Abstract
Carbon–carbon bonds, ubiquitous in lignin, limit monomer yields from current depolymerization strategies, which mainly target C–O bonds. Selective cleavage of the inherently inert σ-type C–C bonds without pre-functionalization remains challenging. Here we report the breaking of C–C bonds in lignin obtained upon initial disruption of labile C–O bonds, achieving monocyclic hydrocarbon yields up to an order of magnitude higher than previously reported. The use of a Pt (de)hydrogenation function leads to olefinic groups close to recalcitrant C–C bonds, which can undergo β-scission over zeolitic Brønsted acid sites. After confirming that this approach can selectively cleave common C–C linkages (5–5′, β–1′, β–5′ and β–β′) in lignin skeletons, we demonstrate its utility in the valorization of various representative lignins. A techno-economic analysis shows the promise of our method for producing gasoline- and jet-range cycloalkanes and aromatics, while a life-cycle assessment confirms its potential for CO2-neutral fuel production.
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Data availability
All data are available within the manuscript and Supplementary Information. The atomic coordinates of the optimized computational models are provided in Supplementary Data 1. Source data are provided with this paper.
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Acknowledgements
This research was supported financially by the Chemelot Institute for Science and Technology awarded to E.J.M.H. Z.L. acknowledges support for the RCF experiments, TEA and LCA calculations from the National Natural Science Foundation of China (grant no. 52206236), the Natural Science Foundation of Jiangsu Province (grant no. BK20220837) and the Fundamental Research Funds for the Central Universities (3203002211A1). J.T.B.d.B. and J.S.L. were supported by the Swiss National Science Foundation through the National Competence Center Catalysis (grant no. 51NF40_180544). The contribution of A.R. was supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 883753 (IDEALFUEL).
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Z.L. and E.J.M.H. conceived the idea for lignin depolymerization. Z.L. and A.R. performed the reactions of lignin and lignin model compounds. C.L. conducted the DFT calculations. Y.W. and J.X. carried out the TEA and LCA calculations with guidance from H.Z. and R.X. P.D.K., M.D.B. and J.T.B.d.B., supervised by J.S.L., prepared the technical lignins. Z.L. and E.H. wrote the manuscript in close consultation with M.D.B., D.F.d.W., C.L., H.Z. and R.X. All authors contributed to the manuscript.
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Nature Chemical Engineering thanks Changzhi Li, Joseph Samec, Yanqin Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Data 1
Atomic coordinates of the optimized computational models.
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Luo, Z., Liu, C., Radu, A. et al. Carbon–carbon bond cleavage for a lignin refinery. Nat Chem Eng 1, 61–72 (2024). https://doi.org/10.1038/s44286-023-00006-0
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DOI: https://doi.org/10.1038/s44286-023-00006-0
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