Letter | Published:

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts

Nature volume 544, pages 8083 (06 April 2017) | Download Citation

Abstract

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications1,2,3, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation4,5 before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200–350 degrees Celsius)6,7,8, so the focus for vehicle and portable PEMFC applications9 has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks10,11. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150–190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production—which far exceeds that of previously reported low-temperature APRM catalysts—to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

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Acknowledgements

We received financial support from the 973 Project (grants 2011CB201402 and 2013CB933100) and the Natural Science Foundation of China (grants 91645115, 21473003, 91645115, 21222306, 21373037, 21577013 and 91545121). The electron-microscopy work was supported in part by the Chinese Academy of Sciences (CAS) Pioneer Hundred Talents Program; by the US Department of Energy (DOE), Office of Science, Basic Energy Science, Materials Sciences and Engineering Division (to W.Z.); and through a user project at Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. The XAS experiments were conducted in the Shanghai Synchrotron Radiation Facility (SSRF) and Beijing Synchrotron Radiation Facility (BSRF). This research used Beamline 17-BM of the Advanced Photon Source (APS), a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357 (to W.X.). We also acknowledge National Thousand Young Talents Program of China the CAS Hundred Talents Program and the Shanxi Hundred Talent Program.

Author information

Author notes

    • Lili Lin
    • , Wu Zhou
    •  & Rui Gao

    These authors contributed equally to this work.

Affiliations

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

    • Lili Lin
    • , Siyu Yao
    • , Qiaolin Yu
    •  & Ding Ma
  2. School of Physical Sciences, CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing 100049, China

    • Wu Zhou
  3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    • Wu Zhou
  4. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, PO Box 165, Taiyuan, Shanxi 030001, China

    • Rui Gao
    • , Yong-Wang Li
    •  & Xiao-Dong Wen
  5. Synfuels China Co. Ltd, Beijing 100195, China

    • Rui Gao
    • , Yong-Wang Li
    •  & Xiao-Dong Wen
  6. Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), Dalian University of Technology, Dalian 116024, China

    • Xiao Zhang
    •  & Chuan Shi
  7. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Wenqian Xu
  8. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

    • Shijian Zheng
  9. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China

    • Zheng Jiang

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Contributions

D.M. designed the study. L.L. performed most of the reactions. W.Z. and S.Z. performed the electron-microscopy characterization and proposed the structural model for the active sites. C.S. and X.Z. synthesized part of the molybdenum carbides. R.G., Y.-W.L. and X.-D.W. finished the DFT calculations. S.Y., W.X. and Z.J. carried out the X-ray structure characterization and analysis. L.L., D.M., X.-D.W., S.Y., C.S. and W.Z. wrote the paper. The other authors provided reagents, performed some of the experiments and revised the paper.

Competing interests

D.M., L.L. and S.Y. declare a financial interest: patents related to this research have been filed by Peking University. The University’s policy is to share financial rewards from the exploitation of patents with the inventors.

Corresponding authors

Correspondence to Chuan Shi or Xiao-Dong Wen or Ding Ma.

Reviewer Information Nature thanks D. Vlachos and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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

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DOI

https://doi.org/10.1038/nature21672

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