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Lattice-strained metal–organic-framework arrays for bifunctional oxygen electrocatalysis

Nature Energy volume 4, pages 115–122 (2019)Cite this article

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An Author Correction to this article was published on 19 March 2020

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Abstract

Oxygen electrocatalysis is central to technologies such as fuel cells and electrolysers, but challenges remain due to the lack of effective earth-abundant electrocatalysts and insufficient understanding of catalytic mechanisms. Here we demonstrate that robust bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity can be achieved by inducing lattice strain in noble-metal-free metal–organic frameworks (MOFs). Lattice-strained NiFe MOFs exhibit mass activities of 500 A gmetal−1 at a half-wave potential of 0.83 V for the ORR and 2,000 A gmetal−1 at an overpotential of 0.30 V for the OER, which are 50–100 times that of pristine NiFe metal–organic frameworks. The catalyst maintains ~97% of its initial activity after 200 h of continuous ORR/OER reaction at a high current density of 100–200 mA cm−2. Using operando synchrotron spectroscopies, we observed a key superoxide *OOH intermediate emerging on Ni4+ sites during both the ORR and OER processes, which suggests a four-electron mechanistic pathway.

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Fig. 1: Structural characterizations of lattice-strained MOFs.
Fig. 2: Performance of lattice-strained MOFs for oxygen electrocatalysis.
Fig. 3: Atomic and electronic structures of lattice-strained MOFs.
Fig. 4: The formation of a superoxide intermediate and high-valence Ni4+ species during the ORR and OER.
Fig. 5: Mechanistic insight into the electrocatalytic activity of the lattice-strained MOFs.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

Change history

  • 19 March 2020

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Acknowledgements

This work was supported by the National Key Research and Development Programme of China (grant nos 2017YFA0402800), the National Natural Science Foundation of China (grant no. U1532265, 11875257, 21603207, 11621063 and 21533007), and the Fundamental Research Funds for the Central Universities (grant nos WK2310000054 and WK2310000070).

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Author notes

  1. These authors contributed equally: Weiren Cheng, Xu Zhao.

Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, China

    Weiren Cheng, Xu Zhao, Hui Su, Fumin Tang, Wei Che, Hui Zhang & Qinghua Liu

Authors
  1. Weiren Cheng
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  3. Hui Su
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Contributions

Q.L. and W.Cheng conceived the project. W.Cheng, X.Z. and H.S. carried out the experiments. Q.L., F.T., W.Che and H.Z. analysed the experimental data. All authors contributed to writing the manuscript.

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Correspondence to Qinghua Liu.

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Cheng, W., Zhao, X., Su, H. et al. Lattice-strained metal–organic-framework arrays for bifunctional oxygen electrocatalysis. Nat Energy 4, 115–122 (2019). https://doi.org/10.1038/s41560-018-0308-8

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