ZSM-23沸石纳米片的合成探究

doi:10.1016/S1872-2067(26)65085-1

催化学报

ZSM-23沸石纳米片的合成探究

刘培^a,1, 刘晓娜^b,1, 张磊^c, 翟羿^a, 童颜^d, 骆剑锋^a, 吴勤明^a,e,*, 陈伟^f,*, 杜晓辉^g, 刘小龙^d, 刘中民^b,*, 肖丰收^a,e,*

^a浙江大学化学工程与生物工程学院, 浙江杭州 310028, 中国;
^b中国科学院大连化学物理研究所, 国家低碳催化技术工程研究中心, 辽宁大连 116023, 中国;
^c常州大学石油化工学院, 先进催化与绿色制造协同创新中心, 江苏省先进催化材料与技术重点实验室, 江苏常州 213164, 中国;
^d中山大学材料学院, 广东广州 510275, 中国;
^e怀柔实验室山西研究院, 山西太原 030032, 中国;
^f根特大学分子模拟中心, 东弗兰德省, 比利时;
^g中国石油天然气股份有限公司石油化工研究院兰州化工研究中心, 甘肃兰州 730060, 中国

收稿日期:2025-12-08 接受日期:2026-01-31
通讯作者: ^*电子信箱: qinmingwu@zju.edu.cn (吴勤明), Wei.Chen@UGent.be (陈伟), zml@dicp.ac.cn (刘中民), fsxiao@zju.edu.cn (肖丰收).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1503602); 国家自然科学基金(22522208, 22288101, 22402176); 浙江省自然科学基金(LR24B030001); 中央高校基本科研业务费专项资金(226-2025-00116); 中国石油科技重点研究项目(2023ZZ36).

Insights into synthesis of ZSM-23 zeolite nanosheets

Pei Liu^a,1, Xiaona Liu^b,1, Lei Zhang^c, Yi Zhai^a, Yan Tong^d, Jianfeng Luo^a, Qinming Wu^a,e,*, Wei Chen^f,*, Xiaohui Du^g, Xiaolong Liu^d, Zhongmin Liu^b,*, Feng-Shou Xiao^a,e,*

^aCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, Zhejiang, China;
^bNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^cCollaborative Innovation Center of Advanced Catalysis and Green Manufacturing, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China;
^dSchool of Materials, Sun Yat-Sen University, Guangzhou 510275, Guangdong, China;
^eShanxi Research Institute, Huairou Research Laboratory, Taiyuan 030032, Shanxi, China;
^fCenter for Molecular Modeling, Ghent University, Technologiepark 46, 9052 Zwijnaarde, Belgium;
^gLanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, Gansu, China

Received:2025-12-08 Accepted:2026-01-31
Contact: ^*E-mail: qinmingwu@zju.edu.cn (Q. Wu), Wei.Chen@UGent.be (W. Chen), zml@dicp.ac.cn (Z. Liu), fsxiao@zju.edu.cn (F.-S. Xiao).
About author:¹Contributed equally to this work.
Supported by:
National Key Research and Development Program of China (2022YFA1503602), the National Natural Science Foundation of China (22522208, 22288101, 22402176), the Zhejiang Provincial Natural Science Foundation of China (LR24B030001), the Fundamental Research Funds for the Central Universities (226-2025-00116), and the PetroChina Science and Technology Major Program (2023ZZ36).

