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Science China Materials

, Volume 62, Issue 3, pp 359–367 | Cite as

Co/N co-doped graphene-like nanocarbon for highly efficient oxygen reduction electrocatalyst

  • Lei Liu (刘磊)
  • Jian Zhang (张建)
  • Wujun Ma (麻伍军)
  • Yunhui Huang (黄云辉)Email author
Articles
  • 136 Downloads

Abstract

The development of efficient and inexpensive graphene-based electrocatalysts is of great significance to promote the commercial application of fuel cell and metal-air batteries. In this paper, a new type of Co and N co-doped graphene-like nanocarbon (Co/N-GLC) material was prepared by nano-silicon protection and high temperature pyrolysis. The obtained Co/N-GLC catalyst not only has a similar morphology of graphene, but also possesses a high specific surface area (809 m2 g−1) with hierarchical porous structure (micropores/mesopores), and relative high active dopants content. These properties endow it with a good oxygen reduction activity in alkaline media, which can be comparable to commercial Pt/C catalyst. Moreover, the assembled zinc-air batteries using Co/N-GLC catalyst as the air electrode display a better discharge performance and higher stability compared to that of Pt/C electrode. This work demonstrates that the prepared graphene-like carbon catalyst has a good prospect, which can replace noble metal catalyst at the cathode in metalair batteries.

Keywords

graphene-like nanocarbon oxygen reduction reaction electrocatalyst zinc-air battery 

钴/氮共掺杂多孔类石墨烯催化剂的制备及其高效氧还原性能表征

摘要

本文通过纳米硅作为保护层结合高温热解得到一种新型钴/氮共掺杂多孔类石墨烯纳米碳材料氧还原催化剂(Co/N-GLC). 结果显 示, Co/N-GLC具有类似于石墨烯的碳纳米薄层结构, 并展现出分级多孔(微孔/介孔)特性, 其比表面积高达809 m2 g−1; 此外, Co/N-GLC还 拥有较高的吡啶氮和石墨氮含量. 这些优异的特性使得Co/N-GLC在碱性介质中具有出色的氧还原活性, 接近于商业Pt/C催化剂. 同时, 在 锌空气电池测试中, Co/N-GLC具有接近Pt/C电极的放电性能和优异的稳定性, 表明该催化剂有望替代贵金属催化剂, 具有很好的应用前 景.

Notes

Acknowledgements

This work was supported by the National Natural Science Foundation of China (51602113 and 51702111) and China Postdoctoral Science Foundation (2016M590692).

Supplementary material

40843_2018_9322_MOESM1_ESM.pdf (438 kb)
Co/N co-doped graphene-like nanocarbon for highly efficient oxygen reduction electrocatalyst

