Liu Jiao, Zhao Ying, Dang Li-Long, Yang Guoping, Ma Lu-Fang, Li Dong-Sheng, Wang Yaoyu
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, P. R. China.
Chem Commun (Camb). 2020 Aug 11;56(62):8758-8761. doi: 10.1039/d0cc03111a. Epub 2020 Jul 3.
In this study, two new monometallic organic frameworks (MOFs), namely {[ZnL(NMP)(HO)]·HO} (1) and {[PbL(HO)]·HO} (2), were synthesized for the first time by a new bifunctional N,O-containing 2-(1H-tetrazol-5-yl)terephthalic acid (HL) ligand. Then, based on the HSAB principle, another porous Pb-Zn heterometallic organic framework (HMOF), namely {[PbZnL(HO)]·0.5NMP·HO} (3), was successfully obtained for the first time by combining Pb(ii) and Zn(ii) ions with HL. The MOFs 1 and 2 are 3D densely packed frameworks, whereas the HMOF 3 is a porous 3D framework (28.9% porosity) with 1D open channels modified by Lewis basic sites (exposed N atoms) and Lewis acidic sites (unsaturated bimetallic sites). The HMOF 3 has a strong boiling water/acid-base resistance (pH = 2-12) and shows an enhanced high-efficiency catalytic effect for CO conversion (98%) under ambient temperature and pressure conditions. In addition, fine color regulations of the MOFs were successfully realized by doping different kinds of metal ions into them. This study aims to provide a new way and field of vision for the construction of HMOFs and their multi-functional materials.
在本研究中,首次通过一种新型含氮、氧的双功能2-(1H-四唑-5-基)对苯二甲酸(HL)配体合成了两种新型单金属有机框架(MOF),即{[ZnL(NMP)(H₂O)]·H₂O}(1)和{[PbL(H₂O)]·H₂O}(2)。然后,基于软硬酸碱(HSAB)原理,通过将Pb(ii)和Zn(ii)离子与HL结合,首次成功获得了另一种多孔Pb-Zn异金属有机框架(HMOF),即{[PbZnL(H₂O)]·0.5NMP·H₂O}(3)。MOF 1和2是三维紧密堆积框架,而HMOF 3是具有一维开放通道的多孔三维框架(孔隙率为28.9%),这些通道由路易斯碱位点(暴露的N原子)和路易斯酸位点(不饱和双金属位点)修饰。HMOF 3具有很强的耐沸水/酸碱性能(pH = 2 - 12),并且在常温常压条件下对CO转化显示出增强的高效催化效果(98%)。此外,通过向MOF中掺杂不同种类的金属离子,成功实现了对其精细的颜色调控。本研究旨在为HMOF及其多功能材料的构建提供一种新的途径和视野。