Controlled Synthesis and Application of Nano-Sized Single-Crystal ZSM-5 Zeolite

JIN Yu; QI Fang; ZHU Ganyu; LI Huiquan; LI Shaopeng; GUO Hongfan

doi:10.11949/0438-1157.20251491

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Controlled Synthesis and Application of Nano-Sized Single-Crystal ZSM-5 Zeolite

更新时间：2026-04-29

- Controlled Synthesis and Application of Nano-Sized Single-Crystal ZSM-5 Zeolite
- CIESC Journal (2026)
- 作者机构：
  
  1.沈阳化工大学化学工程学院，辽宁沈阳 110142
  2.中国科学院过程工程研究所战略金属资源绿色循环利用国家工程研究中心，北京 100190
  3.中国科学院大学化学工程学院，北京 100049
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20251491
  CLC： TQ 17
- Received：31 December 2025，
  
  Revised：2026-04-29，
  
  Accepted：29 April 2026，
- 稿件说明：
移动端阅览
JIN Yu, QI Fang, ZHU Ganyu, et al. Controlled Synthesis and Application of Nano-Sized Single-Crystal ZSM-5 Zeolite[J/OL]. CIESC Journal, 2026.
DOI：

JIN Yu, QI Fang, ZHU Ganyu, et al. Controlled Synthesis and Application of Nano-Sized Single-Crystal ZSM-5 Zeolite[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20251491.

摘要

ZSM-5分子筛是典型多孔硅铝酸盐材料，因其优异的水热稳定性、耐酸性、择形催化等特点被广泛应用于化工、环境等领域。但是，分子筛的单一微孔结构导致其应用时仍面临扩散限制、活性位点可及性差、积碳失活较快等问题。本研究以四丙基氢氧化铵（TPAOH）为单一模板剂、氯化铝（AlCl

）为高活性铝物种，采用一锅法高效合成纳米单晶ZSM-5分子筛，考察了铝源、硅铝比、TPAOH添加量及晶化温度对分子筛结晶特征、形貌结构、孔结构及铝配位环境的影响，明确了结晶机理和甲醇制丙烯（MTP）催化性能。结果表明：硅铝比增大与晶化温度升高，均导致分子筛的相对结晶度与BET比表面积呈先增后减的非单调变化，同时促使晶体粒径减小。TPAOH添加量增大则持续提升的相对结晶度与BET比表面积，并显著细化晶体粒径。在铝源为氯化铝、硅铝比100、

(TPAOH)/

(SiO

)为0.35以及晶化温度170℃的优化条件下，纳米单晶ZSM-5分子筛粒径为~110 nm，BET比表面积为398.72 m

/g，平均孔径为5.44 nm，MTP反应中甲醇转化率维持在80%以上，丙烯选择性最高达到60%。纳米ZSM-5分子筛晶体生长过程历经“成核-熟化-稳定”多阶段。本研究可为高性能纳米单晶ZSM-5分子筛材料的设计与制备提供重要参考。

Abstract

ZSM-5 zeolite is a typical porous aluminosilicate material widely used in chemical engineering

environmental protection

and other fields due to its excellent hydrothermal stability

acid resistance

and shape-selective catalysis. However

the sole microporous structure of zeolites still presents challenges in applications

such as diffusion limitations

poor accessibility of active sites

and rapid deactivation by coking. In this study

nano-sized single-crystal ZSM-5 zeolite was efficiently synthesized via a one-pot method using TPAOH as the sole template and AlCl

as the highly active aluminum source. The effects of aluminum source

Si/Al ratio

TPAOH content

and crystallization temperature on the crystallization characteristics

morphology

pore structure

and aluminum coordination environment of the zeolite were investigated

and the crystallization mechanism and catalytic performance in methanol to propylene (MTP) were elucidated. The results show that increasing the Si/Al ratio and crystallization temperature both lead to a non-monotonic change in the relative cryst

allinity and BET specific surface area of the zeolite

which first increase and then decrease

while also reducing the crystal size. Increasing the TPAOH content continuously enhances the relative crystallinity and BET specific surface area and significantly refines the crystal size. Under the optimized conditions using aluminum chloride as the aluminum source

Si/Al ratio of 100

(TPAOH)/

(SiO

) = 0.35

and crystallization temperature of 170℃

the obtained nano-sized single-crystal ZSM-5 zeolite exhibits a crystal size of approximately 110 nm

a BET specific surface area of 398.72 m

an average pore size of 5.44 nm

maintains a methanol conversion rate above 80% in the MTP reaction

and achieves a maximum propylene selectivity of 60%. The crystal growth process of the nano-sized ZSM-5 zeolite undergoes multiple stages of "nucleation-ripening-stabilization." This study provides an important reference for the design and preparation of high-performance nano-sized single-crystal ZSM-5 zeolite materials.

