Hu Zhigang, Faucher Samuel, Zhuo Yingying, Sun Yao, Wang Songnan, Zhao Dan
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585 (Singapore).
Department of Mechanical Engineering, National University of Singapore, Singapore 117575 (Singapore).
Chemistry. 2015 Nov 23;21(48):17246-55. doi: 10.1002/chem.201503078. Epub 2015 Oct 19.
The strategy to functionalize water-stable metal-organic frameworks (MOFs) in order to improve their CO2 uptake capacities for efficient CO2 separation remains limited and challenging. We herein present an effective approach to functionalize a prominent water-stable MOF, UiO-66(Zr), by a combination of optimization and metalated-ligand exchange. In particular, by systematic optimization, we have successfully obtained UiO-66(Zr) of the highest BET surface area reported so far (1730 m(2) g(-1) ). Moreover, it shows a hybrid Type I/IV N2 isotherm at 77 K and a mesopore size of 3.9 nm for the first time. The UiO-66 MOF underwent a metalated-ligand-exchange (MLE) process to yield a series of new UiO-66-type MOFs, among which UiO-66-(COONa)2 -EX and UiO-66-(COOLi)4 -EX MOFs have both enhanced CO2 working capacity and IAST CO2 /N2 selectivity. Our approach has thus suggested an alternative design to achieve water-stable MOFs with high crystallinity and gas uptake for efficient CO2 separation.
为提高水稳定金属有机框架材料（MOFs）对二氧化碳的吸附能力以实现高效二氧化碳分离而进行功能化的策略仍然有限且具有挑战性。在此，我们提出一种通过优化和金属化配体交换相结合的方法来对一种著名的水稳定MOF——UiO-66(Zr)进行功能化。特别是，通过系统优化，我们成功获得了迄今为止报道的具有最高BET表面积（1730 m² g⁻¹）的UiO-66(Zr)。此外，它在77 K时首次呈现出I型/IV型混合氮气等温线，中孔尺寸为3.9 nm。UiO-66 MOF经历了金属化配体交换（MLE）过程，生成了一系列新型UiO-66型MOFs，其中UiO-66-(COONa)₂-EX和UiO-66-(COOLi)₄-EX MOFs的二氧化碳工作容量和IAST二氧化碳/氮气选择性均有所提高。因此，我们的方法为实现具有高结晶度和气体吸附能力的水稳定MOFs以进行高效二氧化碳分离提供了一种替代设计。
