Journal of Solid State Electrochemistry

, Volume 22, Issue 9, pp 2715–2723 | Cite as

Transition metal-doped carbon sphere as enhanced catalysts for oxygen reduction

  • Wenjun Zhao
  • Zhao Tan
  • Yi Tan
  • Chuanqi Feng
  • Huimin WuEmail author
  • Guangxue ZhangEmail author
Original Paper


Herein, carbon sphere (CS-T) were successfully prepared by pyrolyzation melamine formaldehyde resin. And then different transition metals (Fe, Co, Ni) were doped on carbon sphere (CS-M-900). The scanning electron microscopes and elemental mappings prove that the transition metal particles are uniformly doped on the carbon sphere. Meanwhile, the X-ray photoelectron spectrum prove that the transition metals are zero-valence. Furthermore, the electrochemical testings showed the CS-Co-900 had more positive onset potential (0.93 V), half-wave potential (0.84 V), and peak potential (0.81 V). Furthermore, the CS-Co-900 had lower charge transfer resistance (44 Ω) and smaller Tafel slope (65 mV/dec). Most importantly, the oxygen reduction reaction on the CS-Co-900 turned out to be a four electron procedure with excellent methanol tolerance. The improved electrochemical properties towards oxygen reduction reactions of carbon sphere via cobalt doping suggested a design strategy towards future high-performance electrochemical devices.


Melamine formaldehyde resin Carbon sphere Transition metal doping Oxygen reduction 


Funding information

We acknowledge financial support from the National Natural Science Foundation of China (grant no. 21205030), and by key project of Hubei provincial education department (D20171001) and Hubei Key Laboratory of Ferro & Piezoelectric Materials and Devices (201710).

Supplementary material

10008_2018_3988_MOESM1_ESM.docx (1.3 mb)
ESM 1 (DOCX 1330 kb)


