Skip to main content
SpringerLink
Log in

Mechanisms and Intermediates of Metal Surface Reactions: Bond-Order Conservation Viewpoint

  • Chapter
Theoretical Aspects of Heterogeneous Catalysis

Part of the book series: Van Nostrand Reinhold Catalysis Series ((NRECSES))

  • 193 Accesses

Abstract

Heterogeneous catalysis was and remains one of the most empirical chemical endeavors. Catalyst development is still a domain of predominantly Edisonian research, a matter of trial-and-error efforts, intuitive assessments, and a great deal of luck. The reason for this is that the course of a catalytic reaction is determined by many factors, both thermo-dynamic and kinetic, and the composition and structure of a catalyst may be crucial as well. In this complex chain of events, there is one link that is common and critical for all the variety of catalytic processes. This link is chemisorption. Whatever the mechanism of a heterogeneous catalytic reaction may be, it includes chemisorption, transformations of chemi-sorbed species (dissociation, recombination, isomerization, etc.) and, finally, their desorption.1–3 Thus, understanding heterogeneous catalysis is impossible without the knowledge of chemisorption patterns and, ultimately, the reaction energy profiles. What is the state of affairs in these quarters?

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 39.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 54.99
Price excludes VAT (USA)
  • Compact, lightweight 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. Somorjai, G.A., Chemistry in Two Dimensions: Surfaces. Ithaca, New York: Cornell University Press, 1981.

    Google Scholar 

  2. King, D.A., Woodruff, D.P. (eds.), The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis. Amsterdam: Elsevier, Vol. 2, 1983; Vol. 3, 1984; Vol. 4, 1982.

    Google Scholar 

  3. Anderson, J.R., Boudart, M. (eds.), Catalysis: Science and Technology. West Berlin: Springer-Verlag, Vol. 3, 1982; Vol. 4, 1983, Vol. 5, 1984.

    Google Scholar 

  4. Rhodin, T.N., Ertl, G. (eds.), The Nature of the Surface Chemical Bond. Amsterdam: North-Holland, 1979.

    Google Scholar 

  5. Smith, J.R. (ed.), Theory of Chemisorption. West Berlin: Springer-Verlag, 1980.

    Google Scholar 

  6. Veillard, A. (ed.), Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series. Dordrecht: Reidel, 1986. (b) Sauer, J., Chem. Rev. 89: 199 (1989).

    Google Scholar 

  7. Arlinghaus, F.J., Gay, J.G., Smith, J.R., in Ref. 2, Chap. 4.

    Google Scholar 

  8. Feibelman, P.J., Phys. Rev. B 35: 2626 (1987). (b) Feibelman, P.J., Hamann, D.R., Surf. Sci. 182: 411 (1987).

    Article  CAS  Google Scholar 

  9. Soukiassian, P., Rivan, R., Lecant, J., Wimmer, E., Chubb, S.R., Freeman, A.J., Phys. Rev. B 31: 4911 (1985). (b) Freeman, A.J., Fu, C.L., Wimmer, E., J. Vac. Sci. Technol. A 4: 7265 (1986). (c) Chubb, S.R., Wimmer, E., Freeman, A.J., Hiskes, J.R., Karo, A.M., J. Vac. Sci. Technol. B 36: 4112 (1987).

    Article  CAS  Google Scholar 

  10. Baetzold, R.C., Solid State Commun. 44: 781 (1982). (b) Baetzold, R.C., J. Am. Chem. Soc. 105: 4271 (1983). (c) Baetzold, R.C., Phys. Rev. B 29: 4211 (1984). (d) Baetzold, R.C., Phys. Rev. B 30: 6870 (1984). (e) Baetzold, R.C., Surf Sci. 150: 193 (1985). (f) Baetzold, R.C., J. Chem. Phys. 82: 5729 (1985). (g) Baetzold, R.C., Langmuir 3: 189 (1987).

