Nano Materials Science 1 (2019) 131–136

Contents lists available at ScienceDirect

Nano Materials Science

journal homepage: www.keaipublishing.com/cn/journals/nano-materials-science/

High efficient oxygen reduction performance of Fe/Fe3C nanoparticles in

situ encapsulated in nitrogen-doped carbon via a novel microwave-assisted
carbon bath method
Mincong Liu a, Xue Yin a, Xuhong Guo a, b, **, Libing Hu a, Huifang Yuan a, Gang Wang a, Fu Wang c,
Long Chen a, Lili Zhang d, *, Feng Yu a, ***
a
Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, 832003,
PR China
b
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, PR China
c
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai, 200240, PR China
d
Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research, Jurong Island, 627833, Singapore

A R T I C L E I N F O A B S T R A C T

Keywords: Fe-based carbon materials are widely considered promising to replace Pt/C as next-generation electrocatalysts
Fe/Fe3C nanoparticles towards oxygen reduction reaction (ORR). However, the preparation of Fe-based carbon materials is still carried
Prussian blue out by conventional heating method (CHM). Herein, a novel microwave-assisted carbon bath method (MW-CBM)
Microwave
was proposed, which only took 35 min to synthesize Fe/Fe3C nanoparticles encapsulated in N-doped carbon layers
Carbon bath method
Oxygen reduction reaction
derived from Prussian blue (PB). The catalyst contained large specific surface area and mesoporous structure,
abundant Fe-Nx and C–N active sites, unique core-shell structure. Due to the synergistic effects of these features,
the as-prepared Fe/Fe3C@NC-2 displayed outstanding ORR activity with onset potential of 0.98 VRHE and half-
wave potential of 0.87 VRHE, which were more positive than 20 wt.% Pt/C (0.93 VRHE and 0.82 VRHE). Besides,
Fe/Fe3C@NC-2 gave a better stability and methanol tolerance than Pt/C towards ORR in alkaline media, too.

1. Introduction
The oxygen reduction reaction (ORR) as a cathode reaction plays a
crucial role in fuel cells and metal-air batteries, which have attracted
much attention due to clean, efficient and sustainable process [1–4].
Currently, Pt-based electrocatalysts are vital for boosting ORR, but there
remains the disadvantages of high cost, methanol crossover effect and
poor stability [5]. Therefore, it is necessary to develop non-noble metal
ORR catalysts with low price and high performance to promote the
large-scale application of direct methanol fuel cell [6].
Recently, Fe3C nanostructures have attracted broad attention as good
electrocatalysts [7–9]. Li et al. [10], reported Fe3C nanoparticles encased
in graphitic layers by pyrolysis of a mixture of ferrocene and cyanamide.
However, the catalysts gave the poor ORR activity if the Fe3C nano-
particles were directly exposed to the electrolyte after destroying the
protective graphitic shells by ball-malling. Not only that, the recent ar-
ticles reported that Fe, N co-doped carbon materials had more
outstanding electrocatalytic performance [11]. Shan et al. [12], indicated
that the excellent catalytic performance of catalysts not only benefited
from the unique core-shell structure, but also Fe-Nx active sites and the
pyridinic and graphitic N sites worked synergistically to promote cata-
lytic activity. Also, the large specific surface area and well porous
structure were also beneficial to enhance the catalytic performance [13].
Cong et al. [14], further confirmed that the superiority of the core shell
structure and the presence of the porous structure exposed more active
sites and promoted the transport of the electrolyte, leading to exhibit
excellent ORR activity.
In addition, the embedding of Fe into the Fe3C nanoparticles
increased the activity of the catalysts. As reported in Bao’s research [15],
indicating that the encapsulated Fe particles changed the charge density

* Corresponding author.
** Corresponding author. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi
University, Shihezi, 832003, PR China.
*** Corresponding author.
E-mail addresses: zhang_lili@ices.a-star.edu.sg (L. Zhang), yufeng923@hotmail.com (F. Yu).

