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Experimental Sabatier plot for predictive design of active and stable Pt-alloy oxygen reduction reaction catalysts

Nature Catalysis volume 5, pages 513–523 (2022)Cite this article

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Abstract

A critical technological roadblock to the widespread adoption of proton-exchange membrane fuel cells is the development of highly active and durable platinum-based catalysts for accelerating the sluggish oxygen reduction reaction, which has largely relied on anecdotal discoveries so far. While the oxygen binding energy ∆EO has been frequently used as a theoretical descriptor for predicting the activity, there is no known descriptor for predicting durability. Here we developed a binary experimental descriptor that captures both the strain and Pt transition metal coupling contributions through X-ray absorption spectroscopy and directly correlated the binary experimental descriptor with the calculated ∆EO of the catalyst surface. This leads to an experimentally validated Sabatier plot to predict both the catalytic activity and stability for a wide range of Pt-alloy oxygen reduction reaction catalysts. Based on the binary experimental descriptor, we further designed an oxygen reduction reaction catalyst wherein high activity and stability are simultaneously achieved.

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Fig. 1: Design and comparison of sd-PtNi and fd-PtNi catalysts.
Fig. 2: Development of the BED and the Sabatier plot.
Fig. 3: Experimentally validated sd-PtNiCo catalyst with high activity and stability.
Fig. 4: Experimentally validated Sabatier plot of Pt-alloy catalysts and stability analysis.

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Data availability

The atomic coordinates of the DFT calculation data and simulated XANES data are available in the Supplementary Data. The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

Y.H., Q.J., W.A.G. and X.D. gratefully acknowledge the support of the Office of Naval Research (award N000141812155). The XAS data were collected at beamlines 6-BM, 7-BM and 8-ID of the National Synchrotron Light Source II, a US Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. We acknowledge the use of facilities and instrumentation at the University of California Irvine Materials Research Institute, supported in part by the National Science Foundation Materials Research Science and Engineering Center programme through the University of California Irvine Center for Complex and Active Materials (DMR-2011967). We also thank the Electron Imaging Center of Nanomachines at the California NanoSystems Institute (CNSI) for TEM support. A.F. and W.A.G. received support from the National Science Foundation (CBET-1805022 and CBET-2005250). A.F., G.B. and L.S. gratefully acknowledge the contribution of the International Research Network on Nanoalloys Centre national de la recherche scientifique (CNRS) and computational support from the CINECA supercomputing centre within the Italian SuperComputing Resource Allocation (ISCRA) programme.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA

    Jin Huang, Zeyan Liu, Miao Feng, Sung-Joon Lee, Enbo Zhu, Yang Liu & Yu Huang

  2. CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa, Italy

    Luca Sementa, Giovanni Barcaro & Alessandro Fortunelli

  3. College of Materials Science and Engineering, Fuzhou University, Fuzhou, P. R. China

    Miao Feng

  4. Department of Chemistry and Chemical Biology, Northeastern University, Boston, MA, USA

    Ershuai Liu, Li Jiao & Qingying Jia

  5. Irvine Materials Research Institute, University of California, Irvine, CA, USA

    Mingjie Xu

  6. Department of Materials Science, University of California, Irvine, CA, USA

    Mingjie Xu

  7. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Denis Leshchev

  8. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Mufan Li, Chengzhang Wan, Bosi Peng & Xiangfeng Duan

  9. California NanoSystems Institute, University of California, Los Angeles, CA, USA

    Xiangfeng Duan & Yu Huang

  10. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA

    William A. Goddard III

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Contributions

J.H., M.F., M.L., Y.L., C.W., S.-J.L., B.P. and Z.L. conducted the synthesis of electrocatalysts, structural characterization and electrochemical experiments. M.X. and J.H. conducted the TEM and EDX characterizations. Q.J., E.L., L.J. and D.L. conducted the XAS studies. A.F., L.S., G.B., Q.J., J.H. and W.A.G. performed the modelling and data analyses. The project was conceived by Y.H. and supervised by Y.H. (project design, syntheses and evaluation of the catalysts); Q.J. (XAS studies); and A.F. and W.A.G. (computational studies). J.H., Y.H., Q.J. and A.F. wrote the original draught. J.H., Y.H., Q.J., A.F., W.A.G. and Z.L. revised the manuscript.

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Correspondence to William A. Goddard III, Alessandro Fortunelli, Qingying Jia or Yu Huang.

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

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Supplementary Information

Supplementary Notes 1–3, Figs. 1–34, Tables 1–6 and refs. 1–12.

Supplementary Data

Coordination of DFT models.

Source data

Source Data Fig. 2

Source data of the XANES simulation.

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Huang, J., Sementa, L., Liu, Z. et al. Experimental Sabatier plot for predictive design of active and stable Pt-alloy oxygen reduction reaction catalysts. Nat Catal 5, 513–523 (2022). https://doi.org/10.1038/s41929-022-00797-0

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