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Solar energy-driven lignin-first approach to full utilization of lignocellulosic biomass under mild conditions

Nature Catalysis volume 1, pages 772–780 (2018)Cite this article

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Abstract

The lignin-first concept offers an opportunity to utilize the entire lignocellulosic biomass efficiently. However, current conversion strategies rely on high-temperature hydrogenolysis by supported metal catalysts, leading to low-functionalized products or difficulty in separation of solid catalyst from cellulose/hemicellulose. Here, we report the fractionation and valorization of lignocellulose via solar energy-driven conversion of native lignin at room temperature. We found that cadmium sulfide quantum dots not only catalyse the cleavage of β-O-4 bonds in lignin models quantitatively but also are efficient for the conversion of native lignin within biomass into functionalized aromatics under visible light, while cellulose/hemicellulose remain almost intact. Further, the colloidal character of quantum dots enables their facile separation and recycling by a reversible aggregation–colloidization strategy. The β-O-4 bond in lignin is cleaved by an electron–hole coupled photoredox mechanism based on a Cα radical intermediate, in which both photogenerated electrons and holes participate in the reaction.

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Fig. 1: Routes for the valorization of lignocellulosic biomass.
Fig. 2: Photocatalytic cleavage of β-O-4 bond in lignin model compounds.
Fig. 3: Photocatalytic conversion of native lignin in birch woodmeal.
Fig. 4: Valorization of entire lignocellulosic biomass.
Fig. 5: Mechanism for solar energy-driven cleavage of β-O-4 bond.

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Data availability

The data supporting the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21690082, 91545203 and 21503176).

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Author notes

  1. These authors contributed equally to this work: Xuejiao Wu, Xueting Fan, Shunji Xie

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Xuejiao Wu, Xueting Fan, Shunji Xie, Jinchi Lin, Jun Cheng, Qinghong Zhang, Liangyi Chen & Ye Wang

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  1. Xuejiao Wu
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Contributions

X.W. and X.F. performed most of the experiments and DFT computations, and analysed the data. S.X. performed some of the experiments and analysed the experimental data. J.L. performed characterizations for CdS QDs. J.C. guided the computational work, analysed all the data and co-wrote the paper. Q.Z. analysed all the data and co-wrote the paper. L.C. performed a part of characterizations and analysed the characterization results. Y.W. designed and guided the study and co-wrote the paper. All of the authors discussed the results and reviewed the manuscript.

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Correspondence to Jun Cheng, Qinghong Zhang or Ye Wang.

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Supplementary Methods; Supplementary Figures 1–10; Supplementary Tables 1–9; Supplementary References

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Wu, X., Fan, X., Xie, S. et al. Solar energy-driven lignin-first approach to full utilization of lignocellulosic biomass under mild conditions. Nat Catal 1, 772–780 (2018). https://doi.org/10.1038/s41929-018-0148-8

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