Theoretical Elucidation of beta-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid
文献类型：期刊论文
| 作者 | Zhang, Yaqin; Huo, Feng; Wang, Yanlei; Xia, Yu; Tan, Xin; Zhang, Suojiang; He, Hongyan |
| 刊名 | FRONTIERS IN CHEMISTRY
 |
| 出版日期 | 2019-02-15 |
| 卷号 | 7页码:11 |
| 关键词 | lignin ionic liquid DFT molecular dynamics beta-O-4 bond reaction mechanism |
| ISSN号 | 2296-2646 |
| DOI | 10.3389/fchem.2019.00078 |
| 英文摘要 | While the depolymerization of lignin to chemicals catalyzed by ionic liquids has attracted significant attention, the relevant molecular mechanism, especially the cleavage of specific bonds related to efficient depolymerization, still needs to be deeply understood for the complexity of this natural aromatic polymer. This work presents a detailed understanding of the cleavage of the most abundant beta-O-4 bond in the model system, guaiacylglycerol beta-guaiacyl ether, by a Bronsted acidic IL (1-methyl-3-(propyl-3-sulfonate) imidazolium bisulfate ([C(3)SO(3)Hmim][HSO4]) using density functional theory calculation and molecular dynamics simulation. It has been found that [C(3)SO(3)Hmim][HSO4] generates zwitterion/H2SO4 via proton transfer with an energy barrier of 0.38 kcal/mol, which plays a dominant role in the lignin depolymerization process. Subsequently, the reaction can be carried out via three potential pathways, including (1) the dehydration of alpha-C-OH, (2) dehydration of gamma-C-OH, and (3) the protonation beta-O. The electrophilic attack of H2SO4 and the hydrogen-bonding interaction between GG and zwitterion are the two most important factors to promote the depolymerization reaction. In all steps, the dehydration of alpha-C-OH route is computed to be favored for the experiment. The relatively higher energy barrier for beta-O-4 bond dissociation among these reaction steps is attributed to the hindrance of the self-assembled clusters of GG in the mixed system. Further, the dense distribution of H13([C(3)SO(3)Hmimi) surrounding O21(GG), indicated by sharp peaks in RDFs, reveals that -SO3H in cations plays a substantial role in solvating lignin. Hopefully, this work will demonstrate new insights into lignin depolymerization by functionalized ILs in biomass conversion chemistry. |
| WOS关键词 | LIGNOCELLULOSIC BIOMASS ; MOLECULAR-DYNAMICS ; FORCE-FIELD ; DEPOLYMERIZATION ; CONVERSION ; EFFICIENT ; CELLULOSE ; MECHANISM ; CATALYST ; DFT |
| 资助项目 | National Natural Science Foundation of China[21406230] ; National Natural Science Foundation of China[21736003] ; National Natural Science Foundation of China[2176278] ; Beijing Natural Science Foundation[2182068] ; Youth Innovation Promotion Association of CAS[2017066] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000458772100001 |
| 出版者 | FRONTIERS MEDIA SA |
| 资助机构 | National Natural Science Foundation of China ; Beijing Natural Science Foundation ; Youth Innovation Promotion Association of CAS |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/27977]  |
| 专题 | 中国科学院过程工程研究所 |
| 通讯作者 | He, Hongyan |
| 作者单位 | Chinese Acad Sci, Inst Proc Engn, Beijing Key Lab Ion Liquids Clean Proc, CAS Key Lab Green Proc & Engn,State Key Lab Multi, Beijing, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhang, Yaqin,Huo, Feng,Wang, Yanlei,et al. Theoretical Elucidation of beta-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid[J]. FRONTIERS IN CHEMISTRY,2019,7:11. |
| APA | Zhang, Yaqin.,Huo, Feng.,Wang, Yanlei.,Xia, Yu.,Tan, Xin.,...&He, Hongyan.(2019).Theoretical Elucidation of beta-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid.FRONTIERS IN CHEMISTRY,7,11. |
| MLA | Zhang, Yaqin,et al."Theoretical Elucidation of beta-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid".FRONTIERS IN CHEMISTRY 7(2019):11. |
入库方式： OAI收割
来源：过程工程研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。