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Cited by 13Catalysis for Biomass ConversionLignin and Wood ChemistryCatalysis and Hydrodesulfurization Studies

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A solution for 4-propylguaiacol hydrodeoxygenation without ring saturation

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Zhang, Zihao, Li, Qiang, Wu, Xiangkun, Bourmaud, Claire, Vlachos, Dionisios G., Luterbacher, Jeremy, Bodi, Andras, Hemberger, Patrick·2024·Nature Communications
DOI 10.1038/s41467-024-50724-zPMC PMC11283461
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Abstract

We investigate solvent effects in the hydrodeoxygenation of 4-propylguaiacol (4PG, 166 amu), a key lignin-derived monomer, over Ru/C catalyst by combined operando synchrotron photoelectron photoion coincidence (PEPICO) spectroscopy and molecular dynamics simulations. With and without isooctane co-feeding, ring-hydrogenated 2-methoxy-4-propylcyclohexanol (172 amu) is the first product, due to the favorable flat adsorption configuration of 4PG on the catalyst surface. In contrast, tetrahydrofuran (THF)—a polar aprotic solvent that is representative of those used for lignin solubilization and upgrading—strongly coordinates to the catalyst surface at the oxygen atom. This induces a local steric hindrance, blocking the flat adsorption of 4PG more effectively, as it needs more Ru sites than the tilted adsorption configuration revealed by molecular dynamics simulations. Therefore, THF suppresses benzene ring hydrogenation, favoring a demethoxylation route that yields 4-propylphenol (136 amu), followed by dehydroxylation to propylbenzene (120 amu). Solvent selection may provide new avenues for controlling catalytic selectivity.

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Research works printed but not linked: 48

