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Visible-light-driven coproduction of diesel precursors and hydrogen from lignocellulose-derived methylfurans

Nature Energy volume 4, pages 575–584 (2019)Cite this article

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Abstract

Photocatalytic hydrogen production from biomass is a promising alternative to water splitting thanks to the oxidation half-reaction being more facile and its ability to simultaneously produce solar fuels and value-added chemicals. Here, we demonstrate the coproduction of H2 and diesel fuel precursors from lignocellulose-derived methylfurans via acceptorless dehydrogenative C−C coupling, using a Ru-doped ZnIn2S4 catalyst and driven by visible light. With this chemistry, up to 1.04 g gcatalyst−1 h−1 of diesel fuel precursors (~41% of which are precursors of branched-chain alkanes) are produced with selectivity higher than 96%, together with 6.0 mmol gcatalyst−1 h−1 of H2. Subsequent hydrodeoxygenation reactions yield the desired diesel fuels comprising straight- and branched-chain alkanes. We suggest that Ru dopants, substituted in the position of indium ions in the ZnIn2S4 matrix, improve charge separation efficiency, thereby accelerating C−H activation for the coproduction of H2 and diesel fuel precursors.

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Fig. 1: Conceptual process diagram for the production of diesel fuels from lignocellulosic waste.
Fig. 2: Characterization of the Ru-ZnIn2S4 photocatalyst.
Fig. 3: Visible-light-driven conversion of 2,5-DMF/2-MF into diesel fuel by photocatalytic dehydrocoupling followed by HDO.
Fig. 4: Mechanistic studies of photocatalytic acceptorless dehydrocoupling by activation of furfuryl (or benzylic) C−H bonds.
Fig. 5: Operando and photophysical characterization of the Ru-ZnIn2S4 photocatalyst.

Data availability

Additional and supporting data are provided in the Supplementary Information. Further data that support the plots within this Article and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Shih, C. F., Zhang, T., Li, J. & Bai, C. Powering the future with liquid sunshine. Joule 2, 1925–1949 (2018).

    Article  Google Scholar 

  2. Li, X. B. et al. Self-assembled framework enhances electronic communication of ultrasmall-sized nanoparticles for exceptional solar hydrogen evolution. J. Am. Chem. Soc. 139, 4789–4796 (2017).

    Article  Google Scholar 

  3. Selcuk, S. & Selloni, A. Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces. Nat. Mater. 15, 1107–1112 (2016).

    Article  Google Scholar 

  4. Han, G. et al. Visible-light-driven valorization of biomass intermediates integrated with H2 production catalyzed by ultrathin Ni/CdS nanosheets. J. Am. Chem. Soc. 139, 15584–15587 (2017).

    Article  Google Scholar 

  5. Shi, R. et al. Interstitial P-doped CdS with long-lived photogenerated electrons for photocatalytic water splitting without sacrificial agents. Adv. Mater. 30, 1705941 (2018).

    Article  Google Scholar 

  6. Shown, I. et al. Carbon-doped SnS2 nanostructure as a high-efficiency solar fuel catalyst under visible light. Nat. Commun. 9, 169 (2018).

    Article  Google Scholar 

  7. Yang, W. et al. Enhanced photoexcited carrier separation in oxygen-doped ZnIn2S4 nanosheets for hydrogen evolution. Angew. Chem. Int. Ed. 55, 6716–6720 (2016).

    Article  Google Scholar 

  8. Luo, N. et al. Photocatalytic oxidation–hydrogenolysis of lignin β-O-4 models via a dual light wavelength switching strategy. ACS Catal. 6, 7716–7721 (2016).

    Article  Google Scholar 

  9. Guo, M., Song, W. & Buhain, J. Bioenergy and biofuels: history, status and perspective. Renew. Sust. Energ. Rev. 42, 712–725 (2015).

    Article  Google Scholar 

  10. Zhang, P. et al. Streamlined hydrogen production from biomass. Nat. Catal. 1, 332–338 (2018).

    Article  Google Scholar 

  11. Wakerley, D. W. et al. Solar-driven reforming of lignocellulose to H2 with a CdS/CdOx photocatalyst. Nat. Energy 2, 17021 (2017).

