周期有序介孔Rh(Ⅰ)有机金属催化剂用于水介质Heck反应的研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1195.

周期有序介孔Rh(Ⅰ)有机金属催化剂用于水介质Heck反应的研究

黄建林, 杨旭石, 王梅桃, 李和兴, 张昉

上海师范大学化学系, 上海市稀土功能材料重点实验室, 上海 200234

收稿日期:2009-12-09 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 张昉, 男, 博士, 讲师, 主要从事绿色催化新材料的研究. E-mail: zhangfang@shnu.edu.cn
基金资助:
国家自然科学基金(批准号: 50943048)资助.

Study on Periodic Mesoporous Rh(Ⅰ) Organometallic Catalyst for Water-medium Heck Reaction

HUANG Jian-Lin, YANG Xu-Shi, WANG Mei-Tao, LI He-Xing, ZHANG Fang*

Shanghai Key Laboratory of Rare Earth Functional Materials, Department of Chemistry, Shanghai Normal University, Shanghai 200234, China

Received:2009-12-09 Online:2010-06-10 Published:2010-06-10
Contact: ZHANG Fang. E-mail: zhangfang@shnu.edu.cn
Supported by:
国家自然科学基金(批准号: 50943048)资助.

摘要/Abstract

摘要：

以1,4-双(三乙氧基硅基)苯和2-(二苯基膦)乙基三乙氧基硅烷为混合硅源, 在表面活性剂作用下共缩聚得到二苯基膦功能化的有序介孔有机硅材料[PPh₂-PMO(Ph)], 通过配位作用将Rh(Ⅰ)有机金属催化剂固载到PPh₂-PMO上得到Rh(Ⅰ)-PPh₂-PMO(Ph)非均相催化剂, 并采用FTIR, NMR, XRD, TEM和氮气吸附等手段对催化剂进行了表征. 考察了该催化剂在水介质Heck反应中的催化性能, 实验结果表明, 所制备的Rh(Ⅰ)-PPh₂-PMO(Ph)具有与均相催化剂Rh(PPh₃)₃Cl相当的催化活性, 这主要归因于催化剂的高比表面积、有序介孔结构有利于提高Rh(Ⅰ)活性位的分散度, 减少了传质阻力; 同时PMO构建形成的微环境增强了表面疏水性, 有利于反应底物的吸附和扩散. 此外, 催化剂重复使用多次后活性仍没有明显降低.

关键词: 周期有序介孔材料; 有机金属催化剂; 固载化; Heck反应; 水介质

Abstract:

Periodic mesoporous Rh(Ⅰ) organometallic catalyst[Rh(Ⅰ)-PPh₂-PMO(Ph)] was synthesized by coordinating Rh(PPh₃)₃Cl complex with PPh₂-ligand originally incorporated into the phenyl-bridged periodic mesoporous organosilica(PMO) via surfactant-directed co-condensation approach. The Rh(Ⅰ) heterogeneous catalyst were characterized by FTIR, NMR, XRD, TEM and N₂ sorption technologies. This catalyst can be effectively applied in water-medium Heck reaction, which results demonstrated it afforded similar catalytic performance to that of the corresponding homogeneous catalyst. It could be attributed to the large surface area and ordered mesoporous channels of the PMOs support, leading to the high dispersion of Rh(Ⅰ) active sites and the reduced diffusion limit. Meanwhile, the phenyl fragments embedded in the pore walls could enhance surface hydrophobility, which further promoted the diffusion and adsorption of organic molecules, leading to the enhanced activity. Besides, the Rh(Ⅰ)-PPh₂-PMO(Ph) could be used repetitively, showing a good potential in industrial applications.

Key words: Periodic mesoporous silica material; Organometallic catalyst; Immobilization; Heck reaction; Water-medium

TrendMD:

黄建林, 杨旭石, 王梅桃, 李和兴, 张昉. 周期有序介孔Rh(Ⅰ)有机金属催化剂用于水介质Heck反应的研究. 高等学校化学学报, 2010, 31(6): 1195.

HUANG Jian-Lin, YANG Xu-Shi, WANG Mei-Tao, LI He-Xing, ZHANG Fang*. Study on Periodic Mesoporous Rh(Ⅰ) Organometallic Catalyst for Water-medium Heck Reaction. Chem. J. Chinese Universities, 2010, 31(6): 1195.

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