Skip to main content
SpringerLink
Log in

Comparative study of various preparation methods of metal-free N and S Co-doped porous graphene as an ORR catalyst in alkaline solution

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

In this work, various methods (chemical vapor deposition (CVD), hydrothermal, and pyrolysis) have been applied for preparing sulfur–nitrogen co-doped porous graphene. Afterwards, the electrochemical behavior of the samples prepared through different techniques was investigated for oxygen reduction reaction (ORR). The prepared heteroatoms-doped electro-catalysts were thoroughly characterized by X-ray diffraction, Raman spectroscopy, N2 adsorption-desorption, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy techniques. The results showed that co-doping of S and N into porous graphene significantly enhanced the ORR performance. The obtained results showed that the efficiency trend of preparation methods on the ORR performance followed as pyrolysis > CVD > hydrothermal. In addition, the electron transfer numbers in these methods at optimal conditions were 4.1, 3.4, and 2.6, respectively. Among different preparation techniques, pyrolysis as a post-synthesis doping technique has exhibited the most efficient ORR process, in which electron transfer follows the 4e pathway. Moreover, the catalyst prepared by the pyrolysis method has an onset potential of 0.93V which is very close to the conventional Pt/C 20 wt.% (0.99 V) electro-catalysts because of surface doping and better control over the final product. Finally, the microbial fuel cell test showed a high peak power density of 30.94 mW m−2 for the optimal sample, which is close to the Pt/C 20 wt.% (38.63 mW m−2) cathodes, because of the synergistic effect of N and S co-doped carbon structure.

Graphical abstract

Synthesis and characterization of heteroatom co-doped graphenes using CVD, Pyrolysis and hydrothermal techniques are reported and their electrochemical behaviors evaluated. The results represent the high dependence of ORR activity of the prepared electrocatalysts to the synthesis method and the electrocatalyst via pyrolysis method shows high selectivity for the 4e- reduction.

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

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5

Similar content being viewed by others

References

  1. Zhu C and Dong S 2013 Recent progress in graphene-based nanomaterials as advanced electrocatalysts towards oxygen reduction reaction Nanoscale 5 1753

    Article  CAS  PubMed  Google Scholar 

  2. Nie Y, Li L and Wei Z 2015 Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction Chem. Soc. Rev. 44 2168

    Article  CAS  PubMed  Google Scholar 

  3. Li Y, Li M, Jiang L, Lin L, Cui L and He X 2014 Advanced oxygen reduction reaction catalyst based on nitrogen and sulfur co-doped graphene in alkaline medium Phys. Chem. Chem. Phys. 16 23196

    Article  CAS  PubMed  Google Scholar 

  4. Park J E, Jang Y J, Kim Y J, Song M S, Yoon S, Kim D H and Kim S J 2014 Sulfur-doped graphene as a potential alternative metal-free electrocatalyst and Pt-catalyst supporting material for oxygen reduction reaction Phys. Chem. Chem. Phys. 16 103

    Article  CAS  PubMed  Google Scholar 

  5. Wang X, Wang J, Wang D, Dou S, Ma Z, Wu J, et al. 2014 One-pot synthesis of nitrogen and sulfur co-doped graphene as efficient metal-free electrocatalysts for the oxygen reduction reaction Chem. Commun. 50 4839

    Article  CAS  Google Scholar 

  6. Akhter T, Islam M M, Faisal S N, Haque E, Minett A I, Liu H K, et al. 2016 Self-assembled N/S codoped flexible graphene paper for high performance energy storage and oxygen reduction reaction ACS Appl. Mater. Interfaces 8 2078

    Article  CAS  PubMed  Google Scholar 

  7. Li J, Zhang Y, Zhang X, Huang J, Han J, Zhang Z, et al. 2017 S, N dual-doped graphene-like carbon nanosheets as efficient oxygen reduction reaction electrocatalysts ACS Appl. Mater. Interfaces 9 398

    Article  CAS  PubMed  Google Scholar 

  8. Sarapuu A, Kibena-Põldsepp E, Borghei M and Tammeveski K 2018 Electrocatalysis of oxygen reduction on heteroatom-doped nanocarbons and transition metal-nitrogen-carbon catalysts for alkaline membrane fuel cells J. Mater. Chem. A 6 776

    Article  CAS  Google Scholar 

  9. Chen Y, Wang J, Liu H, Banis M N, Li R, Sun X, et al. 2011 Nitrogen doping effects on carbon nanotubes and the origin of the enhanced electrocatalytic activity of supported Pt for proton-exchange membrane fuel cells J. Phys. Chem. C 115 3769

    Article  CAS  Google Scholar 

  10. Imran Jafri R, Rajalakshmi N and Ramaprabhu S 2010 Nitrogen doped graphene nanoplatelets as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell J. Mater. Chem. 20 7114

    Article  CAS  Google Scholar 

  11. Qin L, Ding R, Wang H, Wu J, Wang C, Zhang C, et al. 2016 Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction Nano Res. 10 305

