Skip to main content

Advertisement

Log in

Facile synthesis of nitrogen-doped carbon nanosheets as metal-free catalyst with excellent oxygen reduction performance in alkaline and acidic media

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

In this work, a low-cost, high-performance, and environmentally friendly metal-free electrocatalyst based on N-doped carbon nanosheets (NCNs) was fabricated via the one-step pyrolysis of cheap corn starch and urea for the oxygen reduction reaction (ORR) in alkaline and acidic media. The results indicate that the nitrogen could be simply embedded into the carbon nanosheets by pyrolysis process. The effects of annealing temperature and raw material on NCN’s structure and electrocatalytic properties were investigated to optimize the preparation process. The results show that the total nitrogen content decreases while Brunauer–Emmett–Teller (BET) surface area, crystallization degree, graphitization degree, and electrical conductivity increase with the increase of pyrolysis temperature from 800 to 1000 °C. The measurements on the ORR activities by rotating disk electrode (RDE) in alkaline media (0.1 M KOH) and acidic media (0.5 M H2SO4) were investigated, and a nearly four-electron reaction pathway was observed. In comparison to commercial 20 % Pt/C catalyst (Pt/C), NCN exhibited excellent ORR electrocatalytic activity, methanol tolerant ability, and stability, making them promising metal-free alternative to Pt-based cathode catalysts in fuel cells. In addition, the findings obtained from this study may provide a scalable fabrication method for preparation of such low cost and high-efficiency metal-free oxygen reduction electrocatalyst derived from cheap biomass-based molecules.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Liu Q, Zhang JY (2013) Graphene supported Co-g-C3N4 as a novel metal-macrocyclic electrocatalyst for the oxygen reduction reaction in fuel cells. Langmuir 29:3821–3828

    Article  CAS  Google Scholar 

  2. Lefevre M, Proietti E, Jaouen F, Dodelet JP (2009) Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324:71–74

    Article  CAS  Google Scholar 

  3. Deng DH, Yu L, Chen XQ, Wang GX, Jin L, Pan XL, Deng J, Sun GQ, Bao XH (2013) Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. Angew Chem-Int Edit 52:371–375

    Article  CAS  Google Scholar 

  4. Li WM, Wu J, Higgins DC, Choi JY, Chen ZW (2012) Determination of iron active sites in pyrolyzed iron-based catalysts for the oxygen reduction reaction. ACS Catal 2:2761–2768

    Article  CAS  Google Scholar 

  5. Wang H, Zhang Z, Yang YX, Wang KL, Ji S, Key JL, Ma YY, Wang RF (2015) A Co-N-doped carbonized egg white as a high-performance, non-precious metal, electrocatalyst for oxygen reduction. J Solid State Electrochem 19:1727–1733

    Article  CAS  Google Scholar 

  6. Yang DS, Bhattacharjya D, Inamdar S, Park J, Yu JS (2012) 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

    Article  CAS  Google Scholar 

  7. Song P, Bo X, Nsabimana A, Guo L (2014) Additional doping of phosphorus into polypyrrole functionalized nitrogenous carbon nanotubes as novel metal-free oxygen reduction electrocatalyst in alkaline solution. Int J Hydrog Energy 39:15464–15473

    Article  CAS  Google Scholar 

  8. Li M, Jiang LQ, Lin L, Li YF, Yu DL, Cui LL, He XQ (2014) Fabrication of graphene-supported tetraferrocenylporphyrin electrocatalyst for oxygen reduction and its unique electrochemical response in both alkaline and acid media. J Solid State Electrochem 18:2743–2753

    Article  CAS  Google Scholar 

  9. Hayes WI, Joseph P, Mughal MZ, Papakonstantinou P (2015) Production of reduced graphene oxide via hydrothermal reduction in an aqueous sulphuric acid suspension and its electrochemical behaviour. J Solid State Electrochem 19:361–380

    Article  CAS  Google Scholar 

  10. Yang LJ, Jiang SJ, Zhao Y, Zhu L, Chen S, Wang XZ, Wu Q, Ma J, Ma YW, Hu Z (2011) Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem-Int Edit 50:7132–7135

