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Vol. 10 No. 2 (2018)

Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

https://doi.org/10.1007/s40820-017-0181-1
Daguo Gu
School of Materials Engineering, Yancheng Institute of Technology, Yancheng 224051, Jiangsu Province, People’s Republic of China
Yao Zhou
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Ruguang Ma
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Fangfang Wang
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Qian Liu
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Jiacheng Wang
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China

Corresponding Author: Jiacheng Wang

jiacheng.wang@mail.sic.ac.cn

Nano-Micro Letters, Vol. 10 No. 2 (2018), Article Number: 29

Abstract

A series of N-doped carbon materials (NCs) were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile one-step pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C3N4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6, show the highest N content of ~6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of ~66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal–air batteries.


Highlights:


1 N-doped carbon nanoflakes (NCs) were synthesized via facile one-pot pyrolysis of citric acid and dicyanamide.
2 The as-synthesized NCs have a stacked, few-layered graphene-like structure enriched with pyridinic and graphitic N groups.
3 The optimized NCs show better long-term stability and highly active in electrocatalytic oxygen reduction with a close four-electron reaction pathway.

Keywords

Nitrogen doping Graphene-like Carbon nanoflakes Electrocatalyst Oxygen reduction reaction
Gu, Daguo, Yao Zhou, Ruguang Ma, Fangfang Wang, Qian Liu, and Jiacheng Wang. 2017. “Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes As Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction”. Nano-Micro Letters 10 (2):29. https://doi.org/10.1007/s40820-017-0181-1.
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References
  1. S. Park, Y. Shao, J. Liu, Y. Wang, Oxygen electrocatalysts for water electrolyzers and reversible fuel cells: status and perspective. Energy Environ. Sci. 5(11), 9331–9344 (2012). https://doi.org/10.1039/c2ee22554a
  2. X. Ge, A. Sumboja, D. Wuu, T. An, B. Li, F.W.T. Goh, T.S.A. Hor, Y. Zong, Z. Liu, Oxygen reduction in alkaline media: from mechanisms to recent advances of catalysts. ACS Catal. 5(8), 4643–4667 (2015). https://doi.org/10.1021/acscatal.5b00524
  3. L. Dai, Y. Xue, L. Qu, H.-J. Choi, J.-B. Baek, Metal-free catalysts for oxygen reduction reaction. Chem. Rev. 115(11), 4823–4892 (2015). https://doi.org/10.1021/cr5003563
  4. G. Wu, K.L. More, C.M. Johnston, P. Zelenay, High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332(6028), 443–447 (2011). https://doi.org/10.1126/science.1200832
  5. X.-L. Cai, C.-H. Liu, J. Liu, Y. Lu, Y.-N. Zhong et al., Synergistic effects in CNTs-PdAu/Pt trimetallic nanops with high electrocatalytic activity and stability. Nano Micro Lett. 9(4), 48 (2017). https://doi.org/10.1007/s40820-017-0149-1
  6. W. Yu, M.D. Porosoff, J.G. Chen, Review of Pt-based bimetallic catalysis: from model surfaces to supported catalysts. Chem. Rev. 112(11), 5780–5817 (2012). https://doi.org/10.1021/cr300096b
