Enhanced catalytic properties of MOF-199 with water treatment in the direct hydroxylation of benzene

doi:10.16085/j.issn.1000-6613.2016.04.023

Abstract

Abstract: Cu(OAc)₂·H₂O was treated with benzenetricarboxylic acid under stirring to form metal-organic framework MOF-199, which was then characterized by XRD, IR and BET. The obtained MOF-199 was treated with water and then applied for the hydroxylation of benzene as catalyst. The effect factors of MOF-199 amount, reaction temperature, reaction time, H₂O₂ amount on the yield and the selectivity of benzene oxygenates were investigated. Results indicated suitable conditions for the preparation of benzene oxygenates, were that the water-treated MOF-199 (140mg, 0.23mmol), acetonitrile (4mL), benzene (1.1mL) and H₂O₂ (3.3mL) were mixed together, and then reacted for 30min at 60℃ in a water bath. The corresponding oxygenates had a yield of 23.3%, the selectivity to phenol of 53.1%, and the turnover frequency(TOF) was 25.0h^-1. Pretreatment of MOF-199 catalyst with water significantly accelerated the catalytic oxidation of benzene to the corresponding oxygenates and preserved the metal-organic framework of MOF-199 due to the formation of a new reaction mode.

Key words: metal-organic framework, MOF-199, hydrate, benzene, catalysis

摘要： 以一水合乙酸铜和均苯三酸为原料,采用常温搅拌法合成金属有机框架化合物MOF-199,用XRD、IR、BET对其表征.将MOF-199用水处理后作为催化剂用于苯羟基化反应,考察了催化剂的用量、反应温度、反应时间、双氧水添加量对催化反应的影响.较优反应条件为:MOF-199(140mg,0.23mmol)、乙腈4mL、苯1.1mL、H₂O₂3.3mL,在60℃的水浴中反应30min,所得苯的氧化物的产率为23.3%,苯酚的选择性为53.1%,转化频率(TOF值)为25.0h^-1.水处理显著提高了MOF-199的催化活性,并形成了一种新的氧化模式,在一定程度上保护了MOF-199的框架结构.

关键词: 金属有机框架化合物, MOF-199, 水合物, 苯, 催化

CLC Number:

O625.1

LIU Yanfeng, ZHANG Tianyong, WU Wubin, LI Bin, ZHOU Zheng, ZHOU Haohao. Enhanced catalytic properties of MOF-199 with water treatment in the direct hydroxylation of benzene[J]. Chemical Industry and Engineering Progree, 2016, 35(04): 1113-1120.

刘艳凤, 张天永, 吴武斌, 李彬, 周政, 周浩浩. 水处理提高MOF-199催化苯羟基化反应性能[J]. 化工进展, 2016, 35(04): 1113-1120.

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