Electrochimica Acta 205 (2016) 53–61

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Fe/IRMOF-3 derived porous carbons as non-precious metal

electrocatalysts with high activity and stability towards oxygen
reduction reaction
Hui Suna,c, Haixia Sua , Xingyu Maa , Pengfang Zhanga , Xin Zhanga,* , Xiaoping Daia ,
Jinsen Gaoa , Chi Chenb , Shi-Gang Sunb,**
a
State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing 102249, China
b
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
c
Institute of New Energy, State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

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

Article history:
Received 8 December 2015 By doping iron into isoreticular metal organic framework-3 (IRMOF-3) as a precursor and then annealing
Received in revised form 11 March 2016 at 900
C under inert gas atmosphere, we have successfully prepared high efficient electrocatalyst of x%
Accepted 8 April 2016 Fe/IRMOF-3-900 (x ranges from 1% to 10%) with porous carbon sphere structure. The electrocatalytic
Available online 11 April 2016 properties of the x%Fe/IRMOF-3-900 towards oxygen reduction reaction (ORR) are investigated by using
rotating ring disk electrode (RRDE). The results demonstrate that the 1%Fe/IRMOF-3-900 exhibits the
Keywords: highest ORR activity: the onset and half-wave potentials are measured at 1.02 V and 0.88 V vs. RHE,
Metal organic framework respectively, together with electron transfer number of 3.90 at 0.4 V, kinetic current density of
Electrocatalyst
4.5 mA cm2 at 0.88 V, and excellent longtime stability in alkaline solution. Such high ORR activity is is
Porous carbon
superior to many MOFs derived noble metal free electrocatalysts reported so far, and attributed to that
Oxygen reduction reaction
Active sites the 1%Fe doped could retain the well-defined cubic morphology of the IRMOF-3, resulting in high surface
area and large total pore volume, high nitrogen content and high density of electrocatalytic active N-
species. This study provides a new strategy for preparation of non-precious metal ORR catalysts using the
MOF as a precursor.
ã 2016 Published by Elsevier Ltd.

1. Introduction of PEMFCs [6,7]. To overcome this problem, the exploration of non-

Fuel cells are efficient energy conversion devices with high
efficiency and low pollutant emission, among them the proton
exchange membrane fuel cells (PEMFCs) are one of a promising
clean power source for transportation applications [1,2]. Efficient
catalysts for the oxygen reduction reaction (ORR) are the key to
achieve optimal performance of PEMFCs. Thus, a high active
catalyst enabling four-electron (4e) ORR and with ordered porous
structure for efficient oxygen diffusion and water transportation is
essential to improve the reaction rate and depress the over
potential. At present, Pt-based materials are the most efficient ORR
catalysts used in PEMFCs [3–5], while their low abundance, high
cost, poor durability consist in a main obstacle in the development
* Corresponding author. Tel.: +86 10 18911226208.
** Corresponding author.
E-mail addresses: zhangxin@cup.edu.cn (X. Zhang), sgsun@xmu.edu.cn
(S.-G. Sun).
precious metal ORR catalysts has been extensively conducted in
recent years [8], especially those of iron metals (Fe and Co) and/or
N doped carbon materials [9,10]. Polyaniline [9,11–15], dopamine
[16,17], graphene [18–21] are most used carbon sources for these
materials. However, these carbon sources could not provide
ordered porous structure, which are important to generate
channels for efficient oxygen diffusion and transport of water
generated from the ORR.
Recently, metal-organic frameworks (MOFs) have attracted
extensive interest in ORR catalyst exploration as an ideal precursor
to construct mesoporous carbons [22–26]. MOFs are composed of
well-organized metal ions (most used Zn2+) and organic ligands,
which presents highly ordered 3-diminsion framework structures
[27]. MOFs derived porous carbons as electrocatalysts own two
main advantages: (i) the MOFs could provide a large surface area
and various pore distributions for the electrocatalysts [28,29]; (ii)
the MOFs structures can be designed by varying the types of metal
ions and bridging organic ligands, resulting in a great opportunity
to tune the porosity and activity of electrocatalysts [30]. Two

