Hole‐Mediated Lattice Oxygen Redox Design for Perovskite Oxide Catalysts
Present design and application of perovskite oxide catalysts assume lattice oxygen redox (LOR) mechanisms that depend on lattice oxygen activity without consideration of the entire redox cycle. Herein, using in situ characterizations and theoretical calculations, we uncover a hole-mediated LOR cycle on p-type Sr-deficient SrFeO<sub>3-δ</sub> (SFO-Srv) perovskites in CO oxidation reaction. Sr vacancies activate surface lattice oxygen of SFO-Srv and promote formation of highly covalent Fe<sup>(4-x)+</sup>-O<sup>(2-x)-</sup> sites. In situ electrical conductivity measurement demonstrates that holes directly participate in the entire LOR cycle, and are reversibly consumed and regenerated in reducing/oxidizing atmosphere via Fe<sup>(4-x)+</sup>-O<sup>(2-x)-</sup> sites of SFO-Srv. Hole-mediated LOR in SFO-Srv, as revealed by in situ soft X-ray absorption spectroscopy, occurs through changing in covalency of Fe-O bonds, O 2p hole state, and electron density of Fe sites. <sup>18</sup>O<sub>2</sub> labeling experiment further confirms an improved Mars-van Krevelen pathway in the hole-mediated LOR cycle, which accounts for a ten-times enhancement of SFO-Srv for CO reaction rate over that of SFO alone.
Authors
- Yimin A. Wu (ORCID: https://orcid.org/0000-0002-3807-8431)
- Jingze Shao (ORCID: https://orcid.org/0009-0008-5605-4450)
- Haozhe Liu (ORCID: https://orcid.org/0000-0001-5720-2031)
- Subhajit Jana (ORCID: https://orcid.org/0000-0003-3064-2621)
- Yue Peng (ORCID: https://orcid.org/0000-0001-5772-3443)
- Xinbo Li
- Zhen Li (ORCID: https://orcid.org/0000-0003-1433-6552)
- Ya‐Wen Zhang (ORCID: https://orcid.org/0000-0002-1871-7507)
- Xiyang Wang (ORCID: https://orcid.org/0000-0002-7591-6676)
- Yaowen Wang (ORCID: https://orcid.org/0000-0003-1816-4436)
- Zhiyao Wu
- Liping Li
- Guangshe Li (ORCID: https://orcid.org/0000-0001-8592-8729)
- Yingge Cong
Institutions
- Guangxi University (CN)
- University of Waterloo (CA)
- Jilin University (CN)
- Chinese Academy of Sciences (CN)
- Peking University (CN)
- Suzhou Institute of Biomedical Engineering and Technology (CN)
- Beijing National Laboratory for Molecular Sciences (CN)
- State Key Joint Laboratory of Environment Simulation and Pollution Control (CN)
- Center for High Pressure Science and Technology Advanced Research (CN)
- State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
- University of Hong Kong (HK)
- Tsinghua University (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-02-18
- DOI
- https://doi.org/10.1002/anie.202424347
- Citations
- 7
- Primary Topic
- Electrocatalysts for Energy Conversion
- Type
- article
- Field-Weighted Citation Impact
- 2.54
Funders
- Canadian Light Source
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- National Synchrotron Radiation Laboratory
- Natural Sciences and Engineering Research Council of Canada
- Suzhou Institute of Nanotechnology, Chinese Academy of Sciences