Skip to main content
SpringerLink
Log in

Role of Point Defects in the Catalytic Activation of Pd Atoms Supported on the MgO Surface

  • Chapter
Book cover Theoretical Aspects of Heterogeneous Catalysis

Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 8))

Conclusions

The results presented in the previous sections demonstrate the importance of point defects at the surface of oxide materials in determining the chemical activity of deposited metal atoms or clusters. A single Pd atom in fact is not a good catalyst of the cyclization reaction of acetylene to benzene except when it is deposited on a defect site of the MgO(100) surface. A detailed analysis of the reaction mechanism, based on the calculation of the activation barriers for the various steps of the reaction, and of a study of the preferred site for Pd binding, based on the MgO/Pd/CO adsorption properties, has shown that the defects which are most likely involved in the chemical activation of Pd are the oxygen vacancies, or F centers, located at the terraces of the MgO surface and populated by two (neutral F centers) or one (charged paramagnetic F+ centers) electrons.

This combined theoretical-experimental approach shows the potentiality of generating defective surfaces to modify the chemical activity of supported nano-aggregates for catalytic applications. It also shows the importance to obtain an atomistic control on the species deposited on the surface for the proper characterization of their activity. Through a specifically designed experimental apparatus which makes it possible to deposit size-selected metal clusters it has become possible to study the properties of a supported cluster as a function of its size. This opens new, unprecedented perspectives for the understanding of size-dependent activity and selectivity of a supported metal catalyst. To reach this ambitious goal theory plays a role which cannot be overlooked.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Pacchioni, G.; Theory of point defects on ionic oxides, in: The Chemical Physics of Solid Surfaces, (Woodruff, P.; Ed.) Vol. 9, Elsevier: Amsterdam 2001.

    Google Scholar 

  2. Pacchioni, G.; Ricart, J. M.; Illas, F. J. Am. Chem. Soc., 1994, 116, 10152.

    Article  CAS  Google Scholar 

  3. Ferrari, A. M.; Pacchioni, G. J. Phys. Chem. 1995, 99, 17010.

    Article  CAS  Google Scholar 

  4. Scorza, E.; Birkenheuer, U.; Pisani, C. J. Chem. Phys. 1997, 107, 9645.

    Article  CAS  Google Scholar 

  5. Pacchioni, G.; Ferrari, A. M.; Giamello, E. Chem. Phys. Lett. 1996, 255, 58.

    Article  CAS  Google Scholar 

  6. Giamello, E.; Paganini, M. C.; Chiesa, M.; Murphy, D. M.; Pacchioni, G.; Soave, R.; Rockenbauer, A. J. Phys. Chem. B 2000, 104, 1887.

    Article  CAS  Google Scholar 

  7. D’Ercole, A.; Pisani, C.; J. Chem. Phys. 1999, 111, 9743.

    Google Scholar 

  8. Sterrer, M.; Diwald, O.; Knözinger, E. J. Phys. Chem. B 2000, 104, 3601.

    Article  CAS  Google Scholar 

  9. Bogicevic, A.; Jennison, D. R. Surf. Sci. 1999, 437, L741.

    Article  CAS  Google Scholar 

  10. Giamello, E.; Paganini, M. C.; Murphy, D. M.; Ferrari, A. M.; Pacchioni, G. J. Phys. Chem. B 1997, 101, 971.

    Article  CAS  Google Scholar 

  11. Pacchioni, G.; Pescarmona, P. Surf. Sci. 1998, 412/413, 657.

    Article  CAS  Google Scholar 

  12. H.-J. Freund, Angew. Chem. Int. Ed. Engl. 1997, 36, 452.

    Article  Google Scholar 

  13. C. T. Campbell, Surf. Sci. Rep 1997, 27, 1.

    Article  CAS  Google Scholar 

  14. Henry, C. Surf. Sci. Rep. 1998, 31, 231.

    Article  CAS  Google Scholar 

  15. Haas, G.; Menck, A.; Brune, H.; Barth, J. V., Venables, J. A.; Kern, K. Phys. Rev. B 2000, 61, 11105.

    CAS  Google Scholar 

  16. Sanchez, A.; Abbet, S.; Heiz, U.: Schneider. W.-D.; Häkkinen, H.; Barnett, R. N.; Landmann, U. J Phys. Chem. A 1999, 103, 9573.

