等级孔结构协同Fe改性提升ZSM-5分子筛催化苯甲醇烷基化性能  

Synergistic Effects of Hierarchically Interconnected Porous Structure and Fe Modification on Zeolite ZSM-5 for Efficient Benzyl Alcohol Alkylation

作　　者：宋宇航 刘湛 吕佳敏 余申 李小云[2] 孙明慧[1] 陈丽华[1] 苏宝连[1,3] SONG Yuhang;LIU Zhan;LYU Jiamin;YU Shen;LI Xiaoyun;SUN Minghui;CHEN Lihua;SU Baolian(State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,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,比利时

出　　处：《高等学校化学学报》2024年第5期28-37,共10页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2022YFB3504000);国家自然科学基金(批准号:22302152,U20A20122,22293020,U22B6011);中央高校基本科研业务费专项资金(批准号:2024IVA090)资助.

摘　　要：针对ZSM-5分子筛微孔扩散限制和催化活性位单一的问题,使用有序大孔-介孔碳模板为硬模板并结合原位引入金属策略,一步晶化合成了具有高结晶度、高比表面积的有序贯通大孔-介孔-微孔等级结构的Fe/ZSM-5分子筛单晶.通过X射线衍射(XRD)、紫外-可见光谱(UV-Vis)、H_(2)程序升温还原实验(H2-TPR)和X射线光电子能谱(XPS)等手段对催化剂中活性Fe的存在形式进行了表征.结果表明,该材料中位于离子交换位及铁氧八面体(六配位)的孤立Fe(III)是主要的氧化还原活性中心,当Fe负载量(质量分数)为1%时,苯甲醇转化率最高为59.3%,产物选择性为83.2%,最终收率达到49.3%,在循环使用5次后仍保持高催化活性.Constructing hierarchically porous structures and embedding metal species into zeolite frameworks can effectively enable fast diffusion and synergistic catalysis.We report a one-step synthesis method to synthesize hierarchically macro-meso-microporous zeolite ZSM-5 single crystals containing Fe metal nanoclusters,that has advantages compared to multistep methods such as impregnation and ion exchange.Zeolite ZSM-5-Fe catalysts were prepared by steam assisted crystallization with addition of hierarchically porous carbon template and a Fe precursor.The catalyst was systematically characterized by means of X-ray diffraction(XRD),ultraviolet-visible spectroscopy(UV-Vis),H2-temperature program reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicated that the isolated Fe(III)located at ion exchange sites and ferrite octahedron(six-coordinate)were the main redox-active centers.At a loading amount(mass fraction)of 1%,the highest benzyl alcohol conversion rate reached 59.3%,with a product selectivity of 83.2%,and a final yield of 49.3%.The catalyst maintained high catalytic activity even after five cycles,demonstrating its remarkable stability.

关 键 词：ZSM-5分子筛 等级结构 过渡金属铁 芳烃烷基化 

分 类 号：O611[理学—无机化学] O643[理学—化学]