Citation: PENG San, GUO Hui-Lin, KANG Xiao-Feng. Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction[J]. Acta Physico-Chimica Sinica, ;2014, 30(9): 1778-1786. doi: 10.3866/PKU.WHXB201407112 shu

Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction

1.
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, P. R. China

Received Date: 15 May 2014
Available Online: 11 July 2014
Fund Project:

Nitrogen-doped graphene (NG) was prepared by chemical reduction of graphene oxide ( ) using dimethyl ketoxime (DMKO) as reducing and doping agents. The morphologies, structures, compositions, and electrocatalytic activities of the as-prepared materials were investigated using field-emission transmission electron microscopy (FETEM), ultraviolet- visible (UV-Vis) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), zeta potential and nanoparticle analyses, cyclic voltammetry (CV), and the rotating disk electrode (RDE) method. The results showed that sheets were effectively reduced by DMKO. NG samples with different nitrogen contents were obtained by adjusting the mass ratio of to DMKO; the nitrogen contents were in the range 4.40%-5.89% (atomic fraction). NG-1, obtained using a /DMKO mass ratio of 1:0.7, showed excellent electrocatalytic activity in the oxygen reduction reaction (ORR) in an O₂-saturated 0.1 mol·L^-1 KOH solution. The peak current was 0.93 mA·cm^-2, and the number of electrons transferred per O₂ was 3.6; this was attributed to the increase in the number of ORR active sites in the presence of pyridinic-N. In addition, the electrocatalytic activity of NG was found to be dependent on the graphitic-N content, which determined the limiting current density, because of its higher electronic conductivity. The pyridinic-N content improved the onset potential, because of its lower overpotential for the ORR. NG therefore exhibited a high selectivity in the ORR, with od tolerance of methanol cross-over effects. It is therefore superior to commercial Pt/C catalysts.
- Graphene,
- Nitrogen doping,
- Oxygen reduction reaction,
- Electrocatalysis
1. [1]
  
