymer and MOC, revealing excellent dispersion of up to 30\% of MOC with almost complete phase separation from the matrix. Thethermal properties and transport properties were successfully describedusing the Fox equation and the Maxwell model, respectively. Mostinterestingly, thin film composites (TFCs) performed much better at 3times higher cage concentrations than the corresponding self-standingthick films because the faster solvent evaporation limited crystalgrowth to sub-micron size, favouring a fine homogeneous distribution ofthe MOC in the polymer matrix. Based on their pure and mixed gaspermeation, the TFC-MMMs show promise for the future development ofnew-generation gas separation membranes.
2025
Istituto per la Tecnologia delle Membrane - ITM
Mixed matrix membranes
Thin film composites
Gas separation
Metal-organic cages
Spin-coating
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/517779
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