Catalysis Letters

, Volume 36, Issue 1–2, pp 1–8 | Cite as

Structural effects in electrocatalysis: electrooxidation of carbon monoxide on Pt3Sn single-crystal alloy surfaces

  • Hubert A. Gasteiger
  • Nenad M. Marković
  • Philip N. RossJr.


The kinetics of the electrochemical oxidation of carbon monoxide (CO) and CO/hydrogen mixtures (0.1 and 2% CO) in sulfuric acid electrolyte at 25–62°C was studied on different surfaces of the ordered single crystal Pt3Sn alloy. Characterization of the surface composition and structure was determined in UHV using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and low energy ion scattering (LEIS) prior to determining the electrode kinetics using the classical rotating disk method (RDE) with CO dissolved in the electrolyte. Clean annealed and sputtered-cleaned but not-annealed surfaces of (110) and (111) orientation were studied. A remarkable difference in activity was observed between the annealed (111) surface and the sputtered but not-annealed (110) surface, with both surfaces having the same nominal surface composition, 20–25 at% Sn, but different local structures. The onset potential for CO oxidation on the (111) surface was shifted cathodically by 0.13 V relative to that for the sputtered (110) surface, and the onset comes remarkably close to 0 V on the reversible hydrogen potential scale. Relative to pure Pt surfaces (of any crystal structure), the potential shift is more than 0.5 V, corresponding to a catalytic activity that is higher by more than four orders of magnitude. Comparable shifts were observed for the oxidation of CO/H2 mixtures. Both the structure sensitivity and the high catalytic activity of the Pt3Sn surface are attributed to an adsorbed state of CO unique to this alloy and occurs at relatively high coverage on the (111) surface.


electrocatalysis carbon monoxide platinum-tin alloy single crystal electrooxidation 


