硅酸盐学报

天然糖类模板辅助合成多级孔ZSM-5分子筛研究进展

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李剑 ¹ , 朱海山 ¹ , 沈健 ² , 杨丽娜 ¹

硅酸盐学报 | 综合评述 2025,53(11): 3420-3432

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硅酸盐学报 |综合评述 2025 , 53 (11) : 3420 -3432

天然糖类模板辅助合成多级孔ZSM-5分子筛研究进展

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李剑¹, 朱海山¹, 沈健², 杨丽娜¹

作者信息

^1．辽宁石油化工大学石油化工学院，辽宁抚顺 113001

^2．泉州职业技术大学，福建晋江 362268

通讯作者:

杨丽娜（1976—），女，博士，教授。

作者简介:

李剑（1974—），男，博士，教授。

Advances in the Template-Assisted Synthesis of Hierarchical ZSM-5 Zeolite from Natural Sugars

Jian LI¹, Haishan ZHU¹, Jian SHEN², Lina YANG¹

Affiliations

^1.School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China

^2.Quanzhou Vocational and Technical University, Jinjiang 362268, Fujian, China

Corresponding Author:

YANG Lina (1976-), female, Ph.D., Professor. E-mail: yanglnzg@163.com

LI Jian (1974-), male, Ph.D., Professor. E-mail: jlqdsd@163.com

出版时间: 2025-11-20 doi: 10.14062/j.issn.0454-5648.20250323

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摘要

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天然糖类作为绿色模板在多级孔ZSM-5分子筛合成中，不但能发挥结构导向作用，还可调控晶粒尺寸与酸中心分布，因此成为研究热点。本文综述了以天然糖类及其衍生物为模板辅助合成多级孔ZSM-5的研究进展，重点讨论了糖类模板的作用原理及其对分子筛结构、性质及催化性能的影响。研究表明：糖类模板的类型直接影响分子筛的孔径、酸性及形貌。葡萄糖和蔗糖模板倾向于形成较小介孔的ZSM-5，而淀粉、纤维素及其衍生物有助于构建较大介孔甚至微-介-大孔ZSM-5分子筛。此外，不同糖类模板可诱导特殊形貌的形成，如葡萄糖和淀粉可促进b轴方向生长，淀粉与蔗糖模板倾向于形成链状结构，纤维素衍生物则有助于构建中空球形结构。最后，指出未来研究应聚焦于开发新型合成方法、深入探索糖类模板与多级孔结构的构效关系、以及优化模板剂用量以实现孔结构和酸位点的精准调控。

关键词

糖类 / 生物质 / 多级孔 / ZSM-5分子筛 / 合成

Abstract

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Hierarchical ZSM-5 zeolite show significant advantages in the fields of catalysis, adsorption and separation due to their unique micro- or meso-macroporous hierarchical structure, but the traditional templating method suffers from the problems of high cost, process complexity and environmental burden. As green template agents, natural sugars (glucose, starch, cellulose, etc.) have the advantages of wide source, environmental friendliness and rich functional groups, which can not only regulate the grain size, pore structure and acidic distribution of molecular sieves through hydrogen bonding and electrostatic interactions, but also induce the formation of molecular sieves with special morphology, which provides a new strategy for the precise design of high-performance catalysts.

Recent studies have focused on the mechanism of action and performance optimization of different sugar templates, and the morphology, particle size and properties of natural sugar templates are closely related to the structural properties of hierarchical ZSM-5 zeolite. For example, glucose selectively binds to the molecular sieve crystal surface through hydroxyl groups and promotes b-axis orientation to enhance propylene selectivity, and the amphiphilic nature of its derivatives (e.g., alkyl polyglucosides) can precisely regulate mesopore distribution; sucrose templates enhance mesopore connectivity to optimize the diffusion of small molecules by inducing chain assembly; starch forms a wide pore size distribution by virtue of its large molecular weight, and enhances thermal stability and acidic strength by inducing chain assembly through branched chain structure; and the templates are also used in the study of the molecular sieve structure. Cellulose and its derivatives (e.g., carboxymethyl cellulose) enhance the structural stability through cross-linking effect, and the abundant hydroxyl and carboxyl groups in the long chains interact with the silica hydroxyl groups in the zeolite gel to build a hollow spherical multistage pore system. In addition, starch-coated silica nanorods and cellulose carbonized templates further expanded the pore types (trimodal pore structure), which showed excellent catalytic activity in esterification and cracking reactions. It was also shown that the amount of sugar templates directly affects the crystallinity, the number of acid sites and the pore volume, which needs to be optimized experimentally to balance the performance parameters, and when the acid content is sufficiently high, the content of mesopore and the pore size become the key factors to improve the catalytic efficiency of the molecular sieves.