    Article  CAS  Google Scholar 

  11. Yang Z, Yao Z, Li G, Fang G, Nie H, Liu Z, Zhou X, Xa C, Huang S (2012) Sulfur-doped Graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 6:205–211

    Article  CAS  Google Scholar 

  12. Wen Z, Wang X, Mao S, Bo Z, Kim H, Cui S, Lu G, Feng X, Chen J (2012) Crumpled nitrogen-doped graphene nanosheets with ultrahigh pore volume for high-performance supercapacitor. Adv Mater 24:5610–5616

    Article  CAS  Google Scholar 

  13. Xue Y, Liu J, Chen H, Wang R, Li D, Qu J, Dai L (2012) Nitrogen-doped graphene foams as metal-free counter electrodes in high-performance dye-sensitized solar cells. Angew Chem-Int Edit 51:12124–12127

    Article  CAS  Google Scholar 

  14. Soin N, Roy SS, Sharma S, Thundat T, McLaughlin JA (2013) Electrochemical and oxygen reduction properties of pristine and nitrogen-doped few layered graphene nanoflakes (FLGs). J Solid State Electrochem 17:2139–2149

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  16. Liu R, Wu D, Feng X, Muellen K (2010) Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem-Int Edit 49:2565–2569

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. Zhang L, Xia Z (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped Graphene for fuel cells. J Phys Chem C 115:11170–11176

    Article  CAS  Google Scholar 

  19. Wang HB, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2:781–794

    Article  CAS  Google Scholar 

  20. Ma G, Jia R, Zhao J, Wang Z, Song C, Jia S, Zhu Z (2011) Nitrogen-doped hollow carbon nanoparticles with excellent oxygen reduction performances and their electrocatalytic kinetics. J Phys Chem C 115:25148–25154

    Article  CAS  Google Scholar 

  21. Chen S, Bi J, Zhao Y, Yang L, Zhang C, Ma Y, Wu Q, Wang X, Hu Z (2012) Nitrogen-doped carbon nanocages as efficient metal-free electrocatalysts for oxygen reduction reaction. Adv Mater 24:5593–5597

    Article  CAS  Google Scholar 

  22. Zhao Y, Yang L, Chen S, Wang X, Ma Y, Wu Q, Jiang Y, Qian W, Hu Z (2013) Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes? J Am Chem Soc 135:1201–1204

    Article  CAS  Google Scholar 

  23. Maiyalagan T (2008) Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes. Appl Catal B-Environ 80:286–295

    Article  CAS  Google Scholar 

  24. Geng D, Chen Y, Chen Y, Li Y, Li R, Sun X, Ye S, Knights S (2011) High oxygen-reduction activity and durability of nitrogen-doped graphene. Energy Environ Sci 4:760–764

    Article  CAS  Google Scholar 

  25. Wang L, Yin FX, Yao CX (2014) N-doped graphene as a bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions in an alkaline electrolyte. Int J Hydrog Energy 39:15913–15919

    Article  CAS  Google Scholar 

  26. Wu ZS, Yang SB, Sun Y, Parvez K, Feng XL, Mullen K (2012) 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient eletrocatalysts for the oxygen reduction reaction. J Am Chem Soc 134:9082–9085

    Article  CAS  Google Scholar 

  27. Bao JF, Kishi N, Soga T (2014) Synthesis of nitrogen-doped graphene by the thermal chemical vapor deposition method from a single liquid precursor. Mater Lett 117:199–203

    Article  CAS  Google Scholar 

  28. Xue Y, Wu B, Jiang L, Guo Y, Huang L, Chen J, Tan J, Geng D, Luo B, Hu W, Yu G, Liu Y (2012) Low temperature growth of highly nitrogen-doped single crystal graphene arrays by chemical vapor deposition. J Am Chem Soc 134:11060–11063

    Article  CAS  Google Scholar 

  29. Zhang C, Fu L, Liu N, Liu M, Wang Y, Liu Z (2011) Synthesis of nitrogen-doped graphene using embedded carbon and nitrogen sources. Adv Mater 23:1020–1024

    Article  CAS  Google Scholar 

  30. Li N, Wang ZY, Zhao KK, Shi ZJ, Gu ZN, Xu SK (2010) Large scale synthesis of N-doped multi-layered graphene sheets by simple arc-discharge method. Carbon 48:255–259

