Skip to main content
SpringerLink
Log in

First-principles analysis of the hydrogenation of carbon monoxide over palladium

  • Published:
Topics in Catalysis Aims and scope Submit manuscript

Abstract

The reaction paths for the hydrogenation of CO to methanol over Pdx (x = 1–4 and 19) cluster models were examined using first-principle density functional quantum chemical calculations. The predicted adsorption energies for the most favorable binding modes for CO, H2, HCO, H3CO, CH3OH, C, O and H on a Pd19 model Pd(111) clusters were -147, -62, -340, -51, -195, -33, -610, -349 and -251 kJ/mol, respectively. The most favorable modes for CO, CH3O, H, C and O on Pd(111) were all found to be the 3-fold fcc site. The most favorable modes for the formyl and formaldehyde surface intermediates at low coverage were the 3-fold (ζ2µ3), and the di-σ sites, respectively. At higher surface coverages, however, the atop ζ1 (C) and the π modes for the formyl and formaldehyde intermediates were more likely. The computed adsorption energies were subsequently used to compute overall reaction energies for the hydrogenation of CO to methanol. The initial hydrogenation of CO to the ζ1 (C) HCO intermediate was found to be +52 kJ/mol endothermic and has been speculated as a possible rate-limiting step. The remaining surface hydrogenation steps become increasingly more exothermic as more hydrogen was added. The elementary steps of formyl to formaldehyde, formaldehyde to methoxide and methoxide to methanol were computed to be -9, -26 and -33 kJ/mol, respectively. The overall energy for CO dissociation was found to be highly unlikely at +260 kJ/mol and a clear indication that methanation and chain growth chemistry is not very likely over Pd. The most favorable reaction coordinate for the hydrogenation of CO to the ζ1 (C) formyl intermediate was that which proceeds over a single Pd site where there is a migratory insertion of the CO into a Pd–H bond. The barrier for this path was computed to be +78 kJ/mol on the Pd19 cluster. There was a very weak dependence on cluster size. This is a likely indication that this reaction is structure insensitive. A second path which involved the coupling of H and CO over a bridge site was found to be +130 kJ/mol which is less likely, but may also occur under different conditions.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. V. Ponec, in: Handbook of Heterogeneous Catalysis, eds. H. Knözinger, G. Ertl and J. Weitkamp (VCH, Weinheim, 1997) pp. 1876–1894.

  2. M.A. Vannice, in: Catalysis Science and Technology, eds. J.R. Anderson and M. Boudart (Springer, Berlin, 1982) pp. 140–194.

    Google Scholar 

  3. F. Solymosi, I. Tombacz and M. Kocsis, J. Catal. 75 (1982) 78.

    Article  CAS  Google Scholar 

  4. D. Schanke, S. Vada, E.A. Blekkan, A.M. Hilmen, A. Hoff and A. Holmen, J. Catal. 156 (1995) 85.

    Article  CAS  Google Scholar 

  5. B. Sarup and B.W. Wojciechowski, Canad. J. Chem. Eng. 67 (1989) 62.

    Article  CAS  Google Scholar 

  6. J.L. Robbins and E. Marucchi-Soos, J. Phys. Chem. 93 (1989) 2885.

    Article  CAS  Google Scholar 

  7. J. van de Loosdrecht, M. van der Haar, A.M. van der Kraan, A.J. van Dillen and J.W. Geuss, Appl. Catal. A 150 (1997) 365.

    Article  CAS  Google Scholar 

  8. W. Wang and Y. Chen, Appl. Catal. 77 (1991) 223.

    Article  CAS  Google Scholar 

  9. A. Kogelbauer, J.G. Goodwin Jr. and R. Oukaci, J. Catal. 160 (1996) 125.

    Article  CAS  Google Scholar 

  10. B. Johnson, C.H. Bartholomew and D.W. Goodman, J. Catal. 128 (1991) 231.

    Article  CAS  Google Scholar 

  11. S. Ho, M. Houalla and D.M. Hercules, J. Phys. Chem. 94 (1990) 6396.

    Article  CAS  Google Scholar 

  12. J.J.C. Geerlings, M.C. Zonnevylle and C.P.M. de Groot, Surf. Sci. 241 (1991) 302.

    Article  CAS  Google Scholar 

  13. L.M. Gandia and M. Montes, J. Molec. Catal. 94 (1994) 347.

    Article  CAS  Google Scholar 

  14. V. Ponec and G.C. Bond, Catalysis by Metals and Alloys, Studies in Surface Science and Catalysis (Elsevier, Amsterdam, 1995).

