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N,O-codoped 3D graphene fibers with densely arranged sharp edges as highly efficient electrocatalyst for oxygen reduction reaction

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Abstract

To replace the noble-metal Pt catalysts for oxygen reduction reaction (ORR), developing efficient and earth-abundant electrocatalysts is of great importance. Both the morphology and composition engineering of graphene could effectively modify the electronic structure to optimize its electrocatalytic performance for ORR. Here, we report an effective method to dope carbon materials with N, by which the N doping concentration and form could be well controlled. We first grow 3D graphene fibers (3DGFs) by thermal chemical vapor deposition, which are then treated with acid or heated in air and heated in NH3 in succession, obtaining N,O-codoped 3DGFs. The codoped 3DGFs exhibit outstanding electrocatalytic performance toward ORR with onset potential of 1.01 V, half-wave potential of 0.883 V, long-term operation stability with 90% current retention after 50 h, and a good methanol tolerance in alkaline solutions, which are superior to 20 wt% Pt/C catalyst and other reported advanced metal-free catalysts. The excellent catalytic performance of the 3DGFs probably arises from the synergic effect of the morphology and composition engineering, e.g., the edges and doping, especially the pyridine N. The present work is expected to open up new approach to design outstanding metal-free carbon-based electrocatalysts for ORR.

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References

  1. Qu LT, Liu Y, Baek JB, Dai LM (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3):1321–1326

    Article  Google Scholar 

  2. 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):760–764

    Article  Google Scholar 

  3. Shen AL, Zou YQ, Wang Q, Dryfe RAW, Huang XB, Dou S, Dai LM, Wang SY (2014) Oxygen reduction reaction in a droplet on graphite: direct evidence that the edge is more active than the basal plane. Angew Chem Int Edit 53(40):10804–10808

    Article  Google Scholar 

  4. Li Y, Zhao Y, Cheng HH, Hu Y, Shi GQ, Dai LM, Qu LT (2012) Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. J Am Chem Soc 134(1):15–18

    Article  Google Scholar 

  5. Duan JJ, Chen S, Jaroniec M, Qiao SZ (2015) Heteroatom-doped graphene-based materials for energy-relevant electrocatalytic processes. ACS Catal 5(9):5207–5234

    Article  Google Scholar 

  6. Zheng Y, Jiao Y, Chen J, Liu J, Liang J, Du A, Zhang WM, Zhu ZH, Smith SC, Jaroniec M, Lu GQ, Qiao SZ (2011) Nanoporous graphitic-C3N4@carbon metal-free electrocatalysts for highly efficient oxygen reduction. J Am Chem Soc 133(50):20116–20119

    Article  Google Scholar 

  7. Tao L, Wang Q, Dou S, Ma ZL, Huo J, Wang SY, Dai LM (2016) Edge-rich and dopant-free graphene as a highly efficient metal-free electrocatalyst for the oxygen reduction reaction. Chem Commun 52(13):2764–2767

    Article  Google Scholar 

  8. Li YG, Zhou W, Wang HL, Xie LM, Liang YY, Wei F, Idrobo JC, Pennycook SJ, Dai HJ (2012) An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat Nanotechnol 7(6):394–400

    Article  Google Scholar 

  9. Wang HB, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2(5):781–794

    Article  Google Scholar 

  10. Zheng Y, Jiao Y, Jaroniec M, Jin YG, Qiao SZ (2012) Nanostructured metal-free electrochemical catalysts for highly efficient oxygen reduction. Small 8(23):3550–3566

    Article  Google Scholar 

  11. Dai LM, Chang DW, Baek JB, Lu W (2012) Carbon nanomaterials for advanced energy conversion and storage. Small 8(8):1130–1166

    Article  Google Scholar 

  12. Yu DS, Nagelli E, Du F, Dai LM (2010) Metal-free carbon nanomaterials become more active than metal catalysts and last longer. J Phys Chem Lett 1(14):2165–2173

    Article  Google Scholar 

  13. Qiu YJ, Yu J, Shi TN, Zhou XS, Bai XD, Huang JY (2011) Nitrogen-doped ultrathin carbon nanofibers derived from electrospinning: large-scale production, unique structure, and application as electrocatalysts for oxygen reduction. J Power Sources 196(23):9862–9867

    Article  Google Scholar 

  14. Liu DD, Tao L, Yan DF, Zou YQ, Wang SY (2018) Recent advances on non-precious metal porous carbon-based electrocatalysts for oxygen reduction reaction. Chemelectrochem 5(14):1775–1785

    Article  Google Scholar 

  15. Wu ZS, Ren W, Gao L, Zhao J, Chen Z, Liu B, Tang D, Yu B, Jiang C, Cheng H-M (2009) Synthesis of graphene sheets with high electrical conductivity and good thermal stability by hydrogen arc discharge exfoliation. ACS Nano 3(2):411–417

    Article  Google Scholar 

  16. Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN (2008) Superior thermal conductivity of single-layer graphene. Nano Lett 8(3):902–907

    Article  Google Scholar 

  17. Lee C, Wei X, Kysar JW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321(5887):385–388

    Article  Google Scholar 

  18. Jiao Y, Zheng Y, Jaroniec M, Qiao SZ (2014) Origin of the electrocatalytic oxygen reduction activity of graphene-based catalysts: a roadnnap to achieve the best performance. J Am Chem Soc 136(11):4394–4403

    Article  Google Scholar 

  19. Sheng ZH, Gao HL, Bao WJ, Wang FB, Xia XH (2012) Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells. J Mater Chem 22(2):390–395

    Article  Google Scholar 

  20. Zhang LP, Xia ZH (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C 115(22):11170–11176

    Article  Google Scholar 

  21. Wang X, Li XY, Ouyang CB, Li Z, Dou S, Ma ZL, Tao L, Huo J, Wang SY (2016) Nonporous MOF-derived dopant-free mesoporous carbon as an efficient metal-free electrocatalyst for the oxygen reduction reaction. J Mater Chem A 4(24):9370–9374

    Article  Google Scholar 

  22. Jia Y, Zhang LZ, Du AJ, Gao GP, Chen J, Yan XC, Brown CL, Yao XD (2016) Defect graphene as a trifunctional catalyst for electrochemical reactions. Adv Mater 28(43):9532–9538

    Article  Google Scholar 

  23. Jiang YF, Yang LJ, Sun T, Zhao J, Lyu ZY, Zhuo O, Wang XZ, Wu Q, Ma J, Hu Z (2015) Significant contribution of intrinsic carbon defects to oxygen reduction activity. ACS Catal 5(11):6707–6712

    Article  Google Scholar 

  24. Stamatin SN, Hussainova I, Ivanov R, Colavita PE (2016) Quantifying graphitic edge exposure in graphene-based materials and its role in oxygen reduction reactions. ACS Catal 6(8):5215–5221

    Article  Google Scholar 

  25. Tang C, Zhang Q (2017) Nanocarbon for oxygen reduction electrocatalysis: dopants, edges, and defects. Adv Mater 29(13):1604103

    Article  Google Scholar 

  26. Wang YQ, Tao L, Xiao ZH, Chen R, Jiang ZQ, Wang SY (2018) 3D carbon electrocatalysts in situ constructed by defect-rich nanosheets and polyhedrons from NaCl-sealed zeolitic imidazolate frameworks. Adv Funct Mater 28(11):1705356

    Article  Google Scholar 

  27. Yang DF, Guo L, Xie C, Wang YY, Li YX, Li H, Wang SY (2018) N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction. Sci China Mater 61(5):679–685

    Article  Google Scholar 

  28. McClure JP, Thornton JD, Jiang R, Chu D, Cuomo JJ, Fedkiw PS (2012) Oxygen reduction on metal-free nitrogen-doped carbon nanowall electrodes. J Electrochem Soc 159(11):F733–F742

    Article  Google Scholar 

  29. Chi YW, Hu CC, Shen HH, Huang KP (2016) New approach for high-voltage electrical double-layer capacitors using vertical graphene nanowalls with and without nitrogen doping. Nano Lett 16(9):5719–5727

    Article  Google Scholar 

  30. Zeng J, Ji XX, Ma YH, Zhang ZX, Wang SG, Ren ZH, Zhi CY, Yu J (2018) 3D graphene fibers grown by thermal chemical vapor deposition. Adv Mater 30(12):1705380

    Article  Google Scholar 

  31. Wu Y, Qiao P, Chong T, Shen Z (2002) Carbon nanowalls grown by microwave plasma enhanced chemical vapor deposition. Adv Mater 14(1):64–67

    Article  Google Scholar 

  32. Subramanian NP, Li XG, Nallathambi V, Kumaraguru SP, Colon-Mercado H, Wu G, Lee JW, Popov BN (2009) Nitrogen-modified carbon-based catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells. J Power Sources 188(1):38–44

    Article  Google Scholar 

  33. Ferrari AC, Meyer JC, Scardaci V, Casiraghi C, Lazzeri M, Mauri F, Piscanec S, Jiang D, Novoselov KS, Roth S, Geim AK (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97(18):187401

    Article  Google Scholar 

  34. Reina A, Jia X, Ho J, Nezich D, Son H, Bulovic V, Dresselhaus MS, Kong J (2009) Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett 9(1):30–35

    Article  Google Scholar 

  35. Pei ZX, Li HF, Huang Y, Xue Q, Huang Y, Zhu MS, Wang ZF, Zhi CY (2017) Texturing in situ: N,S-enriched hierarchically porous carbon as a highly active reversible oxygen electrocatalyst. Energy Environ Sci 10(3):742–749

