Electrocatalysis

, Volume 5, Issue 3, pp 262–272 | Cite as

Mechanistic Principles of Platinum Oxide Formation and Reduction

  • Steven G. Rinaldo
  • Wendy Lee
  • Jürgen Stumper
  • Michael Eikerling
Article

Abstract

In polymer electrolyte fuel cells, the platinum catalyst in its active form is found predominantly in an oxidized state. Formation and reduction of surface oxide species determine both the electrocatalytic activity of the oxygen reduction reaction as well as the rate of corrosive Pt dissolution. Understanding of mechanisms and rates of oxide formation and reduction is therefore essential in view of both performance and durability. Pt(111) is the generic model system for fundamental studies in fuel cell electrochemistry and cyclic voltammetry at Pt(111) gives an unabated view of the oxide formation and reduction processes. The unresolved challenge is to develop an electrochemical kinetic model that allows the current response measured in cyclic voltammetry to be de-convoluted and interpreted in relation to independent spectroscopic, imaging and theoretical data. Accordingly, a kinetic model for Pt(111) oxide formation and reduction within the voltage range of 0.65–1.15 V is developed and evaluated against electrochemical, spectroscopic and computational studies. Considering the complexity of surface processes involved and the simplicity of the proposed model, the agreement with the extensive range of data is convincing. The model provides a comprehensive picture of surface electrochemical processes that occur at Pt(111) in the normal operational voltage range of the cathode catalyst for polymer electrolyte fuel cells in automotive applications.

Keywords

Fuel cell Electrochemistry Kinetic model Single crystal Oxidation Reduction Cyclic voltammetry 

Notes

Acknowledgments

We gratefully acknowledge the financial support of this work by the Natural Sciences and Engineering Research Council of Canada Collaborative Research and Development Grants program as well as by the collaborating company, AFCC. We would like to thank Jingwei Hu (AFCC), Andreas Putz (AFCC), Chris Richards (AFCC) and Heather Baroody (SFU) for insightful discussions and the reviewers for bringing some critical references to our attention.

