AlCl3和甘油/ChCl在三组分深共晶木质素转化和溶解中的协同作用。

IF 6.6 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2025-09-30 DOI:10.1002/cssc.202501796
Chenyu Ge, Juan Zhao, Ruoyu Zhang, Changwei Hu
{"title":"AlCl3和甘油/ChCl在三组分深共晶木质素转化和溶解中的协同作用。","authors":"Chenyu Ge, Juan Zhao, Ruoyu Zhang, Changwei Hu","doi":"10.1002/cssc.202501796","DOIUrl":null,"url":null,"abstract":"<p><p>\"Lignin-first\" approach has attracted much attention on biomass utilization. Deep eutectic solvents (DESs) have the advantages of being versatile and tunable, among which three-constituent DES (glycerol/ChCl/AlCl<sub>3</sub>·6H<sub>2</sub>O) is found efficient for lignin extraction in biomass fractionation. Herein, how this kind of three-constituent DES affects the fractionation efficiency of lignin is investigated in detail at molecular level. Molecular dynamics simulations indicate that glycerol and ChCl provide strong interaction with the small fragments of lignin. Chloride anion is found to contribute mostly electrostatic interaction to lignin-solvent interactions, while choline cation and glycerol provide strong van der Waals interaction, which also contributes to the higher solubility of the small fragments of lignin. According to DFT calculations, Al<sup>3+</sup> is more likely to coordinate with glycerol, forming chelated [Al(C<sub>3</sub>H<sub>8</sub>O<sub>3</sub>)<sub>2</sub>]<sup>3+</sup>, which can effectively catalyze the cleavage of βO4 bond of lignin through Lewis acid catalysis, including the isomerization of hydroxyl via E1 and Markovnikov reactions, significantly reducing the energy barrier by about 24 kcal mol<sup>-1</sup>, favoring the fractionation of lignin. This mechanism is also verified experimentally. This work gives out deep understanding for lignin fractionation in solvent pretreatment, providing guiding clues for the design of more efficient solvent system in biomass utilization.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501796"},"PeriodicalIF":6.6000,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synergistic Effect of AlCl<sub>3</sub> and Glycerol/ChCl in the Conversion and Dissolution of Lignin in Three-Constituent Deep Eutectics.\",\"authors\":\"Chenyu Ge, Juan Zhao, Ruoyu Zhang, Changwei Hu\",\"doi\":\"10.1002/cssc.202501796\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>\\\"Lignin-first\\\" approach has attracted much attention on biomass utilization. Deep eutectic solvents (DESs) have the advantages of being versatile and tunable, among which three-constituent DES (glycerol/ChCl/AlCl<sub>3</sub>·6H<sub>2</sub>O) is found efficient for lignin extraction in biomass fractionation. Herein, how this kind of three-constituent DES affects the fractionation efficiency of lignin is investigated in detail at molecular level. Molecular dynamics simulations indicate that glycerol and ChCl provide strong interaction with the small fragments of lignin. Chloride anion is found to contribute mostly electrostatic interaction to lignin-solvent interactions, while choline cation and glycerol provide strong van der Waals interaction, which also contributes to the higher solubility of the small fragments of lignin. According to DFT calculations, Al<sup>3+</sup> is more likely to coordinate with glycerol, forming chelated [Al(C<sub>3</sub>H<sub>8</sub>O<sub>3</sub>)<sub>2</sub>]<sup>3+</sup>, which can effectively catalyze the cleavage of βO4 bond of lignin through Lewis acid catalysis, including the isomerization of hydroxyl via E1 and Markovnikov reactions, significantly reducing the energy barrier by about 24 kcal mol<sup>-1</sup>, favoring the fractionation of lignin. This mechanism is also verified experimentally. This work gives out deep understanding for lignin fractionation in solvent pretreatment, providing guiding clues for the design of more efficient solvent system in biomass utilization.</p>\",\"PeriodicalId\":149,\"journal\":{\"name\":\"ChemSusChem\",\"volume\":\" \",\"pages\":\"e202501796\"},\"PeriodicalIF\":6.6000,\"publicationDate\":\"2025-09-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemSusChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cssc.202501796\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemSusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cssc.202501796","RegionNum":2,"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

摘要

“木质素优先”方法已成为生物质利用领域的热点。深共晶溶剂(DESs)具有通用性和可调性,其中甘油/ChCl/AlCl3·6H2O(三组分)是生物质分馏中木质素萃取的有效溶剂。本文从分子水平上详细研究了这种三组分DES对木质素分馏效率的影响。分子动力学模拟表明,甘油和ChCl与木质素的小片段有很强的相互作用。发现氯阴离子对木质素-溶剂相互作用的贡献主要是静电相互作用,而胆碱阳离子和甘油则提供了强的范德华相互作用,这也有助于木质素小片段的高溶解度。根据DFT计算,Al3+更容易与甘油配位,形成螯合的[Al(C3H8O3)2]3+,通过Lewis酸催化,可有效催化木质素β - _(_) _(_) _(_) _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _() _())键的裂解,包括通过E1和Markovnikov反应羟基的异构化,显著降低约24 kcal mol-1的能垒,有利于木质素的分馏。该机理也得到了实验验证。本研究为木质素在溶剂预处理中的分馏提供了深入的认识,为设计更高效的生物质利用溶剂体系提供了指导线索。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Synergistic Effect of AlCl3 and Glycerol/ChCl in the Conversion and Dissolution of Lignin in Three-Constituent Deep Eutectics.

"Lignin-first" approach has attracted much attention on biomass utilization. Deep eutectic solvents (DESs) have the advantages of being versatile and tunable, among which three-constituent DES (glycerol/ChCl/AlCl3·6H2O) is found efficient for lignin extraction in biomass fractionation. Herein, how this kind of three-constituent DES affects the fractionation efficiency of lignin is investigated in detail at molecular level. Molecular dynamics simulations indicate that glycerol and ChCl provide strong interaction with the small fragments of lignin. Chloride anion is found to contribute mostly electrostatic interaction to lignin-solvent interactions, while choline cation and glycerol provide strong van der Waals interaction, which also contributes to the higher solubility of the small fragments of lignin. According to DFT calculations, Al3+ is more likely to coordinate with glycerol, forming chelated [Al(C3H8O3)2]3+, which can effectively catalyze the cleavage of βO4 bond of lignin through Lewis acid catalysis, including the isomerization of hydroxyl via E1 and Markovnikov reactions, significantly reducing the energy barrier by about 24 kcal mol-1, favoring the fractionation of lignin. This mechanism is also verified experimentally. This work gives out deep understanding for lignin fractionation in solvent pretreatment, providing guiding clues for the design of more efficient solvent system in biomass utilization.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信