物理化学学报 >> 2011, Vol. 27 >> Issue (02): 499-504.doi: 10.3866/PKU.WHXB20110227

催化和表面科学 上一篇    下一篇

MCM-41介孔材料负载金属的一步法合成及其对酯化反应的催化作用

赵会玲, 许胜, 周建海, 胡军, 刘洪来   

  1. 华东理工大学教育部先进材料及其制备重点实验室, 化学系, 上海 200237
  • 收稿日期:2010-09-10 修回日期:2010-12-01 发布日期:2011-01-25
  • 通讯作者: 胡军 E-mail:junhu@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(20776045, 20736002)和长江学者创新团队(IRT0721)资助项目

One-Step Synthesis of Metal-Doped Mesoporous MCM-41 Materials and Their Application in Esterification Catalysis

ZHAO Hui-Ling, XU Sheng, ZHOU Jian-Hai, HU Jun, LIU Hong-Lai   

  1. Laboratory for Advanced Materials, Department of Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. China
  • Received:2010-09-10 Revised:2010-12-01 Published:2011-01-25
  • Contact: HU Jun E-mail:junhu@ecust.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20736045, 20776002) and Program for Changjiang Scholars and Innovative Research Team in University of China (IRT0721).

摘要:

以增溶了茂金属的十六烷基三甲基溴化铵(CTAB)胶束为模板, 采用一步法合成了介孔表面负载有金属(铁、钛和锆)的介孔材料MCM-41, 通过等离子体电感耦合发射光谱仪(ICP-AES)测定铁、钛和锆负载量(质量分数)分别为1.71%、0.95%和0.81%. 通过X射线衍射(XRD)图谱和N2吸脱附等温线可知, 负载金属的介孔材料M-MCM-41(T) 仍具有较高的比表面以及规整的六方有序孔道结构, 去除模板剂的焙烧温度对孔道结构有一定影响. 由一步法合成的金属负载介孔材料对乙酸正丁酯的酯化反应具有很高的催化活性, 其中Fe-MCM-41在单位时间单位金属催化生成的产物量(TOF)为55643 g·h-1·g-1, 而Zr-MCM-41的TOF高达125320 g·h-1·g-1. 与纯茂金属相比, 由茂金属合成的金属负载介孔材料可显著提高酯化反应的催化活性.

关键词: 茂金属, M-MCM-41, 一步法合成, 酯化, 催化效率

Abstract:

Metals (Fe, Ti, Zr) were doped into mesoporous MCM-41 by a one-step method using cetyltriethylammonium bromide (CTAB) micelles with micellar solubilized metallocenes as templates. X- ray diffraction (XRD) and N2 adsorption-desorption isotherms show that after metallocene doping, M- MCM-41(T) materials still preserved the ordered hexagonal structure and high BET surface area. Inductively coupled plasma atomic emission spectrometry (ICP-AES) indicated that the mass fractions of the metals in the corresponding samples are: 1.71% Fe in Fe-MCM-41(400), 0.95% Ti in Ti-MCM-41(550) and 0.81% Zr in Zr-MCM-41(550). All the M-MCM-41(T) materials showed a particular high catalysis effect for the esterification of acetic acid and n-butanol. The TOF of Fe-MCM-41(400) and Zr-MCM-41(550) were 55643 g·h-1·g-1 and 125320 g·h-1·g-1, respectively, which is much higher than that of the corresponding pure metallocenes.

Key words: Metallocene, M-MCM-41, One-step impregnation, Esterification, Catalysis effect

MSC2000: 

  • O643