    Article  CAS  Google Scholar 

  17. Abbet, S.; Sanchez, A.; Heiz, U.; Schneider, W.-D.; Ferrari, A. M.; Pacchioni, G.; Rösch, N. J. Am. Chem. Soc. 2000, 122, 3453.

    Article  CAS  Google Scholar 

  18. Abbet, S.; Sanchez, A.; Heiz, U.; Schneider, W.-D.; Ferrari, A. M.; Pacchioni, G.; Rösch, N., Surf. Sci. 2000, 454/456, 984.

    Article  Google Scholar 

  19. Tysoe, W. T.; Nyberg, G. L.; Lambert, R. M. J. Chem. Soc., Chem. Commun. 1983, 623–625.

    Google Scholar 

  20. Sesselmann, W. S.; Woratschek, B.; Ertl, G.; Kuppers, J.; Haberland, H. Surf. Sci. 1983, 130, 245.

    Article  CAS  Google Scholar 

  21. Holmblad, P. M.; Rainer, D. R.; Goodman, D. W. J. Phys. Chem. B 1997, 101, 8883–8886.

    Article  CAS  Google Scholar 

  22. Abdelrehim, I. M.; Pelhos, K.; Madey, T. E.; Eng, J.; Chen, J. G. J. Mol Catal. A 1998, 131, 107.

    CAS  Google Scholar 

  23. Gentle, T. M.; Muetterties, E. L. J. Phys. Chem. 1983, 87, 2469–2472.

    Article  CAS  Google Scholar 

  24. Rucker, T. G.; Logan, M. A.; Gentle. T. M.; Muetterties, E. L.; Somorjai, G. A. J. Phys. Chem. 1986, 90, 2703.

    Article  CAS  Google Scholar 

  25. Hoffmann, H.; Zaera, F.; Ormerod, R. M.; Lambert, R. M.; Yao, J. M.; Saldin, D. K., Wang, L. P., Bennett, D. W.; Tysoe, W. T. Surf. Sci. 1992, 268, 1.

    Article  CAS  Google Scholar 

  26. Patterson, C. H.; Lambert, R. M. J. Am. Chem. Soc. 1988, 110, 6871.

    CAS  Google Scholar 

  27. Ormerod, R. M.; Lambert, R. M. J. Phys. Chem. 1992, 96, 8111–8116.

    Article  CAS  Google Scholar 

  28. Ormerod, R. M.; Lambert, R. M.; Hoffmann, H.; Zaera, F., Yao. J. M.; Saldin. D. K.; Wang, L. P.; Bennet, D. W.; Tysoe, W. T. Surf. Sci. 1993, 295, 277.

    Article  CAS  Google Scholar 

  29. Pacchioni, G.; Lambert, R. M Surf. Sci. 1994, 304, 208–222.

    Article  CAS  Google Scholar 

  30. Abbet, S.; Sanchez, A.; Heiz, U.; Schneider, W-D., J. Catal. 2001, 198, 122.

    Article  CAS  Google Scholar 

  31. Becke, A.D. Phys. Rev. A 1988, 38, 3098.

    Article  CAS  Google Scholar 

  32. Perdew, J.P. Phys. Rev. 1986, 33, 8622; ibidem 1986, 34, 7406.

    Google Scholar 

  33. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.

    CAS  Google Scholar 

  34. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.

    CAS  Google Scholar 

  35. Pacchioni, G.; Bagus, P.S.; Parmigiani, F. Eds., Cluster Models for Surface and Bulk Phenomena, NATO ASI Series B, Vol. 283, Plenum Press: New York, 1992.

    Google Scholar 

  36. Pacchioni, G.; Ferrari, A. M.; Marquez, A. M.; Illas, F. J. Comp. Chem. 1997, 18, 617.

    CAS  Google Scholar 

  37. Wyckoff, R. W. G. Crystal Structures, 2nd ed., Interscience Publisher: New York, 1965.

    Google Scholar 

  38. Yudanov, I. V.; Nasluzov, V. A.; Neyman, K. M.; Rösch, N. Int. J. Quant. Chem. 1997, 65, 975.

    Article  CAS  Google Scholar 

  39. Nygren, M. A.; Pettersson, L. G. M.; Barandiaran, Z.; Seijo, L. J. Chem. Phys. 1994, 100, 2010.

    Article  CAS  Google Scholar 

  40. Gaussian98, Frisch, M.J. et al., Gaussian Inc.: Pittsburgh, PA, 1998.

    Google Scholar 

  41. Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553.

