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Unravelling the Role of Structural Geometry and Chemical State of Well-Defined Oxygen Vacancies on Pristine CeO2 for H2O2 Activation

  • Zicong Tan
    Zicong Tan
    Department of Chemistry, City University of Hong Kong, Hong Kong SAR, China
    More by Zicong Tan
  • Jieru Zhang
    Jieru Zhang
    Department of Chemistry, City University of Hong Kong, Hong Kong SAR, China
    More by Jieru Zhang
  • Yu-Cheng Chen
    Yu-Cheng Chen
    Department of Mechanical Engineering, City University of Hong Kong, Hong Kong SAR, China
  • Jyh-Pin Chou
    Jyh-Pin Chou
    Department of Physics, National Changhua University of Education, Changhua 500, Taiwan
    More by Jyh-Pin Chou
  • , and 
  • Yung-Kang Peng*
    Yung-Kang Peng
    Department of Chemistry, City University of Hong Kong, Hong Kong SAR, China
    City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057, China
    *Email: [email protected]
Cite this: J. Phys. Chem. Lett. 2020, 11, 14, 5390–5396
Publication Date (Web):June 17, 2020
https://doi.org/10.1021/acs.jpclett.0c01557
Copyright © 2020 American Chemical Society
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Abstract

Although H2O2 has been often employed as a green oxidant for many CeO2-catalyzed reactions, the underlying principle of its activation by surface oxygen vacancy (Vo) is still elusive due to the irreversible removal of postgenerated Vo by water (or H2O2). The metastable Vo (ms-Vo) naturally preserved on pristine CeO2 surfaces was adopted herein for an in-depth study of their interplay with H2O2. Their well-defined local structures and chemical states were found facet-dependent affecting both the adsorption and subsequent activation of H2O2. It is concluded that a strong adsorption of H2O2 on ms-Vo may not guarantee its subsequent activation. The ms-Vo can be only free for the next catalytic cycle when the electron density of surface Ce is high enough to reduce/break the O–O bond of adsorbed H2O2. This explains the 211.8 and 35.8 times enhancement in H2O2 reactivity when the CeO2 surface is changed from (111) and (110) to (100).

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  • XRD, BET, XPS characterization of CeO2 shapes, and the corresponding adsorption/activation study of H2O2 on CeO2 surfaces (PDF)

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