  1. 1.
    Gewirth AA, Thorum MS (2010) Electroreduction of dioxygen for fuel cell applications: materials and challenges. Inorg Chem 49(8):3557–3566CrossRefPubMedGoogle Scholar
  2. 2.
    Zhao JJ, Liu YM, Quan X, Chen S, Yu HT, Zhao HM (2017) Nitrogen-doped carbon with a high degree of graphitization derived from biomass as high performance electrocatalyst for oxygen reduction reaction. Appl Surf Sci 396:986–993CrossRefGoogle Scholar
  3. 3.
    Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486(7401):43–51CrossRefPubMedGoogle Scholar
  4. 4.
    Sealy C (2008) The problem with platinum. Mater Today 11(12):65–68CrossRefGoogle Scholar
  5. 5.
    Wang DW, Su DS (2014) Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ Sci 7(2):576–591CrossRefGoogle Scholar
  6. 6.
    Gong KP, Du F, Xia ZH, Durstock M, Dai LM (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323(5915):760–764CrossRefPubMedGoogle Scholar
  7. 7.
    Niu W, Li L, Liu X, Wang N, Liu J, Zhou W, Tang Z, Chen S (2015) Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction. J Am Chem Soc 137(16):5555–5562CrossRefPubMedGoogle Scholar
  8. 8.
    Noffke BW, Li Q, Raghavachari K, Li LS (2016) A model for the pH-dependent selectivity of the oxygen reduction reaction electrocatalyzed by N-doped graphitic carbon. J Am Chem Soc 138(42):13923–13929CrossRefGoogle Scholar
  9. 9.
    Zheng Y, Jiao Y, Zhu Y, Cai Q, Vasileff A, Li LH, Han Y, Chen Y, Qiao SZ (2017) Molecule-level g-C3N4 coordinated transition metals as a new class of electrocatalysts for oxygen electrode reactions. J Am Chem Soc 139(9):3336–3339CrossRefPubMedGoogle Scholar
  10. 10.
    Jiang WJ, Gu L, Li L, Zhang Y, Zhang X, Zhang LJ, Wang JQ, Hu JS, Wei Z, Wan LJ (2016) Understanding the high activity of Fe–N–C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe–Nx. J Am Chem Soc 138(10):3570–3578CrossRefPubMedGoogle Scholar
  11. 11.
    Ferrero GA, Preuss K, Marinovic A, Jorge AB, Mansor N, Brett DJ, Fuertes AB, Sevilla M, Titirici MM (2016) Fe-N-doped carbon capsules with outstanding electrochemical performance and stability for the oxygen reduction reaction in both acid and alkaline conditions. ACS Nano 10(6):5922–5932CrossRefPubMedGoogle Scholar
  12. 12.
    Shang L, Yu H, Huang X, Bian T, Shi R, Zhao Y, Waterhouse GI, Wu LZ, Tung CH, Zhang T (2016) Well-dispersed ZIF-derived co, N co-doped carbon nano frames through mesoporous-silica-protected calcination as efficient oxygen reduction electrocatalysts. Adv Mater 28(8):1668–1674CrossRefPubMedGoogle Scholar
  13. 13.
    Ma N, Jia Y, Yang XF, She XL, Zhang LZ, Peng Z, Yao XD, Yang DJ (2016) Seaweed biomass derived (Ni, Co)/CNT nano aerogels: efficient bifunctional electrocatalysts for oxygen evolution and reduction reactions. J Mater Chem A 4(17):6376–6384CrossRefGoogle Scholar
  14. 14.
    Yu H, Fisher A, Cheng D, Cao D (2016) Cu, N-co-doped hierarchical porous carbons as electrocatalysts for oxygen reduction reaction. ACS Appl Mater Interfaces 8(33):21431–21439CrossRefPubMedGoogle Scholar
  15. 15.
    Zhong H, Zhang H, Liu S, Deng C, Wang M (2013) Nitrogen-enriched carbon from melamine resins with superior oxygen reduction reaction activity. ChemSusChem 6(5):807–812CrossRefPubMedGoogle Scholar
  16. 16.
    Pi YT, Xing XY, Lu LM, He ZB, Ren TZ (2016) Hierarchical porous activated carbon in OER with high efficiency. RSC Adv 6(104):102422–102427CrossRefGoogle Scholar
  17. 17.
    Liu MX, Ma XM, Gan LH, Xu ZJ, Zhu DZ, Chen LW (2014) A facile synthesis of novel mesoporous Ge@C sphere anode with stable and high capacity for lithium. J Mater Chem A 2(40):17107–17114CrossRefGoogle Scholar
  18. 18.
    Zhu TT, Zhou J, Li ZH, Li SJ, Si WJ, Zhuo SP (2014) Hierarchical porous and N-doped carbon nanotubes derived from polyaniline for electrode materials in supercapacitors. J Mater Chem A 2(31):12545–12551CrossRefGoogle Scholar
  19. 19.