    Google Scholar 

  42. Lopez, N.; Illas, F.; Rösch, N.; Pacchioni, G. J. Chem. Phys. 1999, 110, 4873.

    Article  CAS  Google Scholar 

  43. Musolino, V.; Selloni, A.; Car, R. J. Chem. Phys. 1998, 108, 5044.

    Article  CAS  Google Scholar 

  44. Lopez, N.; Illas, F. J. Phys. Chem. 1998, 102, 1430.

    CAS  Google Scholar 

  45. Ferrari, A. M.; Xiao, C; Neyman, K.; Pacchioni, G.; Rösch, N. Phys. Chem. Chem. Phys. 1999, 1, 4655.

    Article  CAS  Google Scholar 

  46. Flank, A. M.; Delanay, R.; Legarde, P.; Pompa, M.; Jupille, J. Phys. Rev. B 1996, 53, R1737.

    Article  CAS  Google Scholar 

  47. Matveev, A. V.; Neyman, K. M.; Yudanov, I. V.; Rösch, N. Surf. Sci. 1999, 426, 123.

    Article  CAS  Google Scholar 

  48. Goellner, J. F.; Neyman, K. M.; Mayer, M.; Nörtemann, F.; Gates, B. C.; Rösch, N. Langmuir 2000, 16, 2736.

    Article  CAS  Google Scholar 

  49. Dewar, M. J. S. Bull. Soc. Chem. Fr. 1951, 18, C71.

    Google Scholar 

  50. Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2939.

    Google Scholar 

  51. Bagus, P.S.; Nelin, C.J.; Bauschlicher, C. W. J. Chem. Phys. 1984, 80, 4378.

    Article  CAS  Google Scholar 

  52. Bagus, P. S.; Illas, F. J. Chem. Phys. 1992, 96, 8962.

    CAS  Google Scholar 

  53. Pacchioni, G. Surf. Rev. & Letters 2000, 7, 277.

    CAS  Google Scholar 

  54. Paganini, M. C.; Chiesa, M.; Giamello, E.; Coluccia, S.; Martra, G.; Murphy, D. M.; Pacchioni, G. Surf. Sci. 1999, 421, 246.

