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Evaluation of the Oxygen Mobility in CePO4-Supported Catalysts: Mechanistic Implications on the Water–Gas Shift Reaction
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    C: Surfaces, Interfaces, Porous Materials, and Catalysis

    Evaluation of the Oxygen Mobility in CePO4-Supported Catalysts: Mechanistic Implications on the Water–Gas Shift Reaction
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    • Sara Navarro-Jaén*
      Sara Navarro-Jaén
      Departamento de Química Inorgánica e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla- CSIC, Av. Américo Vespucio 49 41092 Seville, Spain
      *Email: [email protected]
    • Luis F. Bobadilla
      Luis F. Bobadilla
      Departamento de Química Inorgánica e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla- CSIC, Av. Américo Vespucio 49 41092 Seville, Spain
    • Francisca Romero-Sarria
      Francisca Romero-Sarria
      Departamento de Química Inorgánica e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla- CSIC, Av. Américo Vespucio 49 41092 Seville, Spain
    • Oscar H. Laguna
      Oscar H. Laguna
      Departamento de Química Inorgánica e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla- CSIC, Av. Américo Vespucio 49 41092 Seville, Spain
    • Nicolas Bion
      Nicolas Bion
      Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers- CNRS, 4 rue Michel Brunet, TSA51106, F86073 Poitiers, Cedex 9 France
      More by Nicolas Bion
    • José A. Odriozola
      José A. Odriozola
      Departamento de Química Inorgánica e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla- CSIC, Av. Américo Vespucio 49 41092 Seville, Spain
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2020, 124, 30, 16391–16401
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    https://doi.org/10.1021/acs.jpcc.0c03649
    Published July 3, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    The hexagonal and monoclinic phases of CePO4 have been demonstrated to be excellent catalytic supports for Pt-based water–gas shift (WGS) catalysts. Consequently, the elucidation of the WGS reaction mechanism in these materials constitutes a fundamental aspect in order to explain their catalytic behavior. Because the observed WGS reaction path is closely related to the absence or presence of oxygen vacancies in the support, the study of the oxygen mobility in these solids constitutes a key factor for the understanding of the structure of the materials and its influence on the reaction mechanism. In this study, the oxygen mobility in CePO4 supports and the corresponding Pt catalysts has been evaluated by means of isotopic exchange experiments using 18O2 and C18O2 as probe molecules. Results demonstrate that the evaluated solids present a low exchange activity when 18O2 is used, indicating the absence of oxygen vacancies in these solids, thus suggesting a poor influence of the WGS redox mechanism. On the contrary, a high oxygen exchange activity is observed using C18O2, demonstrating that the exchange in these materials takes place through the formation of carbonate-like intermediates, thus suggesting the associative mechanism of the WGS reaction as the preferred path in these solids. Operando diffuse reflectance infrared spectroscopy experiments under WGS reaction conditions confirm these results, proving that the WGS reaction in the studied materials takes place through a formate-mediated associative mechanism.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.0c03649.

    • WGS catalytic performance of the Pt catalysts, mean Pt particle size, metal dispersion values, and TEM micrographs (PDF).

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    Cited By

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    This article is cited by 6 publications.

    1. Qiguang Dai, Ronghua Xu, Hangqi Xia, Boyuan Qiao, Qiang Niu, Li Wang, Aiyong Wang, Yun Guo, Yanglong Guo, Wei Wang, Wangcheng Zhan. Catalytic Hydrolysis–Oxidation of Halogenated Methanes over Phase- and Defect-Engineered CePO4: Halogenated Byproduct-Free and Stable Elimination. Environmental Science & Technology 2024, 58 (30) , 13562-13573. https://doi.org/10.1021/acs.est.4c04436
    2. Max L. Bols, Jing Ma, Fatima Rammal, Dieter Plessers, Xuejiao Wu, Sara Navarro-Jaén, Alexander J. Heyer, Bert F. Sels, Edward I. Solomon, Robert A. Schoonheydt. In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis. Chemical Reviews 2024, 124 (5) , 2352-2418. https://doi.org/10.1021/acs.chemrev.3c00602
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    4. S. Abima, S. Sumathi. Influence of method of synthesis on the colour and NIR reflective properties of bismuth and vanadium doped cerium phosphate. Journal of Solid State Chemistry 2023, 324 , 124140. https://doi.org/10.1016/j.jssc.2023.124140
    5. Valeriia Maslova, Elodie Fourré, Gleb Veryasov, Nikolai Nesterenko, André Grishin, Christophe Louste, Michelle Nassar, Nadia Guignard, Sandrine Arrii, Catherine Batiot‐Dupeyrat. Ammonia Decomposition in Electric Field over Ce‐based Materials. ChemCatChem 2023, 15 (4) https://doi.org/10.1002/cctc.202201626
    6. Cuixia Cheng, Fang Chen, Huiyang Yi, Yinfang Cheng, Guosong Lai. Synthesis, optical and electrochemical performance of CePO4 micro-rods. Materials Science and Engineering: B 2021, 272 , 115319. https://doi.org/10.1016/j.mseb.2021.115319

    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2020, 124, 30, 16391–16401
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.0c03649
    Published July 3, 2020
    Copyright © 2020 American Chemical Society

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