Topics in Catalysis

, Volume 36, Issue 1–4, pp 65–76 | Cite as

Growth of Copper on Single Crystalline ZnO: Surface Study of a Model Catalyst


Copper, vapor-deposited on the polar, Zn-terminated ZnO(0001) surface is investigated in view of its suitability as model system for the technologically important Cu/ZnO catalyst. The structure and electronic properties of Cu clusters on ZnO(0001)–Zn have been studied with scanning tunneling microscopy (STM), low energy electron diffraction (LEED), ultraviolet photoelectron spectroscopy (UPS), and low-energy He+ ion scattering (LEIS). At room temperature copper grows as two-dimensional (2D) clusters only at very low coverages of 0.001–0.05 equivalent monolayers (ML). At coverages greater than 0.01 ML, 3D clusters start to develop. This is contrasted to Cu growth on the oxygen-terminated ZnO(0001bar) surface, where a strong adhesion between Cu and the ZnO substrate results in an initial wetting of the surface by Cu. On ZnO(0001)–Zn, surface roughness and sputter damage change the growth mode to more 2D-like. Annealing in UHV results in well-separated, hexagonal clusters rotationally aligned with the substrate. Annealing of 2–5 ML Cu deposits on the ZnO(0001)–Zn surface in 10−6 mbar O2 results in the formation of a (√3 × √3)R30° superstructure with respect to the ZnO lattice. This superstructure likely contains Cu+ sites. The suitability of the different surface morphologies to probe specific sites that are thought to be active for catalytic processes is discussed.


Cu/ZnO catalyst zinc oxide methanol synthesis surface alloy adsorption Cu growth oxygen annealing STM 


