Abstract Mixed-matrix membrane (MMM) is an effective way to overcome trade-off limitations of conventional polymeric membranes. However, the existence of defect voids at the polymer/filler interface often limits their performance improvement. Similar issues are also present in thermally rearranged polybenzoxazole (TR-PBO)-derived MMMs. To address this challenge, the selection of fillers is of great importance. Herein, a novel organic porous nanosphere (TC-cPSB), which is prepared by the polycondensation of 9,9-bis(4-aminophenyl) fluorene (BAFL) and terephthalaldehyde (TPAL) followed by thermal crosslinking, is chosen to engineer the polymer/filler interface. Benefiting from strong intermolecular interaction (π-π stacking and hydrogen bonding), the TC-cPSB nanosphere can well disperse in TR-PBO matrix with a defect-free interface. With an increase in TC-cPSB loading, well-designed MMMs exhibit a significant “anti-trade-off” phenomenon whereby gas permeability and selectivity increase simultaneously, following the trend predicted by the Maxwell model. Compared with TR-PBO membrane, the MMM containing 15 wt% of nanosphere shows an increase of 282% and 217.6% in H2/CO2 selectivity and H2 permeability, respectively, which is far beyond 2008 Robeson upper bound.

中文翻译：

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Cardo 型多孔有机纳米球：调整热重排混合基质膜中的界面相容性以改善氢气纯化

摘要 混合基质膜 (MMM) 是克服传统聚合物膜权衡限制的有效方法。然而，聚合物/填料界面处缺陷空隙的存在通常限制了它们的性能改进。类似的问题也存在于热重排聚苯并恶唑 (TR-PBO) 衍生的 MMM 中。为了应对这一挑战，填料的选择非常重要。在此，选择通过 9,9-双（4-氨基苯基）芴（BAFL）和对苯二醛（TPAL）缩聚然后热交联制备的新型有机多孔纳米球（TC-cPSB）来设计聚合物/填充界面。受益于强大的分子间相互作用（π-π 堆积和氢键），TC-cPSB 纳米球可以很好地分散在 TR-PBO 基质中，具有无缺陷的界面。随着 TC-cPSB 负载的增加，精心设计的 MMM 表现出显着的“反权衡”现象，即遵循 Maxwell 模型预测的趋势，气体渗透率和选择性同时增加。与TR-PBO 膜相比，含有15 wt% 纳米球的MMM 在H2/CO2 选择性和H2 渗透率方面分别提高了282% 和217.6%，远远超过了2008 Robeson 的上限。