    Jin YY, Tian K, Wei L, Zhang XY, Guo X (2016) Hierarchical porous microspheres of activated carbon with a high surface area from spores for electrochemical double-layer capacitors. J Mater Chem A 4(41):15968–15979CrossRefGoogle Scholar
  20. 20.
    Zhou TS, Zhou Y, Ma RG, Zhou ZZ, Liu GH, Liu Q, Zhu YF, Wang JC (2016) In situ formation of nitrogen-doped carbon nanoparticles on hollow carbon spheres as efficient oxygen reduction electrocatalysts. Nano 8:18134–18142Google Scholar
  21. 21.
    Lee JS, Park GS, Kim ST, Liu ML, Cho J (2013) A highly efficient electrocatalyst for the oxygen reduction reaction: N-doped Ketjenblack incorporated into Fe/Fe3C-functionalized melamine foam. Angew Chem Int Ed 52(3):1026–1030CrossRefGoogle Scholar
  22. 22.
    Zhang XH, Lu P, Cui XZ, Chen LS, Zhang C, Li ML, Xu YF, Shi JL (2016) Probing the electro-catalytic ORR activity of cobalt-incorporated nitrogen-doped CNTs. J Catal 344:455–464CrossRefGoogle Scholar
  23. 23.
    Wu MS, Chen FY, Lai YH, Sie YJ (2017) Electrocatalytic oxidation of urea in alkaline solution using nickel/nickel oxide nanoparticles derived from nickel-organic framework. Electrochim Acta 258:167–174CrossRefGoogle Scholar
  24. 24.
    Wu J, Yang SW, Li JP, Yang YC, Wang G, Bu XM, He P, Sun J, Yang JH, Deng Y, Ding GQ, Xie XM (2016) Electron injection of phosphorus doped g-C3N4 quantum dots: controllable photoluminescence emission wavelength in the whole visible light range with high quantum yield. Adv Optical Mater 4(12):2095–2101CrossRefGoogle Scholar
  25. 25.
    Zhao Y, Zhao F, Wang XP, Xu CY, Zhang ZP, Shi GQ, Qu LT (2014) Graphitic carbon nitride nanoribbons: graphene-assisted formation and synergic function for highly efficient hydrogen evolution. Angew Chem 53(50):13934–13939CrossRefGoogle Scholar
  26. 26.
    Niu YL, Huang XQ, Wu XS, Zhao L, Hu WH, Li CM (2017) One-pot synthesis of Co/N-doped mesoporous graphene with embedded Co/CoOx nanoparticles for efficient oxygen reduction reaction. Nano 9:10233–10239Google Scholar
  27. 27.
    Datsyuk V, Kalyva M, Papagelis K, Parthenios J, Tasis D, Siokou A, Kallitsis I, Galiotis C (2008) Chemical oxidation of multiwalled carbon nanotubes. Carbon 46(6):833–840CrossRefGoogle Scholar
  28. 28.
    Lozzi L, Passacantando M, Picozzi P, Santucci S, Den Haas H (1995) Oxidation of the Fe/Cu (100) interface. Surf Sci 331:703–709CrossRefGoogle Scholar
  29. 29.
    Kishi K, Nishioka J (1990) Interaction of Fe/Cu(100), Fe-Ni/Cu(100) and Ni/Fe/Cu(100) surfaces with O2 studied by XPS. Surf Sci 227(1-2):97–106CrossRefGoogle Scholar
  30. 30.
    Shabanova IN, Trapeznikov VA (1975) A study of the electronic structure of Fe3C, Fe3Al and Fe3Si by x-ray photoelectron spectroscopy. J Electron Spectrosc Relat Phenom 6(4):297–307CrossRefGoogle Scholar
  31. 31.
    Hsu LS, Williams RS (1994) Electronic-structure study of the Ni/Ga and the Ni In intermetallic compounds using X-ray photoemission spectroscopy. J Phys Chem Solids 55:305–312CrossRefGoogle Scholar
  32. 32.
    Mansour AN (1994) Nickel monochromated Al K α XPS spectra from the physical electronics model 5400 spectrometer. Surf Sci Spectra 3(3):221–230CrossRefGoogle Scholar
  33. 33.
    Lian KK, Kirk DW, Thorpe SJ (1995) Investigation of a “two-state” Tafel phenomenon for the oxygen evolution reaction on an amorphous Ni-Co alloy. J Electrochem Soc 142(11):3704–3712CrossRefGoogle Scholar
  34. 34.
    Yao Y, Zhang BQ, Shi JY, Yang QH (2015) Preparation of nitrogen-doped carbon nanotubes with different morphologies from melamine-formaldehyde resin. ACS Appl Mater Interfaces 7(13):7413–7420CrossRefPubMedGoogle Scholar
  35. 35.
    Su YH, Zhu YH, Jiang HL, Shen JH, Yang XL, Zou WJ, Chen JD, Li CZ (2014) Cobalt nanoparticles embedded in N-doped carbon as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. Nano 6:15080–15089Google Scholar
  36. 36.
    Yu BB, Min H, Wu HM, Wang SF, Ding Y, Wang GX (2017) Production of MoS2/CoSe2 hybrids and their performance as oxygen reduction reaction catalysts. J Mater Sci 52(6):3188–3198CrossRefGoogle Scholar
  37. 37.
