Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts

Arantxa Davo-Quilionero, Miriam Navlani-Garcia, Dolores Lozano-Castello, Agustin Bueno-Lopez*, James A. Anderson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

157 Citations (Scopus)


Model CuO/Ce0.8X0.2O delta catalysts (with X = Ce, Zr, La, Pr, or Nd) have been prepared in order to obtain CuO/ceria materials with different chemical features and have been characterized by X-ray diffraction, Raman spectroscopy, N-2 adsorption, and H-2 temperature-programmed reduction. CO-PROX experiments have been performed in a fixed-bed reactor and in an operando DRIFTS cell coupled to a mass spectrometer. The CO oxidation rate over CuO/ceria catalysts correlates with the formation of the Cu+-CO carbonyl above a critical temperature (90 degrees C for the experimental conditions in this study) because copper-carbonyl formation is the rate-limiting step. Above this temperature, CO oxidation capacity depends on the redox properties of the catalyst. However, decomposition of adsorbed intermediates is the slowest step below this threshold temperature. The hydroxyl groups on the catalyst surface play a key role in determining the nature of the carbon-based intermediates formed upon CO chemisorption and oxidation. Hydroxyls favor the formation of bicarbonates with respect to carbonates, and catalysts forming more bicarbonates produce faster CO oxidation rates than those which favor carbonates.

Original languageEnglish
Pages (from-to)1723-1731
Number of pages9
JournalACS Catalysis
Issue number3
Early online date1 Feb 2016
Publication statusPublished - Mar 2016

Bibliographical note

The authors thank the financial support of Generalitat
Valenciana (Project PROMETEOII/2014/010 and Grant
BEST/2014/250), the Spanish Ministry of Economy and
Competitiveness (Projects CTQ2012-30703, CTQ2012-31762,
MAT2014-61992-EXP, and Grant PRX14/00249), and the UE
(FEDER funding).


  • PROX
  • copper
  • ceria
  • CO oxidation
  • H-2 purification
  • hydrogen-rich stream
  • gas shift catalysts
  • operando-drifts
  • solid-solutions
  • soot oxidation
  • CEO2
  • oxygen
  • H-2
  • CU
  • CEO2-ZRO2


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