Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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


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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. 1.

    Winter, M. & Brodd, R. J. What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104, 4245–4270 (2004).

    Article  CAS  PubMed  Google Scholar 

  2. 2.

    Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012).

    Article  CAS  PubMed  Google Scholar 

  3. 3.

    Cheng, F. & Chen, J. Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts. Chem. Soc. Rev. 41, 2172–2192 (2012).

    Article  CAS  PubMed  Google Scholar 

  4. 4.

    Chen, A. & Holt-Hindle, P. Platinum-based nanostructured materials: synthesis, properties, and applications. Chem. Rev. 110, 3767–3804 (2010).

    Article  CAS  Google Scholar 

  5. 5.

    Gasteiger, H. A. & Markovic, N. M. Just a dream—or future reality? Science 324, 48–49 (2009).

    Article  CAS  Google Scholar 

  6. 6.

    Wang, Y. J. et al. Carbon-supported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chem. Rev. 115, 3433–3467 (2015).

    Article  CAS  Google Scholar 

  7. 7.

    Tang, H. et al. Molecular architecture of cobalt porphyrin multilayers on reduced graphene oxide sheets for high-performance oxygen reduction reaction. Angew. Chem. Int. Ed. 52, 5585–5589 (2013).

    Article  CAS  Google Scholar 

  8. 8.

    Dai, L., Xue, Y., Qu, L., Choi, H. J. & Baek, J. B. Metal-free catalysts for oxygen reduction reaction. Chem. Rev. 115, 4823–4892 (2015).

    Article  CAS  Google Scholar 

  9. 9.

    Liu, X. & Dai, L. Carbon-based metal-free catalysts. Nat. Rev. Mater. 1, 16064 (2016).

    Article  CAS  Google Scholar 

  10. 10.

    Gong, K., Du, F., Xia, Z., Durstock, M. & Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).

    Article  CAS  Google Scholar 

  11. 11.

    Liang, J., Jiao, Y., Jaroniec, M. & Qiao, S. Z. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew. Chem. Int. Ed. 51, 11496–11500 (2012).

    Article  CAS  Google Scholar 

  12. 12.

    Yang, D.-S., Bhattacharjya, D., Inamdar, S., Park, J. & Yu, J.-S. Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. J. Am. Chem. Soc. 134, 16127–16130 (2012).

    Article  CAS  PubMed  Google Scholar 

  13. 13.

    Silva, R., Voiry, D., Chhowalla, M. & Asefa, T. Efficient metal-free electrocatalysts for oxygen reduction: polyaniline-derived N- and O-doped mesoporous carbons. J. Am. Chem. Soc. 135, 7823–7826 (2013).

    Article  CAS  PubMed  Google Scholar 

  14. 14.

    Zhang, C., Mahmood, N., Yin, H., Liu, F. & Hou, Y. Synthesis of phosphorus-doped graphene and its multifunctional applications for oxygen reduction reaction and lithium ion batteries. Adv. Mater. 25, 4932–4937 (2013).

    Article  CAS  Google Scholar 

  15. 15.

    Zhao, Y. et al. Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes? J. Am. Chem. Soc. 135, 1201–1204 (2013).

    Article  CAS  Google Scholar 

  16. 16.

    Zhang, J., Zhao, Z., Xia, Z. & Dai, L. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotech. 10, 444–452 (2015).

    Article  CAS  Google Scholar 

  17. 17.

    Li, Y. et al. An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes. Nat. Nanotech. 7, 394–400 (2012).

    Article  CAS  Google Scholar 

  18. 18.

    Liang, H. W., Zhuang, X., Bruller, S., Feng, X. & Mullen, K. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat. Commun. 5, 4973 (2014).

    Article  CAS  PubMed  Google Scholar 

  19. 19.

    Li, Q., Zhang, S., Dai, L. & Li, L.-S. Nitrogen-doped colloidal graphene quantum dots and their size-dependent electrocatalytic activity for the oxygen reduction reaction. J. Am. Chem. Soc. 134, 18932–18935 (2012).

    Article  CAS  PubMed  Google Scholar 

  20. 20.

    Gottfried, J. M., Flechtner, K., Kretschmann, A., Lukasczyk, T. & Steinrück, H.-P. Direct synthesis of a metalloporphyrin complex on a surface. J. Am. Chem. Soc. 128, 5644–5645 (2006).

    Article  CAS  PubMed  Google Scholar 

  21. 21.

    Zhang, C., Hao, R., Liao, H. & Hou, Y. Synthesis of amino-functionalized graphene as metal-free catalyst and exploration of the roles of various nitrogen states in oxygen reduction reaction. Nano Energy 2, 88–97 (2013).

    Article  CAS  Google Scholar 

  22. 22.

    Guo, D. et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351, 361–365 (2016).

    Article  CAS  PubMed  Google Scholar 

  23. 23.

    Li, J. et al. Graphdiyne: a metal-free material as hole transfer layer to fabricate quantum dot-sensitized photocathodes for hydrogen production. J. Am. Chem. Soc. 138, 3954–3957 (2016).

    Article  CAS  PubMed  Google Scholar 

  24. 24.

    Wang, S. et al. A novel and highly efficient photocatalyst based on P25-graphdiyne nanocomposite. Small 8, 265–271 (2012).

    Article  CAS  PubMed  Google Scholar 

  25. 25.

    Yang, N. et al. Photocatalytic properties of graphdiyne and graphene modified TiO2: from theory to experiment. ACS Nano 7, 1504–1512 (2013).

    Article  CAS  PubMed  Google Scholar 

  26. 26.

