Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent.
Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent.
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DOI：
10.1039/c4sc03217a
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发表时间：
2015-03-01
期刊：
影响因子：
8.4
通讯作者：
James SL
中科院分区：
文献类型：
--
作者：
Crawford D;Casaban J;Haydon R;Giri N;McNally T;James SL
连续流动机械化学和熔融相合成在公斤h-1速率从固体试剂，或者没有溶剂，或只有最低限度的溶剂，报告。在无溶剂或低溶剂条件下研磨固体试剂（机械化学）作为一种通用合成技术正在兴起，它是传统溶剂密集型方法的替代品。然而，如果要实现清洁生产的承诺，就必须找到扩大这种合成的方法。在这里，我们展示了使用双螺杆和单螺杆挤出机连续合成各种金属络合物，包括Ni（salen），Ni（NCS）2（PPh 3）2以及商业上重要的金属有机框架（MOFs）Cu 3（BTC）2（HKUST-1），Zn（2-甲基咪唑）2（ZIF-8，MAF-4）和Al（富马酸盐）（OH）。值得注意的是，Al（富马酸盐）（OH）以前没有被机械化学合成。发生定量转化，以得到产品在千克h-1的速率，活化后，表现出的表面积和孔体积相当于那些由传统的溶剂基方法生产的材料。一些反应可以在完全无溶剂的条件下进行，而另一些反应需要加入少量溶剂（通常为3-4摩尔当量）。还通过双螺杆和单螺杆挤出成功地证明了ZIF-8的连续纯熔融相合成。后一种技术以4 kg h-1提供ZIF-8。这些方法的时空产率（STY）高达144 × 103 kg/m3/天，比其他制造MOFs的方法的STY大几个数量级。挤出方法显然能够在无溶剂或低溶剂条件下放大机械化学和熔融相合成，并且还可以更普遍地应用于合成。
Continuous flow mechanochemical and melt-phase synthesis at kg h–1 rates from solid reagents and either no solvent, or only minimal solvent, is reported. Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h–1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h–1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.
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影响因子：
3.4
作者：
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通讯作者：
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通讯作者：
Friscic, Tomislav
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通讯作者：
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