Liu Bo, Zhao Ruili, Yue Kefen, Shi Jingtao, Yu Yang, Wang Yaoyu
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China.
Dalton Trans. 2013 Oct 14;42(38):13990-6. doi: 10.1039/c3dt51258d. Epub 2013 Aug 9.
By employing the mixed-linker synthetic strategy, two new cobalt(II) cluster-based frameworks, [Co(2.5)(btc)(atz)2(Hatz)(DMF)]·2DMF (1) and [Co(2.5)(btc)(Hbtc)0.5(atz)(CH3CN)(H2O)]·H2O (2), constructed from the same initial materials Co(NO3)2, 1,3,5-benzenetricarboxylic acid (H3btc) and 3-amino-1,2,4-triazole (Hatz), have been synthesized by solvothermal reactions. Crystal-structure analyses demonstrated that 1 and 2 are three-dimensional (3D) porous frameworks based on Co-triazolate chain/layer and tricarboxylate pillars. Thermogravimetric analysis (TGA) and power X-ray diffraction (PXRD) measurements showed that both of them have high thermal stability and good water stability. Remarkably, both the structures of desolvated 1 and 2 contain suitable pore sizes and highly polar channel systems functionalized by amino groups, open metal sites, carbonyl or free carboxylic acid sites and uncoordinated triazolate nitrogen atoms on the pore surfaces, exhibiting multipoint interactions between CO2 molecules and frameworks, resulting in high CO2 uptake and selectivity for CO2 over N2.
通过采用混合连接体合成策略，利用相同的起始原料硝酸钴、1,3,5-苯三甲酸（H3btc）和3-氨基-1,2,4-三唑（Hatz），通过溶剂热反应合成了两个基于钴（II）簇的新型框架化合物，即[Co(2.5)(btc)(atz)2(Hatz)(DMF)]·2DMF（1）和[Co(2.5)(btc)(Hbtc)0.5(atz)(CH3CN)(H2O)]·H2O（2）。晶体结构分析表明，1和2是基于钴-三唑链/层和三羧酸支柱的三维（3D）多孔框架。热重分析（TGA）和粉末X射线衍射（PXRD）测量表明，它们都具有高的热稳定性和良好的水稳定性。值得注意的是，脱溶剂后的1和2的结构都含有合适的孔径和由氨基、开放金属位点、羰基或游离羧酸位点以及孔表面未配位的三唑氮原子功能化的高极性通道系统，表现出CO2分子与框架之间的多点相互作用，从而导致对CO2的高吸附量以及对CO2相对于N2的高选择性。
