Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3

    Research output: Contribution to journalArticle

    Published

    Standard

    Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3. / Dann, Ellie K.; Gibson, Emma K.; Catlow, C. Richard A.; Celorrio, Veronica; Collier, Paul; Eralp, Tugce; Amboage, Monica; Hardacre, Christopher; Stere, Cristina; Kroner, Anna; Raj, Agnes; Rogers, Scott; Goguet, Alexandre; Wells, Peter P.

    In: Journal of Catalysis, Vol. 373, 01.05.2019, p. 201-208.

    Research output: Contribution to journalArticle

    Harvard

    Dann, EK, Gibson, EK, Catlow, CRA, Celorrio, V, Collier, P, Eralp, T, Amboage, M, Hardacre, C, Stere, C, Kroner, A, Raj, A, Rogers, S, Goguet, A & Wells, PP 2019, 'Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3', Journal of Catalysis, vol. 373, pp. 201-208. https://doi.org/10.1016/j.jcat.2019.03.037

    APA

    Vancouver

    Author

    Dann, Ellie K. ; Gibson, Emma K. ; Catlow, C. Richard A. ; Celorrio, Veronica ; Collier, Paul ; Eralp, Tugce ; Amboage, Monica ; Hardacre, Christopher ; Stere, Cristina ; Kroner, Anna ; Raj, Agnes ; Rogers, Scott ; Goguet, Alexandre ; Wells, Peter P. / Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3. In: Journal of Catalysis. 2019 ; Vol. 373. pp. 201-208.

    Bibtex

    @article{940cbaff2285411a83779d18dd932b4c,
    title = "Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3",
    abstract = "Spatially resolved, combined energy dispersive EXAFS (EDE) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements have been performed over a fixed catalyst bed of Pd/γ-Al 2 O 3 during kinetic oscillations of CO oxidation. The kinetic oscillations of CO oxidation over Pd (or for that matter Pt or Rh) catalysts are a complicated phenomenon that require characterisation techniques with high time resolution and spatial resolution in order to make links between catalyst structure and surface reactivity. By measuring the extent of Pd oxidation at the nanoparticle surface, from Pd K-edge EDE, and matching this with the CO coverage, from DRIFTS spectra, at multiple positions of the fixed bed reactor it is found that the majority of the catalyst undergoes a sharp transition from the CO poisoned catalyst to the highly active, oxidised Pd surface. This transition occurs initially at the end of the catalyst bed, nearest the outlet, and propagates upstream with increasing temperature of the reactor. The oscillations in Pd surface oxide formation and CO coverage are observed only in the first ∼1 mm of the bed, which gives rise to oscillations in CO 2 and O 2 concentrations observed by end-pipe mass spectrometry after the light-off temperature. The catalyst initially exists as less active, CO poisoned metallic Pd nanoparticles before light-off which transition to a highly active state after light-off when the Pd nanoparticle surface becomes dominated by chemisorbed oxygen. Kinetic oscillations only occur at the front of the catalyst bed where there is sufficient concentration of CO in the gas phase to compete with O 2 for adsorption sites at the catalyst surface. We demonstrate the complex nature of the evolving catalyst structure and surface reactivity during catalytic operation and the need for spatially resolved operando methods for understanding and optimising catalyst technologies.",
    keywords = "CO oxidation, DRIFTS, Operando spectroscopy, Pd/Al O, XAFS",
    author = "Dann, {Ellie K.} and Gibson, {Emma K.} and Catlow, {C. Richard A.} and Veronica Celorrio and Paul Collier and Tugce Eralp and Monica Amboage and Christopher Hardacre and Cristina Stere and Anna Kroner and Agnes Raj and Scott Rogers and Alexandre Goguet and Wells, {Peter P.}",
    year = "2019",
    month = "5",
    day = "1",
    doi = "10.1016/j.jcat.2019.03.037",
    language = "English",
    volume = "373",
    pages = "201--208",
    journal = "Journal of Catalysis",
    issn = "0021-9517",
    publisher = "Academic Press Inc.",

    }

    RIS

    TY - JOUR

    T1 - Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/Γ-Al 2 O 3

    AU - Dann, Ellie K.

    AU - Gibson, Emma K.

    AU - Catlow, C. Richard A.

