Wei Luo, Jie Shi, Tiesen Li, Tinghai Wang, Jiangyong Liu, Qingyan Cui, Yisheng Tan, Yuanyuan Yue, Xiaojun Bao
{"title":"Catalytic Dehydration of Glycerol to Acrolein over ZSM-5 Zeolites: Synergistic Effect of Pore Structure and Aluminum Distribution","authors":"Wei Luo, Jie Shi, Tiesen Li, Tinghai Wang, Jiangyong Liu, Qingyan Cui, Yisheng Tan, Yuanyuan Yue, Xiaojun Bao","doi":"10.1021/acssuschemeng.4c07302","DOIUrl":null,"url":null,"abstract":"The catalytic dehydration of glycerol to acrolein offers a sustainable route for efficiently utilizing low-cost and renewable bioglycerol. This work deeply explores glycerol dehydration to acrolein over ZSM-5 zeolite catalysts with various pore structures and aluminum distributions. The results reveal that glycerol conversion is enhanced through the construction of a mesoporous structure and the increase in Brønsted acid sites of the catalysts, but acrolein selectivity is not directly related to these factors. Further characterizations, density functional theory calculation, kinetic study, and reaction mechanism analysis demonstrate that the richest Al<sub>single</sub> sites in the zeolite framework and the least Al<sub>pair</sub> sites in the straight and sinusoidal channels can prevent the generated acrolein from adsorbing on adjacent Al sites. This allows acrolein to immediately escape from the catalyst surface, reducing side reactions and enhancing its selectivity. Therefore, the synergistic between the mesoporous structure and more Al<sub>single</sub> sites in the ZSM-5 zeolite framework promotes acrolein yield. Additionally, a descriptor φ, reflecting the amount of Al<sub>single</sub> sites and the external specific surface area of the ZSM-5 zeolite, is first proposed to more clearly elucidate the structure–performance relationship. This study provides a new perspective for understanding the mechanism of catalytic dehydration of glycerol to acrolein, guiding the development of highly efficient catalysts. It is significant for the sustainable development of the biodiesel and acrolein production industry.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"99 1","pages":""},"PeriodicalIF":7.1000,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acssuschemeng.4c07302","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The catalytic dehydration of glycerol to acrolein offers a sustainable route for efficiently utilizing low-cost and renewable bioglycerol. This work deeply explores glycerol dehydration to acrolein over ZSM-5 zeolite catalysts with various pore structures and aluminum distributions. The results reveal that glycerol conversion is enhanced through the construction of a mesoporous structure and the increase in Brønsted acid sites of the catalysts, but acrolein selectivity is not directly related to these factors. Further characterizations, density functional theory calculation, kinetic study, and reaction mechanism analysis demonstrate that the richest Alsingle sites in the zeolite framework and the least Alpair sites in the straight and sinusoidal channels can prevent the generated acrolein from adsorbing on adjacent Al sites. This allows acrolein to immediately escape from the catalyst surface, reducing side reactions and enhancing its selectivity. Therefore, the synergistic between the mesoporous structure and more Alsingle sites in the ZSM-5 zeolite framework promotes acrolein yield. Additionally, a descriptor φ, reflecting the amount of Alsingle sites and the external specific surface area of the ZSM-5 zeolite, is first proposed to more clearly elucidate the structure–performance relationship. This study provides a new perspective for understanding the mechanism of catalytic dehydration of glycerol to acrolein, guiding the development of highly efficient catalysts. It is significant for the sustainable development of the biodiesel and acrolein production industry.
期刊介绍:
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.