Citation: HAYIERBIEK Kulisong, ZHAO Shu-Xian, YANG Yang, ZENG Han. Performance of Nitrogen-Doped Carbon Nanocomposite with Entrapped Enzyme-Based Fuel Cell[J]. Acta Physico-Chimica Sinica, ;2015, 31(9): 1715-1726. doi: 10.3866/PKU.WHXB201506231 shu

Performance of Nitrogen-Doped Carbon Nanocomposite with Entrapped Enzyme-Based Fuel Cell

1.
Chemistry and Chemical Engineering Academy, Xinjiang Normal University, Urumuqi 830054, P. R. China

Received Date: 31 March 2015
Available Online: 23 June 2015
Fund Project: 国家自然科学基金(21363024) (21363024) 新疆师范大学博士科研启动基金(XJNUBS1228) (XJNUBS1228)新疆维吾尔自治区2013年度高校科研计划青年教师培育项目(XJEDU2013S29)资助 (XJEDU2013S29)

A nanocomposite composed of N-doped mesoporous carbon material (NDMPC) and carboxymethylated chitosan (CMCH) was fabricated by mechanical co-mixing and used as an enzyme matrix. A novel glucose/O₂ enzymatic biofuel cell was fabricated with a Nafion ion-exchange membrane consisting of a laccase (Lac)-entrapped biocathode and glucose oxidase-incorporated bioanode. Enzyme electrodes were prepared by the dripping coat and air-dried method. The performance of the laccase-based electrode as a biocathode in a fuel cell and an oxygen electro-chemical sensor was characterized by cyclic voltammetry in combination with the rotating disk electrode technique, linear scanning voltammetry (LSV), and chronoamperometry. UV-Vis spectrometry and graphite furnace atomic absorption spectroscopy were used to investigate the configuration of enzyme molecules on the surface of electrode and to evaluate the enzyme loading of the matrix on the electrode interface. The results from the experiments showed that the laccasebased cathode displayed direct electron transfer between the active centre in laccase (T₁) and the conductive matrix without any external electron mediators (apparent electron transfer rate 0.013 s^-1). A minor overpotential for oxygen reduction (150 mV) was also observed. Through further comparison of the intra-molecule electron relay rate (1000 s^-1), substrate turnover frequency (0.023 s^-1), and previous enzyme-conductive matrix electron transfer rate, quantitative analysis showed that the latter was the rate-determining step in the whole catalytic cycle of the oxygen reduction reaction. This laccase-based electrode as an oxygen electrochemical sensor for detecting oxygen showed a low detection limit (0.04 μmol·dm^-3), high sensitivity (12.1 μA·μmol^-1·dm³), and affinity for oxygen (K_M = 8.2 μmol·dm^-3). This laccase-based cathode also had advantages such as excellent reproducibility, long-term usability, thermal stability, and pH endurance. The results for the fabricated biofuel cell showed an open circuit voltage of 0.38 V and a maximal energy output density of 19.2 μW·cm^-2, maintaining greater than 60% of the initial value even after continuous work for 3 weeks under optimal conditions.
- Laccase,
- Nitrogen-doped meso-porous carbon material,
- Carboxymethylated Chitosan,
- Direct electron transfer,
- Oxygen reduction reaction,
- Electrochemical sensor,
- Bio-fuel cell
1. [1]
  
