Adsorption of carbon dioxide on Cu(110) and on hydrogen and oxygen covered Cu(110) surfaces

Abstract

The interaction of CO₂ with a clean Cu(110) surface and with pre-adsorbed oxygen and hydrogen on this surface has been studied in ultra-high vacuum at temperatures between 20 and 500 K with temperature programmed thermal desorption, low-energy electron diffraction, Auger electron spectroscopy, high-resolution electron energy loss spectroscopy and work function change measurements. CO₂ adsorbs only molecularly on the clean and on the hydrogen(1×2) and oxygen(2×1) reconstructed Cu(110) surface, respectively. The initial sticking probability of CO₂ is not affected by co-adsorption of oxygen or hydrogen, although the CO₂ adsorption is energetically stabilised in this case by 1.3 and 5.4 kJ mol^-1, respectively. On clean Cu(110), the isosteric heat of adsorption rises with coverage from ∽13 to 25 kJ mol^-1 at saturation. High-resolution electron energy loss spectroscopy suggests that the isolated carbon dioxide molecule is adsorbed in a linear configuration on the clean and on the reconstructed surfaces, while for coverages >0.1 three-dimensional clustering occurs. Our experiments reveal that neither dissociation into oxygen and carbon monoxide nor hydrogenation of carbon dioxide occurs under the experimental conditions.