https://doi.org/10.1016/j.nanoms.2019.04.003

Available online 21 June 2019

2589-9651/© 2019 Chongqing University. Production and hosting by Elsevier B.V. on behalf of KeAi. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Liu et al.
Fig. 1. (a) Schematic illustration for synthesis of Fe/Fe3C@NC via MW-CBM; (b–c) SEM images and N2 adsorption-desorption isotherms and corresponding pore size
distribution (inset) of Fe/Fe3C@NC and Fe/Fe3C@NC-2; (d) TEM image and (e–g) HRTEM images for Fe/Fe3C@NC-2.
of CNT and doping N into the carbon further decreased the adsorption
free energy which had synergistic effect in facilitating O2 adsorption and
reduction. Hu et al. [16], revealed the origin of high catalytic perfor-
mance of the Fe–N–C catalysts by a series of designed experiments, and
indicated that not only the synergistic effect of Fe/Fe3C and Fe-Nx
enhanced the catalystic, but also the interaction between the Fe and
Fe-Nx structures was beneficial to O2 adsorption. Wang et al. [17], re-
ported synthesizing Fe3C/Fe2O3/Fe heterostructures which promoted
electron transfer from the carbon support to active Fe3C through
O–Fe–C–Fe–C bonds, improving ORR kinetics.
Herein, this work brings forward a microwave-assisted carbon bath
method (MW-CBM) and successfully synthesized Fe/Fe3C nano-
particles wrapped in N-doped carbon shells using Prussian blue (PB) as
precusors. We have been prepared LiFePO4/C [18], LFePO4/MEGO
[19] as lithium ion electrode materials, and Ni/VMT [20] as CO
methanation catalysts. Compared with conventional heating method
(CHM), MW-CBM considerably affords advantages such as fast heating
rate, high thermal efficiency, uniform heating, less side reaction [21].
In addition, the columnar carbon material used in MW-CBM can
effectively absorb the microwave which can raise the temperature to
heat treat the precursor. In addition, the columnar carbon materials
can effectively avoid the direct contact between air and the samples to
prevent sample oxidation. The obtained catalysts exhibit superior ORR
performance, which is entirely attributable to the synergistic effects of
Fe-Nx active sites and Fe/Fe3C nanoparticles encased in N-doped car-
bon layers and the large specific surface area and mesoporous
structure.
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Nano Materials Science 1 (2019) 131–136
2. Experimental
1.0 g of commercial PB was put into graphite crucible which was
buried in a 100 mL crucible by using commercial columnar carbon and
subsequently placed in a commercial microwave oven under microwave
irradiation with 750 W for 35 min. The obtained was named Fe/
Fe3C@NC without further treatment.
For comparison, another 1.0 g of commercial PB was treated under
the same condition, and then the obtained product (Fe/Fe3C@NC) was
further treated by 2 M HCL with ultrasound for 1 h, and named as Fe/
Fe3C@NC-2.
A Hitachi S4800 scanning electron microscopy (SEM) was used to
determine the morphology. Transmission electron microscopy (TEM)
surveys were examined with a field emission Tecnai G2 F20 electron
microscope. X-ray diffraction (XRD) measurement was recorded on a
Bruker D8 Advance X-ray diffractometer with Cu–K radiation, and the
