Dinker Manish Kumar, Li Meng-Meng, Liu Yang, Zuo Mingrui, Ding Lifeng, Kou Jiahui, Sun Lin-Bing
State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), College of Chemical Engineering, Nanjing Tech University, Nanjing, 211816, China.
Department of Chemistry, Xi'an JiaoTong-Liverpool University, Suzhou, 215123, China.
Small. 2024 Oct;20(43):e2403174. doi: 10.1002/smll.202403174. Epub 2024 Jun 21.
Porosity in bulky solvents can be created by the methods of dispersing and dissolving porous hosts or by their chemical adornment. And the ensuing liquids with cavities offer requisite high gas uptakes. Intriguingly, metal-organic cages (MOCs) as discrete nanoporous hosts have been utilized recently as soluble entities to obtain a series of interesting type II porous liquids (PLs). Yet, factors affecting the fabrication of type II PLs have not been disclosed. Herein, three metallocages (NUT-101, ZrT-1-NH, and ZrT-1) with the same zirconocene nodes but different organic ligands are chosen as porous hosts and a polyethylene-glycol (PEG) linked bis-imidazolium based IL, IL(NTf), is used as a bulky solvent. It is revealed for the first time that the generation of type II PL depends upon the flexibility of MOCs and the interaction between MOCs and solvent molecules. The maximum solubility is observed with NUT-101 (5%) in IL(NTf) while ZrT-1-NH and ZrT-1 remain least soluble (0.5% and 0.2%). As a result, PL-NUT-101-5% with most intrinsic cavities shows higher CO uptake (0.576 mmol g) than PL-ZrT-1-NH-0.5% and PL-ZrT-1-0.2% as well as those reported type II PLs.
在体积较大的溶剂中，可以通过分散和溶解多孔主体或对其进行化学修饰的方法来产生孔隙率。随后产生的带有空腔的液体具有所需的高气体吸收量。有趣的是，金属有机笼（MOCs）作为离散的纳米多孔主体，最近已被用作可溶性实体，以获得一系列有趣的II型多孔液体（PLs）。然而，影响II型PLs制备的因素尚未公开。在此，选择三种具有相同二茂锆节点但有机配体不同的金属笼（NUT-101、ZrT-1-NH和ZrT-1）作为多孔主体，并使用一种基于聚乙二醇（PEG）连接的双咪唑鎓的离子液体IL(NTf)作为体积较大的溶剂。首次揭示了II型PL的产生取决于MOCs的柔韧性以及MOCs与溶剂分子之间的相互作用。在IL(NTf)中，NUT-101的最大溶解度为5%，而ZrT-1-NH和ZrT- 的溶解度最低（分别为0.5%和0.2%）。结果，具有最多固有空腔的PL-NUT-101-5%比PL-ZrT-1-NH-0.5%和PL-ZrT-1-0.2%以及那些已报道的II型PLs表现出更高的CO吸收量（0.576 mmol g）。
