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Co(CN)3 catalysts with well-defined coordination structure for the oxygen reduction reaction

Nature Catalysis volume 6, pages 1164–1173 (2023)Cite this article

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Abstract

Metal-nitrogen-doped carbon (M-N-C) catalysts are promising platinum group metals alternatives for fuel cell cathodes; however, their randomly formed, unpredictable coordinations complicate any structure–property investigation and lead to low active site density. Here we achieve dense and well-defined cobalt sites on the surfaces of Co(CN)3 microcrystals, which are identified by single-crystal X-ray diffraction and X-ray absorption spectroscopy. In situ infrared spectroscopy and density functional theory calculations elucidate that the high oxygen reduction reaction performance (half-wave potential is 0.90 V versus RHE) of the cubic Co(CN)3 is due to its tailored coordination environment that optimizes *OH desorption. The cyanide linkage with minimized spacing between cobalt atoms maximizes active sites’ spatial density, which boosts the anion-exchange membrane fuel cell peak power density to 1.67 W cm−2. The microcrystals with well-defined coordination structures can be used as Co-N-C analogues for their structure–property relationship investigations.

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Fig. 1: Morphology characterizations of the Co(CN)3 catalysts.
Fig. 2: Structure characterizations of the Co(CN)3 catalysts.
Fig. 3: Electrocatalytic ORR performance of the Co(CN)3 catalysts.
Fig. 4: Theoretical analysis.

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Data availability

The crystallographic information file obtained directly from SCXRD has been deposited in the CCDC with reference number of 2291782. Other datasets generated during and/or analysed during the current study are available from the corresponding authors on reasonable request. Source data are provided with this paper.

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Acknowledgements

X.S. acknowledges financial support from the National Key Research and Development Program of China (2018YFA0702002, 2022YFA1504000), the Beijing Natural Science Foundation (Z210016) and the National Natural Science Foundation of China (21935001), Z.Z. acknowledges financial support from the National Key Research and Development Program of China (2019YFA0210300), S.T. acknowledges financial support from the National Natural Science Foundation of China (22101015) and the Fundamental Research Funds of Beijing University of Chemical Technology (buctrc202107) and J.D. acknowledges financial support from the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y2022006).

Author information

Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, China

    Kai Sun, Hao Sun, Shubo Tian & Xiaoming Sun

  2. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Juncai Dong

  3. State Key Lab of Organic–Inorganic Composites, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, China

    Xingdong Wang, Jinjie Fang & Zhongbin Zhuang

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Contributions

K.S. designed and performed the synthetic and electrochemical experiments, characterized the catalyst and analysed the data. J.D. completed the XAFS characterization and corresponding data analysis. H.S. conducted the DFT calculations. X.W. assisted with the AEMFC testing. J.F. assisted with the in situ ATR-SEIRAS tests and data analysis. S.T., Z.Z. and X.S. supervised the execution of the overall project. The results of the manuscript were discussed by all authors.

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Correspondence to Zhongbin Zhuang, Shubo Tian or Xiaoming Sun.

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Nature Catalysis thanks Yaqiong Su 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. 1–29, Tables 1–5 and Notes 1 and 2.

Crystallographic Data 1

Crystallographic Information File obtained directly from SCXRD with CCDC no. 2291782.

Crystallographic Data 2

Crystallographic Information File of Co(CN)3 refined by XAS.

Crystallographic Data 3

The optimised strctures using for calcuating the density of states of each crystal plane and partial density of states of cobalt in each crystal plane of Co(CN)3.

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Sun, K., Dong, J., Sun, H. et al. Co(CN)3 catalysts with well-defined coordination structure for the oxygen reduction reaction. Nat Catal 6, 1164–1173 (2023). https://doi.org/10.1038/s41929-023-01047-7

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