  (1) Armstrong, F. A.; Hirst, J. Pro Natl. Acad. Sci. U. S. A. 2011, 108, 14049. doi: 10.1073/pnas.1103697108
2. [2]
  (2) Hussein, L.; Rubenwolf, S.; Von Stetten V.; Urban, G.; Zengerle, R.; Krueger, M.; Kerzenmacher, S. Biosens. Bioelectron. 2011, 26, 4133. doi: 10.1016/j.bios.2011.04.008
3. [3]
  (3) Martinez-Ortiz, J.; Flores, R.; Vazquez-Duhalt, R. Biosens. Bioelectron. 2011, 26, 2626. doi: 10.1016/j.bios.2010.11.022
4. [4]
  (4) Qiao, Y.; Li, C. M. J. Mater. Chem. 2011, 21, 4027. doi: 10.1039/C0JM02871A
5. [5]
  (5) Zayats, M.; Katz, E.; Baron, R.; Willner, I. A. J. Am. Chem. Soc. 2005, 127, 12400. doi: 10.1021/ja052841h
6. [6]
  (6) Liu, Y.; Qu, X. H.; Guo, H. W.; Chen, H. J.; Liu, B. F.; Dong, S. J. Biosens. Bioelectron. 2006, 21, 2195. doi: 10.1016/j.bios.2005.11.014
7. [7]
  (7) Klis, M.; Karbarz, M.; Stojek, Z.; Rogalski, J.; Bilewicz, R. J. Phys. Chem. C. 2009, 113, 6062. doi: 10.1021/jp8094159
8. [8]
  (8) Jensen, U. B.; Lorcher, S.; Vagin, M.; Chevallier, J.; Shipovskov, S.; Koroleva, O.; Besenbacher, F.; Ferapontova, E. Electrochim. Acta 2012, 62, 218. doi: 10.1016/j.electacta.2011.12.026
9. [9]
  (9) Osman, M. H.; Shah, A. A.; Walsh, F. C. Biosens. Bioelectron. 2011, 26, 3087. doi: 10.1016/j.bios.2011.01.004
10. [10]
  (10) Ramasamy, R. P.; Luckarift, H. R.; Ivnitski, D. M.; Atanassov, P. B.; Johnson, G. R. Chem. Commun. 2010, 46, 6045. doi: 10.1039/c0cc00911c
11. [11]
  (11) Mao, F.; Mano, N.; Heller, A. J. Am. Chem. Soc. 2003, 125, 4951. doi: 10.1021/ja029510e
12. [12]
  (12) Barriere, F.; Ferry, Y.; Rochefort, D.; Leech, D. Electrochem. Commun. 2004, 6, 237. doi: 10.1016/j.elecom.2003.12.006
13. [13]
  (13) Xian, Y. Z.; Xian, Y.; Zhou, L. H.; Wu, F. H.; Ling, Y.; Jin, L, T. Electrochem. Commun. 2007, 9, 142. doi: 10.1016/j.elecom. 2006.08.049
14. [14]
  (14) Wei, W.; Li, P. P.; Li, Y.; Cao, X. D.; Liu, S. Q. Electrochem. Commun. 2012, 22, 181. doi: 10.1016/j.elecom.2012.06.021
15. [15]
  (15) Trohalaki, S.; Pachter, R.; Luckarift, H. R.; Johnson, G. R. Fuel Cells 2012, 12, 656. doi: 10.1002/fuce.v12.4
16. [16]
  (16) Miyake, T.; Yoshino, S.; Yamada, T.; Hata, K.; Nishizawa, M. J. Am. Chem. Soc. 2011, 133, 5129. doi: 10.1021/ja111517e
17. [17]
  (17) Zeng, H.; Liao, L. W.; Li, M. F.; Tao, Q.; Kang, J.; Chen, Y. X. Acta Phys. -Chim. Sin. 2010, 26, 3217. [曾涵, 廖铃文, 李明芳, 陶骞, 康婧, 陈艳霞. 物理化学学报, 2010, 26, 3217.] doi: 10.3866/PKU.WHXB20101208
18. [18]
  (18) Zhu, Y. F.; Kaskel, S.; Shi, J. L.; Wage, T.; Pee, K. H. V. Chem. Mater. 2007, 19, 6408. doi: 10.1021/cm071265g
19. [19]
  (19) Pang, H. L.; Liu, J.; Hu, D.; Zhang, X. H.; Chen, J. H. Electrochim. Acta 2010, 55, 6611. doi: 10.1016/j.electacta. 2010.06.013
20. [20]
