Abstract
High-temperature reduction (HTR) of palladium catalysts supported on some reducible oxides, such as Pd/CeO2, and Pd/TiO2 catalysts, led to a strong metal-support interaction (SMSI), which was found to be the main reason for their high and stable activity for methanol synthesis from hydrogenation of carbon dioxide. But low-temperature-reduced (LTR) catalysts exhibited high methane selectivity and were oxidized to PdO quickly in the same reaction. Besides palladium, platinum exhibited similar behavior for this reaction when supported on these reducible oxides. Mechanistic studies of the Pd/CeO2 catalyst clarified the promotional role of the SMSI effect, and the spillover effect on the HTR Pd/CeO2 catalyst. Carbon dioxide was decomposed on Ce2O3, which was attached to Pd, to form CO and surface oxygen species. The carbon monoxide formed was hydrogenated to methanol successively on the palladium surface while the surface oxygen species was hydrogenated to water by spillover hydrogen from the gas phase. A reaction model for the hydrogenation of carbon dioxide was suggested for both HTR and LTR Pd/CeO2 catalysts. Methanol synthesis from syngas on the LTR or HTR Pd/CeO2 catalysts was also conducted. Both alcohol and hydrocarbons were formed significantly on the HTR catalyst from syngas while methanol formed predominantly on the LTR catalyst. Characterization of these two catalysts elucidated the reaction performances.
Similar content being viewed by others
References
S.J. Tauster, S.C. Fung and R.L. Garten, J. Am. Chem. Soc. 100 (1978) 170.
S.J. Tauster and S.C. Fung, J. Catal. 55 (1978) 29.
K. Foger, in: Catalysis, Science and Technology eds. J.R. Anderson and M. Boudart, Vol. 6 (Springer-Verlag, Berlin, 1984) ch. 4.
G.L. Haller and D.E. Resasco, Adv. Catal. 36 (1989) 173.
J.P. Hindermann, G.J. Hutchings and A. Kiennemann, Catal. Rev. Sci. Eng. 35 (1993) 1.
P. Meriaudeau, O.H. Ellestad, M. Dufaux and C. Naccache, J. Catal. 75 (1982) 243.
K. Foger, J. Catal. 78 (1982) 406.
M.D. Mitchell and M.A. Vannice, Ind. Eng. Chem. Fundam. 23 (1984) 88.
M.A. Vannice, C. Sudhakar and M. Freeman, J. Catal. 108 (1987) 97.
A.K. Datye, D.S. Kalakkad, M.H. Yao and D.J. Smith, J. Catal. 155 (1995) 148.
C. de Leitenburg and A. Trovarelli, J. Catal. 156 (1995) 171.
G.S. Zafiris and R.J. Gorte, J. Catal. 139 (1993) 561.
Y. Amenomiya and T. Tagawa, in: "Proc. 8th Int. Congr. Catal.", Vol. 2, Berlin, 1984, p. 557.
B. Denise and R.P.A. Sneeden, Appl. Catal. 28 (1986) 235.
K. Fujimoto and T. Shikada, Appl. Catal. 31 (1987) 13.
L. Fan, Y. Sakaiya and K. Fujimoto, Appl. Catal. 180 (1999) L1.
M. Poutsma, L.F. Elek, P.A. Ibarbia, A.P. Risch and J.A. Rabo, J. Catal. 52 (1978) 157.
R.F. Hicks, O.-J. Yen and A.T. Bell, J. Catal. 89 (1984) 498.
W. Shen, Y. Ichihashi, M. Okamura and Y. Matsumura, Catal. Lett. 64 (2000) 23.
W. Shen, Y. Matsumura, J. Mol. Catal. A. 153 (2000) 165.
Y. Liu, K. Suzuki, S. Hamakawa, T. Hayakawa, K. Murata, T. Ishii and M. Kumagai, Chem. Lett. (2000) 486.
Y. Liu, K. Suzuki, S. Hamakawa, T. Hayakawa, K. Murata, T. Ishii and M. Kumagai, Catal. Lett. 66 (2000) 205.
M.A. Vannice, J. Catal. 40 (1975) 129.
F. Solymosi, A. Erdohelyi and M. Kocsis, J. Catal. 65 (1980) 428.
A. Erdohelyi, M. Pasztor and F. Solymosi, J. Catal. 98 (1986) 166.
F. Solymosi, A. Erdohelyi and M. Lancz, J. Catal. 95 (1985) 567.
L. Fan and K. Fujimoto, J. Catal. 150 (1994) 217.
L. Fan and K. Fujimoto, Bull. Chem. Soc. Jpn. 67 (1994) 1773.
L. Fan and K. Fujimoto, Chem. Lett. (1994) 105.
C.P. Shao, Y. Iwasawa, L. Fan and K. Fujimoto, Appl. Catal. A 128 (1995) L1.
M.A. Vannice, in: "Catalysis, Science and Technology", Vol. 3 (Springer-Verlag, Berlin, 1982) ch. 3.
C. Li, K. Domen and T. Onishi, J. Am. Chem. Soc. 111 (1989) 7683.
T. Jin and J.M. White, J. Phys. Chem. 91 (1987) 5937.
T. Yamada and M. Funabiki, Stud. Surf. Sci. Catal. 77 (1993) 329.
T. Sodegawa and F. Nozaki, J. Catal. 104 (1987) 339.
L. Fan and K. Fujimoto, J. Catal. 172 (1997) 238.
J. Herrmann, L. Dibansa and R. Harivolona, J. Catal. 159 (1996) 361.
A. Bensalem, J. Muller, D. Tessier and F. Bozon-Verduraz, J. Chem. Soc. Faraday Trans. 92 (1996) 3233.
F.L. Normand, J. Phys. Chem. 92 (1988) 2561.
G. Praline and J.M. White, J. Electron. Spectrosc. Relat. Phenom. 21 (1980) 17.
B.E. Koel, and J.M. White, J. Electron. Spectrosc. Relat. Phenom. 21 (1980) 31.
F. Kerkhof and J. Moulijn, J. Phys. Chem. 83 (1979) 1612.
R.T.K. Baker, E.B. Prestridge and R.L. Garten, J. Catal. 56 (1979) 390.
J.A. Horsley, J. Am. Chem. Soc. 101 (1979) 2870.
R. Burch and A.R. Flambard, J. Catal. 78 (1982) 389.
J. Santos, J. Phillips and J.A. Dumesic, J. Catal. 81 (1983) 147.
H.R. Sadeghi and V.E. Henrich, J. Catal. 87 (1984) 279.
C. Padeste, N. Cant and D.L. Trimm, Catal. Lett. 24 (1994) 95.
C. Padeste, N. Cant and D.L. Trimm, Catal. Lett. 18 (1993) 305.
T. Arai, K. Maruya, K. Domen and T. Onishi, J. Catal. 141 (1993) 533.
R.T. Hicks and A.T. Bell, J. Catal. 90 (1984) 205.
A. Erdohelyi, J. Cserenyi, E. Papp and F. Solymosi, Appl. Catal. A 108 (1994) 205.
M.S. Brogan, T.J. Dines and J.A. Cairns, J. Chem. Soc. Faraday Trans. 90 (1994) 1461.
M. Che and A.J. Tench, Adv. Catal. 32 (1983) 1.
J. Soria, A.M. Arias and J.C. Conesa, J. Chem. Soc. Faraday Trans. 91 (1995) 1669.
C. Li, Q. Xin and X. Guo, Catal. Lett. 12 (1992) 297.
R.L. Flesner, K.B. Kester, B. Chen and J.L. Falconer, Stud. Surf. Sci. Catal. 77 (1993) 277.
W. Shen and Y. Matsumura, Phys. Chem. Chem. Phys. 2 (2000) 1519.
A.M. Bradshaw and F.M. Hoffmann, Surf. Sci. 72 (1978) 513.
J.E. Hulse and M. Moskovits, Surf. Sci. 57 (1976) 125.
S.D. Bader, J.M. Blakely, R.T. Panosh, Surf. Sci. 74 (1978) 405.
Z. Zhang, A. Kladi and X.E. Verykios, J. Catal. 148 (1994) 737.
M.R. Prairie, A. Renken and M. Gratzel, J. Catal. 129 (1991) 130.
S. Naito, S. Aida, T. Tsunematsu and T. Miyao, Chem. Lett. (1998) 941.
Y. Matsumura, W. Shen, Y. Ichihashi and M. Okamura, Chem. Lett. (1999) 1101.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tsubaki, N., Fujimoto, K. Promotional SMSI Effect on Supported Palladium Catalysts for Methanol Synthesis. Topics in Catalysis 22, 325–335 (2003). https://doi.org/10.1023/A:1023548608733
Issue Date:
DOI: https://doi.org/10.1023/A:1023548608733