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

Jiahui He, Tengjiao Wang, Xueqian Bi, Yubo Tian, Chuande Huang (), Weibin Xu, Yue Hu, Zhen Wang, Bo Jiang (), Yuming Gao, Yanyan Zhu () and Xiaodong Wang ()
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Jiahui He: Chinese Academy of Sciences
Tengjiao Wang: Dalian University of Technology
Xueqian Bi: Chinese Academy of Sciences
Yubo Tian: Chinese Academy of Sciences
Chuande Huang: Chinese Academy of Sciences
Weibin Xu: Chinese Academy of Sciences
Yue Hu: Chinese Academy of Sciences
Zhen Wang: Chinese Academy of Sciences
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

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-49776-y

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