催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (3): 416-424.DOI: 10.1016/S1872-2067(11)60334-3

• 研究论文 • 上一篇    下一篇

无机氧化物载体对催化 CO2 与环氧化合物合成环状碳酸酯的促进作用

曹婷, 孙立婷, 石玉, 华丽, 张然, 郭立, 朱闻闻, 侯震山*   

  1. 华东理工大学工业催化研究所, 结构可控先进功能材料及其制备教育部重点实验室, 上海 200237
  • 收稿日期:2011-09-13 修回日期:2011-10-18 出版日期:2012-03-15 发布日期:2015-07-27

The Role of Inorganic Oxide Supports in Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides

CAO Ting, SUN Liting, SHI Yu, HUA Li, ZHANG Ran, GUO Li, ZHU Wenwen, HOU Zhenshan*   

  1. Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China
  • Received:2011-09-13 Revised:2011-10-18 Online:2012-03-15 Published:2015-07-27

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摘要： 以一系列无机氧化物与四丁基溴化铵为双组分催化剂体系, 考察了其催化 CO2 和环氧化合物合成环状碳酸酯的反应性能. 结果表明, 在四丁基溴化铵与这些本身并没有催化活性的无机氧化物共同作用下, 反应活性明显提高, 表现出很强的协同催化作用. 另外, 通过对 SiO2 的表面硅烷基化, 考察了其表面羟基数量对反应活性的影响, 发现当 SiO2 的表面经过硅烷基化以后, 反应活性大幅度降低, 表明无机氧化物表面羟基对 CO2 环加成反应活性有非常显著的促进作用.

关键词: 无机氧化物, 二氧化碳, 环状碳酸酯, 二氧化硅, 羟基, 硅烷基化, 协同催化

Abstract: An inorganic oxide support coupled with a quaternary ammonium salt is an efficient catalyst for the cycloaddition of CO2 and epoxide to produce cyclic carbonates under relatively mild reaction conditions (90 oC, 4 MPa). When tetrabutylammonium bromide (TBAB) was used alone, the activity of the cycloaddition reaction between carbon dioxide and epoxide was only moderate. When an inorganic oxide, especially one that has abundant surface hydroxyl groups was also employed, the reaction was accelerated significantly. This demonstrated that the inorganic oxide and TBAB had a strong synergetic effect for the cycloaddition reaction. Silica was chosen as a model oxide to study the role of surface hydroxyl groups in the reaction. When the surface of silica was silylated with trimethylchlorosilane or dimethyldichlorosilane, the catalytic activity decreased sharply due to surface silylation, which indicated clearly that the surface hydroxyl groups on the silica played a decisive role in influencing the catalytic activity.

Key words: inorganic oxide, carbon dioxide, cyclic carbonate, silica, hydroxyl groups, silylation, synergetic effect