关键词

Keywords

references

Fu D L , van der Heijden O , Stanciakova K , et al . Disentangling reaction processes of zeolites within single-oriented channels [J ] . Angewandte Chemie International Edition , 2020 , 59 ( 36 ): 15502 - 15506 .

Miyamoto M , Ono S , Oumi Y , et al . Nanoporous ZSM-5 crystals coated with silicalite-1 for enhanced p-xylene separation [J ] . ACS Applied Nano Materials , 2019 , 2 ( 5 ): 2642 - 2650 .

Rac V , Rakić V , Stošić D , et al . Enhanced accessibility of active sites in hierarchical ZSM-5 zeolite for removal of pharmaceutically active substances: Adsorption and microcalorimetric study [J ] . Arabian Journal of Chemistry , 2020 , 13 ( 1 ): 1945 - 1954 .

冀钟 , 赵彦玲 , 陈雨濛 , 等 . ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究 [J ] . 化工学报 , 2024 , 75 ( 6 ): 2332 - 2343 .

Ji Z , Zhao Y L , Chen Y M , et al . Adsorption performance and mechanism of ZSM-5 molecular sieves on typical coating VOCs [J ] . CIESC Journal , 2024 , 75 ( 6 ): 2332 - 2343 .

陈光敏 , 孙永杰 , 陈鹏飞 , 等 . 碱处理改性ZSM-5吸附分离间/对甲酚异构体 [J ] . 高校化学工程学报 , 2025 , 39 ( 3 ): 401 - 409 .

Chen G M , Sun Y J , Chen P F , et al . Adsorption separation of p/m-cresol on alkali-treated ZSM-5 [J ] . Journal of Chemical Engineering of Chinese Universities , 2025 , 39 ( 3 ): 401 - 409 .

Meng F J , Wang Y Q , Wang S H . Methanol to gasoline over zeolite ZSM-5: Improved catalyst performance by treatment with HF [J ] . RSC Advances , 2016 , 6 ( 63 ): 58586 - 58593 .

Zhang Q , Hu S , Zhang L L , et al . Facile fabrication of mesopore-containing ZSM-5 zeolite from spent zeolite catalyst for methanol to propylene reaction [J ] . Green Chemistry , 2014 , 16 ( 1 ): 77 - 81 .

Alipour S M , Halladj R , Askari S . Effects of the different synthetic parameters on the crystallinity and crystal size of nanosized ZSM-5 zeolite [J ] . Reviews in Chemical Engineering , 2014 , 30 ( 3 ): 289 - 322 .

Yan Y E , Guo X , Zhang Y H , et al . Future of nano-/hierarchical zeolites in catalysis: Gaseous phase or liquid phase system [J ] . Catalysis Science & Technology , 2015 , 5 ( 2 ): 772 - 785 .

Chen H Y , Yang M F , Shang W J , et al . Organosilane surfactant-directed synthesis of hierarchical ZSM-5 zeolites with improved catalytic performance in methanol-to-propylene reaction [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 32 ): 10956 - 10966 .

Meng L Q , Zhu X C , Wannapakdee W , et al . A dual-templating synthesis strategy to hierarchical ZSM-5 zeolites as efficient catalysts for the methanol-to-hydrocarbons reaction [J ] . Journal of Catalysis , 2018 , 361 : 135 - 142 .

Hartmann M , Schwieger W . Hierarchically-structured porous materials: From basic understanding to applications [J ] . Chemical Society Reviews , 2016 , 45 ( 12 ): 3311 - 3312 .

Rezaei F , Webley P . Structured adsorbents in gas separation processes [J ] . Separation and Purification Technology , 2010 , 70 ( 3 ): 243 - 256 .

Choi M , Na K , Kim J , et al . Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts [J ] . Nature , 2009 , 461 ( 7261 ): 246 - 249 .

金科 , 王晨光 , 马隆龙 , 等 . 核壳纳米材料制备及其在CO/CO 2 热催化加氢中的应用 [J ] . 化工学报 , 2022 , 73 ( 3 ): 990 - 1007 .

Jin K , Wang C G , Ma L L , et al . Preparation of core-shell nanomaterials and their application in thermocatalytic hydrogenation of CO/CO 2 [J ] . CIESC Journal , 2022 , 73 ( 3 ): 990 - 1007 .

Mintova S , Gilson J P , Valtchev V . Advances in nanosized zeolites [J ] . Nanoscale , 2013 , 5 ( 15 ): 6693 - 6703 .

