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Frontiers of Environmental Science & Engineering

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Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (2) : 30    https://doi.org/10.1007/s11783-019-1209-1
RESEARCH ARTICLE
One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells
Xingguo Guo, Qiuying Wang, Ting Xu, Kajia Wei, Mengxi Yin, Peng Liang, Xia Huang, Xiaoyuan Zhang()
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
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Abstract

• Nano Fe2O3 and N-doped graphene was prepared via a one-step ball milling method.

• The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite.

• Active sites like nano Fe2O3, pyridinic N and Fe-N groups were formed in Fe-N-G.

• The improvement of Fe-N-G was due to full exposure of active sites on graphene.

Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m2 in microbial fuel cells and a current density of 23.8 A/m2 at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe2O3 nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.
Keywords Microbial fuel cells      Air cathodes      Nano Fe2O3 and nitrogen-doped graphene      Oxygen reduction reaction     
Corresponding Author(s): Xiaoyuan Zhang   
Issue Date: 15 January 2020
 Cite this article:   
Xingguo Guo,Qiuying Wang,Ting Xu, et al. One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells[J]. Front. Environ. Sci. Eng., 2020, 14(2): 30.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1209-1
https://academic.hep.com.cn/fese/EN/Y2020/V14/I2/30
Fig.1  XRD patterns of graphite, G, N-G and Fe-N-G.
Fig.2  SEM images of (a) G; (b) N-G; (c)  (d) Fe-N-G; and (e) EDS mapping scanning of Fe-N-G; TEM images of (f) G; (g) Fe-N-G; and (h) Fe-N-G with Fe2O3 particles, where the inset shows the diffraction pattern of the selected area, and (i) high-resolution TEM images of the Fe-N-G samples.
Fig.3  (a) Survey XPS spectra of the  ball milling N-G and Fe-N-G; (b) the N1s spectrum of N-G; (c) N1s; and (d) the Fe 2p spectrum of Fe-N-G
Fig.4  Raman spectra of the pristine  graphite, ball milling graphene and Fe-N-G catalysts.
Fig.5  (a) (c) Power densities and (b)  electrode potentials (vs. SHE) as a function of current density in microbial fuel cells (MFCs) with different cathodes; (d) Comparison of the Fe-N-G catalysts with graphite or graphene-based catalysts reported in the last five years (MPD: the maximum power density of MFCs; MCD: the maximum current density of MFCs; NaAc: sodium acetate).
Fig.6  (a) Current–potential curves in  abiotic electrochemical cells obtained in chronoamperometry tests; (b) LSV curves based on an RDE test; (c) Tafel plots for ORR based on RDE tests; and (d) the calculated percentage of peroxide (down) and electron transfer.
Samples LSV Tafel RRDE EIS
Eonset (V) E1/2
(V)		 jlimited
(mA/cm2)		 Slope (–b)
(mV/dec)		 n
(at –0.15 V)		 H2O2 (%)
(at –0.15 V)		 Rohm
(Ω)		 Rct
(Ω)
Fe-N-G 0.392 0.076 –4.30 79 3.96 2 13.2 2.31
Pt 0.416 0.106 4.51? 78 ~4 ~0 23.6 4.42
N-G 0.211 –0.069 –4.15 141 3.95 2 17.1 5.08
G 0.118 –0.013 –1.57 109 3.95 2 17.7 6.81
Graphite ~0 Na Na 163 3.23 35 12.8 9.06
Tab.1  Electrochemical parameters for ORR estimated from LSV curves, Tafel plots, calculated from RRDE results and EIS results (vs. SHE)
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[1] Yong XIAO,Yue ZHENG,Song WU,Zhao-Hui YANG,Feng ZHAO. Nitrogen recovery from wastewater using microbial fuel cells[J]. Front. Environ. Sci. Eng., 2016, 10(1): 185-191.
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