Qiu Zhensong, Cui Jiyu, Yang Lifeng, Zhang Zhaoqiang, Suo Xian, Cui Xili, Xing Huabin
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, PR China.
Engineering Research Center of Functional Materials Intelligent Manufacturing of Zhejiang Province, ZJU-Hangzhou Global Scientific and Technological Innovation Center Hangzhou 311200, China.
J Am Chem Soc. 2024 Apr 10;146(14):9939-9946. doi: 10.1021/jacs.4c00468. Epub 2024 Mar 28.
Selective recognition of 1,3-butadiene from complex olefin isomers is vital for 1,3-butadiene purification, but the lack of porous materials with suitable pore structures results in poor selectivity and low capacity in C4 olefin separation. Herein, two sulfonate-functionalized organic frameworks, ZU-601 and ZU-602, are designed and show impressive separation performance toward C4 olefins. Benefiting from the suitable aperture size caused by the flexibility of coordinated organic ligand, ZU-601, ZU-602 that are pillared with different sulfonate anions could discriminate C4 olefin isomers with high uptake ratio: 1,3-butadiene/1-butene (207), 1,3-butadiene/-2-butene (10.1). Meanwhile, their layer-stacked structure enables the utilization of both intra- and interlayer space, enhancing the accommodation of guest molecules. ZU-601 exhibits record high 1,3-butadiene adsorption capacity of 2.90 mmol g (0.5 bar, 298 K) among the reported flexible porous materials with high 1,3-butadiene/1-butene selectivity. The breakthrough experiments confirm their superior separation ability even for all five C4 olefin isomers, and the molecular-level structural change is well elucidated via powder, crystal analysis, and simulation studies. The work provides ideas toward advanced materials design with simultaneous high separation capacity and high separation selectivity for challenging separations.
从复杂的烯烃异构体中选择性识别1,3 - 丁二烯对于1,3 - 丁二烯的纯化至关重要，但缺乏具有合适孔结构的多孔材料导致C4烯烃分离中的选择性差和容量低。在此，设计了两种磺酸酯功能化有机框架ZU - 601和ZU - 602，它们对C4烯烃显示出令人印象深刻的分离性能。得益于配位有机配体的灵活性所导致的合适孔径大小，用不同磺酸根阴离子支撑的ZU - 601、ZU - 602能够以高吸附比区分C4烯烃异构体：1,3 - 丁二烯/1 - 丁烯（207），1,3 - 丁二烯/反 - 2 - 丁烯（10.1）。同时，它们的层状堆积结构使得能够利用层内和层间空间，增强了客体分子的容纳能力。在已报道的具有高1,3 - 丁二烯/1 - 丁烯选择性的柔性多孔材料中，ZU - 601展现出创纪录的2.90 mmol g（0.5 bar，298 K）的1,3 - 丁二烯吸附容量。突破实验证实了它们即使对于所有五种C4烯烃异构体都具有卓越的分离能力，并且通过粉末、晶体分析和模拟研究很好地阐明了分子水平的结构变化。这项工作为具有同时高分离容量和高分离选择性的先进材料设计提供了思路，以应对具有挑战性的分离。
