Boosting Ethylene/Ethane Separation within Copper(I)-Chelated Metal–Organic Frameworks through Tailor-Made Aperture and Specific π-Complexation
Boosting Ethylene/Ethane Separation within Copper(I)-Chelated Metal–Organic Frameworks through Tailor-Made Aperture and Specific π-Complexation
复制标题
通过定制孔径和特定α-络合促进铜(I)螯合金属有机框架内的乙烯/乙烷分离
DOI：
10.1002/advs.201901918
复制
发表时间：
2020
期刊：
影响因子：
15.1
通讯作者：
Guodong Qian
中科院分区：
文献类型：
--
作者：
Ling Zhang;Libo Li;Enlai Hu;Ling Yang;Ling Yang;Lijia Yao;Ke Jiang;Yuanjing Cui;Yu Yang;Bin Li;Banglin Chen;Guodong Qian
开发吸附分离乙烯(C2H4)和乙烷(C2H6)的新材料在石化工业中具有重要意义，但由于其分子尺寸和物理性质相近，仍然具有很大的挑战性。在金属-有机骨架(MOF)中使用等网格化学能够精确地设计和建造具有合适的孔径大小和用于气体分离的功能位置的目标材料。研究表明，微孔铜(I)络合微孔膜的孔径微调和π络合作用可显著提高吸附选择性。在UIO-66骨架中明智地选择具有不同数目的羧基的有机连接物不仅允许微调孔径，还可以将铜(I)离子固定在骨架上。因此，CuI@UIO-66-(COOH)2具有最佳的孔窗口大小，并与C2H4分子形成π-络合作用。它能快速吸附π-络合作用驱动的C2H4，同时由于选择性的筛分而有效地减少了C2H6的吸附。因此，这种材料表现出超高的C2H4/C2H6选择性(80.8)，超过了大多数先前描述的基准材料。通过对50/50v/v C2H4/C2H6混合气体在常温下的突破性实验，验证了CuI@UIO-66-(COOH)2的优异分离性能。
The development of new materials for separating ethylene (C2H4) from ethane (C2H6) by adsorption is of great importance in the petrochemical industry, but remains very challenging owing to their close molecular sizes and physical properties. Using isoreticular chemistry in metal–organic frameworks (MOFs) enables the precise design and construction of target materials with suitable aperture sizes and functional sites for gas separations. Herein, it is described that fine‐tuning of pore size and π‐complexation simultaneously in microporous copper(I)‐chelated MOFs can remarkably boost the C2H4/C2H6adsorption selectivity. The judicious choice of organic linkers with a different number of carboxyl groups in the UiO‐66 framework not only allows the fine tuning of the pore size but also immobilizes copper(I) ions onto the framework. The tailor‐made adsorbent, CuI@UiO‐66‐(COOH)2, thus possesses the optimal pore window size and chelated Cu(I) ions to form π‐complexation with C2H4molecules. It can rapidly adsorb C2H4driven by the strong π‐complexation interactions, while effectively reducing C2H6uptake due to the selective size‐sieving. Therefore, this material exhibits an ultrahigh C2H4/C2H6selectivity (80.8), outperforming most previously described benchmark materials. The exceptional separation performance of CuI@UiO‐66‐(COOH)2is validated by breakthrough experiments for 50/50 v/v C2H4/C2H6mixtures under ambient conditions.