Wu Enyu, Gu Xiao-Wen, Liu Di, Zhang Xu, Wu Hui, Zhou Wei, Qian Guodong, Li Bin
State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian, 223300, China.
Nat Commun. 2023 Oct 2;14(1):6146. doi: 10.1038/s41467-023-41692-x.
One-step adsorption separation of CH from ternary C hydrocarbon mixtures remains an important and challenging goal for petrochemical industry. Current physisorbents either suffer from unsatisfied separation performance, poor stability, or are difficult to scale up. Herein, we report a strategy of constructing multiple supramolecular binding sites in a robust and scalable MOF (Al-PyDC) for highly efficient one-step CH purification from ternary mixtures. Owing to suitable pore confinement with multiple supramolecular binding sites, Al-PyDC exhibits one of the highest CH and CH uptakes and selectivities over CH at ambient conditions. The gas binding sites have been visualized by single-crystal X-ray diffraction studies, unveiling that the low-polarity pore surfaces with abundant electronegative N/O sites provide stronger multiple supramolecular interactions with CH and CH over CH. Breakthrough experiments showed that polymer-grade CH can be separated from ternary mixtures with a maximum productivity of 1.61 mmol g. This material can be prepared from two simple reagents using a green synthesis method with water as the sole solvent, and its synthesis can be easily scaled to multikilogram batches. Al-PyDC achieves an effective combination of benchmark separation performance, high stability/recyclability, green synthesis and easy scalability to address major challenges for industrial one-step CH purification.
从三元碳氢化合物混合物中一步吸附分离乙烯对石化行业来说仍然是一个重要且具有挑战性的目标。目前的物理吸附剂要么分离性能不尽人意,稳定性差,要么难以放大生产。在此,我们报道了一种在坚固且可扩展的金属有机框架(Al-PyDC)中构建多个超分子结合位点的策略,用于从三元混合物中高效一步纯化乙烯。由于具有多个超分子结合位点的合适孔限域作用,Al-PyDC在环境条件下表现出最高的乙烯和乙烷吸附量以及对乙烯相对于乙烷的选择性之一。通过单晶X射线衍射研究可视化了气体结合位点,揭示了具有丰富电负性N/O位点的低极性孔表面与乙烯和乙烷之间提供了比与乙烷更强的多重超分子相互作用。突破实验表明,聚合物级乙烯可以从三元混合物中分离出来,最大生产率为1.61 mmol g⁻¹。这种材料可以使用绿色合成方法,以水作为唯一溶剂,由两种简单试剂制备,并且其合成可以轻松扩展到多千克批次。Al-PyDC实现了基准分离性能、高稳定性/可回收性、绿色合成和易于扩展性的有效结合,以应对工业一步纯化乙烯的主要挑战。