    Google Scholar 

  15. Y.A. Ryndin, R.F. Hicks, A.T. Bell and Y.I. Yermakov, J. Catal. 70 (1981) 287.

    Article  CAS  Google Scholar 

  16. R.F. Hicks and A.T. Bell, J. Catal. 91 (1985) 104.

    Article  CAS  Google Scholar 

  17. a.D.W.G. Berlowitz, J. Catal. 108 (1987) 367.

    Article  Google Scholar 

  18. F. Fajula, R.G. Anthony and J.J. Lunsford, J. Catal. 73 (1982) 237.

    Article  CAS  Google Scholar 

  19. E. Shustorovich and A.T. Bell, Surf. Sci. 253 (1991) 386.

    Article  CAS  Google Scholar 

  20. B. Sen and M.A. Vannice, J. Catal. 113 (1988) 59.

    Google Scholar 

  21. Z.M. Liu and M.A. Vannice, Surf. Sci. 316 (1994) 337.

    Article  CAS  Google Scholar 

  22. J.M.G. Kaspar, G.P. Escobar and A. Trovarelli, J. Molec. Catal. 72 (1992) 243.

    Article  CAS  Google Scholar 

  23. R.M. Makouangou, D.Y. Murzin, A.E. Dauscher and R.A. Touroude, Ind. Eng. Chem. Res. 33 (1994) 1881.

    Article  CAS  Google Scholar 

  24. M.A. Vannice and B. Sen, J. Catal. 115 (1989) 65.

    Article  CAS  Google Scholar 

  25. P. Beccat, J.C. Bertolini, Y. Gauthier, J. Massardier and P. Ruiz, J. Catal. 126 (1990) 451.

    Article  CAS  Google Scholar 

  26. L. Mercadante, G. Neri, C. Milone, A. Donato and S. Galvagno, J. Molec. Catal. A: Chem. 100 (1996) 115.

    Google Scholar 

  27. a.J.C.B. Simonik, Coll. Czech. Chem. Comm. 37 (1972) 353.

