Topics in Catalysis

, Volume 59, Issue 2–4, pp 337–346 | Cite as

A Relevant Estimation of the TOF for Methanol Oxidation Over Au/CeO2: A Combined SSITKA and FTIR Operando Contribution

  • Ingrit Castellanos
  • Philippe Bazin
  • Sébastien Thomas
  • Olivier MarieEmail author
  • Marco Daturi
Original Paper


The importance to eliminate methanol from the environment arises from its classification as a volatile organic compound. For this purpose, it is advantageous to use effective catalysts that operate under ambient conditions. The cerium oxide doped with gold is a good candidate thanks to the high reducibility of ceria and the gold activity at low temperatures. Indeed, in previous studies it was evidenced that Au/CeO2 are highly effective not only for room temperature methanol trapping (upon adsorption) but also for catalytic full oxidation with air. Aiming at understanding the reaction mechanism, the FTIR operando survey of the catalyst under reaction flow conditions was performed. Distinct adsorbed species were observed and among them both spectators and reaction intermediates ones. More precisely, methoxy species formed upon methanol dissociative adsorption over CeO2 seemed to behave both as spectator and intermediate species most probably depending on their proximity with gold nanoparticles. Combining the Steady State Isotopic Transient Kinetic Analysis method and Fourier Transform Infrared spectroscopy operando setup, a more precise description of the methanol oxidation was possible thanks to the observation of the delayed evolution of distinct species at the catalyst surface. Moreover, in order to optimize the reaction conditions when moving from the laboratory scale to the industrial scale (pilot) it is of primary importance to know the intrinsic reaction rate parameters. The kinetic constants and the fraction of involved superficial sites were thus computed allowing an evaluation of a relevant turn over frequency.


Methanol Catalysis CeO2 Gold SSITKA FT-IR operando 


  1. 1.
    Scirè S, Minicò S, Crisafulli C, Satriano C, Pistone A (2003) Catalytic combustion of volatile organic compounds on gold/cerium oxide catalysts. Appl Catal B 40(1):43–49CrossRefGoogle Scholar
  2. 2.
    Bazin P, Thomas S, Marie O, Daturi M (2012) New insights into the methanol oxidation mechanism over Au/CeO2 catalyst through complementary kinetic and FTIR operando SSITKA approaches. Catal Today 182(1):3–11CrossRefGoogle Scholar
  3. 3.
    Rousseau S, Marie O, Bazin P, Daturi M, Verdier S, Harlé V (2010) Investigation of methanol oxidation over Au/catalysts using operando IR spectroscopy: determination of the active sites, intermediate/spectator species, and reaction mechanism. J Am Chem Soc 132(31):10832–10841. doi: 10.1021/ja1028809 CrossRefGoogle Scholar
  4. 4.
    Lai S-Y, Qiu Y, Wang S (2006) Effects of the structure of ceria on the activity of gold/ceria catalysts for the oxidation of carbon monoxide and benzene. J Catal 237(2):303–313. doi: 10.1016/j.jcat.2005.11.020 CrossRefGoogle Scholar
  5. 5.
    Binet C, Daturi M (2001) Methanol as an IR probe to study the reduction process in ceria–zirconia mixed compounds. Catal Today 70(1–3):155–167. doi: 10.1016/S0920-5861(01)00415-1 CrossRefGoogle Scholar
  6. 6.
    Haruta M, Kobayashi T, Sano H, Yamada N (1987) Chem Lett 16:405CrossRefGoogle Scholar
  7. 7.
    Uriz I, Arzamendi G, Dieguez PM, Laguna OH, Centeno MA, Odriozola JA, Gandia LM (2013) Preferential oxidation of CO over Au/CuOx–CeO2 catalyst in microstructured reactors studied through CFD simulations. Catal Today 216:283–291. doi: 10.1016/j.cattod.2013.04.023 CrossRefGoogle Scholar
  8. 8.
    Arena F, Famulari P, Trunfio G, Bonura G, Frusteri F, Spadaro L (2006) Probing the factors affecting structure and activity of the Au/CeO2 system in total and preferential oxidation of CO. Appl Catal B 66(1–2):81–91CrossRefGoogle Scholar
  9. 9.
    Avgouropoulos G, Manzoli M, Boccuzzi F, Tabakova T, Papavasiliou J, Ioannides T, Idakiev V (2008) Catalytic performance and characterization of Au/doped-ceria catalysts for the preferential CO oxidation reaction. J Catal 256(2):237–247CrossRefGoogle Scholar
  10. 10.
    Monyanon S, Pongstabodee S, Luengnaruemitchai A (2007) Preferential oxidation of carbon monoxide over Pt, Au monometallic catalyst, and Pt–Au bimetallic catalyst supported on ceria in hydrogen-rich reformate. J Chin Inst Chem Eng 38(5–6):435–441CrossRefGoogle Scholar
  11. 11.
    Panzera G, Modafferi V, Candamano S, Donato A, Frusteri F, Antonucci PL (2004) CO selective oxidation on ceria-supported Au catalysts for fuel cell application. J Power Sources 135(1–2):177–183CrossRefGoogle Scholar
  12. 12.
    Haruta M (2011) Spiers memorial lecture role of perimeter interfaces in catalysis by gold nanoparticles. Faraday Discuss 152:11–32CrossRefGoogle Scholar
  13. 13.
    Happel J, Hnatow MA (1976) Resolution of kinetic models by steady state tracing. J Catal 42(1):54–59. doi: 10.1016/0021-9517(76)90090-7 CrossRefGoogle Scholar
  14. 14.
    Shannon SL, Goodwin JG (1995) Characterization of catalytic surfaces by isotopic-transient kinetics during steady-state reaction. Chem Rev 95(3):677–695. doi: 10.1021/cr00035a011 CrossRefGoogle Scholar
  15. 15.
    Wuttke S, Bazin P, Vimont A, Serre C, Seo Y-K, Hwang YK, Chang J-S, Férey G, Daturi M (2012) Discovering the active sites for C3 separation in MIL-100(Fe) by using operando IR spectroscopy. Chem A Eur J 18(38):11959–11967. doi: 10.1002/chem.201201006 CrossRefGoogle Scholar
  16. 16.
    Thomas S, Marie O, Bazin P, Daturi M, Corbetta M, Lietti L, Visconti CG (2013) Récents Progrès en Génie des Procédés 104Google Scholar
  17. 17.
    Vannice MA (2005) Kinetics of catalytic reactions. Springer, New-YorkCrossRefGoogle Scholar
  18. 18.
    Burcham LJ, Wachs IE (1999) The origin of the support effect in supported metal oxide catalysts: in situ infrared and kinetic studies during methanol oxidation. Catal Today 49(4):467–484CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Ingrit Castellanos
    • 1
  • Philippe Bazin
    • 1
  • Sébastien Thomas
    • 1
  • Olivier Marie
    • 1
    Email author
  • Marco Daturi
    • 1
  1. 1.Laboratoire Catalyse & SpectrochimieCaenFrance

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