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Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis

Nature Chemistry volume 10, pages 924–931 (2018)Cite this article

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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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Fig. 1: Synthesis of sp-N-doped few-layer GDY.
Fig. 2: Morphological and structural characterization of BGDY, FLGDYO and NFLGDY.
Fig. 3: Structural characterization of NFLGDY catalysts using N K-edge XANES spectroscopy and XPS.
Fig. 4: Electrocatalytic ORR activity of NFLGDY and commercial Pt/C in O2-saturated 0.1 M KOH.
Fig. 5: Electrochemical characterization of NFLGDY and commercial Pt/C for the ORR under both acidic and alkaline conditions.

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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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Authors and 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.

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

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

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Zhao, Y., Wan, J., Yao, H. et al. Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis. Nature Chem 10, 924–931 (2018). https://doi.org/10.1038/s41557-018-0100-1

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