双溶剂法制备Pd/MIL-100及其催化Suzuki偶联反应的研究  

Preparation of Pd/MIL-100 by bi-solvent impregnation method and its application in Suzuki-coupling reaction

作　　者：李千帆 李铁夫 刘颖雅 孙志超 遇治权[1,2] 王瑶 王安杰[1,2] LI Qian-fan;LI Tie-fu;LIU Ying-ya;SUN Zhi-chao;YU Zhi-quan;WANG Yao;WANG An-jie(School of Chemical Engineering,Dalian University of technology,Dalian 116024,China;State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China)

机构地区：[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

出　　处：《现代化工》2023年第2期86-91,97,共7页Modern Chemical Industry

基　　金：国家重点研发计划(2016YFE0109800);国家自然科学基金(22172015,21972014,21603024)。

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、K_(2)CO_(3)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。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/H_(2)O(2∶1)is used as solvent,K_(2)CO_(3)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.

关 键 词：钯 金属有机骨架 SUZUKI偶联反应 联苯 

分 类 号：O643.32[理学—物理化学]