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  1. 1.
    Geissler, K., Newson, E., Vogel, F., Truong, T.-B., Hottinger, P., Wokaun, A. 2001Topics Catal.3289Google Scholar
  2. 2.
    Klier, K. 1982Adv. Catal.31243Google Scholar
  3. 3.
    Cheng, W.-H., Kung, H.H. 1994Chemical Industries (Dekker)571Google Scholar
  4. 4.
    Spencer, M.S. 1998Catal. Lett.5037CrossRefGoogle Scholar
  5. 5.
    Burch, R., Chappell, R.J., Golunski, S.E. 1989J. Chem. Soc., Faraday Trans.853569Google Scholar
  6. 6.
    Burch, R., Golunski, S.E., Spencer, M.S. 1990J. Chem. Soc., Faraday Trans.862683Google Scholar
  7. 7.
    Spencer, M.S. 1999Topics Catal.8259CrossRefGoogle Scholar
  8. 8.
    Fujitani, T., Nakamura, J. 2000Appl. Catal. A. Gen191111CrossRefGoogle Scholar
  9. 9.
    Nakamura, J., Choi, Y., Fujitani, T. 2003Topics Catal.22277CrossRefGoogle Scholar
  10. 10.
    Wagner, J.B., Hansen, P.L., Molenbroek, A.M., Topsøe, H., Clausen, B.S., Helveg, S. 2003J. Phys. Chem. B1077753Google Scholar
  11. 11.
    Choi, Y., Futagami, K., Fujitani, T. 2001J. Nakamura, Appl. Catal. A: Gen208163Google Scholar
  12. 12.
    Harikumar, K.R., Santra, A.K., Rao, C.N.R. 1996Appl. Surf. Sci.93135CrossRefGoogle Scholar
  13. 13.
    Chinchen, G.C., Waugh, K.C. 1986Catal J.97280Google Scholar
  14. 14.
    Pan, W.X., Cao, R., Roberts, D.L., Griffin, G.L. 1988J. Catal.114440Google Scholar
  15. 15.
    Yoshihara, J., Campbell, C.T. 1996J. Catal.161776CrossRefGoogle Scholar
  16. 16.
    Askgaard, T.S., Norskov, J.K., Ovesen, C.V., Stoltze, P. 1995J. Catal.156229CrossRefGoogle Scholar
  17. 17.
    Günter, M.M., Ressler, T., Bems, B., Büscher, C., Genger, T., Hinrichsen, O., Muhler, M., Schlögel, R. 2001Catal. Lett.7137Google Scholar
  18. 18.
    Grunwaldt, J.D., Molenbroek, A.M., Topsøe, N.Y., Topsøe, H., Clausen, B.S. 2000J. Catal.194452CrossRefGoogle Scholar
  19. 19.
    Clausen, B.S., Schiøtz, J., Gråbæk, L., Ovesen, C.V., Jacobsen, K.W., Nørskov, J.K., Topsøe, H. 1994Topics Catal.1367CrossRefGoogle Scholar
  20. 20.
    Sakahara, S., Yajima, K., Belosludov, R., Takami, S., Kubo, M., Miyamoto, A. 2002Appl. Surf. Sci.189253CrossRefGoogle Scholar
  21. 21.
    Kau, L.S., Hodgson, K.O., Solomon, E.I. 1989J. Am. Chem. Soc.1117103CrossRefGoogle Scholar
  22. 22.
    Meitzner, G., Iglesia, E. 1999Catal. Today53433CrossRefGoogle Scholar
  23. 23.
    Kulkarni, G.U., Rao, C.N.R. 2003Topics Catal.22183CrossRefGoogle Scholar
  24. 24.
    Agrell, J., Boutonnet, M., Melian-Cabrera, I., Fierro, J.L.G. 2003Appl. Catal. A: Gen.253201Google Scholar
  25. 25.
    Bowker, M., Houghton, H., Waugh, K.C., Giddings, T., Green,  M. 1983J. Catal.84252CrossRefGoogle Scholar
  26. 26.
    Grunze, M., Hirschwald, W., Hofmann, D. 1981J. Crystal Growth52241Google Scholar
  27. 27.
    Koplitz, L.V., Dulub, O., Diebold, U. 2003J. Phys. Chem. B10710583CrossRefGoogle Scholar
  28. 28.
    Dulub, O., Boatner, L.A., Diebold, U. 2002Surf. Sci.504271CrossRefGoogle Scholar
  29. 29.
    Baumer, M., Freund, H.-J. 1999Prog. Surf. Sci.61127Google Scholar
  30. 30.
    Goodman, D.W. 1995Surf. Sci. Rev. Lett.29Google Scholar
  31. 31.
    Sloczynski, J., Grabowski, R., Kozlowska, A., Olszewski, P.K. 2003J. Stoch, Phys. Chem. Chem. Phys.54631Google Scholar
  32. 32.
    Yoshihara, J., Parker, S.C., Campbell, C.T. 1999Surf. Sci.439153CrossRefGoogle Scholar
  33. 33.
    Yoshihara, J., Campbell, J.M., Campbell, C.T. 1998Surf. Sci.406235CrossRefGoogle Scholar
  34. 34.
    Meyer, B., Marx, D., Dulub, O., Diebold, U., Kunat, M., Langenberg,  D., Woell, C. 2004Angew. Chem. Int. Edit.436641Google Scholar
  35. 35.
    Raimondi, F., Wambach, J., Wokaun, A. 2003Phys. Chem. Chem. Phys.54015CrossRefGoogle Scholar
  36. 36.
    B. Meyer and D. Marx, Phys. Rev. B 69 (2004) 235420/1Google Scholar
  37. 37.
    Bromley, S.T., French, S.A., Sokol, A.A., Catlow, C.R.A., Sherwood,  P. 2003J. Phys. Chem. B1077045CrossRefGoogle Scholar
