Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation
Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation
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DOI：
10.3390/cryst10010017
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发表时间：
2019-12
期刊：
影响因子：
2.7
通讯作者：
Huan V Doan;F. Cheng;Thandeka Dyirakumunda;M. Elsegood;J. Chin;Oliver Rowe;C. Redshaw;V. Ting
中科院分区：
文献类型：
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作者：
Huan V Doan;F. Cheng;Thandeka Dyirakumunda;M. Elsegood;J. Chin;Oliver Rowe;C. Redshaw;V. Ting
在本报告中，我们探索了超临界CO2（scCO2）在合成众所周知的金属有机框架（MOF）（包括Zn-MOF-74和UiO-66）中的应用，以及制备[Cu24(OH-mBDC)24]n金属有机多面体（MOP）和两种新的MOF结构{[Zn2(L1)(DPE)]∙4H2O}n和{[Zn3(L1)3(4,4′-偶氮基)]∙7.5H2O}n，其中 BTC = 苯-1,3,5-三羧酸酯，BDC = 苯-1,4-二羧酸酯，L1 = 4-羧基-亚苯基-亚甲基氨基-4-苯甲酸酯，DPE = 1,2-二(4-吡啶基)乙烯，4.4′-偶氮基 = 4,4′-偶氮吡啶，并将结果与低温（即 40 °C）下的传统溶剂热制剂进行比较。这项工作的目的是看看 SCCO2 路线与溶剂热法是否会产生相同或不同的产品。我们有兴趣了解哪种方法产生最高的产量、最干净的产品以及产生什么类型的形态。虽然没有证据表明这些 MOF/MOP 中存在额外的介孔或大孔，也没有通过向这些系统中添加 scCO2 来显着提高产品产量，但结果表明，scCO2 的使用会对结晶度、晶体尺寸和形态产生影响。
In this report, we explore the use of supercritical CO2 (scCO2) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu24(OH-mBDC)24]n metal-organic polyhedra (MOPs) and two new MOF structures {[Zn2(L1)(DPE)]∙4H2O}n and {[Zn3(L1)3(4,4′-azopy)]∙7.5H2O}n, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L1 = 4-carboxy-phenylene-methyleneamino-4-benzoate, DPE = 1,2-di(4-pyridyl)ethylene, 4.4′-azopy = 4,4′- azopyridine, and compare the results versus traditional solvothermal preparations at low temperatures (i.e., 40 °C). The objective of the work was to see if the same or different products would result from the scCO2 route versus the solvothermal method. We were interested to see which method produced the highest yield, the cleanest product and what types of morphology resulted. While there was no evidence of additional meso- or macroporosity in these MOFs/MOPs nor any significant improvements in product yields through the addition of scCO2 to these systems, it was shown that the use of scCO2 can have an effect on crystallinity, crystal size and morphology.