Knebel Alexander, Bavykina Anastasiya, Datta Shuvo Jit, Sundermann Lion, Garzon-Tovar Luis, Lebedev Yury, Durini Sara, Ahmad Rafia, Kozlov Sergey M, Shterk Genrikh, Karunakaran Madhavan, Carja Ionela Daniela, Simic Dino, Weilert Irina, Klüppel Manfred, Giese Ulrich, Cavallo Luigi, Rueping Magnus, Eddaoudi Mohamed, Caro Jürgen, Gascon Jorge
Institute of Physical Chemistry and Electrochemistry, Leibniz University Hannover, Hannover, Germany.
Advanced Catalytic Materials, KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia.
Nat Mater. 2020 Dec;19(12):1346-1353. doi: 10.1038/s41563-020-0764-y. Epub 2020 Aug 10.
The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.
定义明确的分子空腔与化学官能团相结合,使得晶体多孔固体在从催化到气体分离等众多技术应用中颇具吸引力。然而,与聚合物等其他广泛应用的合成固体不同,晶体延伸固体缺乏可加工性,这阻碍了它们的应用。在这项工作中,我们证明了金属有机框架材料(一种高度结晶的多孔固体)可以通过使用N - 杂环卡宾配体进行外表面功能化而实现溶液可加工。对著名的沸石咪唑酯框架ZIF - 67的相对较大纳米颗粒(250纳米)进行选择性外表面功能化,能够稳定具有永久孔隙率的可加工分散体。所得的III型多孔液体既可以直接用作液体吸附剂,也可以与先进聚合物共同加工,以制备出具有优异机械性能且在从丙烷中挑战性地分离丙烯方面表现出色的高负载混合基质膜。我们预计这种方法可以扩展到其他金属有机框架材料和其他应用中。