http://dx.doi.org/10.1016/j.electacta.2016.04.037
0013-4686/ ã 2016 Published by Elsevier Ltd.
54 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61
methods are mainly used to prepare MOFs derived ORR catalysts:
One is to employ normal Zn2+ based MOFs as the precursor to
prepare N doped porous carbon materials [31–34]; Another is to
synthesize Fe or Co contained MOFs for producing electrocatalysts
with the Fe/C/N or Co/C/N as active ORR centers [35–40]. The most
frequently used MOFs are the zeoliticimidazolate frameworks
(ZIFs) as precursors for the preparation of noble metal free
catalysts [31,32,35,36]. It is worthwhile pointing out that the most
reported MOFs derived noble metal free catalysts suffered from
two main problems: (1) the low onset and low half-wave potentials
compared to commercial Pt/C catalysts; (2) the high yield of H2O2,
i.e. the small electron transfer number and thus low efficiency of
ORR. Herein, we report novel non-precious metal ORR catalysts of x
%Fe/IRMOF-3-900 by using Fe/IRMOF-3 as precursor. The results
demonstrate that the 1%Fe/IRMOF-3-900 exhibits superior activity
comparable to other MOF derived noble metal free catalysts
reported so far, and could yield an electron transfer number as high
as 3.9 with an onset potential of 1.02 V vs. RHE in alkaline medium.
2. Experimental
2.1. Chemicals
2-Aminoterephthalic acid (HO2C-C6H3NH2-CO2H, NH2-BDC,
>99%), commercial Pt/C (20 wt%) and Nafion monomer solution
(5 wt%) were bought from Alfa Aesar. Sodium hydroxide (NaOH,
98%) was purchased from Sigma Aldrich. Zinc nitrate hexahydrate
(Zn(NO3)26H2O, 99%), iron nitrate nonahydrate (Fe(NO3)39H2O,
98.5%), N,N-dimethylformamide (DMF, HCON(CH3)2, 99.5%),
ethanol (CH3COOH, 99.7%), ammonium ferric sulfate dodecahy-
drate (NH4Fe(SO4)212H2O, 99%), sulfosalicylic acid (HO3SC6H3-2-
(OH)CO2H2H2O, 99%), ammonium chloride (NH4Cl, 99.5%) and
sodium hydroxide (NaOH, 96%) were purchased from Sinopharm
chemical reagent Co. Ltd. Sulfuric acid (H2SO4, 98%), nitric acid
(HNO3, 69.2%) and ammonium hydroxide (NH3H2O, 28%) were
purchased from Beijing Chemical Works. Nitrogen (N2, 99.999%)
and oxygen(O2, 99.999%) were provided by Beijing AP BAIF Gases
Industry Co, Ltd. NH3-NH4Cl buffer (pH 10) was prepared by NH4Cl
and NH3H2O. All chemical materials in synthesis were analytical
regents, except otherwise specified, and used without further
purification. Millipore water (Milli-Q) was used for the synthesis of
materials. All solutions were prepared in calibrated apparatus at
25
C.
2.2. Preparation of x%Fe/IRMOF-3 precursors
x%Fe/IRMOF-3 precursors were synthesized by adopting the
same route as the preparation of IRMOF-3 reported in literature
[41], excepting that different amounts of Fe(NO3)39H2O were
added into the IRMOF-3 synthetic solution that was formed by
dissolving Zn(NO3)26H2O (35.2 mmol, 10.470 g) and NH2-BDC
(11.2 mmol, 2.130 g) in 280 mL DMF and stirred for 0.5 h at room
temperature in air. The content of doped Fe(NO3)39H2O was 1%
(0.352 mmol, 0.142 g), 5% (1.76 mmol, 0.711 g) and 10% (3.52 mmol,
1.422 g), denoted as 1% Fe/IRMOF-3, 5% Fe/IRMOF-3 and 10% Fe/
IRMOF-3, respectively. The solution was then transferred to a
500 mL teflon-lined autoclave, sealed and kept at 105
C for 18 h.
The resulting brown solid was collected by centrifugation and
washed twice with ethanol, and was finally dried in vacuum at
80
C for 24 h to produce red powders.
2.3. Preparation of x%Fe/IRMOF-3-900 ORR catalysts
The x%Fe/IRMOF-3-900 ORR catalysts were obtained by
annealing the x%Fe/IRMOF-3 precursor under following condi-
tions: A quartzboat (3 cm diameter, 10 cm length) containing the
above-mentioned x%Fe/IRMOF-3 precursor was placed inside a
tube furnace. The tube was purged with nitrogen (N2) for 90 min
before heat treatment. The precursors were annealed at 900
C for
2 h at a heating rate of 10
C min1 under N2 flow with a flowing
rate of 30 mL min1. The heat-treated sample was then pre-leached
in 0.5 M H2SO4 at 85
C for 9 hours to remove unstable and inactive
