Design and Precursor-based Solid-State Synthesis of Mixed-Linker Zr-MIL-140A.
Design and Precursor-based Solid-State Synthesis of Mixed-Linker Zr-MIL-140A.
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DOI：
10.1021/acs.inorgchem.0c02221
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发表时间：
2020-09
影响因子：
4.6
通讯作者：
S. Leubner;Renée Siegel;Julia Franke;M. Wharmby;C. Krebs;H. Reinsch;J. Senker;N. Stock
中科院分区：
文献类型：
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作者：
S. Leubner;Renée Siegel;Julia Franke;M. Wharmby;C. Krebs;H. Reinsch;J. Senker;N. Stock
乙酸，一种替代的绿色溶剂，用于溶剂热合成四种2D材料，其组成为[Zr 2 O2（OAc）2（BDC-F）]、[Zr 2 O2（OAc）2（BDC-F4）]、[Zr 2 O2（OAc）2（BDC）]和[Zr 2 O2（OAc）2（NDC）]（BDC，对苯二甲酸酯; BDC-F，2-氟对苯二甲酸酯; BDC-F4，对苯二甲酸二甲酯; NDC，2，6-萘二甲酸酯）。前三种化合物随后与对苯二甲酸在固态反应中反应以形成多孔MIL-140 A型金属-有机骨架和混合连接基衍生物（[ZrO（BDC）1-x（BDC-Y）x]，x = 0-0.18，Y = F，F4）。借助时间分辨同步加速器和温度分辨内部X射线粉末衍射实验研究了MIL-140 A形成的反应动力学。彻底的组成分析和固态NMR光谱实验被用来评估不同的连接分子的晶体学排序。此外，还发现了基于乙酸的直接合成MIL-140 A-NO2和新型MIL-140 A-（CH 3）2衍生物的路线。
Acetic acid, an alternative green solvent, was utilized for the solvothermal synthesis of four 2D materials of composition [Zr2O2(OAc)2(BDC-F)], [Zr2O2(OAc)2(BDC-F4)], [Zr2O2(OAc)2(BDC)], and [Zr2O2(OAc)2(NDC)] (BDC, terephthalate; BDC-F, 2-fluoroterephthalate; BDC-F4, tetrafluoroterephthalate; NDC, 2,6-naphthalenedicarboxylate). The first three compounds were subsequently reacted with terephthalic acid in solid-state reactions to form porous MIL-140A-type metal-organic frameworks and mixed-linker derivatives ([ZrO(BDC)1-x(BDC-Y)x], x = 0-0.18, Y = F, F4). The reaction kinetics of the formation of MIL-140A were investigated with the aid of time-resolved synchrotron and temperature-resolved in-house X-ray powder diffraction experiments. Thorough compositional analyses and solid-state NMR spectroscopic experiments were used to assess the crystallographic ordering of the different linker molecules. Additionally, acetic acid-based routes for the direct synthesis of MIL-140A-NO2 and a novel MIL-140A-(CH3)2 derivative were discovered.