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 journalArticle

71 Citations (Scopus)

Abstract

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
Volume6
Issue number3
Early online date1 Feb 2016
DOIs
Publication statusPublished - Mar 2016

Keywords

  • 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

Cite this

Davo-Quilionero, A., Navlani-Garcia, M., Lozano-Castello, D., Bueno-Lopez, A., & Anderson, J. A. (2016). Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts. ACS Catalysis, 6(3), 1723-1731. https://doi.org/10.1021/acscatal.5b02741

Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts. / Davo-Quilionero, Arantxa; Navlani-Garcia, Miriam; Lozano-Castello, Dolores; Bueno-Lopez, Agustin; Anderson, James A.

In: ACS Catalysis, Vol. 6, No. 3, 03.2016, p. 1723-1731.

Research output: Contribution to journalArticle

Davo-Quilionero, A, Navlani-Garcia, M, Lozano-Castello, D, Bueno-Lopez, A & Anderson, JA 2016, 'Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts', ACS Catalysis, vol. 6, no. 3, pp. 1723-1731. https://doi.org/10.1021/acscatal.5b02741
Davo-Quilionero A, Navlani-Garcia M, Lozano-Castello D, Bueno-Lopez A, Anderson JA. Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts. ACS Catalysis. 2016 Mar;6(3):1723-1731. https://doi.org/10.1021/acscatal.5b02741
Davo-Quilionero, Arantxa ; Navlani-Garcia, Miriam ; Lozano-Castello, Dolores ; Bueno-Lopez, Agustin ; Anderson, James A. / Role of Hydroxyl Groups in the Preferential Oxidation of CO over Copper Oxide-Cerium Oxide Catalysts. In: ACS Catalysis. 2016 ; Vol. 6, No. 3. pp. 1723-1731.
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abstract = "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.",
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note = "ACKNOWLEDGMENTS 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).",
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AU - Bueno-Lopez, Agustin

AU - Anderson, James A.

N1 - ACKNOWLEDGMENTS 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).

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N2 - 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.

AB - 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.

KW - PROX

KW - copper

KW - ceria

KW - CO oxidation

KW - H-2 purification

KW - hydrogen-rich stream

KW - gas shift catalysts

KW - operando-drifts

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KW - soot oxidation

KW - CEO2

KW - oxygen

KW - H-2

KW - CU

KW - CEO2-ZRO2

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