催化学报

催化学报 ›› 2014, Vol. 35 ›› Issue (4): 457-461.DOI: 10.1016/S1872-2067(14)60059-0

• 研究快讯 • 上一篇    下一篇

核壳结构TiO2@SiO2催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯

唐荣芝a,c, 陈彤a, 陈勇b, 张元卓a,c, 王公应a   

  1. a 中国科学院成都有机化学研究所, 四川成都610041;
    b 后勤工程学院国防建筑规划与环境工程系, 重庆401311;
    c 中国科学院大学, 北京100049
  • 收稿日期:2013-12-30 修回日期:2014-01-24 出版日期:2014-03-20 发布日期:2014-03-21
  • 通讯作者: 陈彤
  • 基金资助:

    国家高技术研究发展计划（863 计划，SS2013AA031703）；四川省科技支撑计划（2013GZX0135）；四川省青年科技创新研究团队项目（2013TD0010）.

Core-shell TiO2@SiO2 catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate

Rongzhi Tanga,c, Tong Chena, Yong Chenb, Yuanzhuo Zhanga,c, Gongying Wanga   

  1. a Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China;
    b Department of National Defence Architectural Planning and Environmental Engineering, Logistic Engineering University, Chongqing 401311, China;
    c University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2013-12-30 Revised:2014-01-24 Online:2014-03-20 Published:2014-03-21
  • Supported by:

    This work was supported by the National High Technology Research and Development Program of China (863 Program, SS2013AA031703), Sichuan Province Science and Technology Support Program (2013GZX0135), Sichuan Province Science and Technology Innovation Research Team Program (2013TD0010).

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摘要：

以反相微乳液法和沉淀法相结合制备了核壳结构TiO2@SiO2，首次用于碳酸二甲酯与苯酚酯交换合成碳酸二苯酯反应，显示较好的催化活性. 采用200 ℃焙烧的TiO2@SiO2，用量0.20 g，反应9 h，苯酚转化率达41.8%，酯交换选择性为100%. 透射电镜显示TiO2@SiO2核厚壳薄，TiO2核直径220-300 nm，SiO2壳厚度40-60 nm，具有介孔结构. TiO2@SiO2对碳酸二甲酯与苯酚酯交换反应有好的重复使用性，使用4次苯酚转化率仍保持在40%以上. TiO2与SiO2发生相互作用，Ti进入骨架形成Ti-O-Si键，骨架Ti的形成提高了TiO2@SiO2的催化性能.

关键词: 核壳结构, TiO2@SiO2, 碳酸二苯酯, 碳酸二甲酯, 酯交换

Abstract:

Core-shell TiO2@SiO2 was prepared using a combination of reverse microemulsion and precipitation methods and used as a heterogeneous catalyst for the transesterification of dimethyl carbonate and phenol. TiO2@SiO2 calcined at 200 ℃ gave the best catalytic performance. When the amount of catalyst was 0.20 g, the phenol conversion and transesterification selectivity were 41.8% and 100%, respectively. Transmission electron microscopy was used to characterize the core-shell TiO2@SiO2 structure, and the results showed that TiO2@SiO2 is bilayer with a TiO2 core of diameter 220-300 nm and SiO2 shell of thickness 40-60 nm. The TiO2@SiO2 was reusable, and phenol conversion remained above 40% when the TiO2@SiO2 was used four times. The catalytic performance of TiO2@SiO2 in the transesterification of dimethyl carbonate and phenol was promoted by the formation of Ti-O-Si bonds.

Key words: Core-shell, TiO2@SiO2, Diphenyl carbonate, Dimethyl carbonate, Transesterification