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

Nature volume 495, pages 85–89 (2013)Cite this article

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Abstract

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.

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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.

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Acknowledgements

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.

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Authors and Affiliations

  1. Leibniz-Institut für Katalyse Eingetragener Verein an der Universität Rostock, Albert-Einstein Straße 29a, Rostock, 18059, Germany

    Martin Nielsen, Elisabetta Alberico, Wolfgang Baumann, Hans-Joachim Drexler, Henrik Junge & Matthias Beller

  2. Istituto di Chimica Biomolecolare, CNR, traversa La Crucca 3, Sassari 07040, Italy,

    Elisabetta Alberico

  3. Dipartimento di Chimica e Farmacia, Universitá di Sassari, Sassari, 07100, Italy

    Serafino Gladiali

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  1. Martin Nielsen
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  4. Hans-Joachim Drexler
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  5. Henrik Junge
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  7. Matthias Beller
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Contributions

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.

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Correspondence to Matthias Beller.

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The authors declare no competing financial interests.

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

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Nielsen, M., Alberico, E., Baumann, W. et al. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide. Nature 495, 85–89 (2013). https://doi.org/10.1038/nature11891

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