{"title":"通过种子诱导无溶剂结晶为甲醇-烯烃转化量身定制纳米ZSM-5","authors":"Qi Zhou, Qiong Zhang, Ruoling Sun, Bo Liu, Zongqing Guo, Yuan Gao, Rongli Jiang","doi":"10.1016/j.micromeso.2025.113881","DOIUrl":null,"url":null,"abstract":"<div><div>ZSM-5 catalysts are central to the methanol-to-olefins (MTO) process, yet their conventional hydrothermal synthesis requires excessive solvents and organic templates, hindering sustainability and economic feasibility. Here, we develop a seed-assisted, solvent-free synthesis strategy that precisely controls nucleation to produce nanosized ZSM-5 with hierarchical porosity and tunable acidity. Introducing 5–20 wt% of preformed seeds significantly accelerates nucleation, reduces crystal size from 15 μm to submicron scale of 0.4 μm, and enhances both crystallinity and mesoporosity while preserving phase purity. Among these, the 10 wt% seeded sample (ZA-10) achieves the optimal balance between crystal refinement and textural improvement. Systematic aluminum tuning at a Si/Al ratio of 30 further optimizes acid site distribution and pore structure, yielding a catalyst with the highest density of weak acid sites and largest mesopore volume. Consequently, ZA-10 demonstrates outstanding catalytic stability, maintaining over 90 % methanol conversion for 94 h and delivering 32.6 % propylene selectivity. In contrast, unseeded catalysts rapidly deactivate due to their larger crystal size and limited porosity. These findings confirm that integrating seed-assisted nucleation with controlled aluminum incorporation effectively overcomes key limitations of solvent-free ZSM-5 synthesis, providing a eco-friendly pathway toward high-performance MTO catalysts.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113881"},"PeriodicalIF":4.7000,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tailoring nanosized ZSM-5 through seed-induced solvent-free crystallization for methanol-to-olefins conversion\",\"authors\":\"Qi Zhou, Qiong Zhang, Ruoling Sun, Bo Liu, Zongqing Guo, Yuan Gao, Rongli Jiang\",\"doi\":\"10.1016/j.micromeso.2025.113881\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>ZSM-5 catalysts are central to the methanol-to-olefins (MTO) process, yet their conventional hydrothermal synthesis requires excessive solvents and organic templates, hindering sustainability and economic feasibility. Here, we develop a seed-assisted, solvent-free synthesis strategy that precisely controls nucleation to produce nanosized ZSM-5 with hierarchical porosity and tunable acidity. Introducing 5–20 wt% of preformed seeds significantly accelerates nucleation, reduces crystal size from 15 μm to submicron scale of 0.4 μm, and enhances both crystallinity and mesoporosity while preserving phase purity. Among these, the 10 wt% seeded sample (ZA-10) achieves the optimal balance between crystal refinement and textural improvement. Systematic aluminum tuning at a Si/Al ratio of 30 further optimizes acid site distribution and pore structure, yielding a catalyst with the highest density of weak acid sites and largest mesopore volume. Consequently, ZA-10 demonstrates outstanding catalytic stability, maintaining over 90 % methanol conversion for 94 h and delivering 32.6 % propylene selectivity. In contrast, unseeded catalysts rapidly deactivate due to their larger crystal size and limited porosity. These findings confirm that integrating seed-assisted nucleation with controlled aluminum incorporation effectively overcomes key limitations of solvent-free ZSM-5 synthesis, providing a eco-friendly pathway toward high-performance MTO catalysts.</div></div>\",\"PeriodicalId\":392,\"journal\":{\"name\":\"Microporous and Mesoporous Materials\",\"volume\":\"400 \",\"pages\":\"Article 113881\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Microporous and Mesoporous Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1387181125003968\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Microporous and Mesoporous Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1387181125003968","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Tailoring nanosized ZSM-5 through seed-induced solvent-free crystallization for methanol-to-olefins conversion
ZSM-5 catalysts are central to the methanol-to-olefins (MTO) process, yet their conventional hydrothermal synthesis requires excessive solvents and organic templates, hindering sustainability and economic feasibility. Here, we develop a seed-assisted, solvent-free synthesis strategy that precisely controls nucleation to produce nanosized ZSM-5 with hierarchical porosity and tunable acidity. Introducing 5–20 wt% of preformed seeds significantly accelerates nucleation, reduces crystal size from 15 μm to submicron scale of 0.4 μm, and enhances both crystallinity and mesoporosity while preserving phase purity. Among these, the 10 wt% seeded sample (ZA-10) achieves the optimal balance between crystal refinement and textural improvement. Systematic aluminum tuning at a Si/Al ratio of 30 further optimizes acid site distribution and pore structure, yielding a catalyst with the highest density of weak acid sites and largest mesopore volume. Consequently, ZA-10 demonstrates outstanding catalytic stability, maintaining over 90 % methanol conversion for 94 h and delivering 32.6 % propylene selectivity. In contrast, unseeded catalysts rapidly deactivate due to their larger crystal size and limited porosity. These findings confirm that integrating seed-assisted nucleation with controlled aluminum incorporation effectively overcomes key limitations of solvent-free ZSM-5 synthesis, providing a eco-friendly pathway toward high-performance MTO catalysts.
期刊介绍:
Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal.
Topics which are particularly of interest include:
All aspects of natural microporous and mesoporous solids
The synthesis of crystalline or amorphous porous materials
The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic
The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions
All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials
Adsorption (and other separation techniques) using microporous or mesoporous adsorbents
Catalysis by microporous and mesoporous materials
Host/guest interactions
Theoretical chemistry and modelling of host/guest interactions
All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.