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《工程(英文)》 >> 2022年 第11卷 第4期 doi: 10.1016/j.eng.2021.10.013

具有客体适应型孔道的阴离子柱撑超微孔材料实现顺-/反-烯烃高效分离

a Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c Advanced Membranes & Porous Materials Center, King Abdullah University of Science and Technology, Thuwal 23955, Saudi Arabia

收稿日期: 2021-04-30 修回日期: 2021-09-13 录用日期: 2021-10-21 发布日期: 2021-12-08

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摘要

顺-/反-烯烃异构体在石油化工行业具有重要应用价值,然而其极为相似的物理化学性质为节能高效的分离纯化技术的开发带来了巨大的挑战。本文设计的阴离子柱撑超微孔金属-有机框架材料,即ZU-36-Ni和ZU-36-Fe,首次实现了基于分子筛分效应的顺-/反-2-丁烯高效分离。ZU-36-Ni 具有智能的客体适应型孔道结构,其对反-2-丁烯呈现出高吸附容量(2.45 mmol∙g−1)并对顺-2-丁烯高效排阻,可从混合气中分离获得99.99%的高纯度顺-2-丁烯气体。密度泛函理论计算表明:当反-2-丁烯进入孔道时,ZU-36-Ni 的有机配体在主-客体相互作用下可定向旋转,从而导致孔穴扩张并使孔道更加适应反-2-丁烯形状及尺寸,加之ZU-36-Ni 具有可匹配反-2-丁烯三维尺寸的最优孔穴维度,使得反-2-丁烯可以被高效吸附。ZU-36-Ni的适应性行为可最大限度地强化ZU-36-Ni 和反-2-丁烯的主-客体作用,不仅有利于提升反-2-丁烯的优先吸附及动力学扩散行为,同时可实现对顺-2-丁烯的高效分子筛分。本工作为拓展孔穴工程在先进智能或适应型多孔材料在客体分子辨识领域的应用提供了新思路。

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