
Carbon–carbon bond cleavage for a lignin refinery
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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. Access through your institution Buy or subscribe This is a preview of
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during checkout ADDITIONAL ACCESS OPTIONS: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS LIGNIN
DEOXYGENATION FOR THE PRODUCTION OF SUSTAINABLE AVIATION FUEL BLENDSTOCKS Article 26 November 2024 OXIDATIVE CLEAVAGE OF C–C BONDS IN LIGNIN Article 23 September 2021 ROOM TEMPERATURE
CATALYTIC UPGRADING OF UNPURIFIED LIGNIN DEPOLYMERIZATION OIL INTO BISPHENOLS AND BUTENE-2 Article Open access 13 July 2024 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. REFERENCES *
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58575 (2019). Google Scholar Download references 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). AUTHOR INFORMATION Author notes * These authors contributed equally: Zhicheng Luo, Chong Liu, Alexandra Radu. AUTHORS AND AFFILIATIONS *
Laboratory of Inorganic Materials and Catalysis, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands Zhicheng Luo, Alexandra
Radu, Davey F. de Waard, Panos D. Kouris, Michael D. Boot & Emiel J. M. Hensen * MOE Key Laboratory of Energy Thermal Conversion & Control, School of Energy and Environment,
Southeast University, Nanjing, China Zhicheng Luo, Yun Wang, Jun Xiao, Huiyan Zhang & Rui Xiao * State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, China Chong Liu * Laboratory of Sustainable and Catalytic Processing, Institute of Chemical Sciences and Engineering, Ecole
Polytechnique Fédérale de Lausanne, Lausanne, Switzerland Jean T. Behaghel de Bueren & Jeremy S. Luterbacher Authors * Zhicheng Luo View author publications You can also search for this
author inPubMed Google Scholar * Chong Liu View author publications You can also search for this author inPubMed Google Scholar * Alexandra Radu View author publications You can also search
for this author inPubMed Google Scholar * Davey F. de Waard View author publications You can also search for this author inPubMed Google Scholar * Yun Wang View author publications You can
also search for this author inPubMed Google Scholar * Jean T. Behaghel de Bueren View author publications You can also search for this author inPubMed Google Scholar * Panos D. Kouris View
author publications You can also search for this author inPubMed Google Scholar * Michael D. Boot View author publications You can also search for this author inPubMed Google Scholar * Jun
Xiao View author publications You can also search for this author inPubMed Google Scholar * Huiyan Zhang View author publications You can also search for this author inPubMed Google Scholar
* Rui Xiao View author publications You can also search for this author inPubMed Google Scholar * Jeremy S. Luterbacher View author publications You can also search for this author inPubMed
Google Scholar * Emiel J. M. Hensen View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS 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. CORRESPONDING AUTHORS Correspondence to Zhicheng Luo, Rui Xiao or Emiel J. M. Hensen. ETHICS DECLARATIONS COMPETING
INTERESTS The authors declare no competing interests. PEER REVIEW PEER REVIEW INFORMATION _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. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations. EXTENDED DATA SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Notes 1–5, Figs. 1–29, Tables 1–27 and references 1–40.
SUPPLEMENTARY DATA 1 Atomic coordinates of the optimized computational models. SOURCE DATA SOURCE DATA FIG. 2 Statistical source data. SOURCE DATA FIG. 3 Statistical source data. SOURCE DATA
FIG. 5 Statistical source data. SOURCE DATA FIG. 6 Statistical source data. RIGHTS AND PERMISSIONS Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights
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terms of such publishing agreement and applicable law. Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE 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 Download citation * Received: 13 April 2023 * Accepted: 22 November 2023 * Published: 11 January
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