共价交联策略强化CO2/C2H2高效分离用IL@MOF复合材料的稳定性★

doi:10.6023/A26010035

摘要/Abstract

发展新型固体吸附剂从CO₂/C₂H₂混合物中高效分离C₂H₂具有重要的工业价值。本文针对离子液体负载金属-有机骨架复合材料中活性组分易流失、稳定性差的问题,提出一种采用双环氧基团交联剂对离子液体进行共价交联的策略。该策略基于环氧基团与胺基的开环聚合反应,在离子液体内构筑稳定的共价网络,进而将其牢固负载于ZIF-8表面形成具有核壳结构的[EGDE]/[TEPA][Py]@ZIF-8吸附剂,可实现CO₂/C₂H₂的高效分离。交联后的复合材料仍保留良好的CO₂吸附能力（63.75 cm³g^-1）和CO₂/C₂H₂选择性（>10⁴）,并且热稳定性相较于原始复合材料得到了显著提升。经5次吸附-脱附循环后CO₂吸附容量并未出现明显变化。此外,穿透实验进一步验证了在动态条件下复合材料具有优异的CO₂/C₂H₂分离性能。

关键词: 复合材料, 气体分离, CO₂捕集, 交联, 稳定性

The separation of carbon dioxide (CO₂) and acetylene (C₂H₂) using solid adsorbents represents a viable approach for producing C₂H₂ in industrial applications. To address the issues of ionic liquid (IL) leaching and limited stability in IL-incorporated metal-organic framework (MOF) composites, we developed a strategy involving the covalent crosslinking of the IL using a diepoxy crosslinker. The covalent cross-linked network not only effectively restricts the migration and leaching of ionic liquids on the MOF surface but also enhances the overall chemical and thermal stability of the composite material. Specifically, this strategy is based on the ring-opening polymerization reaction between the epoxy groups on the cross-linker (ethylene glycol diglycidyl ether) and the amine groups on the ionic liquid ([TEPA][Py], where [TEPA] is tetraethylenepentamine and [Py] is pyrazole). This constructs a stable covalent network within the ionic liquid, which is then firmly anchored onto the surface of ZIF-8 to form a core-shell structured adsorption separation material for CO₂/C₂H₂ separation. Although the crosslinked composite exhibited a lower CO₂ uptake (63.75 cm³ g^-1) compared to its non-crosslinked counterpart (80.29 cm³ g^-1), it maintained considerable adsorption capacity alongside high CO₂/C₂H₂selectivity (>10⁴). The thermal stability of the composites was evaluated by thermogravimetric analysis (TGA). The results show that the crosslinked ionic liquid composite retained a larger mass at a given temperature compared to the pristine composite, demonstrating its enhanced thermal stability.The cross-linked adsorbent exhibited exceptional retention of its adsorption capacity over five consecutive adsorption-desorption cycles, with a negligible capacity loss of less than 0.6%. This performance stands in striking contrast to the severe degradation observed for the non-crosslinked composite, which suffered a rapid capacity loss of over 17% under identical conditions, providing direct evidence for the successful suppression of IL leaching. Finally, dynamic breakthrough experiments conducted under mixed-gas conditions confirmed the exceptional CO₂/C₂H₂separation performance and practical potential of the developed cross-linked IL@MOF composite.

Key words: Composites, Gas Separation, CO₂ Capture, Crosslinking, Stability

引用此文

冯超越, 薛波, 车国强, 刘大欢. 共价交联策略强化CO₂/C₂H₂高效分离用IL@MOF复合材料的稳定性^★[J]. 化学学报, doi: 10.6023/A26010035.

Feng Chaoyue, Xue Bo, Che Guoqiang, Liu Dahuan. Covalent Cross‑Linking Strategy for Enhancing the Stability of IL@MOF Composites for Efficient CO₂/C₂H₂ Separation[J]. Acta Chimica Sinica, doi: 10.6023/A26010035.

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共价交联策略强化CO₂/C₂H₂高效分离用IL@MOF复合材料的稳定性^★

Covalent Cross‑Linking Strategy for Enhancing the Stability of IL@MOF Composites for Efficient CO₂/C₂H₂ Separation

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