Skip to main content

Thank you for visiting 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.

  • Letter
  • Published:

Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide


Hydrogen produced from renewable resources is a promising potential source of clean energy. With the help of low-temperature proton-exchange membrane fuel cells, molecular hydrogen can be converted efficiently to produce electricity1,2,3,4,5. The implementation of sustainable hydrogen production and subsequent hydrogen conversion to energy is called “hydrogen economy”2. Unfortunately, its physical properties make the transport and handling of hydrogen gas difficult. To overcome this, methanol can be used as a material for the storage of hydrogen, because it is a liquid at room temperature and contains 12.6 per cent hydrogen. However, the state-of-the-art method for the production of hydrogen from methanol (methanol reforming) is conducted at high temperatures (over 200 degrees Celsius) and high pressures (25–50 bar), which limits its potential applications6,7,8. Here we describe an efficient low-temperature aqueous-phase methanol dehydrogenation process, which is facilitated by ruthenium complexes. Hydrogen generation by this method proceeds at 65–95 degrees Celsius and ambient pressure with excellent catalyst turnover frequencies (4,700 per hour) and turnover numbers (exceeding 350,000). This would make the delivery of hydrogen on mobile devices—and hence the use of methanol as a practical hydrogen carrier—feasible.

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

Access options

Buy this article

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

Figure 1: Methanol reforming by homogeneous catalysis.
Figure 2: Approaching ‘real’ aqueous methanol reforming.
Figure 3: Proposed catalytic cycle for Ru-promoted aqueous-phase methanol dehydrogenation.

Similar content being viewed by others


  1. Stolten, D. (ed.) Hydrogen and Fuel Cells (Wiley-VCH, 2010)

  2. Muradov, N. Z. & Veziroğlu, T. N. “Green” path from fossil-based to hydrogen economy: an overview of carbon-neutral technologies. Int. J. Hydrogen Energy 33, 6804–6839 (2008)

    Article  CAS  Google Scholar 

  3. European Commission. European Hydrogen and Fuel Cell Technology Platform “Implementation Plan – Status 2006” (European Technology Platform for Hydrogen and Fuel Cells, European Commission, 2007)

  4. United States Department of Energy. A National Vision of America’s Transition to a Hydrogen Economy — to 2030 and Beyond (United States Department of Energy, 2002)

  5. Pingween, M., Jingguang, L. & Mytelka, L. Hydrogen and Fuel-Cell Activities in China, 2007 295–308 (United Nations Univ. Press, 2008)

    Google Scholar 

  6. Palo, D. R., Dagle, R. A. & Holladay, J. D. Methanol steam reforming for hydrogen production. Chem. Rev. 107, 3992–4021 (2007)

    Article  CAS  Google Scholar 

  7. Cortright, R. D., Davda, R. R. & Dumesic, J. A. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature 418, 964–967 (2002)

    Article  CAS  ADS  Google Scholar 

  8. Shabaker, J. W., Davda, R. R., Huber, G. W., Cortright, R. D. & Dumesic, J. A. Aqueous-phase reforming of methanol and ethylene glycol over alumina-supported platinum catalysts. J. Catal. 215, 344–352 (2003)

    Article  CAS  Google Scholar 

  9. Florusse, L. J. et al. Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate. Science 306, 469–471 (2004)

    Article  CAS  ADS  Google Scholar 

  10. Ashcroft, A. T., Cheetham, A. K., Green, M. L. H. & Vernon, P. D. F. Partial oxidation of methane to synthesis gas using carbon dioxide. Nature 352, 225–226 (1991)

    Article  CAS  ADS  Google Scholar 

  11. Welch, G. C., San Juan, R. R., Masuda, J. D. & Stephan, D. W. Reversible metal-free hydrogen activation. Science 314, 1124–1126 (2006)

    Article  CAS  ADS  Google Scholar 

  12. Denney, M. C., Pons, V., Hebden, T. J., Heinekey, D. M. & Goldberg, K. I. Efficient catalysis of ammonia borane dehydrogenation. J. Am. Chem. Soc. 128, 12048–12049 (2006)

    Article  CAS  Google Scholar 

  13. Reece, S. Y. et al. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science 334, 645–648 (2011)

    Article  CAS  ADS  Google Scholar 

  14. Olah, G., Prakash, G. K. S. & Goeppert, A. Anthropogenic chemical carbon cycle for a sustainable future. J. Am. Chem. Soc. 133, 12881–12898 (2011)

    Article  CAS  Google Scholar 

  15. Boddien, A. et al. Efficient dehydrogenation of formic acid using an iron catalyst. Science 333, 1733–1736 (2011)

    Article  CAS  ADS  Google Scholar 

  16. Nielsen, M. et al. Efficient hydrogen production from alcohols under mild reaction conditions. Angew. Chem. Int. Edn 50, 9593–9597 (2011)