species from the materials, and then thoroughly washed in
Millipore water and freeze-drying. Finally, the noble-metal free
ORR catalysts were obtained and denoted as x%Fe/IRMOF-3-900.
2.4. Characterization
Characterization of powder X-ray diffraction (XRD) was carried
out on a Brüker D8 Advanced diffract meter under conditions of
40 kV and 40 mA for CuKa (l=0.15406 nm), with a scan range
between 560
at a speed of 5
min1 in 2u. The morphology and
structure of the samples were further analyzed using FEI Quanta
200F field emission scanning electron microscope (SEM) and JEM-
2100F high-resolution transmission electron microscopy (TEM).
The surface area were measured by using nitrogen adsorption-
desorption isotherms on a Micromeritics ASAP 2020 system (USA)
at 77 K. The specific surface area was determined through
Brunauer-Emmett-Teller (BET) method. The Raman spectra of
the samples were recorded on inVia Reflex in Renishaw instrument
under argon ion laser with an excitation wavelength of 532 nm.
X-ray photoelectron spectroscopy (XPS) was carried out using a
Qtac-100 LEISS-XPS instrument, using monochromatic Al Ka
radiation (1486.6 eV), and all binding energies were referenced
to the C1s peak at 284.6 eV.
2.5. The determination of iron content of samples
The sulfosalicylic spectrophotometric method was always used
for the determination of trace Fe3+ ion [42]. For the preparation of x
%Fe/IRMOF-3 solution, 10 mg of x%Fe/IRMOF-3 were added to
0.5 mL of concentrated nitric acid to be dissolved followed by
adding sodium hydroxide to adjust the pH value to 10 and this
solution was diluted to 50 mL. Subsequently, 1 mL of 0.2 M HNO3,
0.25 M sulfosalicylic acid and NH3/NH4Cl buffer (pH 10) were
added to 2 mL of the as-prepared x%Fe/IRMOF-3 solution, keeping
undisturbed for one hour. Finally, the detection of absorption peaks
was carried out by UV–vis spectrophotometer. The absorbance at
the maximum absorption wavelength was recorded and Fe3+
content in the sample could be calculated by standard work curve
of Fe3+ ion. For the preparation of x%Fe/IRMOF-3-900 solution, x%
Fe/IRMOF-3-900 was heat-treated in a muffle furnace at 600
C for
6 h in the air. After that, the obtained red brown product was
dissolved in 2 mL concentrated nitric acid, then the same
procedure was performed for preparing x%Fe/IRMOF-3 solution.
2.6. Electrochemical measurements
Electrochemical studies were carried out in a standard three-
electrode cell connected to a CHI-760D bipotentiostat (CH Instru-
ments, Inc., China) at room temperature. Graphite rod was used as
counter electrode to avoid any potential contamination of a non-
precious metal catalyst (NPMC) by Pt foil. Hg/HgO was used as a
reference electrode, and all results were calibrated with respect to
reversible hydrogen electrode (RHE). In our measurements, E
(RHE) = E(Hg/HgO) + 0.918 V. All the potentials reported in our
work are against RHE.
A rotating ring disk electrode (RRDE) consists of a Pt ring
(5.52 mm inner-diameter and 7.16 mm outer-diameter) and a
glassy carbon disk (5.0 mm diameter), which served as substrate of
working electrode. The RRDE measurements were conducted by
using linear sweep voltammetry (LSV) in the potential range from
 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61
0.4 to 1.1 V at rotating speed of 900 rpm and scan rate of 10 mV s1
in an O2-saturated 0.1 M NaOH solution at room temperature.
To prepare the working electrode, a homogeneous catalyst ink
was made by mixing of 6.0 mg x%Fe/IRMOF-3-900 ORR catalyst,
50 mLNafion solution (5 wt%, Alfa Aesar) and 0.95 mL
water–ethanol solution with volume ratio of 1:1, and then putting
into a sonication bath for 1 hour.The catalyst loading on the glassy
carbon disk of the RRDE was 1.0 mg cm2.
The hydrogen peroxide yield (H2O2, %) and electron transfer
numbers (n) in the ORR were also calculated from RRDE
experimental data according to the following Eqs. (1) and (2),
respectively
200Iring =N
H2 O2 ð%Þ ¼
Iring =N þ Idisk