    Article  Google Scholar 

  12. Soo L T, Loh K S, Mohamad A B, Daud W R W and Wong W Y 2016 Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction J. Alloys Compd. 677 112

    Article  CAS  Google Scholar 

  13. Tang S, Zhou X, Xu N, Bai Z, Qiao J and Zhang J 2016 Template-free synthesis of three-dimensional nanoporous N-doped graphene for high performance fuel cell oxygen reduction reaction in alkaline media Appl. Energy 175 405

    Article  CAS  Google Scholar 

  14. Wu H, Guo C, Li J, Ma Z, Feng Q and Chen C 2016 A graphene-based electrocatalyst co-doped with nitrogen and cobalt for oxygen reduction reaction Int. J. Hydrog. Energy 41 20494

    Article  CAS  Google Scholar 

  15. Zangeneh Kamali K and Moradi Golsheikh A 2016 Green and facile approach to synthesis of well-dispersed nitrogen-doped graphene without using surfactant or stabilizer with potential application for oxygen reduction reaction Colloid. Surf. A 509 574

    Article  CAS  Google Scholar 

  16. Haque E, Sarkar S, Hassan M, Hossain M S, Minett A I, Dou S X and Gomes V G 2016 Tuning graphene for energy and environmental applications: Oxygen reduction reaction and greenhouse gas mitigation J. Power Sources 328 472

    Article  CAS  Google Scholar 

  17. Kong D, Yuan W, Li C, Song J, Xie A and Shen Y 2017 Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction Appl. Surf. Sci. 393 144

    Article  CAS  Google Scholar 

  18. Bayram E, Yilmaz G and Mukerjee S 2016 A solution-based procedure for synthesis of nitrogen doped graphene as an efficient electrocatalyst for oxygen reduction reactions in acidic and alkaline electrolytes Appl. Catal. B Environ. 192 26

    Article  CAS  Google Scholar 

  19. Vikkisk M, Kruusenberg I, Joost U, Shulga E, Kink I and Tammeveski K 2014 Electrocatalytic oxygen reduction on nitrogen-doped graphene in alkaline media Appl. Catal. B Environ. 147 369

    Article  CAS  Google Scholar 

  20. Zhang H, Liu X, He G, Zhang X, Bao S and Hu W 2015 Bioinspired synthesis of nitrogen/sulfur co-doped graphene as an efficient electrocatalyst for oxygen reduction reaction J. Power Sources 279 252

    Article  CAS  Google Scholar 

  21. Bhange S N, Unni S M and Kurungot S 2016 Nitrogen and sulphur co-doped crumbled graphene for the oxygen reduction reaction with improved activity and stability in acidic medium J. Mater. Chem. A 4 6014

    Article  CAS  Google Scholar 

  22. Gracia-Espino E 2016 Behind the synergistic effect observed on phosphorus-nitrogen codoped graphene during the oxygen reduction reaction J. Phys. Chem. C 120 27849

    Article  CAS  Google Scholar 

  23. Kim I T, Song M J, Kim Y B and Shin M W 2016 Microwave-hydrothermal synthesis of boron/nitrogen co-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction reaction Int. J. Hydrog. Energy 41 22026

    Article  CAS  Google Scholar 

  24. Pan F, Duan Y, Zhang X and Zhang J 2016 A facile synthesis of nitrogen/sulfur Co-doped graphene for the oxygen reduction reaction ChemCatChem 8 163

    Article  CAS  Google Scholar 

  25. Xu H, Chen X, Pan S, Qin Y, Chen X, Tao Y and Kong Y 2016 S and N codoped three-dimensional graphene-MnS hybrids with high electrocatalytic activity for oxygen reduction reaction Synth. Met. 221 55

    Article  CAS  Google Scholar 

  26. Bag S and Raj C R 2016 On the electrocatalytic activity of nitrogen-doped reduced graphene oxide: Does the nature of nitrogen really control the activity towards oxygen reduction? J. Chem. Sci. 128 339

    Article  CAS  Google Scholar 

  27. Bag S, Mondal B, Das and Raj C R 2015 Nitrogen and sulfur dual-doped reduced graphene oxide: Synergistic effect of dopants towards oxygen reduction reaction Electrochim. Acta 163 16

    Article  CAS  Google Scholar 

  28. Bag S, Roy K, Gopinath C S and Raj C R 2014 Facile single-step synthesis of nitrogen-doped reduced graphene oxide-Mn3O4 hybrid functional material for the electrocatalytic reduction of oxygen ACS Appl. Mater. Interfaces 6 2692

    Article  CAS  PubMed  Google Scholar 

  29. Guo D, Shibuya R, Akiba C, Saji S S, Kondo T and Nakamura J 2016 Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts Science 351 361

    Article  CAS  PubMed  Google Scholar 

  30. Liu Z, Nie H, Yang Z, Zhang J, Jin Z, Lu Y, et al. 2013 Sulfur-nitrogen co-doped three-dimensional carbon foams with hierarchical pore structures as efficient metal-free electrocatalysts for oxygen reduction reactions Nanoscale 5 3283

