, Volume 25, Issue 9, pp 4295–4303 | Cite as

Nitrogen, phosphorus co-doped mesoporous carbon materials as efficient catalysts for oxygen reduction reaction

  • Mengying Li
  • Chengyin Wang
  • Shengnan Hu
  • Huimin WuEmail author
  • Chuanqi Feng
  • Yanqing ZhangEmail author
Original Paper


Carbon, phosphorus or nitrogen-doped carbon and nitrogen, and phosphorus co-doped carbon materials were successfully synthesized. The scanning electron microscopy and transmission electron microscope indicated that the samples exhibited three-dimensional layered structure. While the X-ray diffraction and Raman results suggested that the samples were typical carbon materials with high purity, besides, the nitrogen adsorption-desorption isotherm results showed that the nitrogen, phosphorus co-doped carbon material had the highest specific surface area of 2346.2 m2 g−1 with uniform mesoporous (3.8 nm) and considerable pore volume (0.69 cm3 g−1). The cyclic voltammetry, electrochemical impedance spectra, liner sweep voltammetry, and chronoamperometry were tested in oxygen-saturated 0.1 M KOH solution. The electrochemical tests suggested that the nitrogen, phosphorus co-doped carbon material had a positive onset potential (0.92 V), half-wave potential (0.81 V), low resistance (73 Ω), and low Tafel slope (70 mV/decade) at low current region. More importantly, the oxygen reduction reaction was a 4-electron pathway with excellent methanol tolerance.


Carbon material Co-doped High specific surface area Mesoporous Oxygen reduction reaction 


Funding information

Financial support was provided by the Education Department of Hubei province (D20171001).

Supplementary material

11581_2019_2976_MOESM1_ESM.doc (3.8 mb)
ESM 1 (DOC 3860 kb)


