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Support Effect and Active Sites on Promoted Ruthenium Catalysts for Ammonia Synthesis

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Abstract

The catalytic activities of three supported, barium-promoted ruthenium catalysts for ammonia synthesis are reported. The three supports are silicon nitride (Si3N4), magnesium aluminum spinel (MgAl2O4), and graphitized carbon (C). The effect of the promoter on the activity is strongly dependent on the choice of support material in accordance with several previous observations. Here, this dependence is ascribed to a difference in the affinity of the promoter for the different supports. It is shown how it is possible to image the barium promoter present on the surface of ruthenium crystals in passivated catalysts by conventional high-resolution transmission electron microscopy (HRTEM). By comparison with in situ HRTEM images obtained lately from similar catalysts, and with reference to recent density functional theory (DFT) calculations, we suggest that active B5-type sites on the surfaces of the ruthenium crystals are promoted by nearby promoter atoms via electrostatic interactions.

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References

  1. A. Mittasch, US Patent 1,173,532 (1913).

  2. K. Aika and A. Ozaki, J. Catal. 16 (1970) 97.

    Google Scholar 

  3. K. Aika, H. Hori and A. Ozaki, J. Catal. 27 (1972) 424.

    Google Scholar 

  4. R.M. Elofson and F.F. Gadallah, US Patent 4,142,993 (1979).

  5. K. Aika and K. Tamaru, in: Ammonia: Catalysis and Manufacture, ed. A. Nielsen (Springer, Berlin, 1995), p. 103.

    Google Scholar 

  6. S.R. Tennison, in: Catalytic Ammonia Synthesis, ed. J.R. Jennings (Plenum Press, New York, 1991), p. 303.

    Google Scholar 

  7. L. Forni, D. Molinari, I. Rossetti and N. Pernicone, Appl. Catal. A. 185 (1999) 269.

    Google Scholar 

  8. Z. Kowalczyk, S. Jodzis, W. Raróg, J. Zieliński and J. Pielaszek, Appl. Catal. A 173 (1998) 153.

    Google Scholar 

  9. C.J.H. Jacobsen and S.E. Nielsen, Safety in Ammonia Plants and Related Facilities, AIChE, 2002.

  10. Nitrogen & Methanol, May–June (2002) 34.

  11. H. Bielawa, O. Hinrichsen, A. Birkner and M. Muhler, Angew. Chem. 40 (2001) 1061.

    Google Scholar 

  12. C.J.H. Jacobsen, J. Catal. 200 (2001) 1.

    Google Scholar 

  13. T.W. Hansen, J.B. Wagner, P.L. Hansen, S. Dahl and C.J.H. Jacobsen, Science 294 (2001) 1508.

    Google Scholar 

  14. S. Dahl, A. Logadottir, R.C. Egebjerg, J.H. Larsen, I. Chorkendorff, E. Törnqvist and J.K. Nørskov, Phys. Rev. Lett. 83 (1999) 1814.

    Google Scholar 

  15. S. Dahl, E. Törnqvist and I. Chorkendorff, J. Catal. 192 (2000) 381.

    Google Scholar 

  16. S. Dahl, J. Sehested, C.J.H. Jacobsen, E. Törnqvist and I. Chorkendorff, J. Catal. 192 (2000) 391.

    Google Scholar 

  17. S. Dahl, P.A. Taylor, E. Törnqvist and I. Chorkendorff, J. Catal. 178 (1998) 679.

    Google Scholar 

  18. N.D. Spencer, R.C. Spencer and G.A. Somorjai, J. Catal. 74 (1982) 129.

    Google Scholar 

  19. F. Bozso, G. Ertl and M. Weiss, J. Catal. 50 (1977) 519.

    Google Scholar 

  20. S. Dahl, E. Törnqvist and C.J.H. Jacobsen, J. Catal. 198 (2001) 97.

    Google Scholar 

  21. R. Van Hardeveld and A. Van Montfoort, Surf. Sci. 4 (1966) 396.

    Google Scholar 

  22. C.J.H. Jacobsen, S. Dahl, P.L. Hansen, E. Törnqvist, L. Jensen, H. Topsøe, D.V. Prip, P.B. Møenshaug and I. Chorkendorff, J. Mol. Catal. 163 (2000) 19.

    Google Scholar 

  23. A. Logadottir, T.H. Rod, J.K. Nørskov, B. Hammer, S. Dahl and C.J.H. Jacobsen, J. Catal. 197 (2001) 229.

    Google Scholar 

  24. S. Dahl, A. Logadottir, C.J.H. Jacobsen and J.K. Nørskov, Appl. Catal. A 222 (2001) 19.

    Google Scholar 

  25. J. Dohrup, C.J.H. Jacobsen and C. Olsen, European Patent Appl. 1,013,603 (2000).

  26. B. Fastrup, Cat. Lett. 48 (1997) 111.

    Google Scholar 

  27. J. Sehested, C.J.H. Jacobsen, E. Törnqvist, S. Rokni and P. Stoltze, J. Catal. 188 (1999) 83.

    Google Scholar 

  28. R.F. Egerton, Electron Energy-loss in the Electron Microscope, 2nd ed. (Plenum Press, New York, 1996).

    Google Scholar 

  29. Z. Kowalczyk, S. Jodzis, W. Raróg, J. Zieliński, J. Pielaszek and A. Presz, Appl. Catal. A 184 (1999) 95.

    Google Scholar 

  30. D. Szmigiel, H. Bielawa, M. Kurtz, O. Hinrichsen, M. Muhler, W. Raróg, S. Jodzis, Z. Kowalszyk, L. Znak and J. Zielinski, J. Catal. 205 (2002) 205.

    Google Scholar 

  31. J.J. Mortensen, B. Hammer and J.K. Nørskov, Phys. Rev. Lett. 80 (1998) 4333.

    Google Scholar 

  32. J.J. Mortensen, B. Hammer and J.K. Nørskov, Surf. Sci. 414 (1998) 315.

    Google Scholar 

  33. S. Hagen, R. Barfod, R. Fehrmann, C.J.H. Jacobsen, H.T. Teunissen, K. Ståhl and I. Chorkendorff, Chem. Commun. (2002) 1206.

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Hansen, T.W., Hansen, P.L., Dahl, S. et al. Support Effect and Active Sites on Promoted Ruthenium Catalysts for Ammonia Synthesis. Catalysis Letters 84, 7–12 (2002). https://doi.org/10.1023/A:1021028718491

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