Au/MOF-5催化剂在三组分偶联反应中的催化性能

doi:10.11949/j.issn.0438-1157.20141894

摘要/Abstract

摘要： 采用浸渍法制备了Au/MOF-5催化剂,用X射线衍射(XRD)、N₂物理吸附、红外光谱(IR)、热重分析(TG-DTA)、电感耦合等离子体原子发射光谱(ICP-AES)和透射电镜(TEM)对催化剂进行表征,并探索其在醛、炔和胺三组分(A³)偶联反应中的催化性能。实验结果表明:Au/MOF-5对醛、炔和胺三组分偶联反应具有较好的催化活性,而且对产物炔丙基胺的选择性为100%。Au/MOF-5对反应底物具有较宽的适用范围,对于芳香醛和脂肪醛、二级胺和N-烷基取代苯胺、芳香炔和脂肪炔均具有较好的催化活性,而且对于吸电子芳香醛的催化活性大于供电子芳香醛。Au/MOF-5可以循环使用至少3次,催化活性变化不大。

关键词: 配合物, 催化剂, 化学反应, 活性

Abstract: Gold was supported on a functionalized MOF-5 by impregnation method. The catalyst Au/MOF-5 was characterized by powder X-ray diffraction (XRD), N₂ adsorption-desorption, infrared spectra (IR), thermogravimetric analysis and differential thermal analyses (TG-DTA), transmission electro microscopy (TEM), and inductivity coupled plasma (ICP). Its catalytic performance was examined in one-pot synthesis of structurally divergent propargylamines via three component coupling of aldehyde, alkyne, and amine (A³) in 1,4-dioxane. The results showed that the Au/MOF-5 catalyst displayed high activity (high aldehyde consumption rate and turn-over number at 120℃: 18.7 mmol·(g Au)^-1·h^-1and 14.7, based on total gold content) and 100% selectivity for propargylamines. Various aromatic and aliphatic aldehydes were also able to undergo the A³ coupling on the catalyst Au/MOF-5. It was also found that the conversion of benzaldehyde was higher on the catalyst for aryl aldehydes with electron-withdrawing group bonded on benzene ring than for those with an electron-donating group. There was good conversion of benzaldehyde for secondary amines and N-alkyl aniline such as piperidine, pyrrolidine, morpholine, diethylamine, and N-methylaniline. It was also found that the conversion of benzaldehyde decreased with increasing chain length of straight-chain alkyl substituted phenylacetylene. Au/MOF-5 catalyst could be recycled at least three times, and the activity only decreased slightly.

Key words: complexes, catalyst, chemical reaction, reactivity

中图分类号:

O643

刘丽丽, 台夕市, 刘美芳, 李玉峰, 冯一民, 孙晓日. Au/MOF-5催化剂在三组分偶联反应中的催化性能[J]. 化工学报, 2015, 66(5): 1738-1747.

LIU Lili, TAI Xishi, LIU Meifang, LI Yufeng, FENG Yimin, SUN Xiaori. Supported Au/MOF-5: a highly active catalyst for three-component coupling reactions[J]. CIESC Journal, 2015, 66(5): 1738-1747.

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