Understanding Catalytic Mechanisms of Alkane Oxychlorination from the Perspective of Energy Levels

  • Hua-Min Zhang
    Hua-Min Zhang
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
  • Qi-Yuan Fan
    Qi-Yuan Fan
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
    More by Qi-Yuan Fan
  • Qing-Hong Zhang*
    Qing-Hong Zhang
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
    *Email: [email protected]
  • Jin-Can Kang
    Jin-Can Kang
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
    More by Jin-Can Kang
  • Ye Wang*
    Ye Wang
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
    *Email: [email protected]
    More by Ye Wang
  • , and 
  • Jun Cheng*
    Jun Cheng
    State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
    *Email: [email protected]
    More by Jun Cheng
Cite this: J. Phys. Chem. C 2020, 124, 11, 6070–6077
Publication Date (Web):March 2, 2020
https://doi.org/10.1021/acs.jpcc.9b10464
Copyright © 2020 American Chemical Society
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Abstract

Identifying surface-active sites and reaction pathways is of great significance in heterogeneous catalysis. However, even for the simplest catalytic reaction, there could exist a myriad of possible active sites and reaction intermediates, rending exhaustive computational and experimental investigations of all possible reaction pathways difficult. For the oxychlorination of C3H8 over CeO2 catalyst, electron affinity and Brønsted basicity of a variety of surface sites and reaction intermediates have been calculated using density functional theory (DFT), and a diagram of the corresponding energy levels is used to help identify the relevant reaction sites and intermediates. It is found that surface Cl radicals that are generated from Cl oxidation by peroxide at oxygen vacancies play an important role in the C–H activation of alkanes. The formation of C3H7Cl and C3H5Cl intermediates regulates reaction channels and prohibits overoxidation. We show that thermodynamic analysis based on energy levels is useful to elucidate reaction sites and mechanisms for oxidative dehydrogenation.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.9b10464.

  • Calculation of electron affinity, proton affinity, and hydrogenation energy (Section 1); thermodynamic triangle of deprotonation, oxidation, and dehydrogenation reaction (Figure S1); electronic structure analysis of “proton anchored on reference O” site (Figure S2, Table S1); structures and spin states of different surface sites/species on CeO2 surface (Figures S3–S10); configurations of intermediates and transition states in energy profiles of C3H8 conversion (Section 2); and size effect of calculation model (Section 3) (PDF)

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Cited By


This article is cited by 4 publications.

  1. Xiao Jiang, Lohit Sharma, Victor Fung, Sang Jae Park, Christopher W. Jones, Bobby G. Sumpter, Jonas Baltrusaitis, Zili Wu. Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis. ACS Catalysis 2021, 11 (4) , 2182-2234. https://doi.org/10.1021/acscatal.0c03999
  2. Guido Zichittella, Yevhen Polyhach, René Tschaggelar, Gunnar Jeschke, Javier Pérez‐Ramírez. Quantification of Redox Sites during Catalytic Propane Oxychlorination by Operando EPR Spectroscopy. Angewandte Chemie 2021, 133 (7) , 3640-3646. https://doi.org/10.1002/ange.202013331
  3. Guido Zichittella, Yevhen Polyhach, René Tschaggelar, Gunnar Jeschke, Javier Pérez‐Ramírez. Quantification of Redox Sites during Catalytic Propane Oxychlorination by Operando EPR Spectroscopy. Angewandte Chemie International Edition 2021, 60 (7) , 3596-3602. https://doi.org/10.1002/anie.202013331
  4. Yahya Gambo, Sagir Adamu, Abdulrahman A. Abdulrasheed, Rahima A. Lucky, Mohammed S. Ba-Shammakh, Mohammad. M. Hossain. Catalyst design and tuning for oxidative dehydrogenation of propane – A review. Applied Catalysis A: General 2021, 609 , 117914. https://doi.org/10.1016/j.apcata.2020.117914