Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Molecular nitrogen promotes catalytic hydrodeoxygenation

Nature Catalysis volume 2, pages 1078–1087 (2019)Cite this article

Subjects

Abstract

Although molecular dinitrogen (N2) is widely used as a carrier or inert gas for many catalytic reactions, it is rarely considered as a catalytic promoter. Here, we report that N2 could be used to reduce the activation energy for catalytic hydrodeoxygenation over ruthenium-based catalysts. Specifically, we report a 4.3-fold activity increase in the catalytic hydrodeoxygenation of p-cresol to toluene over a titanium oxide supported ruthenium catalyst (Ru/TiO2) by simply introducing 6 bar N2 under batch conditions at 160 °C and 1 bar hydrogen. Detailed investigations indicate that N2 can be adsorbed and activated on the metallic ruthenium surface to form hydrogenated nitrogen species, which offer protic hydrogen to lower the activation energy of direct carbonaromatic–oxygen bond scission and the hydrogenation of hydroxy groups. Thus, by employing different ruthenium catalysts, including Ru/TiO2, Ru/Al2O3, Ru/ZrO2 and Ru/C, we demonstrate that N2 promotion of hydrodeoxygenation can be regarded as a general strategy.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Structural characterization of the Ru/TiO2 catalyst.
Fig. 2: Catalytic performance promoted by N2 in the hydrodeoxygenation of p-cresol using the Ru/TiO2 catalyst.
Fig. 3: Understanding the promotion of HDO by N2.
Fig. 4: DFT calculations of the HDO reaction.
Fig. 5: Illustration of the combination of N2 activation and HDO reaction over Ru/TiO2.

Similar content being viewed by others

Data Availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author uon reasonable request.

References

  1. Shaver, M. P. & Fryzuk, M. D. Activation of molecular nitrogen: coordination, cleavage and functionalization of N2 mediated by metal complexes. Adv. Synth. Catal. 345, 1061–1076 (2003).

    CAS  Google Scholar 

  2. Erisman, J. W., Sutton, M. A., Galloway, J., Klimont, Z. & Winiwarter, W. How a century of ammonia synthesis changed the world. Nat. Geosci. 1, 636–639 (2008).

    CAS  Google Scholar 

  3. Hori, M. & Mori, M. Synthesis of heterocycles utilizing N2-TiCI4-Li-TMSCI. J. Org. Chem. 60, 1480–1481 (1995).

    CAS  Google Scholar 

  4. Vol’pin, M. E., Shur, V. B. & Berkovich, E. G. Transformations of molecular nitrogen into aromatic amines under the action of titanium compounds. Inorg. Chim. Acta 280, 264–274 (1998).

    Google Scholar 

  5. Kitano, M. et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem. 4, 934–940 (2012).

    CAS  PubMed  Google Scholar 

  6. Aika, K., Hori, H. & Ozaki, A. Activation of nitrogen by alkali metal promoted transition metal I. ammonia synthesis over ruthenium promoted by alkali metal. J. Catal. 27, 424–431 (1972).

    CAS  Google Scholar 

  7. Schulz, H. Short history and present trends of Fischer–Tropsch synthesis. Appl. Catal. A 186, 3–12 (1999).

    CAS  Google Scholar 

  8. Kunkes, E. L. et al. Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes. Science 322, 417–421 (2008).

    CAS  PubMed  Google Scholar 

  9. Mellmer, M. A. et al. Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds. Nat. Catal. 1, 199–207 (2018).

    CAS  Google Scholar 

  10. Vispute, T. P., Zhang, H., Sanna, A., Xiao, R. & Huber, G. W. Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils. Science 330, 1222–1227 (2010).

    CAS  PubMed  Google Scholar 

  11. Xu, C., Arancon, R. A., Labidi, J. & Luque, R. Lignin depolymerisation strategies: towards valuable chemicals and fuels. Chem. Soc. Rev. 43, 7485–7500 (2014).