  1. Alonso, D. M., Wettstein, S. G. & Dumesic, J. A. Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chem. Soc. Rev. 41, 8075–8098 (2012). · DOI
  2. Liu, C., Wang, H., Karim, A. M., Sun, J. & Wang, Y. Catalytic fast pyrolysis of lignocellulosic biomass. Chem. Soc. Rev. 43, 7594–7623 (2014). · DOI
  3. Questell-Santiago, Y. M., Galkin, M. V., Barta, K. & Luterbacher, J. S. Stabilization strategies in biomass depolymerization using chemical functionalization. Nat. Rev. Chem. 4, 311–330 (2020). · DOI
  4. Ambursa, M. M. et al. A review on catalytic hydrodeoxygenation of lignin to transportation fuels by using nickel-based catalysts. Renew. Sust. Energy Rev. 138, 110667 (2021). · DOI
  5. Stone, M. L. et al. Continuous hydrodeoxygenation of lignin to jet-range aromatic hydrocarbons. Joule 6, 2324–2337 (2022). · DOI
  6. Lu, Y., Zhang, Z., Wang, H. & Wang, Y. Toward efficient single-atom catalysts for renewable fuels and chemicals production from biomass and CO2. Appl. Catal. B: Environ. 292, 120162 (2021). · DOI
  7. Li, G., Han, J., Wang, H., Zhu, X. & Ge, Q. Role of dissociation of phenol in its selective hydrogenation on Pt (111) and Pd (111). ACS Catal. 5, 2009–2016 (2015). · DOI
  8. Zhang, J., Sun, J. & Wang, Y. Recent advances in the selective catalytic hydrodeoxygenation of lignin-derived oxygenates to arenes. Green Chem. 22, 1072–1098 (2020). · DOI
  9. Liu, H., Jiang, T., Han, B., Liang, S. & Zhou, Y. Selective phenol hydrogenation to cyclohexanone over a dual supported Pd–Lewis acid catalyst. Science 326, 1250–1252 (2009). · DOI
  10. Wang, X., Arai, M., Wu, Q., Zhang, C. & Zhao, F. Hydrodeoxygenation of lignin-derived phenolics–a review on the active sites of supported metal catalysts. Green Chem. 22, 8140–8168 (2020). · DOI
  11. Shi, D., Arroyo-Ramírez, L. & Vohs, J. M. The use of bimetallics to control the selectivity for the upgrading of lignin-derived oxygenates: reaction of anisole on Pt and PtZn catalysts. J. Catal. 340, 219–226 (2016). · DOI
  12. Dong, L. et al. Selective hydrodeoxygenation of lignin oil to valuable phenolics over Au/Nb2O5 in water. Green Chem. 21, 3081–3090 (2019). · DOI
  13. Lang, M. & Li, H. Toward value-added arenes from lignin-derived phenolic compounds via catalytic hydrodeoxygenation. ACS Sustain. Chem. Eng. 10, 13208–13243 (2022). · DOI
  14. Rong, S. et al. Synergetic effect between Pd clusters and oxygen vacancies in hierarchical Nb2O5 for lignin-derived phenol hydrodeoxygenation into benzene. Renew. Energy 187, 271–281 (2022). · DOI
  15. Newman, C. et al. Effects of support identity and metal dispersion in supported ruthenium hydrodeoxygenation catalysts. Appl. Catal. A: Gen. 477, 64–74 (2014). · DOI
  16. Huang, Y. B., Yan, L., Chen, M.-Y., Guo, Q. X. & Fu, Y. Selective hydrogenolysis of phenols and phenyl ethers to arenes through direct C–O cleavage over ruthenium–tungsten bifunctional catalysts. Green Chem. 17, 3010–3017 (2015). · DOI
  17. Zou, H. et al. Boosting catalytic selectivity through a precise spatial control of catalysts at pickering droplet interfaces. J. Am. Chem. Soc. 145, 2511–2522 (2023). · DOI
  18. Deng, Y. et al. Solvent tunes the selectivity of hydrogenation reaction over α-MoC catalyst. J. Am. Chem. Soc. 140, 14481–14489 (2018). · DOI
  19. Zhao, Z. et al. Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water. Nat. Catal. 2, 431–436 (2019). · DOI
  20. Mellmer, M. A. et al. Solvent effects in acid‐catalyzed biomass conversion reactions. Angew. Chem. Int. Ed. 53, 11872–11875 (2014). · DOI
  21. Heroguel, F., Nguyen, X. T. & Luterbacher, J. S. Catalyst support and solvent effects during lignin depolymerization and hydrodeoxygenation. ACS Sustain. Chem. Eng. 7, 16952–16958 (2019). · DOI
  22. Bodi, A., Hemberger, P. & Pérez-Ramírez, J. Photoionization reveals catalytic mechanisms. Nat. Catal. 5, 850–851 (2022). · DOI
  23. Hemberger, P. et al. Photoelectron photoion coincidence spectroscopy provides mechanistic insights in fuel synthesis and conversion. Energy Fuels 35, 16265–16302 (2021). · DOI
  24. Hemberger, P., van Bokhoven, J. A., Pérez-Ramírez, J. & Bodi, A. New analytical tools for advanced mechanistic studies in catalysis: photoionization and photoelectron photoion coincidence spectroscopy. Catal. Sci. Technol. 10, 1975–1990 (2020). · DOI
  25. Pan, Z. et al. Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis. Nat. Commun. 14, 4512 (2023). · DOI
  26. Pan, Z., Bodi, A., van Bokhoven, J. A. & Hemberger, P. Operando PEPICO unveils the catalytic fast pyrolysis mechanism of the three methoxyphenol isomers. Phys. Chem. Chem. Phys. 24, 21786–21793 (2022). · DOI
  27. Hemberger, P., Custodis, V. B., Bodi, A., Gerber, T. & van Bokhoven, J. A. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis. Nat. Commun. 8, 1–9 (2017). · DOI
  28. Pan, Z., Puente-Urbina, A., Bodi, A., van Bokhoven, J. A. & Hemberger, P. Isomer-dependent catalytic pyrolysis mechanism of the lignin model compounds catechol, resorcinol and hydroquinone. Chem. Sci. 12, 3161–3169 (2021). · DOI
  29. Zhang, Z. et al. CO cofeeding affects product distribution in CH3Cl coupling over ZSM‐5 zeolite: pressure twists the plot. Angew. Chem. Int. Ed. 63, e202401060 (2024). · DOI
  30. Zhang, Z. et al. Unraveling radical and oxygenate routes in the oxidative dehydrogenation of propane over boron nitride. J. Am. Chem. Soc. 145, 7910–7917 (2023). · DOI
  31. Hemberger, P. et al. Photoion mass-selected threshold photoelectron spectroscopy to detect reactive intermediates in catalysis: from instrumentation and examples to peculiarities and a database. J. Phys. Chem. C 127, 16751–16763 (2023). · DOI
  32. Shiner, D., Gilligan, J., Cook, B. & Lichten, W. H2, D2, and HD ionization potentials by accurate calibration of several iodine lines. Phys. Rev. A 47, 4042 (1993). · DOI
  33. Michaelides, A., Alavi, A. & King, D. Different surface chemistries of water on Ru {0001}: from monomer adsorption to partially dissociated bilayers. J. Am. Chem. Soc. 125, 2746–2755 (2003). · DOI
  34. Li, Q. & López, N. Chirality, rigidity, and conjugation: a first-principles study of the key molecular aspects of lignin Depolymerization on Ni-based catalysts. ACS Catal. 8, 4230–4240 (2018). · DOI
  35. Chen, B. W. J., Zhang, X. & Zhang, J. Accelerating explicit solvent models of heterogeneous catalysts with machine learning interatomic potentials. Chem. Sci. 14, 8338–8354 (2023). · DOI
  36. Li, Q. & Vlachos, D. G. 5–5 lignin linkage cleavage over Ru: a density functional theory study. ACS Sustain. Chem. Eng. 9, 16143–16152 (2021). · DOI
  37. Chiu, C. C., Genest, A., Borgna, A. & Rösch, N. Hydrodeoxygenation of guaiacol over Ru (0001): a DFT study. ACS Catal. 4, 4178–4188 (2014). · DOI
  38. Bodi, A., Hemberger, P., Gerber, T. & Sztáray, B. A new double imaging velocity focusing coincidence experiment: i2PEPICO. Rev. Sci. Instrum. 83, 083105 (2012). · DOI
  39. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996). · DOI
  40. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996). · DOI · Paper page
  41. Jinnouchi, R., Karsai, F. & Kresse, G. On-the-fly machine learning force field generation: application to melting points. Phys. Rev. B 100, 014105 (2019). · DOI
  42. Jinnouchi, R., Karsai, F., Verdi, C., Asahi, R. & Kresse, G. Descriptors representing two-and three-body atomic distributions and their effects on the accuracy of machine-learned inter-atomic potentials. J. Chem. Phys. 152, 234102 (2020). · DOI
  43. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996). · DOI · Paper page
  44. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994). · DOI · Paper page
  45. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999). · DOI · Paper page
  46. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011). · DOI · Paper page
  47. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188 (1976). · DOI · Paper page
  48. Makov, G. & Payne, M. C. Periodic boundary conditions in ab initio calculations. Phys. Rev. B 51, 4014 (1995). · DOI