References

  1. 1.
    C. Schönbein, Philos. Mag. Ser. 3 14, 43 (1839)Google Scholar
  2. 2.
    W. Grove, Phil. Mag. Ser. 3 14, 127 (1839)Google Scholar
  3. 3.
    M.K. Debe, Nature 486, 43 (2012)CrossRefGoogle Scholar
  4. 4.
    I. Raistrick, Ext. Abstr. 169th Meeting Electrochem. Soc., Boston, MA May 4–9 86-1, 60 (1986)Google Scholar
  5. 5.
    H. Angerstein-Kozlowsk, B. Conway, W. Sharp, J. Electroanal. Chem. Interfacial Electrochem. 43, 9 (1973)CrossRefGoogle Scholar
  6. 6.
    B. Conway, Prog. Surf. Sci. 49, 331 (1995)CrossRefGoogle Scholar
  7. 7.
    N. Markovic, B. Grgur, P. Ross, J. Phys. Chem. B 101, 5405 (1997)CrossRefGoogle Scholar
  8. 8.
    J. Clavilier, A. Rodes, K. Elachi, M. Zamakchari, J. Chim. Phys. Phys. Chim. Biol. 88, 1291 (1991)Google Scholar
  9. 9.
    N. Markovic, T. Schmidt, B. Grgur, H. Gasteiger, R. Behm, P. Ross, J. Phys. Chem. B 103, 8568 (1999)CrossRefGoogle Scholar
  10. 10.
    K. Yamamoto, D. Kolb, R. Kotz, G. Lehmpfuhl, J. Electroanal. Chem. Interfacial Electrochem. 96, 233 (1979)CrossRefGoogle Scholar
  11. 11.
    G. Jerkiewicz, G. Vatankhah, J. Lessard, M. Soriaga, Y. Park, Electrochim. Acta 49, 1451 (2004)Google Scholar
  12. 12.
    D. Gilroy, B. Conway, Can. J. Chem. 46, 875 (1968)CrossRefGoogle Scholar
  13. 13.
    B. Conway, S. Gottesfeld, J. Chem. Soc. Faraday Trans. 1 69, 1090 (1973)CrossRefGoogle Scholar
  14. 14.
    E. Yeager, W. Ogrady, M. Woo, P. Hagans, J. Electrochem. Soc. 125, 348 (1978)CrossRefGoogle Scholar
  15. 15.
    S. Feldberg, C. Enke, C. Bricker, J. Electrochem. Soc. 110, 826 (1963)CrossRefGoogle Scholar
  16. 16.
    V. Birss, M. Chang, J. Segal, J. Electroanal. Chem. 355, 181 (1993)CrossRefGoogle Scholar
  17. 17.
    A. Zolfaghari, G. Jerkiewicz, J. Electroanal. Chem. 467, 177 (1999)CrossRefGoogle Scholar
  18. 18.
    A. Zolfaghari, M. Chayer, G. Jerkiewicz, J. Electrochem. Soc. 144, 3034 (1997)CrossRefGoogle Scholar
  19. 19.
    M. Farebrother, M. Goledzinowski, G. Thomas, V. Birss, J. Elec troanal. Chem. Interfacial Electrochem. 297, 469 (1991)CrossRefGoogle Scholar
  20. 20.
    M. Alsabet, M. Grden, G. Jerkiewicz, J. Electronal. Chem. 589, 120 (2006)CrossRefGoogle Scholar
  21. 21.
    A. Damjanovic, L. Yeh, J. Electrochem. Soc. 126, 555 (1979)CrossRefGoogle Scholar
  22. 22.
    L. Harris, A. Damjanovic, J. Electrochem. Soc. 122, 593 (1975)CrossRefGoogle Scholar
  23. 23.
    D. Heyd, D. Harrington, J. Elecyroanal. Chem. 335, 19 (1992)CrossRefGoogle Scholar
  24. 24.
    A. Damjanovic, L. Yeh, J. Wolf, J. Electrochem. Soc. 127, 874 (1980)CrossRefGoogle Scholar
  25. 25.
    M. vanderGeest, N. Dangerfield, D. Harrington, J. Electroanal. Chem. 420, 89 (1997)CrossRefGoogle Scholar
  26. 26.
    B. Conway, G. Jerkiewicz, J. Electroanal. Chem. 339, 123 (1992)CrossRefGoogle Scholar
  27. 27.
    A. Ward, A. Damjanovic, E. Gray, M. Ojea, J. Electrochem. Soc. 123, 1599 (1976)CrossRefGoogle Scholar
  28. 28.
    M. Wakisaka, S. Asizawa, H. Uchida, M. Watanabe, Phys. Chem. Chem. Phys. 12, 4184 (2010)CrossRefGoogle Scholar
  29. 29.
    K. Vetter, J. Schultze, J. Electroanal. Chem. Interfacial Electrochem. 34, 131 (1972)Google Scholar
  30. 30.
    D. Gilroy, J. Electroanal, Chem. Interfacial Electrochem. 71, 257 (1976)CrossRefGoogle Scholar
  31. 31.
    A. Sun, J. Franc, D. Macdonald, J. Electrochem. Soc. 153, B260 (2006)CrossRefGoogle Scholar
  32. 32.
    D. Harrington, J. Electroanal. Chem. 420, 101 (1997)CrossRefGoogle Scholar
  33. 33.
    K. Vetter, J. Schultze, J. Electroanal. Chem. Interfacial Elec trochem. 34, 141 (1972)Google Scholar
  34. 34.
    B. Conway, B. Barnett, H. Angerstein-Kozlowska, B. Tilak, J. Chem. Phys. 93, 8361 (1990)CrossRefGoogle Scholar
  35. 35.
    S. Zeitler, E. Wendler-Kalsch, W. Preidel, V. Tegeder, Mater. Corros. 48, 303 (1997)CrossRefGoogle Scholar
  36. 36.
    X. Wang, R. Kumar, D. Myers, Electrochem. Solid-State Lett. 9, A 225 (2006)CrossRefGoogle Scholar
  37. 37.
    A.A. Topalov, I. Katsounaros, M. Auinger, S. Cherevko, J.C. Meier, S.O. Klemm, K.J. Mayrhofer, Angew. Chem. Int. Ed. 51, 12613 (2012)CrossRefGoogle Scholar
  38. 38.
    M. Wakisaka, H. Suzuki, S. Mitsui, H. Uchida, M. Watanabe, Langmuir 25, 1897 (2009)CrossRefGoogle Scholar
  39. 39.
    V. Viswanathan, H. Hansen, J. Rossmeisl, T. Jaramillo, H. Pitsch, J. Norskov, J. Phys. Chem. C 116, 4698 (2012)CrossRefGoogle Scholar