    Article  Google Scholar 

  12. Kuehnel, M. F. & Reisner, E. Solar hydrogen generation from lignocellulose. Angew. Chem. Int. Ed. 57, 3290–3296 (2018).

    Article  Google Scholar 

  13. Latorre-Sanchez, M., Primo, A. & Garcia, H. P-doped graphene obtained by pyrolysis of modified alginate as a photocatalyst for hydrogen generation from water–methanol mixtures. Angew. Chem. Int. Ed. 52, 11813–11816 (2013).

    Article  Google Scholar 

  14. Karp, E. M. et al. Renewable acrylonitrile production. Science 358, 1307–1310 (2017).

    Article  Google Scholar 

  15. Zhou, Z.-z, Liu, M. & Li, C.-J. Selective copper–N-heterocyclic carbene (copper-NHC)-catalyzed aerobic cleavage of β-1 lignin models to aldehydes. ACS Catal. 7, 3344–3348 (2017).

    Article  Google Scholar 

  16. Bond, J. Q. et al. Production of renewable jet fuel range alkanes and commodity chemicals from integrated catalytic processing of biomass. Energy Environ. Sci. 7, 1500–1523 (2014).

    Article  Google Scholar 

  17. Via, L. D., Recchi, C., Davies, T. E., Greeves, N. & Lopez-Sanchez, J. A. Visible-light-controlled oxidation of glucose using titania-supported silver photocatalysts. ChemCatChem 8, 3475–3483 (2016).

    Article  Google Scholar 

  18. Xie, S. et al. Visible light-driven C–H activation and C–C coupling of methanol into ethylene glycol. Nat. Commun. 9, 1181 (2018).

    Article  Google Scholar 

  19. Deneyer, A. et al. Direct upstream integration of biogasoline production into current light straight run naphtha petrorefinery processes. Nat. Energy 3, 969–977 (2018).

    Article  Google Scholar 

  20. de Beeck, B. O. et al. Direct catalytic conversion of cellulose to liquid straight-chain alkanes. Energy Environ. Sci. 8, 230–240 (2015).

    Article  Google Scholar 

  21. Climent, M. J., Corma, A. & Iborra, S. Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chem. 16, 516–547 (2014).

    Article  Google Scholar 

  22. Shylesh, S., Gokhale, A. A., Ho, C. R. & Bell, A. T. Novel strategies for the production of fuels, lubricants and chemicals from biomass. Acc. Chem. Res. 50, 2589–2597 (2017).

    Article  Google Scholar 

  23. Zhu, Y. et al. Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts. Catal. Sci. Technol. 5, 4208–4217 (2015).

    Article  Google Scholar 

  24. Yang, X. et al. Efficient synthesis of furfuryl alcohol and 2-methylfuran from furfural over mineral-derived Cu/ZnO catalysts. ChemCatChem 9, 3023–3030 (2017).

    Article  Google Scholar 

  25. Chatterjee, M., Ishizaka, T. & Kawanami, H. Hydrogenation of 5-hydroxymethylfurfural in supercritical carbon dioxide–water: a tunable approach to dimethylfuran selectivity. Green Chem. 16, 1543–1551 (2014).

    Article  Google Scholar 

  26. Thananatthanachon, T. & Rauchfuss, T. B. Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent. Angew. Chem. Int. Ed. 49, 6616–6618 (2010).

    Article  Google Scholar 

  27. Guo, W. et al. Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over a cobalt and copper bimetallic catalyst on N-graphene-modified Al2O3. Green Chem. 18, 6222–6228 (2016).

    Article  Google Scholar 

  28. Win, D. T. Furfural-gold from garbage. AU J. Technol. 8, 185–190 (2005).

    Google Scholar 

  29. Lange, J. P., van der Heide, E., van Buijtenen, J. & Price, R. Furfural—a promising platform for lignocellulosic biofuels. ChemSusChem 5, 150–166 (2012).

    Article  Google Scholar 

  30. Li, G. et al. Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose. ChemSusChem 5, 1958–1966 (2012).

    Article  Google Scholar 

  31. Corma, A., de la Torre, O. & Renz, M. Production of high quality diesel from cellulose and hemicellulose by the Sylvan process: catalysts and process variables. Energy Environ. Sci. 5, 6328–6344 (2012).