4Idisk
n¼
Iring =N þ Idisk
Where, Idisk and Iring stand for the disk and ring current,
respectively, and N is the ring collection efficiency. The N was
determined to be 0.386 in a solution of 5 mM K4Fe(CN)6 + 1 M Sr
(NO3)2.
3. Results and discussion
Fig. 1A represented the synthesis process of x%Fe/IRMOF-3-900.
The morphologies of the samples were characterized by scanning
electron microscope (SEM). The pure IRMOF-3 crystals of well-
defined cubic morphology were illustrated in Fig. 1B. After adding
Fe3+ ions, it was seen that only 1% Fe3+ dopant could maintain the
well-defined cubic morphology of the IRMOF-3 (Fig. 1C). The Fe3+
could replace Zn2+ with the low loadings of Fe while some parts of
Fe3+may be also distributed into the surface or pore size of IRMOF-
3 with the present characterizations. We did parallel experiment
by using FeCl2 instead of Fe(NO3)3. We found that the solution will
quickly change the color from green to brown due to the nitrate in
the solution oxide Fe2+ to Fe3+. Thus, there was Fe3+ iron in the x%
Fe/IRMOF-3 samples. The morphology of x%Fe/IRMOF-3 changed
from cube to rod when the contents of Fe3+ dopant increased from
1% to 10% as shown in Fig. S1 in the Supporting Information. It was
Fig. 1. (A) Schematic presentation of synthesis process of the Fe/IRMOF-3-900 catalysts; SEM images of (B) IRMOF-3, (C) 1%Fe/IRMOF-3 precursor.
55
shown that with higher contents of Fe3+ dopant the cubic
morphology had been distorted.
Sphere particles formed after pyrolysis of the 1%Fe/IRMOF-3 at
900
C (Fig. 2A and Fig. S2A), with a much small size about 10 mm in
comparison with the size of the cubic 1%Fe/IRMOF-3 (150 mm) as
indicated in Fig. 1C. There was irregular morphology with 5% and
10% Fe3+ dopant (Fig. S2B and Fig. S2C). The dramatic decrease in
particle size was due to Zn atoms evaporation from MOFs structure
during the high temperature pyrolysis at 900
C. Since the boiling
point of the Zn metal was 908
C, Zn nanoparticles would be
emitted completely under N2 flowing [43]. The porous structure on
surface of the 1%Fe/IRMOF-3-900 was observed by the transmis-
sion electron microscopy (TEM) characterization (Fig. 2B). It is
ð1Þ considered that nanoscale pores have active effect for the ORR
[35,44,45]. We could see that many nanoparticles were deposited
on the carbon structure (Fig. 2C). The high-resolution TEM
(HRTEM) image in Fig. 2D revealed Fe3C nanoparticles were
encapsulated within the graphitic carbon layers. The lattice fringes
ð2Þ
of about 0.21 nmand 0.34 nm can match well with the (211) plane
of Fe3C and the (002) plane of graphite carbon, respectively.
According to the above data, it can be concluded that the structure
with Fe3C core and graphite carbon shell is formed. It has been
demonstrated that this kind of core/shell structures often possess a
higher electrocatalytic activity owing to the coexistence of
graphite carbon with the rapid electron transport and Fe3C
nanoparticles with better catalytic activity [37,46,47]. The struc-
ture of 5%Fe/IRMOF-3-900 and 10%Fe/IRMOF-3 were similar to 1%
Fe/IRMOF-3-900 (Fig. S3).
Fig. 3A compared X-ray diffraction (XRD) patterns of IRMOF-
3 and as-prepared x%Fe/IRMOF-3 precursors. From the XRD data, it
could be seen that as-prepared x%Fe/IRMOF-3 precursors showed
characteristic angles of 6.9
, 9.7
and 13.8
, corresponding to the
IRMOF-3. It was confirmed that the crystal structure of IRMOF-
3 could be maintained in all the three precursors even adding the
Fe ions, which may be attributed to a small quantity of Fe doping
[48,49]. The actual iron content in these three samples were 0.6 wt
% for 1%Fe/IRMOF-3, 1.0 wt% for 5%Fe/IRMOF-3 and 2.1 wt% for 10%
Fe/IRMOF-3by using the sulfosalicylic spectrophotometric method
[42] (Table 1). It should be pointed out that the intensities of
diffraction peaks at 2u = 6.9
and 9.7
have been changed in 5%Fe/
IRMOF-3 and 10%Fe/IRMOF-3 samples compared with IRMOF-3,
56 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61