scanning rate is 10
/min, the scanning range is 10
–90
, the current is
40 mA, the voltage is 40 kV. The surface chemical compositions were
analyzed using an Thermo ESCALAB 250XI X-ray photoelectron spec-
troscope (XPS). The Raman spectra were recorded on a LabRAM HR800
Laser Confocal Micro-Raman Spectroscope with a laser wavelength of
532 nm. A Micromeritics ASAP 2020 apparatus was used to analyze the
specific surface area and pore size distribution derived from N2 adsorp-
tion/desorption isotherm by using Brunauer-Emmett-Teller (BET) and
Barrett-Joyner-Halenda (BJH) methods.
The electrochemical performances of the prepared samples were
measured using a CHI760D electrochemical station with a three-
M. Liu et al.
Fig. 2. (a) XRD patterns and (b) Raman spectra of Fe/Fe3C@NC and Fe/Fe3C@NC-2; Survey XPS spectra (c) and high resolution XPS spectra of (d) C 1s, (e) Fe 2p, (f) N
1s for Fe/Fe3C@NC and Fe/Fe3C@NC-2.
electrode cell. The sample ink was prepared by a mixture of the catalyst
powder (5 mg), 5 wt% Nafion solution (25 μL) and ethanol (475 μL)
under ultrasonication (30min). Subsequently, the as-prepared catalytic
ink (10 μL) was loaded on GC electrode (3 mm). Therefore, the catalyst
loading was controlled at 0.0142 mg/cm2. All the experiments were
carried out in 0.1 M KOH solution. In a typical ORR procedure the
electron transfer numbers can be evaluated based on the slopes of
Koutecky-Levich (K-L) plots using the following equation:
1 1 1 porous structure of Fe/Fe3C@NC and Fe/Fe3C@NC-2 in the inset of
¼ þ
J Jk Bω1=2
where, J is the measured current density on RDE, Jk represents the kinetic
current density, ω denotes the electrode rotation speed, and B is
expressed according to the equation given below:
B ¼ 0.2nFC0D2/3
0 ν
1/6
where n stands for the electron transfer number per O2 molecule in ORR
procedure, F is 96485C mol1 (the Faraday constant), C0 is 1.2 
103 mol L1 (the dissolved O2 concentration), D0 is 1.9  105 cm2 s1
Nano Materials Science 1 (2019) 131–136
(the O2 diffusion coefficient), and ν is the electrolyte kinematic viscosity
(0.01 cm2 s1).
3. Result and discussion
The fabrication procedures for porous core-shell Fe/Fe3C@NC was
well illustrated in Fig. 1a. Fig. 1b and c showed typical SEM images of Fe/
Fe3C@NC and Fe/Fe3C@NC-2, indicating that a large number of nano-
particles attached to the catalysts surface. The BET results revealed the
(1)
Fig. 1a and b, respectively. Fe/Fe3C@NC-2 exhibited higher surface area
and larger pore volume than Fe/Fe3C@NC (251.1 vs 52.2 m2/g, 1.15 vs
0.24 cm3/g) which was caused by acid treatment. The N2 adsorption/
desorption isotherms of both catalysts are of type IV with obvious hys-
teresis loops, characteristic of mesoporous structure. The pore size dis-
(2) tributions of Fe/Fe3C@NC and Fe/Fe3C@NC-2 were mainly centered at
around 3.0 nm and 50.0 nm on the basis of the density functional theory
(DFT). The high specific surface area and large pore volume of Fe/
Fe3C@NC-2 were beneficial to enhance the ORR performances because it
not only facilitated rapid transportation of electrolytes and electrons, but
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M. Liu et al. Nano Materials Science 1 (2019) 131–136