  7. A. Song, W. Yang, W. Yang, G. Sun, X. Yin, L. Gao, Y. Wang, X. Qin, G. Shao, Facile synthesis of cobalt nanops entirely encapsulated in slim nitrogen-doped carbon nanotubes as oxygen reduction catalyst. ACS Sustain. Chem. Eng. 5(5), 3973–3981 (2017). https://doi.org/10.1021/acssuschemeng.6b03173
  8. C. Yuan, H.B. Wu, Y. Xie, X.W. Lou, Mixed transition-metal oxides: design, synthesis, and energy-related applications. Angew. Chem. Int. Ed. 53(6), 1488–1504 (2014). https://doi.org/10.1002/anie.201303971
  9. J. Guo, Y. Cheng, Z. Xiang, Confined-space-assisted preparation of Fe3O4-nanop-modified Fe–N–C catalysts derived from a covalent organic polymer for oxygen reduction. ACS Sustain. Chem. Eng. 5(9), 7871–7877 (2017). https://doi.org/10.1021/acssuschemeng.7b01367
  10. Y. Zhong, X. Xia, F. Shi, J. Zhan, J. Tu, H.J. Fan, Transition metal carbides and nitrides in energy storage and conversion. Adv. Sci. 3(5), 1500286 (2016). https://doi.org/10.1002/advs.201500286
  11. H. Shi, Y. Shen, F. He, Y. Li, A. Liu, S. Liu, Y. Zhang, Recent advances of doped carbon as non-precious catalysts for oxygen reduction reaction. J. Mater. Chem. A 2(38), 15704–15716 (2014). https://doi.org/10.1039/C4TA02790F
  12. C. Shang, M. Li, Z. Wang, S. Wu, Z. Lu, Electrospun nitrogen-doped carbon nanofibers encapsulating cobalt nanops as efficient oxygen reduction reaction catalysts. Chemelectrochem 3(9), 1437–1445 (2016). https://doi.org/10.1002/celc.201600275
  13. Y. Chen, Q. Liu, J. Wang, Highly porous nitrogen-doped carbon nanofibers as efficient metal-free catalysts toward the electrocatalytic oxygen reduction reaction. Nano Adv. 1(2), 79–89 (2016). https://doi.org/10.22180/na174
  14. Q. Shi, Y.-P. Lei, Y.-D. Wang, Z.-M. Wang, In-situ preparation and electrocatalytic oxygen reduction performance of N-doped graphene@CNF. J. Inorg. Mater. 31(4), 351–357 (2016). https://doi.org/10.15541/jim20150400
  15. Y. Zhou, J. Wang, Direct observation of Fe-N4 species as active sites for the electrocatalytic oxygen reduction. Nano Adv. 2(3), 45–46 (2017). https://doi.org/10.22180/na212
  16. J. Li, J. Chen, H. Wang, Y. Ren, K. Liu, Y. Tang, M. Shao, Fe/N co-doped carbon materials with controllable structure as highly efficient electrocatalysts for oxygen reduction reaction in Al–air batteries. Nano Adv. 8(Supplement C), 49–58 (2017). https://doi.org/10.1016/j.ensm.2017.03.007
  17. H. Wang, T. Maiyalagan, X. Wang, Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal. 2(5), 781–794 (2012). https://doi.org/10.1021/cs200652y
  18. J. Wu, L. Ma, R.M. Yadav, Y. Yang, X. Zhang, R. Vajtai, J. Lou, P.M. Ajayan, Nitrogen-doped graphene with pyridinic dominance as a highly active and stable electrocatalyst for oxygen reduction. ACS Appl. Mater. Interfaces 7(27), 14763–14769 (2015). https://doi.org/10.1021/acsami.5b02902
  19. J.H. Yu, L.L. Xu, Q.Q. Zhu, X.X. Wang, M.J. Yun, L.F. Dong, Superior electrochemical performance of graphene via carboxyl functionalization and surfactant intercalation. J. Inorg. Mater. 31(2), 220–224 (2016). https://doi.org/10.15541/jim20150378
