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Subsurface A-site vacancy activates lattice oxygen in perovskite ferrites for methane anaerobic oxidation to syngas

Author

Listed:
  • Jiahui He

    (Chinese Academy of Sciences
    Chemical Engineering Research Center for the Ministry of Education for Advance Use Technology of Shanbei Energy)

  • Tengjiao Wang

    (Dalian University of Technology)

  • Xueqian Bi

    (Chinese Academy of Sciences
    Dalian Maritime University)

  • Yubo Tian

    (Chinese Academy of Sciences
    Zhengzhou University)

  • Chuande Huang

    (Chinese Academy of Sciences)

  • Weibin Xu

    (Chinese Academy of Sciences
    University of Chinese Academy of Science)

  • Yue Hu

    (Chinese Academy of Sciences
    University of Chinese Academy of Science)

  • Zhen Wang

    (Chinese Academy of Sciences
    University of Chinese Academy of Science)

  • Bo Jiang

    (Dalian University of Technology)

  • Yuming Gao

    (Dalian University of Technology)

  • Yanyan Zhu

    (Chemical Engineering Research Center for the Ministry of Education for Advance Use Technology of Shanbei Energy)

  • Xiaodong Wang

    (Chinese Academy of Sciences)

Abstract

Tuning the oxygen activity in perovskite oxides (ABO3) is promising to surmount the trade-off between activity and selectivity in redox reactions. However, this remains challenging due to the limited understanding in its activation mechanism. Herein, we propose the discovery that generating subsurface A-site cation (Lasub.) vacancy beneath surface Fe-O layer greatly improved the oxygen activity in LaFeO3, rendering enhanced methane conversion that is 2.9-fold higher than stoichiometric LaFeO3 while maintaining high syngas selectivity of 98% in anaerobic oxidation. Experimental and theoretical studies reveal that absence of Lasub.-O interaction lowered the electron density over oxygen and improved the oxygen mobility, which reduced the barrier for C-H bond cleavage and promoted the oxidation of C-atom, substantially boosting methane-to-syngas conversion. This discovery highlights the importance of A-site cations in modulating electronic state of oxygen, which is fundamentally different from the traditional scheme that mainly credits the redox activity to B-site cations and can pave a new avenue for designing prospective redox catalysts.

Suggested Citation

  • Jiahui He & Tengjiao Wang & Xueqian Bi & Yubo Tian & Chuande Huang & Weibin Xu & Yue Hu & Zhen Wang & Bo Jiang & Yuming Gao & Yanyan Zhu & Xiaodong Wang, 2024. "Subsurface A-site vacancy activates lattice oxygen in perovskite ferrites for methane anaerobic oxidation to syngas," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-49776-y
    DOI: 10.1038/s41467-024-49776-y
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    References listed on IDEAS

    as
    1. Yan Liu & Lang Qin & Zhuo Cheng & Josh W. Goetze & Fanhe Kong & Jonathan A. Fan & Liang-Shih Fan, 2019. "Near 100% CO selectivity in nanoscaled iron-based oxygen carriers for chemical looping methane partial oxidation," Nature Communications, Nature, vol. 10(1), pages 1-6, December.
    2. Xing Zhu & Yunfei Gao & Xijun Wang & Vasudev Haribal & Junchen Liu & Luke M. Neal & Zhenghong Bao & Zili Wu & Hua Wang & Fanxing Li, 2021. "A tailored multi-functional catalyst for ultra-efficient styrene production under a cyclic redox scheme," Nature Communications, Nature, vol. 12(1), pages 1-11, December.
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