Fig. 3. (a) LSV curves at a sweep rate of 10 mV/s for Fe/Fe3C@NC, Fe/Fe3C@NC-2 and 20 wt.% Pt/C in O2-saturated 0.1 M KOH with a rotating speed of 1600 rpm;
(b) (CV) curves of Fe/Fe3C@NC-2 in N2-saturated or O2-saturated 0.1 M KOH electrolyte at a scan rate of 50 mV/s; (c) LSVs oxygen reduction on Fe/Fe3C@NC-2 at
various rotation speeds and corresponding K-L plots (inset); (d) Tafel slope tests of Fe/Fe3C@NC-2 and 20 wt.% Pt/C; (e) Long-term stability tests and (f) tolerance to
alcohol poisoning tests of Fe/Fe3C@NC-2 and 20 wt.% Pt/C via the ORR cathodic current-time (i-t) method.

also exposed more active sites [22]. The TEM image in Fig. 1d revealed
the existence of non-uniform core-shell nanoparticles in Fe/Fe3C@NC-2.
The detailed structure of nanoparticles can be demonstrated by HRTEM
in Fig. 1e and f. It was clearly identified that graphite layers with an
interlayer spacing of 0.36 nm, corresponding to (002) plane of graphitic
carbon, closely encased in Fe/Fe3C nanoparticle. Furthermore, in the
HRTEM image (Fig. 1f and g) existed the distinct lattice distance of
0.197 nm, which was indexed to the (112) plane of Fe3C. Previous re-
ports had demonstrated that although wrapped Fe3C nanoparticles was
not in direct contact with the electrolyte, it could activate circumambient
graphitic shells toward improving ORR activity [23].
As can be seen from Fig. 2a, XRD patterns of Fe/Fe3C@NC and Fe/
Fe3C@NC-2 catalysts all presented a broad diffraction peak at 26.5
,
corresponded to the (002) plane of graphitized carbon, while the two
phases were assigned to α-Fe (JCPDS, No. 06-0696) and γ-Fe (JCPDS, No.
52-0512). Apart from the three phases, a certain amount of feature peaks
were considered to be Fe3C (JCPDS, No. 35-0772). It could be observed
that the crystallinity of Fe/Fe3C@NC-2 was significantly improved after
the acid treatment. The intensity ratio of ID/IG from Raman spectra was
0.98, 1.02 for Fe/Fe3C@NC, Fe/Fe3C@NC-2, respectively (Fig. 2b).
These results indicated that the catalysts possessed higher degree of
graphitic crystalline, but Fe/Fe3C@NC-2 exhibited more defects sites
after acid treatment [24].
High–resolution X-ray photoelectron (XPS) measurements were used
to evaluate the surface properties of Fe/Fe3C@NC and Fe/Fe3C@NC-2.
The full XPS spectrum in Fig. 2c showed the presence of C, N, O, Fe in
catalyst. The deconvolution of the C 1s spectrum showed that there was
C–– C–C, C–N and C–O, indicating the existence of carbon atoms
connected to N and O heteroatoms (Fig. 2d). As for Fe 2p (Fig. 2e), the
two pairs of peaks could be attributed to Fe3þ and Fe2þ. And the peak at

