氟化铵刻蚀对ZSM-5分子筛结构及酸性的调控机制

doi:10.11938/cjmr20263207

波谱学杂志 ›› 2026, Vol. 43 ›› Issue (2): 136-145.doi: 10.11938/cjmr20263207cstr: 32225.14.cjmr20263207

氟化铵刻蚀对ZSM-5分子筛结构及酸性的调控机制

王靖¹^,², 肖瑶¹^,^§(), 俞鑫¹^,², 易先锋¹^,^#(), 郑安民¹^,³^,^*()

¹ 中国科学院精密测量科学与技术创新研究院，磁共振波谱与成像全国重点实验室，湖北武汉 430071
² 中国科学院大学，北京 100049
³ 武汉科技大学化学与化工学院，核磁共振与分子科学交叉研究院，湖北武汉 430081

收稿日期:2026-02-07 出版日期:2026-06-05 在线发表日期:2026-03-19
通讯作者: 肖瑶,易先锋,郑安民 E-mail:xiaoyao@wipm.ac.cn;yxf@wipm.ac.cn;zhenganm@wipm.ac.cn
基金资助:
湖北省自然科学基金资助项目(2023AFA101);湖北省自然科学基金资助项目(2025AFA008);武汉市自然科学基金资助项目(2024040701010058)

Influence Mechanism of NH₄F Etching on the Structure and Acidity of ZSM-5 Zeolite

WANG Jing¹^,², XIAO Yao¹^,^§(), YU Xin¹^,², YI Xianfeng¹^,^#(), ZHENG Anmin¹^,³^,^*()

¹ State Key Laboratory of Magnetic Resonance Spectroscopy and Imaging, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China
² University of Chinese Academy of Sciences, Beijing 100049, China
³ Interdisciplinary Institute of NMR and Molecular Sciences, School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China

Received:2026-02-07 Published:2026-06-05 Online:2026-03-19
Contact: XIAO Yao, YI Xianfeng, ZHENG Anmin E-mail:xiaoyao@wipm.ac.cn;yxf@wipm.ac.cn;zhenganm@wipm.ac.cn

摘要/Abstract

摘要：

氟化铵（NH₄F）刻蚀是构建多级孔分子筛的有效方法，但其对分子筛活性位结构与酸性的影响规律尚不明确．该工作结合多种探针分子辅助的固体核磁共振技术，通过系统分析不同浓度NH₄F刻蚀ZSM-5分子筛活性位的局域结构及酸性，发现NH₄F刻蚀程度显著影响了酸性位的含量、强度、类型及空间可接近性，并与多级孔结构的发育直接相关．该工作从原子层面阐释了NH₄F刻蚀对分子筛活性位结构及酸性的调变机制，为多级孔分子筛催化剂的理性设计与优化提供了理论基础．

关键词: 固体核磁共振, 酸性, 探针分子, 氟化铵刻蚀, 多级孔分子筛

Abstract:

Ammonium fluoride (NH₄F) etching is an effective method for constructing hierarchical zeolites, yet its precise impact on the detailed structure and acidity remains unclear. This study employs probe molecule-assisted solid-state NMR technique to systematically investigate the evolution of acid site structures and properties during NH₄F etching of ZSM-5 zeolites. The results reveal that the degree of NH₄F etching significantly manipulates the amount, strength, type, and spatial accessibility of acid sites, and it is also directly associated with the development of hierarchical pore structures. This work elucidates the influence mechanism of NH₄F etching on zeolite structure and acidic property at the atomic level, providing a theoretical foundation for the rational design and optimization of efficient hierarchical zeolites.

Key words: solid-state NMR, acidic property, probe molecule, NH₄F etching, hierarchical zeolites

中图分类号:

O482.53

王靖, 肖瑶, 俞鑫, 易先锋, 郑安民. 氟化铵刻蚀对ZSM-5分子筛结构及酸性的调控机制[J]. 波谱学杂志, 2026, 43(2): 136-145.

WANG Jing, XIAO Yao, YU Xin, YI Xianfeng, ZHENG Anmin. Influence Mechanism of NH₄F Etching on the Structure and Acidity of ZSM-5 Zeolite[J]. Chinese Journal of Magnetic Resonance, 2026, 43(2): 136-145.

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Sample	S_BET^a /m²g^-1	S_micro^a /m²g^-1	V_pore^a /cm³g^-1	V_micro^a /cm³g^-1	V_meso^a /cm³g^-1	Crystallinity^b /%	Si/Al^c
Z5-parent	431	406	0.21	0.17	0.04	100	29.8
Z5-10%F	424	405	0.21	0.17	0.04	91	31.9
Z5-20%F	407	386	0.26	0.16	0.10	86	32.6
Z5-40%F	407	363	0.30	0.15	0.15	80	34.0

氟化铵刻蚀对ZSM-5分子筛结构及酸性的调控机制

Influence Mechanism of NH₄F Etching on the Structure and Acidity of ZSM-5 Zeolite

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氟化铵刻蚀对ZSM-5分子筛结构及酸性的调控机制

Influence Mechanism of NH4F Etching on the Structure and Acidity of ZSM-5 Zeolite

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Influence Mechanism of NH₄F Etching on the Structure and Acidity of ZSM-5 Zeolite