Mintova S , Grand J , Valtchev V . Nanosized zeolites: Quo vadis? [J ] . Comptes Rendus Chimie , 2016 , 19 ( 1/2 ): 183 - 191 .

Zhang H B , Ma Y C , Song K S , et al . Nano-crystallite oriented self-assembled ZSM-5 zeolite and its LDPE cracking properties: Effects of accessibility and strength of acid sites [J ] . Journal of Catalysis , 2013 , 302 : 115 - 125 .

Zhang Q , Chen G R , Wang Y Y , et al . High-quality single-crystalline MFI-type nanozeolites: A facile synthetic strategy and MTP catalytic studies [J ] . Chemistry of Materials , 2018 , 30 ( 8 ): 2750 - 2758 .

张佳 , 吴磊 , 李耀峰 , 等 . 纳米ZSM-5分子筛合成及应用研究进展 [J ] . 化工科技 , 2026 , 34 ( 1 ): 77 - 82 .

Zhang J , Wu L , Li Y F , et al . Research progress in synthesis and application of nano ZSM-5 [J ] . Science & Technology in Chemical Industry , 2026 , 34 ( 1 ): 77 - 82 .

张娇玉 , 朱生华 , 唐瑞源 , 等 . 改性纳米ZSM-5分子筛催化甲醇制对二甲苯的反应性能 [J ] . 西安石油大学学报(自然科学版) , 2024 , 39 ( 5 ): 109 - 115, 126 .

Zhang J Y , Zhu S H , Tang R Y , et al . Study on catalytic performance of methanol to p-xylene over modified nano-sized ZSM-5 zeolites [J ] . Journal of Xi'an Shiyou University (Natural Science Edition) , 2024 , 39 ( 5 ): 109 - 115, 126 .

王晗斌 , 张鹏 , 杨帆 , 等 . 晶种辅助预晶化法合成纳米ZSM-5分子筛及其在丙烷芳构化反应中的应用 [J ] . 低碳化学与化工 , 2024 , 49 ( 2 ): 67 - 73, 104 .

Wang H B , Zhang P , Yang F , et al . Synthesis of nano ZSM-5 molecular sieve by seed-assisted and pre-crystallization and its application in aromatization of propane [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 2 ): 67 - 73, 104 .

Zhang C S , Wu Q M , Lei C , et al . An efficient, rapid, and non-centrifugation synthesis of nanosized zeolites by accelerating the nucleation rate [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 42 ): 21156 - 21161 .

岳明波 , 杨娜 , 王一萌 . 晶种导向干凝胶法制备成型ZSM-5分子筛 [J ] . 物理化学学报 , 2012 , 28 ( 9 ): 2115 - 2121 .

Yue M B , Yang N , Wang Y M . Synthesis of shaped ZSM-5 zeolites by dry-gel conversion with seed gel as directing agent [J ] . Acta Physico-Chimica Sinica , 2012 , 28 ( 9 ): 2115 - 2121 .

Lu S Q , Gao F , Wang Y F , et al . Accelerated crystallization of fluoride-mediated dry gel into ZSM-5 for enhanced carbon dioxide adsorption in humid conditions [J ] . Surfaces and Interfaces , 2025 , 66 : 106584 .

Hu J H , Jiang H , Guo Y T , et al . Efficient synthesis of smaller crystal ZSM-5 zeolite in low TPAOH-to-silica ratio dry-gel hydrothermal system [J ] . Microporous and Mesoporous Materials , 2025 , 390 : 113596 .

Zong L K , Xu H X , Wang X Y , et al . The green and sustainable synthesis of nanometer ZSM-5 without organotemplates via utilizing the recycled mother liquid [J ] . New Journal of Chemistry , 2021 , 45 ( 19 ): 8582 - 8590 .

Chen Z W , Li Z , Zhang Y , et al . A green route for the synthesis of nano-sized hierarchical ZSM-5 zeolite with excellent DTO catalytic performance [J ] . Chemical Engineering Journal , 2020 , 388 : 124322 .

Zhang C S , Fan K , Ma G , et al . Efficient synthesis of mesoporous nano ZSM-5 zeolite crystals without a mesoscale template [J ] . Crystals , 2021 , 11 ( 10 ): 1247 .

Sang J C , Wang Y Q , Liu W R , et al . Fabrication of coffin-like multilamellar ZSM-5 monocrystals via bio-renewable surfactant alkyl polyglucoside 1214 and its application in methanol-to-propylene reaction [J ] . Chemical Engineering Journal , 2024 , 483 : 149371 .

张卿 , 张海荣 , 付玉川 , 等 . 铝源对合成ZSM-5分子筛晶粒大小及形貌的影响 [J ] . 现代化工 , 2009 , 29 ( S1 ): 118 - 120 .

Zhang Q , Zhang H R , Fu Y C , et al . Effect of aluminium sources on crystal size and morphology of ZSM-5 zeolite [J ] . Modern Chemical Industry , 2009 , 29 ( S1 ): 118 - 120 .

梁瑞康 , 刘卓 , 孙泽平 , 等 . 铝源对HZSM-5分子筛中骨架铝落位及其甲缩醛气相羰基化性能的影响 [J ] . 工业催化 , 2023 , 31 ( 7 ): 23 - 31 .

Liang R K , Liu Z , Sun Z P , et al . Effects of aluminium sources on the framework aluminum siting of HZSM-5 zeolite and its catalytic performance in dimethoxymethane carbonylation [J ] . Industrial Catalysis , 2023 , 31 ( 7 ): 23 - 31 .

李知行 , 代卫炯 , 刘相洋 , 等 . ZSM-5分子筛结构与反应性的研究进展 [J ] . 化工进展 , 2025 , 44 ( 2 ): 788 - 808 .

Li Z X , Dai W J , Liu X Y , et al . Insight into structure and reactivity of ZSM-5 [J ] . Chemical Industry and Engineering Progress , 2025 , 44 ( 2 ): 788 - 808 .

Dedecek J , Balgová V , Pashkova V , et al . Synthesis of ZSM-5 zeolites with defined distribution of Al atoms in the framework and multinuclear MAS NMR analysis of the control of Al distribution [J ] . Chemistry of Materials , 2012 , 24 ( 16 ): 3231 - 3239 .

Ferreira A F P , Mittelmeijer-Hazeleger M C , Bergh J V D , et al . Adsorption of hexane isomers on MFI type zeolites at ambient temperature: Understanding the aluminium content effect [J ] . Microporous and Mesoporous Materials , 2013 , 170 : 26 - 35 .

Lin L F , Zhao S F , Zhang D W , et al . Acid strength controlled reaction pathways for the catalytic cracking of 1-pentene to propene over ZSM-5 [J ] . ACS Catalysis , 2015 , 5 ( 7 ): 4048 - 4059 .

Groen J C , Peffer L A A , Moulijn J A , et al . On the introduction of intracrystalline mesoporosity in zeolites upon desilication in alkaline medium [J ] . Microporous and Mesoporous Materials , 2004 , 69 ( 1/2 ): 29 - 34 .

Wan Z J , Wu W , Li G , et al . Effect of SiO 2 /Al 2 O 3 ratio on the performance of nanocrystal ZSM-5 zeolite catalysts in methanol to gasoline conversion [J ] . Applied Catalysis A: General , 2016 , 523 : 312 - 320 .

Alotaibi F M , Ding L H , Sitepu H , et al . A facile synthesis of hierarchical nanosized zeolite beta and its application in direct crude oil hydrocracking [J ] . Catalysis Communications , 2024 , 187 : 106871 .

Nastro A , Crea F , Hayhurst D T , et al . The effects of varying the tetraalkylammonium template on high-silica zeolite synthesis [J ] . Studies in Surface Science and Catalysis , 1989 , 49 : 321 - 330 .

Hansen T W , DeLaRiva A T , Challa S R , et al . Sintering of catalytic nanoparticles: Particle migration or ostwald ripening? [J ] . Accounts of Chemical Research , 2013 , 46 ( 8 ): 1720 - 1730 .

Nada M H , Larsen S C . Insight into seed-assisted template free synthesis of ZSM-5 zeolites [J ] . Microporous and Mesoporous Materials , 2017 , 239 : 444 - 452 .

Hou Y X , Li X Y , Sun M H , et al . The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance [J ] . Frontiers of Chemical Science and Engineering , 2021 , 15 ( 2 ): 269 - 278 .

凌旸 , 章冠群 , 马延航 . 基于透射电子显微镜的沸石分子筛结构研究进展 [J ] . 高等学校化学学报 , 2021 , 42 ( 1 ): 201 - 216 .

Ling Y , Zhang G Q , Ma Y H . Progress of zeolite structural analysis based on transmission electron microscopy [J ] . Chemical Journal of Chinese Universities , 2021 , 42 ( 1 ): 201 - 216 .

Xiong G , Meng F F , Liu J X , et al . Rapid hydrothermal synthesis of hierarchical ZSM-5/beta composite zeolites [J ] . RSC Advances , 2021 , 11 ( 35 ): 21235 - 21247 .

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