Skip to main content
SpringerLink
Log in

Inside-out dual-doping effects on tubular catalysts: Structural and chemical variation for advanced oxygen reduction performance

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Dual-doping of carbon, especially the combination of nitrogen and a secondary heteroatom, has been demonstrated efficient to optimize the oxygen reduction reaction (ORR) performance. However, the optimum dual-doping is still not clear due to the lack of strong experimental proofs, which rely on a reliable method to prepare carbon materials that can rule out the interference factors and then emphasize only the doping effects. In this work, an inside-out doping method is reported to prepare carbon submicrotubes (CSTs) as a material to study the principles of designing dual-doping catalysts for ORR. The interference factors including the metal impurities and doping gradient in the bulk phase are excluded, and the doping effects including the structural and chemical variation of carbon are studied. P-doping exhibited a higher pore-forming ability to perforate carbon and a lower doping content, but a higher ORR catalytic activity as compared with S- and B-doped N-CSTs, demonstrating the N,P co-doping is more efficient in making carbon-based catalysts for ORR. First-principle calculations reveal that the edge C situated around the oxidized P site nearby a graphitic N atom is the active site that shows the lowest ORR overpotential comparable to Pt-based catalysts. This study suggests that the catalytic activity of dual-heteroatoms-doped carbons not only depends on the intrinsic chemical bonding between heteroatoms and carbon, but also is affected by the structural variation generated by introducing different atoms, which can be extended to the study of other kinds of functionalization of carbon and potential reactions besides ORR.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.

    Article  Google Scholar 

  2. Electrocatalysis for the generation and consumption of fuels. Nat. Rev. Chem. 2018, 2, 0125.

  3. Yi, J.; Liang, P. C.; Liu, X. Y.; Wu, K.; Liu, Y. Y.; Wang, Y. G.; Xia, Y. Y.; Zhang, J. J. Challenges, mitigation strategies and perspectives in development of zinc-electrode materials and fabrication for rechargeable zinc-air batteries. Energy Environ. Sci. 2018, 11, 3075–3095.

    Article  CAS  Google Scholar 

  4. Stephens, I. E. L.; Bondarenko, A. S.; Grønbjerg, U.; Rossmeisl, J.; Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ. Sci. 2012, 5, 6744–6762.

    Article  CAS  Google Scholar 

  5. He, W. H.; Wang, Y.; Jiang, C. H.; Lu, L. H. Structural effects of a carbon matrix in non-precious metal O2-reduction electrocatalysts. Chem. Soc. Rev. 2016, 45, 2396–2409.

    Article  CAS  Google Scholar 

  6. Zhao, Z. P.; Chen, C. L.; Liu, Z. Y.; Huang, J.; Wu, M. H.; Liu, H. T.; Li, Y. J.; Huang, Y. Pt-based nanocrystal for electrocatalytic oxygen reduction. Adv. Mater. 2019, 31, 1808115.

    Article  Google Scholar 

  7. Feng, S. Q.; Liu, C.; Chai, Z. G.; Li, Q.; Xu, D. S. Cobalt-based hydroxide nanoparticles@N-doping carbonic frameworks core-shell structures as highly efficient bifunctional electrocatalysts for oxygen evolution and oxygen reduction reactions. Nano Res. 2018, 11, 1482–1489.

    Article  CAS  Google Scholar 

  8. Chung, H. T.; Cullen, D. A.; Higgins, D.; Sneed, B. T.; Holby, E. F.; More, K. L.; Zelenay, P. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science 2017, 357, 479–484.

    Article  CAS  Google Scholar 

  9. Qu, L. T.; Liu, Y.; Baek, J. B.; Dai, L. M. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 2010, 4, 1321–1326.

    Article  CAS  Google Scholar 

  10. Lai, L. F.; Potts, J. R.; Zhan, D.; Wang, L.; Poh, C. K.; Tang, C. H.; Gong, H.; Shen, Z. X.; Lin, J. Y.; Ruoff, R. S. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ. Sci. 2012, 5, 7936–7942.

