SCI和EI收录∣中国化工学会会刊

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 Yao1,2, Yao Li1,2, Xiaomin Liu1, Xiaochun Zhang1, Jianji Wang3, Xiaoqian Yao1, Suojiang Zhang1   

  1. 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 Yao1,2, Yao Li1,2, Xiaomin Liu1, Xiaochun Zhang1, Jianji Wang3, Xiaoqian Yao1, Suojiang Zhang1   

  1. 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: 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