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Insight into the competitiveness of C–C coupling reactions of 5-hydroxymethylfurfural with lignocellulosic compounds in one pot

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Abstract

The multifunctional groups of 5-hydroxymethylfurfural (5-HMF) make it could extend carbon chain by different C–C coupling reactions and extensively applied in the bio-jet fuel synthesis. Herein, one-pot reaction of lignocellulose derived chemicals with 5-HMF was studied by experimental and density functional theory (DFT) methods. The kinetic models of products were established and the apparent activation energies of the products by C–C coupling reaction of phenol, anisole, guaiacol, cyclohexanone and acetone with 5-HMF on Hβ were 95.3 kJ/mol, 104.8 kJ/mol, 90.4 kJ/mol, 90.0 kJ/mol and 112.2 kJ/mol, indicating these reactions centering on 5-HMF competitive intensively. Then the effects of the catalysis were analyzed by applying commercial catalysis to the mixed coupling reaction of 5-HMF. It was found that Brønsted acid is more favorable to alkylation reaction, and Lewis acid is more beneficial to aldol condensation reaction. By Fukui function, due to the nucleophilic index of cyclohexanone (2.74 eV) is higher than that (2.48 eV) of acetone, and the Mulliken electronegativity (3.43 eV) is weaker than that (3.55 eV) of acetone, cyclohexanone is more conducive than acetone to the aldol condensation reaction. This work provides data reference for product regulation in the bio-jet fuel synthesis.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (2210081015), the Natural science Foundation of Shandong Province (ZR2023MB042), the Talent Foundation funded by Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering (STHGYX2222), the Open Fund of the Key Laboratory of Multiphase Flow Reaction and Separation Engineering of Shandong Province (2021MFRSE-B01), the Foundation (KF202013) of Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education of China.

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Authors and Affiliations

  1. Key Laboratory of Multiphase Flow Reaction and Separation Engineering of Shandong Province, College of Chemical Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao, 266042, China

    Linyan Song, Genkuo Nie, Xiulei Chen, Shiwei Liu, Hailong Yu & Shitao Yu

  2. Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China

    Genkuo Nie & Guihua Yang

  3. State Key Laboratory of Safety and Control for Chemicals, SINOPEC Research Institute of Safety Engineering, Qingdao, 266071, China

    Hongyu Wang

  4. College of Materials Science and Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao, 266042, China

    Xuguang Liu

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  1. Linyan Song
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Contributions

All authors read and approved the final manuscript. LS: data curation, formal analysis, investigation, methodology, software, writing–original draft. GN: data curation, formal analysis, investigation, methodology, software, writing–original draft. XC: software. HW: resources, software. SL: resources. HY: formal analysis, resources. XL: resources, validation. GY: funding acquisition, investigation, methodology, resources. SY: project administration, resources, supervision, validation, visualization.

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Correspondence to Genkuo Nie.

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Song, L., Nie, G., Chen, X. et al. Insight into the competitiveness of C–C coupling reactions of 5-hydroxymethylfurfural with lignocellulosic compounds in one pot. Reac Kinet Mech Cat (2024). https://doi.org/10.1007/s11144-024-02622-0

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