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:

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Nature Materials volume 19, pages 1207–1214 (2020)Cite this article

Subjects

An Author Correction to this article was published on 28 July 2020

This article has been updated

Abstract

A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 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

Fig. 1: Dissolution trends for Pt surfaces.
Fig. 2: The effect of subsurface Au on Pt dissolution rates.
Fig. 3: Effect of surface Au on Pt(111) dissolution and ORR rates.
Fig. 4: Pt3Au NPs.

Similar content being viewed by others

Data availability

All the data are available in the main text and in the Supplementary Information, and are also available from corresponding author upon reasonable request. Source data for the bar graphs are provided with this paper.

Change history

References

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

    CAS  Google Scholar 

  2. Stamenkovic, V. R., Strmcnik, D., Lopes, P. P. & Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 16, 57–69 (2016).

    Google Scholar 

  3. Eberle, U. & Von Helmolt, R. Sustainable transportation based on electric vehicle concepts: a brief overview. Energy Environ. Sci. 3, 689–699 (2010).

    CAS  Google Scholar 

  4. Yoshida, T. & Kojima, K. Toyota MIRAI fuel cell vehicle and progress toward a future hydrogen society. Electrochem. Soc. Interface 24, 45–49 (2015).

    CAS  Google Scholar 

  5. Gittleman, C. S., Kongkanand, A., Masten, D. & Gu, W. Materials research and development focus areas for low cost automotive proton-exchange membrane fuel cells. Curr. Opin. Electrochem 18, 81–89 (2019).

    CAS  Google Scholar 

  6. Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).

    CAS  Google Scholar 

  7. Li, M. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).

    CAS  Google Scholar 

  8. Stephens, I. E. L., Rossmeisl, J. & Chorkendorff, I. Toward sustainable fuel cells. Science 354, 1378–1379 (2016).

    CAS  Google Scholar 

  9. Wang, L. et al. Tunable intrinsic strain in two-dimensional transition metal electrocatalysts. Science 363, 870–874 (2019).

    CAS  Google Scholar 

  10. Chattot, R. et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat. Mater. 17, 827–833 (2018).

    CAS  Google Scholar 

  11. Escudero-Escribano, M. et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 352, 73–76 (2016).

    CAS  Google Scholar 

  12. Kang, Y. et al. Multimetallic core/interlayer/shell nanostructures as advanced electrocatalysts. Nano Lett. 14, 6361–6367 (2014).

    CAS  Google Scholar 

  13. Strasser, P. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).

    CAS  Google Scholar 

  14. Ye, X., Ruban, A. V. & Mavrikakis, Manos Adsorption and dissociation of O2 on Pt–Co and Pt–Fe alloys. J. Am. Chem. Soc. 126, 4717–4725 (2004).

    Google Scholar 

  15. Chen, C. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 343, 1339–1343 (2014).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  17. Ferreira, P. J. et al. Instability of Pt/C electrocatalysts in proton exchange membrane fuel cells: a mechanistic investigation. J. Electrochem. Soc. 152, 2256–2271 (2005).

    Google Scholar 

  18. Shao-Horn, Y. et al. Instability of supported platinum nanoparticles in low-temperature fuel cells. Top. Catal. 46, 285–305 (2007).

    CAS  Google Scholar 

  19. Borup, R. et al. Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem. Rev. 107, 3904–3951 (2007).

    CAS  Google Scholar 

  20. Mayrhofer, K. J. J. et al. Non-destructive transmission electron microscopy study of catalyst degradation under electrochemical treatment. J. Power Sources 185, 734–739 (2008).

    CAS  Google Scholar 

  21. Mayrhofer, K. J. J. et al. Fuel cell catalyst degradation on the nanoscale. Electrochem. Commun. 10, 1144–1147 (2008).

    CAS  Google Scholar 

  22. Takahashi, I. & Kocha, S. S. Examination of the activity and durability of PEMFC catalysts in liquid electrolytes. J. Power Sources 195, 6312–6322 (2010).

    CAS  Google Scholar 

  23. Wang, X., Kumar, R. & Myers, D. J. Effect of voltage on platinum dissolution relevance to polymer electrolyte fuel cells. Electrochem. Solid-State Lett. 9, 225–227 (2006).

    Google Scholar 

  24. Pizzutilo, E. et al. On the need of improved accelerated degradation protocols (ADPs): examination of platinum dissolution and carbon corrosion in half-cell tests. J. Electrochem. Soc. 163, F1510–F1514 (2016).

    CAS  Google Scholar 

  25. Meier, J. C. et al. Degradation mechanisms of Pt/C fuel cell catalysts under simulated start–stop conditions. ACS Catal. 2, 832–843 (2012).

    CAS  Google Scholar 

  26. Hodnik, N. et al. Severe accelerated degradation of PEMFC platinum catalyst: a thin film IL-SEM study. Electrochem. Commun. 30, 75–78 (2013).

