Mahdi Ahmadi

Application of conventional polymeric membranes in CO₂ separation processes are limited by the existing trade-off between permeability and selectivity represented by the renowned upper bound. Addition of porous nanofillers in polymeric membranes is a promising approach to transcend the upper bound, owing to their superior separation capabilities. Porous nanofillers entice increased attention over nonporous counterparts due to their inherent CO₂ uptake capacities and secondary transport pathways when added to polymer matrices. Infinite possibilities of tuning the porous architecture of these nanofillers also facilitate simultaneous enhancement of permeability, selectivity and stability features of the membrane conveniently heading in the direction towards industrial realization. This review focuses on presenting a complete synopsis of inherent capacities of several porous nanofillers, like metal organic frameworks (MOFs), Zeolites, and porous organic frameworks (POFs) and the effects on their addition to polymeric membranes. Gas permeation performances of select hybrids with these three-dimensional (3D) fillers and porous nanosheets have been summarized and discussed with respect to each type. Consequently, the benefits and shortcomings of each class of materials have been outlined and future research directions concerning the hybrids with 3D fillers have been suggested.

Membrane technology has the potential to be an eco-friendly and energy-saving solution for the separation of CO₂ from different gaseous streams due to the lower cost and the superior manufacturing features. However, the performances of membranes made of conventional polymers are limited by the trade-off between the permeability and selectivity. Improving the membrane performance through the addition of nanofillers within the polymer matrix offers a promising strategy to achieve superior separation performance. This review aims at providing a complete overview of the recent advances in nanocomposite membranes for enhanced CO₂ separation. Nanofillers of various dimensions and properties are categorized and effects of nature and morphology of the 0D to 2D nanofillers in the corresponding nanocomposite membranes of different polymeric matrixes are discussed with regard to the CO₂ permeation properties. Moreover, a comprehensive summary of the performance data of various nanocomposite membranes is presented. Finally, the advantages and challenges of various nanocomposite membranes are discussed and the future research and development opportunities are proposed.

Microporous metal-imidazolate framework (MMIF), a highly CO2 selective MOF, was incoporated into a polymeric membrane for separation of CO2 from CH4 and N2 for the first time. MMIF nanoparticles of 50-200 nm were synthesized using the sonication method and dispersed into Matrimid®, a commercial polyimide, with MOF loading of 10 and 20 % by weight to fabricate mixed matrix membranes (MMMs). Morphology, thermal behavior, and glass transition temperature of the membranes were characterized, and single and mixed gas permeation measurements at 35^○C and 4 bar feed pressure were carried out to reveal their separation performance. Both 10% and 20% MMIF containing Matrimid® membranes exhibited enhanced gas permeabilities for all three gases. Contrary to expectations, ideal selectivity of membranes was not improved possibly due to the flexible framework of MMIF. On the other hand, mixed gas permeability measurements showed significant improvement in CO2/CH4 separation factor by 130% and CO2/N2 separation factor by 79% owing to competitive adsorption favoring CO2.