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现代化工  2023, Vol. 43 Issue (2): 86-91,97    DOI: 10.16606/j.cnki.issn0253-4320.2023.02.018
  科研与开发 本期目录 | 过刊浏览 | 高级检索 |
双溶剂法制备Pd/MIL-100及其催化Suzuki偶联反应的研究
李千帆1,2, 李铁夫1,2, 刘颖雅1,2, 孙志超1,2, 遇治权1,2, 王瑶1, 王安杰1,2
1. 大连理工大学化工学院, 辽宁 大连 116024;
2. 大连理工大学精细化工国家重点实验室, 辽宁 大连 116024
Preparation of Pd/MIL-100 by bi-solvent impregnation method and its application in Suzuki-coupling reaction
LI Qian-fan1,2, LI Tie-fu1,2, LIU Ying-ya1,2, SUN Zhi-chao1,2, YU Zhi-quan1,2, WANG Yao1, WANG An-jie1,2
1. School of Chemical Engineering, Dalian University of technology, Dalian 116024, China;
2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
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摘要 采用溶剂热法合成了MIL-100(Cr),通过双溶剂浸渍法负载Pd纳米粒子制备负载型Pd/MIL-100催化剂。以溴苯与苯硼酸偶联合成联苯为模型反应,考察了溶剂、碱助剂、温度等因素对Suzuki偶联反应性能的影响。结果表明,以V(EtOH)∶V(H2O)=2∶1为溶剂、K2CO3为碱助剂,在60℃反应0.5 h,溴苯转化率达到97%,目标产物联苯选择性>99%;催化剂对于对位和间位供电子基团取代的芳基硼酸具有良好的底物适用性;Pd/MIL-100催化剂循环使用3次仍保持良好的催化活性及稳定性。XRD、XPS、ICP及TEM表征结果表明,催化剂失活的主要原因是由于Pd纳米粒子在MIL-100表面发生了迁移团聚。
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李千帆
李铁夫
刘颖雅
孙志超
遇治权
王瑶
王安杰
关键词:    金属有机骨架  Suzuki偶联反应  联苯    
Abstract: MIL-100(Cr) is synthesized through solvothermal method,and used to support Pd nanoparticles through a double-solvent impregnation method to prepare Pd/MIL-100,a supported catalyst.Taking the coupling reaction of bromobenzene and phenylboronic acid to synthesize biphenyl as a model reaction,the effects of solvents,base auxiliary,substrate concentration,temperature as well as catalyst dosage on the catalytic activity of the prepared catalyst in Suzuki coupling reaction are investigated.The conversion rate of bromobenzene reaches 97% and the selectivity of biphenyl exceeds 99% when EtOH/H2O (2∶1) is used as solvent,K2CO3 as base auxiliary,and the reaction has performed for 30 min at 60℃.Moreover,Pd/MIL-100 catalyst shows a good substrate applicability for a series of aryl boronic acids by para- and meta-substituted electron donor groups.Recycling experiments show that Pd/MIL-100 catalyst maintains good catalytic activity and stability after 3 consecutive runs.The deactivation mechanism for the catalyst is analyzed by means of XRD,XPS,ICP and TEM.It is discovered that the migration and aggregation of Pd nanoparticles on the surface of MIL-100 is the main reason for the deactivation.
Key words:  palladium    metal-organic framework    Suzuki coupling reaction    biphenyl
               出版日期:  2023-02-20
ZTFLH:  O643.32+2  
基金资助: 国家重点研发计划(2016YFE0109800);国家自然科学基金(22172015,21972014,21603024)
通讯作者:  刘颖雅(1978-),女,博士,副教授,硕士生导师,主要从事MOF、COF材料的多相催化及吸附应用研究,通讯联系人,yingya.liu@dlut.edu.cn。    E-mail:  yingya.liu@dlut.edu.cn
作者简介:  李千帆(1999-),女,硕士研究生,研究方向为金属有机骨架材料的制备及其催化,liqianfan66@126.com。
引用本文:    
李千帆, 李铁夫, 刘颖雅, 孙志超, 遇治权, 王瑶, 王安杰. 双溶剂法制备Pd/MIL-100及其催化Suzuki偶联反应的研究[J]. 现代化工, 2023, 43(2): 86-91,97.
LI Qian-fan, LI Tie-fu, LIU Ying-ya, SUN Zhi-chao, YU Zhi-quan, WANG Yao, WANG An-jie. Preparation of Pd/MIL-100 by bi-solvent impregnation method and its application in Suzuki-coupling reaction. Modern Chemical Industry, 2023, 43(2): 86-91,97.
链接本文:  
https://www.xdhg.com.cn/CN/10.16606/j.cnki.issn0253-4320.2023.02.018  或          https://www.xdhg.com.cn/CN/Y2023/V43/I2/86
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