Page 119 - 《精细化工》2021年第8期

第 38 卷第 8 期 精 细 化 工 Vol.38, No.8
202 1 年 8 月 FINE CHEMICALS Aug. 2021

催化与分离提纯技术
溶胶-凝胶法制介孔 Pd/m-TiO 催化
2

连续流 Suzuki 偶联反应

1
1
薄晓帆 ，万 力 ，辛 忠 1,2*
（1. 华东理工大学 上海市多相结构材料化学工程重点实验室，上海 200237；2. 华东理工大学 化工学
院 化学工程联合国家重点实验室，上海 200237）

摘要：以 PdCl 2 和钛酸正丁酯为原料、聚乙烯吡咯烷酮为金属保护剂、三嵌段共聚物 EO 96 PO 70 EO 96 为模板剂，
采用溶胶-凝胶法制备了一系列不同 Pd 负载量（质量分数 0.1%~1.0%）的非均相 Pd/m-TiO 2 催化剂。采用 N 2 吸
附-脱附等温线、XRD 和 TEM 对其进行了表征。结果表明，催化剂具有有序介孔结构，孔径在 8.7~10.2 nm 之
间，Pd 粒子均匀分布在载体上，粒子尺寸为 11.3~13.3 nm。在微填充床反应器中进行了连续流 Pd/m-TiO 2 催化
溴苯与苯硼酸的 Suzuki 偶联反应，确定了最优工艺条件：N,N-二甲基甲酰胺（DMF）和水〔V(DMF)∶V(H 2 O)=1∶1〕
为溶剂，碱为 K 3 PO 4 ，流速为 0.20 mL/min，溴苯、苯硼酸和 K 3 PO 4 的浓度分别为 0.10、0.12 和 0.15 mol/L，Pd
负载量为 0.7%（质量分数）的 m-TiO 2 （记为 0.7% Pd/m-TiO 2 ）为催化剂，反应温度为 80 ℃，反应时间 6.8 min。
在最优反应条件下考察了不同取代芳烃的 Suzuki 偶联反应，反应收率均达到了 99%，0.7% Pd/m-TiO 2 使用 5 次
后仍保持良好的催化活性。
关键词：连续流；Suzuki 偶联反应；溶胶-凝胶法；介孔材料；Pd 催化剂
中图分类号：TQ426.81；TQ241.3 文献标识码：A 文章编号：1003-5214 (2021) 08-1613-08

Sol-gel prepared mesoporous Pd/m-TiO 2 for continuous-flow

Suzuki coupling reaction

1
1
BO Xiaofan , WAN Li , XIN Zhong 1,2*
（1. Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, East China University of Science and
Technology, Shanghai 200237, China; 2. State Key Laboratory of Chemical Engineering, School of Chemical
Engineering, East China University of Science and Technology, Shanghai 200237, China）

Abstract: A series of heterogeneous Pd/m-TiO 2 catalysts with different palladium loading amounts (mass
fraction 0.1%~1.0%) were prepared by sol-gel method using PdCl 2 and n-butyl titanate as raw materials,
polyvinylpyrrolidone as metal protective agent, triblock copolymer EO 96PO 70EO 96 as template agent. The
structure was characterized by N 2 adsorption-desorption isotherm, XRD and TEM. The results showed that
the catalysts had an ordered mesoporous structure with 8.7~10.2 nm pore size distribution and good
palladium dispersion with 11.3~13.3 nm particle size. Then Pd/m-TiO 2 catalysts were fixed by
micro-packed reactor to catalyze Suzuki coupling reaction of bromobenzene and phenylboric acid in
continuous flow. The optimal continuous flow process was determined: mixed solvent of DMF and water
[V(DMF)∶V(H 2O)=1∶1], K 3PO 4 as alkali, flow rate of 0.20 mL/min, bromobenzene concentration of 0.10

mol/L, phenylboronic acid concentration of 0.12 mol/L, K 3PO 4 concentration of 0.15 mol/L, m-TiO 2 with
palladium loading amount of 0.7% (mass fraction) (noted as 0.7% Pd/m-TiO 2) as catalyst, reaction
temperature of 80 ℃ and reaction time of 6.8 min. The Suzuki coupling reaction of different substituted
aromatic hydrocarbons was investigated under the optimal reaction conditions. The yield of Suzuki
coupling reaction was up to 99%, and 0.7% Pd/m-TiO 2 still maintained good catalytic activity after using

收稿日期：2021-03-03; 定用日期：2021-04-07; DOI: 10.13550/j.jxhg.20210218
基金项目：中央高校基本科研专项资金（JKA01211721）；上海市领军人才（2013）
作者简介：薄晓帆（1995—），男，硕士生，E-mail: fanfanfan24@163.com。联系人：辛 忠（1962—），男，教授，E-mail: xzh@ecust.edu.cn。