References

1. G. Ertl, Surf. Sci., 1967, 7, 309.
2. G. C. Chinchen, P. J. Denny, D. G. Parker, M. S. Spencer and D. A. Whan, Appl. Catal., 1987, 30, 333.
3. G. C. Chinchen, M. S. Spencer, K. C. Waugh and D. A. Whan, J. Chem. Soc., Faraday Trans., 1, 1987, 83, 2193.
4. Y. B. Kagan, L. G. Liberov, E. V. Slivinskii, S. M. Loktev, G. L. Lin, A. Y. Rozovskii and A. N. Bashkirov, Dokl. Akad. Nauk. SSSR, 1975, 221, 1093.
5. M. Bowker, R. A. Hadden, H. Houghton, J. N. K. Hyland and K. C. Waugh, J. Catal., 1988, 109, 263.
6. G. C. Chinchen, C. Plant, M. S. Spencer and D. A. Whan, Surf. Sci., 1987, 184, L370.
7. I. E. Wachs and R. J. Madix, Catalysis, 1978, 53, 208.
8. T. Schneider and W. Hirschwald, Catal. Lett., 1992, 14, 197.
9. C. T. Campbell, comment on ref. 8, Catal Lett., 1992, 16, 455.
10. T. Schneider and W. Hirschwald, response to ref. 9, Catal. Lett., 1992, 16, 459.
11. J. Nakamura, J. A. Rodriguez and C. T. Campbell, J. Phys. Condens. Matter, 1989, 1, SB 149.
12. S. S. Fu and G. A. Somorjai, Surf. Sci., 1992, 262, 68.
13. I. A. Bönicke, W. Kirstein and F. Thieme, Surf. Sci., 1994, 307–309, 177.
14. W. Akemann and A. Otto, Surf. Sci., 1993, 287/288, 104.
15. W. Akemann and A. Otto, Surf. Sci., 1992, 272, 211.
16. R. G. Copperthwaite, P. R. Davies, M. A. Morris, M. W. Roberts and R. A. Ryder, Catal. Lett., 1988, 1, 11.
17. R. P. Eischens and W. A. Pliskin, Adv. Catal., 1957, 9, 662.
18. B. Bartos, H.-J. Freund, H. Kuhlenbeck, M. Neumann, H. Lindner and K. Müller, Surf. Sci., 1987, 179, 59.
19. G. Illing, D. Heskett, E. W. Plummer, H.-J. Freund, J. Somers, Th. Lindner, A. M. Bradshaw, U. Buskotte, M. Neumann, U. Starke, K. Heinz, P. L. de Andres, D. Saldin and J. B. Pendry, Surf. Sci., 1988, 206, 1.
20. J. Wambach, G. Illing and H.-J. Freund, Chem. Phys. Lett., 1991, 184, 239.
21. A. Kiennemann, J. Idriss, J. P. Hintermann, J. C. Lavalley, A. Vallet, P. Chaumette and P. Courty, Appl. Catal., 1990, 59, 165.
22. I. Chorkendorf and P. B. Rasmussen, Surf. Sci., 1992, 248, 35.
23. I. Chorkendorf, P. B. Rasmussen, H. Christoffersen and P. A. Taylor, Surf. Sci., 1993, 287/288, 208.
24. P. B. Rasmussen, P. M. Holmblad, H. Christoffersen, P. A. Taylor and I. Chorkendorf, Surf. Sci., 1993, 287/288, 79.
25. P. B. Rasmussen, P. A. Taylor and I. Chorkendorf, Surf. Sci., 1992, 269/270, 352.
26. P. A. Taylor, P. B. Rasmussen, C. V. Ovesen, P. Stoltze and I. Chorkendorf, Surf. Sci., 1992, 261, 191.
27. I. Chorkendorf, P. A. Taylor and P. B. Rasmussen, J. Vac. Sci. Technol., 1992, A10, 2277.
28. P. A. Taylor, P. B. Rasmussen and I. Chorkendorf, J. Vac. Sci. Technol., 1992, A10, 2570.
29. P. B. Rasmussen, M. Kazuta and I. Chorkendorf, Surf. Sci., 1994, 318, 267.
30. K.-H. Ernst, M. Domagala and C. T. Campbell, unpublished results.
31. K.-H. Ernst, C. T. Campbell and G. Moretti, J. Catal., 1992, 134, 66.
32. J. George, P. Zeppenfeld, R. David, M. Büchel and G. Comsa, Surf. Sci., 1993, 289, 201 and references therein.
33. D. Coulman, J. Witterlin, R. J. Behm and G. Ertl, Phys. Rev. Lett., 1990, 64, 1761.
34. J. P. Camplin, S. K. Clowes, J. C. Cook and E. M. McCash, Surf. Rev. Lett., 1997, 4, 1365 and references therein.
35. K. Christmann, Mol. Phys., 1989, 66, 1.
36. D. Schlatterbeck, Diploma thesis, Freie Universität Berlin, 1992.
37. H. Conrad, H. Herz and J. Küppers, J. Phys. E, 1979, 12, 369.
38. R. Unwin, W. Stenzel, A. Garbout and H. Conrad, Rev. Sci. Instrum., 1984, 55, 1809.
39. K. Bange, D. E. Grider, T. E. Madey and J. E. Sass, Surf. Sci., 1984, 136, 38.
40. D. H. S. Ying and R. J. Madix, J. Catal., 1980, 61, 48.
41. M. Bowker and R. J. Madix, Surf. Sci., 1981, 102, 542.
42. F. Henn, J. A. Rodriguez and C. T. Campbell, Surf. Sci., 1990, 236, 282.
43. B. E. Hayden, K. Prince, D. P. Woodruff and A. M. Bradshaw, Surf. Sci., 1983, 133, 589.
44. P. A. Redhead, Vacuum, 1962, 12, 203.
45. J. Topping, Proc. R. Soc. London A, 1927, 114, 67.
46. H. A. Stuart, Molekülstruktur, Verlag von Julius Springer, Berlin, 1934, p. 362.
47. K. Christmann, Introduction to Surface Physical Chemistry, Steinkopff, Darmstadt, 1991.
48. R. Masel, Principles of Adsorption and Reaction on Solid Surfaces, Wiley Series in Chemical Engineering, Wiley & Sons, New York, 1996, and references therein.
49. Physikalisch-Chemisches Taschenbuch, ed. H. Staude, Akadem. Verlagsges. Geest & Portig KG, Leipzig, 1949, vol. II, p. 1186.
50. G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules, Van Nostrand Reinhold Company, New York, 1945, p. 272ff.
51. W. E. Osberg and D. F. Hornig, J. Chem. Phys., 1952, 20, 1345; M. J. Jacox and D. E. Milligan, Spectrochim. Acta, 1961, 17, 1196.
52. A. P. Baddorf, I.-W. Lyo, E. W. Plummer and H. L. Davis, J. Vac. Sci. Technol., 1987, A5, 782.
53. S. Engel, PhD Thesis, Freie Universität Berlin, 1991; S. Engel and K. Christmann, in preparation.
54. H. Ibach and D. L. Mills, Electron Energy Loss Spectroscopy and Surface Vibrations, Academic Press, New York, 1982.
55. K.-H. Ernst and C. T. Campbell, Surf. Sci. Lett., 1991, 259, L736.
56. C. T. Campbell and K.-H. Ernst, in Surface Science of Catalysis, ed. D. J. Dwyer, ACS Symp. Ser. 482, American Chemical Society, Washington, DC, 1992, ch. 8.
57. J. Nakamura, J. M. Campbell and C. T. Campbell, J. Chem. Soc., Faraday Trans., 1990, 86, 2725.
58. C. Harendt, J. Goschnik and W. Hirschwald, Surf. Sci., 1985, 152/153, 453.
59. T. Schneider, Thesis, Freie Universität Berlin, 1990.
60. R. Spitzl, H. Niehus, B. Poelsema and G. Comsa, Surf. Sci., 1990, 239, 243.