  38. 38.
    Dulub O., Meyer B., Diebold, to be publishedGoogle Scholar
  39. 39.
    Cimino, A., Mazzone, G., Ports, P. 1964Z. Physik. Chem.41154Google Scholar
  40. 40.
    Diebold, U., Koplitz, L.V., Dulub, O. 2004Appl. Surf. Sci.237336CrossRefGoogle Scholar
  41. 41.
    Tasker, P.W. 1979J. Phys., C124977CrossRefGoogle Scholar
  42. 42.
    Noguera, C. 2000J. Phys.: Condensed Matter12R367CrossRefGoogle Scholar
  43. 43.
    Nosker, R.W., Mark, P., Levine, J.D. 1970Surf. Sci.19291CrossRefGoogle Scholar
  44. 44.
    Becker, T., Hovel, S., Kunat, M., Boas, C., Burghaus, U., Wöll,  C. 2001Surf. Sci.486L502Google Scholar
  45. 45.
    Jedrecy, N., Sauvage-Simkin, M., Pinchaux, R. 2000Appl. Surf. Sci.162–16369Google Scholar
  46. 46.
    Göpel, W., Pollmann, J., Ivanov, I., Reihl, B. 1982Phys. Rev. B263144Google Scholar
  47. 47.
    O. Dulub, U. Diebold and G. Kresse, Phys. Rev. Lett. 90 (2003) 016102/1Google Scholar
  48. 48.
    Kresse, G., Dulub, O., Diebold, U. 2003Phys. Rev. B68245409Google Scholar
  49. 49.
    Kunat, M., Girol, S.G., Becker, T., Burghaus, U., Wöll, C. 2002Phys. Rev. B66081402CrossRefGoogle Scholar
  50. 50.
    V. Staemmler, K. Fink, B. Meyer, D. Marx, M. Kunat, S. Gil Girol, U. Burghaus and C. Wöll, Phys. Rev. Lett. 90 (2003) 106102/1Google Scholar
  51. 51.
    Højrup Hansen, K., Worren, T., Stempel, S., Lægsgaard, E., Bäumer,  M., Freund, H.J., Besenbacher, F., Stensgaard, I. 1999Phys. Rev. Lett.834120Google Scholar
  52. 52.
    Worren, T., Højrup Hansen, K., Laegsgaard, E., Besenbacher, F., Stensgaard, I. 2001Surf. Sci.4778CrossRefGoogle Scholar
  53. 53.
    Hansen, P.L., Wagne, J.B., Helveg, S., Rostrup-Nielsen, J.R., Clausen Topsøe, B.S. H. 2002Science2952053CrossRefGoogle Scholar
  54. 54.
    P. Lazcano, P. Häberle, M. Batzill, U. Diebold, to be publishedGoogle Scholar
  55. 55.
    Didziulis, S.V., Butcher, K.D., Cohen, S.L., Solomon, E.I. 1989J. Am. Chem. Soc.1117110CrossRefGoogle Scholar
  56. 56.
    Wöll, C. 2004J. Phys.: Condensed Matter16S2981Google Scholar
  57. 57.
    Komolov, S.A., Lazneva, E.F., Egebjerg, T., Møller, P.J. 1997J. Phys.: Condensed Matter97297CrossRefGoogle Scholar
  58. 58.
    Matsumoto, T., Bennett, R.A., Stone, P., Yamada, T., Domen, K., Bowker, M. 2001Surf. Sci.471225CrossRefGoogle Scholar
  59. 59.
    Jiang, Y., Adams, J.B., Sun, D. 2004J. Phys. Chem. B10812851Google Scholar
  60. 60.
    Vitos, L., Ruban, A.V., Skriver, H.L., Kollar, J. 1998Surf. Sci.411186CrossRefGoogle Scholar
  61. 61.
    B. Meyer and D. Marx, Phys. Rev. B 67 (2003) 035403/1Google Scholar
  62. 62.
    Lenglet, M., Kartouni, K., Machefert, J., Claude, J.M., Steinmetz, P., Beauprez, E., Heinrich, J., Celati, N. 1995Mat. Res. Bull.30393CrossRefGoogle Scholar
  63. 63.
    Wieder, H., Czanderna, A.W. 1962J. Phys. Chem.66816Google Scholar
  64. 64.
    Hapase, M.G., Gharpurey, M.K., Biswas, A.B. 1968Surf. Sci.987CrossRefGoogle Scholar
  65. 65.
    Clarke, E.G.,Jr., Czanderna, A.W. 1975Surf. Sci.49529CrossRefGoogle Scholar
  66. 66.
    Yanase, A., Matsui, H., Tanaka, K., Komiyama, H. 1989Surf. Sci.219L601CrossRefGoogle Scholar
  67. 67.
    Gutierrez-Sosa, A., Crook, S., Haq, S., Lindsay, R., Ludviksson, A., Parker, S., Campbell, C.T., Thornton, G. 1997Faraday Discuss105355Google Scholar
  68. 68.
    Gutierrez-Sosa, A., Evans, T.M., Woodhead, A.P., Lindsay, R., Muryn, C.A., Thornton, G., Yoshihara, J., Parker, S.C., Campbell, C.T., Oldman, R.J. 2001Surf. Sci.4771Google Scholar
  69. 69.
    Lindsay, R., Gutierrez-Sosa, A., Thornton, G., Ludviksson, A., Parker,  S., Campbell, C.T. 1999Surf. Sci.439131CrossRefGoogle Scholar
  70. 70.
    Yasuda, H., Mori, H. 1992Phys. Rev. Lett.693747CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2005

Authors and Affiliations

  1. 1.Department of PhysicsTulane UniversityNew OrleansUSA

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