    Article  CAS  Google Scholar 

  11. Shustorovich, E., Solid State Commun. 44: 567 (1982). (b) Shustorovich, E.,7. Phys. Chem. 88: 1927, 3490 (1984).

    Article  CAS  Google Scholar 

  12. Shustorovich, E., Baetzold, R., Muetterties, E.L., J. Phys. Chem. 87: 1100 (1983).

    Article  CAS  Google Scholar 

  13. For an excellent analysis of theoretical issues of chemisorption, see: Einstein, T.L., Hertz, J.A., and Schrieffer, J.R., in Ref. 5, Chap. 7.

    Google Scholar 

  14. Einstein, A., Ideas and Opinions. New York: Crown Publishers, Inc., 1982, pp. 274, 292.

    Google Scholar 

  15. Shustorovich, E., Surf. Sci. Repts. 6: 1 (1986). (b) Shustorovich, E., Acc. Chem. Res. 21: 183 (1988). (c) Shustorovich, E., J. Mol. Catal. 54: 301 (1989).

    Article  CAS  Google Scholar 

  16. Shustorovich, E. Adv. Catal. 37 (1990).

    Google Scholar 

  17. Shustorovich, E., J. Am. Chem. Soc. 106: 6479 (1984). (b) Shustorovich, E., Surf. Sci. 150: L115 (1985). (c) Shustorovich, E., Surf. Sci. 163: L645 (1985). (d) Shustorovich, E., Surf. Sci. 163: L730 (1985). (e) Shustorovich, E., Surf Sci. 175: 561 (1986). (f) Shustorovich, E., Surf. Sci. 176: L863 (1986). (g) Shustorovich, E., Surf Sci. 181: L205 (1987). (h) Shustorovich, E., Surf Sci. 187: L627 (1987). (i) Shustorovich, E., Surf Sci. 205: 336 (1988). (j) Shustorovich, E., J. Phys. Chem. (in press).

    Article  CAS  Google Scholar 

  18. Shustorovich, E., Bell, A.T., J. Catal. 113: 341 (1988). (b) Shustorovich, E., Bell, A.T., Surf. Sci. 205: 492 (1988). (c) Shustorovich, E., Bell, A.T., Surf Sci. 222: 371 (1989). (d) Bell, A.T., Shustorovich, E., J. Catal. 121: 1 (1990).

    Article  CAS  Google Scholar 

  19. See, for instance, (a) Abel, G.C., Phys. Rev. B 31: 6184 (1985). (b) Skriver, H.L., Phys. Rev. B 31: 1909 (1985). (c) Haydock, R., Philos. Mag. 35: 845 (1977); 38: 155 (1978).

    Article  Google Scholar 

  20. Rose, J.H., Smith, J.R., Ferrante, J., Phys. Rev. B 28: 1835 (1983). (b) Rose, J.H., Smith, J.R., Guinea, F., Ferrante, J., Phys. Rev. B 29: 2963 (1984). (c) Ferrante, J., Smith, J.R., Phys. Rev. B 31: 3427 (1985).

    Article  CAS  Google Scholar 

  21. Morse, P.M., Phys. Rev. 34: 57 (1929).

    Article  CAS  Google Scholar 

  22. Johnston, H.S., Parr, C., J. Am. Chem. Soc. 85: 2544 (1963). (b) Marcus, R.A., J. Phys. Chem. 72: 891 (1968).

    Article  CAS  Google Scholar 

  23. See, for instance, (a) Wolfe, S., Mitchell, D.J., Schlegel, H.B., J. Am. Chem. Soc. 103: 7692, 7694 (1981). (b) Dunning, T.H., Jr., Harding, L.B., Bair, R.A., Eades, R.A., Shepard, R.L., J. Phys. Chem. 90: 344 (1986).

    Article  CAS  Google Scholar 

  24. Dunitz, J.D., X-ray Analysis and the Structure of Organic Molecules. Ithaca, New York: Cornell University Press, 1979, pp. 341–360.