    Article  Google Scholar 

  32. Huber, G. W., Chheda, J. N., Barrett, C. J. & Dumesic, J. A. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science 308, 1446–1450 (2005).

    Article  Google Scholar 

  33. Gumidyala, A., Wang, B. & Crossley, S. Direct carbon–carbon coupling of furanics with acetic acid over Bronsted zeolites. Sci. Adv. 2, e1601072 (2016).

    Article  Google Scholar 

  34. Bond, J. Q., Alonso, D. M., Wang, D., West, R. M. & Dumesic, J. A. Integrated catalytic conversion of gamma-valerolactone to liquid alkenes for transportation fuels. Science 327, 1110–1113 (2010).

    Article  Google Scholar 

  35. Balakrishnan, M., Sacia, E. R. & Bell, A. T. Syntheses of biodiesel precursors: sulfonic acid catalysts for condensation of biomass-derived platform molecules. ChemSusChem 7, 1078–1085 (2014).

    Article  Google Scholar 

  36. Jiao, X. et al. Defect-mediated electron-hole separation in one-unit-cell ZnIn2S4 layers for boosted solar-driven CO2 reduction. J. Am. Chem. Soc. 139, 7586–7594 (2017).

    Article  Google Scholar 

  37. Yang, Y., Sun, C., Ren, Y., Hao, S. & Jiang, D. New route toward building active ruthenium nanoparticles on ordered mesoporous carbons with extremely high stability. Sci. Rep. 4, 4540 (2014).

    Article  Google Scholar 

  38. Ohba, T. et al. EXAFS studies of Pd nanoparticles: direct evidence for unusual Pd–Pd bond elongation. Chem. Lett. 44, 803–805 (2015).

    Article  Google Scholar 

  39. Niu, L. et al. Photo-induced oxidant-free oxidative C–H/N–H cross-coupling between arenes and azoles. Nat. Commun. 8, 14226 (2017).

    Article  Google Scholar 

  40. Meng, L. et al. Gold plasmon-induced photocatalytic dehydrogenative coupling of methane to ethane on polar oxide surfaces. Energy Environ. Sci. 11, 294–298 (2018).

    Article  Google Scholar 

  41. Dutta, S. & Saha, B. Hydrodeoxygenation of furylmethane oxygenates to jet and diesel range fuels: probing the reaction network with supported palladium catalyst and hafnium triflate promoter. ACS Catal. 7, 5491–5499 (2017).

    Article  Google Scholar 

  42. Ji, S., Cao, W., Yu, Y. & Xu, H. Dynamic diselenide bonds: exchange reaction induced by visible light without catalysis. Angew. Chem. Int. Ed. 53, 6781–6785 (2014).

    Article  Google Scholar 

  43. Nomura, M., Takayama, C. & Kajitani, M. Electrochemical behavior of nickeladithiolene S,S′-dialkyl adducts: evidence for the formation of a metalladithiolene radical by electrochemical redox reactions. Inorg. Chem. 42, 6441–6446 (2003).

    Article  Google Scholar 

  44. Naesborg, L. et al. Direct enantio- and diastereoselective oxidative homocoupling of aldehydes. Chem. Eur. J. 24, 14844–14848 (2018).

    Article  Google Scholar 

  45. King, E. R., Hennessy, E. T. & Betley, T. A. Catalytic C–H bond amination from high-spin iron imido complexes. J. Am. Chem. Soc. 133, 4917–4923 (2011).

    Article  Google Scholar 

  46. Mironenko, A. V. & Vlachos, D. G. Conjugation-driven ‘reverse Marslvan Krevelen’-type radical mechanism for low-temperature C–O bond activation. J. Am. Chem. Soc. 138, 8104–8113 (2016).

    Article  Google Scholar 

  47. Kang, Y. et al. Selective breaking of hydrogen bonds of layered carbon nitride for visible light photocatalysis. Adv. Mater. 28, 6471–6477 (2016).

    Article  Google Scholar 

  48. Li, H. et al. Construction and nanoscale detection of interfacial charge transfer of elegant Z-scheme WO3/Au/In2S3 nanowire arrays. Nano Lett. 16, 5547–5552 (2016).

