Atomic and macroscopic reaction rates of a surface-catalyzed reaction

Science

Volumn 278, Issue 5345, 1997, Pages 1931-1934

  Wintterlin, J ^a   Volkening S ^a   Janssens, T V W ^a   Zambelli, T ^a   Ertl, G ^a  

^a FRITZ HABER INSTITUT DER MAX PLANCK GESELLSCHAFT   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; IMAGING; PRIORITY JOURNAL; SCANNING TUNNELING MICROSCOPY; TEMPERATURE DEPENDENCE;

EID: 2642636864     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.278.5345.1931     Document Type: Article

References (33)

1. K. J. Laidler, Chemical Kinetics (Harper & Row, New York, 1987).
2. L. Ruan, F. Besenbacher, I. Stensgaard, E. Lægsgaard, Phys. Rev. Lett. 69, 3523 (1992); F. M. Leibsle, P. W. Murray, S. M. Francis, G. Thornton, M. Bowker, Nature 363, 706 (1993); F. M. Leibsle et al., Phys. Rev. Lett. 72, 2569 (1994); W. W. Crew and R. J. Madix, Surf. Sci. 319, L34 (1994); P. T. Sprunger, Y. Okawa, F. Besenbacher, I. Stensgaard, K. Tanaka, ibid. 344, 98 (1995).
3. L. Ruan, F. Besenbacher, I. Stensgaard, E. Lægsgaard, Phys. Rev. Lett. 69, 3523 (1992); F. M. Leibsle, P. W. Murray, S. M. Francis, G. Thornton, M. Bowker, Nature 363, 706 (1993); F. M. Leibsle et al., Phys. Rev. Lett. 72, 2569 (1994); W. W. Crew and R. J. Madix, Surf. Sci. 319, L34 (1994); P. T. Sprunger, Y. Okawa, F. Besenbacher, I. Stensgaard, K. Tanaka, ibid. 344, 98 (1995).
4. L. Ruan, F. Besenbacher, I. Stensgaard, E. Lægsgaard, Phys. Rev. Lett. 69, 3523 (1992); F. M. Leibsle, P. W. Murray, S. M. Francis, G. Thornton, M. Bowker, Nature 363, 706 (1993); F. M. Leibsle et al., Phys. Rev. Lett. 72, 2569 (1994); W. W. Crew and R. J. Madix, Surf. Sci. 319, L34 (1994); P. T. Sprunger, Y. Okawa, F. Besenbacher, I. Stensgaard, K. Tanaka, ibid. 344, 98 (1995).
5. L. Ruan, F. Besenbacher, I. Stensgaard, E. Lægsgaard, Phys. Rev. Lett. 69, 3523 (1992); F. M. Leibsle, P. W. Murray, S. M. Francis, G. Thornton, M. Bowker, Nature 363, 706 (1993); F. M. Leibsle et al., Phys. Rev. Lett. 72, 2569 (1994); W. W. Crew and R. J. Madix, Surf. Sci. 319, L34 (1994); P. T. Sprunger, Y. Okawa, F. Besenbacher, I. Stensgaard, K. Tanaka, ibid. 344, 98 (1995).
6. L. Ruan, F. Besenbacher, I. Stensgaard, E. Lægsgaard, Phys. Rev. Lett. 69, 3523 (1992); F. M. Leibsle, P. W. Murray, S. M. Francis, G. Thornton, M. Bowker, Nature 363, 706 (1993); F. M. Leibsle et al., Phys. Rev. Lett. 72, 2569 (1994); W. W. Crew and R. J. Madix, Surf. Sci. 319, L34 (1994); P. T. Sprunger, Y. Okawa, F. Besenbacher, I. Stensgaard, K. Tanaka, ibid. 344, 98 (1995).
7. W. W. Crew and R. J. Madix, Surf. Sci. 349, 275 (1996).
8. T. Zambelli, J. Wintterlin, J. Trost, G. Ertl, Science 273, 1688 (1996).
9. In one study about CO oxidation on Cu(110) (3), a kinetic analysis was performed, but the authors had to assume a reaction model (basically a mean-field approximation) because at 400 K, the CO molecules and the reactive O species were not resolved. Also, no temperature variation was performed.
10. T. Engel and G. Ertl, in Advances in Catalysis, D. D. Eley, H. Pines, P. Weisz, Eds. (Academic Press, New York, 1979), vol. 28, pp. 1-78.