    Article  CAS  Google Scholar 

  17. Morton, D. & Cole-Hamilton, D. J. Molecular hydrogen complexes in catalysis: highly efficient hydrogen production from alcoholic substrates catalysed by ruthenium complexes. J. Chem. Soc. Chem. Commun. 17, 1154–1156 (1988)

    Article  Google Scholar 

  18. Nielsen, M., Junge, H., Kammer, A. & Beller, M. Towards a green process for bulk-scale synthesis of ethyl acetate: efficient acceptorless dehydrogenation of ethanol. Angew. Chem. Int. Edn 51, 5711–5713 (2012)

    Article  CAS  Google Scholar 

  19. Baratta, W., Bossi, G., Putignano, E. & Rigo, P. Pincer and diamine Ru and Os diphosphane complexes as efficient catalysts for the dehydrogenation of alcohols to ketones. Chemistry 17, 3474–3481 (2011)

    Article  CAS  Google Scholar 

  20. Fujita, K., Yoshida, T., Imori, Y. & Yamaguchi, R. Dehydrogenative oxidation of primary and secondary alcohols catalyzed by a Cp*Ir complex having a functional C,N-chelate ligand. Org. Lett. 13, 2278–2281 (2011)

    Article  CAS  Google Scholar 

  21. Zhang, J., Leitus, G., Ben-David, Y. & Milstein, D. Facile conversion of alcohols into esters and dihydrogen catalyzed by new ruthenium complexes. J. Am. Chem. Soc. 127, 10840–10841 (2005)

    Article  CAS  Google Scholar 

  22. Spasyuk, D., Smith, S. & Gusev, D. G. From esters to alcohols and back with ruthenium and osmium catalysts. Angew. Chem. Int. Edn 51, 2772–2775 (2012)

    Article  CAS  Google Scholar 

  23. Kawahara, R., Fujita, K. & &Yamaguchi, R. Dehydrogenative oxidation of alcohols in aqueous media using water-soluble and reusable Cp*Ir catalysts bearing a functional bipyridine ligand. J. Am. Chem. Soc. 134, 3643–3646 (2012)

    Article  CAS  Google Scholar 

  24. Maenaka, Y., Suenobu, T. & Fukuzumi, S. Hydrogen evolution from aliphatic alcohols and 1,4-selective hydrogenation of NAD+ catalyzed by a [C,N] and a [C,C] cyclometalated organoiridium complex at room temperature in water. J. Am. Chem. Soc. 134, 9417–9427 (2012)

    Article  CAS  Google Scholar 

  25. Gunanathan, C. & Milstein, D. Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and “green” catalysis. Acc. Chem. Res. 44, 588–602 (2011)

    Article  CAS  Google Scholar 

  26. Gunanathan, C., Ben-David, Y. & Milstein, D. Direct synthesis of amides from alcohols and amines with liberation of H2 . Science 317, 790–792 (2007)

    Article  CAS  ADS  Google Scholar 

  27. Bertoli, M. et al. Osmium and ruthenium catalysts for dehydrogenation of alcohols. Organometallics 30, 3479–3482 (2011)

    Article  CAS  Google Scholar 

  28. Friedrich, A., Drees, M., Schmedt auf der Günne, J. & Schneider, S. Highly stereoselective proton/hydride exchange: assistance of hydrogen bonding for the heterolytic splitting of H2 . J. Am. Chem. Soc. 131, 17552–17553 (2009)

    Article  CAS  Google Scholar 

  29. Käß, M., Friedrich, A., Drees, M. & Schneider, S. Ruthenium complexes with cooperative PNP ligands: bifunctional catalysts for the dehydrogenation of ammonia–borane. Angew. Chem. Int. Edn 48, 905–907 (2009)

    Article  Google Scholar 

  30. Baratta, W. et al. Ruthenium(II) terdentate CNN complexes: superlative catalysts for the hydrogen-transfer reduction of ketones by reversible insertion of a carbonyl group into the Ru-H bond. Angew. Chem. Int. Ed. 44, 6214–6219 (2005)

    Article  CAS  Google Scholar 

Download references


M.N. thanks the Alexander von Humboldt Foundation for financial support. We thank the BMBF and the Ministry of Science and Education of Mecklenburg-Western Pommerania for the basic funding of this project.

Author information

Authors and Affiliations



M.B., M.N. and H.J. designed the project on methanol dehydrogenation. M.N., E.A., H.J., S.G. and M.B. developed the project. M.N. and E.A. performed the catalytic experiments. E.A., W.B., M.N. and H.-J.D. performed mechanistic and analytic studies. M.N., E.A., H.J., S.G. and M.B. wrote the manuscript.

Corresponding author

Correspondence to Matthias Beller.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Text and Data, Supplementary Figures 1-19, Supplementary Tables 1-4 and Supplementary References. (PDF 1848 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Nielsen, M., Alberico, E., Baumann, W. et al. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide. Nature 495, 85–89 (2013).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.


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