  20. Y. Zheng, Y. Jiao, J. Chen, J. Liu, J. Liang et al., Nanoporous graphitic-C3N4@Carbon metal-free electrocatalysts for highly efficient oxygen reduction. J. Am. Chem. Soc. 133(50), 20116–20119 (2011). https://doi.org/10.1021/ja209206c
  21. G. Tuci, C. Zafferoni, A. Rossin, A. Milella, L. Luconi et al., Chemically functionalized carbon nanotubes with pyridine groups as easily tunable N-decorated nanomaterials for the oxygen reduction reaction in alkaline medium. Chem. Mater. 26(11), 3460–3470 (2014). https://doi.org/10.1021/cm500805c
  22. T.Y. Ma, S. Dai, M. Jaroniec, S.Z. Qiao, Graphitic carbon nitride nanosheet-carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. Angew. Chem. Int. Ed. 53(28), 7281–7285 (2014). https://doi.org/10.1002/anie.201403946
  23. R.J. White, N. Yoshizawa, M. Antonietti, M. Titirici, A sustainable synthesis of nitrogen-doped carbon aerogels. Green Chem. 13(9), 2428–2434 (2011). https://doi.org/10.1039/c1gc15349h
  24. Z. Lin, G.H. Waller, Y. Liu, M. Liu, C.-P. Wong, 3D Nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction. Nano Energy 2(2), 241–248 (2013). https://doi.org/10.1016/j.nanoen.2012.09.002
  25. M. Zhou, H.-L. Wang, S. Guo, Towards high-efficiency nanoelectrocatalysts for oxygen reduction through engineering advanced carbon nanomaterials. Chem. Soc. Rev. 45(5), 1273–1307 (2016). https://doi.org/10.1039/C5CS00414D
  26. H. Xia, J. Zhang, Z. Yang, S. Guo, S. Guo, Q. Xu, 2D MOF nanoflake-assembled spherical microstructures for enhanced supercapacitor and electrocatalysis performances. Nano Micro Lett. 9(4), 43 (2017). https://doi.org/10.1007/s40820-017-0144-6
  27. Y. Jiao, Y. Zheng, K. Davey, S.Z. Qiao, Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped grapheme. Nat. Energy 1, 16130 (2016). https://doi.org/10.1038/nenergy.2016.130
  28. X.Q. Wang, J.S. Lee, Q. Zhu, J. Liu, Y. Wang, S. Dai, Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction. Chem. Mater. 22(7), 2178–2180 (2010). https://doi.org/10.1021/cm100139d
  29. L. Qu, Y. Liu, J.B. Baek, L. Dai, Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3), 1321–1326 (2010). https://doi.org/10.1021/nn901850u
  30. H.M. Jeong, J.W. Lee, W.H. Shin, Y.J. Choi, H.J. Shin, J.K. Kang, J.W. Choi, Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett. 11(6), 2472–2477 (2011). https://doi.org/10.1021/nl2009058
  31. D. Deng, X. Pan, L. Yu, Y. Cui, Y. Jiang et al., Toward N-doped graphene via solvothermal synthesis. Chem. Mater. 23(5), 1188–1193 (2011). https://doi.org/10.1021/cm102666r
  32. R. Ma, Y. Zhou, P. Li, Y. Chen, J. Wang, Q. Liu, Self-assembly of nitrogen-doped graphene-wrapped carbon nanops as an efficient electrocatalyst for oxygen reduction reaction. Electrochim. Acta 216, 347–354 (2016). https://doi.org/10.1016/j.electacta.2016.09.027
  33. X.C. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen, M. Antonietti, A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 8(1), 76–80 (2009). https://doi.org/10.1038/nmat2317
  34. F.Z. Su, S.C. ew, G. Lipner, X.Z. Fu, M. Antonietti, S. Blechert, X.C. Wang, mpg-C3N4-catalyzed selective oxidation of alcohols using O2 and visible light. J. Am. Chem. Soc. 132(46), 16299–16301 (2010). https://doi.org/10.1021/ja102866p
