催化学报 ›› 2009, Vol. 30 ›› Issue (1): 43-47.

• 研究论文 • 上一篇    下一篇

离子液体-乙腈混合溶剂中电催化CO2与甲醇合成碳酸二甲酯

肖丽平,张贵荣,张丽,钮东方,陆嘉星   

  1. 华东师范大学化学系, 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
  • 收稿日期:2009-01-25 出版日期:2009-01-25 发布日期:2012-10-17

Electrosynthesis of Dimethyl Carbonate in [bmim]BF4-MeCN Solvent

XIAO Liping, ZHANG Guirong, ZHANG Li, NIU Dongfang, LU Jiaxing*   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China
  • Received:2009-01-25 Online:2009-01-25 Published:2012-10-17

摘要: 常温常压下分别在离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF4)-MeCN混合溶剂和纯MeCN溶剂中研究了CO2在Cu电极上的循环伏安行为. 结果表明, CO2均发生不可逆还原反应生成CO-2. 与纯MeCN溶剂相比,在混合溶剂中CO2还原峰电位均有正移. 这表明溶剂中的咪唑型离子液体对活化CO2有催化作用. 在混合溶剂中,以CO2和MeOH为原料合成碳酸二甲酯(DMC), 考察了[bmim]BF4/MeCN体积比、工作电极材料、MeOH浓度和电解电位等对DMC产物收率的影响. 与其他DMC合成方法相比,本法反应条件温和、设备简单、合成产物收率较高. 在优化的条件下, DMC产物收率可达79.6%. 并提出了合成DMC可能的反应机理.

关键词: 离子液体, 1-丁基-3-甲基咪唑四氟硼酸盐, 乙腈, 二氧化碳, 甲醇, 电催化, 碳酸二甲酯

Abstract: The electrosynthesis of dimethyl carbonate (DMC) from CO2 and MeOH in the [bm im]BF4-MeCN solvent with different V([bmim]BF4)/V(MeCN) was realized in an undivided cell under mild conditions. The ionic liquid [bmim]BF4 containe d in the mixed solvent possessed catalytic effect on the CO2 electrolysis. The cathodic peak for CO2 reduction shifted positively in the mixed solvent. Unde r the optimal conditions, the highest DMC yield reached 79.6%. A possible reacti on mechanism for electrosynthesis of DMC was proposed.

Key words: ionic liquid, 1-butyl-3-methyl imidazolium tetrafluoroborate, acetonitrile, carbon dioxide, methanol, electrocatalysis, dimethyl carbonate