Cu基等级孔ZSM-5分子筛单晶的制备及硝基苯加氢催化性能  

Preparation of Cu-based Hierarchical Pore ZSM-5 Zeolite Single Crystals and Their Catalytic Properties for Nitrobenzene Hydrogenation

作　　者：谢小兰 刘湛 吕佳敏 余申 李小云[2] 苏宝连[1,3] 陈丽华 XIE Xiaolan;LIU Zhan;LYU Jiamin;YU Shen;LI Xiaoyun;SU Baolian;CHEN Lihua(State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan 430070,China;State Key Laboratory of Silicate Material for Architecture,Wuhan University of Technology,Wuhan 430070,China;Laboratory of Inorganic Materials Chemistry,University of Namur,Namur B-5000,Belgium)

机构地区：[1]武汉理工大学材料复合新技术国家重点实验室,武汉430070 [2]武汉理工大学硅酸盐建筑材料国家重点实验室,武汉430070 [3]那慕尔大学无机材料化学实验室,那慕尔B-5000

出　　处：《高等学校化学学报》2023年第10期211-218,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:U20A20122,22293020)资助。

摘　　要：为了解决晶内等级孔创制过程中分子筛骨架不可逆损坏的问题,本文利用具有反蛋白石结构的有序大孔-介孔碳作为硬模版,自下而上原位合成了具有规则贯通大孔-介孔-微孔等级多孔结构的硅铝分子筛ZSM-5单晶材料(OMMS-ZSM-5),其具有较高的外比表面积(195.8 m~2/g)和孔体积(0.27 cm~3/g).以该OMMS-ZSM-5为载体,采用浸渍法制备了不同Cu负载量(质量分数分别为1%, 5%, 10%)的系列Cu-OMMS-ZSM-5催化剂,探究了不同金属载量催化剂在硝基苯液相加氢反应中的催化能力.对所制备催化剂的理化性质进行了表征,发现Cu元素以CuO的形式高度分散,当负载量为9.58%时,硝基苯转化率最高达到96.8%,苯胺选择性达到99.3%.与Cu基微米ZSM-5分子筛催化材料相比, Cu-OMMS-ZSM-5的苯胺选择性提高了32.4%,硝基苯转化率提高了26.1%,并在循环3次后仍然保持很高的催化活性.In order to solve the problem of irreversible damage of zeolite framework in the process of intracrystalline hierarchically porous creation,a single crystal of silica-alumina zeolite ZSM-5(OMMS-ZSM-5)with hierarchically ordered macro-meso-microporous structure was successfully bottom-up in situ synthesized by using ordered macro-mesomicroporous carbon with anti-opal structure as a hard template,which possesses high external specific surface area(195.8 m2/g)and pore volume(0.27 cm3/g).In addition,a series of Cu-OMMS-ZSM-5 catalysts with different Cu loadings(mass fraction:1%,5%,10%)was prepared by impregnation method using OMMS-ZSM-5 as a carrier to investigate the catalytic ability of different metal loading catalysts in the liquid-phase hydrogenation reaction of nitro-benzene.The physical and chemical properties of the prepared catalysts were comprehensively characterized by SEM,TEM,XRD,NMR,N2adsorption-desorption,NH_(3)-TPD,XPS and H2-TPR tests,which shows that the Cu Chem.J.Chinese Universities,2023,44(10),20230109 elements are highly dispersed in the form of CuO,and the conversion of nitrobenzene reaches up to 96.8%and the selectivity of aniline reaches 99.3%when the loading is 9.58%(mass fraction).Compared with the Cu-based micron ZSM-5 zeolite catalytic material,the aniline selectivity and the nitrobenzene conversion of Cu-OMMS-ZSM-5 are improved by 32.4%and 26.1%,respectively,and the high catalytic activity is maintained after three cycles.

关 键 词：等级孔分子筛 CU-ZSM-5 硝基苯加氢 苯胺 

分 类 号：O643[理学—物理化学]