Fig. 2. (A) SEM images of 1%Fe/IRMOF-3-900 catalyst; (B and C) TEM images of 1%Fe/IRMOF-3-900 catalysts, (D) HRTEM images of 1%Fe/IRMOF-3-900 catalysts.

which could be induced by Fe ions. Fig. 3B illustrated XRD patterns
of the three samples after annealing. The diffraction peak at 26.1

appeared in all XRD patterns is ascribed to (002) plane of graphitic
carbon, and the peaks at 43.8
and 50.8
could be assigned to
cementite (Fe3C) and magnetite (Fe3O4), respectively [37,38].
Typically, the strongest Fe3C peak emerged in the 10%Fe/IRMOF-
3 might reveal the highest content of Fe3C in contrast to other two
samples. It should be noted that the peak at 46.1
observed
especially in the XRD pattern of 10%Fe/IRMOF-3-900 could be
assigned to metallic Fe, indicating that the high temperature
yielded carbon had reduced excess iron compound to iron. Fig. 3C
displayed nitrogen adsorption–desorption isotherms of as-pre-
pared x%Fe/IRMOF-3-900 catalysts. All samples feature Type IV
isotherm and H1 hysteresis loop, according to the IUPAC

Fig. 3. (A) XRD patterns of as-prepared IRMOF-3 and Fe/IRMOF-3; (B) XRD patterns of as-prepared Fe/IRMOF-3-900; (C) Nitrogen adsorption–desorption isotherms of as-
prepared IRMOF-3 and Fe/IRMOF-3-900; (D) Pore size distribution of as-prepared IRMOF-3 and Fe/IRMOF-3-900.
 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61 57

Table 1
Carbon, nitrogen, oxygen and Fe contents and relative ratio of N species.

Catalyst Bulk contenta Surface contentb Ratio of different nitrogen speciesb

Fe/wt% C/at% N/at% O/at% Fe/at% Fe/wt% Grapitic-N Pyrrolic-N Pyridinic-N

1%Fe/IRMOF-3 0.6 – – – – – – – –
5%Fe/IRMOF-3 1.0    – – – – –
10%Fe/IRMOF-3 2.1    – – – – –
1%Fe/IRMOF-3-900 2.0 68.1 11.5 20.1 0.3 1.3 83.7 1.2 15.1
5%Fe/IRMOF-3-900 5.1 72.9 8.4 17.6 1.2 4.6 83.7 2.2 14.1
10%Fe/IRMOF-3-900 12.3 75.7 8.1 14.2 2 8.2 83.1 5.1 11.8
IRMOF-3-900  89.6 3.3 7.1 – – 32.9 40.4 26.7
a
Fe content (wt%) analyzed by sulfosalicylic spectrophotometric method.
b
Determined from XPS analysis.

