核壳结构块体的构筑及催化氯苯燃烧性能  

Fabrication of Core-shell Structured Monoliths and Their Catalytic Performance for Chlorobenzene Combustion

作　　者：刁振恒 李昊 国文 郑鹏飞 王斌 吉洪轮 田亚杰 孙德[2] 李莉[1] DIAO Zhenheng;LI Hao;GUO Wen;ZHENG Pengfei;WANG Bin;JI Honglun;TIAN Yajie;SUN De;LI Li(State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry,Jilin University,Changchun 130012,China;School of Chemical Engineering,Changchun University of Technology,Changchun 130012,China;School of Energy Science and Technology,Henan University,Zhengzhou 450046,China)

机构地区：[1]吉林大学无机合成与制备化学国家重点实验室,化学学院,长春130012 [2]长春工业大学化学工程学院,长春130012 [3]河南大学能源科学与技术学院,郑州450046

出　　处：《高等学校化学学报》2025年第3期63-71,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22008012,22008055);吉林省教育厅科学研究项目(批准号:JJKH20231127KH);吉林大学实验技术项目(批准号:SYXM2024a002)资助。

摘　　要：基于同轴3D打印策略,构筑了以HZSM-5分子筛(Z5)为外壳活性位点,铈锰负载HZSM-5(CM/Z5),Silicalite-1或ZrO_(2)为内核活性位点的核壳结构块体催化剂.探究了载体种类对块体催化氯苯燃烧性能的影响机理,解析了核壳结构在氯苯燃烧过程中的作用机制.与HZSM-5和Silicalite-1载体相比,ZrO_(2)载体更有利于氧空位形成,但HZSM-5载体的Br?nsted酸位与铈锰组分的氧空位协同作用大幅提高了氯苯转化率和HCl选择性.HZSM-5外壳作为脱氯中心,限制了氯组分在铈锰氧化物表面的沉积,减缓了催化剂氯中毒,提高了催化剂的稳定性.以HZSM-5为内核载体构筑的CM/Z5@Z5块体因壳层脱氯、内核中酸性位与氧空位协同脱氯-深度氧化的串级催化过程,呈现出良好的催化活性、稳定性及HCl和CO_(2)选择性,其催化氯苯转化的T_(50)(转化率达50%时的反应温度)和T_(90)(转化率达90%时的反应温度)分别低至206和294℃.Core-shell structured monolith catalysts with HZSM-5(Z5)zeolite as the active sites of the shell and Ce-Mn species doped HZSM-5(CM/Z5),Silicalite-1 or ZrO_(2) as the active sites of the core were fabricated by coaxial3D printing.The influencing mechanism of the carrier kind on the catalytic performance of chlorobenzene combustion,as well as the function mechanism of the core-shell structure during the catalytic process,were both investigated.Compared with HZSM-5 and Silicalite-1,ZrO_(2) as the carrier benefited the formation of oxygen vacancies in catalysts.But HZSM-5 as the carrier could enhance chlorobenzene conversion and HCl selectivity,due to the synergistic effect between Br?nsted acid sites in HZSM-5 carrier and oxygen vacancies in Ce-Mn species.The HZSM-5 shell exhibited excellent performance in the dechlorination process,which limited the deposition of chlorine(Cl)specie on the surface of Ce-Mn oxides,retarded the Cl poisoning of the catalyst and thus enhanced the catalyst stability.The CM/Z5@Z5 monolith prepared with HZSM-5 as the carrier exhibited excellent catalytic activity,stability,and selectivities to HCl and CO_(2),with the T_(50)and T_(90)of chlorobenzene conversion of 206 and 294℃,respectively.This is due to the tandem process of dechlorination by the HZSM-5 shell and the dechlorination-deep oxidation by the synergistic effect between Br?nsted acid sites and oxygen vacancies.

关 键 词：同轴3D打印 HZSM-5分子筛 铈锰氧化物 催化氯苯燃烧 核壳块体催化剂 

分 类 号：O643.3[理学—物理化学]