    CAS  PubMed  Google Scholar 

  12. Li, C., Zhao, X., Wang, A., Huber, G. W. & Zhang, T. Catalytic transformation of lignin for the production of chemicals and fuels. Chem. Rev. 115, 11559–11624 (2015).

    CAS  PubMed  Google Scholar 

  13. Luo, Z., Wang, Y., He, M. & Zhao, C. Precise oxygen scission of lignin derived aryl ethers to quantitatively produce aromatic hydrocarbons in water. Green. Chem. 18, 433–441 (2016).

    CAS  Google Scholar 

  14. Shao, Y. et al. Selective production of arenes via direct lignin upgrading over a niobium-based catalyst. Nat. Commun. 8, 16104 (2017).

    PubMed  PubMed Central  Google Scholar 

  15. Omotoso, T., Boonyasuwat, S. & Crossley, S. P. Understanding the role of TiO2 crystal structure on the enhanced activity and stability of Ru/TiO2 catalysts for the conversion of lignin-derived oxygenates. Green. Chem. 16, 645–652 (2014).

    CAS  Google Scholar 

  16. Liu, G. et al. MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 9, 810–816 (2017).

    CAS  PubMed  Google Scholar 

  17. 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).

    CAS  Google Scholar 

  18. Newman, C. et al. Effects of support identity and metal dispersion in supported ruthenium hydrodeoxygenation catalysts. Appl. Catal. A 477, 64–74 (2014).

    CAS  Google Scholar 

  19. Cui, X. et al. Highly selective hydrogenation of arenes using nanostructured ruthenium catalysts modified with a carbon-nitrogen matrix. Nat. Commun. 7, 11326 (2016).

    PubMed  PubMed Central  Google Scholar 

  20. Li, Z., Assary, R. S., Atesin, A. C., Curtiss, L. A. & Marks, T. J. Rapid ether and alcohol C-O bond hydrogenolysis catalyzed by tandem high-valent metal triflate + supported Pd catalysts. J. Am. Chem. Soc. 136, 104–107 (2014).

    CAS  PubMed  Google Scholar 

  21. Bergem, H., Xu, R., Brown, R. C. & Huber, G. W. Low temperature aqueous phase hydrogenation of the light oxygenate fraction of bio-oil over supported ruthenium catalysts. Green. Chem. 19, 3252–3262 (2017).

    CAS  Google Scholar 

  22. Gilkey, M. J., Brady, C., Vlachos, D. G. & Xu, B. Characterization of oxidation states in metal/metal oxide catalysts in liquid-phase hydrodeoxygenation reactions with a trickle bed reactor. Ind. Eng. Chem. Res. 57, 5591–5598 (2018).

    CAS  Google Scholar 

  23. Omotoso, T. O., Baek, B., Grabow, L. C. & Crossley, S. P. Experimental and first-principles evidence for interfacial activity of Ru/TiO2 to toluene. ChemCatChem 9, 2642–2651 (2017).

    CAS  Google Scholar 

  24. Nelson, R. C. et al. Experimental and theoretical insights into the hydrogen-efficient direct hydrodeoxygenation mechanism of phenol over Ru/TiO2. ACS Catal. 5, 6509–6523 (2015).

    CAS  Google Scholar 

  25. Jiménez, I., Gago, R. & Albella, J. M. Spectroscopy of π bonding in hard graphitic carbon nitride films: superstructure of basal planes and hardening mechanisms. Phys. Rev. B 62, 4262–4264 (2000).

    Google Scholar 

  26. Kalescky, R., Kraka, E. & Cremer, D. Identification of the strongest bonds in chemistry. J. Phys. Chem. A 117, 8981–8995 (2013).

    CAS  PubMed  Google Scholar 

  27. Chen, G. et al. Interfacial electronic effects control the reaction selectivity of platinum catalysts. Nat. Mater. 15, 564–569 (2016).

