Abstract
Gas adsorption on solid surfaces is the basis of heterogeneous catalysis. Gas–surface interactions may be complex and in many cases the fundamental mechanisms of the chemisorption process are hard to discern. The macroscopic kinetics of a heterogeneous catalytic reaction are usually modelled within the Langmuir model1, which assumes that free adsorption sites are occupied at random. The adsorption of oxygen on a platinum (111) surface has been studied extensively as a model system for surface chemical processes generally2,3,4,5,6,7,8,9,10,11,12,13,14,15, owing to its significance in platinum catalysed oxidation reactions such as that of CO and NO. Here we show that even for this well studied system the chemisorption process may be much more complicated than the Langmuir model implies. Our observations with the scanning tunnelling microscope show that the dissociation probability for an oxygen molecule becomes affected by chemisorbed species in the vicinity that have dissociated already. This introduces a dynamic heterogeneity in the adsorption mechanism which leads to kinetically limited ordering of the adsorbate. This effect is likely to be quite general and to affect the bulk kinetics of catalytic reactions conducted at the high temperatures and pressures of most industrial heterogeneous catalysis.
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References
Boudart, M. & Djega-Mariaddassow, G. Kinetics of Heterogeneous Catalytic Reactions (Princeton Univ. Press, (1984)).
Gland, J. L. Molecular and atomic adsorption of oxygen on the Pt(111) and Pt(S)-12(111) × (111) - surfaces. Surf. Sci. 93, 487–514 (1980).
Gland, J. L., Sexton, B. A. & Fisher, G. B. Oxygen interaction with the Pt(111) surface. Surf. Sci. 95, 587–602 (1980).
Campbell, C. T., Ertl, G., Kuipers, H. & Segner, J. Amolecular beam study of the adsorption and desorption of oxygen from a Pt(111) surface. Surf. Sci. 107, 220–236 (1981).
Steininger, H., Lehwald, S. & Ibach, H. Adsorption of oxygen on Pt(111). Surf. Sci. 123, 1–17 (1982).
Avery, N. R. An EELS and TDS study of molecular oxygen desorption and decomposition on Pt(111). Chem. Phys. Lett. 96, 371–373 (1983).
Luntz, A. C., Williams, M. D. & Bethune, D. S. The sticking of O2on a Pt(111) surface. J. Chem. Phys. 89, 4381–4395 (1988).
Williams, M. D., Bethune, D. S. & Luntz, A. C. Coexistence of precursor and direct dynamics: The sticking of O2on a Pt(111) surface. J. Chem. Phys. 88, 2843–2845 (1988).
Winkler, A., Guo, X., Siddiqui, H. R., Hagans, P. L. & Yates, J. J. T. Kinetics and energetics of oxygen adsorption on Pt(111) and Pt(112)—a comparison of flat and stepped surfaces. Surf. Sci. 201, 419–443 (1988).
Luntz, A. C., Grimblot, J. & Fowler, D. E. Sequential precursors in dissociative chemisorption: O2on Pt(111). Phys. Rev. B 39, 12903–12906 (1989).
Wurth, W. et al. Bonding, structure, and magnetism of physisorbed and chemisorbed O2on Pt(111). Phys. Rev. Lett. 65, 2426–2429 (1990).
Rettner, C. T. & Mullins, C. B. Dynamics of the chemisorption of O2on Pt(111): Dissociation via direct population of a molecularly chemisorbed precursor at high incidence kinetic energy. J. Chem. Phys. 94, 1626–1635 (1991).
Puglia, C. et al. Physisorbed, chemisorbed and dissociated O2on Pt(111) studied with different core level spectroscopy methods. Surf. Sci. 342, 119–133 (1995).
Wintterlin, J., Schuster, R. & Ertl, G. Existence of a “hot” atom mechanism for the dissociation of O2on Pt(111). Phys. Rev. Lett. 77, 123–126 (1996).
Artsykhovich, A. N., Ukraintsev, V. A. & Harrison, I. Low temperature sticking and desorption dynamics of oxygen on Pt(111). Surf. Sci. 347, 303–318 (1996).
Stipe, B. C. et al. Single-molecule dissociation by tunneling electrons. Phys. Rev. Lett. 78, 4410–4413 (1997).
Witten, T. A. & Sander, L. M. Diffusion-limited aggregation, a kinetic critical phenomenon. Phys. Rev. Lett. 47, 1400–1403 (1981).
Acknowledgements
The work of T.Z. was supported by the Deutscher Akademischer Austauschdienst (DAAD). Discussions with B.S. Stipe and A. C. Lutz are gratefully acknowledged.
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Zambelli, T., Barth, J., Wintterlin, J. et al. Complex pathways in dissociative adsorption of oxygen on platinum. Nature 390, 495–497 (1997). https://doi.org/10.1038/37329
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DOI: https://doi.org/10.1038/37329
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