    CAS  Google Scholar 

  27. Uchimura, M. & Kocha, S. The impact of cycle profile on PEMFC durability. ECS Trans. 11, 1215–1226 (2007).

    CAS  Google Scholar 

  28. Wilson, M. S., Garzon, F. H., Gottesfeld, S. & Kurt, E. Surface area loss of supported platinum in polymer electrolyte fuel cells. J. Electrochem. Soc. 140, 2872–2877 (1993).

    CAS  Google Scholar 

  29. Smith, M. C., Gilbert, J. A., Mawdsley, J. R., Seifert, S. & Myers, D. J. In situ small-angle X-ray scattering observation of Pt catalyst particle growth during potential cycling. J. Am. Chem. Soc. 130, 8112–8113 (2008).

    CAS  Google Scholar 

  30. Li, D. et al. Functional links between Pt single crystal morphology and nanoparticles with different size and shape: the oxygen reduction reaction case. Energy Environ. Sci. 7, 4061–4069 (2014).

    CAS  Google Scholar 

  31. Tang, L. et al. Electrochemical stability of nanometer-scale Pt particles in acidic environments. J. Am. Chem. Soc. 132, 596–600 (2010).

    CAS  Google Scholar 

  32. Tang, L., Li, X., Cammarata, R. C., Friesen, C. & Sieradzki, K. Electrochemical stability of elemental metal nanoparticles. J. Am. Chem. Soc. 132, 11722–11726 (2010).

    CAS  Google Scholar 

  33. Topalov, A. A. et al. Dissolution of platinum: limits for the deployment of electrochemical energy conversion? Angew. Chem. Int. Ed. 51, 12613–12615 (2012).

    CAS  Google Scholar 

  34. Lopes, P. P. et al. Relationships between atomic level surface structure and stability/activity of platinum surface atoms in aqueous environments. ACS Catal. 6, 2536–2544 (2016).

    CAS  Google Scholar 

  35. Cherevko, S. et al. Dissolution of platinum in the operational range of fuel cells. ChemElectroChem 2, 1471–1478 (2015).

    CAS  Google Scholar 

  36. Lopes, P. P. et al. Dynamics of electrochemical Pt dissolution at atomic and molecular levels. J. Electroanal. Chem. 819, 123–129 (2018).

    CAS  Google Scholar 

  37. Pavlišič, A. et al. Platinum dissolution and redeposition from Pt/C fuel cell electrocatalyst at potential cycling. J. Electrochem. Soc. 165, F3161–F3165 (2018).

    Google Scholar 

  38. Jacobse, L., Huang, Y. F., Koper, M. T. M. & Rost, M. J. Correlation of surface site formation to nanoisland growth in the electrochemical roughening of Pt(111). Nat. Mater. 17, 277–282 (2018).

    CAS  Google Scholar 

  39. Ott, S. et al. Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells. Nat. Mater. 19, 77–85 (2020).

    CAS  Google Scholar 

  40. Sui, S. et al. A comprehensive review of Pt electrocatalysts for the oxygen reduction reaction: nanostructure, activity, mechanism and carbon support in PEM fuel cells. J. Mater. Chem. A 5, 1808–1825 (2017).

    CAS  Google Scholar 

  41. Markovic, N. M. & Ross, P. N. Jr. Surface science studies of model fuel cell electrocatalysts. Surf. Sci. Rep. 45, 117–229 (2002).

    CAS  Google Scholar 

  42. Van Der Vliet, D. F. et al. Mesostructured thin films as electrocatalysts with tunable composition and surface morphology. Nat. Mater. 11, 1051–1058 (2012).

    Google Scholar 

  43. Snyder, J. et al. Thin film approach to single crystalline electrochemistry. J. Phys. Chem. C 117, 23790–23796 (2013).

    CAS  Google Scholar 

  44. Kinoshita, K. Electrochemical Oxygen Technology (John Wiley & Sons, 1992).

  45. Bi, W., Gray, G. E. & Fuller, T. F. PEM fuel cell PtC dissolution and deposition in Nafion electrolyte. Electrochem. Solid-State Lett. 10, 101–104 (2007).

    Google Scholar 

  46. Macauley, N. et al. Pt band formation enhances the stability of fuel cell membranes. ECS Electrochem. Lett. 2, 33–35 (2013).

    Google Scholar 

  47. Zhang, J., Sasaki, K., Sutter, E. & Adzic, R. R. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science 315, 220–222 (2007).

    CAS  Google Scholar 

  48. Kodama, K., Jinnouchi, R., Takahashi, N., Murata, H. & Morimoto, Y. Activities and stabilities of Au-modified stepped-Pt single-crystal electrodes as model cathode catalysts in polymer electrolyte fuel cells. J. Am. Chem. Soc. 138, 4194–4200 (2016).

    CAS  Google Scholar 

  49. Wang, C. et al. Multimetallic Au/FePt3 nanoparticles as highly durable electrocatalyst. Nano Lett. 11, 919–926 (2011).