  1. 1.
    Xua H, Chen XH, Pan SH, Qin Y, Chen XS, Tao YX (2016) Kong Y S and N codoped three-dimensional graphene-MnS hybrids with high electrocatalytic activity for oxygen reduction reaction. Synth Met 221:55–60CrossRefGoogle Scholar
  2. 2.
    Zhang BW, Wang YX, Chou SL, Liu HK, Dou SX (2019) Fabrication of superior single-atom catalysts toward diverse electrochemical reactions. Small Methods:1800497Google Scholar
  3. 3.
    Zhang BW, Yang HL, Wang YX, Dou SX, Liu HK (2018) A comprehensive review on controlling surface composition of Pt-based bimetallic electrocatalysts. Adv Energy Mater 8:1703597CrossRefGoogle Scholar
  4. 4.
    Greer JR (2014) Nanoframe catalysts. Science 343:1319–1320CrossRefPubMedGoogle Scholar
  5. 5.
    Stamenkovic VR, Fowler B, Mun BS, Wang G, Ross PN, Lucas CA, Markovic NM (2007) Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science 315(5811):493–497CrossRefPubMedGoogle Scholar
  6. 6.
    Zhong BW, Zhang ZC, Liao HG, Gong Y, Gu L, Gu XM, You LX, Liu S, Huang L, Tian XC, Huang R, Zhu FC, Liu T, Jiang YX, Zhou ZY, Sun SG (2016) Tuning Pt-skin to Ni-rich surface of Pt3Ni catalysts supported on porous carbon for enhanced oxygen reduction reaction and formic electro-oxidation. Nano Energy 19:198–209CrossRefGoogle Scholar
  7. 7.
    Nie Y, Li L, Wei ZD (2015) Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction. Chem Soc Rev 44:2168–2201CrossRefPubMedGoogle Scholar
  8. 8.
    Wang HL, Yu WH, Shi J, Mao N, Chen SG, Liu W (2016) Biomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteries. Electrochim Acta 188:103–110CrossRefGoogle Scholar
  9. 9.
    Gu XX, Wang YZ, Lai C, Qiu JX, Li S, Hou YL, Martens W, Mahmood N, Zhang SQ (2014) Microporous bamboo biochar for lithium-sulfur batteries. Nano Res 8:129–139CrossRefGoogle Scholar
  10. 10.
    Candelaria LS, Shao YY, Li XL, Xiao J, Zhang JG, Wang Y, Liu J, Li JH, Cao GZ (2012) Nanostructured carbon for energy storage and conversion. Nano Energy 1:195–220CrossRefGoogle Scholar
  11. 11.
    Han Y, Dong XT, Zhang C, Liu SX (2012) Hierarchical porous carbon hollow-spheres as a high performance electrical double-layer capacitor material. J Power Sources 211:92–96CrossRefGoogle Scholar
  12. 12.
    Wang Q, Wang YB, Wei T, Zhang ML (2014) Three-dimensional flower-like and hierarchical porous carbon materials as high-rate performance electrodes for supercapacitors. Carbon 67:119–127CrossRefGoogle Scholar
  13. 13.
    Li TT, Yang GW, Wang J, Zhou YY, Han HY (2013) Excellent electrochemical performance of nitrogen-enriched hierarchical porous carbon electrodes prepared using nano-CaCO3 as template. J Solid State Electrochem 17:2651–2660CrossRefGoogle Scholar
  14. 14.
    Zhang BW, Sheng T, Wang YX, Chou SL, Davey K, Dou SX, Qiao SZ (2019) Long-life room-temperature sodium–sulfur batteries by virtue of transition-metal-nanocluster–sulfur interactions. Angew Chem Int Ed 58:1484–1488CrossRefGoogle Scholar
  15. 15.
    Zhang BZ, Sheng T, Liu YD, Wang YX, Zhang L, Lai WH, Wang L, Yang JP, Gu FQ, Chou SL, Liu HK, Dou SX (2018) Atomic cobalt as an efficient electrocatalyst in sulfur cathodes for superior room-temperature sodium-sulfur batteries. Nat Commun 9:4082CrossRefPubMedPubMedCentralGoogle Scholar
  16. 16.
    Sa YJ, Park C, Jeong YJ, Park SH, Lee Z, Kim KT, Park GG, Joo SH (2014) Carbon nanotubes/heteroatom-doped carbon core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells. Angew Chem 53:4102–4106CrossRefGoogle Scholar
  17. 17.
    Choi CH, Lim HK, Chung MW, Park JC, Shin H, Kim H, WOO SI (2014) Long-range electron transfer over graphene-based catalyst for high-performing oxygen reduction reactions: importance of size, N-doping, and metallic impurities. J Am Chem Soc 136:9070–9077CrossRefPubMedGoogle Scholar
  18. 18.
    Tylus U, Jia QY, Strickland K, Ramaswamy N, Serov A, Atanassov P, Mukerjee S (2014) Elucidating oxygen reduction active sites in pyrolyzed metal–nitrogen coordinated non-precious-metal electrocatalyst systems. J Phys Chem C 118:8999–9008CrossRefGoogle Scholar
  19. 19.
    Ramaswamy N, Tylus U, Jia QY, Mukerjee S (2013) Activity descriptor identification for oxygen reduction on nonprecious electrocatalysts: linking surface science to coordination chemistry. J Am Chem Soc 135:15443–15449CrossRefPubMedGoogle Scholar
  20. 20.
    Jang D, Lee S, Kim S, Choi K, Park S, Oh J, Park S (2018) Production of P, N co-doped graphene-based materials by a solution process and their electrocatalytic performance for oxygen reduction reaction. ChemNanoMat 4:118–123CrossRefGoogle Scholar
  21. 21.
    Pi YT, Xing XY, Lu LM, He ZB, Ren TZ (2016) Hierarchical porous activated carbon in OER with high efficiency. RSC Adv 6:102422–102427CrossRefGoogle Scholar
  22. 22.
    Liu MX, Ma XM, Gan LH, Xu ZJ, Zhu DZ, Chen LW (2014) A facile synthesis of a novel mesoporous Ge@C sphere anode with stable and high capacity for lithium ion batteries. J Mater Chem A 21:7107–17114Google Scholar
  23. 23.
    Zhu TT, Zhou J, Li ZH, Li SH, Si WJ, Zhuo SP (2015) Preparation and supercapacitive performance of N, S co-doped activated carbon materials. Acta Phys -Chim Sin 31:676–684Google Scholar
  24. 24.
    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 4:15968–15979CrossRefGoogle Scholar
  25. 25.
    Xue YH, Yu DS, Dai LM, Wang RG, Li DQ, Roy A, Lu F, Chen H, Liu Y, Qu J (2013) Three-dimensional B,N-doped graphene foam as a metal-free catalyst for oxygen reduction reaction. PhysChem Chem Phys 15:12220Google Scholar
  26. 26.
    Nagaraju G, Lim JH, Cha SM, Yu JS (2016) Three-dimensional activated porous carbon with meso/macropore structures derived from fallen pine cone flowers: a low-cost counter electrode material in dye-sensitized solar cells. J Alloys Compd 693:1297–1304CrossRefGoogle Scholar
  27. 27.
    Liu JW, Shao MW, Liu ZP, Qian YT (2003) A medial-reduction route to hollow carbon spheres. Carbon 41:1682–1685CrossRefGoogle Scholar
  28. 28.
    Jia DD, Yu X, Tan H, Li XQ, Han F, Li LL, Liu H (2016) Hierarchical porous carbon with ordered straight micro-channels templated by continuous filament glass fiber arrays for high performance supercapacitors. J Mater Chem A 5:1516–1525CrossRefGoogle Scholar
  29. 29.
    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 4:2095–2101CrossRefGoogle Scholar
  30. 30.
    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 53:13934–13939CrossRefGoogle Scholar
  31. 31.
    Meng Z, Xie Y, Cai TW, Sun ZX, Jiang KM, Han WQ (2016) Graphene-like g-C3N4 nanosheets/sulfur as cathode for lithium–sulfur battery. Electrochim Acta 210:829–836CrossRefGoogle Scholar
  32. 32.
    Han Q, Wang B, Gao J, Cheng ZH, Zhao Y, Zhang ZP, Qu LT (2016) Atomically thin mesoporous nanomesh of graphitic C3N4 for high-efficiency photocatalytic hydrogen evolution. ACS Nano 10:2745–2751CrossRefPubMedGoogle Scholar
  33. 33.
    Liu XJ, Zou SZ, Chen SW (2016) Ordered mesoporous carbons codoped with nitrogen and iron as effective catalysts for oxygen reduction reaction. Nanoscale 8:19249–19255CrossRefPubMedGoogle Scholar
  34. 34.
    Men B, Sun YZ, Li MJ, Hu CQ, Zhang M, Wang LN, Tang Y, Chen YM, Wan PY, Pan JQ (2016) Hierarchical metal-free nitrogen-doped porous graphene/carbon composites as an efficient oxygen reduction reaction catalyst. ACS Appl Mater Interfaces 8:1415–1423CrossRefPubMedGoogle Scholar
  35. 35.
    Ma TY, Ran JR, Dai S, Jaroniec M, Qiao SZ (2015) Phosphorus-doped graphitic carbon nitrides grown in situ on carbon-fiber paper: flexible and reversible oxygen electrodes. Angew Chem Int Ed 54:4646–4650CrossRefGoogle 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 52:3188–3198CrossRefGoogle 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 40:10427–10438CrossRefGoogle Scholar
  38. 38.
    Ma TY, Dai S, Jaroniec M, Qiao SZ (2014) Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. J Am Chem Soc 136:13925–13931CrossRefPubMedGoogle Scholar
  39. 39.
    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 2:1916–1923CrossRefGoogle Scholar
  40. 40.
    Chen WF, James TM, Etsuko F (2013) Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem Commun 49:8896–8909CrossRefGoogle Scholar
  41. 41.
    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
  42. 42.
    Jin JY, Yu BB, Wu HM, Wang SF, Feng CQ (2017) Synthesis and electrocatalytic activity of Co1_xMoxSe2 for oxygen reduction. J Alloys Compd 703:652–655CrossRefGoogle Scholar
  43. 43.
    Jiang S, Sun YJ, Dai HC, Hu JT, Ni PJ, Wang YL, Li Z, Li Z (2015) Nitrogen and fluorine dual-doped mesoporous graphene: high-performance metal-free ORR electrocatalyst with super-low HO2 yield. Nanoscale 7:10584–10589CrossRefPubMedGoogle Scholar
  44. 44.
    Mao S, Wen ZH, Huang TZ, Hou Y, Che JH (2014) High-performance bi-functional electrocatalysts of 3D crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ Sci 7:609–616CrossRefGoogle Scholar
  45. 45.
    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
  46. 46.
    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 89:223–228CrossRefGoogle Scholar
  47. 47.
    Xiao Z, Gao XY, Shi MH, Ren GY, Xiao GZ, Zhu Y, Jiang L (2016) China rose-derived tri-heteroatom co-doped porous carbon as an efficient electrocatalysts for oxygen reduction reaction. RSC Adv 6:86401–86409CrossRefGoogle Scholar
  48. 48.
    Wu XB, Xie ZY, Sun M, Lei T, Zuo ZM, Xie XM, Liang YL, Huang QZ (2016) Edge-rich and (N, S)-doped 3D porous graphene as an efficient metal-free electrocatalyst for the oxygen reduction reaction. RSC Adv 6:90384–90387CrossRefGoogle Scholar
  49. 49.
    Li LJ, Dai PC, Gu X, Wang Y, Yan LT, Zhao XB (2017) High oxygen reduction activity on a metal–organic framework derived carbon combined with high degree of graphitization and pyridinic-N dopants. J Mater Chem A 5:789–795CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials and Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Ministry of Education and College of Chemistry and Chemical EngineeringHubei UniversityWuhanPeople’s Republic of China
  2. 2.College of Chemistry and Chemical EngineeringYangzhou UniversityYangzhouPeople’s Republic of China
  3. 3.Wuhan University of Science of TechnologyWuhanChina

Personalised recommendations