负载型离子液体在C-H键电氧化活化中的应用研究  

Application of Composite Ionic Liquid in Electro-Oxidation Activation of a C-H Bond

作　　者：陈姿颖[1] 武倩倩[1] 张健青[1] 朱英红[1] 马淳安[1] CHEN Zi-ying WU Qian-qian ZHANG Jian-qing ZHU Ying-hong MA Chun-an(College of Chemical Engineering, Zhejiang University of Technology, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Hangzhou 310032, China)

机构地区：[1]浙江工业大学化学工程学院绿色化学合成技术国家重点实验室培育基地,浙江杭州310032

出　　处：《电化学》2017年第1期1-6,共6页Journal of Electrochemistry

基　　金：973前期研究专项(No.2012CB722604)资助

摘　　要：本文将1-乙基-3-甲基咪唑醋酸盐离子液体修饰在多壁碳纳米管上,制备出离子液体/碳纳米管复合材料,并研究了对甲氧基甲苯(p-MT)在该复合离子液体水溶液体系中的电氧化性能.同时,通过循环伏安法和计时电流法考查了扫描速率、温度、反应底物浓度等因素对电氧化性能的影响,研究了p-MT在该体系中的动力学过程.实验结果表明,p-MT在复合离子液体水溶液体系中发生不可逆的电氧化反应,且该过程受扩散控制,扩散系数为7.69×10^(-10)cm^2·s^(-1).适当地升高温度和增大反应底物浓度都有利于促进p-MT中C-H键选择性电氧化为相应醛基,选择性可达到95%.通过在不同结构电解槽中进行恒电位电解研究,发现离子液体/MWCNTs复合电解质在一室型电解槽中进行p-MT电氧化的电解效率更高、对目标产物对甲氧基苯甲醛(p-MBA)的选择性也更好.In this paper,the ionic liquid/carbon nanotube composite material was prepared through modifying the ionic liquid1-ethyl-3-methylimidazolium acetate to multi-walled carbon nanotubes.The electro-oxidation properties of p-methoxy toluene（p-MT） were studied using the composite as an electrolyte.The effects of scanning speed,temperature and substrate concentration were studied by cyclic voltammetry and chronoamperometry.The electrochemical kinetics of p-MT in this system was also studied.The results showed that the electrochemical oxidation of p-MT in the composite electrolyte solution was irreversible.The process was mainly controlled by diffusion,and the diffusion coefficient（D） was 7.69 × 10^-10cm2·s-1.Increasing the reaction temperature and the concentration of substrate could promote the electro-oxidation of the C-H bond to the corresponding aldehyde,and the selectivity of p-methoxybenzaldehyde（p-MBA） could improve to 95%.The electrolysis in one-pot was more efficiency and achieved better selectivity than that in the H-type.

关 键 词：C-H键氧化 离子液体/碳纳米管复合材料 电氧化活化 对甲氧基苯甲醛 

分 类 号：O645.1[理学—物理化学] O641.1[理学—化学]