CoO_(x)引入Pd/HAC催化剂增强乙炔双羰化反应活性  

CoO_(x) Particles Anchored on Pd/HAC Catalyst for Enhancing the Acetylene Dicarbonylation Performance

作　　者：郭贤哲 王东伟 张晓慧 马占伟[1] 苟发荣 胡斌[1] GUO Xian-zhe;WANG Dong-wei;ZHANG Xiao-hui;MA Zhan-wei;GOU Fa-rong;HU Bin(State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000 [2]中国科学院大学,北京100049

出　　处：《分子催化（中英文）》2024年第1期1-6,I0001,共7页Journal of Molecular Catalysis(China)

基　　金：National Natural Science Foundation of China(22102194);Science and Technology Plan of Gansu Province(20JR10RA044,23JRRA630,20YF3GA009);Youth Innovation Promotion Association of CAS(2022427).

摘　　要：使用[Pd_(2)(μ-CO)_(2)Cl_(4)]_(2)−原位生成Pd纳米粒子和等体积浸渍法,制备了一系列CoO_(x)-Pd/HAC催化剂,并考察了其在乙炔二羰基化反应中的反应活性.结果表明,3%Co-Pd/HAC催化剂在乙炔二羰基化反应中具有最佳活性(乙炔转化率75.4%,马来酸二甲酯选择性86.2%).采用X射线衍射(XRD)、氢温度程序还原(H2-TPR)、透射电镜(TEM)等手段对催化剂进行了表征.适量金属钴氧化物的加入可以驱动钯纳米颗粒表面的电子迁移,产生更多的高价钯物种,增强CO的吸附能力,驱动羰基化反应步骤Pd^(δ+)↔Pd^(0)循环过程,从而提高乙炔双羰基化反应活性.经过7个循环实验,Co-Pd/HAC催化剂有微弱失活现象,但对丁烯二酸二甲酯的选择性没有显著影响.A series of CoOx-Pd/HAC catalysts were prepared by[Pd_(2)(μ-CO)_(2)Cl_(4)]_(2)−in situ formation of Pd nanoparticles by equivalent impregnation method,and their reactivity in acetylene dicarbonylation was investigated.It was found that the 3%Co-Pd/HAC catalyst has the best activity in the acetylene dicarbonylation(acetylene conversion 75.4%,dimethyl maleate selectivity 86.2%).The catalyst was characterized by X-ray diffraction(XRD),hydrogen temperature programmed reduction(H_(2)-TPR)and transmission electron microscopy(TEM)and more.Moreover,the incorporation of an appropriate amount of metal cobalt oxide could drive electron migration on the surface of palladium nanoparticles,generate more high-valence Pd species,and increase the CO adsorption capacity,drive the dicarbonylation reaction step to Pd^(δ+)↔Pd^(0) cycle process,so as to improve the acetylene dicarbonylation reaction activity.After seven cycles of experiments,the Co-Pd/HAC catalyst has a weak deactivation phenomenon,but has no significant effect on the selectivity of dimethyl butene-dicarboxylate.

关 键 词：乙炔双羰化 多相催化 钯碳 马来酸二甲酯 

分 类 号：O643.32[理学—物理化学]