  40. 40.
    A. Panchenko, M. Koper, T. Shubina, S. Mitchell, E. Roduner, J. Electrochem. Soc. 151, A2016 (2004)CrossRefGoogle Scholar
  41. 41.
    M. Koper, J. Lukkien, Surf. Sci. 498, 105 (2002)CrossRefGoogle Scholar
  42. 42.
    C. Hermse, A. van Bavel, M. Koper, J. Lukkien, R. van Santen, A. Jansen, Surf. Sci. 572, 247 (2004)CrossRefGoogle Scholar
  43. 43.
    M. Koper, J. Lukkien, J. Electroanal. Chem. 485, 161 (2000)CrossRefGoogle Scholar
  44. 44.
    J.R. Strobl, D.A. Harrington, J. Chem. Phys. 139, 104104 (2013)CrossRefGoogle Scholar
  45. 45.
    B. Tilak, B. Conway, H. Angerstein-Kozlowska, J. Electroanal. Chem. Interfacial Electrochem. 48, 1 (1973)CrossRefGoogle Scholar
  46. 46.
    E.F. Holby, D. Morgan, J. Electrochem. Soc. 159, B578 (2012)CrossRefGoogle Scholar
  47. 47.
    A. Appleby, J. Electrochem. Soc. 120, 1205 (1973)CrossRefGoogle Scholar
  48. 48.
    A. Berna, V. Climent, J.M. Feliu, Electrochem. Commun. 9, 2789 (2007)CrossRefGoogle Scholar
  49. 49.
    V. Climent, R. Gomez, J.M. Orts, J.M. Feliu, J. Phys. Chem. B 110, 11344 (2006)CrossRefGoogle Scholar
  50. 50.
    R. Gomez, J. Orts, B. Alvarez-Ruiz, J. Feliu, J. Phys. Chem. B 108, 228 (2004)CrossRefGoogle Scholar
  51. 51.
    J. Mostany, E. Herrero, J. Feliu, J. Lipkowski, J. Electronal. Chem. 558, 19 (2003)CrossRefGoogle Scholar
  52. 52.
    J. Clavilier, J. Feliu, A. Fernandezvega, A. Aladaz, J. Electroanal. Chem. 294, 193 (1990)CrossRefGoogle Scholar
  53. 53.
    S. Mitchell, G. Brown, P. Rikvold, J. Electroanal. Chem. 493, 68 (2000)CrossRefGoogle Scholar
  54. 54.
    A.M. Gómez-Marín, J.M. Feliu, Electrochim. Acta 104, 367 (2013)CrossRefGoogle Scholar
  55. 55.
    A.M. Gómez-Marín, J. Clavilier, J.M. Feliu, J. Electroanal. Chem. 688, 360 (2013)CrossRefGoogle Scholar
  56. 56.
    K.A. Jaaf-Golze, D. Kolb, D. Scherson, J. Electroanal. Chem. Interfacial Electrochem. 200, 353 (1986)CrossRefGoogle Scholar
  57. 57.
    S. Nie, P. Feibelman, N. Bartelt, K. Thürmer, Phys. Rev. Lett. 105, 26102 (2010)CrossRefGoogle Scholar
  58. 58.
    H. Ogasawara, B. Brena, D. Nordlund, M. Nyberg, A. Pelmenschikov, L. Pettersson, A. Nilsson, Phys. Rev. Lett. 89, 276102 (2002)CrossRefGoogle Scholar
  59. 59.
    C. Clay, S. Haq, A. Hodgson, Phys. Rev. Lett. 92, 46102 (2004)CrossRefGoogle Scholar
  60. 60.
    X. Su, L. Lianos, Y. Shen, G. Somorjai, Phys. Rev. Lett. 80, 1533 (1998)CrossRefGoogle Scholar
  61. 61.
    T. Iwasita, X. Xia, J. Electroanal. Chem. 411, 95 (1996)CrossRefGoogle Scholar
  62. 62.
    B. Andreaus, M. Eikerling, J. Electroanal. Chem. 607, 121 (2007)CrossRefGoogle Scholar
  63. 63.
    M. Wakisaka, S. Asizawa, H. Uchida, M. Watanabe, Phys. Chem. Chem. Phys. 12, 4184 (2010)CrossRefGoogle Scholar
  64. 64.
    A. Roudgar, M. Eikerling, R. van Santen, Phys. Chem. Chem. Phys. 12, 614 (2010)CrossRefGoogle Scholar
  65. 65.
    J.K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. Kitchin, T. Bligaard, H. Jonsson, J. Phys. Chem. B 108, 17886 (2004)CrossRefGoogle Scholar
  66. 66.
    L. Wang, A. Roudgar, M. Eikerling, J. Phys. Chem. C 113, 17989 (2009)CrossRefGoogle Scholar
  67. 67.
    D.C. Ford, Y. Xu, M. Mavrikakis, Surf. Sci. 587, 159 (2005)CrossRefGoogle Scholar
  68. 68.
    N. Marković, P. Ross Jr., Surf. Sci. Rep. 45, 117 (2002)CrossRefGoogle Scholar
  69. 69.
    J.D. Hunter, Comput. Sci. Eng. 9, 90 (2007)CrossRefGoogle Scholar
  70. 70.
    V. Komanicky, K. Chang, A. Menzel, N. Markovic, H. You, X. Wang, D. Myers, J. Electrochem. Soc. 153, B446 (2006)CrossRefGoogle Scholar
  71. 71.
    A.M. Gómez-Marín, J.M. Feliu, Electrochim. Acta 82, 558 (2012)CrossRefGoogle Scholar
  72. 72.
    M. Wakisaka, H. Suzuki, S. Mitsui, H. Uchida, M. Watanabe, J. Phys. Chem. C 112, 2750 (2008)CrossRefGoogle Scholar
  73. 73.
    F. Abild-Pedersen, J.P. Greeley, F. Studt, J. Rossmeisl, T.R. Fronczek-Munter, P.G. Moses, E. Skulason, T. Bligaard, J.K. Nørskov, Phys. Rev. Lett. 99 (2007)Google Scholar
  74. 74.
    D. Savinova, E. Molodkina, A. Danilov, Y. M. Polukarov, Russ. J. Electrochem. 40, 683 (2004)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Steven G. Rinaldo
    • 1
    • 2
  • Wendy Lee
    • 2
  • Jürgen Stumper
    • 2
  • Michael Eikerling
    • 1
  1. 1.Simon Fraser UniversityBurnabyCanada
  2. 2.Automotive Fuel Cell Cooperation CorporationBurnabyCanada

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