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  1. [1]
    H. Tobias, M.T. Paffett, P.A. Pappin, J. Valerio and S. Gottesfeld, in:Proc. Workshop on Direct Methanol-Air Fuel Cells, eds. A.R. Landgrebe, R.K. Sen and D.J. Wheeler, The Electrochemical Society, Pennington (1992) Vol. 92–14, p. 37.Google Scholar
  2. [2]
    H.S. Murray, in:Fuel Cell, 1985 Fuel Cell Seminar, Book of Abstracts, sponsored by the National Fuel Cell Coordinating Group, Tucson, Arizona, May 1985, p. 129.Google Scholar
  3. [3]
    H.A. Gasteiger, N.M. Marković and P.N. Ross Jr., J. Phys. Chem. 99 (1995) 8290.Google Scholar
  4. [4]
    H.A. Gasteiger, N.M. Marković and P.N. Ross Jr., J. Phys. Chem., in press.Google Scholar
  5. [5]
    H.A. Gasteiger, N.M. Marković and P.N. Ross Jr., J. Phys. Chem. 99 (1995) 8945.Google Scholar
  6. [6]
    M.L. Sattler andP.N. Ross Jr., Ultramicroscopy 20 (1986) 21.Google Scholar
  7. [7]
    V. Radmilović, H.A. Gasteiger and P.N. Ross Jr., J. Catal. 154 (1995) 98.Google Scholar
  8. [8]
    A.N. Haner, P.N. Ross Jr. and U. Bardi, Catal. Lett. 8 (1991) 1.Google Scholar
  9. [9]
    A.N. Haner, P.N. Ross Jr. and U. Bardi, Surf. Sci. 249 (1991) 15.Google Scholar
  10. [10]
    A. Atrei, U. Bardi, G. Rovida, M. Torrini, E. Zanazzi and P.N. Ross Jr. Phys. Rev. B 46 (1992) 1649.Google Scholar
  11. [11]
    A. Haner, P.N. Ross Jr.U. Bardi and A. Atrei, J. Vac. Sci. Technol. A 10 (1992) 2718.Google Scholar
  12. [12]
    R.A.van Santen and W.M.H. Sachtler, J. Catal. 33 (1974) 202.Google Scholar
  13. [13]
    P. Biloen, R. Bouwman, R.A. van Santen and H. Brongersma, Appl. Surf. Sci. 2 (1979) 532, and references therein.Google Scholar
  14. [14]
    A. Haner andP.N. Ross Jr., J. Phys. Chem. 95 (1991) 3740.Google Scholar
  15. [15]
    H.A. Gasteiger, P.N. Ross Jr. and E.J. Cairns, Surf. Sci. 293 (1993) 67.Google Scholar
  16. [16]
    S. Motoo and M. Watanabe, J. Electroanal. Chem. 69 (1976) 429.Google Scholar
  17. [17]
    S.D. Gardner, G.B. Hoflund, B.T. Upchurch, D.R. Schryer, E. J. Kielin and J. Schryer, J. Catal. 129 (1991) 114.Google Scholar
  18. [18]
    A. Boulahouache, G. Kons, H.-G. Lintz and P. Schulz, Appl. Catal. A 91 (1992) 115.Google Scholar
  19. [19]
    R. Kumar and S. Ahmed, in:Proc. First Int. Symp. on New Materials for Fuel Cell Systems, eds. O. Savadogo, P.R. Roberge and T.N. Veziroglu, École Polytechnique de Montréal, Montreal, (1995) pp. 224–238.Google Scholar
  20. [20]
    S. Gottesfeld and J. Pafford, J. Electrochem. Soc. 135 (1988) 2651.Google Scholar
  21. [21]
    H.A. Gasteiger, N. Marković, P.N. Ross Jr. and E.J. Cairns, J. Electrochem. Soc. 141 (1994) 1795.Google Scholar
  22. [22]
    P.N. Ross Jr., J. Power Sources, submitted.Google Scholar
  23. [23]
    D.L. Maricle and B.L. Murach, Extended Abstracts, Electrochemical Society Spring Meeting, Reno, May 1995, Vol. 95-1, pp. 736–737.Google Scholar
  24. [24]
    H.A. Gasteiger, N.M. Marković and P.N. Ross Jr., in preparation.Google Scholar
  25. [25]
    D.R. Schryer, B.T. Upchurch, B.D. Sidney, K.G. Brown, G.B. Hoflund and R.K. Herz, J. Catal. 130 (1991) 314.Google Scholar
  26. [26]
    H.A. Gasteiger, N. Marković, P.N. Ross Jr. and E.J. Cairns, Electrochim. Acta 39 (1994) 1825.Google Scholar
  27. [27]
    K. Wang, H.A. Gasteiger, N.M. Marković and P.N. Ross Jr., in preparation.Google Scholar
  28. [28]
    C.T. Campbell, G. Ertl, H. Kuipers and J. Segner, J. Chem. Phys. 73 (1980) 5862.Google Scholar
  29. [29]
    G. Ertl, N. Neumann and K.M. Streit, Surf. Sci. 64 (1977) 393.Google Scholar
  30. [30]
    A.B. Anderson and E. Grantscharova, J. Phys. Chem. 99 (1995) 9143.Google Scholar
  31. [31]
    P.N. Ross Jr., J. Vac. Sci. Technol. A 10(1992) 2546.Google Scholar
  32. [32]
    M.J. Weaver, S.-C. Chang, L.-W.H. Leung, X. Jiang, M. Rubel, M. Szklarczyk, D. Zurawski and A. Wieckowski, J. Electroanal. Chem. 327 (1992) 247.Google Scholar
  33. [33]
    This laboratory, unpublished results.Google Scholar
  34. [34]
    P.R. Norton, J.A. Davies and T.E. Jackman, Surf. Sci. 122 (1982) L593.Google Scholar
  35. [35]
    T.E. Jackman, J.A. Davies, D.P. Jackson, W.N. Unertl and P.R. Norton, Surf. Sci. 120 (1980) 389.Google Scholar

Copyright information

© J.C. Baltzer AG, Science Publishers 1996

Authors and Affiliations

  • Hubert A. Gasteiger
    • 1
  • Nenad M. Marković
    • 1
  • Philip N. RossJr.
    • 1
  1. 1.Materials Sciences Division, Lawrence Berkeley LaboratoryUniversity of CaliforniaBerkeleyUSA

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