    CAS  PubMed  Google Scholar 

  28. Luksirikul, P., Tedsree, K., Moloney, M. G., Green, M. L. & Tsang, S. C. Electron promotion by surface functional groups of single wall carbon nanotubes to overlying metal particles in a fuel-cell catalyst. Angew. Chem. Int. Ed. 51, 6998–7001 (2012).

    CAS  Google Scholar 

  29. Elmasides, C., Kondarides, D. I., Grünert, W. & Verykios, X. E. XPS and FTIR study of Ru/Al2O3 and Ru/TiO2 catalysts: reduction characteristics and interaction with a methane-oxygen mixture. J. Phys. Chem. B 103, 5227–5239 (1999).

    CAS  Google Scholar 

  30. Li, H.-J., Yeh, C.-H. & Ho, J.-J. The catalytic adsorption and dissociation of carbon dioxide on a double icosahedral Ru19 nanocluster—A theoretical study. Chem. Phys. Lett. 585, 149–152 (2013).

    CAS  Google Scholar 

  31. Zhang, S.-T. et al. Density functional theory study on the metal–support interaction between Ru cluster and anatase TiO2(101) surface. J. Phys. Chem. C. 118, 3514–3522 (2014).

    CAS  Google Scholar 

  32. Honkala, K. et al. Ammonia synthesis from first-principles calculations. Science 307, 555–558 (2005).

    CAS  PubMed  Google Scholar 

  33. Jacobsen, C. J. H. et al. Structure sensitivity of supported ruthenium catalysts for ammonia synthesis. J. Mol. Catal. A 163, 19–26 (2000).

    CAS  Google Scholar 

  34. Ma, X. L., Liu, J. C., Xiao, H. & Li, J. Surface single-cluster catalyst for N2-to-NH3 thermal conversion. J. Am. Chem. Soc. 140, 46–49 (2018).

    CAS  PubMed  Google Scholar 

  35. Liu, J. C. et al. Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat. Commun. 9, 1610 (2018).

    PubMed  PubMed Central  Google Scholar 

  36. Chang, C.-R., Wang, Y.-G. & Li, J. Theoretical investigations of the catalytic role of water in propene epoxidation on gold nanoclusters: A hydroperoxyl-mediated pathway. Nano Res 4, 131–142 (2010).

    Google Scholar 

  37. Chang, C.-R., Huang, Z.-Q. & Li, J. The promotional role of water in heterogeneous catalysis: mechanism insights from computational modeling. WiREs Comput. Mol. Sci. 6, 679–693 (2016).

    CAS  Google Scholar 

  38. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1991).

    Google Scholar 

  39. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    CAS  Google Scholar 

  40. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    CAS  PubMed  Google Scholar 

  41. Anisimov, V. I., Aryasetiawan, F. & Lichtenstein, A. First-principles calculations of the electronic structure and spectra of strongly correlated systems: dynamical mean-field theory. J. Phys. Condens. Matter 9, 7359–7367 (1997).

    CAS  Google Scholar 

  42. Tang, Y., Zhao, S., Long, B., Liu, J.-C. & Li, J. On the nature of support effects of metal dioxides MO2 (M = Ti, Zr, Hf, Ce, Th) in single-atom gold catalysts: importance of quantum primogenic effect. J. Phys. Chem. C. 120, 17514–17526 (2016).

