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Understanding the mechanism of cellulose dissolution in 1-butyl-3-methylimidazolium chloride ionic liquid via quantum chemistry calculations and molecular dynamics simulations

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Abstract

While N,N′-dialkylimidazolium ionic liquids (ILs) have been well-established as effective solvents for dissolution and processing of cellulose, the detailed mechanism at the molecular level still remains unclear. In this work, we present a combined quantum chemistry and molecular dynamics simulation study on how the ILs dissolve cellulose. On the basis of calculations on 1-butyl-3-methylimidazolium chloride, one of the most effective ILs dissolving cellulose, we further studied the molecular behavior of cellulose models (i.e. cellulose oligomers with degrees of polymerization n = 2, 4, and 6) in the IL, including the structural features and hydrogen bonding patterns. The collected data indicate that both chloride anions and imidazolium cations of the IL interact with the oligomer via hydrogen bonds. However, the anions occupy the first coordination shell of the oligomer, and the strength and number of hydrogen bonds and the interaction energy between anions and the oligomer are much larger than those between cations and the oligomer. It is observed that the intramolecular hydrogen bond in the oligomer is broken under the combined effect of anions and cations. The present results emphasize that the chloride anions play a critically important role and the imidazolium cations also present a remarkable contribution in the cellulose dissolution. This point of view is different from previous one that only underlines the importance of the chloride anions in the cellulose dissolution. The present results improve our understanding for the cellulose dissolution in imidazolium chloride ILs.

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Acknowledgment

We thank the grant from the National Natural Science Foundation of China (No. 20773078) and the Higher Educational Science and Technology Program of Shandong Province (No. J11LB08).

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Authors and Affiliations

  1. Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Jinan, 250100, People’s Republic of China

    Hao Xu, Wenxiao Pan, Ruoxi Wang, Dongju Zhang & Chengbu Liu

  2. School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, People’s Republic of China

    Hao Xu, Wenxiao Pan, Ruoxi Wang, Dongju Zhang & Chengbu Liu

  3. Criminal Scientific and Technological Department, Shandong Police College, Jinan, 250014, People’s Republic of China

    Ruoxi Wang

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  1. Hao Xu
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  2. Wenxiao Pan
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Correspondence to Dongju Zhang.

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Xu, H., Pan, W., Wang, R. et al. Understanding the mechanism of cellulose dissolution in 1-butyl-3-methylimidazolium chloride ionic liquid via quantum chemistry calculations and molecular dynamics simulations. J Comput Aided Mol Des 26, 329–337 (2012). https://doi.org/10.1007/s10822-012-9559-9

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