  35. M. Beckert, M. Menzel, F.J. Tölle, B. Bruchmann, R. Mülhaupt, Nitrogenated graphene and carbon nanomaterials by carbonization of polyfurfuryl alcohol in the presence of urea and dicyandiamide. Green Chem. 17(2), 1032–1037 (2015). https://doi.org/10.1039/C4GC01676A
  36. P. Chen, L.-K. Wang, G. Wang, M.-R. Gao, J. Ge et al., Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass: an efficient catalyst for oxygen reduction reaction. Energy Environ. Sci. 7(12), 4095–4103 (2014). https://doi.org/10.1039/C4EE02531H
  37. M. Zhang, C. Hou, A. Halder, H. Wang, Q. Chi, Graphene papers: smart architecture and specific functionalization for biomimetics, electrocatalytic sensing and energy storage. Mater. Chem. Front. 1(1), 37–60 (2017). https://doi.org/10.1039/C6QM00145A
  38. H.Q. Sun, Y.X. Wang, S.Z. Liu, L. Ge, L. Wang, Z.H. Zhu, S.B. Wang, Facile synthesis of nitrogen doped reduced graphene oxide as a superior metal-free catalyst for oxidation. Chem. Commun. 49(85), 9914–9916 (2013). https://doi.org/10.1039/c3cc43401j
  39. Y. Gogotsi, J.A. Libera, N. Kalashnikov, M. Yoshimura, Graphite polyhedral crystals. Science 290(5490), 317–320 (2000). https://doi.org/10.1126/science.290.5490.317
  40. R. Ma, B.Y. Xia, Y. Zhou, P. Li, Y. Chen, Q. Liu, J. Wang, Ionic liquid-assisted synthesis of dual-doped graphene as efficient electrocatalysts for oxygen reduction. Carbon 102, 58–65 (2016). https://doi.org/10.1016/j.carbon.2016.02.034
  41. R. Ma, E. Song, Y. Zhou, Z. Zhou, G. Liu, Q. Liu, J. Liu, Y. Zhu, J. Wang, Ultrafine WC nanops anchored on Co-encased, N-doped carbon nanotubes for efficient hydrogen evolution. Energy Storage Mater. 6, 104–111 (2016). https://doi.org/10.1016/j.ensm.2016.10.006
  42. L. Wang, C. Yang, S. Dou, S. Wang, X. Gao, J. Ma, Y. Yu, Nitrogen-doped hierarchically porous carbon networks: synthesis and applications in lithium-ion battery, sodium-ion battery and zinc–air battery. Electrochim. Acta 219, 592–603 (2016). https://doi.org/10.1016/j.electacta.2016.10.050
  43. J.C. Wang, I. Senkovska, M. Oschatz, M.R. Lohe, L. Borchardt, A. Heerwig, Q. Liu, S. Kaskel, Imine-linked polymer derived nitrogen-doped microporous carbons with excellent CO2 capture properties. ACS Appl. Mater. Interfaces 5(8), 3160–3167 (2013). https://doi.org/10.1021/am400059t
  44. F.-X. Hu, L. Li, K. Lin, L. Cui, C.-J. Shi, A.S. Sayyar, S. Cui, Preparation of N-doped hollow carbon spheres and investigation of their optical properties. J. Inorg. Mater. 31(8), 827–833 (2016). https://doi.org/10.15541/jim20150648
  45. R. Ma, X. Ren, B.Y. Xia, Y. Zhou, C. Sun, Q. Liu, J. Liu, J. Wang, Novel synthesis of N-doped graphene as an efficient electrocatalyst towards oxygen reduction. Nano Res. 9(3), 808–819 (2016). https://doi.org/10.1007/s12274-015-0960-2
  46. J. Wang, I. Senkovska, M. Oschatz, M.R. Lohe, L. Borchardt, A. Heerwig, Q. Liu, S. Kaskel, Highly porous nitrogen-doped polyimine-based carbons with adjustable microstructures for CO2 capture. J. Mater. Chem. A 1(36), 10951–10961 (2013). https://doi.org/10.1039/c3ta11995e
  47. D. Wei, Y.L. Liu, Y. Wang, H. Zhang, L.H. Huang, G. Yu, Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 9(5), 1752–1758 (2009). https://doi.org/10.1021/nl803279t
  48. G.-Z. Xu, W.-W. Jin, X.-R. Zeng, J.-Z. Zou, X.-B. Xiong, L. Huang, Z.-N. Zhao, Tailoring of pore structure of coal-based carbon foam. J. Inorg. Mater. 31(9), 961–968 (2016). https://doi.org/10.15541/jim20150628
  49. X.H. Zhao, X.P. Gao, H.B. Zhao, X.X. Zhang, Z.X. Hao, Highly efficient synthesis of LTA-type aluminophosphate molecular sieve by improved ionothermal method with low dosage of structure-directing agent. J. Inorg. Mater. 31(11), 1212–1218 (2016). https://doi.org/10.15541/jim20160062
  50. L.L. Sun, K. Yan, W. Luo, J. Zhou, Hollow ZSM-5 zeolite microspheres with improved adsorption and catalytic properties. J. Inorg. Mater. 31(8), 834–840 (2016). https://doi.org/10.15541/jim20150611
  51. W. He, C. Jiang, J. Wang, L. Lu, High-rate oxygen electroreduction over graphitic-N species exposed on 3D hierarchically porous nitrogen-doped carbons. Angew. Chem. Int. Ed. 53(36), 9503–9507 (2014). https://doi.org/10.1002/anie.201404333
  52. J.C. Wang, R.G. Ma, Z.Z. Zhou, G.H. Liu, Q. Liu, Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction. Sci. Rep. 5, 9304 (2015). https://doi.org/10.1038/srep09304
  53. H. Cui, H. Yu, J. Zheng, Z.J. Wang, Y. Zhu, S.P. Jia, J. Jia, Z. Zhu, N-doped graphene frameworks with superhigh surface area: excellent electrocatalytic performance for oxygen reduction. Nanoscale 8(5), 2795–2803 (2016). https://doi.org/10.1039/C5NR06319A
  54. L.F. Lai, J.R. Potts, D. Zhan, L. Wang, C.K. Poh et al., Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ. Sci. 5(7), 7936–7942 (2012). https://doi.org/10.1039/c2ee21802j
  55. Y. Zhang, J. Ge, L. Wang, D. Wang, F. Ding, X. Tao, W. Chen, Manageable N-doped graphene for high performance oxygen reduction reaction. Sci. Rep. 3, 2771 (2013). https://doi.org/10.1038/srep02771
  56. A. Aijaz, N. Fujiwara, Q. Xu, From metal-organic framework to nitrogen-decorated nanoporous carbons: superior CO2 uptake and highly efficient catalytic oxygen reduction. J. Am. Chem. Soc. 136(19), 6790–6793 (2014). https://doi.org/10.1021/ja5003907
  57. H.B. Yang, J. Miao, S.F. Hung, J. Chen, H.B. Tao et al., Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: development of highly efficient metal-free bifunctional electrocatalyst. Sci. Adv. 2(4), 1501122 (2016). https://doi.org/10.1126/sciadv.1501122
  58. T. Iwazaki, H. Yang, R. Obinata, W. Sugimoto, Y. Takasu, Oxygen-reduction activity of silk-derived carbons. J. Power Sources 195(18), 5840–5847 (2010). https://doi.org/10.1016/j.jpowsour.2009.12.135
  59. Y. Jia, L. Zhang, A. Du, G. Gao, J. Chen, X. Yan, C.L. Brown, X. Yao, Defect graphene as a trifunctional catalyst for electrochemical reactions. Adv. Mater. 28(43), 9532–9538 (2016). https://doi.org/10.1002/adma.201602912
  60. F.D.K. Gong, Z. Xia, M. Durstock, L. Dai, Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323(5915), 760–764 (2009). https://doi.org/10.1126/science.1168049
  61. H. Kim, K. Lee, S.I. Woo, Y. Jung, On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. Phys. Chem. Chem. Phys. 13(39), 17505–17510 (2011). https://doi.org/10.1039/c1cp21665a
  62. F.A. De Bruijn, V.A.T. Dam, G.J.M. Janssen, Review: durability and degradation issues of PEM fuel cell components. Fuel Cells 8(1), 3–22 (2008). https://doi.org/10.1002/fuce.200700053
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