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Oxovanadium complexes catalyzed oxidation of lignin and lignin dimers in acetonitrile/water under O2

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Abstract

Selective oxidation of lignin is increasingly investigated due to its advantage of retaining the aromatic rings to produce value-added platform chemicals. In this paper, oxovanadium complexes catalyzed oxidation of lignin and lignin dimers in acetonitrile/water system under O2 was reported. Under optimal conditions of VO(acac)2 catalyzed oxidation, 95 mol% of lignin dimer 2-phenoxy acetophenone was converted, producing 43 mol% of phenol and 83 mol% of benzoic acid. The catalytic ability of V(acac)3 was higher than that of VO(acac)2, but it caused heavier repolymerization and lower product yields. VO(acac)2 catalyzed oxidation system also cleaved various β-O-4 lignin dimers, achieving > 95 mol% conversion. Whereas, yields of phenols from these dimers were lower than 5 mol%. These phenolics were shown to polymerize under reaction conditions. Furthermore, this oxidation system depolymerized poplar organosolv lignin. After oxidation, aromatic and C-O aliphatic functionalities in the heavy fractionation largely disappeared, and the weight-average molecular weight decreased from 5720 to 1140 Da.

Graphical abstract

Oxovanadium complexes show the good ability for the catalytic oxidation of lignin and lignin dimers in MeCN/H2O co-solvent in the presence of O2, achieving higher than 95 mol% conversion of β-O-4 lignin dimers and lowering the molecular weight of poplar organosolv lignin from 5720 to 1140 Da.

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Funding

This work was supported by the National Key R&D Program of China (Grant no. 2018YFB1501500), the China Postdoctoral Science Foundation (Grant no. 2020M681454), the Fundamental Research Funds for the Central Universities (Grant no. 2242021R20005), and the Zhishan Postdoctoral Foundation of Southeast University.

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Authors and Affiliations

  1. Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, 210096, China

    Chao Liu, Fei Lin, Xiangchen Kong, Yuyang Fan, Weicong Xu & Rui Xiao

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  1. Chao Liu
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  2. Fei Lin
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  3. Xiangchen Kong
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  4. Yuyang Fan
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Correspondence to Rui Xiao.

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Highlights

MeCN/H2O was developed as the medium for oxovanadium catalyzed lignin oxidation.

Oxovanadium complexes can effectively cleave lignin linkages in MeCN/H2O under O2.

Vanadium valence changes during lignin oxidation were verified by EPR and 51V NMR.

Phenolic product-induced condensation during lignin oxidation was confirmed by LC-MS.

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Liu, C., Lin, F., Kong, X. et al. Oxovanadium complexes catalyzed oxidation of lignin and lignin dimers in acetonitrile/water under O2. Biomass Conv. Bioref. 14, 607–619 (2024). https://doi.org/10.1007/s13399-021-02175-5

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