New group 13 MIL-53 derivates based on 2,5-thiophenedicarboxylic acid
New group 13 MIL-53 derivates based on 2,5-thiophenedicarboxylic acid
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DOI：
10.1002/zaac.201700260
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发表时间：
2017-10
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通讯作者：
C. B. L. Tschense;N. Reimer;Chin-Wen Hsu;H. Reinsch;Renée Siegel;Wu Chen;Chia‐Her Lin;A. Cadiau-A.-Cad
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作者：
C. B. L. Tschense;N. Reimer;Chin-Wen Hsu;H. Reinsch;Renée Siegel;Wu Chen;Chia‐Her Lin;A. Cadiau-A.-Cad
报道了一种由2，5-噻吩二甲酸酯（TDC）与Al、Ga或In构筑的具有MIL-53拓扑结构的刚性金属有机骨架（MOF）。其结构包含共享MO 6-八面体的反式角的链，通过连接分子连接以形成微孔方形1D通道。结合粉末X射线衍射（PXRD），密度泛函理论（DFT）计算和1H，13 C和27 Al固态NMR光谱（ssNMR）被用来详细分析结构。该合成很容易放大使用微波辅助溶剂热条件。所有材料在空气中具有高达420 °C的高热稳定性，并对N2，H2，CO2和CH 4具有永久性孔隙率。Al-MIL-53-TDC显示出高的比表面积as，BET = 1150 m2 g-1，表观体积Vmic = 0.48 cm 3g-1，以及具有S形形状的每个总式5.5 H2O分子的吸水量（469 mg/g），这有利于热转化过程。值得注意的是，该材料在-196 °C和1巴下吸附2.1重量%的出，这超过了基于线性官能化碳酸酯的其他Al-MIL-53化合物。
A new rigid metal-organic framework (MOF) with MIL-53 topology built of 2,5-thiophenedicarboxylate (TDC) and Al, Ga or In is reported. Its structure contains chains of trans corner sharing MO6-octahedra, connected by the linker molecules to form microporous square shaped 1D channels. A combination of powder X-ray diffraction (PXRD), density functional theory (DFT) calculations and 1H, 13C and 27Al solid-state NMR spectroscopy (ssNMR) was used to analyse the structures in detail. The synthesis is easily scaled-up using microwave assisted solvothermal conditions. All materials possess a high thermal stability up to 420 °C in air and permanent porosity towards N2, H2, CO2, and CH4. Al-MIL-53-TDC shows a high specific surface area of as,BET = 1150 m2g-1 with a micropore volume of Vmic = 0.48 cm3g-1 as well as water uptake of 5.5 H2O molecules per sum formula (469 mg/g) with an a sigmoidal shape, advantageous for heat-transformation processes. Noteworthy, this material adsorbs 2.1 wt% H2 at -196 °C and 1 bar which surpasses other Al-MIL-53 compounds based on linear functionalized terephthalates.