物理化学学报 >> 2012, Vol. 28 >> Issue (09): 2148-2154.doi: 10.3866/PKU.WHXB201206121

催化和表面科学 上一篇    下一篇

SO42-/SnO2-Fe2O3固体酸催化下的环酮Baeyer-Villiger氧化反应及缩合反应

杨志旺, 陈丽娜, 洪伟, 康瑞雪, 王佳, 贾娜, 赵磊, 马恒昌   

  1. 西北师范大学化学化工学院, 生态环境相关高分子材料教育部重点实验室, 甘肃省高分子材料重点实验室, 兰州730070
  • 收稿日期:2012-03-26 修回日期:2012-06-12 发布日期:2012-08-02
  • 通讯作者: 杨志旺 E-mail:yangzw@nwnu.edu.cn
  • 基金资助:

    国家自然科学基金(21163016, 21174114), 甘肃省自然科学基金(1010RJZA024), 西北师范大学“知识与科技创新工程项目”(NWNU-KJCXGC-03-63)资助

Baeyer-Villiger Oxidation and Acetalization of Cyclic Ketones on SO42-/SnO2-Fe2O3 Solid Acid Catalysts

YANG Zhi-Wang, CHEN Li-Na, HONG Wei, KANG Rui-Xue, WANG Jia, JIA Na, ZHAO Lei, MA Heng-Chang   

  1. Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China
  • Received:2012-03-26 Revised:2012-06-12 Published:2012-08-02
  • Contact: YANG Zhi-Wang E-mail:yangzw@nwnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21163016, 21174114), Gansu Provincial Natural Science Foundation, China (1010RJZA024), and Scientific Research Fund of Northwest Normal University, China (NWNU-KJCXGC-03-63).

摘要:

采用共沉淀的方法制备了不同Fe 掺杂量的SO42-/SnO2-Fe2O3固体超强酸催化剂. 利用傅里叶变换红外(FTIR)光谱, 粉末X射线衍射(XRD), N2吸附-脱附实验(BET), 热重(TG)分析和扫描电镜(SEM)等方法对样品进行了表征. 考察了所得催化剂对4-叔丁基环己酮与乙二醇缩合反应的催化性能. 实验结果表明, 与未经过掺杂改性的SO42-/SnO2固体酸催化剂相比, 改性后催化剂的催化性能得到了改善. 研究了以Fe/Sn 摩尔比为0.5的SO42-/SnO2-Fe2O3固体酸为催化剂, 部分醛酮类化合物与乙二醇及1,2-丙二醇的缩合反应. 考察了反应时间、催化剂用量等因素对反应的影响. 同时, 将所得催化剂应用于环酮Baeyer-Villiger 氧化反应中, 催化剂表现出良好的催化活性, 且催化剂具有一定的循环使用性.

关键词: 固体酸, 缩合反应, Baeyer-Villiger 氧化, Fe2O3-掺杂, 硫酸氧化锡

Abstract:

Fe-doped SO42-/SnO2 (STF) solid acid catalysts with different amounts of iron were prepared via co-condensation, followed by sulfation and calcination. These materials were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray powder diffraction (XRD), N2 adsorption-desorption analysis (BET), thermogravimetric (TG) analysis, and scanning electron microscopy (SEM). The Fe-doped catalysts exhibited more activity than undoped catalysts in acetalization reactions of 4-tert-butylcyclohexanone and diols. The catalytic acetalization of several ketones and 1,2-diols with the SO42-/SnO2-Fe2O3 catalysts (with the Fe/Sn molar ratio of 0.5) were studied. The influence of the reaction time and the amount of the catalysts on the acetalization were also investigated. In addition, the high performance of this Fe-modified catalyst was demonstrated in the Baeyer-Villiger oxidation of cyclic ketones. The catalyst can be recycled several times without any significant loss in catalytic activity.

Key words: Solid acid, Acetalization, Baeyer-Villiger oxidation, Fe2O3-doping, Sulfated tin oxide

MSC2000: 

  • O643