    Article  Google Scholar 

  36. Yao Y, Chen Z, Zhang A, Zhu J, Wei X, Guo J, Wu WD, Chen XD, Wu Z (2017) Surface-coating synthesis of nitrogen-doped inverse opal carbon materials with ultrathin micro/mesoporous graphene-like walls for oxygen reduction and supercapacitors. J Mater Chem A 5(48):25237–25248

    Article  Google Scholar 

  37. Huang J, Han J, Gao T, Zhang X, Li J, Li Z, Xu P, Song B (2017) Metal-free nitrogen-doped carbon nanoribbons as highly efficient electrocatalysts for oxygen reduction reaction. Carbon 124:34–41

    Article  Google Scholar 

  38. Mulyadi A, Zhang Z, Dutzer M, Liu W, Deng Y (2017) Facile approach for synthesis of doped carbon electrocatalyst from cellulose nanofibrils toward high-performance metal-free oxygen reduction and hydrogen evolution. Nano Energy 32:336–346

    Article  Google Scholar 

  39. Xiang Q, Yin W, Liu Y, Yu D, Wang X, Li S, Chen C (2017) A study of defect-rich carbon spheres as a metal-free electrocatalyst for an efficient oxygen reduction reaction. J Mater Chem A 5(46):24314–24320

    Article  Google Scholar 

  40. Pampel J, Fellinger TP (2016) Opening of bottleneck pores for the improvement of nitrogen doped carbon electrocatalysts. Adv Energy Mater 6(8):1502389

    Article  Google Scholar 

  41. Yu HJ, Shang L, Bian T, Shi R, Waterhouse GIN, Zhao YF, Zhou C, Wu LZ, Tung CH, Zhang TR (2016) Nitrogen-doped porous carbon nanosheets templated from g-C3N4 as metal-free electrocatalysts for efficient oxygen reduction reaction. Adv Mater 28(25):5080–5086

    Article  Google Scholar 

  42. Liu Q, Wang Y, Dai L, Yao J (2016) Scalable fabrication of nanoporous carbon fiber films as bifunctional catalytic electrodes for flexible Zn–Air batteries. Adv Mater 28(15):3000–3006

    Article  Google Scholar 

  43. Yang HB, Miao J, Hung S-F, Chen J, Tao HB, Wang X, Zhang L, Chen R, Gao J, Chen HM (2016) 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):e1501122

    Article  Google Scholar 

  44. Tang C, Wang HF, Chen X, Li BQ, Hou TZ, Zhang B, Zhang Q, Titirici MM, Wei F (2016) Topological defects in metal-free nanocarbon for oxygen electrocatalysis. Adv Mater 28(32):6845–6851

    Article  Google Scholar 

  45. Liu RL, Wu DQ, Feng XL, Mullen K (2010) Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem Int Edit 49(14):2565–2569

    Article  Google Scholar 

  46. Aijaz A, Fujiwara N, Xu Q (2014) From metal-organic framework to nitrogen-decorated nanoporous carbons: high CO2 uptake and efficient catalytic oxygen reduction. J Am Chem Soc 136(19):6790–6793

    Article  Google Scholar 

  47. Dou S, Shen AL, Tao L, Wang SY (2014) Molecular doping of graphene as metal-free electrocatalyst for oxygen reduction reaction. Chem Commun 50(73):10672–10675

    Article  Google Scholar 

  48. Banhart F, Kotakoski J, Krasheninnikov AV (2011) Structural defects in graphene. ACS Nano 5(1):26–41

    Article  Google Scholar 

  49. Guo DH, Shibuya R, Akiba C, Saji S, Kondo T, Nakamura J (2016) Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science 351(6271):361–365

    Article  Google Scholar 

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Acknowledgements

All authors acknowledge supports from Shenzhen Basic Research Program (JCYJ20160318093244885 and JCYJ20170413112249615) and the National Natural Science Foundation of China (No. 51272057).

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  1. Jie Zeng and Yongbiao Mu have contributed equally to this work

Authors and Affiliations

  1. Shenzhen Engineering Lab for Supercapacitor Materials, Shenzhen Key Laboratory for Advanced Materials, Department of Material Science and Engineering, Shenzhen Graduate School, Harbin Institute of Technology, University Town, Shenzhen, 518055, China

    Jie Zeng, Yongbiao Mu, Xixi Ji, Zijia Lin, Yanhong Lin, Yihui Ma, Zhongxing Zhang, Shuguang Wang, Zhonghua Ren & Jie Yu

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  1. Jie Zeng
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Zeng, J., Mu, Y., Ji, X. et al. N,O-codoped 3D graphene fibers with densely arranged sharp edges as highly efficient electrocatalyst for oxygen reduction reaction. J Mater Sci 54, 14495–14503 (2019). https://doi.org/10.1007/s10853-019-03743-x

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