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Metal-support interactions during the CO2 reforming of CH4 over model TiOx/Pt catalysts

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Abstract

To obtain insight into the importance of metal-support interactions (MSI) in the CO2 reforming of CH4, the reaction was studied using pure TiO2, high-purity Pt powder, and two model TiOx/Pt systems. The latter two TiOx/Pt catalysts, prepared by oxidation of Ti nonylate deposited on the Pt powder surface, contained either one (θ=1) or ten (θ=10) theoretical monolayers of TiO2. The H2 and CO chemisorption capacities showed respective decreases of 1/3 and 1/2 on the latter two catalysts although the N2 BET surface areas were essentially unchanged. XRD analysis of either TiOx/Pt sample detected no TiOx structures. Specific rates (μ mol/(s gcat)), areal rates (μ mol/(s m2)) and turnover frequencies (s-1) for the CO2 reforming of CH4 decreased in the order TiOx/Pt (θ=10)TiOx/Pt( θ=1)>>Pt powder>TiO2. Neither pure Pt powder nor pure TiO2 showed appreciable activity for CH4-CO2 reforming; thus the dramatic increase in activity is attributed to the creation of new sites in the metal-support interfacial region which promote CH4 dissociation, CO2 dissociation and reduction, and subsequent CHxO decomposition. In addition, temperature-programmed hydrogenation of used catalyst samples clearly showed that TiOx overlayers on the Pt surface suppress carbon deposition during reaction via an ensemble effect, thus improving activity maintenance.

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References

  1. M.C.J. Bradford and M.A. Vannice, Appl. Catal. A. 142 (1996) 73, 97.

    Article  CAS  Google Scholar 

  2. Z.Zhang and X.E.Verykios, Appl. Catal. A 138 (1996) 109.

    Article  Google Scholar 

  3. M.C.J. Bradford and M.A. Vannice, J. Catal. (1997), in press.

  4. A. Erdöhelyi, K. Fodor and F. Solymosi, Stud. Surf. Sci. Catal. 107 (1997) 525.

    Article  Google Scholar 

  5. Z. Zhang, V.A. Tsipouriari, A.M. Efstathiou and X.E. Verykios, J. Catal. 158 (1996) 51.

    Article  CAS  Google Scholar 

  6. A. Erdöhelyi, J. Cserényi and F. Solymosi, J. Catal. 141 (1993) 287.

    Article  Google Scholar 

  7. O. Yamazaki, T. Nozaki, K. Omata and K. Fujimoto, Chem. Lett. 10 (1992) 1953.

    Article  Google Scholar 

  8. E.Ruckenstein and Y.H. Hu, Appl. Catal. A 133 (1995) 149.

    Article  Google Scholar 

  9. A.M. Gadalla and M.E. Sommer, J. Am. Ceram. Soc. 72 (1989) 683.

    Article  CAS  Google Scholar 

  10. J.T. Richardson, B. Turk and M.V. Twigg, Appl. Catal. A 148 (1996) 97.

    Article  CAS  Google Scholar 

  11. Y. Chen and J.Ren, Catal. Lett. 29 (1994) 39.

    Article  CAS  Google Scholar 

  12. A. Erdöhelyi, J. Cserényi, E. Papp and F. Solymosi, Appl. Catal. A 108 (1994) 205.

    Article  Google Scholar 

  13. A.M. Efstathiou, A. Kladi, V.A. Tsipouriari and X.E. Verykios, J. Catal. 158 (1996) 64.

    Article  CAS  Google Scholar 

  14. (a)M.A.Vannice and D. Poondi, J. Catal., submitted. (b) D. Poondi, PhD Dissertation, The Pennsylvania State University, USA (1996).

  15. B.D. Cullity, Elements of X-ray Diffraction, 2nd Ed. (Addison-Wesley, Reading, 1978).

    Google Scholar 

  16. J.W. Edington, Practical Electron Microscopy in Materials Science (N.V. Philips Gloeilampenfabrieken, Eindoven, 1976).

    Google Scholar 

  17. R.K. Brandt, M.R. Hughes, L.P. Bourget, K. Truszkowska and R.G.Greenler, Surf. Sci. 286 (1993) 15.

    Article  CAS  Google Scholar 

  18. J. Segner, C.T. Campbell, G. Doyen and G. Ertl, Surf. Sci. 138 (1984) 505.

    Article  CAS  Google Scholar 

  19. G. Ertl, M. Neumann and K.M. Streit, Surf. Sci. 64 (1977) 393.

    Article  CAS  Google Scholar 

  20. J.R. Rostrup-Nielsen and J.-H. Bak Hansen, J. Catal. 144 (1993) 38.

    Article  CAS  Google Scholar 

  21. M. Boudart, Chem.Rev. 95 (1995) 661.

    Article  CAS  Google Scholar 

  22. J.M. Herrmann, M. Gravelle-Rumeau-Maillot and P.C. Gravelle, J. Catal. 104 (1987) 136.

    Article  CAS  Google Scholar 

  23. B.Z. Nikolic, H. Huang, D. Gervasio, A. Lin, C. Fierro, R.R. Adzic and E.B. Yeager, J. Electroanal. Chem. 295 (1990) 415.

    Article  CAS  Google Scholar 

  24. A. Rodes, E. Pastor and T. Iwasita, Anal. Quim. 89 (1993) 458.

    CAS  Google Scholar 

  25. M.C. Rom_an-Mart ¨ nez, D. Cazorla-Amor_os, C. Salinas-Mart ¨ nez de Lecea and A. Linares-Solano, Langmuir 12 (1996) 379.

    Article  Google Scholar 

  26. C.R. Prichard and C.N. Hinshelwood, J. Chem. Soc. 127 (1925) 806.

    CAS  Google Scholar 

  27. G.A. Somorjai, R.W. Joyner and B. Lang, Proc. Roy. Soc. London 331 (1972) 335.

    Article  CAS  Google Scholar 

  28. T.P. Beebe Jr., D.W. Goodman, B.D. Kay and J.T. Yates Jr., J. Chem. Phys. 87 (1987) 2305.

  29. D.J. Trevor, D.M. Cox and A. Kaldor, J. Am. Chem. Soc. 112 (1990) 3742.

    Article  CAS  Google Scholar 

  30. R. vanHardeveld and F. Hartog, Surf. Sci. 15 (1969) 189.

    Article  CAS  Google Scholar 

  31. M.F.Mark and W.F. Maier, J. Catal. 164 (1996) 122.

    Article  Google Scholar 

  32. M. Sigl, M.C.J. Bradford, H. Knözinger and M.A. Vannice, Topics Catal., submitted.

  33. K. Tanaka, K. Miyahara and I. Toyoshima, J. Phys. Chem. 88 (1984) 3504.

    Article  CAS  Google Scholar 

  34. W. Fancheng, W. Huilin, K.R. Tsai, W. Shuijuand and X. Fuchun, Catal. Lett. 12 (1992) 319.

    Article  Google Scholar 

  35. U. Bardi, K. Tamura and Y.Nihei, Catal. Lett. 3 (1989) 117.

    Article  CAS  Google Scholar 

  36. D.J. Dwyer, J.L. Robbins, S.D. Cameron, N. Dudash and J. Hardenbergh in: Strong Metal Support Interactions, ACS Symposium Series 298 (Am. Chem. Soc., Washington, 1986) p. 21.

    Google Scholar 

  37. A.A. Davydov, M.P. Komarova, V.F. Anufrienko and N.G. Maksimov, Kinet. Catal. 14 (1973) 1342.

    Google Scholar 

  38. L. Bonneviot and G.L. Haller, J. Catal. 113 (1988) 96.

    Article  CAS  Google Scholar 

  39. X.S. Li, W.Z. Li, Y.X. Chen and H.L. Wang, Catal. Lett. 32 (1995) 31.

    Article  CAS  Google Scholar 

  40. U. Roland, R. Salzer, T. Braunschweig, F. Roessner and H. Winkler, J. Chem. Soc. Faraday Trans. 9 (1995) 1091.

    Article  Google Scholar 

  41. R.A. Demmin, C.S. Ko and R.J. Gorte, J. Phys. Chem. 89 (1985) 1151.

    Article  CAS  Google Scholar 

  42. B. Sen, P. Chou and M.A. Vannice, J. Catal. 101 (1986) 517.

    Article  CAS  Google Scholar 

  43. M.A. Vannice, L.C. Hasselbring and B. Sen, J. Catal. 97 (1986) 66.

    Article  CAS  Google Scholar 

  44. G.B. Raupp and J.A.Dumesic, J. Phys.Chem. 89 (1985) 5240.

    Article  CAS  Google Scholar 

  45. L-Q. Wang, A.N. Shultz, D.R. Baer and M.H. Engelhard, J. Vac. Sci. Technol. A. 14 (1996) 1532.

    Article  Google Scholar 

  46. B. Sen and J.L. Falconer, J. Catal. 125 (1990) 35.

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  48. M.A.Vannice and C. Sudhakar, J. Phys. Chem. 88 (1984) 2429.

    Article  Google Scholar 

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Bradford, M., Vannice, M. Metal-support interactions during the CO2 reforming of CH4 over model TiOx/Pt catalysts. Catalysis Letters 48, 31–38 (1997). https://doi.org/10.1023/A:1019022903491

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