classification, indicating the presence of relative uniform meso-
pores with narrow distribution in all as-prepared catalysts, which
was further demonstrated by the pore size distribution of these
materials (Fig. 3D). These catalysts possessed a narrow size
distribution of 3.9 nm by using the Barrett-Joyner-Halenda
method. Table 2 showed the BET surface areas and and total pore
volume of the products of IRMOF-3-900 (920 m2 g1 and
1.30 cm3g1), 1%Fe/IRMOF-3-900 (836 m2 g1 and 1.28 cm3g1),
5%Fe/IRMOF-3-900 (680 m2 g1and 1.11 cm3g1) and 10%Fe/
IRMOF-3-900 (539 m2 g1and 0.89 cm3g1). Clearly, IRMOF-3-
900 held the highest surface area and largest total porevolume
among all the samples. It could be thought that the more added
iron, the more generated Fe3C nanoparticles, thus excess Fe3C
would block the channel and decrease the BET surface area [50].
Specifically, the BET surface area of the 1%Fe/IRMOF-3-900 is
comparable to other MOF-derived catalysts so far
[23,35,36,38,51,52]. The porous carbon sphere structure could
help toincrease the BET surface area, and it could thus expect a high
ORR activity for the IRMOF-3 derived electrocatalysts.
To investigate the carbon structure, the Raman spectra was
performed. It indicated a well-defined D band at 1340 cm1 and G
band at 1590 cm1 demonstrated by Fig. 4A which associated with
disorder carbon and graphitic carbon, respectively [12,53]. The
ratio of D/G illustrated the degree of graphitization during the
pyrolysis. The value of 1%Fe/IRMOF-3-900 was determined as 1.03,
which exhibited the lowest value among these three samples
indicating the highest degree of graphitic crystallinity which
would result a positive effect on electrochemical activity [18].
Moreover, it should be noted that the more doping of Fe3+ ions
would decrease the degree of graphitic carbon in the samples.
By using X-ray photoelectron spectroscopy (XPS) to analyse the
nitrogen-bonding configurations and elemental compositions in
the samples were demonstrated in Fig. 4B, revealing that these
three catalysts were predominantly composed of carbon, nitrogen
and oxygen. The detailed information was summarized in Table 1.
The content of iron in the 1%Fe/IRMOF-3-900 sample tested by XPS
is only 0.3 at%, however, it was hard to detect the absorption peaks
of iron in the 1%Fe/IRMOF-3-900 sample (Fig. 4B and Fig. S3),
which meant it was rather low on the surface of these catalysts. The
bulk contents of iron were also tested using the sulfosalicylic
spectrophotometric method as listed in Table 1. It could be seen
that the contents of these three sample were 2.0 wt%, 5.1 wt% and
Table 2
BET surface area and total pore volume.
Catalyst SBET/m2g1 Vtotal/cm3g1
IRMOF-3-900 920 1.30
1%Fe/IRMOF-3-900 836 1.28
5%Fe/IRMOF-3-900 680 1.11
10%Fe/IRMOF-3-900 539 0.89
12.3 wt%, which were slightly higher than those of 1.3 wt%, 4.6 wt%
and 8.2 wt%, respectively, determined by XPS analysis. These
results demonstrated that the iron species were distributed
uniformly in the surface and the porous channel of the bulk.
Fig. 4C-F depicted the high-resolution N1s XPS spectra of the 1%Fe/
IRMOF-3-900, 5%Fe/IRMOF-3-900, 10%Fe/IRMOF-3-900 catalysts
and IRMOF-3-900. The deconvolution of the broad peak yielded
three classic type peaks near 398.6, 400.2 and 401.2 eV, which are
associated with N-containing functional groups of pyridinic-N,
pyrrolic-N and graphitic-N in the Fe/IRMOF-3 derived catalysts,
respectively [12,16,54]. Table 1 showed the N content of the
products of 1%Fe/IRMOF-3-900 (11.5 at.%), 5%Fe/IRMOF-3-900
(8.4 at.%), 10%Fe/IRMOF-3-900 (8.1 at.%) and IRMOF-3-900 (3.3 at.
%). It was worth noting that the N content ofIRMOF-3-900was
much lower than Fe/IRMOF-3-900 bsamples.It would be deduced
that the doped Fe amounts might affect the N contents in the
resulting carbon materials, which also directly affect the catalytic
performance.The ratio of different N-containing functional groups
in each sample was listed in Table 1. It was considered that N atoms
were very important to form the active site of Fe-based ORR
catalysts [45,55], and graphitic-N and pyridinic-Nhave been
reported to play a crucial role in ORR [54,56–58] which might
explain the high ORR activity of the 1%Fe/IRMOF-3-900 catalyst. In
all the Fe/IRMOF-3-900samples, graphitic-N was the dominated