    Seifitokaldani A, Savadogo O, Perrier M (2015) Stability and catalytic activity of titanium oxy-nitride catalyst prepared by in-situ urea-based sol-gel method for the oxygen reduction reaction (ORR) in acid medium. Int J Hydrog Energy 40(33):10427–10438CrossRefGoogle Scholar
  38. 38.
    Mao S, Wen ZH, Huang TZ, Hou Y, Che JH (2014) High-performance bi-functional electrocatalysts of 3D crumpled graphene-cobalt oxide nano-hybrids for oxygen reduction and evolution reactions. Energy Environ Sci 7(2):609–616CrossRefGoogle Scholar
  39. 39.
    Niu WJ, Zhu RH, Hua Y, Zeng HB, Cosnier S, Zhang XJ, Shan D (2016) One-pot synthesis of nitrogen-rich carbon dots decorated graphene oxide as metal-free electrocatalyst for oxygen reduction reaction. Carbon 109:402–410CrossRefGoogle Scholar
  40. 40.
    Wang Y, Song SQ, Maragou V, Shen PK, Tsiakaras P (2009) High surface area tungsten carbide microspheres as effective Pt catalyst support for oxygen reduction reaction. Appl Catal B Environ 89(1-2):223–228CrossRefGoogle Scholar
  41. 41.
    Chen WF, James TM, Etsuko F (2013) Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem Commun 49(79):8896–8909CrossRefGoogle Scholar
  42. 42.
    Wang RF, Wang K, Wang ZH, Song HH, Wang H, Ji S (2015) Pig bones derived N-doped carbon with multi-level pores as electrocatalyst for oxygen reduction. J Power Sources 297:295–301CrossRefGoogle Scholar
  43. 43.
    Jin JY, Yu BB, Wu HM, Wang SF, Feng CQ (2017) Synthesis and electrocatalytic activity of Co1-xMoxSe2 for oxygen reduction. J Alloy Compd 703:652–655CrossRefGoogle Scholar
  44. 44.
    Ma TY, Dai S, Jaroniec M, Qiao SZ (2014) Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrode. J Am Chem Soc 136(39):13925–13931CrossRefPubMedGoogle Scholar
  45. 45.
    Benck JD, Chen ZB, Kuritzky LY, Forman AJ, Jaramillo TF (2012) Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: insights into the origin of their catalytic activity. ACS Catal 2(9):1916–1923CrossRefGoogle Scholar
  46. 46.
    Ye YF, Li HB, Cai F, Yan CC, Si R, Miao S, Li YS, Wang GX, Bao XH (2017) 2D mesoporous carbon doped with Fe-N active sites for efficient oxygen reduction. ACS Catal 7(11):7638–7646CrossRefGoogle Scholar
  47. 47.
    Wu HM, David W, Wang GX, Liu HK (2011) Pt/C catalysts using different carbon supports for the cathode of PEM fuel cells. Adv Sci Lett 4(1):115–120CrossRefGoogle Scholar
  48. 48.
    Wang HT, Wang W, Asif M, Yu Y, Wang ZY, Wang JL, Liu HF, Xiao JW (2017) Cobalt ions-coordinated self-assembly synthesis of nitrogen doped ordered mesoporous carbon nanosheets for efficiently catalyzing oxygen reduction. Nano 9:15534–15541Google Scholar
  49. 49.
    Parwaiz S, Bhunia K, Das AK, Khan MM, Pradhan D (2017) Cobalt-doped ceria/reduced graphene oxide nanocomposite as an efficient oxygen reduction reaction catalyst and supercapacitor material. J Phys Chem C 121(37):20165–20176CrossRefGoogle Scholar
  50. 50.
    Guo JX, Niu QJ, Yuan YC, Maitlo I, Nie J, Ma GP (2017) Electrospun core-shell nanofibers derived Fe-S/N doped carbon material for oxygen reduction reaction. Appl Surf Sci 416:118–123CrossRefGoogle Scholar
  51. 51.
    Kone I, Xie A, Tang Y, Chen Y, Liu J, Chen YM, Sun YZ, Yang XJ, Wan PY (2017) Hierarchical porous carbon doped with iron-nitrogen-sulfur for efficient oxygen reduction reaction. ACS Appl Mater Interfaces 9(24):20963–20973CrossRefPubMedGoogle Scholar
  52. 52.
    Fu SF, Zhu CZ, Song JH, Du D, Lin YH (2017) Metal-organic framework-derived non-precious metal nanocatalysts for oxygen reduction reaction. Adv Energy Mater 7(19):1700363CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials & Key Laboratory for Green Preparation and Application for Functional Materials, Ministry of Education & Hubei Key Laboratory of Ferro & Piezoelectric Materials and Devices, Faculty of Physics & Electronic ScienceHubei UniversityWuhanPeople’s Republic of China
  2. 2.School of Nuclear Technology and Chemistry & BiologyHubei University of Science and TechnologyXianningChina

Personalised recommendations