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Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes

Nature Catalysis volume 5, pages 300–310 (2022)Cite this article

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Abstract

Atom trapping of scarce precious metals onto a suitable support at high temperatures has emerged as an effective approach to build thermally stable single-atom catalysts. Here, following a similar mechanism based on atom trapping through support effects, we demonstrate a reverse atom-trapping strategy to controllably extract strontium atoms from a rigid lanthanum strontium cobalt ferrite ((La0.6Sr0.4)0.95Co0.2Fe0.8O3−δ, LSCF) surface with ease. The lattice oxygen redox activity of LSCF is accordingly fine-tuned, leading to enhanced cathode performance in a solid-oxide fuel cell. An over 30−70% increases in maximum power density of the single cells at intermediate temperatures is achieved by LSCF with surface strontium vacancies compared to the pristine surface. In addition, the strontium-deficient surface excludes strontium segregation and formation of electrochemically inert SrO islands, thus improving the longevity of the cathode. This development can be broadly applicable for modifying structurally stable oxide surfaces, and opens more possibilities of scalable single-atom extraction strategies.

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Fig. 1: Atom trapping versus reverse atom trapping.
Fig. 2: Experimental demonstration and mechanism of reverse atom trapping.
Fig. 3: Atomic-scale imaging of atomic strontium vacancy.
Fig. 4: Structural characterizations of the transition-metal−oxygen bond.
Fig. 5: Cathode performance and theoretical understandings of strontium-deficient LSCF.

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Data availability

Atomic coordinates of the optimized computational models are provided as Supplementary Data 1 with this paper. Other data that support the findings of this study can be found in the article and the Supplementary Information; this information is also available from the corresponding author upon request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0702003 to Y.D.L.), the National Natural Science Foundation of China (21890383 to Y.D.L., 21871159 and 22171157 to D.W., and 52002249 to Y.H.L.), the Beijing Natural Science Foundation (2214061 to Z.Z.), the Science and Technology Key Project of Guangdong Province of China (2020B010188002 to D.W.), the Guangdong Basic and Applied Basic Research Foundation (2019A1515110025 to Y.H.L.), the Fundamental Research Funds for the Central Universities (WUT: 2019III012GX and 2020III002GX to J.S.W.), and the China Postdoctoral Science Foundation (2019M660607 to Z.Z.). The S/TEM work was performed at the Nanostructure Research Center (NRC), which is supported by the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, and the State Key Laboratory of Silicate Materials for Architectures (all of the laboratories are at Wuhan University of Technology). We thank the 1W1B and 4B9B beamlines of Beijing Synchrotron Radiation Facility (BSRF) and the BL14W1 beamline of Shanghai Synchrotron Radiation Facility (SSRF) for providing beam time to support this project. We also thank L. Zheng of Institute of High Energy Physics, Chinese Academy of Sciences and K. Cao of ShanghaiTech University for providing insightful discussions. Z.Z. acknowledges support from the Shuimu Tsinghua Scholar Program.

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Author notes

  1. These authors contributed equally: Zechao Zhuang, Yihang Li, Ruohan Yu.

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, P. R. China

    Zechao Zhuang, Jiarui Yang, Dingsheng Wang & Yadong Li

  2. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, P. R. China

    Yihang Li & Liangdong Fan

  3. Interdisciplinary Research Center of Smart Sensors, Academy of Advanced Interdisciplinary Research, Xidian University, Xi’an, P. R. China

    Yihang Li

  4. Nanostructure Research Centre, Wuhan University of Technology, Wuhan, P. R. China

    Ruohan Yu & Jinsong Wu

  5. State Key Laboratory of Silicate Materials for Architectures, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, P. R. China

    Lixue Xia & Yan Zhao

  6. Center for Marine Materials Corrosion and Protection, College of Materials, Xiamen University, Xiamen, P. R. China

    Zhiquan Lang

  7. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, P. R. China

    Jiexin Zhu

  8. State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, P. R. China

    Jiazhao Huang

  9. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, P. R. China

    Jiaou Wang

  10. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, P. R. China

    Yu Wang

  11. The Institute of Technological Sciences, Wuhan University, Wuhan, P. R. China

    Yan Zhao

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  1. Zechao Zhuang
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Contributions

D.W. and Y.D.L. supervised the research. Z.Z. conceived the idea, designed the experiments and analysed the data. Z.Z. and J.H. prepared the catalysts and Z.Z., Y.H.L., Z.L., J.Z. and J.H. performed the catalyst characterization. Z.Z., Y.H.L. and L.F. conducted the electrochemical tests. R.Y. performed the STEM studies and Z.Z., R.Y. and J.S.W. analysed the data. Z.Z. and Y.Z. developed the theoretical framework and Z.Z., J.Y. and L.X. carried out the DFT computations. Z.Z., J.Y., J.O.W. and Y.W. collected and analysed the X-ray absorption spectroscopy data. Z.Z. wrote the manuscript and all authors contributed to the discussions and revisions of the manuscript.

Corresponding authors

Correspondence to Dingsheng Wang or Yadong Li.

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Nature Catalysis thanks John Buckeridge and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1-32 and Tables 1–7.

Supplementary Data 1

Atomic coordinates of optimized computational models.

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Zhuang, Z., Li, Y., Yu, R. et al. Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes. Nat Catal 5, 300–310 (2022). https://doi.org/10.1038/s41929-022-00764-9

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