    Article  CAS  Google Scholar 

  55. Ojamäe, L.; Pisani, C. J. Chem. Phys. 1998, 109, 10984.

    Google Scholar 

  56. Wichtendahl, R.; Rodriguez-Rodrigo, M.; Härtel, U.; Kuhlenbeck, H.; Freund, H. J. Surf. Sci. 1999, 423, 90.

    Article  CAS  Google Scholar 

  57. Kantorovich, L.N.; Holender, J. M.; Gillan, M. J. Surf. Sci. 1995, 343, 221.

    Article  CAS  Google Scholar 

  58. Ferrari, A. M.; Pacchioni, G. J. Phys. Chem. 1996, 100, 9032.

    Article  CAS  Google Scholar 

  59. Di Valentin C.; Pacchioni, G. to be published.

    Google Scholar 

  60. Hardesty, J. H.; Koerner, J. B.; Albright, T. A.; Le, G. Y. J. Am. Chem. Soc. 1999, 121, 6055.

    Article  CAS  Google Scholar 

  61. Abbet, S.; Riedo, E.; Brune, H.; Heiz, U.; Ferrari, A.M.; Giordano, L.; Pacchioni, G.; to be published.

    Google Scholar 

  62. Herzberg, G. Molecular Spectra and Molecular Structure, Vol. 1, Van Nostrand: Princeton, 1950.

    Google Scholar 

  63. Frank, M., Bäumer, M., Kühnemuth, R., Freund, H.-J., J Phys. Chem B, submitted.

    Google Scholar 

  64. Liang, B., Zhou, M., Andrews, L. J. Phys. Chem. A 2000, 104, 3905.

    CAS  Google Scholar 

  65. Tremblay, B.; Manceron, L., Chem. Phys. 1999, 250, 187.

    Article  CAS  Google Scholar 

  66. Kündig E.P., McIntosh, D., Moskovits, M., Ozin, G.A. J. Am. Chem. Soc. 1973, 95, 7234.

    Google Scholar 

  67. Darling, J.H., Ogden, J.S., J. Chem. Soc., Dalton Tram 1973, 1079.

    Google Scholar 

  68. Yudanov, I. V.; Vent, S.; Neyman, K.; Pacchioni, G.; Rösch, N. Chem. Phys. Lett. 1997, 275, 245.

    Article  CAS  Google Scholar 

  69. Goniakovski, J. Phys. Rev. B 1998, 58, 1189.

    Google Scholar 

  70. Nygren, M. A.; Pettersson, L. G. M. J. Chem. Phys. 1996, 105, 9339.

    Article  CAS  Google Scholar 

  71. Neyman, K. M.; Vent, S.; Pacchioni, G.; Rösch, Nuovo Cimento 1997, 19D, 1743.

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, and Istituto Nazionale per la Fisica della Materia, via R. Cozzi, 53-I-20125, Milano, Italy

    G. Pacchioni & L. Giordano

  2. Dipartimento di Chimica IFM, Università di Torino, via P. Giuria 5, I-10125, Torino, Italy

    A. M. Ferrari

  3. Institute of Surface Chemistry and Catalysis, University of Ulm, D-89069, Ulm, Germany

    S. Abbet & U. Heiz

Authors
  1. G. Pacchioni
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. Giordano
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. M. Ferrari
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Abbet
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. U. Heiz
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Harvard University, Cambridge, MA, USA

    W. N. Lipscomb

  2. Université Libre de Bruxelles, Belgium

    I. Prigogine

  3. Laboratoire de Chimie Physique, Paris, France

    J. Maruani

  4. Rutherford Appleton Laboratory, Oxfordshire, UK

    S. Wilson

  5. Royal Institute of Technology, Stockholm, Sweden

    H. Ågren

  6. Hebrew University of Jerusalem, Israel

    D. Avnir

  7. Florida State University, Tallahassee, FL, USA

    J. Cioslowski

  8. European Academy of Sciences, Paris, France

    R. Daudel

  9. Universität Würzburg, Am Hubland, Germany

    E. K. U. Gross

  10. ETH-Zentrum, Zürich, Switzerland

    W. F. van Gunsteren

  11. University of Tokyo, Japan

    K. Hirao

  12. Komensky University, Bratislava, Slovakia

    I. Hubač

  13. Tulane University, New Orleans, LA, USA

    M. P. Levy

  14. Simon Fraser University, Burnaby, BC, Canada

    G. L. Malli

  15. Università di Pisa, Italy

    R. McWeeny

  16. University of Saskatchewan, Saskatoon, SK, Canada

    P. G. Mezey

  17. Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil

    Marco Antonio Chaer Nascimento

  18. Polish Academy of Sciences, Poznan, Poland

    J. Rychlewski

  19. Yeshiva University, Bronx, NY, USA

    S. D. Schwartz

  20. Instituto de Estructura de la Materia, Madrid, Spain

    Y. G. Smeyers

  21. Cancer Research Center, Heidelberg, Germany

    S. Suhai

  22. Uppsala University, Sweden

    O. Tapia

  23. University of California, La Jolla, CA, USA

    P. R. Taylor

  24. Nottingham Trent University, UK

    R. G. Woolley

Rights and permissions

Reprints and permissions

Copyright information

© 2001 Kluwer Academic Publishers

About this chapter

Cite this chapter

Pacchioni, G., Giordano, L., Ferrari, A.M., Abbet, S., Heiz, U. (2001). Role of Point Defects in the Catalytic Activation of Pd Atoms Supported on the MgO Surface. In: Lipscomb, W.N., et al. Theoretical Aspects of Heterogeneous Catalysis. Progress in Theoretical Chemistry and Physics, vol 8. Springer, Dordrecht. https://doi.org/10.1007/0-306-47667-3_7

Download citation

  • DOI: https://doi.org/10.1007/0-306-47667-3_7

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-1-4020-0127-7

  • Online ISBN: 978-0-306-47667-9

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation