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Microwave plasma synthesized nitrogen-doped carbon nanotubes for oxygen reduction

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Abstract

Nitrogen-doped carbon nanotubes (NCNTs) with nitrogen content of 5.38 at% were successfully synthesized via microwave plasma chemical vapor deposition (MPCVD) technique employing methane and ammonia as precursors. Their high defective and abundant nitrogenous functional groups of superficial structures had been verified and considered to be closely related to their oxygen reduction reaction (ORR) activity. The influence of their structural features on ORR activity in alkaline electrolyte was studied in detail. The electrochemical analysis shows promoted crossover resistance and long-term stability, and comparable electrocatalytic activity of NCNTs with Pt-CNTs, suggesting that the ORR activity of NCNTs has been greatly promoted on account of nitrogen doping. The highest ORR performance was obtained with the loading of 729 μg cm−2, indicating initial potential of 0.87 V versus reversible hydrogen electrode (RHE) and n of 4.1, which are comparable with Pt-CNTs. Such excellent ORR performances of NCNTs obtained in this paper reveal the superiority of low-temperature plasma technique to synthesize favorable NCNTs for oxygen reduction.

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Reference

  1. Zhang M, Dai LM (2012) Carbon nanomaterials as metal-free catalysts in next generation fuel cells. Nano Energy 1:514–517

    Article  CAS  Google Scholar 

  2. Gang W, Piotr Z (2013) Nanostructure nonprecious metal catalysts for oxygen reduction reaction. Acc Chem Res 46(8):1878–1889

    Article  Google Scholar 

  3. Rapidah O, Andrew LD, Zhu ZH (2013) Non precious metal catalysts for the PEM fuel cell cathode. Int J Hydrogen Energy 37:357–372

    Google Scholar 

  4. Yang Z, Nie HG, Chen XA (2013) Recent progress in doped carbon nanomaterials as effective cathode catalysts for fuel cell oxygen reduction reaction. J Power Sources 236:238–249

    Article  CAS  Google Scholar 

  5. Yang LJ, Zhao Y, Chen S (2013) A mini review on carbon-based metal-free electrocatalysts for oxygen reduction reaction. Chin J Catal 34:1986–1991

    Article  CAS  Google Scholar 

  6. Li YG, Zhou W, Wang HL (2012) An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat Nanotechnol 7:394–400

    Article  CAS  Google Scholar 

  7. Ratso S, Kruusenberg I, Vikkisk M (2014) Highly active nitrogen-doped few-layer graphene/carbon nanotube composite electrocatalyst for oxygen reduction reaction in alkaline media. Carbon 73:361–370

    Article  CAS  Google Scholar 

  8. Sharifi T, Hu GZ, Jia XE (2012) Formation of active sites for oxygen reduction reaction by transformation of nitrogen functionalities in nitrogen-doped carbon nanotubes. ACS Nano 6(10):8904–8912

    Article  CAS  Google Scholar 

  9. Zhang CZ, Hao R, Liao HB (2013) Synthesis of amino-functionalized graphene as metal-free catalyst and exploration of the roles various nitrogen states in oxygen reduction reaction. Nano Energy 2:88–97

    Article  CAS  Google Scholar 

  10. Kundu S, Nagaiah TC, Xia W (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 

  11. Han KS, Kim HS, Song MS (2005) Atomspheric-pressure plasma treatment to modify hydrogen storage properties of multiwalled carbon nanotubes. Appl Phys Lett 86:263105

    Article  Google Scholar 

  12. Nursel D (2000) Plasma surface modification of carbon fibers: a review. J Adhes Sci Technol 14(7):975–987

    Article  Google Scholar 

  13. Tim D, Rino M, Nathalie DG (2009) Nonthermal Plasma Technology as a Versatile Strategy for Polymeric Biomaterials Surface Modification: A Review. Biomacromolecules 10(9):2351–2378

    Article  Google Scholar 

  14. Liu CJ, Zhao YC, Chen YS (2014) Surface modification of magnesium alloy via cathodic plasma electrolysis and its influence on corrosion resistance and cytocompatibility. Mater Lett 132:15–18

    Article  CAS  Google Scholar 

  15. Terashima C, Arihara K, Okazaki S (2011) Fabrication of vertically aligned diamond whiskers from highly boron-doped diamond by oxygen plasma etching. ACS Appl Mater Interfaces 3:177–182

    Article  CAS  Google Scholar 

  16. Cámara RM, Crespo E, Portela R (2014) Enhanced photocatalytic activity of TiO2 thin films on plasma-pretreated organic polymers. Catal Today 230:145–151

    Article  Google Scholar 

  17. Raghuram C, Shankhamala KD, Xia W (2009) PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation. Electrochim Acta 54:4208–4215

    Article  Google Scholar 

  18. Loganathan K, Bose D, Weinkauf D (2014) Surface modification of carbon black by nitrogen and allylamine plasma treatment for fuel cell electrocatalyst. Int J Hydrogen Energy 39:15766–15771

    Article  CAS  Google Scholar 

  19. Wang SG, Wang JH, Ma ZB (2003) Vertically aligned carbon nanotubes grown on geometrically different types of surface. Diam Relat Mater 12(12):2175–2177

    Article  CAS  Google Scholar 

  20. Meyyappan M, Delzeit L, Cassell A (2003) A. Carbon nanotube growth by PECVD: A review. Plasma Sources Sci T 12(2):205–216

    Article  CAS  Google Scholar 

  21. Amit B, Debajylti D (2013) Realizing a variety of carbon nanostructures at low temperature using MW-PECVD of (CH4 + H2) plasma. Appl Surf Sci 273:806–815

    Article  Google Scholar 

  22. Ren ZF, Huang ZP, Xu JW (1998) Synthesis of large arrays of well-aligned carbon nanotubes on glass. Science 282:5391

    Article  Google Scholar 

  23. Srivastava SK, Vankar VD, Rao DV (2006) Enhanced field emission characteristics of nitrogen-doped carbon nanotube films grown by microwave plasma enhanced chemical vapor deposition process. Thin Solid Films 515:1851–1856

    Article  CAS  Google Scholar 

  24. Xu JL, Wang SG, Du ZR (2014) High-performance Pt/CNTs catalysts via hydrogen plasma for methanol electrooxidation. Nano 9(2):1450018

    Article  Google Scholar 

  25. Liu H, Zhang Y, Li RY (2010) Structural and morphological control of aligned nitrogen-doped carbon nanotubes. Carbon 48:1498–1507

    Article  CAS  Google Scholar 

  26. Bobby GS, Huang JS (2009) Vincent Meunier. A theoretical and experimental study on manipulating the structure and properties of carbon nanotubes using substitutional dopants. Int J Quantum Chem 109(1):97–118

    Article  Google Scholar 

  27. Wang ZJ, Jia RR, Zheng JF (2011) Nitrogen-Promoted Self-assembly of N-doped Carbon Nanotubes and Their Intrinsic Catalysis for Oxygen Reduction in Fuel Cells. ACS Nano 5(3):1677–1684

    Article  CAS  Google Scholar 

  28. Chen Z, Chen ZW (2010) Effect of different surface morphologies and nitrogen contents on the electrochemical activity of nitrogen doped carbon nanotubes towards oxygen reduction reaction for low temperature fuel cells. ECS Trans 28(17):55–63

    Article  Google Scholar 

  29. Chen Z, Hihhins D, Chen ZW (2012) Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction. Electrochim Acta 55:4799–4804

    Article  Google Scholar 

  30. Xiong C, Wei ZD, Hu BS (2012) Nitrogen-doped carbon nanotubes as catalysts for oxygen reduction reaction. J Power Sources 215:216–220

    Article  CAS  Google Scholar 

  31. Chen Z, Higgins D, Tao HS (2009) Highly Active Nitrogen-Doped Carbon Nanotubes for Oxygen Reduction Reaction in Fuel Cells. J Phys Chem C 113:21008–21013

    Article  CAS  Google Scholar 

  32. Dresselhaus MS, Eklund PC (2000) Phonons in carbon nanotubes. Adv Phys 49(6):705–814

    Article  CAS  Google Scholar 

  33. Zhong RS, Qin YH, Niu DF (2013) Effect of carbon nanofiber surface functional groups on oxygen reduction in alkaline solution. J Power Sources 225:192–199

    Article  CAS  Google Scholar 

  34. Yuan CF, Chen WF, Yan LF (2012) Amino-grafted graphene as a stable and metal-free solid basic catalyst. J Mater Chem 22:7456–7460

    Article  CAS  Google Scholar 

  35. Zhao AQ, Masa J, Muhler M (2013) N-doped carbon synthesized from N-containing polymers as metal-free catalysts for the oxygen reduction under alkaline conditions. Electrochim Acta 98:139–145

    Article  CAS  Google Scholar 

  36. Li H, Liu H, Jong Z (2011) Nitrogen-doped carbon nanotubes with high activity for oxygen reduction in alkaline media. Int J Hydrogen Energy 36:2258–2265

    Article  CAS  Google Scholar 

  37. Geng DS, Liu H, Chen YG (2011) Non-noble metal oxygen reduction electrocatalysts based on carbon nanotubes with controlled nitrogen contents. J Power Sources 196:1795–1801

    Article  CAS  Google Scholar 

  38. Bonakdarpour A, Lefevre M, Yang R (2008) Impact of loading in RRDE experiments on Fe-N-C catalysts: two- or four-electron oxygen reduction? Electrochem Solid-State Lett 11:B105–B108

    Article  CAS  Google Scholar 

  39. Wantanabe M, Igarashi H, Yosioka K (1995) An experimental prediction of the preparation condition of nafion-coated catalyst layers for PEFCs. Electrochim Acta 40(3):329–334

    Article  Google Scholar 

  40. Wong WY, Daud WRW, Mohamad AB (2014) The impact of loading and temperature on the oxygen reduction reaction at nitrogen-doped carbon nanotubes in alkaline medium. Electrochim Acta 129:47–54

    Article  CAS  Google Scholar 

  41. Song C, Zhang J (2008) In: Zhang J (ed) PEM fuel cell electrocatalysts and catalyst layers: fundamental and application. Springer, Berlin

    Google Scholar 

  42. Elezovic NR, Babic BM, Radmilovic VR (2011) Nb-TiO2 supported platinum nanocatalyst for oxygen reduction reaction in alkaline solutions. Electrochim Acta 56:9020–9026

    Article  CAS  Google Scholar 

  43. Markovi NM, Gasteiger HA, Jr. Ross PN (1996) Oxygen reduction on platinum low-index single-crystal surfaces in alkaline solution: Rotating ring diskPt(hkl) studies. J Phys Chem 100:6715–6721

    Article  Google Scholar 

  44. Jukk K, Kongi N, Tarre A (2014) Electrochemical oxygen reduction behavior of platinum nanoparticles supported on multi-walled carbon nanotube/titanium dioxide composites. Int J Electrochem 735:68–76

    CAS  Google Scholar 

  45. Alexeyeva N, Tammeveski K, Lopez-Cude A (2010) Electroreduction of oxygen on Pt nanoparticle/carbon nanotube nanocomposites in acid and alkaline solutions. Electrochim Acta 55:794–803

    Article  CAS  Google Scholar 

  46. Zhu S, Chen Z, Li B (2011) Nitrogen-doped carbon nanotubes as air cathode catalyst in zinc-air battery. Electrochim Acta 56:5080–5084

    Article  CAS  Google Scholar 

  47. Navneet S, Susanta SR, Surbhi S (2013) Electrochemical and oxygen reduction properties of pristine and nitrogen-doped few layered graphene nanoflakes (FLGs). J Solid State Electrochem 17:2139–2149

    Article  Google Scholar 

  48. Gong K, Du F, Xia Z (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–763

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The work was financially supported by the Natural Science Foundation of China (No. 51072140, 51272178, and 51442003), the Natural Science Foundation of Hubei Province (No. 2013CFA012), and the Graduate Innovative Fund of Wuhan Institute of Technology (No. CX2013084).

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Authors and Affiliations

  1. Province Key Laboratory of Plasma Chemistry and Advanced Material, Wuhan Institute of Technology, Wuhan, 430073, China

    Zurong Du, Shenggao Wang, Chuixiong Kong, Quanrong Deng & Geming Wang

  2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430073, China

    Chong Liang & Haolin Tang

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  1. Zurong Du
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  2. Shenggao Wang
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  3. Chuixiong Kong
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  4. Quanrong Deng
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  5. Geming Wang
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Correspondence to Shenggao Wang.

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Du, Z., Wang, S., Kong, C. et al. Microwave plasma synthesized nitrogen-doped carbon nanotubes for oxygen reduction. J Solid State Electrochem 19, 1541–1549 (2015). https://doi.org/10.1007/s10008-015-2773-3

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