物理化学学报 >> 2006, Vol. 22 >> Issue (10): 1272-1276.doi: 10.1016/S1872-1508(06)60062-4

研究论文 上一篇    下一篇

负载离子液体纳米钯催化芳卤羰化反应

林棋;付海燕;袁茂林;陈华;李贤均   

  1. 四川大学化学学院, 绿色化学与技术教育部重点实验室, 成都 610064; 闽江学院化学与化学工程系, 福州 350108
  • 收稿日期:2006-05-28 修回日期:2006-06-28 发布日期:2006-10-11
  • 通讯作者: 陈华 E-mail:scuhchen@163.com

Carbonylation of Aryl Halide Catalyzed by Active-carbon Supported Ionic Liquid-phase Palladium Catalyst

LIN Qi;FU Hai-Yan;YUAN Mao-Lin;CHEN Hua;LI Xian-Jun   

  1. Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China; Department of Chemistry and Chemical Engineering, Minjiang University, Fuzhou 350108, P. R. China
  • Received:2006-05-28 Revised:2006-06-28 Published:2006-10-11
  • Contact: CHEN Hua E-mail:scuhchen@163.com

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摘要： 研究了高分散性的负载离子液体纳米钯催化剂的制备及其催化芳卤羰化反应的性能. 用XRD、HRTEM和XPS等方法对催化剂进行了表征, 结果表明, 钯组分处于高分散零价态, 其平均粒径小于5 nm, 且催化剂表面存在一厚度适中的离子液体液膜, 有利于提高催化剂的稳定性; 该催化剂对PhI、PhBr、PhCl的羰化反应的催化活性优于离子液体两相催化体系, 在优化的反应条件下, 碘苯的转化率可达99.3％, 生成苯甲酸乙酯的转化频率(TOF)可高达4926 h−1, 反应产物中苯甲酸乙酯的选择性大于99％.

关键词: 水溶性钯膦络合物, 芳卤, 羰化反应, 离子液体, 负载离子液体钯催化剂

Abstract: Highly dispersed supported ionic liquid-phase palladium catalyst was prepared and its catalytic performances for carbonylation of aryl halide were investigated. Active-carbon supported ionic liquid-phase palladium catalyst was characterized by XRD, high-resolution TEM (HRTEM), and XPS. The results showed that the active-carbon supported ionic liquid-phase palladium catalyst was reduced to zero valence and that the average particle diameter of the Pd crystallites was less than 5 nm. A thin ionic liquid film was observed on the surface of the catalyst. The results indicated that the supported ionic liquid-phase palladium catalyst exhibited higher activity in the carbonylation of aryl halides compared with the correspording organic-ionic liquid biphasic system. Under the optimum reaction conditions: 140 ℃, pCO=4.0 MPa, n(PhI):n(Pd)=10528:1, the turnover frequency(TOF) of 4926 h−1 was achieved for ethyl benzoate, with the conversion of 99.3%, and the selectivity for forming ethyl benzoate was more than 99%.

Key words: Water-soluble palladium-phosphine complex, Aryl halide, Carbonylation, Ionic liquid, Supported ionic liquid-phase palladium catalyst