    Ren, H. et al. A new graphdiyne nanosheet/Pt nanoparticle-based counter electrode material with enhanced catalytic activity for dye-sensitized solar cells. Adv. Energy Mater. 5, 1500296 (2015).

    Article  CAS  Google Scholar 

  27. 27.

    Parvin, N. et al. Few-layer graphdiyne nanosheets applied for multiplexed real-time DNA detection. Adv. Mater. 29, 1606755 (2017).

    Article  CAS  Google Scholar 

  28. 28.

    Tykwinski, R. R. Evolution in the palladium-catalyzed cross-coupling of sp- and sp 2-hybridized carbon atoms. Angew. Chem. Int. Ed. 42, 1566–1568 (2003).

    Article  CAS  Google Scholar 

  29. 29.

    Viola, A., Collins, J. J., Filipp, N. & Locke, J. S. Acetylenes as potential antarafacial components in concerted reactions. Formation of pyrroles from thermolyses of propargylamines, of a dihydrofuran from a propargylic ether, and of an ethylidenepyrrolidine from a β-amino acetylene. J. Org. Chem. 58, 5067–5075 (1993).

    Article  CAS  Google Scholar 

  30. 30.

    Liu, R. et al. Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions. Nanoscale 6, 11336–11343 (2014).

    Article  CAS  PubMed  Google Scholar 

  31. 31.

    Lv, Q. et al. Nitrogen-doped porous graphdiyne: a highly efficient metal-free electrocatalyst for oxygen reduction reaction. ACS Appl. Mater. Interfaces 9, 29744–29752 (2017).

    Article  CAS  PubMed  Google Scholar 

  32. 32.

    Tobisu, M. & Chatani, N. Catalytic reactions involving the cleavage of carbon–cyano and carbon–carbon triple bonds. Chem. Soc. Rev. 37, 300–307 (2008).

    Article  CAS  PubMed  Google Scholar 

  33. 33.

    Stankovich, S. et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45, 1558–1565 (2007).

    Article  CAS  Google Scholar 

  34. 34.

    Rimez, B., Rahier, H., Biesemans, M., Bourbigot, S. & Van Mele, B. Modelled decomposition mechanism of flame retarded poly(vinyl acetate) by melamine isocyanurate. J. Therm. Anal. Calorim. 127, 2315–2324 (2016).

    Article  CAS  Google Scholar 

  35. 35.

    Veselá, P. & Slovák, V. Monitoring of N-doped organic xerogels pyrolysis by TG-MS. J. Therm. Anal. Calorim. 113, 209–217 (2013).

    Article  CAS  Google Scholar 

  36. 36.

    Pham, C. V., Krueger, M., Eck, M., Weber, S. & Erdem, E. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment. Appl. Phys. Lett. 104, 132102 (2014).

    Article  CAS  Google Scholar 

  37. 37.

    Lin, Z., Waller, G., Liu, Y., Liu, M. & Wong, C.-P. Facile synthesis of nitrogen-doped graphene via pyrolysis of graphene oxide and urea, and its electrocatalytic activity toward the oxygen-reduction reaction. Adv. Energy Mater. 2, 884–888 (2012).

    Article  CAS  Google Scholar 

  38. 38.

    Zhang, L. S., Liang, X. Q., Song, W. G. & Wu, Z. Y. Identification of the nitrogen species on N-doped graphene layers and Pt/NG composite catalyst for direct methanol fuel cell. Phys. Chem. Chem. Phys. 12, 12055–12059 (2010).

    Article  CAS  PubMed  Google Scholar 

  39. 39.

    Zhong, J. et al. Probing solid state N-doping in graphene by X-ray absorption near-edge structure spectroscopy. Carbon 50, 335–338 (2012).

    Article  CAS  Google Scholar 

  40. 40.

    Li, X. et al. Simultaneous nitrogen doping and reduction of graphene oxide. J. Am. Chem. Soc. 131, 15939–15944 (2009).

    Article  CAS  PubMed  Google Scholar 

  41. 41.

    Liang, Y. et al. Co3O4 Nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).

    Article  CAS  Google Scholar 

  42. 42.

    Meng, C. et al. Atomically and electronically coupled Pt and CoO hybrid nanocatalysts for enhanced electrocatalytic performance. Adv. Mater. 29, 1604607 (2017).

    Article  CAS  Google Scholar 

  43. 43.

    Zhou, R., Zheng, Y., Jaroniec, M. & Qiao, S.-Z. Determination of the electron transfer number for the oxygen reduction reaction: from theory to experiment. ACS Catal. 6, 4720–4728 (2016).

    Article  CAS  Google Scholar 

  44. 44.

    Tang, W., Sanville, E. & Henkelman, G. A grid-based bader analysis algorithm without lattice bias. J. Phys. Condens. Matter 21, 084204 (2009).

    Article  CAS  PubMed  Google Scholar 

  45. 45.

    Rossmeisl, J., Qu, Z. W., Zhu, H., Kroes, G. J. & Nørskov, J. K. Electrolysis of water on oxide surfaces. J. Electroanal. Chem. 607, 83–89 (2007).

    Article  CAS  Google Scholar 

  46. 46.

    Zhou, S., Liu, N., Wang, Z. & Zhao, J. Nitrogen-doped graphene on transition metal substrates as efficient bifunctional catalysts for oxygen reduction and oxygen evolution reactions. ACS Appl. Mater. Interfaces 9, 22578–22587 (2017).

    Article  CAS  PubMed  Google Scholar 

Download references


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.

Author information




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.

Corresponding authors

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

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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).

Download citation

Further reading


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing