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Hollow fillers with tailored nanostructures and functionalities have become promising candidates for advanced mixed matrix membranes (MMMs). Herein, polydopamine/poly (ethylene glycol) (PEG) composite microcapsules are synthesized by hard template method and embedded into the Pebax matrix to fabricate MMMs for CO 2 capture. As a well-known biomimetic adhesive, polydopamine in the capsule wall renders adequate polymer-filler interfacial adhesion. The template removal process produces through-wall mesopores, which allow rapid gas diffusion into the lumen, further significantly reducing the trans-membrane mass transfer resistance. The remaining PEG in the capsule wall not only increases CO 2 -2 -affinity, but also avoids excessive chain rigidification at polymer-filler interface. In this way, the composite capsules, compared with those without PEG, confer significantly enhanced separation performance on membranes. The optimal gas transport property of the resultant membranes is obtained with a CO 2 permeability of 510 Barrer and an ideal selectivity of 84.6 for CO 2 /N 2 at humidified state, i.e., 108%, 98% higher than those of neat Pebax membrane, respectively. In addition, owing to dopamine-enabled strong adhesion, the MMMs exhibit better stability than Pebax membrane in the long-term test at 85 °C.

Dual-filler MMMs have attracted special interests in recent years because of the possibility of producing synergetic effect. This study is aimed at exploring the underlying synergy between two-dimensional (2D) nanosheets and a non-2D filler in mixed matrix membranes for gas separation. MXene or graphene oxide (GO) as typical nanosheet filler is selected to be in pair with a non-2D filler, SiO 2 or halloysite nanotubes (HNTs), with Pebax as the polymer matrix. In this way, four pairs of binary fillers are designed and the corresponding four groups of MMMs are fabricated. By tuning the mass ratio of binary fillers, synergetic effect is found for each group of MMMs. However, the two 2D fillers found different preferential non-2D partners. GO works better with HNTs than SiO 2 , while MXene prefers SiO 2 to HNTs. To be noted, GO/HNTs renders the membranes the maximum enhancement of CO 2 permeability (153%) and CO 2 /N 2 selectivity (72%) compared to Pebax control membrane, while each of them as single filler only brought about very limited enhancement of CO 2 separation performance. The possible mechanisms are thoroughly discussed in terms of filler dispersion, nanosheet flexibility, and the tortuosity and connectivity of the surface diffusion pathways along nanosheets.

Two-dimensional (2D) lamellar membranes, with highly ordered nanochannels between the adjacent layers, have revealed potential application prospects in various fields. To separate gases with similar kinetic diameters, intercalation of a functional liquid, especially an ionic liquid (IL), into 2D lamellar membranes is proved to be an efficient method due to the capacity of imparting solubility-based separation and sealing undesired defects. Stable immobilization of a high content of liquid is challenging but extremely required to achieve and maintain high separation performance. Herein, we describe the intercalation of a typical IL, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]­[BF4]), into the ionized nanochannels of sulfonated MXene lamellar membranes, where the sulfonate groups are anchored onto MXene nanosheets through a facile method based on metal-catechol chelating chemistry. Thanks to the intrinsic benefits of MXene as building blocks and the decorated sulfonate groups, the optimal membrane possesses adequate interlayer spacing (∼1.8 nm) and high IL uptake (∼47 wt %) and therefore presents a CO2 permeance of 519 GPU and a CO2/N2 selectivity of 210, outperforming the previously reported liquid-immobilized lamellar membranes. Moreover, the IL loss rate of the membrane within 7 days at elevated pressure (5 bar) is measured to be significantly decreased (from 43.2 to 9.0 wt %) after growing sulfonate groups on the nanochannel walls, demonstrating the excellent IL storage stability.

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