催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (10): 880-884.

• 研究论文 • 上一篇    下一篇

电催化活化二氧化碳合成苯氨基甲酸乙酯

钮东方,徐承天,张丽,罗仪文,张凯,陆嘉星   

  1. 华东师范大学化学系, 上海市绿色化学及化工过程绿色化重点实验室, 上海 200062
  • 收稿日期:2007-10-25 出版日期:2007-10-25 发布日期:2011-10-28

Activation of Carbon Dioxide by Electrocatalysis for Synthesis of Ethyl Carbanilate

NIU Dongfang, XU Chengtian, ZHANG Li, LUO Yiwen, ZHANG Kai, LU Jiaxing*   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China
  • Received:2007-10-25 Online:2007-10-25 Published:2011-10-28

PDF

1388

被引次数

32

摘要： 在常温常压下,通过循环伏安法探讨了Ni(bpy)3Cl2催化剂对CO2间接电化学活化的机理及CO2与苯胺、碘乙烷合成苯氨基甲酸乙酯的反应机理. 结果表明, Ni(bpy)3Cl2催化剂对CO2的活化具有很高的催化效率, DMF溶液中加入Ni(bpy)3Cl2催化剂可使CO2的电化学还原电位由-2.3V移到-1.6V, 从而可大大改善合成苯氨基甲酸乙酯反应的条件,苯氨基甲酸乙酯的选择性可达100%. 考察了催化剂用量、电解电位、工作电极材料、温度和支持电解质及通电量对苯氨基甲酸乙酯收率的影响. 结果表明,在优化的条件下,苯氨基甲酸乙酯的收率为60.8%.

关键词: 二氧化碳, 二氯•, 三(2, 2′-联吡啶)合镍(Ⅱ), 电催化, 碘乙烷, 苯胺, 苯氨基甲酸乙酯

Abstract: CO2 was elctrochemically activated by the Ni(bpy)3Cl2 catalyst and reacted with aniline and iodoethane to ethyl carbanilate under mild conditions (p(CO2)=0.1 MPa, 20 ℃). The CO2 activation mechanism and the synthesis reaction mechanism were proposed. The electroreductive potential of CO2 was moved from-2.1V to-1.6V owing to the Ni(bpy)3Cl2 catalyst in DMF solution, indicating that the reaction condition was effectively improved. The catalyst showed a good effect on the CO2 activation, and the selectivity for ethyl carbanilate was 100%. The effects of the catalyst, the electrolytic potentials, the nature of the working electrode, the temperature, the supporting electrolytes, and the passed charge amount per mole of aniline supplied to the electrode on the yield of ethyl carbanilate were studied. Under the optimized electrolytic conditions, the maximal yield of ethyl carbanilate was 60.8%.

Key words: carbon dioxide, tri(2, 2′-bipyridyl)nickel(Ⅱ) chloride, electrocatalysis, iodoethane, aniline, ethyl carbanilate