    Article  CAS  Google Scholar 

  31. Deng DH, Pan XL, Yu LA, Cui Y, Jiang YP, Qi J, Li WX, Fu QA, Ma XC, Xue QK, Sun GQ, Bao XH (2011) Toward N-doped graphene via solvothermal synthesis. Chem Mat 23:1188–1193

    Article  CAS  Google Scholar 

  32. Yang S, Zhi L, Tang K, Feng X, Maier J, Muellen K (2012) Efficient synthesis of heteroatom (N or S)-doped graphene based on ultrathin graphene oxide-porous silica sheets for oxygen reduction reactions. Adv Funct Mater 22:3634–3640

    Article  CAS  Google Scholar 

  33. Li XL, Wang HL, Robinson JT, Sanchez H, Diankov G, Dai HJ (2009) Simultaneous nitrogen doping and reduction of graphene oxide. J Am Chem Soc 131:15939–15944

    Article  CAS  Google Scholar 

  34. Li X-H, Wang X, Antonietti M (2012) Mesoporous g-C3N4 nanorods as multifunctional supports of ultrafine metal nanoparticles: hydrogen generation from water and reduction of nitrophenol with tandem catalysis in one step. Chem Sci 3:2170–2174

    Article  CAS  Google Scholar 

  35. Wang S, Yu D, Dai L (2011) Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J Am Chem Soc 133:5182–5185

    Article  CAS  Google Scholar 

  36. Liu J, Zhang T, Wang Z, Dawson G, Chen W (2011) Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity. J Mater Chem 21:14398–14401

    Article  CAS  Google Scholar 

  37. Xu J, Li Y, Peng S, Lu G, Li S (2013) Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution: the effect of the pyrolysis temperature of urea. Phys Chem Chem Phys 15:7657–7665

    Article  CAS  Google Scholar 

  38. Ruiz-Hitzky E, Darder M, Fernandes FM, Zatile E, Javier Palomares F, Aranda P (2011) Supported Graphene from natural resources: easy preparation and applications. Adv Mater 23:5250–5255

    Article  CAS  Google Scholar 

  39. Westenfelder B, Meyer JC, Biskupek J, Kurasch S, Scholz F, Krill CE III, Kaiser U (2011) Transformations of carbon adsorbates on graphene substrates under extreme heat. Nano Lett 11:5123–5127

    Article  CAS  Google Scholar 

  40. Holst JR, Gillan EG (2008) From triazines to heptazines: deciphering the local structure of amorphous nitrogen-rich carbon nitride materials. J Am Chem Soc 130:7373–7379

    Article  CAS  Google Scholar 

  41. Jun Y-S, Hong WH, Antonietti M, Thomas A (2009) Mesoporous, 2D hexagonal carbon nitride and titanium nitride/carbon composites. Adv Mater 21:4270

    Article  CAS  Google Scholar 

  42. Barreiro A, Boerrnert F, Avdoshenko SM, Rellinghaus B, Cuniberti G, Ruemmeli MH, Vandersypen LMK (2013) Understanding the catalyst-free transformation of amorphous carbon into graphene by current-induced annealing. Sci Rep 3:1–6

  43. Paredez P, Maia da Costa MEH, Zagonel LF, Ribeiro CTM, Alvarez F (2007) Growth of nitrogenated fullerene-like carbon on Ni islands by ion beam sputtering. Carbon 45:2678–2684

    Article  CAS  Google Scholar 

  44. Kudin KN, Ozbas B, Schniepp HC, Prud’homme RK, Aksay IA, Car R (2008) Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett 8:36–41

    Article  CAS  Google Scholar 

  45. Pimenta MA, Dresselhaus G, Dresselhaus MS, Cancado LG, Jorio A, Saito R (2007) Studying disorder in graphite-based systems by Raman spectroscopy. Phys Chem Chem Phys PCCP 9:1276–1291

    Article  CAS  Google Scholar 

  46. Ryu Z, Zheng J, Wang M, Zhang B (1999) Characterization of pore size distributions on carbonaceous adsorbents by DFT. Carbon 37:1257–1264

