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Pt/Fe2O3 with Pt–Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading

Abstract

Platinum is the archetypal electrocatalyst for oxygen reduction—a key reaction in fuel cells and zinc–air batteries. Although dispersing platinum as single atoms on a support is a promising way to minimize the amount required, catalytic activity and selectivity are often low due to unfavourable O2 adsorption. Here we load platinum onto α-Fe2O3 to construct a highly active and stable catalyst with dispersed Pt–Fe pair sites. We propose that the Pt–Fe pair sites have partially occupied orbitals driven by strong electronic coupling, and can cooperatively adsorb O2 and dissociate the O=O bond, whereas OH* can desorb from the platinum site. In alkaline conditions, the catalyst exhibits onset and half-wave potentials of 1.15 V and 1.05 V (versus the reversible hydrogen electrode), respectively, mass activity of 14.9 A mg−1Pt (at 0.95 V) and negligible activity decay after 50,000 cycles. It also shows better performance than 20% Pt/C in a zinc–air battery and H2–O2 fuel cell in terms of specific energy density and platinum utilization efficiency.

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Fig. 1: Single-site Pt–Fe pair in Pt1–Fe/Fe2O3(012).
Fig. 2: Electronic structure of single-site Pt–Fe pair.
Fig. 3: Oxygen reduction reaction activities in 0.1 M KOH solution.
Fig. 4: Zinc–air battery and H2–O2 fuel cell performances.
Fig. 5: XPS at various applied potentials.
Fig. 6: Proposed ORR mechanism.

Data availability

The authors declare that all data supporting the findings of this study are available in the article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

J.-J.Z., L.P. and Z.-F.H. appreciate the support from the National Natural Science Foundation of China (grant nos. 22161142002, 21978200, 22008170). J.L. acknowledges the support from the National Research Foundation of Korea (NRF) grants funded by the Korean government (MSIT) (grant nos. NRF-2019R1A4A1025848 and NRF-2021R1C1C1013953). The wavefunction plots were drawn with the help of the VASPMO program developed by Y. Wang. We also thank the ZK Chemical Research Service Platform.

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J.-J.Z. conceived the idea. J.-J.Z., R.G. and L.P. co-wrote the paper. R.G. and L.P. synthesized the catalysts and performed the catalysis experiments, the theoretical model construction and DFT calculations. J.W. and J.L. contributed to the EXAFS spectroscopy. Z.-F.H. and R.Z. contributed to the EIS measurement and polished the manuscript. W. Wang supplied part of the data and experiments. J.Z. and W.Z. contributed to the fuel cell measurement. All of the authors contributed to the overall scientific interpretation and edited the manuscript.

Corresponding authors

Correspondence to Lun Pan, Jongwoo Lim or Ji-Jun Zou.

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Supplementary Information

Supplementary Figs. 1–35, Tables 1–10 and Notes 1–4.

Supplementary Data 1

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Numerical source data for Figs. 3c,d,f.

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Gao, R., Wang, J., Huang, ZF. et al. Pt/Fe2O3 with Pt–Fe pair sites as a catalyst for oxygen reduction with ultralow Pt loading. Nat Energy 6, 614–623 (2021). https://doi.org/10.1038/s41560-021-00826-5

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