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Methane Activation on Metal-Doped (111) and (100) Ceria Surfaces with Charge-Compensating Oxygen Vacancies

  • Giulia Righi*
    Giulia Righi
    Department of Physics, Informatics and Mathematics, University of Modena and Reggio—Emilia, via Campi 213/A, 41100 Modena, Italy
    CNR-S3 Institute of Nanoscience, via Campi 213/A, 41100 Modena, Italy
    *Email: [email protected]
    More by Giulia Righi
  • Rita Magri
    Rita Magri
    Department of Physics, Informatics and Mathematics, University of Modena and Reggio—Emilia, via Campi 213/A, 41100 Modena, Italy
    CNR-S3 Institute of Nanoscience, via Campi 213/A, 41100 Modena, Italy
    More by Rita Magri
  • , and 
  • Annabella Selloni
    Annabella Selloni
    Department of Chemistry, Princeton University, Princeton, New Jersey 08540, United States
Cite this: J. Phys. Chem. C 2020, 124, 32, 17578–17585
Publication Date (Web):July 17, 2020
https://doi.org/10.1021/acs.jpcc.0c03320
Copyright © 2020 American Chemical Society
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Abstract

Reducing the temperature for methane activation is an important objective that would benefit many technological applications. In this work, we explore the possibility to achieve this goal using single-atom catalysts (SACs) on ceria surfaces. We focus on Ag SACs, which have recently been suggested to be promising catalysts for both H2 and CH4 oxidation. Using first-principles calculations, we investigate methane activation on CeO2(111) and CeO2(100), two frequently exposed surfaces on ceria nanoparticles. The presence of Ag is found to reduce the activation energy for methane dissociation on both surfaces. On Ag-doped CeO2(111), the formation of methanol via the Mars–van Krevelen mechanism has a slightly lower energy barrier than the dissociation to CH3 + H, suggesting that methanol is a likely product of methane activation on this surface. A novel aspect of this work is the focus on stable surface structures where each Ag dopant substituting Ce forms a complex with a charge-compensating surface oxygen vacancy. These complexes are found to play a critical role and accounting for their presence is essential for a proper description of the surface reactivity.

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  • Top and side view of CeO2(111) and CeO2(100) (Figure S1), effect of coverage on the computed adsorption energies (Table S1); comparison of the computed adsorption energies with previous works (Table S2); Gibbs free energy of the oxidized and reduced Ag-doped (111) and (100) surfaces (Figure S2); top views of the Ag/CeO2(111) and Ag/CeO2(100) surfaces (Figure S3); molecular and dissociative adsorption of CH4 on the Ag/CeO2(111) surface (Figure S4); adsorption energies of molecular and dissociated CH4 on the Ag/CeO2(111) surface (Table S3); adsorption energies of molecular and dissociated CH4 on the Ag/CeO2(111), Ag/CeO2(111), and Ag/CeO2(111) computed with and without long-range interactions (Table S4); MEP of CH4 dissociation on the reduced CeO2–x(111) surface (Figure S5); MEP of the dissociative adsorption of CH4 to form methanol on the Ag/CeO2–x(111) surface (Figure S6); MEP of the reaction CH3OH → CH3 + H on Ag/CeO2–x(111) (Figure S6); desorption of CH3OH and adsorption of O2 at the resulting surface oxygen vacancy on the Ag/CeO2–x(111) surface (Figure S7); and MEPs of the dissociative adsorption of CH4 on the oxidized Ag/CeO2(111) surface (Figure S8) (PDF)

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Cited By


This article is cited by 4 publications.

  1. João Paulo A. de Mendonça, Tuanan C. Lourenço, Luis Paulo M. Freitas, Anderson A. E. Santo, Gustavo T. Feliciano, Juarez L. F. Da Silva. Molecular dynamics investigation of the structural and energetic properties of CeO 2 –MO x (M = Gd, La, Ce, Zr) nanoparticles. Materials Advances 2021, 2 (23) , 7759-7772. https://doi.org/10.1039/D1MA00543J
  2. Ling Zhang, Lu Sun, Qingling Meng, Jinge Wu, Xiamin Hao, Shuwei Zhai, Wenzhen Dou, Yizhen Jia, Miao Zhou. Strain‐Engineered Formation, Migration, and Electronic Properties of Polaronic Defects in CeO 2. physica status solidi (b) 2021, 258 (6) , 2100020. https://doi.org/10.1002/pssb.202100020
  3. Wang Jianchen, Kang Yong, Fangkuan Sun. Mass production of thermally stable Pt single-atom catalysts for the catalytic oxidation of sulfur dioxide. Catalysis Science & Technology 2021, 13 https://doi.org/10.1039/D1CY01578H
  4. Meema Bhati, Jignesh Dhumal, Kavita Joshi. Lowering the C–H bond activation barrier of methane by means of [email protected](111): periodic DFT investigations. New Journal of Chemistry 2021, 117 https://doi.org/10.1039/D1NJ04525C