Page 188 - 201811

第 35 卷第 11 期 精 细 化 工 Vol.35, No.11
2018 年 11 月 FINE CHEMICALS Nov. 2018

催化与分离提纯技术
双金属异相催化剂 Fe O @La-MOF-Schiff-Pd/Ni 的
4
3
制备及其催化 Suzuki 偶联反应

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由立新，赵柏蓓，陈小玲，熊 刚，孙亚光
（沈阳化工大学 应用化学学院，辽宁 沈阳 110142）

摘要：将 Fe 3 O 4 纳米粒子负载到金属有机骨架 La-MOF 中，然后向其中引入 Pd/Ni 活性位点，制得含磁性纳米
粒子的 Pd/Ni 双金属异相催化剂（Fe 3 O 4 @La-MOF-Schiff-Pd/Ni），并通过 SEM、TEM、EDS、ICP、PXRD 和
XPS 对其进行了表征。结果表明，Fe 3 O 4 纳米粒子被成功嵌入到了 La-MOF 中，经过后合成修饰后，Pd 和 Ni
活性位点被均匀分散在 MOF 框架中。该催化剂在 Suzuki 偶联反应中表现出较高的催化活性，以碘苯（1.0 mmol）
和苯硼酸（1.2 mmol）为反应物时，最佳催化反应条件为：以无水乙醇为溶剂、无水碳酸钾为碱、反应温度 80 ℃、
反应时间为 6 h、催化剂用量 8 mg，在该条件下联苯产率达 95%。该催化剂可以通过外加磁铁进行分离回收，
经过 5 次循环使用后仍然保持较高的催化活性，产物产率为 82%。Suzuki 偶联反应机理探究结果表明，Pd 和
Ni 可能具有协同催化效应。底物拓展实验表明，Fe 3 O 4 @La-MOF-Schiff-Pd/Ni 双金属催化剂对含不同取代基的
芳基溴化物和碘化物具有较好的普适性。
关键词：Suzuki 偶联反应；钯；金属有机框架；磁性纳米粒子；催化技术
中图分类号：O614.82 文献标识码：A 文章编号：1003-5214 (2018) 11-1974-07

Preparation and Catalytic Performance in Suzuki Coupling Reaction of

Bimetal Heterogeneous Catalyst (Fe 3O 4@La-MOF-Schiff-Pd/Ni)

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YOU Li-xin, ZHAO Bai-bei, CHEN Xiao-ling, XIONG Gang, SUN Ya-guang
（College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China）

Abstract: Pd/Ni bimetal heterogeneous catalyst (Fe 3O 4@La-MOF-Schiff-Pd/Ni) containging magnenic
Fe 3O 4 nanoparticles was prepared by a post-synthesis modification method and characterized by scanning
electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrum (EDS),
inductive coupled plasma optical emission spectroscope (ICP), powder X-ray diffraction (PXRD) and X-ray
photoelectron spectroscope (XPS). The results showed that Fe 3O 4 nanoparticles were successfully
embedded in La-MOF. The active sites of Pd and Ni were uniformly dispersed in the La-MOF after the
post-synthetic modification. The catalyst exhibited high catalytic activity in the Suzuki coupling reaction.
When iodobenzene (1.0 mmol) and phenylboronic acid (1.2 mmol) were used as reactants, K 2CO 3 was used
as base, anhydrous ethanol was used as solvent, the amount of catalyst used was 8 mg, the yield of biphenyl
was 95% at a reaction temperature of 80 ℃ and a reaction time of 6 h. The catalyst could be easily
recovered by magnetic separation and maintain high catalytic activity (82%) after 5 cycles. The proposed
mechanism for the Suzuki coupling reaction revealed that Pd and Ni had a synergistic effect on catalytic
activity. Moreover, the as-synthesized bimetallic catalyst demonstrated a common applicability to aryl
bromides and iodides containing different substituents.
Key words: Suzuki coupling reaction; palladium; metal-organic frameworks; magnetic nanoparticles;
catalysis technology
Foundation items: National Natural Science Foundation of China (21671139); Distinguished Professor

收稿日期：2017-12-26; 定用日期：2018-05-31; DOI: 10.13550/j.jxhg.20171041
基金项目：国家自然科学基金（21671139）；辽宁省特聘教授项目（2013204）；辽宁省自然科学基金计划重点项目（20170540713）
作者简介：由立新（1974—），男，副教授。联系人：孙亚光（1972—），教授，电话：024-89389359，E-mail：sunyaguang@syuct.edu.cn。