RETURN TO ISSUEPREVC: Chemical and Cata...C: Chemical and Catalytic Reactivity at InterfacesNEXT

Co–CeO2 Interaction Induces the Mars–van Krevelen Mechanism in Dehydrogenation of Ethane

  • Yukiko Hosono
    Yukiko Hosono
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
  • Hikaru Saito
    Hikaru Saito
    Department of Materials Molecular Science, Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Aichi, Japan
    More by Hikaru Saito
  • Takuma Higo
    Takuma Higo
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
    More by Takuma Higo
  • Kosuke Watanabe
    Kosuke Watanabe
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
  • Kazuharu Ito
    Kazuharu Ito
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
    More by Kazuharu Ito
  • Hideaki Tsuneki
    Hideaki Tsuneki
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
  • Shun Maeda
    Shun Maeda
    Steel Castings R&D Group, Materials Technology Department, Kubota Corporation, 1-1-1 Nakamiya-Oike, Hirakata 573-8573, Osaka, Japan
    More by Shun Maeda
  • Kunihide Hashimoto
    Kunihide Hashimoto
    Steel Castings R&D Group, Materials Technology Department, Kubota Corporation, 1-1-1 Nakamiya-Oike, Hirakata 573-8573, Osaka, Japan
  • , and 
  • Yasushi Sekine*
    Yasushi Sekine
    Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo 169-8555, Japan
    *Email: [email protected]
Cite this: J. Phys. Chem. C 2021, 125, 21, 11411–11418
Publication Date (Web):May 19, 2021
https://doi.org/10.1021/acs.jpcc.1c02855
Copyright © 2021 The Authors. Published by American Chemical Society
Article Views
413
Altmetric
-
Citations
-
LEARN ABOUT THESE METRICS
Read OnlinePDF (2 MB)
Supporting Info (1)»

Abstract

Introducing a catalyst for dehydrogenation of ethane (EDH) for steam cracking represents a promising solution with high feasibility to realize efficient ethylene production. We investigated EDH over transition-metal-doped CeO2 catalysts at 873 K in the presence of steam. Ce0.8Co0.2O2 exhibited high EDH activity and selectivity to ethylene (ca. 95%). In the absence of H2O, the catalytic activity dropped rapidly, indicating the promotive effect of H2O on ethylene formation. Catalytic experiments with water isotopes (D2O and H218O) demonstrated that EDH over Ce0.8Co0.2O2 proceeds through the Mars–van Krevelen (MvK) mechanism in which the reactive lattice oxygen in Ce0.8Co0.2O2 contributes to EDH. The consumed lattice oxygen was subsequently regenerated with H2O. X-ray diffraction and in situ X-ray absorption fine structure spectroscopy revealed that cobalt species were mainly present as CoO under EDH conditions and that redox between Co2+ and Co0 proceeded concomitantly with EDH. In contrast with Ce0.8Co0.2O2, no contribution of the lattice oxygen of CoO to EDH was verified in the case of CoO supported on α-Al2O3, which exhibited lower activity than Ce0.8Co0.2O2. Therefore, Co–CeO2 interactions are expected to play a crucially important role in controlling the characteristics of the reactive lattice oxygen suitable for EDH via the MvK mechanism.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.1c02855.

  • Experiment flow of activity test using H218O; C2H6 conversion, C2H4 formation rate, and selectivity to each product; C2H4 formation rate and C2H6 conversion–C2H4 selectivity plot; XRD pattern of bare CeO2 and y mol % Co/CeO2 (y = 5–20); TEM and high-angle annular dark field images with EDX mapping; XRD patterns of fresh and spent (after the wet test) 20 mol % Co/α-Al2O3; experiment flow of in situ Co K-edge XAFS spectroscopy; XANES spectra of Ce0.8Co0.2O2 under H2O atmosphere and reaction gas atmosphere; In situ Ce K-edge XANES spectra of Ce0.8Co0.2O2 under H2O atmosphere and reaction gas atmosphere; catalytic performance of bare CeO2 and Ce0.9M0.1O2; catalytic performance of bare CeO2 and Ce1–xCoxO2 (x = 0–0.4); and BET surface area of bare CeO2 and Ce1–xCoxO2 (x = 0–0.4) (PDF).

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By


This article has not yet been cited by other publications.