    CAS  Google Scholar 

  28. C.M.P. Birchem, Y. Berthier and G. Cordier, J. Catal. 146 (1994) 503.

    Article  CAS  Google Scholar 

  29. V. Satagopan and S.B. Chandalia, J. Chem. Tech. Biotechnol. 59 (1994) 257.

    Article  CAS  Google Scholar 

  30. G. Neri, L. Mercadante, C. Milone, R. Pietropaolo and S. Gavagno, J. Molec. Catal. A: Chem. 105 (1996) 93.

    Article  Google Scholar 

  31. K.a.Y.I. Yoshikawa, J. Molec. Catal.: A Chem. 100 (1995) 115.

    Article  CAS  Google Scholar 

  32. J. Jenck and J.E. Germain, J. Catal. 65 (1980) 141.

    Article  CAS  Google Scholar 

  33. I. Paseka, J. Catal. 121 (1990) 349.

    Article  CAS  Google Scholar 

  34. A.K. Bhattacharya, M.A. Chesters, M.E. Pemble and N. Sheppard, Surf. Sci. 206 (1988) L845.

    Article  CAS  Google Scholar 

  35. J.F. Edwards and G.L. Schrader, J. Phys. Chem. 89 (1985) 782.

    Article  CAS  Google Scholar 

  36. H. He and K. Tanka, Catal. Lett. 25 (1994) 105.

    Article  CAS  Google Scholar 

  37. C. Houtman and M.A. Barteau, Langmuir 6 (1990) 1558.

    Article  CAS  Google Scholar 

  38. C. Houtman and M.A. Barteau, Surf. Sci. 248 (1991) 57.

    Article  CAS  Google Scholar 

  39. Y. Je and A.L. Companion, Surf. Sci. Lett. 271 (1992) L345.

    Article  CAS  Google Scholar 

  40. J. Lahtinen, T. Anraku and G.A. Somorjai, J. Catal. 142 (1993) 206.

    Article  CAS  Google Scholar 

  41. W.J. Mitchell, J. Xie, T.A. Jachimowski and W.H.Weinberg, J. Am. Chem. Soc. 117 (1995) 2606.

    Article  CAS  Google Scholar 

  42. I. Ratajczykowa, Surf. Sci. 152–153 (1985) 627.

    Article  Google Scholar 

  43. L.J. Richter and W. Ho, J. Chem. Phys. 83 (1985) 2165.

    Article  CAS  Google Scholar 

  44. J. Xie, J. Mitchell, K.J. Lyons and W.H. Weinberg, J. Chem. Phys. 101 (1994) 9195.

    Article  CAS  Google Scholar 

  45. J.L. Davis and M.A. Barteau, Surf. Sci. 208 (1989) 383.

    Article  CAS  Google Scholar 

  46. J.L. Davis and M.A. Barteau, Langmuir 256 (1989) 50.

    Google Scholar 

  47. J.L. Davis and M.A. Barteau, Surf. Sci. 256 (1991) 50.

    Article  CAS  Google Scholar 

  48. J.L. Davis and M.A. Barteau, J. Molec. Catal. 77 (1992) 109.

    Article  CAS  Google Scholar 

  49. J.A. Gates and L.L. Kesmodel, J. Catal. 83 (1983) 437.

    Article  CAS  Google Scholar 

  50. P.S. Cremer, X. Su, Y.R. Shen and G.A. Somorjai, J. Am. Chem. Soc. 118 (1996) 2942.

    Article  CAS  Google Scholar 

  51. C. Mijoule, Y. Bouteiller and D.R. Salahub, Surf. Sci. 253 (1991) 375.

    Article  CAS  Google Scholar 

  52. G. Pacchioni and J. Koutecky, J. Phys. Chem. 91 (1987) 2658.

    Article  CAS  Google Scholar 

  53. S. Sung and R. Hoffmann, J. Am. Chem. Soc. 107 (1985) 578.

    Article  CAS  Google Scholar 

  54. F. Delbecq and P. Sautet, Langmuir 9 (1993) 197.

    Article  CAS  Google Scholar 

  55. F. Delbecq and P. Sautet, Surf. Sci. 295 (1993) 353.

    Article  CAS  Google Scholar 

  56. T. Ziegler, Chem. Rev. 91 (1991) 651.

    Article  CAS  Google Scholar 

  57. R.A. van Santen and M. Neurock, Catal. Rev. 37 (1995) 557.

    CAS  Google Scholar 

  58. M. Neurock and R.A. van Santen, in: Handbook of Catalysis, eds. H. Knözinger, G. Ertl and J. Weitkamp (Springer, Berlin, 1996), in press.

    Google Scholar 

  59. M. Neurock, W.D. Provine, D.A. Dixon, G.W. Coulston and J.J. Lerou, Chem. Eng. Sci. 51 (1996) 1691.

    Article  CAS  Google Scholar 

  60. J.L. Whitten and H. Yang, Surf. Sci. Rep. 218 (1996) 55.

    Article  Google Scholar 

  61. J.K. Nørskov, Surf. Sci. 299–300 (1994) 690.

    Article  Google Scholar 

  62. G. Pacchioni, Heter. Chem. Rev. 2 (1995) 213.

    CAS  Google Scholar 

  63. Paul and Sautet.

  64. J. Andzelm and E. Wimmer, J. Chem. Phys. 96 (1992) 1280.

    Article  CAS  Google Scholar 

  65. R.G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules (Oxford Univ. Press, Oxford, 1989).

    Google Scholar 

  66. D.R. Salahub, R. Fournier, P. Mlynarski, I. Papai, A. St-Amant and J. Ushio, in: Density Functional Methods in Chemistry, eds. J. Andzelm and J. Labinowski (Springer, Berlin, 1991).

    Google Scholar 

  67. D.R. Salahub, M. Castro and E.I. Proynov, in: Relativistic and Electron Correlation Effects in Molecules and Solid, NATO ASI, B318, ed. G.L. Malli (Plenum Press, New York, 1994).

    Google Scholar 

  68. S.H. Vosko, L. Wilk and M. Nusair, Can. J. Phys. 58 (1980) 1200.

    Article  CAS  Google Scholar 

  69. A.D. Becke, Phys. Rev. A 38 (1988) 3098.

    Article  CAS  Google Scholar 

  70. A. Becke, ACS Symp. Series 394 (1989) 165.

    Article  CAS  Google Scholar 

  71. J.P. Perdew, Phys. Rev. B 33 (1986) 8822.

    Article  Google Scholar 

  72. J. Andzelm and E. Wimmer, J. Chem. Phys. 96 (1991) 1280.

    Article  Google Scholar 

  73. J. Andzelm, E. Radzio and D.R. Salahub, J. Comput. Chem. 6 (1985) 520.

    Article  CAS  Google Scholar 

  74. H. Chen, M. Krasowski and G. Fitzgerald, J. Chem. Phys. 98(1993) 8710.

    Article  CAS  Google Scholar 

  75. T. Nakao, D.A. Dixon and H. Chen, J. Phys. Chem. 97 (1993) 12665.

    Article  CAS  Google Scholar 

  76. M. Neurock, 1998, in preparation.

  77. M. Neurock, G.W. Coulston and D.A. Dixon, unpublished work.

  78. M. Neurock, Appl. Catal. A 160 (1996) 169.

    Article  Google Scholar 

  79. E. Shustorovich and A.T. Bell, J. Catal. 113 (1988) 341.

    Article  CAS  Google Scholar 

  80. A.T. Bell, in: Metal-Surface Reaction Energetics: Theory and Applications to Heterogeneous Catalysis, Chemisorption, and Surface Diffusion, ed. E. Shustorovich (VCH, New York, 1991) pp. 191–226.