species and almost the same (about 83%), while the pyridinic-N has
decreased slightly from 15.1%, 14.1% to 11.8% with increasing Fe
content. More importantly, thepyrrolic-N had increased from 1.2%,
2.2% to 5.1% along with the increase in Fe content. The highest
content of pyridinic-N and lowest content of pyrrolic-N in the 1%
Fe/IRMOF-3-900 suggest that it will hold the highest ORR activity
among the three IRMOF-3 derived catalysts. Compared to the Fe/
IRMOF-3-900 samples, pyrrolic-N in the IRMOF-3-900sample
reached 40.4%, which has a negative effect on the electrocatalytic
activity, and graphitic-N was only 32.9%, indicating the doped Fe
ion would produce more graphitic-N species which might affect
the catalytic performance.
The ORR activity of x%Fe/IRMOF-3-900 catalysts were shown in
Fig. 5. For comparison, curves recorded on commercial 20% Pt/C
commercial catalyst were also displayed. From the linear sweep
voltammograms (LSVs) of different catalysts recorded with a
rotation rate of 900 rpm shown in Fig. 5A, we observed that 1%Fe/
IRMOF-3-900 exhibited the highest ORR activity among the x%Fe/
IRMOF-3-900 catalysts indicating that the percentage of iron was
not the bigger the better. The limiting current density measured on
the 1%Fe/IRMOF-3-900 was 4.6 mA cm2 that was even bigger than
the value measured on commercial 20% Pt/C under same
conditions, although the half-wave potential (0.88 V) was slightly
negative than on commercial 20% Pt/C (0.90 V). Furthermore, the
1%Fe/IRMOF-3-900 catalyst in alkaline medium showed more
positive onset potential and much higher current density than
manyMOF-derived ORR electrocatalysts reported up to date
58 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61
Fig. 4. The structure characterization of as-prepared four products: (A) Raman spectra, (B) XPS spectra. High-resolution N1s XPS spectra of the four products: (C) 1%Fe/
IRMOF-3-900, (D) 5%Fe/IRMOF-3-900, (E) 10%Fe/IRMOF-3-900, (F) Fe/IRMOF-3-900.
(Table S1). The high limiting current on 1%Fe/IRMOF-3-900 might
be attributed to its mesoporous structure, which could increase the
density of active sites for ORR.
The high activity of the 1%Fe/IRMOF-3-900 catalyst was also
confirmed by the H2O2 yield (Fig. 5B) and the electron transfer
number (n) involved in the electrode reaction (see insert Fig. 5B) as
calculated from the ring currents (Fig. 5A). The n determined on the
1%Fe/IRMOF-3-900 was 3.90 at 0.40 V, which was significantly
higher than on IRMOF-3-900 (3.42), 5%Fe/IRMOF-3-900 (3.62) and
10%Fe/IRMOF-3-900 (3.51). Such value of 3.90 was also comparable
to those reported for MOFs-derived catalysts so far (Table S1)
[31,33,34,36,37], and suggested that the ORR on the 1%Fe/IRMOF-
3-900 catalyst occurs mainly in a four-electron transfer process.
It should be also noted that the 1%Fe/IRMOF-3-900 resulted in a
much more positive ORR onset potential (1.02 V) than IRMOF-3-
900 (0.96 V), 5%Fe/IRMOF-3-900 (0.96 V) and 10%Fe/IRMOF-3-900
(0.96 V), even comparable with the commercial 20% Pt/C (1.04 V)
(Fig. 5C). Remarkably, the kinetic current density JK at 0.88 V on 1%
Fe/IRMOF-3-900 (4.5 mA cm2) was much bigger than on
5%Fe/IRMOF-3-900 (0.9 mA cm2) and 10%Fe/IRMOF-3-900
(0.56 mA cm2) at the same loading (Fig. 5D), evaluated according
to the equation of 1/J = 1/JL + 1/JK, whereas J is the current density
measured at 0.88 V and JL is the limiting current density. The
excellent electrocatalytic performances of the 1%Fe/IRMOF-3-
900 could be ascribed mainly to two origins. Firstly, the x%Fe/
IRMOF-3-900 derived from carbonation of IRMOF-3 possessed
much high BET surface and mesoporous feature which served
larger area for the active site loading. As mentioned above, the 1%
Fe/IRMOF-3-900 exhibited the highest BET surface and largest total
pore volume among three samples and less Fe3C nanoparticles,
which might block the tunnel and affect the catalytic activity (Fig. 2
and Table 1). Secondly, it has been known that the structure with
Fe3C core and N-containing carbon shell would have higher
catalytic activity [37,46,47]. Due to more graphitic-N and pyridinic-
Nformed, the catalyst would show higher activity [54,56,57]. The
IRMOF-3 cubes would help to generate the graphitic-N and
 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61 59