  (1) Debe, M. K. Nature 2012, 486, 43. doi: 10.1038/nature11115
2. [2]
  (2) Yang, R.; Leisch, J.; Strasser, P.; Toney, M. F. Chem. Mater. 2010, 22, 4712. doi: 10.1021/cm101090p
3. [3]
  (3) Chen, A.; Holt-Hindle, P. Chem. Rev. 2010, 110, 3767. doi: 10.1021/cr9003902
4. [4]
  (4) Zheng, Y.; Jiao, Y.; Jaroniec, M.; Jin, Y.; Qiao, S. Z. Small 2012, 8, 3550.
5. [5]
  (5) Zhang, L.; Zhang, J.;Wilkinson, D. P.;Wang, H. J. Power Sources 2006, 156, 171. doi: 10.1016/j.jpowsour.2005.05.069
6. [6]
  (6) Zhang, M.; Dai, L. Nano Energy, 2012, 1, 514. doi: 10.1016/j.nanoen.2012.02.008
7. [7]
  (7) Nallathambi, V.; Lee, J.W.; Kumaraguru, S. P.;Wu, G.; Popov, B. N. J. Power Sources 2008, 183, 34. doi: 10.1016/j.jpowsour.2008.05.020
8. [8]
  (8) Hu, Y. J.; Jin, J.; Zhang, H.;Wu, P.; Cai, C. X. Acta Phys. -Chim. Sin. 2010, 26, 2073. [胡耀娟, 金娟, 张卉, 吴萍, 蔡称心. 物理化学学报, 2010, 26, 2073.] doi: 10.3866/PKU.WHXB20100812
9. [9]
  (9) Bunch, J. S.; Verbridge, S. S.; Alden, J. S.; van der Zande, A. M.; Parpia, J. M.; Craighead, H. G.; McEuen, P. L. Nano Lett. 2008, 8, 2458. doi: 10.1021/nl801457b
10. [10]
  (10) Park, S.; Ruoff, R. S. Nat. Nanotechnol. 2009, 4, 217. doi: 10.1038/nnano.2009.58
11. [11]
  (11) Novoselov, K. S.; Jiang, Z.; Zhang, Y.; Morozov, S. V.; Stormer, H. L.; Zeitler, U.; Maan, J. C.; Boebinger, G. S.; Kim, P.; Geim, A. K. Science 2007, 315, 1379. doi: 10.1126/science.1137201
12. [12]
  (12) Balandin, A. A.; Ghosh, S.; Bao,W.; Calizo, I.; Teweldebrhan, D.; Miao, F.; Lau, C. N. Nano Lett. 2008, 8, 902. doi: 10.1021/nl0731872 doi: 10.1021/nl0731872
13. [13]
  (13) Avouris, P.; Chen, Z.; Perebeinos, V. Nat. Nanotechnol. 2007, 2, 605. doi: 10.1038/nnano.2007.300
14. [14]
  (14) Wang, X.; Li, X.; Zhang, L.; Yoon, Y.;Weber, P. K.;Wang, H.; Guo, J.; Dai, H. Science 2009, 324, 768. doi: 10.1126/science.1170335
15. [15]
  (15) Jeon, I. Y.; Choi, H. J.; Choi, M.; Seo, J. M.; Jung, S. M.; Kim, M. J.; Zhang, S.; Zhang, L.; Xia, Z.; Dai, L.; Park, N.; Baek, J. B. Scientific Reports 2013, 3, 1810.
16. [16]
  (16) Geng, D.; Chen, Y.; Chen, Y.; Li, Y.; Li, R.; Sun, X.; Ye, S.; Knights, S. Energy Environ. Sci. 2011, 4, 760. doi: 10.1039/c0ee00326c
17. [17]
  (17) Qu, L.; Liu, Y.; Baek, J. B.; Dai, L. ACS Nano 2010, 4, 1321. doi: 10.1021/nn901850u
18. [18]
  (18) Shao, Y.; Zhang, S.; Engelhard, M. H.; Li, G.; Shao, G.;Wang, Y.; Liu, J.; Aksay, I. A.; Lin, Y. J. Mater. Chem. 2010, 20, 7491. doi: 10.1039/c0jm00782j
19. [19]
  (19) Sheng, Z. H.; Shao, L.; Chen, J. J.; Bao,W. J.;Wang, F. B.; Xia, X. H. ACS Nano 2011, 5, 4350. doi: 10.1021/nn103584t
20. [20]
  (20) Ma, G. X.; Zhao, J. H.; Zheng, J. F.; Zhu, Z. P. New Carbon Mater. 2012, 27, 258. [马贵香, 赵江红, 郑剑锋, 朱珍平. 新型炭材料, 2012, 27, 258.]
21. [21]
  (21) Unni, S. M.; Devulapally, S.; Karjule, N.; Kurun t, S. J. Mater. Chem. 2012, 22, 23506. doi: 10.1039/c2jm35547g
22. [22]
  (22) Yang, S.; Zhi, L.; Tang, K.; Feng, X.; Maier, J.; Müllen, K. Adv. Funct. Mater. 2012, 22, 3634. doi: 10.1002/adfm.v22.17
23. [23]
  (23) Li, N.;Wang, Z.; Zhao, K.; Shi, Z.; Gu, Z.; Xu, S. Carbon 2010, 48, 255. doi: 10.1016/j.carbon.2009.09.013
24. [24]
  (24) Su, P.; Guo, H. L.; Peng, S.; Ning, S. K. Acta Phys. -Chim. Sin. 2012, 28, 2745. [苏鹏, 郭慧林, 彭三, 宁生科. 物理化学学报, 2012, 28, 2745.] doi: 10.3866/PKU.WHXB201208221
25. [25]
  (25) Li, X.;Wang, H.; Robinson, J. T.; Sanchez, H.; Diankov, G.; Dai, H. J. Am. Chem. Soc. 2009, 131, 15939. doi: 10.1021/ja907098f
26. [26]
  (26) Su, P.; Guo, H. L.; Tian, L.; Ning, S. K. Carbon 2012, 50, 5351. doi: 10.1016/j.carbon.2012.07.001
27. [27]
  (27) Wang, Y.; Shao, Y.; Matson, D.W.; Li, J.; Lin, Y. ACS Nano 2010, 4, 1790. doi: 10.1021/nn100315s
28. [28]
  (28) Lin, Z.;Waller, G. H.; Liu, Y.; Liu, M.;Wong, C. P. Carbon 2013, 53, 130. doi: 10.1016/j.carbon.2012.10.039
29. [29]
  (29) Subramanian, N. P.; Li, X.; Nallathambi, V.; Kumaraguru, S. P.; Colon-Mercado, H.;Wu, G.; Lee, JW.; Popov, B. N. J. Power Sources 2009, 188, 38. doi: 10.1016/j.jpowsour.2008.11.087
30. [30]
  (30) Saidi,W. A. J. Phys. Chem. Lett. 2013, 4, 4160. doi: 10.1021/jz402090d
31. [31]
  (31) Lai, L.; Potts, J. R.; Zhan, D.;Wang, L.; Poh, C. K.; Tang, C.; ng, H.; Shen, Z.; Lin, J.; Ruoff, R. S. Energy Environ. Sci. 2012, 5, 7936. doi: 10.1039/c2ee21802j
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沈阳化工大学材料科学与工程学院沈阳 110142