Metadata

Authors
Zhang, Z., Li, Q., Wu, X., Bourmaud, C., Vlachos, D. G., Luterbacher, J., Bodi, A., & Hemberger, P.
Affiliations
  • Paul Scherrer Institute (CH)
  • University of Delaware (US)
  • École Polytechnique Fédérale de Lausanne (CH)
Corresponding author
  • Vlachos, Dionisios G.
  • Luterbacher, Jeremy
  • Hemberger, Patrick
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2024-07-27
Volume
15
Issue
1
Pages
6330-6330
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-024-50724-z
PMC
PMC11283461
OpenAlex
W4401050625
Cited by
13
References
4
Citations by year
2026: 9 · 2025: 4
FWCI
1.37
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • DORA PSI (Paul Scherrer Institute) (submittedVersion, cc-by)
  • Infoscience (Ecole Polytechnique Fédérale de Lausanne) (submittedVersion, cc-by-nc-nd)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
Funders
  • Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung (200021_182605, 180544, CRSII5_180258)
  • PSI CROSS project funding initiative
  • National Science Foundation (1919839)
  • Growing Convergence Research (GCR) program at the National Science Foundation (NSF): NSFGCR CMMI
Topics
  • Physical Sciences › Chemical Engineering › Catalysis › Catalysis for Biomass Conversion
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Lignin and Wood Chemistry
  • Physical Sciences › Chemical Engineering › Catalysis › Catalysis and Hydrodesulfurization Studies
Keywords
4-propylguaiacol, hydrodeoxygenation, lignin monomers, solvent effects, tetrahydrofuran, ruthenium catalysts, Ru/C, demethoxylation, dehydroxylation, adsorption configuration, steric hindrance, catalyst selectivity, lignin valorization

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