134
M. Liu et al.
Table 1
Fe/Fe3C@NC-2 compared with other similar materials.
Catalyst Preparation Heating time (~h) Onset potential (V
method vs.RHE)
Fe3C/C CHM – 1.05
Fe3C@C CHM 9 –
Fe–N–C CHM 3.5 0.90
Fe/ CHM – –
Fe3C@C–FeNC
Fe/Fe3C@NC-2 MW-CBM 0.5 0.98
711.08 eV of Fe3þ 2p3/2 was an evidence of the existence of Fe-Nx sites
[14,25]. The low signals of Fe0 at 706.7 and 719.7 eV, suggesting that the
existence of α-Fe phase [26]. Also, the peak at 711.08 eV of
Fe/Fe3C@NC-2 showed a right shift by 0.31 eV compared with
Fe/Fe3C@NC (710.67 eV). This indicated less charge density on central
Fe atoms, which is a clue of the stronger interaction between Fe-Nx and
Fe nanoparticles [16,27]. The N 1s spectrum (Fig. 2f) was deconvoluted
into four pesks, including pyridinic N (398.6 eV), pyrrolic N (399.5 eV),
graphitic N (400.9 eV) and oxidized N (403.8 eV). Fe/Fe3C@NC-2 con-
tained more percentage of pyridinic N (33.46%) than Fe/Fe3C@NC
(23.53%). It was commonly believed that pyridinic N showed advantage
for ORR [28]. Since the binding energy of pyridine N and Fe-Nx was only
slightly different, it was accepted that the peak at pyridinic N also had a
contribution from Fe-Nx active site [29]. Hence, the peak at 711.08 eV of
Fe3þ 2p3/2 and the binding energy of pyridine N indicated the presence of
Fe-Nx sites.
Based on structure and morphology analysis, the superior catalytic
activity of Fe/Fe3C@NC-2 could be attributed to the synergistic effect of
the following aspects: (1) the encapsulated Fe/Fe3C nanoparticles
enhanced the activity of N-doped graphite shells [30]; (2) C–N and
Fe-Nx active sites were now widely considered to be beneficial to the ORR
reaction [31]; (3) Fe nanoparticles changed the charge density of the
surrounding Fe-Nx active sites which was conducive to the adsorption of
O2 adsorption and reduction [16,27]; (4) The increase of specific surface
area and mesoporous structure not only exposed more catalytically active
sites, but also facilitated the electron transport and decreased the diffu-
sion resistance [22,32,33].
The electrochemical activity of the catalysts was assessed for ORR by
a rotating disc electrode (RDE) in alkaline medium (0.1 M KOH). To
investigate the ORR performance, the linear sweep voltammogram (LSV)
measurements for the Fe/Fe3C@NC, Fe/Fe3C@NC-2 and 20 wt% Pt/C
were examined at a scan rate of 10 mV/s and 1600 rpm in N2-saturated
electrolytes (Fig. 3a). As expected, Fe/Fe3C@NC-2 displayed outstanding
ORR activity with 0.98 VRHE onset potential, 0.87 VRHE half-wave po-
tential and 6.87 mA cm2 limited current density, which was higher than
Fe/Fe3C@NC (0.94 VRHE, 0.82 VRHE and 5.3 mA cm2) and 20 wt.% Pt/C
(0.93 VRHE, 0.82 VRHE and 5.18 mA cm2). The ORR activities were
comparable to recent reports electrodes of Fe3C based catalysts (Table 1).
Fig. 3b showed that CV displayed a well-defined oxygen reduction peak
in O2-saturated electrolytes at a scan rate of 50 mV/s, but the peak dis-
appeared in N2-saturated electrolytes, indicating that the obvious elec-
trocatalytic activity toward ORR of Fe/Fe3C@NC-2. A relatively wide
current platform below 0.7 VRHE appeared in the LSV curves of Fe/
Fe3C@NC-2 (Fig. 3c) at different rotating speeds of 400 ~ 2500 rpm,
indicating that the diffusion-controlled process with regard to the con-
centration of dissolved O2 has an efficient first-order reaction kinetics,
which was further evidenced by the corresponding Koutecky–Levich (K-
L) plots (inset of Fig. 3c). The average transferred electron number was
calculated to be about 3.8 from K-L plots, indexing an almost four-
electron reaction pathway.
Tafel slope, a vital index to measure the kinetics of an electrocatalytic
process, was calculated to be 80 mV/dec for the Fe/Fe3C@NC-2 catalyst,
much lower than that of Pt/C (95 mV/dec), indicating a more desirable
ORR kinetics occurred (Fig. 3d). Moreover, the long-term stability of Fe/
Fe3C@NC-2 and 20 wt.% Pt/C catalyst were tested by current-time
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Nano Materials Science 1 (2019) 131–136
Half-wave Potential (V Limiting-current density (mA/ Ref.
vs.RHE) cm2)
0.83 – [10]
0.80 – [12]
0.79 5.52 [15]
0.89 – [17]
0.87 6.87 this work
chronoamperometric (Fig. 3e), respectively. After 30000s, Fe/
Fe3C@NC-2 retained 77.2% of the initial current density (vs. 33.5% for
20 wt% Pt/C catalyst), which showed an excellent durability. The
methanol poisoning tests in O2-saturated 0.1 M KOH were performed for
Fe/Fe3C@NC-2 and the commercial Pt/C (20 wt%). As shown in Fig. 3f,
Fe/Fe3C@NC-2 kept 84.7% of its initial current upon adding 3 M meth-
anol after 200s. On the contrary, the 20 wt% Pt/C only retained 56.5% of
its initial current, revealing that the Fe/Fe3C@NC-2 showed a better
selective ability towards ORR than 20 wt.% Pt/C.
4. Conclusions
In conclusion, we have developed a new MW-CBM to synthesize core-
shell structure derived from PB in 35 min, which Fe3C nanoparticles were
encapsulated by N-doped graphitic shells. SEM, TEM/HRTEM, XRD, XPS,
BET and Raman spectra were used to characterize the catalysts, and the
results indicated that the prepared catalysts had a regular core-shell
structure, a good mesoporous structure, and the N atom was in-situ
incorporated into the carbon support to form C–N and Fe-Nx active
site. Thanks to these, Fe/Fe3C@NC-2 showed excellent an ORR wave
potential at 0.87 VRHE and the limited current density at 6.87 mA cm2,
which were higher than those obtained by 20 wt.% Pt/C. This work
provides a novel method to prepare high performance catalysts faster and
better, which opens a new path for the synthesis of high-performance
ORR catalysts toward energy conversion and storage devices.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgement
This work was supported by the National Natural Science Foundation
of China (U1303291), and the Program for Changjiang Scholars and
Innovative Research Team in University (No. IRT_15R46).
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