    CAS  Google Scholar 

  50. Ruban, A. V., Skriver, H. L. & Nørskov, J. K. Surface segregation energies in transition-metal alloys. Phys. Rev. B 59, 15990–16000 (1999).

    Google Scholar 

  51. Strmcnik, D. et al. When small is big: the role of impurities in electrocatalysis. Top. Catal. 58, 1174–1180 (2015).

    CAS  Google Scholar 

  52. Li, D. et al. Surfactant removal for colloidal nanoparticles from solution synthesis: the effect on catalytic performance. ACS Catal. 2, 1358–1362 (2012).

    CAS  Google Scholar 

  53. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    CAS  Google Scholar 

  54. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    CAS  Google Scholar 

  55. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    CAS  Google Scholar 

  56. Haynes, W. M., Bruno, T. J., Lide, D. R. in CRC Handbook of Chemistry and Physics 95th edn (ed. Haynes, W. M.) 145–152 (CRC, 2015).

  57. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Google Scholar 

Download references

Acknowledgements

This work was done at the Argonne National Laboratory, which is operated for the US Department of Energy (DOE) Office of Science by the UCArgonne, LLC, under contract no. DE-AC02-06CH11357. The research efforts on single-crystalline systems, well-defined thin films and in situ dissolution measurements were supported by the Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. Synthesis and characterization of the nanoscale materials was supported by the US DOE Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. Transmission electron microscopy studies were accomplished at the Center for Nanoscale Materials at the Argonne National Laboratory, an Office of Science user facility supported by the US DOE Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02- 06CH11357, and at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, an Office of Science user facility supported by the US DOE Office of Science, Office of Basic Energy Sciences, with work supported by the Hydrogen & Fuel Cell Technologies Office, Energy Efficiency and Renewable Energy, US Department of Energy. Computational modelling work at University of Wisconsin-Madison was supported by the Department of Energy, Basic Energy Sciences, Division of Chemical Sciences (grant DE-FG02-05ER15731), and was partially performed using supercomputer resources at the National Energy Research Scientific Computing Center (NERSC). NERSC is supported by the US DOE, Office of Science, under contract no. DE-AC02-05CH11231.

Author information

Authors and Affiliations

  1. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Pietro P. Lopes, Dongguo Li, Haifeng Lv, Dusan Tripkovic, Yisi Zhu, Yijin Kang, Nigel Becknell, Dusan Strmcnik, Nenad M. Markovic & Vojislav R. Stamenkovic

  2. Department of Chemical Engineering, John Hopkins University, Baltimore, MD, USA

    Chao Wang

  3. Faculty for Technology and Metallurgy, University of Belgrade, Belgrade, Serbia

    Dusan Tripkovic

  4. Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI, USA

    Roberto Schimmenti & Manos Mavrikakis

  5. Faculty of Science and Engineering, Doshisha University, Kyoto, Japan

    Hideo Daimon

  6. Department of Chemical Engineering, Drexel University, Philadelphia, PA, USA

    Joshua Snyder

  7. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Karren L. More

Authors
  1. Pietro P. Lopes
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dongguo Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Haifeng Lv
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dusan Tripkovic
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yisi Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Roberto Schimmenti
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Hideo Daimon
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yijin Kang
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Joshua Snyder
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Nigel Becknell
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Karren L. More
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Dusan Strmcnik
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Nenad M. Markovic
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Manos Mavrikakis
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Vojislav R. Stamenkovic
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

P.P.L., H.D., C.W. and V.R.S. conceived the idea and designed the experiments. P.P.L. performed in situ dissolution measurements on all the systems. C.W., D.L. and J.S. developed and performed thin-film depositions. H.L., Y.K., N.B. and D.L. performed the synthesis and characterization of nanoscale materials. M.M. and R.S. designed and performed the theoretical modelling work. D.T. and Y.S. performed STM and AFM measurements. K.L.M. performed the HR-STEM and EDS characterizations. P.P.L., D.L., D.S., M.M., N.M.M. and V.R.S. analysed and discussed the results. C.W., P.P.L. and V.R.S. drafted the manuscript. V.R.S. supervised the research. All the authors approved the final version of the manuscript.

Corresponding author

Correspondence to Vojislav R. Stamenkovic.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Tables 1 and 2, Figs. 1–13, captions and notes for Tables 1 and 2 and Figs. 1–13 and references 1–6.

Source data

Source Data Fig. 1

Numerical data used to generate bar graphs displayed in panels g, h, and i.

Source Data Fig. 2

Numerical data used to generate bar graph displayed in panel f.

Source Data Fig. 3

Numerical data used to generate graph displayed in panel c.

Source Data Fig. 4

Numerical data used to generate bar graph data displayed in panel h.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lopes, P.P., Li, D., Lv, H. et al. Eliminating dissolution of platinum-based electrocatalysts at the atomic scale. Nat. Mater. 19, 1207–1214 (2020). https://doi.org/10.1038/s41563-020-0735-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-020-0735-3

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