    Google Scholar 

  25. For coverage effects, there will be another form of BOC.17c,17e

    Google Scholar 

  26. Van Hove, M.A., in Ref. 3, Chap. 4. (b) Somorjai, G.A., Van Hove, M.A., Struct. Bonding (West Berlin) 38: 1 (1979).

    Google Scholar 

  27. For a recent review, see, (a) Hoffmann, F.M., Surf Sci. Rep. 3: 107 (1983). (b) Biberian, J.P., Van Hove, M.A., Surf Sci. 118: 443 (1982); 138: 361 (1984).

    Article  CAS  Google Scholar 

  28. Hayden, B.E., Bradshaw, A.M., Surf Sci. 125: 787 (1983). (b) Mieher, W.D., Whitman, L.J., Ho, W., J. Chem. Phys. 91: 3228 (1989).

    Article  CAS  Google Scholar 

  29. Gurney, B.A., Richter, L.J., Villarubia, J.S., Ho, W., J. Chem. Phys. 87: 6710 (1987). (b) Raval, R., Parker, S.F., Pemble, M.E., Hollins, P., Pritchard, J., Chesters, M.A., Surf Sci. 203: 353 (1988).

    Article  CAS  Google Scholar 

  30. Bauhofer, J., Hock, M., Küppers, J., Surf Sci. 191: 395 (1987). (b) Andersson, S., Solid State Commun. 21: 75 (1977). (c) Tang, S.L., Lee, M.B., Yang, Q.Y., Beckerle, J.D., Ceyer, S.T., J. Chem. Phys. 84: 1876 (1986).

    Article  CAS  Google Scholar 

  31. However, there is a definitive correlation between n and the C-0 stretching frequency,27a which can also be explained by our model.15a, l7d

    Google Scholar 

  32. Shinn, N.D., Madey, T.E., J. Chem. Phys. 83: 5928 (1985). (b) Benndorf, C.N., Kruger, B., Thieme, F., Surf. Sci. 163: L675 (1985). (c) Fulmer, J.P., Zaera, F., Tysoe, W.T., J. Chem. Phys. 87: 7265 (1987).

    Article  CAS  Google Scholar 

  33. Campbell, C.T., Ertl, G., Kuipers, H., Segner, J., Surf Sci. 107: 220 (1981).

    Article  CAS  Google Scholar 

  34. Bagus, P.S., Bauschlicher, C.W., Nelin, C.J., Laskovski, B.C., Seel, M., J. Chem. Phys. 81: 3594 (1984).

    Article  CAS  Google Scholar 

  35. Reference 15a, Table 10, p. 25.

    Google Scholar 

  36. Anderson, A.B., Awad, M.K., J. Am. Chem. Soc. 107: 7854 (1985). (b) Mehandru, S.P., Anderson, A.B., Surf Sci. 169: L281 (1986). (c) Kang, D.B., Anderson, A.B., Surf Sci. 155: 639 (1985).

    Article  CAS  Google Scholar 

  37. Tomanek, D., Bennemann, K.H., Surf Sci. 127: L111 (1983).

    Article  CAS  Google Scholar 

  38. Ertl, G., in Ref. 4, Chap. 5, Tables 5.3 and 5.5.

    Google Scholar 

  39. Broden, G., Gafner, G., Bonzel, H.P., Appl. Phys. 13, 333 (1977). (b) Erickson, J.W., Estrup, P.J., Surf. Sci. 167: 519 (1986). (c) Umbach, E., Menzel, D., Surf. Sci. 135: 199 (1983).

