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A Janus dual-atom catalyst for electrocatalytic oxygen reduction and evolution

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Abstract

Dual-atom catalysts, which exhibit high activity and atom utilization, show promise for sustainable energy conversion and storage technologies. However, the rational design and synthesis of a dual-atom catalyst with structurally homogeneous and flexible active sites remains challenging. In this work, we developed a strategy for the synthesis of a carbon-based catalyst with diatomic Fe–Co sites in which the Fe and Co atoms are coordinated to N and O atoms, respectively, and linked through bridging N and O atoms (FeCo–N3O3@C). The Janus FeCo–N3O3@C quaternary dimer is a stable and efficient bifunctional catalyst in the electrocatalytic oxygen reduction reaction (half-wave potential E1/2 = 0.936 V) and oxygen evolution reaction (potential E = 1.528 V at 10 mA cm−2). When assembled in a Zn–air battery, it exhibits superior performance over a benchmark Pt/C + RuO2 air cathode. A series of ex situ and in situ characterizations, combined with theoretical calculations, revealed that the bifunctional performance of the catalyst originates from the strong coupling of the Fe–N3 and Co–O3 moieties, which alters the d-orbital energy level of the metal atoms, optimizing the adsorption–desorption of oxygenated intermediates and improving the reaction kinetics of the oxygen reduction and evolution reactions. The in-depth insights gained into the fundamental mechanism of this dual-atom catalyst at the atomic and electronic level will facilitate the rational design of further highly efficient multifunctional catalysts with customized activities for specific reactions.

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Fig. 1: A survey of atomically dispersed metal catalysts based on carbon substrates.
Fig. 2: Synthetic scheme and morphological characterization of the FeCo–N3O3@C catalyst.
Fig. 3: Structural characterization of the FeCo–N3O3@C catalyst.
Fig. 4: Catalytic performance of FeCo–N3O3@C in the ORR and OER.
Fig. 5: DFT calculations and in situ SR-FTIR and XANES measurements.
Fig. 6: Performances of ZABs based on FeCo–N3O3@C and Pt/C + RuO2.

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Data supporting the findings of this study are available in the article and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (grant nos. 2023YFF0716100 and 2021YFA1600800 to W.Y.), the National Natural Science Foundation of China (grant nos. 12275271 to C.W., 12305364 to Q.J., 22102167 to Y.Z. and 22325101 to D.W.), the Collaborative Innovation Program of Hefei Science Center, CAS (grant no. 2022HSC-CIP028 to H.T.), the Users with Excellence Program of Hefei Science Center, CAS (grant nos. 2020HSC-CIP013 to W.Y. and 2021HSC-UE002 to C.W.), the Key Program of Research and Development of Hefei Science Center, CAS (grant no. 2021HSC-KPRD002 to W.Y.), the Fundamental Research Funds for the Central Universities (grant no. WK 2310000103 to C.W.) and partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication and the USTC Instruments Center for Physical Science. The calculations were performed at the USTC Supercomputing Center and Ningbo Artificial Intelligence and High Performance Computing Center. We thank the BSRF, SSRF and beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at the NSRL for synchrotron beamtime.

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H.T., B.M.W., D.W. and W.Y. conceived and designed the project. H.T., D.W. and W.Y. analysed the results. H.T. and B.T. wrote the paper. B.T. and Q.J. performed the synthesis, characterization and electrochemical measurements. Y.Z. performed the DFT calculations. C.W. contributed to the XANES simulations. B.M. and F.S. performed the XES measurements. L.Z. and H.H. performed the zinc–air battery measurements. H.W. carried out the SEM and TEM characterizations. Z.Z., S.Y. and Q.J. performed the XAFS measurements. All of the authors discussed the results and reviewed the paper.

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Correspondence to Hao Tan, Dingsheng Wang or Wensheng Yan.

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Nature Synthesis thanks Gengtao Fu, Jinwoo Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary Information

Supplementary Figs. 1–42 and Tables 1–7.

Supplementary data 1

Statistical source data for the figures in the Supplementary Information.

Source data

Source Data Fig. 2

Source data for FT-EXAFS spectra and the corresponding fitting curves.

Source Data Fig. 3

Source data for XANES and XES spectra and XANES calculations.

Source Data Fig. 4

Source data for electrochemical ORR and OER performance.

Source Data Fig. 5

Source data for DFT calculations, in situ SR-FTIR spectra and in situ XANES spectra.

Source Data Fig. 6

Source data for Zn−air battery performance.

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Tang, B., Zhou, Y., Ji, Q. et al. A Janus dual-atom catalyst for electrocatalytic oxygen reduction and evolution. Nat. Synth 3, 878–890 (2024). https://doi.org/10.1038/s44160-024-00545-1

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