    Article  CAS  Google Scholar 

  11. Singh, S. K.; Takeyasu, K.; Nakamura, J. Active sites and mechanism of oxygen reduction reaction electrocatalysis on nitrogen-doped carbon materials. Adv. Mater. 2019, 31, 1804297.

    Article  Google Scholar 

  12. Tang, C.; Zhang, Q. Nanocarbon for oxygen reduction electrocatalysis: Dopants, edges, and defects. Adv. Mater. 2017, 29, 1604103.

    Article  Google Scholar 

  13. To, J. W. F.; Ng, J. W. D.; Siahrostami, S.; Koh, A. L.; Lee, Y.; Chen, Z. H.; Fong, K. D.; Chen, S. C.; He, J. J.; Bae, W. G. et al. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration. Nano Res. 2017, 10, 1163–1177.

    Article  CAS  Google Scholar 

  14. Chen, L. L.; Xu, X. L.; Yang, W. X.; Jia, J. B. Recent advances in carbon-based electrocatalysts for oxygen reduction reaction. Chin. Chem. Lett. 2020, 31, 626–634.

    Article  CAS  Google Scholar 

  15. Rao, C. V.; Cabrera, C. R.; Ishikawa, Y. In search of the active site in nitrogen-doped carbon nanotube electrodes for the oxygen reduction reaction. J. Phys. Chem. Lett. 2010, 1, 2622–2627.

    Article  CAS  Google Scholar 

  16. Wu, J. J.; Ma, L. L.; Yadav, R. M.; Yang, Y. C.; Zhang, X.; Vajtai, R.; Lou, J.; Ajayan, P. M. Nitrogen-doped graphene with pyridinic dominance as a highly active and stable electrocatalyst for oxygen reduction. ACS Appl. Mater. Interfaces 2015, 7, 14763–14769.

    Article  CAS  Google Scholar 

  17. Zhang, C. Z.; Hao, R.; Liao, H. B.; Hou, Y. L. Synthesis of aminofunctionalized graphene as metal-free catalyst and exploration of the roles of various nitrogen states in oxygen reduction reaction. Nano Energy 2013, 2, 88–97.

    Article  CAS  Google Scholar 

  18. Geng, D. S.; Yang, S. L.; Zhang, Y.; Yang, J. L.; Liu, J.; Li, R. Y.; Sham, T. K.; Sun, X. L.; Ye, S. Y.; Knights, S. Nitrogen doping effects on the structure of graphene. Appl. Surf. Sci. 2011, 257, 9193–9198.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  20. Xu, J. J.; Xiao, C. H.; Ding, S. J. Red-blood-cell like nitrogen-doped carbons with highly catalytic activity towards oxygen reduction reaction. Chin. Chem. Lett. 2017, 28, 748–754.

    Article  CAS  Google Scholar 

  21. Sun, T.; Wang, J.; Qiu, C. T.; Ling, X.; Tian, B. B.; Chen, W.; Su, C. L. B, N codoped and defect-rich nanocarbon material as a metal-free bifunctional electrocatalyst for oxygen reduction and evolution reactions. Adv. Sci. 2018, 5, 1800036.

    Article  Google Scholar 

  22. Su, Y. Z.; Yao, Z. Q.; Zhang, F.; Wang, H.; Mics, Z.; Cánovas, E.; Bonn, M.; Zhuang, X. D.; Feng, X. L. Sulfur-enriched conjugated polymer nanosheet derived sulfur and nitrogen co-doped porous carbon nanosheets as electrocatalysts for oxygen reduction reaction and zinc-air battery. Adv. Funct. Mater. 2016, 26, 5893–5902.

    Article  CAS  Google Scholar 

  23. Chai, G. L.; Qiu, K. P.; Qiao, M.; Titirici, M. M.; Shang, C. X.; Guo, Z. X. Active sites engineering leads to exceptional ORR and OER bifunctionality in P,N co-doped graphene frameworks. Energy Environ. Sci. 2017, 10, 1186–1195.

    Article  CAS  Google Scholar 

  24. Zhang, J. T.; Zhao, Z. H.; Xia, Z. H.; Dai, L. M. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nanotechnol. 2015, 10, 444–452.

    Article  CAS  Google Scholar 

  25. 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. 2012, 51, 11496–11500.

    Article  CAS  Google Scholar 

  26. Wang, S. Y.; Zhang, L. P.; Xia, Z. H.; Roy, A.; Chang, D. W.; Baek, J. B.; Dai, L. M. BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2012, 51, 4209–4212.

    Article  CAS  Google Scholar 

  27. Fu, S. F.; Zhu, C. Z.; Song, J. H.; Engelhard, M. H.; Li, X. L.; Zhang, P. N.; Xia, H. B.; Du, D.; Lin, Y. H. Template-directed synthesis of nitrogen- and sulfur-codoped carbon nanowire aerogels with enhanced electrocatalytic performance for oxygen reduction. Nano Res. 2017, 10, 1888–1895.

    Article  CAS  Google Scholar 

  28. Wang, J.; Wu, Z. X.; Han, L. L.; Liu, Y. Y.; Guo, J. P.; Xin, H. L.; Wang, D. L. Rational design of three-dimensional nitrogen and phosphorus co-doped graphene nanoribbons/CNTs composite for the oxygen reduction. Chin. Chem. Lett. 2016, 27, 597–601.

    Article  CAS  Google Scholar 

  29. Li, Y. G.; Zhou, W.; Wang, H. L.; Xie, L. M.; Liang, Y. Y.; Wei, F.; Idrobo, J. C.; Pennycook, S. J.; Dai, H. J. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat. Nanotechnol. 2012, 7, 394–400.

    Article  CAS  Google Scholar 

  30. Banks, C. E.; Crossley, A.; Salter, C.; Wilkins, S. J.; Compton, R. G. Carbon nanotubes contain metal impurities which are responsible for the “electrocatalysis” seen at some nanotube-modified electrodes. Angew. Chem., Int. Ed. 2006, 45, 2533–2537.

    Article  CAS  Google Scholar 

  31. El-Sawy, A. M.; Mosa, I. M.; Su, D.; Guild, C. J.; Khalid, S.; Joesten, R.; Rusling, J. F.; Suib, S. L. Controlling the active sites of sulfur-doped carbon nanotube-graphene nanolobes for highly efficient oxygen evolution and reduction catalysis. Adv. Energy Mater. 2016, 6, 1501966.

    Article  Google Scholar 

  32. Wu, G.; Mack, N. H.; Gao, W.; Ma, S. G.; Zhong, R. Q.; Han, J. T.; Baldwin, J. K.; Zelenay, P. Nitrogen-doped graphene-rich catalysts derived from heteroatom polymers for oxygen reduction in nonaqueous lithium-O2 battery cathodes. ACS Nano 2012, 6, 9764–9776.

    Article  CAS  Google Scholar 

  33. Hao, L.; Ning, J.; Luo, B.; Wang, B.; Zhang, Y. B.; Tang, Z. H.; Yang, J. H.; Thomas, A.; Zhi, L. J. Structural evolution of 2D microporous covalent triazine-based framework toward the study of high-performance supercapacitors. J. Am. Chem. Soc. 2015, 137, 219–225.

    Article  CAS  Google Scholar 

  34. Gao, Y.; Xiao, Z. C.; Kong, D. B.; Iqbal, R.; Yang, Q. H.; Zhi, L. J. N,P co-doped hollow carbon nanofiber membranes with superior mass transfer property for trifunctional metal-free electrocatalysis. Nano Energy 2019, 64, 103879.

    Article  CAS  Google Scholar 

  35. Zhang, J. T.; Dai, L. M. Nitrogen, phosphorus, and fluorine tri-doped graphene as a multifunctional catalyst for self-powered electrochemical water splitting. Angew. Chem., Int. Ed. 2016, 55, 13296–13300.

    Article  CAS  Google Scholar 

  36. Hu, C. G.; Dai, L. M. Multifunctional carbon-based metal-free electrocatalysts for simultaneous oxygen reduction, oxygen evolution, and hydrogen evolution. Adv. Mater. 2017, 29, 1604942.

    Article  Google Scholar 

  37. Gong, Y. J.; Fei, H. L.; Zou, X. L.; Zhou, W.; Yang, S. B.; Ye, G. L.; Liu, Z.; Peng, Z. W.; Lou, J.; Vajtai, R. et al. Boron- and nitrogen-substituted graphene nanoribbons as efficient catalysts for oxygen reduction reaction. Chem. Mater. 2015, 27, 1181–1186.

    Article  CAS  Google Scholar 

  38. Ci, L. J.; Song, L.; Jin, C. H.; Jariwala, D.; Wu, D. X.; Li, Y. J.; Srivastava, A.; Wang, Z. F.; Storr, K.; Balicas, L. et al. Atomic layers of hybridized boron nitride and graphene domains. Nat. Mater. 2010, 9, 430–435.

    Article  CAS  Google Scholar 

  39. Wang, S. Y.; Iyyamperumal, E.; Roy, A.; Xue, Y. H.; Yu, D. S.; Dai, L. M. Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction: a synergetic effect by co-doping with boron and nitrogen. Angew. Chem., Int. Ed. 2011, 50, 11756–11760.

    Article  CAS  Google Scholar 

  40. Chen, S. C.; Chen, Z. H.; Siahrostami, S.; Higgins, D.; Nordlund, D.; Sokaras, D.; Kim, T. R.; Liu, Y. Z.; Yan, X. Z.; Nilsson, E. et al. Designing boron nitride islands in carbon materials for efficient electrochemical synthesis of hydrogen peroxide. J. Am. Chem. Soc. 2018, 140, 7851–7859.

    Article  CAS  Google Scholar 

  41. Zheng, Y.; Jiao, Y.; Ge, L.; Jaroniec, M.; Qiao, S. Z. Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis. Angew. Chem., Int. Ed. 2013, 52, 3110–3116.

    Article  CAS  Google Scholar 

  42. Liu, R. L.; Wu, D. Q.; Feng, X. L.; Müllen, K. Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew. Chem., Int. Ed. 2010, 49, 2565–2569.

    Article  CAS  Google Scholar 

  43. Li, M. T.; Zhang, L. P.; Xu, Q.; Niu, J. B.; Xia, Z. H. N-doped graphene as catalysts for oxygen reduction and oxygen evolution reactions: Theoretical considerations. J. Catal. 2014, 314, 66–72.

    Article  CAS  Google Scholar 

  44. Zhao, Z. H.; Li, M. T.; Zhang, L. P.; Dai, L. M.; Xia, Z. H. Design principles for heteroatom-doped carbon nanomaterials as highly efficient catalysts for fuel cells and metal-air batteries. Adv. Mater. 2015, 27, 6834–6840.

    Article  CAS  Google Scholar 

  45. Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.

    Article  Google Scholar 

  46. Zhang, L. P.; Xia, Z. H. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J. Phys. Chem. C 2011, 115, 11170–11176.

    Article  CAS  Google Scholar 

  47. Yang, N.; Li, L.; Li, J.; Ding, W.; Wei, Z. D. Modulating the oxygen reduction activity of heteroatom-doped carbon catalysts via the triple effect: Charge, spin density and ligand effect. Chem. Sci. 2018, 9, 5795–5804.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge the financial support from the National Natural Science Foundation of China (No. 51425302).

Author information

Authors and Affiliations

  1. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, China

    Yang Gao, Debin Kong, Jiaxu Liang, Bin Wang & Linjie Zhi

  2. School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Yang Gao, Daliang Han, Quan-Hong Yang & Linjie Zhi

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Yang Gao & Linjie Zhi

Authors
  1. Yang Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Debin Kong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiaxu Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Daliang Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Quan-Hong Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Linjie Zhi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Debin Kong, Bin Wang or Linjie Zhi.

Electronic Supplementary Material

12274_2021_3484_MOESM1_ESM.pdf

Inside-out dual-doping effects on tubular catalysts: Structural and chemical variation for advanced oxygen reduction performance

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, Y., Kong, D., Liang, J. et al. Inside-out dual-doping effects on tubular catalysts: Structural and chemical variation for advanced oxygen reduction performance. Nano Res. 15, 361–367 (2022). https://doi.org/10.1007/s12274-021-3484-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-021-3484-y

Keywords

Search

Navigation