Abstract
Anions are always considered to explain most of the cellulose dissolution in the ionic liquid; where electron donor theory is always used to elaborate cellulose dissolution in the ionic liquids with different anions. However, the theory does not apply to ionic liquids with different alkyl chain anions. Herein, the hydrogen bond theory was proposed to further explain cellulose dissolution by density functional theory (DFT) calculations. 1-allyl-3-methylimidazole carboxylate ionic liquids with different alkyl chains including ([Amim][HCOO], [Amim][CH3COO], [Amim][CH3CH2COO], [Amim][CH3CH2CH2COO]) were investigated. The DFT results indicated that the alkyl chains of the anions directly affect the hydrogen bond and the interaction energy between the cations and anions; where the length of the hydrogen bonds between cation and anion is the most predominant factor for determining the polarity parameter β value of the ionic liquid itself and therefore governing cellulose dissolution. Moreover, a shorter length of hydrogen bonds between the anions of ionic liquid and cellobiose referred to a better solubility of cellulose in the ionic liquids.
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Notes
Note: The β value and cellulose solubility are the averages at 25–80 °C. Xu and Wang (2020) Carboxylate ionic liquid solvent systems from 2006 to 2020: thermal properties and application in cellulose processing. Green Chemistry 22(22):7622–7664.
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Acknowledgments
The authors would like to acknowledge gratefully for the financial support from the Industry-University Project of Fujian Provincial Department of Science and Technology (2021H6008 and 2021H6005) and National Supercomputing Center in Shenzhen for this intensive research program.
Funding
Industry-University Project of Fujian Provincial Department of Science and Technology, 2021H6008, Shilin Cao, Industry-University Project of Fujian Provincial Department of Science and Technology, 2021H6005, Xiaojuan Ma.
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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by XL, SX, JC, LN, XM, SC and HG. The first draft of the manuscript was written by Xingmei Lu and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
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Lu, X., Xu, S., Chen, J. et al. Cellulose dissolution in ionic liquid from hydrogen bonding perspective: first-principles calculations. Cellulose 30, 4181–4195 (2023). https://doi.org/10.1007/s10570-023-05140-9
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DOI: https://doi.org/10.1007/s10570-023-05140-9