物理化学学报 >> 2011, Vol. 27 >> Issue (04): 946-952.doi: 10.3866/PKU.WHXB20110434

催化和表面科学 上一篇    下一篇

金在氨基硅烷修饰SBA-15上的巴豆醛选择加氢性能

田莉, 周功兵, 李振华, 裴燕, 乔明华, 范康年   

  1. 上海市分子催化和功能材料重点实验室, 复旦大学化学系, 上海 200433
  • 收稿日期:2010-12-17 修回日期:2011-02-24 发布日期:2011-03-29
  • 通讯作者: 裴燕, 乔明华 E-mail:peiyan@fudan.edu.cn; mhqiao@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(21073043, 20803011), 教育部新世纪优秀人才支持计划(NCET-08-0126), 上海市科委科技基金(10JC1401800, 08DZ2270500)和石油化工催化材料与反应工程国家重点实验室(RIPP, SINOPEC)开放基金课题资助项目

Gold Supported on Aminosilane-Functionalized SBA-15 for Chemoselective Hydrogenation of Crotonaldehyde

TIAN Li, ZHOU Gong-Bing, LI Zhen-Hua, PEI Yan, QIAO Ming-Hua, FAN Kang-Nian   

  1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
  • Received:2010-12-17 Revised:2011-02-24 Published:2011-03-29
  • Contact: PEI Yan, QIAO Ming-Hua E-mail:peiyan@fudan.edu.cn; mhqiao@fudan.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21073043, 20803011), Program of New Century Excellent Talents in Universities, China (NCET-08-0126), Science & Technology Commission of Shanghai Municipality, China (10JC1401800, 08DZ2270500), and State Key Laboratory of Catalytic Materials and Reaction Engineering, China (RIPP, SINOPEC).

摘要:

采用三种氨基硅烷试剂(APTS: 3-氨丙基三甲氧基硅烷, TPED: N-(2-氨乙基)-3-氨丙基三甲氧基硅烷, TPDT: 3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷)对介孔SBA-15分子筛进行后嫁接表面功能化(分别记为APTS-SBA-15, TPED-SBA-15和TPDT-SBA-15), 然后利用氨基与氯金酸之间的静电作用及化学还原法, 将金纳米粒子引入分子筛的介孔孔道. 采用N2物理吸附、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等手段对催化剂的结构和电子性质进行了系统表征; 以巴豆醛液相加氢制巴豆醇反应比较了氨基硅烷的种类对催化性能的影响. 结果表明, 氨基硅烷的给电子能力是决定金催化剂上C=O键加氢选择性的主要因素, 氨基硅烷的给电子能力越强, 金活性位上的电子密度越高, 则巴豆醇的选择性和收率就越高.

关键词: Au, SBA-15, 氨基硅烷, 巴豆醛, 选择加氢, 巴豆醇

Abstract:

Three kinds of aminosilane (APTS: 3-aminopropyltrimethoxysilane, TPED: N-[3-(trimethoxysilyl)-propylethylene]diamine, TPDT: trimethoxysilyl propyl diethylenetriamine) functionalized mesoporous SBA- 15 molecular sieves (denoted APTS-SBA-15, TPED-SBA-15 and TPDT-SBA-15) were synthesized by post-grafting. Using the static interaction between the amino group and chloroauric acid followed by chemical reduction, the gold nanoparticles were immobilized into the channels of SBA-15. The Au/aminosilane-SBA-15 catalysts were systematically characterized by N2 physisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The liquid phase hydrogenation of crotonaldehyde to crotyl alcohol (CROL) was used to investigate the effect of aminosilanes on the catalytic performance of the Au/amine-SBA-15 catalysts. The results revealed that the electron-donating ability of the aminosilane determines the selectivity towards the hydrogenation of the C=O bond on the gold catalyst. A stronger aminosilane electron-donating ability results in higher electron density on the gold active sites, which leads to the higher selectivity and yield of CROL.

Key words: Au, SBA-15, Aminosilane, Crotonaldehyde, Selective hydrogenation, Crotyl alcohol

MSC2000: 

  • O643