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Cleavage of the β–O–4 bond in a lignin model compound using the acidic ionic liquid 1-H-3-methylimidazolium chloride as catalyst: a DFT mechanistic study

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Abstract

Understanding the mechanism for the catalyzed cleavage of the β–O–4 ether linkage in lignin is crucial to developing efficient strategies for depolymerizing lignin. In this work, veratrylglycerol-β-guaiacyl ether (VG) was used as a lignin model compound in a theoretical investigation of the mechanism for the cleavage of the β–O–4 bond as catalyzed by the acidic ionic liquid (IL) 1-H-3-methylimidazolium chloride ([HMIM]Cl). The reaction was found to involve two processes—dehydration and hydrolysis—in which the cation functions as a Brønsted acid (donating a proton) and the anion acts as a nucleophile (promoting dehydration) or interacts with the substrate through hydrogen bonding, stabilizing the intermediate. These roles of the anion and cation of [HMIM]Cl explain why the [HMIM]Cl medium catalyzes the depolymerization of lignin. In addition, calculations predict that adding formaldehyde during the depolymerization of VG prevents the condensation of VG without significantly altering the mechanism of depolymerization, thus suggesting a method for potentially improving the efficiency of lignin depolymerization.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (nos. 21703123, 21433006, and 21773139).

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Author notes

  1. Youtao Zhu and Zhe Han contributed equally to this work.

Authors and Affiliations

  1. Advanced Material Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250014, People’s Republic of China

    Youtao Zhu & Zhe Han

  2. Key Lab of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, Shandong University, Jinan, 250100, People’s Republic of China

    Youtao Zhu, Lijun Fu, Chengbu Liu & Dongju Zhang

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  1. Youtao Zhu
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  2. Zhe Han
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  3. Lijun Fu
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Correspondence to Dongju Zhang.

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Zhu, Y., Han, Z., Fu, L. et al. Cleavage of the β–O–4 bond in a lignin model compound using the acidic ionic liquid 1-H-3-methylimidazolium chloride as catalyst: a DFT mechanistic study. J Mol Model 24, 322 (2018). https://doi.org/10.1007/s00894-018-3854-x

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  • DOI: https://doi.org/10.1007/s00894-018-3854-x

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