    AU - Celorrio, Veronica

    AU - Collier, Paul

    AU - Eralp, Tugce

    AU - Amboage, Monica

    AU - Hardacre, Christopher

    AU - Stere, Cristina

    AU - Kroner, Anna

    AU - Raj, Agnes

    AU - Rogers, Scott

    AU - Goguet, Alexandre

    AU - Wells, Peter P.

    PY - 2019/5/1

    Y1 - 2019/5/1

    N2 - Spatially resolved, combined energy dispersive EXAFS (EDE) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements have been performed over a fixed catalyst bed of Pd/γ-Al 2 O 3 during kinetic oscillations of CO oxidation. The kinetic oscillations of CO oxidation over Pd (or for that matter Pt or Rh) catalysts are a complicated phenomenon that require characterisation techniques with high time resolution and spatial resolution in order to make links between catalyst structure and surface reactivity. By measuring the extent of Pd oxidation at the nanoparticle surface, from Pd K-edge EDE, and matching this with the CO coverage, from DRIFTS spectra, at multiple positions of the fixed bed reactor it is found that the majority of the catalyst undergoes a sharp transition from the CO poisoned catalyst to the highly active, oxidised Pd surface. This transition occurs initially at the end of the catalyst bed, nearest the outlet, and propagates upstream with increasing temperature of the reactor. The oscillations in Pd surface oxide formation and CO coverage are observed only in the first ∼1 mm of the bed, which gives rise to oscillations in CO 2 and O 2 concentrations observed by end-pipe mass spectrometry after the light-off temperature. The catalyst initially exists as less active, CO poisoned metallic Pd nanoparticles before light-off which transition to a highly active state after light-off when the Pd nanoparticle surface becomes dominated by chemisorbed oxygen. Kinetic oscillations only occur at the front of the catalyst bed where there is sufficient concentration of CO in the gas phase to compete with O 2 for adsorption sites at the catalyst surface. We demonstrate the complex nature of the evolving catalyst structure and surface reactivity during catalytic operation and the need for spatially resolved operando methods for understanding and optimising catalyst technologies.

    AB - Spatially resolved, combined energy dispersive EXAFS (EDE) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements have been performed over a fixed catalyst bed of Pd/γ-Al 2 O 3 during kinetic oscillations of CO oxidation. The kinetic oscillations of CO oxidation over Pd (or for that matter Pt or Rh) catalysts are a complicated phenomenon that require characterisation techniques with high time resolution and spatial resolution in order to make links between catalyst structure and surface reactivity. By measuring the extent of Pd oxidation at the nanoparticle surface, from Pd K-edge EDE, and matching this with the CO coverage, from DRIFTS spectra, at multiple positions of the fixed bed reactor it is found that the majority of the catalyst undergoes a sharp transition from the CO poisoned catalyst to the highly active, oxidised Pd surface. This transition occurs initially at the end of the catalyst bed, nearest the outlet, and propagates upstream with increasing temperature of the reactor. The oscillations in Pd surface oxide formation and CO coverage are observed only in the first ∼1 mm of the bed, which gives rise to oscillations in CO 2 and O 2 concentrations observed by end-pipe mass spectrometry after the light-off temperature. The catalyst initially exists as less active, CO poisoned metallic Pd nanoparticles before light-off which transition to a highly active state after light-off when the Pd nanoparticle surface becomes dominated by chemisorbed oxygen. Kinetic oscillations only occur at the front of the catalyst bed where there is sufficient concentration of CO in the gas phase to compete with O 2 for adsorption sites at the catalyst surface. We demonstrate the complex nature of the evolving catalyst structure and surface reactivity during catalytic operation and the need for spatially resolved operando methods for understanding and optimising catalyst technologies.

    KW - CO oxidation

    KW - DRIFTS

    KW - Operando spectroscopy

    KW - Pd/Al O

    KW - XAFS

    UR - http://www.scopus.com/inward/record.url?scp=85063948970&partnerID=8YFLogxK

    U2 - 10.1016/j.jcat.2019.03.037

    DO - 10.1016/j.jcat.2019.03.037

    M3 - Article

    VL - 373

    SP - 201

    EP - 208

    JO - Journal of Catalysis

    T2 - Journal of Catalysis

    JF - Journal of Catalysis

    SN - 0021-9517

    ER -

    Download

    Download as: RIS