11. _, in The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis, D. A. King and J. P. Woodruff, Eds. (Elsevier, Amsterdam, 1982), vol. 4, pp. 73-93.
12. C. T. Campbell, G. Ertl, H. Kuipers, J. Segner, J. Chem. Phys. 73, 5862 (1980).
13. N. R. Avery, Chem. Phys. Lett. 96, 371 (1983).
14. H. Froitzheim, H. Hopster, H. Ibach, S. Lehwald, Appl. Phys. 13, 147 (1977).
15. K.-H. Allers, H. Pfnür, P. Feulner, D. Menzel, J. Chem. Phys. 100, 3985 (1994).
16. J. L. Gland and E. B. Kollin, ibid. 78, 963 (1983).
17. M. Silverberg, A. Ben-Shaul, F. Rebentrost, ibid. 83, 6501 (1985).
18. S. Akhter and J. M. White, Surf. Sci. 171, 527 (1986).
19. M. Xu, J. Liu, F. Zaera, J. Chem. Phys. 104, 8825 (1996).
20. J. Wintterlin, R. Schuster, G. Ertl, Phys. Rev. Lett. 77, 123 (1996).
21. N. D. Lang, Comments Condens. Matter Phys. 14, 253 (1989).
22. J. L. Gland, B. A. Sexton, G. B. Fisher, Surf. Sci. 95, 587 (1980).
23. The dynamics of the system is similar to that of O atoms on Ru(0001) at 300 K, where the fluctuations could be followed in real time (J. Wintterlin et al., Surf. Sci., in press).
24. J. L. Gland and E. B. Kollin, Surf. Sci. 151, 260 (1985).
25. G. Ertl, M. Neumann, K. M. Streit, ibid. 64, 393 (1977).
26. That they appear to display different atomic structures is an imaging artifact caused by an asymmetric tip.
27. The somewhat different appearance of the c(4×2) CO phase in this panel is the result of an intermediate change in imaging conditions of the tunneling tip.
28. The slight increase of the normalized rate was caused by the fact that in the course of the reaction, not only the length but also the shape of the boundary and thereby the average coordination of the oxygen atoms at the (2×2) perimeters changed. This effect can be included in a more precise description of the kinetics by Monte Carlo simulations, which we have also performed. In the present context, the rate increase can be neglected.
29. However, for the finding in the third study (15) - that differently prepared oxygen layers (with the same coverages) display different reactivities at 350 K - we do not have an explanation so far. After heating to 600 K and cooling to 350 K, when the effect was observed in the quoted paper, the oxygen distribution is in equilibrium, according to our data, and should be independent of the preparation.
30. At higher temperatures, or equivalently under low-coverage conditions, both cited kinetic studies (8, 12) reveal much larger activation energies (1.05 and 1.7 eV, respectively), indicating a different reaction mechanism. At low coverages, the adsorbates exhibit larger adsorption energies, so that an increase of the activation energy becomes plausible.
31. H. Conrad, G. Ertl, J. Küppers, Surf. Sci. 76, 323 (1978).
32. M. A. Barteau, E. I. Ko, R. J. Madix, ibid. 104, 161 (1981).
33. J. A. Dumesic, D. F. Rudd, L. M. Aparicia, J. E. Rekoske, A. A. Trivino, The Microkinetics of Heterogeneous Catalysis (American Chemical Society, Washington, DC, 1993).