    CAS  Google Scholar 

  43. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    CAS  Google Scholar 

Download references

Acknowledgements

H.D. thanks SCG Chemicals, SCG Packaging (Thailand) and the National Natural Science Foundation of China (Grant No. 21978147). Y.Z. thanks the National Natural Science Foundation of China (Grant No. 21878008) and the Fundamental Research Funds for the Central Universities (BUCTRC201807). X.M. thanks the National Natural Science Foundation of China (21902182) and the Fundamental Research Funds for the Central Universities (2019QH01). J.D. acknowledges support from the Youth Innovation Promotion Association CAS. X.Z. thanks the National Natural Science Foundation of China (Grant No. 11875258). J.-C.B. thanks SCG Chemicals (Thailand) for funding. We also thank the Hefei Light Source and Shanghai Light Source for use of instruments and the Diamond Light Source for access and support in the use of the electron Physical Science Imaging Centre (EM16969, 17397), which contributed to the results presented here. J.L. thanks the National Natural Science Foundation of China (Grand Nos. 21433005, 91645203 and 21590792). The calculations were performed using the supercomputers at Tsinghua National Laboratory for Information Science and Technology. We also thank Y. Li for providing characterization resources and S. Ji for performing ICP analysis. We thank C. Chen for performing TPR measurement, W.-C. Lin for helping with the fixed-bed reactions and Y. Yang for assisting with the FTIR measurements.

Author information

Author notes

  1. These authors contributed equally: Haohong Duan, Jin-Cheng Liu, Ming Xu.

Authors and Affiliations

  1. Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, UK

    Haohong Duan, Jean-Charles Buffet & Dermot O’Hare

  2. The Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, UK

    Haohong Duan, Yufei Zhao, Jianwei Zheng & Shik Chi Edman Tsang

  3. Department of Chemistry, Tsinghua University, Beijing Shi, China

    Haohong Duan

  4. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, China

    Jin-Cheng Liu, Xue-Lu Ma & Jun Li

  5. Beijing National Laboratory for Molecular Engineering, College of Chemistry and Molecular Engineering and College of Engineering, BIC-ESAT, Peking University, Beijing, China

    Ming Xu

  6. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, China

    Yufei Zhao

  7. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Juncai Dong & Dongliang Chen

  8. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, China

    Xusheng Zheng

  9. Department of Materials, University of Oxford, Oxford, UK

    Christopher S. Allen, Mohsen Danaie & Angus I. Kirkland

  10. Electron Physical Sciences Imaging Centre (ePSIC), Diamond Light Source, Oxford, UK

    Christopher S. Allen, Mohsen Danaie & Angus I. Kirkland

  11. Department of Chemistry, City University of Hong Kong, Yeung Kin Man Academic Building, Hong Kong, China

    Yung-Kang Peng

  12. Product & Technology Development Center, SCG Packaging Public Company Limited, ThaPha BanPong Ratchaburi, BanPong, Thailand

    Titipong Issariyakul

  13. Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Jun Li

Authors
  1. Haohong Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jin-Cheng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ming Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yufei Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xue-Lu Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Juncai Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Xusheng Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jianwei Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Christopher S. Allen
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Mohsen Danaie
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Yung-Kang Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Titipong Issariyakul
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Dongliang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Angus I. Kirkland
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Jean-Charles Buffet
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Jun Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Shik Chi Edman Tsang
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Dermot O’Hare
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

H.D. conceived the idea, designed and carried out the synthesis, characterizations and catalytic reactions, analysed the data and wrote the manuscript. J.L. and X.M. performed DFT calculations and wrote the manuscript. Y.Z. carried out catalytic reactions and analysed the data. M.X. performed the in situ XPS and FTIR measurements and analysed the data. J.D, X.Z. and D.C. performed the in situ XPS measurements and data analysis. J.Z. helped design the experiments and analysed the data. C.A., M.D. and A.K. performed the TEM and STEM measurements. Y.-K.P. performed acidity analysis. T.I. conceived the idea and anticipated discussion. J.-C.B. regulated the experiments and anticipated discussion. J.L., S.C.E.T. and D.O.H. supervised the project, helped design the experiments, analysed the data and wrote the manuscript. All the authors commented on the manuscript and have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Jun Li, Shik Chi Edman Tsang or Dermot O’Hare.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figures 1–28, Tables 1–3, Notes 1 and 2 and References.

Supplementary Data 1

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Duan, H., Liu, JC., Xu, M. et al. Molecular nitrogen promotes catalytic hydrodeoxygenation. Nat Catal 2, 1078–1087 (2019). https://doi.org/10.1038/s41929-019-0368-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-019-0368-6

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing