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:

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts

Nature Chemistry volume 1, pages 552–556 (2009)Cite this article

Abstract

The widespread use of low-temperature polymer electrolyte membrane fuel cells for mobile applications will require significant reductions in the amount of expensive Pt contained within their cathodes, which drive the oxygen reduction reaction (ORR). Although progress has been made in this respect, further reductions through the development of more active and stable electrocatalysts are still necessary. Here we describe a new set of ORR electrocatalysts consisting of Pd or Pt alloyed with early transition metals such as Sc or Y. They were identified using density functional theory calculations as being the most stable Pt- and Pd-based binary alloys with ORR activity likely to be better than Pt. Electrochemical measurements show that the activity of polycrystalline Pt3Sc and Pt3Y electrodes is enhanced relative to pure Pt by a factor of 1.5–1.8 and 6–10, respectively, in the range 0.9–0.87 V.

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: Volcano plots and free-energy diagrams for the oxygen reduction reaction on Pt-based transition metal alloys.
Figure 2: Output of computational screening procedure, showing the oxygen binding energy, relative to that of Pt, on a Pt or Pd skin surface, as a function of alloying energy.
Figure 3: Anodic sweeps of cyclic voltammograms of Pt, Pt3Sc and Pt3Y in O2-saturated electrolyte.
Figure 4: Activity increase of Pt3Y and Pt3Sc versus Pt for the oxygen reduction reaction.

Similar content being viewed by others

References

  1. Gasteiger, H. A., Kocha, S. S., Somappli, B. & Wagner, F. T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B-Environ. 56, 9–35 (2005).

    Article  CAS  Google Scholar 

  2. Stamenkovic, V. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007).

    Article  CAS  PubMed  Google Scholar 

  3. Koh, S. & Strasser, P. Electrocatalysis on bimetallic surfaces: modifying catalytic reactivity for oxygen reduction by voltammetric surface dealloying. J. Amer. Chem. Soc. 129, 12624–12625 (2007).

    Article  CAS  Google Scholar 

  4. Chen, S. et al. Origin of oxygen reduction reaction activity on “Pt3Co” nanoparticles: atomically resolved chemical compositions and structures. J. Phys. Chem. C 113, 1109–1125 (2009).

    Article  CAS  Google Scholar 

  5. Wakisaka, W., Suzuki, H., Mitsui, S., Uchida, H. & Watanabe, M. Increased oxygen coverage at Pt-Fe alloy cathode for the enhanced oxygen reduction reaction studied by EC-XPS. J. Phys. Chem. C 112, 2750–2755 (2008).

    Article  CAS  Google Scholar 

  6. Stamenkovic, V. et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew. Chem. Int. Ed. 45, 2897–2901 (2006).

    Article  CAS  Google Scholar 

  7. Paulus, U. A. et al. Oxygen reduction on high surface area Pt-based alloy catalysts in comparison to well defined smooth bulk alloy electrodes. Electrochim. Acta 47, 3787–3798 (2002).

    Article  CAS  Google Scholar 

  8. Paulus, U. A. et al. Oxygen reduction on Carbon-Supported Pt-Ni and Pt-Co Alloy Catalysts. J. Phys. Chem. B 106, 4181–4191 (2002).

    Article  CAS  Google Scholar 

  9. Mayrhofer, K. J. J., Juhart, V., Hartl, K., Hanzlik, M. & Arenz, M. Adsorbate-induced surface segregation for core–shell nanocatalysts. Angew. Chem. Int. Ed. 48, 3529–3531 (2009).

    Article  CAS  Google Scholar 

  10. Koh, S., Leisch, J., Toney, M. F. & Strasser, P. Structure–activity–stability relationships of Pt–Co alloy electrocatalysts in gas-diffusion electrode layers. J. Phys. Chem. C 111, 3744–3752 (2007).

    Article  CAS  Google Scholar 

  11. Koh, S., Toney, M. F. & Strasser, P. Activity–stability relationships of ordered and disordered alloy phases of Pt3Co electrocatalysts for the oxygen reduction reaction (ORR). Electrochim. Acta 52, 2765–2774 (2007).

    Article  CAS  Google Scholar 

  12. Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Article  Google Scholar 

  13. Nørskov, J. K, Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nature Chem. 1, 37–46 (2009).

    Article  Google Scholar 

  14. Strasser, P., Fan, Q., Devenney, M. & Weinberg, W. H. High throughput experimental and theoretical screening of materials—a comparative study of search strategies for new fuel cell anode catalysts. J. Phys. Chem B 107, 11013–11021 (2003).

    Article  CAS  Google Scholar 

  15. Skulason, E. et al. Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode. Phys. Chem. Chem. Phys. 9, 3241–3250 (2007).

    Article  CAS  PubMed  Google Scholar 

  16. Janik, M. J., Taylor, C. D. & Neurock, M. First-principles analysis of the initial electroreduction steps of oxygen over Pt(111). J. Electrochem. Soc. 156, B126–B135 (2009).

    Article  CAS  Google Scholar 

  17. Greeley, J., Rossmeisl, J., Hellman, A. & Nørskov, J. K. Theoretical trends in particle size effects for the oxygen reduction reaction. Z. Phys. Chem. 221, 1209–1220 (2007).

    Article  CAS  Google Scholar 

  18. Stamenkovic, V. R. et al. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Mater. 6, 241–247 (2007).

    Article  CAS  Google Scholar 

  19. Rossmeisl, J., Logadottir, A. & Nørskov, J. K. Electrolysis of water on (oxidized) metal surfaces. Chem. Phys. 319, 178–184 (2005).

    Article  CAS  Google Scholar 

  20. Abild-Pedersen, F. et al. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces. Phys. Rev. Lett. 99, 016105 (2007).

    Article  CAS  PubMed  Google Scholar 

  21. Stamenkovic, V. R., Mun, B. S., Mayrhofer, K. J. & Ross, P. N., Markovic, N. M. Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces. J. Am. Chem. Soc. 128, 8813–8819 (2006).

    Article  CAS  PubMed  Google Scholar 

  22. Johannesson G. H. et al. Combined electronic structure and evolutionary search approach to materials design. Phys. Rev. Lett. 88, 255506 (2002).

    Article  CAS  PubMed  Google Scholar 

  23. Bligaard, T. et al. Pareto-optimal alloys. Appl. Phys. Lett. 83, 4527–4529 (2003).

    Article  CAS  Google Scholar 

  24. Ruban, A. V., Skriver, H. L. & Nørskov, J. K. Crystal-structure contribution to the solid solubility in transition metal alloys. Phys. Rev. Lett. 80, 1240 (1998).

    Article  Google Scholar 

  25. Stamenkovic, V. R., Schmidt, T. J., Ross, P. N. & Markovic, N. M. Surface composition effects in electrocatalysis: kinetics of oxygen reduction on well-defined Pt3Ni and Pt3Co alloy surfaces J. Phys. Chem. B 106, 11970–11979 (2002).

    Article  CAS  Google Scholar 

  26. Neyerlin, K. C., Srivastava, R., Yu, C. & Strasser, P. Electrochemical activity and stability of dealloyed Pt–Cu and Pt-Cu-Co electrocatalysts for the oxygen reduction reaction (ORR). J. Power Sources 186, 261–267 (2009).

    Article  CAS  Google Scholar 

  27. Ball, S. C., Hudson, S. L., Theobald, B. R. C. & Thompsett, D. PtCo, a durable catalyst for automotive proton electrolyte membrane fuel cells? ECS Transactions 11, 1267–1278 (2007).

    Article  CAS  Google Scholar 

  28. Greeley, J. & Nørskov, J. K. Combinatorial density functional theory-based screening of surface alloys for the oxygen reduction reaction. J. Phys. Chem. C 113, 4932–4939 (2009).

    Article  CAS  Google Scholar 

  29. Rossmeisl, J., Qu, Z.-W., Zhu, H., Kroes, G.-J. & Nørskov, J. K. Electrolysis of water on oxide surfaces. J. Electroanal. Chem. 607, 83–89 (2007).

    Article  CAS  Google Scholar 

  30. Takasu, Y., Yoshinaga, N. & Sugimoto, W. Oxygen reduction behavior of RuO2/Ti, IrO2/Ti and IrM (M: Ru, Mo, W, V) Ox/Ti binary oxide electrodes in a sulfuric acid solution. Electrochem. Commun. 10, 668–672 (2008).

    Article  CAS  Google Scholar 

  31. Mano, N., Soukharev, V. & Heller, A. A laccase-wiring redox hydrogel for efficient catalysis of O2 electroreduction. J. Phys. Chem. B 110, 11180–11187 (2006).

    Article  CAS  PubMed  Google Scholar 

  32. Lefèvre, M., Proietti, E., Jaouen, F. & Dodelet, J.-P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324, 71–74 (2009).

    Article  PubMed  Google Scholar 

  33. Gasteiger, H. A. & Markovic, N. M. Just a dream—or future reality? Science 324, 48 (2009).

    Article  CAS  PubMed  Google Scholar 

  34. Zhang, J. L, Vukmirovic, M. B., Xu, Y., Mavrikakis, M. & Adzic, R. R. Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. Angew. Chem. Int. Ed. 44, 2132–2135 (2005).

    Article  CAS  Google Scholar 

  35. Rossmeisl, J., Karlberg, G. S., Jaramillo, T. F. & Nørskov, J. K. Steady state oxygen reduction and cyclic voltammetry. Faraday Discuss. 140, 337–346 (2008).

    Article  CAS  PubMed  Google Scholar 

  36. Karlberg, G. S., Rossmeisl, J. & Nørskov, J. K. Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory. Phys. Chem. Chem. Phys. 9, 5158–5161 (2007).

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

J.G. and T.F.J. are both recipients of H. C. Ørsted Postdoctoral Fellowships from the Technical University of Denmark. Funding by the Danish Council for Technology and Innovation's FTP program and by the Danish Strategic Research Council's HyCycle program is gratefully acknowledged. The Center for Atomic-scale Materials Design is supported by the Lundbeck Foundation. The Center for Individual Nanoparticle Functionality is supported by the Danish National Research Foundation.

Author information

Author notes

  1. J. Greeley & T. F. Jaramillo

    Present address: Present address: Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439 (J.G.), Department of Chemical Engineering, Stanford University, Stanford, California 94305-5025 (T.F.J.),

Authors and Affiliations

  1. Department of Physics, Center for Atomic-scale Materials Design, Building 311

    J. Greeley, H. A. Hansen, J. Rossmeisl & J. K. Nørskov

  2. Technical University of Denmark, Lyngby, DK-2800, Denmark

    J. Greeley, H. A. Hansen, J. Rossmeisl & J. K. Nørskov

  3. Department of Physics, Center for Individual Nanoparticle Functionality, Building 312

    I. E. L. Stephens, A. S. Bondarenko, T. P. Johansson, T. F. Jaramillo & I. Chorkendorff

  4. Technical University of Denmark, Lyngby, DK-2800, Denmark

    I. E. L. Stephens, A. S. Bondarenko, T. P. Johansson, T. F. Jaramillo & I. Chorkendorff

Authors
  1. J. Greeley
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. E. L. Stephens
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. S. Bondarenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. T. P. Johansson
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. H. A. Hansen
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. T. F. Jaramillo
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. J. Rossmeisl
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. I. Chorkendorff
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. J. K. Nørskov
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.G., H.A.H., J.R. and J.K.N. contributed to the computational work in this paper. I.E.L.S., A.S.B., T.P.J., T.F.J., and I.C. contributed to the experimental work.

Corresponding author

Correspondence to J. K. Nørskov.

Ethics declarations

Competing interests

The Technical University of Denmark (DTU) has filed a patent with the authors named as the inventors.

Supplementary information

Supplementary information

Supplementary information (PDF 1002 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Greeley, J., Stephens, I., Bondarenko, A. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chem 1, 552–556 (2009). https://doi.org/10.1038/nchem.367

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.367

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