References

  1. 1.
    Dai L, Xue Y, Qu L, et al. Metal-free catalysts for oxygen reduction reaction. Chem Rev, 2015, 115: 4823–4892CrossRefGoogle Scholar
  2. 2.
    Borghei M, Lehtonen J, Liu L, et al. Advanced biomass-derived electrocatalysts for the oxygen reduction reaction. Adv Mater, 2018, 30: 1703691CrossRefGoogle Scholar
  3. 3.
    Dou S, Tao L, Wang R, et al. Plasma-assisted synthesis and surface modification of electrode materials for renewable energy. Adv Mater, 2018, 30: 1705850–1705874CrossRefGoogle Scholar
  4. 4.
    Wang S, Jiang SP. Prospects of fuel cell technologies. Nat Sci Rev, 2017, 4: 163Google Scholar
  5. 5.
    Seh ZW, Kibsgaard J, Dickens CF, et al. Combining theory and experiment in electrocatalysis: Insights into materials design. Science, 2017, 355: 6321CrossRefGoogle Scholar
  6. 6.
    Zhang J, Li Q, Wu H, et al. Nitrogen-self-doped carbon with a porous graphene-like structure as a highly efficient catalyst for oxygen reduction. J Mater Chem A, 2015, 3: 10851–10857CrossRefGoogle Scholar
  7. 7.
    Liu X, Dai L. Carbon-based metal-free catalysts. Nat Rev Mater, 2016, 1: 16064–16076CrossRefGoogle Scholar
  8. 8.
    Zhang G, Jin X, Li H, et al. N-doped crumpled graphene: bottomup synthesis and its superior oxygen reduction performance. Sci China Mater, 2016, 59: 337–347Google Scholar
  9. 9.
    Cao L, Yang M, Lu Z, et al. Exploring an effective oxygen reduction reaction catalyst via 4e-process based on waved-graphene. Sci China Mater, 2017, 60: 739–746CrossRefGoogle Scholar
  10. 10.
    Li M, Zhang L, Xu Q, et al. N-doped graphene as catalysts for oxygen reduction and oxygen evolution reactions: Theoretical considerations. J Catal, 2014, 314: 66–72CrossRefGoogle Scholar
  11. 11.
    Lee WJ, Lim J, Kim SO. Nitrogen dopants in carbon nanomaterials: defects or a new opportunity? Small Methods, 2017, 1: 1600014CrossRefGoogle Scholar
  12. 12.
    Zhang J, Zhou H, Liu X, et al. Keratin-derived S/N co-doped graphene-like nanobubble and nanosheet hybrids for highly efficient oxygen reduction. J Mater Chem A, 2016, 4: 15870–15879CrossRefGoogle Scholar
  13. 13.
    Zhang J, Zhou H, Zhu J, et al. Facile synthesis of defect-rich and S/N co-doped graphene-like carbon nanosheets as an efficient electrocatalyst for primary and all-solid-state Zn–air batteries. ACS Appl Mater Interfaces, 2017, 9: 24545–24554CrossRefGoogle Scholar
  14. 14.
    Yang ZK, Lin L, Xu AW. 2D nanoporous Fe-N/C nanosheets as highly efficient non-platinum electrocatalysts for oxygen reduction reaction in Zn-air battery. Small, 2016, 12: 5710–5719CrossRefGoogle Scholar
  15. 15.
    Tang C, Wang B, Wang HF, et al. Defect engineering toward atomic Co-Nx-C in hierarchical graphene for rechargeable flexible solid Zn-air batteries. Adv Mater, 2017, 29: 1703185–1703192CrossRefGoogle Scholar
  16. 16.
    Yan D, Guo L, Xie C, et al. N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction. Sci China Mater, 2018, 61: 679–685CrossRefGoogle Scholar
  17. 17.
    Wu H, Jiang X, Ye Y, et al. Nitrogen-doped carbon nanotube encapsulating cobalt nanoparticles towards efficient oxygen reduction for zinc–air battery. J Energy Chem, 2017, 26: 1181–1186CrossRefGoogle Scholar
  18. 18.
    Chen B, Bi H, Ma Q, et al. Preparation of graphene-MoS2 hybrid aerogels as multifunctional sorbents for water remediation. Sci China Mater, 2017, 60: 1102–1108CrossRefGoogle Scholar
  19. 19.
    Sa YJ, Seo DJ, Woo J, et al. A general approach to preferential formation of active Fe–Nx sites in Fe–N/C electrocatalysts for efficient oxygen reduction reaction. J Am Chem Soc, 2016, 138: 15046–15056CrossRefGoogle Scholar
  20. 20.
    Artyushkova K, Kiefer B, Halevi B, et al. Density functional theory calculations of XPS binding energy shift for nitrogen-containing graphene-like structures. Chem Commun, 2013, 49: 2539CrossRefGoogle Scholar
  21. 21.
    Yan D, Li Y, Huo J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions. Adv Mater, 2017, 29: 1606459CrossRefGoogle Scholar
  22. 22.
    Lee DU, Xu P, Cano ZP, et al. Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal–air batteries. J Mater Chem A, 2016, 4: 7107–7134CrossRefGoogle Scholar
  23. 23.
    Chung HT, Cullen DA, Higgins D, et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science, 2017, 357: 479–484CrossRefGoogle Scholar
  24. 24.
    Zhang J, Wu S, Chen X, et al. Egg derived nitrogen-self-doped carbon/carbon nanotube hybrids as noble-metal-free catalysts for oxygen reduction. J Power Sources, 2014, 271: 522–529CrossRefGoogle Scholar
  25. 25.
    Guo D, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351: 361–365CrossRefGoogle Scholar
  26. 26.
    Hang C, Zhang J, Zhu J, et al. In situ exfoliating and generating active sites on graphene nanosheets strongly coupled with carbon fiber toward self-standing bifunctional cathode for rechargeable Zn-air batteries. Adv Energy Mater, 2018, 8: 1703539CrossRefGoogle Scholar
  27. 27.
    Zhang L, Xia Z. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C, 2011, 115: 11170–11176CrossRefGoogle Scholar
  28. 28.
    Zhang L, Niu J, Dai L, et al. Effect of microstructure of nitrogendoped graphene on oxygen reduction activity in fuel cells. Langmuir, 2012, 28: 7542–7550CrossRefGoogle Scholar
  29. 29.
    Tang C, Wang HF, Chen X, et al. Topological defects in metal-free nanocarbon for oxygen electrocatalysis. Adv Mater, 2016, 28: 6845–6851CrossRefGoogle Scholar
  30. 30.
    Imtiaz S, Zhang J, Zafar ZA, et al. Biomass-derived nanostructured porous carbons for lithium-sulfur batteries. Sci China Mater, 2016, 59: 389–407CrossRefGoogle Scholar
  31. 31.
    Lee JS, Nam G, Sun J, et al. Composites of a prussian blue analogue and gelatin-derived nitrogen-doped carbon-supported porous spinel oxides as electrocatalysts for a Zn-air battery. Adv Energy Mater, 2016, 6: 1601052CrossRefGoogle Scholar
  32. 32.
    Zhao H, Sun C, Jin Z, et al. Carbon for the oxygen reduction reaction: a defect mechanism. J Mater Chem A, 2015, 3: 11736–11739CrossRefGoogle Scholar
  33. 33.
    Daems N, Sheng X, Vankelecom IFJ, et al. Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction. J Mater Chem A, 2014, 2: 4085–4110CrossRefGoogle Scholar
  34. 34.
    Jeon IY, Zhang S, Zhang L, et al. Edge-selectively sulfurized graphene nanoplatelets as efficient metal-free electrocatalysts for oxygen reduction reaction: the electron spin effect. Adv Mater, 2013, 25: 6138–6145CrossRefGoogle Scholar
  35. 35.
    Zhang C, Liu Y, Zhou J, et al. Tunability of photo-catalytic selectivity of B-doped anatase TiO2 microspheres in the visible light. Dyes Pigments, 2018, 156: 213–218CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Lei Liu (刘磊)
    • 1
  • Jian Zhang (张建)
    • 1
    • 2
  • Wujun Ma (麻伍军)
    • 3
  • Yunhui Huang (黄云辉)
    • 1
    Email author
  1. 1.School of Materials Science and EngineeringHuazhong University of Science and TechnologyWuhanChina
  2. 2.School of Materials Science and EngineeringNanyang Technological UniversitySingaporeSingapore
  3. 3.School of Chemistry, Biology and Materials EngineeringSuzhou University of Science and TechnologySuzhouChina

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