    Article  CAS  PubMed  Google Scholar 

  31. Wang Y, Zhu M, Li Y, Zhang M, Xue X, Shi Y, et al. 2018 Heteroatom-doped porous carbon from methyl orange dye wastewater for oxygen reduction Green Energy Environ. 3 172

    Article  Google Scholar 

  32. Rashidi A M, Mahmudian L and Dehghani H 2016 Producing graphene and nanoporous graphene, U.S. Patent 20,160,060,123A1, 3

  33. Sadegh Hassani S, Ganjali M R, Samiee L, Rashidi A M, Tasharrofi S, Yadegari A, et al. 2018 Comparative study of various types of metal-free N and S Co-doped porous graphene for high performance oxygen reduction reaction in alkaline solution J. Nanosci. Nanotechnol. 18 4565

    Article  PubMed  Google Scholar 

  34. Lin Z, Waller G H, Liu Y, Liu M and Wong C P 2013 3D Nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction Nano Energy 2 241

    Article  CAS  Google Scholar 

  35. Ziaedini A, Rashedi H, Alaie E and Zeinali M 2018 continuous bioelectricity generation from phenol-contaminated water by mediator-less microbial fuel cells: A comparative study between air-cathode and bio-cathode systems Fuel Cells 18 526

    Article  CAS  Google Scholar 

  36. Patel M A, Luo F, Khoshi M R, Rabie E, Zhang Q, Flach C R, et al. 2016 P-doped porous carbon as metal free catalysts for selective aerobic oxidation with an unexpected mechanism ACS Nano 10 2305

    Article  CAS  PubMed  Google Scholar 

  37. Panomsuwan G, Saito N and Ishizaki T 2016 Nitrogen-doped carbon nanoparticle–carbon nanofiber composite as an efficient metal-free cathode catalyst for oxygen reduction reaction ACS Appl. Mater. Interfaces 8 6962

    Article  CAS  PubMed  Google Scholar 

  38. Lin H, Chu L, Wang X, Yao Z, Liu F, Ai Y, et al. 2016 Boron, nitrogen, and phosphorous ternary doped graphene aerogel with hierarchically porous structures as highly efficient electrocatalysts for oxygen reduction reaction New J. Chem. 40 6022

    Article  CAS  Google Scholar 

  39. Ai W, Luo Z, Jiang J, Zhu J, Du Z, Fan Z, et al. 2014 Nitrogen and sulfur codoped graphene: Multifunctional electrode materials for high-performance Li-ion batteries and oxygen reduction reaction Adv. Mater. 26 6186

    Article  CAS  PubMed  Google Scholar 

  40. Sun Z, Masa J, Weide P, Fairclough S M, Robertson A W, Ebbinghaus P, et al. 2015 High-quality functionalized few-layer graphene: Facile fabrication and doping with nitrogen as a metal-free catalyst for the oxygen reduction reaction J. Mater. Chem. A 3 15444

    Article  CAS  Google Scholar 

  41. Yadegari A, Samiee L, Tasharrofi S, Tajik S, Rashidi A M, Shoghi F, et al. 2017 Nitrogen doped nanoporous graphene: An efficient metal-free electrocatalyst for the oxygen reduction reaction RSC Adv. 7 55555

    Article  CAS  Google Scholar 

  42. Li D, Jia Y, Chang G, Chen J, Liu H, Wang J, et al. 2018 A defect-driven metal-free electrocatalyst for oxygen reduction in acidic electrolyte Chem. 4 2345

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the Research Council of the University of Tehran and Research Institute of Petroleum Industry (RIPI) for the financial support of this work.

Author information

Authors and Affiliations

  1. Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, P.O. Box 1417614411, Tehran, Iran

    Sedigheh Sadegh Hassani & Mohammad Reza Ganjali

  2. Catalysis Research Division, Research Institute of Petroleum Industry (RIPI), 1485733111, Tehran, Iran

    Sedigheh Sadegh Hassani

  3. Energy Technology Research Division, Research Institute of Petroleum Industry (RIPI), 1485733111, Tehran, Iran

    Leila Samiee

  4. Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), 1485733111, Tehran, Iran

    Alimorad Rashidi

  5. Biosensor Research Center, Endocrinology and Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, P.O. Box 1411713137, Tehran, Iran

    Mohammad Reza Ganjali

Authors
  1. Sedigheh Sadegh Hassani
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Leila Samiee
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alimorad Rashidi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohammad Reza Ganjali
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Sedigheh Sadegh Hassani or Leila Samiee.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 1063 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sadegh Hassani, S., Samiee, L., Rashidi, A. et al. Comparative study of various preparation methods of metal-free N and S Co-doped porous graphene as an ORR catalyst in alkaline solution. J Chem Sci 134, 27 (2022). https://doi.org/10.1007/s12039-021-02018-w

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-021-02018-w

Keywords

Search

Navigation