    Article  CAS  Google Scholar 

  47. Leonard ND, Nallathambi V, Barton SC (2011) Carbon supports for non-precious metal proton exchange membrane fuel cells. In: Gasteiger HA, Weber A, Narayanan SR, et al. (eds) Polymer electrolyte fuel cells 11, ECS Transactions, vol 1, vol 41. Electrochemical Soc Inc, Pennington, pp. 1175–1181

    Google Scholar 

  48. Byon HR, Suntivich J, Shao-Horn Y (2011) Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid. Chem Mat 23:3421–3428

    Article  CAS  Google Scholar 

  49. Kundu S, Nagaiah TC, Xia W, Wang Y, Van Dommele S, Bitter JH, Santa M, Grundmeier G, Bron M, Schuhmann W, Muhler M (2009) Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction. J Phys Chem C 113:14302–14310

    Article  CAS  Google Scholar 

  50. Choi JY, Higgins D, Chen ZW (2012) Highly durable graphene nanosheet supported iron catalyst for oxygen reduction reaction in PEM fuel cells. J Electrochem Soc 159:B87–B90

    Article  CAS  Google Scholar 

  51. Dorjgotov A, Ok J, Jeon Y, Yoon SH, Shul YG (2013) Nitrogen-doped ordered porous carbon catalyst for oxygen reduction reaction in proton exchange membrane fuel cells. J Solid State Electrochem 17:2567–2577

    Article  CAS  Google Scholar 

  52. Wang XQ, Lee JS, Zhu Q, Liu J, Wang Y, Dai S (2010) Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction. Chem Mat 22:2178–2180

    Article  CAS  Google Scholar 

  53. Hu H, Zhao ZB, Wan WB, Gogotsi Y, Qiu JS (2013) Ultralight and highly compressible graphene aerogels. Adv Mater 25:2219–2223

    Article  CAS  Google Scholar 

  54. Sheng ZH, Shao L, Chen JJ, Bao WJ, Wang FB, Xia XH (2011) Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 5:4350–4358

    Article  CAS  Google Scholar 

  55. Li XH, Kurasch S, Kaiser U, Antonietti M (2012) Synthesis of monolayer-patched graphene from glucose. Angew Chem-Int Edit 51:9689–9692

    Article  CAS  Google Scholar 

  56. Choi CH, Park SH, Woo SI (2012) Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity. ACS Nano 6:7084–7091

    Article  CAS  Google Scholar 

  57. Yang W, Fellinger TP, Antonietti M (2011) Efficient metal-free oxygen reduction in alkaline medium on high-surface-area mesoporous nitrogen-doped carbons made from ionic liquids and nucleobases. J Am Chem Soc 133:206–209

    Article  CAS  Google Scholar 

  58. Wang D-W, Su D (2014) Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ Sci 7:576–591

    Article  Google Scholar 

  59. Chen P, Xiao TY, Qian YH, Li SS, Yu SH (2013) A nitrogen-doped graphene/carbon nanotube nanocomposite with synergistically enhanced electrochemical activity. Adv Mater 25:3192–3196

    Article  CAS  Google Scholar 

  60. Zhang Y, Ge J, Wang L, Wang D, Ding F, Tao X, Chen W (2013) manageable n-doped graphene for high performance oxygen reduction reaction Scientific Reports 3

  61. Pan F, Jin J, Fu X, Liu Q, Zhang J (2013) Advanced oxygen reduction electrocatalyst based on nitrogen-doped graphene derived from edible sugar and urea. ACS Appl Mater Interfaces 5:11108–11114

    Article  CAS  Google Scholar 

  62. Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486:43–51

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to the National Natural Science Foundation of China (Grant No. 21364004), Gansu Province University Fundamental Research Funds (Grant No. HG20140915), and the University Scientific Research Project of Gansu Province Foundation (Grant No. 2014A-034).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Junyan Zhang.

Electronic supplementary material

ESM 1

(DOCX 1260 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, Q., Ma, Q., Pan, F. et al. Facile synthesis of nitrogen-doped carbon nanosheets as metal-free catalyst with excellent oxygen reduction performance in alkaline and acidic media. J Solid State Electrochem 20, 1469–1479 (2016). https://doi.org/10.1007/s10008-016-3157-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-016-3157-z

Keywords

Navigation