    Google Scholar 

  81. J.C. Campuzano, in: The Chemical Physics of Solid Surfaces and Heterogeneous Catalysis, eds. D.A. King and D.P. Woodruff (Elsevier, Amsterdam, 1981).

    Google Scholar 

  82. G. Ertl and J. Koch, Surf. Sci. 25 (1970) 1906.

    CAS  Google Scholar 

  83. G. Ertl, H. Conrad, J. Koch and E.E. Latta, Surf. Sci. 43 (1974) 462.

    Article  Google Scholar 

  84. A.M. Bradshaw and F.M. Hoffmann, Surf. Sci. 72 (1978) 513.

    Article  CAS  Google Scholar 

  85. R.A. van Santen, M.C. Zonnevylle and A.P.J. Jansen, Phil. Trans. R. Soc. Lond. A 341 (1992) 269.

    CAS  Google Scholar 

  86. R.A. van Santen, Theoretical Heterogeneous Catalysis, Vol. 5 (World Scientific, 1991).

  87. R.A. van Santen and E.J. Baerends, in: Theoretical Treatment of Large Molecules and Their Interactions, ed. Z.B. Maszic (Springer, Berlin, 1991) pp. 323–390.

    Google Scholar 

  88. M. Neurock, R.A. van Santen, W. Biemolt and A.P.J. Jansen, J. Am. Chem. 116 (1994) 6860.

    Article  CAS  Google Scholar 

  89. Y.S. Li, M.A. van Daelen, J.M. Newsam and R.A. van Santen, J. Phys. Chem. 100 (1996) 2279.

    Article  Google Scholar 

  90. H. Conrad, G. Ertl and E.E. Latta, Surf. Sci. 41 (1974) 435.

    Article  Google Scholar 

  91. M.R.A. Blomberg, C.A.M. Karlsson and P.E.M. Siegbahn, J. Phys. Chem. 97 (1993) 9341.

    Article  CAS  Google Scholar 

  92. L. Vattuone, L. Yeo and D.A. King, 104 (1996) 8096.

  93. L. Vattuone, Y.Y. Yeo and D.A. King, Catal. Lett. 41 (1996) 119.

    Article  CAS  Google Scholar 

  94. J.L. Davis and M.A. Barteau, J. Am. Chem. Soc. 111 (1989) 1782.

    Article  CAS  Google Scholar 

  95. H. Yang and J.L. Whitten, Langmuir 11 (1995) 853.

    Article  CAS  Google Scholar 

  96. J.L. Davis and M.A. Barteau, Surf. Sci. 197 (1988) 123.

    Article  CAS  Google Scholar 

  97. E. Kaufmann, P. von Rague Schleyer, S. Gronert, A. Streitwieser Jr. and M. Halpern, J. Am. Chem. Soc. 109 (1987) 2553.

    Article  CAS  Google Scholar 

  98. N. Koga and K. Morokuma, J. Am. Chem. Soc. 108 (1986) 6136.

    Article  CAS  Google Scholar 

  99. A. Rappe, J. Am. Chem. Soc. 109 (1987) 5605.

    Article  CAS  Google Scholar 

  100. M.a.T.Z. Sola, Organometall. 15 (1996) 2611.

    Article  CAS  Google Scholar 

  101. K. Tatsumi, A. Nakamura, P. Hofmann, P. Stauffert and R. Hoffmann, J. Am. Chem. Soc. 107 (1985) 4440.

    Article  CAS  Google Scholar 

  102. L. Versluis, T. Ziegler, E.J. Baerends and W. Ravenek, J. Am. Chem. Soc. 111 (1989) 2018.

    Article  CAS  Google Scholar 

  103. T. Ziegler, L. Versluis and V. Tschinke, J. Am. Chem. Soc. 108 (1986) 612.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, University of Virginia, Charlottesville, VA, 22903-2442, USA

    Matthew Neurock

Authors
  1. Matthew Neurock
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Neurock, M. First-principles analysis of the hydrogenation of carbon monoxide over palladium. Topics in Catalysis 9, 135–152 (1999). https://doi.org/10.1023/A:1019179009796

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1019179009796

Search

Navigation