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.

  • Letter
  • Published:

Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

Nature Materials volume 10, pages 434–438 (2011)Cite this article

Subjects

Abstract

The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system1,2,3,4,5. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution6,7,8,9, earth-abundant alternatives are needed for large-scale use10,11,12,13,14,15. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum6. The incomplete cubane-like clusters (Mo3S4) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor that harvests red photons in the solar spectrum. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10% (ref. 16). The experimental observations are supported by density functional theory calculations of the Mo3S4 clusters adsorbed on the hydrogen-terminated Si(100) surface, providing insights into the nature of the active site.

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

Figure 1: Schematic of the tandem ‘chemical solar cell’.
Figure 2: Photoelectrocatalytic activity measurements on planar and pillared Si together with SEM picture of pillared structure.
Figure 3: Stability of hydrogen evolution as a function of time measured with a gas chromatograph and corresponding current over Mo3S4/Si pillars at URHE=0 V.
Figure 4: Free-energy diagrams for hydrogen evolution under three different conditions.

Similar content being viewed by others

References

  1. Dresselhaus, M. S. & Thomas, I. L. Alternative energy technologies. Nature 414, 332–337 (2001).

    Article  CAS  Google Scholar 

  2. Schlapbach, L. & Züttel, A. Hydrogen-storage materials for mobile applications. Nature 414, 353–358 (2001).

    Article  CAS  Google Scholar 

  3. Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

    Article  CAS  Google Scholar 

  4. Lewis, N. S. & Nocera, D. G. Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).

    Article  CAS  Google Scholar 

  5. Crabtree, G. & Sarrao, J. The road to sustainability. Phys. World 22, 24–30 (2009).

    Article  Google Scholar 

  6. Dominey, R. N. et al. Improvement of photoelectrochemical hydrogen generation by surface modification of p-type silicon semiconductor photocathodes. J. Am. Chem. Soc. 104, 467–482 (1982).

    Article  CAS  Google Scholar 

  7. Heller, A., Aharon-Shalom, E., Bonner, W. A. & Miller, B. Hydrogen-evolving semiconductor photocathodes: Nature of the junction and function of the platinum group metal catalyst. J. Am. Chem. Soc. 104, 6942–6948 (1982).

    Article  CAS  Google Scholar 

  8. Khaselev, O. & Turner, J. A. A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting. Science 280, 425–427 (1998).

    Article  CAS  Google Scholar 

  9. Maeda, K. et al. Photocatalyst releasing hydrogen from water. Nature 440, 295 (2006).

    Article  CAS  Google Scholar 

  10. Hinnemann, B. et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127, 5308–5309 (2005).

    Article  CAS  Google Scholar 

  11. Zong, X. et al. Enhancement of photocatalytic H2 evolution on CdS by loading MoS2 as co-catalyst under visible light irradiation. J. Am. Chem. Soc. 130, 7176–7177 (2008).

    Article  CAS  Google Scholar 

  12. Le Goff, A. et al. From hydrogenases to noble metal-free catalytic nanomaterials for H2 production and uptake. Science 326, 1384–1387 (2009).

    Article  CAS  Google Scholar 

  13. Wang, X. C. et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Mater. 8, 76–80 (2009).

    Article  CAS  Google Scholar 

  14. Karunadasa, H. I., Chang, C. J. & Long, J. R. A molecular molybdenum-oxo catalyst for generating hydrogen from water. Nature 464, 1329–1333 (2010).

    Article  CAS  Google Scholar 

  15. Nann, T. et al. Water splitting by visible light: A nanophotocathode for hydrogen production. Angew. Chem. Int. Ed. 49, 1574–1577 (2010).

    Article  CAS  Google Scholar 

  16. Chen, Z. B. et al. Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols. J. Mater. Res. 25, 3–16 (2010).

    Article  Google Scholar 

  17. Grätzel, M. Photoelectrochemical cells. Nature 414, 338–344 (2001).

    Article  Google Scholar 

  18. Lewis, N. S. Toward cost-effective solar energy use. Science 315, 798–801 (2007).

    Article  CAS  Google Scholar 

  19. Grey, H. B. Powering the planet with solar fuel. Nature Chem. 1, 7 (2009).

    Article  Google Scholar 

  20. Walter, M. G. et al. Solar water splitting cells. Chem. Rev. 110, 6446–6473 (2010).

    Article  CAS  Google Scholar 

  21. Boettcher, S. W. et al. Energy-conversion properties of vapour–liquid–solid grown silicon wire-array photocathodes. Science 327, 185–187 (2010).

    Article  CAS  Google Scholar 

  22. Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).

    Article  Google Scholar 

  23. Hansel, A. & Lindblad, P. Towards optimization of cyanobacteria as biotechnologically relevant producers of molecular hydrogen, a clean and renewable energy source. Appl. Microbiol. Biot. 50, 153–160 (1998).

    Article  CAS  Google Scholar 

  24. Evans, D. J. & Pickett, C. J. Chemistry and the hydrogenases. Chem. Soc. Rev. 32, 268–275 (2003).

    Article  Google Scholar 

  25. Jaramillo, T. F. et al. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007).

    Article  CAS  Google Scholar 

  26. Jaramillo, T. F. et al. Hydrogen evolution on supported incomplete cubane-type [Mo3S4]4+ electrocatalysts. J. Phys. Chem. C 112, 17492–17498 (2008).

    Article  CAS  Google Scholar 

  27. Einsle, O. et al. Nitrogenase MoFe-protein at 1.16 angstrom resolution: A central ligand in the FeMo-cofactor. Science 297, 1696–1700 (2002).

    Article  CAS  Google Scholar 

  28. Ferreira, K. N. et al. Architecture of the photosynthetic oxygen-evolving centre. Science 303, 1831–1838 (2004).

    Article  CAS  Google Scholar 

  29. Parkin, A. et al. Rapid and efficient electrocatalytic CO2/CO interconversions by carboxydothermus hydrogenoformans CO dehydrogenase I on an electrode. J. Am. Chem. Soc. 129, 10328–10329 (2007).

    Article  CAS  Google Scholar 

  30. Sokolov, M. N. et al. in Comprehensive Coordination Chemistry II: From Biology to Nanotechnology, Vol. 4 (eds McCleverty, J. A. & Meyer, T. J.) 761–823 (Elsevier, 2004).

    Google Scholar 

  31. US Department of Energy Hydrogen, Fuel Cells and Infrastructure Technologies Program, Multi-Year Research, Development and Demonstration Plan: Planned Program Activities for 2005–2015 (October 2007).

Download references

Acknowledgements

This work was carried out as part of the Catalysis for Sustainable Energy initiative, which is funded by the Danish Ministry of Science, Technology and Innovation. This material is also based on work funded by the Inner Nordic Energy Research Program (09-064270), the Danish Agency for Science Technology and Innovation (FTP 10-080861) and the US Department of Energy, Office of Basic Energy Science. The Center for Individual Nanoparticle Functionality is funded by the Danish National Research Foundation and the Center for Atomic-scale Materials Design is funded by the Lundbeck Foundation.

Author information

Authors and Affiliations

  1. Department of Physics, CINF, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark

    Yidong Hou, Peter C. K. Vesborg, Lone Bech, Alessandro M. Setti, Søren Dahl & Ib Chorkendorff

  2. Haldor Topsøe A/S, Nymøllevej 55, DK-2800 Kongens Lyngby, Denmark

    Billie L. Abrams & Konrad Herbst

  3. Department of Physics, CAMD, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark

    Mårten E. Björketun, Jan Rossmeisl & Jens K. Nørskov

  4. Department of Micro- and Nanotechnology, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark

    Christian D. Damsgaard, Thomas Pedersen & Ole Hansen

  5. California 94025 and Department of Chemical Engineering, SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, Stanford University, Stanford, California 94305, USA

    Jens K. Nørskov

Authors
  1. Yidong Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Billie L. Abrams
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peter C. K. Vesborg
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mårten E. Björketun
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Konrad Herbst
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Lone Bech
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Alessandro M. Setti
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Christian D. Damsgaard
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Thomas Pedersen
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Ole Hansen
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jan Rossmeisl
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Søren Dahl
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Jens K. Nørskov
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Ib Chorkendorff
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Y.H. and P.C.K.V. fabricated the electrodes, carried out electrochemistry experiments and hydrogen measurements. C.D.D., T.P. and O.H. designed Si pillars; M.E.B. and J.R. did the DFT calculations. K.H. synthesized the Mo3S4 clusters; L.B. and A.M.S. measured XPS and analysed the data. B.L.A., S.D., J.K.N. and I.C. conceived the project, supervised the research work and discussed the results. All authors contributed to the paper writing.

Corresponding author

Correspondence to Ib Chorkendorff.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 1312 kb)

Supplementary Movie

Supplementary Movie (MOV 4983 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hou, Y., Abrams, B., Vesborg, P. et al. Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution. Nature Mater 10, 434–438 (2011). https://doi.org/10.1038/nmat3008

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat3008

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