    Google Scholar 

  40. CRC Handbook of Chemistry and Physics. Boca Raton, Florida: CRC Press, 1984-1985, pp. F171-190.

    Google Scholar 

  41. Ertl, G., in Ref. 3, Vol. 5, Chap. 3, pp. 238–250.

    Google Scholar 

  42. Weinberg, W.H., Surf. Sci. 128: L224 (1983).

    Article  CAS  Google Scholar 

  43. Bowker, M., Barteau, M.A., Madix, R.J., Surf. Sci. 92: 528 (1980).

    Article  CAS  Google Scholar 

  44. Engstrom, J.R., Weinberg, W.H., Phys. Rev. Lett. 55: 2017 (1985).

    Article  CAS  Google Scholar 

  45. Goodman, D.W., Peebles, D.E., White, J.M., Surf. Sci. 140: L239 (1984).

    Article  CAS  Google Scholar 

  46. Peled, H., Asscher, M., Surf Sci. 183: 201 (1987).

    Article  CAS  Google Scholar 

  47. Root, T.W., Schmidt, L.D., Fisher, G.B., Surf. Sci. 134: 30 (1983).

    Article  CAS  Google Scholar 

  48. Ho, P., White, J.M., Surf. Sci. 137: 103 (1984). (b) Ho, W., J. Phys. Chem. 91: 766 (1987).

    Article  CAS  Google Scholar 

  49. Comrie, CM., Weinberg, W.H., Lambert, R.M., Surf. Sci. 57: 619 (1976).

    Article  CAS  Google Scholar 

  50. Vajo, J.J., Tsai, W., Weinberg, W.H., J. Phys. Chem. 89: 3243 (1985).

    Article  CAS  Google Scholar 

  51. For an earlier review, see, (a) Ponec, V., Catal. Rev. 18: 151 (1978). (b) Bell, A.T., Catal. Rev. 23: 23 (1981). (c) Biloen, P., Sachtier, W.M.H., Adv. Catal. 30: 165 (1981). (d) Vannice, M.A., in Ref. 3, Vol. 3, Chap. 3.

    Article  CAS  Google Scholar 

  52. Goodman, D.W., Acc. Chem. Res. 17: 194 (1984). (b) Goodman, D.W., Kelly, R.D., Madley, T.E., White, J.M., J. Catal. 64: 479 (1980). (c) Campbell, C.T., Goodman, D.W., Surf. Sci. 123: 413 (1984).

    Article  CAS  Google Scholar 

  53. Yates, J.T., Jr., Gates, S.M., Russell, J.M., Jr., Surf. Sci. 164: L839 (1985).

    Article  CAS  Google Scholar 

  54. Similar to CO hydrogénation on Ru(001): Hoffmann, F.M., Robbins, J.L., Electr. Spect. Rel. Phen. 45: 421 (1987). (b) Hoffmann, F.M., Robbins, J.L., in Proceedings, 9th International Congress on Catalysis (M.J. Philips and M. Ternan, eds.). Ottawa, The Chemical Institute of Canada, 1988, Vol. 3, p. 1144; Vol. 5, p. 373.

    Google Scholar 

  55. Ryndin, Y.A., Hicks, R.F., Bell, A.T., Yermakov, Y.I., J. Catal. 80: 287 (1981). (b) Berlowitz, P.J., Goodman, D.W., J. Catal. 108: 364 (1987).

    Article  Google Scholar 

  56. Poutsma, M.L., Elek, L.F., Ibaria, P.A., Risch, A.P., Rabo, J.A., J. Catal. 52: 168 (1978). (b) Fajula, F., Anthony, R.G., Lansford, J.H., J. Catal. 73, 237 (1982). (c) Kikuzono, Ya., Kagami, S., Naito, S., Onishi, T., Tamaru, K., Disc. Faraday Soc. 72: 735 (1981).

    Article  Google Scholar 

  57. Ho, S.V., Harriott, P., J. Catal. 64: 272 (1980). (b) Wang, S.-Y., Moon, S.H., Vannice, M.A., J. Catal. 71: 167 (1981). (c) Rieck, J.S., Bell, A.T., J. Catal. 96: 88 (1985); 99: 262 (1986). (d) Mori, T., Miyamoto, A., Niizuma, H., Takahashi, N., Hattori, T., Murakami, Y., J. Phys. Chem. 90: 109 (1986), and references therein.