Finally, the optimization of different synthetic methods and the development of templates for sugar derivatives have further expanded their applications. However, the existing studies still need to break through the industrialization bottleneck of the synthesis process, clarify the constitutive relationship between the dosage and performance of sugar templating agents, and explore the pore-acid synergistic regulation mechanism. Future research should focus on the innovation of green and efficient synthesis technology to promote the large-scale application of hierarchical ZSM-5 zeolite in the fields of energy conversion, environmental protection, and fine chemicals.

Summary and prospects

Natural sugars as templating agents show unique advantages in the synthesis of hierarchical ZSM-5 zeolite, which provide a promising alternative to the traditional templating method due to their green, cost-effective, pore-size-adjustable, and mild template-removal conditions. In addition, the differences between the molecular structures of different sugar templates exhibit unique regulatory properties in the synthesis of hierarchical ZSM-5 zeolite. Specifically, glucose and sucrose induce linear stacking of nanocrystals through hydroxyl coordination, and form a uniform intergranular mesoporous structure by combining with hydrothermal or two-step crystallization, which can effectively enhance the dispersion of loaded metals. But their ability to regulate the pore channels is weak. Other templating agents are needed to synergistically regulate pore structure. For example, polysaccharide templates, such as cellulose and starch, have branched chain structure. By using hydrothermal method or seed crystallization method, they can construct micro-medium-macroporous multilevel pore structure, and realize synergistic distribution of inter-crystalline mesopores and intra-crystalline mesopores. Polysaccharides and sodium alginate, serving as functional sugars, promote the formation of uniform and dendritic mesopores through electrostatic adsorption and carboxyl (—COO—)Al³⁺ chelation, respectively. They also enhance the density of acidic sites (Lewis) on the surface and regulate the morphology of molecular sieves. These modifications tailor the material for high-value-added applications, such as esterification of oleic acid with high acidity, the diffusion-controlled adsorption of macromolecules, and biomass conversion. By improving mass transfer efficiency and accessibility of acidic sites, the sugar templates can significantly enhance the performance of biomass conversion, promote the transformation of biomass from "waste" to "carbon neutral core carrier", and provide a sustainable solution to the goal of "dual carbon".

Although the natural sugar templates in hierarchical ZSM-5 zeolite to make significant progress, the field of research is still facing numerous challenges. Firstly, some of the sugar templates still suffer from complex pretreatment, wide mesopore size distribution, and high mesopore volume, leading to the decrease of crystallinity for synthesis of hierarchical ZSM-5 zeolite. Secondly, the existing synthesis techniques are mainly limited to hydrothermal methods, and other methods such as dry gel conversion and two-step crystallization are hindered in industrialization due to the complexity of the process and cost factors; finally, it is difficult to precisely regulate the pore structure and acidic sites of the molecular sieves, and the constitutive relationship between the templating agent dosage and the material properties has not been fully clarified. Therefore, exploring the controlled depolymerization of polysaccharides and multi-template compounding strategy to break through the bottleneck of crystallinity and mesopore homogeneity, developing more universal synthesis methods, exploring the mechanism of pore-acid synergistic regulation, and in-depth analysis of the mechanism of templating agents are the main directions of the future research, so that we can push forward the practical application of sugar templating method in the large-scale preparation of hierarchical zeolite.

Key words

saccharide / biomass / hierarchical / ZSM-5 zeolite / synthesize

引用本文

李剑, 朱海山, 沈健, 杨丽娜. 天然糖类模板辅助合成多级孔ZSM-5分子筛研究进展. 硅酸盐学报, 2025 , 53 (11) : 3420 -3432 . DOI: 10.14062/j.issn.0454-5648.20250323

Jian LI, Haishan ZHU, Jian SHEN, Lina YANG. Advances in the Template-Assisted Synthesis of Hierarchical ZSM-5 Zeolite from Natural Sugars[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (11) : 3420 -3432 . DOI: 10.14062/j.issn.0454-5648.20250323

基金

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辽宁省科学技术厅项目(20170540585)

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2025年第53卷第11期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250323

接收时间：2025-04-21
首发时间：2026-10-21
出版时间：2025-11-20

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收稿日期：2025-04-21
修回日期：2025-05-13

基金

辽宁省科学技术厅项目(20170540585)

作者信息

^1．辽宁石油化工大学石油化工学院，辽宁抚顺 113001

^2．泉州职业技术大学，福建晋江 362268

通讯作者:

杨丽娜（1976—），女，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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