Cu-BTC及其衍生物在苯甲醇选择氧化反应中的催化活性  

Selective Catalytic Oxidation of Benzyl Alcohol over Cu-BTC and Its Derivatives

作　　者：李和健 吴藏藏 郑丽[1] 廖卫平[1] 徐秀峰[1] 

机构地区：[1]烟台大学应用催化研究所,山东烟台264005

出　　处：《分子催化》2017年第4期341-347,共7页Journal of Molecular Catalysis(China)

基　　金：山东省重点研发计划项目(2016GSF117003)~~

摘　　要：以硝酸铜和均苯三甲酸(BTC)为原料,水热合成了一种金属有机骨架化合物Cu-BTC,在水相中催化苯甲醇选择氧化反应,H2O2氧化剂,优化了Cu-BTC的晶化条件.70℃反应1 h,Cu-BTC(110C/24 h)上的苯甲醇转化率为75.4%、苯甲醛选择性83.5%,但反应后Cu-BTC骨架完全塌陷.在氮气中高温焙烧Cu-BTC,制得衍生物Cu@C,也用于催化苯甲醇氧化反应.结果表明:Cu@C催化剂重复使用5次,可维持较高的苯甲醇转化率,但苯甲醛选择性有所下降.用X射线衍射(XRD)、N2物理吸附(BET)、热分析(TG-DSC)、红外光谱(FTIR)、能量色散X射线光谱分析(EDX)等技术对催化剂进行了结构表征,发现:Cu@C在反应中生成的Cu2O促进了苯甲醛的深度氧化.A metal organic framework compound （MOF） of Cu-BTC was hydro-thermally synthesized by using benzene tri-carboxylic acid （BTC） as organic ligand and copper nitrate as metal cation resource. Then, the oxidation of benzyl alcohol was catalyzed by Cu-BTC as-prepared under the reaction conditions ： H202 as oxidant and water as solvent. 75.4% conversion of benzyl alcohol and 83.5% selectivity of benzaldehyde were obtained over Cu-BTC （ 110C/24 h） at 70 ℃ for 1 h. It was found that the skeleton of Cu-BTC was collapsed after reaction. Subsequently, the Cu@ C was prepared by calcining Cu-BTC in nitrogen atmosphere at high temperature, and the re-usability of Cu@ C catalyst in benzyl alcohol oxidation was evaluated. It was found that the conversion of benzyl alcohol could be kept at about 60%, but the selectivity of benzaldehyde decreased after five runs. In addition, Cu-BTC and Cu@ C samples were characterized by XRD, BET, TG-DSC, FFIR and EDX techniques. The results show that Cu2O formed in spent Cu@ C catalysts promoted the deep oxidation of benzaldehyde to benzoic acid.

关 键 词：苯甲醇选择氧化 Cu-BTC Cu-BTC衍生物 Cu@C 催化活性 

分 类 号：O643.3[理学—物理化学]