    Article  CAS  Google Scholar 

  58. Hsu, D.S.Y., Lin, M.C, J. Chem. Phys. 88: 432 (1988). (b) Hsu, D.S.Y., Hoffbauer, M.A., Lin, M.C, Langmuirl: 302 (1986). (c) Selwyn, G.S., Lin, M.C, Chem. Phys. 67: 213 (1982). (d) Selwyn, G.S., Fujimoto, G.T., Lin, M.C, J. Phys. Chem. 86: 760 (1982).

    Article  CAS  Google Scholar 

  59. Reference 51c. (b) Rofer-DePoorter, C.K., Chem. Rev. 81: 447 (1981). (c) Broden, G., Rhodin, T.N., Bruker, C, Benbow, R., Hurych, Z., Surf. Sci. 59: 593 (1976).

    Google Scholar 

  60. Asscher, M., Kao, C.-T., Somorjai, G.A.,J. Phys. Chem. 92: 2711 (1988). (b) Pirner, M., Bauer, R., Borgmann, D., Wedler, G., Surf. Sci. 189/190: 147 (1987). (c) Kwong, D.W.J., DeLeon, N., Haller, G.L., Chem. Phys. Lett. 144: 533 (1988).

    Article  CAS  Google Scholar 

  61. Hall, R.B., J. Phys. Chem. 91: 1007 (1987). (b) Ho, W., J. Phys. Chem. 91: 766 (1987). (c) Seebauer, E.G., Kong, A.C.F., Schmidt, L.D., Surf. Sci. 193: 417 (1988).

    Article  CAS  Google Scholar 

  62. See, for example, (a) Vannice, M.A., Twu, C.C., J. Catal. 18: 213 (1983). (b) Stoltze, P., orskov, J.K., J. Catal. 110: 1 (1988).

    Article  Google Scholar 

  63. Sinfelt, J.H., J. Phys. Chem. 90: 4711 (1986).

    Article  CAS  Google Scholar 

  64. See also previous reviews: (a) Muetterties, E.L., Chem. Soc. Rev. 11: 283 (1982). (b) Koestner, R.J., Van Hove, M.A., Somorjai, G.A., J. Phys. Chem. 87: 203 (1983). (c) Bertolini, J.C., Massardier, J., in Ref. 2, Vol. 3, Chap. 3. (d) Davis, S.M., Somorjai, G.A., in The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis (D.A. King and D.P. Woodruff, eds.). New York: Elsevier, 1982, Vol. 4., p. 217.

    Article  CAS  Google Scholar 

  65. Gavezzotti, A., Simonetta, M., Surf. Sci. 99: 453 (1980). (b) Simonetta, M., Gavez-zotti, A., J. Mol. Struct. 107: 75 (1984).

    Article  CAS  Google Scholar 

  66. Minot, C., Van Hove, M.A., Somorjai, G.A., Surf Sci. 127: 441 (1983). (b) Silvestre, J, Hoffmann, R., Langmuir 1: 621 (1985).

    Article  CAS  Google Scholar 

  67. Parmeter, J.E., Hills, M.M., Weinberg, W.H.,J. Am. Chem. Soc. 108: 3563 (1986); 109: 72 (1987).

    Article  CAS  Google Scholar 

  68. Jacob, P., Cassuto, A., Menzel, D., Surf. Sci. 187: 407 (1987).

    Article  Google Scholar 

  69. Hills, M.M., Parmeter, J.E., Weinberg, W.H., J. Am. Chem. Soc. 109, 597 (1987).

    Article  CAS  Google Scholar 

  70. Ibach, H., Lehwald, S., J. Vac. Sci. Technol. 15: 407 (1978).

    Article  CAS  Google Scholar 

  71. Wang, P.-K., Slichter, C.P., Sinfelt, J.H., Phys. Rev. Lett. 53: 82 (1984). (b) Wang, P.-K., Slichter, C.P., Sinfelt, J.H., J. Phys. Chem. 89: 3606 (1985). (c) Wang, P.-K., Ansermet, J.-P., Rudaz, S.L., Wang, Zh., Shore, S., Slichter, C.P., Sinfelt, J.H., Science 234: 35 (1986).

    Article  CAS  Google Scholar 

  72. For example, the gas-phase activation barrier for CH2C→HCH is close to zero: Carrington, T., Jr., Hubbard, L.M., Schaefer, H.F., III, Miller, W.H., J. Chem. Phys. 80: 4347 (1984), and references therein.

    Google Scholar 

  73. Salmeron, M., Somorjai, G.A., J. Phys. Chem. 86: 341 (1982).

    Article  CAS  Google Scholar 

  74. Tysoe, W.T., Nyberg, G.L., Lambert, R.M., J. Phys. Chem. 88: 1960 (1984).

    Article  CAS  Google Scholar 

  75. Hills, M.M., Parmeter, J.E., Mullins, C.B., Weinberg, W.H., J. Am. Chem. Soc. 108: 3554 (1986).

    Article  CAS  Google Scholar 

  76. Zuhr, R.A., Hudson, J.B., Surf. Sci. 66: 405 (1977).

    Article  CAS  Google Scholar 

  77. Whitman, L.J., Richter, L.J., Gurney, B.A., Villarrubia, J.S., Ho, W., J. Chem. Phys. 90: 2050 (1989).

    Article  CAS  Google Scholar 

  78. Semancik, S., Estrup, P.J., Surf Sci. 104: 261 (1981).

    Article  Google Scholar 

  79. Ogle, K.M., Creighton, J.R., Akhter, S., White, J.M., Surf Sci. 169: 246 (1986).

    Article  CAS  Google Scholar 

  80. Greenlief, CM., Radloff, P.L., Zhou, X.-L., White, J.M., Surf Sci. 191: 93 (1987).

    Article  CAS  Google Scholar 

  81. See a discussion in Stuve, E.M., Madix, R.J., J. Phys. Chem. 89: 105 (1985).

    Article  CAS  Google Scholar 

  82. Beebe, T.B., Jr., Yates, J.T., Jr., J. Phys. Chem. 91: 254 (1987).

    Article  CAS  Google Scholar 

  83. Zhu, X.-Y., White, J.M., Surf Sci. 214: 240 (1989). (b) Lapinski, M.P., Ekerdt, J.G., J. Phys. Chem. 92: 1708 (1988).

    Article  CAS  Google Scholar 

  84. Anderson, K.G., Ekerdt, J.G., J. Catal. 116: 556 (1989).

    Article  CAS  Google Scholar 

  85. Seip, U., Tsai, M.-C, Küppers, J., Ertl, G., Surf Sci. 147: 65 (1984).

    Article  CAS  Google Scholar 

  86. Stroscio, J.A., Bare, S.R., Ho, W., Surf Sci. 148: 499 (1984).

    Article  CAS  Google Scholar 

  87. See, for example, Peterson, R.J., Hydrogénation Catalysts. Park Ridge, NJ: Noyes Data Corp., 1977.

    Google Scholar 

Download references

Authors
  1. Evgeny Shustorovich
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

Copyright information

© 1990 Van Nostrand Reinhold

About this chapter

Cite this chapter

Shustorovich, E. (1990). Mechanisms and Intermediates of Metal Surface Reactions: Bond-Order Conservation Viewpoint. In: Theoretical Aspects of Heterogeneous Catalysis. Van Nostrand Reinhold Catalysis Series. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-9882-3_9

Download citation

  • DOI: https://doi.org/10.1007/978-94-010-9882-3_9

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-9884-7

  • Online ISBN: 978-94-010-9882-3

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation