Journal of Nanoparticle Research

, Volume 8, Issue 3–4, pp 497–509 | Cite as

CO oxidation activity of Cu–CeO2 nano-composite catalysts prepared by laser vaporization and controlled condensation

  • Rangaraj S. Sundar
  • Sarojini DeeviEmail author


Ceria supported copper catalysts were synthesized by laser vaporization and controlled condensation method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and temperature programmed reduction (TPR). The catalytic activity of the nanopowders for CO oxidation reaction was tested in a fixed bed flow tube reactor in Ar–20%O2–4%CO mixture. Irrespective of the copper content, the catalytic activity of the nanopowders is similar in the initial CO test, and the catalytic activity improves (i.e. the light-off temperature decreases) during a subsequent run. The lowest light-off temperature during the second run is recorded in the material with 20% copper. TEM studies on 20%Cu–CeO2 sample in the as-prepared condition and after CO test exhibit two types of ceria particles namely, polygonal particles 3–5 nm in size and spherical particles of 15–20 nm in size. Rapid cooling of the nanoparticles formed during the laser ablation results in incorporation of a large amount of copper within the ceria as solid solution. Presence of solid solution of copper is confirmed by EDAX and electron diffraction analyses. In addition, copper-rich surface layer of Cu2O is found over the spherical particles. The cerium oxide components are essentially identical before and after CO test, except that the polygonal CeO2 particles contain newly formed fine crystals of CuO. TPR results reveal two reduction peaks, which further supports, the presence of two different copper species in the material. The shift in light-off temperature during the second run is attributed to the synergistic interaction between newly formed CuO crystals with the CeO2 matrix.


Ceria Reduction Peak Copper Content Temperature Program Reduction Cerium Oxide 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



The authors thank Dr. Donald Miser for the TEM analysis.


  1. Avgouropoulos G., Ioannides T., Papadopoulou Ch., Batista J., Hocevar S., Matralis H.K. (2002) A comparative study of Pt/γ–Al2O3, Au/α–Fe2O3 and CuO–CeO2 catalysts for the selective oxidation of carbon monoxide in excess hydrogen. Catal. Today 75: 157–167CrossRefGoogle Scholar
  2. Avgouropoulos G., Ioannides T. (2003) Selective CO oxidation over CuO–CeO2 catalysts prepared via the urea-nitrate combustion method. Appl. Catal. A:General 244: 155–167CrossRefGoogle Scholar
  3. Balducci G., Fornasiero P., Di Monte R., Kaspar J., Meriani S. Graziani M. (1995) An unusual promotion of the redox behaviour of CeO2-ZrO2 solid solutions upon sintering at high temperature. Catal. Lett. 33:193CrossRefGoogle Scholar
  4. Bechara R., Wrobel G., Aissi C.F., Guelton M., Bonnelle J.P., Bbou-Kais A. (1990) Preparation and characterization of copper-thorium oxide catalysts. 1. Solid solution of copper(II) in thoria: An ESR study. Chem. Mater. 2: 518–522CrossRefGoogle Scholar
  5. Bera P., Priolkar K.R., Sarode P.R., Hegde M.S., Emura S., Kumashiro R., Lalla N.P. (2002) Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-δ solid solution, 2002. Chem. Mater. 14:3591–3601CrossRefGoogle Scholar
  6. De Leitenburg C., Trovarelli A., Zamar F., Maschio S., Dolcetti G., Llorca J. (1995) A novel and simple route to catalysts with a high oxygen storage capacity: the direct room-temperature synthesis of CeO2-ZrO2 solid solutions. J. Chem. Soc. Commun. 21: 2181–2182CrossRefGoogle Scholar
  7. Dow W.P., Huang T.J. (1996) Yttria-stabilized zirconia supported copper oxide catalyst: II. Effect of oxygen vacancy of support on catalytic activity for CO oxidation. J. Catal. 160: 171–182CrossRefGoogle Scholar
  8. El-Shall M.S. & S. Li, 1998. In: Duncan M.A. ed. Advances in metal and semiconductor clusters, Vol. 4(3), JAI Press Inc., London, 115–177Google Scholar
  9. El-Shall M.S., Abdelsayed V., Pithawalla Y.B., Alsharaeh E., Deevi S.C. (2003) Vapor phase growth and assembly of metallic, intermetallic, carbon, and silicon nanoparticle filaments. J. Phys. Chem. B 107(13): 2882–2886CrossRefGoogle Scholar
  10. Fierro G., Lojacono M., Inversi M., Porta P., Lavecchia R., Cioci F. (1994) Study of anomalous temperature-programmed reduction profiles of Cu2O, CuO, and CuO-ZnO catalysts. J. Catal. 148:709–721CrossRefGoogle Scholar
  11. Flytzani-Stephanopoulos M., 2001. Nanostructured cerium oxide “Ecocatalysts”, MRS Bulletin, Nov. 885–889Google Scholar
  12. Gardner S.D., Hoflund G.B., Upchurch B.T., Schryer D.R., Kielin E.J., Schryer J. (1991) Comparison of the performance characteristics of Pt/SnOx and Au/MnOx catalysts for low-temperature CO oxidation. J. Catal. 129: 114–120CrossRefGoogle Scholar
  13. Haruta M., Tsubota S., Kobayashi T., Kageyama H., Genet M.J., Delmon B. (1993) Low-temperature oxidation of CO over gold supported on TiO2, α-Fe2O3, and Co3O4. J. Catal. 144: 175–192CrossRefGoogle Scholar
  14. Imanura S., Sawada H., Uemura K., Ishida S. (1988) Oxidation of carbon monoxide catalyzed by manganese–silver composite oxides. J. Catal. 109: 198–205CrossRefGoogle Scholar
  15. Jiang X., Zhou R., Pan P., Zhu B., Yuan X., Zheng X. (1997) Effect of the addition of La2O3 on TPR and TPD of CuO/γ-Al2O3 catalysts. Appl. Catal. A:Gen. 150: 131–141CrossRefGoogle Scholar
  16. Kundakovic Lj., Flytzani-Stephanopoulos M. (1998) Reduction characteristics of copper oxide in cerium and zirconium oxide systems. Applied Catalysis A: General 171: 13–29CrossRefGoogle Scholar
  17. Liu W., Flytzani-Stephanopoulos M. (1995) Total oxidation of carbon monoxide and methane over transition metal fluorite oxide composite catalysts: I. Catalyst composition and activity. J. Catal. 153: 304–316CrossRefGoogle Scholar
  18. Liu W., Flytzani-Stephanopoulos M. (1995b) Total oxidation of carbon-monoxide and methane over transition metal fluorite oxide composite catalysts: II Catalyst characterization and reaction-kinetics. J. Catal. 153: 317–332CrossRefGoogle Scholar
  19. Luo M., Zhong Y., Yuan X., Zheng X. (1997) TPR and TPD studies of CuO/CeO2 catalysts for low temperature CO oxidation. Appl. Catal. A: Gen. 162: 121–131CrossRefGoogle Scholar
  20. Miser D.E. & R.S. Sundar, 2005. ‘HRTEM characterization of an LVCC copper-ceria catalyst and identification of both CuO and Cu2O’, to be communicated to Appl. Catal. A: Gen.Google Scholar
  21. Meriani S. (1989) Features of the Ceria-Zirconia systems. Mater. Sci. Engg. A 109: 121–130CrossRefGoogle Scholar
  22. Schyer D.R., Upchurch B.T., Van Norman J.D., Bromn K.G., Schryer J. (1990) Effects of pretreatment conditions on a Pt/SnO2 catalyst for the oxidation of CO in CO2 lasers, J. Catal. 144: 193–197CrossRefGoogle Scholar
  23. Serre C., Garin F., Belot G., Marie G. (1993) Reactivity of Pt/Al2O3 and Pt-CeO2Al2O3 catalysts for the oxidation of carbon monoxide by oxygen: II. Influence of the pretreatment step on the oxidation mechanism. J. Catal. 141: 9–20CrossRefGoogle Scholar
  24. Skårman B., Grandjean D., Benfield R.E., Hinz A., Andersson A., Wallenberg L.R. (2002(a)) Carbon monoxide oxidation on nanostructured CuOx/CeO2 composite particles characterized by HREM, XPS, XAS, and High-energy diffraction. J. Catalysis 211: 119–133CrossRefGoogle Scholar
  25. Skårman B., Nakayama T., Grandjean D., Benfield R.E., Olsson E., Niihara K., Wallenberg L.R. 1990. Morphology and structure of CuOx/CeO2 nanocomposite catalysts produced by inert gas condensation: An HREM, EFTEM, XPS, and High-energy diffraction study, Chem. Mater. 12: 3686–3699Google Scholar
  26. Trovarelli A. (1996) Catalytic properties of ceria and CeO2 -containing materials Catal. Rev. Sci. Eng. 38: 439–520Google Scholar
  27. Tschöpe A., Ying J.Y., Chiang Y.M. (1995) Processing and structural evolution of nanocrystalline Cu–CeO2-x catalysts, Mater. Sci. Engg. A204: 267–271CrossRefGoogle Scholar
  28. Wang J.B., Shih W.H., Huang T.J. (2000) Study of Sm2O3-doped CeO2/Al2O3-supported copper catalyst for CO oxidation. Appl. Catal. A 203, 2, 191–199CrossRefGoogle Scholar
  29. Wang J.B., Tsai D.H., Huang T.J. (2002(a)) Synergistic catalysis of carbon monoxide oxidation over copper oxide supported on samaria-doped ceria, J. Catal. 208: 370–380CrossRefGoogle Scholar
  30. Wang J.B., Lin S., Huang T. (2002(b)) Selective CO oxidation in rich hydrogen over CuO/samaria-doped ceria, Appl. Catal. A: Gen. 232: 107–120CrossRefGoogle Scholar
  31. Ying J.Y. & A. Tschope, 1996. In: Moser W.R. ed. Advanced catalysts and nanostructured materials-modern synthetic methods, Academic Press, New York, pp. 231–258Google Scholar
  32. Zhang J.J., N. Li, Y.Y. Liu, B.X. Liu, 1998. Chin. Chem. Lett. 9, 873Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  1. 1.Research, Development and Engineering CenterRichmondUSA

Personalised recommendations