  (20) Kulisong, H.; Zeng, H. Chin. J. Appl. Chem. 2013, 30, 1194. [库里松•哈衣尔别克, 曾涵. 应用化学, 2013, 30, 1194.]
21. [21]
  (21) Vinu, A. Adv. Funct. Mater. 2008, 18, 816.
22. [22]
  (22) Qiu, H. J.; Xu, C. X.; Huang, X. R.; Ding, Y.; Qu, Y. B.; Gao, P. J. J. Phys. Chem. C. 2008, 112, 14781. doi: 10.1021/jp805600k
23. [23]
  (23) Zhao, H. Y.; Zhou, H. M.; Zhang, J. X.; Zheng, W.; Zheng, Y. F. Biosens. Bioelectron. 2009, 25, 463. doi: 10.1016/j.bios. 2009.08.005
24. [24]
  (24) Santucci, R.; Ferri, T.; Morpur , L.; Savini, I.; Avigliano, L. Biochem. J. 1998, 332, 611.
25. [25]
  (25) Zheng, H.; Hu, J. B.; Li, Q. L. Acta Chim. Sin. 2006, 64, 806. [郑华, 胡劲波, 李启隆. 化学学报, 2006, 64, 806.]
26. [26]
  (26) Freguia, S.; Virdis, B.; Harnisch, F.; Keller, J. Electrochim. Acta 2012, 82, 165. doi: 10.1016/j.electacta.2012.03.014
27. [27]
  (27) Cracknell, J. A.; Vincent, K. A.; Armstrong, F. A. Chem. Rev. 2008, 108, 2439. doi: 10.1021/cr0680639
28. [28]
  (28) Stolarczyk, K.; Lyp, D.; Zelechowska, K.; Biernat, J. F.; Rogalski, J.; Bilewicz, R. Electrochim. Acta 2012, 79, 74. doi: 10.1016/j.electacta.2012.06.050
29. [29]
  (29) Wang, X. J.; Latonen, R. M.; Sjoberg-Eerola, P.; Eriksson, J. E.; Bobacka, J.; Boer, H.; Bergelin, M. J. Phys. Chem. C 2011, 111, 5919.
30. [30]
  (30) Zhang, L. L.; Bai, L.; Xu, M.; Han, L.; Dong, S. J. Nano Ener. 2015, 11, 48. doi: 10.1016/j.nanoen.2014.10.020
31. [31]
  (31) Tsujimura, S.; Kamitaka, Y.; Kano, K. Fuel Cells 2007, 7, 463.
32. [32]
  (32) Soukharev, V.; Mano, N.; Heller, A. J. Am. Chem. Soc. 2004, 126, 8368. doi: 10.1021/ja0475510
33. [33]
  (33) Mano, N.; Kim, H. H.; Zhang, Y. C.; Heller, A. J. Am. Chem. Soc. 2002, 124, 6480. doi: 10.1021/ja025874v
34. [34]
  (34) Jiang, D. S.; Long, S. Y.; Huang, J.; Xiao, H. Y.; Zhou, J. Y. Bio. Eng. J. 2005, 25, 15. doi: 10.1016/j.bej.2005.03.007
35. [35]
  (35) Masson, J. F.; Kranz, C.; Mizaikoff, B. Anal. Chem. 2007, 79, 8531. doi: 10.1021/ac071090u
36. [36]
  (36) Liu, Y.; Wang, M. K.; Zhao, F.; Xu, Z. A.; Dong, S. J. Biosens. Bioelectron. 2005, 21, 984. doi: 10.1016/j.bios.2005.03.003
37. [37]
  (37) Ikeda, T. Electrochim. Acta 2012, 82, 158. doi: 10.1016/j.electacta.2012.01.114
38. [38]
  (38) Zheng, W.; Zhao, H. Y.; Zhang, J. X.; Zhou, H. M.; Xu, X. X.; Zheng, Y. F.; Wang, Y. B.; Cheng, Y.; Jang, B. Z. Electrochem. Commun. 2010, 12, 869. doi: 10.1016/j.elecom.2010.04.006
39. [39]
  (39) Katz, E.; Willner, I.; Kotlyar, A. B. J. Electroanal. Chem. 1999, 479, 64. doi: 10.1016/S0022-0728(99)00425-8
40. [40]
  (40) Li, X.; Zhang, L.; Su, L.; Ohsaka, T.; Mao, L. Fuel Cells 2019, 9, 85. doi: 10.1002/fuce.v9:1
41. [41]
  (41) Ammam, M.; Fransaer, J. Biotechnol. Bioeng. 2012, 109, 1601. doi: 10.1002/bit.v109.7
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