摘要/Abstract

摘要： 一维沸石分子筛(如ZSM-23)通常呈现微米级长度的针状形貌, 这种形貌不仅会显著影响催化性能, 也存在潜在的健康风险. 本文首次报道了利用一种新型Gemini型季铵盐(Bis-Benz-Pyr²⁺)作为有机模板, 成功合成了厚度仅约10 nm的ZSM-23沸石纳米片; 该模板剂不仅能够导向ZSM-23沸石微孔结构的形成, 并协同促进纳米片沿a轴和b轴方向生长. 表征结果表明, 所制备的ZSM-23沸石纳米片具有高结晶度、典型的纳米片形貌、较大的外表面积以及完全四配位的铝物种. 非常重要的是, 在正十六烷加氢异构反应中, 相较于以N,N-二甲基甲酰胺为模板合成的常规ZSM-23沸石, ZSM-23沸石纳米片展现出更高的正十六烷转化率和异十六烷产率. 这些研究结果为后续开发高效沸石催化剂奠定了坚实基础.
X-射线衍射结果证实, 该纳米片具有较高结晶度. 高倍透射电镜结果显示, 沿[001]方向观察, ZSM-23晶体优先沿ab平面生长; 沿[210]方向观察, 其沿[001]方向的厚度约为10 nm. 进一步对纳米片尺寸进行统计分析, 显示其沿a轴、b轴和c轴的尺寸分别为500, 250, 和9 nm. ²⁷Al核磁证实铝物种均为骨架铝; ¹³C核磁表明多数模板剂完整存在于ZSM-23沸石结构中. Ar与N₂吸附结果表明, ZSM-23沸石纳米片具有较大外比表面积; Ar吸附孔径分布图显示其存在32‒80 nm的孔径. 理论模拟表明, Bis-Benz-Pyr²⁺的稳定化能为‒8.73 kJ/(mol·Si), 远低于吡咯烷的‒1.05 kJ/(mol·Si), 证实其是ZSM-23沸石的优良模板剂. 晶面形成能分析显示: 当引入Bis-Benz-Pyr²⁺后, [001]晶面形成能较[010]和[100]更负, 说明沿a, b轴形成纳米片形貌具有热力学优势, 进一步证实该模板剂对ZSM-23沸石纳米片形貌的形成具有关键导向作用. 晶化过程跟踪显示, 随晶化时间延长, ZSM-23沸石纳米片仅沿ab平面扩展, 厚度始终基本不变, 这一生长特性与理论计算高度一致. 将该纳米片用于正十六烷加氢异构反应, 相较于常规棒状ZSM-23沸石, 其展现出更高的正十六烷转化率和异十六烷收率.
综上, 新型模板剂实现了ZSM-23沸石纳米片的精准合成, 其独特形貌赋予优异催化性能, 为高效沸石催化剂设计提供新思路.

关键词: ZSM-23沸石分子筛, 纳米片, 有机模板, 加氢异构

Abstract: Precise control of crystal growth allows for zeolites with tailored morphology, and one of the typical zeolite families is one-dimensional zeolites such as ZSM-23, which normally displays a needle-like morphology with micron-level length. This morphology not only strongly influences catalytic performances but also has potentially healthy issue. Herein, we for the first time show a successful synthesis of ZSM-23 zeolite nanosheets with a thickness of only about 10 nm from a novel gemini-type quaternary ammonium as an organic template. Characterizations of the samples demonstrate that ZSM-23 zeolite nanosheets along a and b axes have high crystallinity, large external surface area, and fully four-coordinated aluminum species. Very importantly, ZSM-23 zeolite nanosheets exhibit higher n-hexadecane (C₁₆) conversion and iso-C₁₆ yield in n-C₁₆ hydroisomerization than those of conventional ZSM-23 zeolite synthesized from N,N-dimethylformamide. These findings offer a favorable opportunity for the subsequent development of efficient zeolite catalysts in the future.

Key words: ZSM-23 zeolite, Nanosheets, Organic template, Hydroisomerization

刘培, 刘晓娜, 张磊, 翟羿, 童颜, 骆剑锋, 吴勤明, 陈伟, 杜晓辉, 刘小龙, 刘中民, 肖丰收. ZSM-23沸石纳米片的合成探究[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65085-1.

Pei Liu, Xiaona Liu, Lei Zhang, Yi Zhai, Yan Tong, Jianfeng Luo, Qinming Wu, Wei Chen, Xiaohui Du, Xiaolong Liu, Zhongmin Liu, Feng-Shou Xiao. Insights into synthesis of ZSM-23 zeolite nanosheets[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65085-1.

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