    Article  Google Scholar 

  49. Zhu, J. et al. Direct imaging of highly anisotropic photogenerated charge separations on different facets of a single BiVO4 photocatalyst. Angew. Chem. Int. Ed. 54, 9111–9114 (2015).

    Article  Google Scholar 

  50. Huang, X. et al. Efficient plasmon-hot electron conversion in Ag-CsPbBr3 hybrid nanocrystals. Nat. Commun. 10, 1163 (2019).

    Article  Google Scholar 

  51. Gou, X. et al. Shape-controlled synthesis of ternary chalcogenide ZnIn2S4 and CuIn(S,Se)2 nano-/microstructures via facile solution route. J. Am. Chem. Soc. 128, 7222–7229 (2006).

    Article  Google Scholar 

  52. Xia, Q.-N. et al. Pd/NbOPO4 multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans. Angew. Chem. Int. Ed. 53, 9755–9760 (2014).

    Article  Google Scholar 

  53. Luo, N. et al. Visible-light-driven self-hydrogen transfer hydrogenolysis of lignin models and extracts into phenolic products. ACS Catal. 7, 4571–4580 (2017).

    Article  Google Scholar 

  54. Briois, V. et al. SAMBA: The 4–40 keV X-ray absorption spectroscopy beamline at SOLEIL. UVX 2010, 41–47 (2011).

    Google Scholar 

  55. Ankudinov, A. L., Ravel, B., Rehr, J. J. & Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure. Phys. Rev. B 58, 7565–7576 (1998).

    Article  Google Scholar 

  56. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).

    Article  Google Scholar 

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Acknowledgements

The authors acknowledge SOLEIL for provision of synchrotron radiation facilities and thank G. Alizon for technical assistance in using beamline SAMBA. The authors also acknowledge financial support from the National Natural Science Foundation of China (21721004, 21690082, 21690084, 21690080), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB17020300, XDB17000000), the National Natural Science Foundation of China (21711530020), the University of Trieste (programme FRA 2018, project INSIDE), the Italian Ministry for University and Research (MIUR, programme FFABR 2017) and the INSTM consortium.

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Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Nengchao Luo, Jian Zhang, Tingting Hou, Wei Nie, Jianmin Lu, Long Lin, Changtong Ma, Min Wang, Fengtao Fan & Feng Wang

  2. University of Chinese Academy of Sciences, Beijing, China

    Nengchao Luo, Tingting Hou, Wei Nie, Long Lin & Changtong Ma

  3. Department of Chemical and Pharmaceutical Sciences, INSTM Research Unit, ICCOM-CNR Trieste Research Unit, University of Trieste, Trieste, Italy

    Tiziano Montini & Paolo Fornasiero

  4. Synchrotron SOLEIL, Saint Aubin, Paris, France

    Emiliano Fonda

  5. State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Junxue Liu & Shengye Jin

  6. Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Juelich GmbH, Juelich, Germany

    Marc Heggen

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Contributions

N.L. and F.W. conceived the research. N.L. conducted most of the experiments in this work, analysed the data and wrote the manuscript. XANES/EXAFS experiments and their discussion were done by T.M., assisted by E.F. T.M., P.F. and E.F. fully revised the manuscript. J.Z. and N.L. designed and fabricated the LED photoreactor. The variation of CPD was measured by W.N., assisted by F.F. J.M.L. carried out the DFT calculations. Transient absorption analysis was done by J.X.L., assisted by S.J. HAADF-STEM and EDX mappings were performed by M.H. Cyclic voltammetry was measured by L.L. Mott–Schottky measurements were done by C.M. T.H. and M.W. added to the discussion and contributed to the preparation of the manuscript. F.W. planned, supervised and led the project.

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Correspondence to Feng Wang.

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Supplementary methods, Supplementary Notes 1-2, Supplementary Tables 1-8, Supplementary Figs. 1–58, Supplementary references

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Luo, N., Montini, T., Zhang, J. et al. Visible-light-driven coproduction of diesel precursors and hydrogen from lignocellulose-derived methylfurans. Nat Energy 4, 575–584 (2019). https://doi.org/10.1038/s41560-019-0403-5

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