Pérez-Miana Marta, Luque-Alled José Miguel, Mayoral Álvaro, Martínez-Visus Íñigo, Foster Andrew B, Budd Peter M, Coronas Joaquín
Nanoscience and Materials Institute of Aragon (INMA), CSIC-Universidad de Zaragoza, Mariano Esquillor St., Zaragoza, 50018, Spain.
Department of Chemical and Environmental Engineering, Universidad de Zaragoza, María de Luna, 3 St., Zaragoza, 50018, Spain.
Angew Chem Int Ed Engl. 2025 May 26;64(22):e202420879. doi: 10.1002/anie.202420879. Epub 2025 Apr 14.
This study aims to enhance the compatibility between filler and polymer in mixed matrix membranes (MMMs), addressing an important challenge in membrane development. ZIF-94, known for its affinity to CO, was partially modified with 2-undecylimidazolate (umIm) through the solvent-assisted ligand exchange (SALE) method to improve its compatibility with the prototypical polymer of intrinsic microporosity PIM-1. The modified ZIF-94 (ZIF-94-umIm) can be considered as an amphiphilic MOF with both hydrophilic and hydrophobic moieties, while maintaining a considerably high CO adsorption capacity (2.34 mmol g at 90 kPa and 0 °C). Gas separation experiments were performed using mixed gas compositions of 15/85 CO/N at 3 bar and 35 °C. The resulting MMM with a 5 wt.% loading exhibited an enhanced CO separation performance, with ca. 70% and 10% increases in CO permeability (8900 Barrer) and CO/N selectivity (20.2), respectively, compared to pristine PIM-1 membranes. In addition, thin film nanocomposite membranes were prepared showing a 23.5 CO/N selectivity at 2350 GPU of CO. This modification strategy shows a great potential for improving the CO capture technologies, highlighting the potential of tailoring MOF fillers for advanced membrane materials in gas separation applications.
本研究旨在提高混合基质膜（MMM）中填料与聚合物之间的相容性，解决膜开发中的一个重要挑战。以对CO具有亲和力而闻名的ZIF-94通过溶剂辅助配体交换（SALE）方法用2-十一烷基咪唑（umIm）进行了部分改性，以提高其与固有微孔聚合物PIM-1的相容性。改性后的ZIF-94（ZIF-94-umIm）可被视为一种具有亲水和疏水部分的两亲性金属有机框架（MOF），同时保持相当高的CO吸附容量（在90 kPa和0°C下为2.34 mmol/g）。在3 bar和35°C下使用15/85 CO/N2的混合气体组成进行了气体分离实验。与原始PIM-1膜相比，负载量为5 wt.%的所得MMM表现出增强的CO分离性能，CO渗透率（8900 Barrer）和CO/N2选择性（20.2）分别提高了约70%和10%。此外，制备的薄膜纳米复合膜在CO通量为2350 GPU时显示出23.5的CO/N2选择性。这种改性策略在改进CO捕获技术方面显示出巨大潜力，突出了为气体分离应用中的先进膜材料定制MOF填料的潜力。
