基于磺酸基团改性配体的新型金属有机骨架的合成及晶体结构

    Synthesis and Crystal Structures of New Metal-Organic Frameworks Based on Sulfonic Acid Group Functionalized Ligand

    • 摘要: 为解决金属有机-骨架(MOFs)电导率低的问题,研究利用溶剂热的方法使用磺酸基团改性配体(4,8-二磺酸基-2,6-二羧基萘,H4L)分别和Fe(NO33·9H2O、Ni(CH3COO)2·4H2O、CoCl2·6H2O构筑了3个新型的金属-有机骨架:FeL0.5(NMP)2n(BUT-203)、NiL0.5(DMA)2n(BUT-204)和CoL0.5(DMA)(dpe)·H2O(BUT-205).并且对它们进行了单晶X射线衍射(SXRD)、红外(FT-IR)、热重分析(TGA)、元素(EA)以及交流阻抗分析表征.单晶X射线衍射分析显示,BUT-203和BUT-204具有相同的一维链状结构,BUT-205是具有gwg拓扑的三维骨架材料.交流阻抗研究发现,三维结构的BUT-205电导率可达5.66×10-4 S/cm,明显高于一维结构的BUT-203和BUT-204的质子电导率,说明在配体相同的情况下,三维结构可提高MOFs的质子电导率.

       

      Abstract: To obtain metal-organic frameworks (MOFs) with high proton conductivity, three new MOFs, FeL0.5(NMP)2n(BUT-203), NiL0.5(DMA)2n (BUT-204), andCoL0.5(DMA)(dpe)·H2O (BUT-205) were synthesized through the solvothermal reaction between a sulfonic acid group functionalized ligand, 4, 8-disulfonaphthalene-2, 6-dicarboxylic acid (H4L) and Fe(NO3)3·9H2O, Ni(CH3COO)2·4H2O, or CoCl2·6H2O, respectively, and characterized by single-crystal X-ray diffraction (SXRD), thermogravimetric analysis (TGA), infrared spectroscopy (FT-IR), and elemental analysis (EA). BUT-203 and BUT-204 are isostructural structures with one-dimensional chain, while BUT-205 is a three-dimensional framework with gwg topology. Impendence tests show that BUT-205 with three-dimensional structure possesses proton conductivity with a value of 5.661×10-4 S/cm, obviously higher than that of one-dimensional BUT-203 and BUT-204. This fact reveals that the three-dimensional structure can effectively improve the proton conductivity of MOFs.

       

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