Abstract

The oxygen reduction reaction (ORR) is a fundamental reaction for energy storage and conversion. It has mainly relied on platinum-based electrocatalysts, but the chemical doping of carbon-based materials has proven to be a promising strategy for preparing metal-free alternatives. Nitrogen doping in particular provides a diverse range of nitrogen forms. Here, we introduce a new form of nitrogen doping moieties —sp-hybridized nitrogen (sp-N) atoms into chemically defined sites of ultrathin graphdiyne, through pericyclic replacement of the acetylene groups. The as-prepared sp-N-doped graphdiyne catalyst exhibits overall good ORR performance, in particular with regards to peak potential, half-wave potential and current density. Under alkaline conditions it was comparable to commercial Pt/C, and showed more rapid kinetics. And although its performances are a bit lower than those of Pt/C in acidic media they surpass those of other metal-free materials. Taken together, experimental data and density functional theory calculations suggest that the high catalytic activity originates from the sp-N dopant, which facilitates O2 adsorption and electron transfer on the surface of the catalyst. This incorporation of chemically defined sp-N atoms provides a new synthetic route to high-performance carbon-based and other metal-free catalysts.

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Acknowledgements

This study was supported by the National Science Fund for Distinguished Young Scholars (no. 21325105), the National Natural Science Foundation of China (nos 21590795, 21401199, 21790050 and 21790051), the National Key Research and Development Program of China (2016YFB0600903 and 2016YFA0200104), the Chinese Academy of Sciences (CAS) Interdisciplinary Innovation Team, a Australian Research Council (ARC) Discovery Project (no. 160104817) and the Foundation for State Key Laboratory of Biochemical Engineering. The authors also thank H.D.Xia. for the testing and analysis of the TG–DTA–MS system.

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Affiliations

  1. State Key Laboratory of Biochemical Engineering, CAS Center for Excellence in Nanoscience, Institute of Process Engineering, Chinese Academy of Sciences, Zhongguancun, Beijing, China

    • Yasong Zhao
    • , Jiawei Wan
    • , Lijuan Zhang
    • , Nailiang Yang
    •  & Dan Wang
  2. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

    • Yasong Zhao
    •  & Kaifeng Lin
  3. Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Beijing, China

    • Huiying Yao
    •  & Jia Zhu
  4. Qiangdao University of Science and Technology, No.53 Zhengzhou Rd, Qingdao, Shandong, China

    • Lei Wang
    •  & Dan Wang
  5. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui, China

    • Daobin Liu
    •  & Li Song
  6. Institute of Physics, Chinese Academy of Sciences, Beijing, China

    • Lin Gu
  7. Department of Chemistry, Tsinghua University, Beijing, China

    • Lei Liu
  8. Centre for Clean Environment and Energy, Gold Coast Campus Griffith University, Southport, Queensland, Australia

    • Huijun Zhao
    •  & Dan Wang
  9. CAS Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    • Yuliang Li

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Contributions

D.W. conceived the idea and supervised the research. Y.L. provided the BGDY sample. Under the instruction of D.W., Y.Z. modified the BGDY and further performed doping, basic characterizations and catalyst testing. L.S. and D.L. performed the XANES experiments and analysed the data. L.G. characterized the HAADF and EELS images of NFLGDY. J.Z. and H.Y. performed theoretical calculations. L.Z. assisted the implementation of the calculations. L.L. assisted with the analysis of the N-doping mechanism of NFLGDY. D.W., Y.Z., N.Y., J.W. and Y.L. analysed and discussed the experimental data and drafted the manuscript. Y.L. and H.Z. improved the writing of the manuscript. K.L. and L.W provided some useful suggestions.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Nailiang Yang or Jia Zhu or Yuliang Li or Dan Wang.

Supplementary information

  1. Supplementary Information

    Supplementary characterization and calculation details, Supplementary Figures 1–31, Supplementary Tables 1–6

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DOI

https://doi.org/10.1038/s41557-018-0100-1

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