Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

doi:10.1016/j.cjche.2015.07.018

Chinese Journal of Chemical Engineering ›› 2015, Vol. 23 ›› Issue (11): 1894-1906.DOI: 10.1016/j.cjche.2015.07.018

• 能源、资源与环境技术 • 上一篇下一篇

Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

Yingying Yao^1,2, Yao Li^1,2, Xiaomin Liu¹, Xiaochun Zhang¹, Jianji Wang³, Xiaoqian Yao¹, Suojiang Zhang¹

1 Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
2 School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
3 Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007, China

收稿日期:2015-03-18 修回日期:2015-04-24 出版日期:2015-11-28 发布日期:2015-12-18
通讯作者: Xiaoqian Yao, Suojiang Zhang
基金资助:
Supported by the National Natural Science Foundation of China (21210006, 21276255, 21406230, 91434111) and the Natural Science Foundation of Beijing of China (2131005, 2142029).

Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

Yingying Yao^1,2, Yao Li^1,2, Xiaomin Liu¹, Xiaochun Zhang¹, Jianji Wang³, Xiaoqian Yao¹, Suojiang Zhang¹

1 Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
2 School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
3 Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007, China

Received:2015-03-18 Revised:2015-04-24 Online:2015-11-28 Published:2015-12-18
Contact: Xiaoqian Yao, Suojiang Zhang
Supported by:
Supported by the National Natural Science Foundation of China (21210006, 21276255, 21406230, 91434111) and the Natural Science Foundation of Beijing of China (2131005, 2142029).

摘要/Abstract

摘要： Ionic liquids (ILs) have attractedmany attentions in the dissolution of cellulose due to their unique physicochemical properties as green solvents. However, themechanism of dissolution is still under debate. In this work, computational investigation for themechanisms of dissolution of cellulose in [Bmim]Cl, [Emim]Cl and [Emim]OAc ILs was performed, and itwas focused on the process of breakage of cellulose chain and ring opening using cellobiose as a model molecule. The detailed mechanism and reaction energy barriers were computed for various possible pathways by density functional theoretical method. The key findingwas that ILs catalyze the dissolution process by synergistic effect of anion and cation, which led to the cleavage of cellulose chain and formation of derivatives of cellulose. The investigation on ring opening process of cellobiose suggested that carbene formed in ILs played an important role in the side reaction of cellulose, and it facilitated the formation of a covalent bond between cellulose and imidazolium core. These computation results may provide new perspective to understand and apply ILs for pretreatment of cellulose.

关键词: Ionic liquids, Cellulose, Dissolution mechanism

Abstract: Ionic liquids (ILs) have attractedmany attentions in the dissolution of cellulose due to their unique physicochemical properties as green solvents. However, themechanism of dissolution is still under debate. In this work, computational investigation for themechanisms of dissolution of cellulose in [Bmim]Cl, [Emim]Cl and [Emim]OAc ILs was performed, and itwas focused on the process of breakage of cellulose chain and ring opening using cellobiose as a model molecule. The detailed mechanism and reaction energy barriers were computed for various possible pathways by density functional theoretical method. The key findingwas that ILs catalyze the dissolution process by synergistic effect of anion and cation, which led to the cleavage of cellulose chain and formation of derivatives of cellulose. The investigation on ring opening process of cellobiose suggested that carbene formed in ILs played an important role in the side reaction of cellulose, and it facilitated the formation of a covalent bond between cellulose and imidazolium core. These computation results may provide new perspective to understand and apply ILs for pretreatment of cellulose.

Key words: Ionic liquids, Cellulose, Dissolution mechanism

Yingying Yao, Yao Li, Xiaomin Liu, Xiaochun Zhang, Jianji Wang, Xiaoqian Yao, Suojiang Zhang. Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory[J]. Chinese Journal of Chemical Engineering, 2015, 23(11): 1894-1906.

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Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

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