Fig. 5. (A) RRDE LSVs for ORR on x%Fe/IRMOF-3-900 catalysts, measured in O2-saturated 0.1 M NaOH. Catalyst loading: 1.0 mg cm2; Scan rate: 10 mV s1; Rotating speed:
900 rpm. As a comparison, a curve recorded on commercial 20% Pt/C commercial catalyst is also displayed. (B) The peroxide yield obtained from RRDE curves for the x%Fe/
IRMOF-3-900, the insert shows the electron transfer number (n). (C) Comparison of the corresponding onset potentials and half-wave potentials measured on IRMOF-3-900,
1%Fe/IRMOF-3-900, 5%Fe/IRMOF-3-900, 10%Fe/IRMOF-3-900 and commercial 20% Pt/C. (D) Comparison of specific activity (JK) at 0.88 and 0.90 V for x%Fe/IRMOF-3-900 and
commercial 20% Pt/C.

pyridinic-N which hold a higher electrocatalytic activity. Especial-
ly, the 1%Fe/IRMOF-3-900 also owned the highest ratio of
graphitic-N and pyridinic-Nwhich promoted the activity.
In addition to the activity, we compared the results of 10000 s
stability for 1%Fe/IRMOF-3-900 with commercial commercial 20%
Pt/C by chronoamperometry at a constant voltage of 0.8 V in O2-
saturated 0.1 M NaOH solution. As shown in Fig. 6A, the 1%Fe/
IRMOF-3-900 maintained a high relative current of 91.5% after
10000 s, which clearly demonstrated the 1%Fe/IRMOF-3-900 was a
much enhanced stability of catalyst for ORR. For commercial 20%
Pt/C catalyst, only 65.0% of the initial catalytic current was
remained in the same testing conditions, indicating the poor
stability of the Pt/C electrode. We also measured the electro-
catalytic selectivity of 1%Fe/IRMOF-3-900 and commercial 20% Pt/
C against the electrooxidation of methanol. No noticeable change
was observed in the oxygen reduction current for 1%Fe/IRMOF-3-
900 while an obvious change was detected for the commercial 20%
Pt/C catalyst after adding the methanol (insert in Fig. 6A). These
results demonstrated that the 1%Fe/IRMOF-3-900 electrode rep-
resented better duration stability and high selectivity for ORR than
commercial 20% Pt/C electrode for ORR in an alkaline medium. The
poor stability of Pt/C can be attributed to two reasons for the: (i)
Increase of Pt oxides. (ii) The surfaces become roughened due to
the formation of Pt oxides [59]. Although, the electrolyte solution
used in the reaction is alkaline, the lower concentration and
shorter reaction time make dissolution rate of glass slow. Thus, the
dissolution of glass is not the main reason for the poor stability of
Pt/C over 10000 s.
The 1%Fe/IRMOF-3-900 catalyst also showed tremendously
longtime stability. For example, RRDE measurements showed no
obvious decrease of the ORR voltammetric currents after
5000 cycles. As demonstrated by Fig. 6B, the 1%Fe/IRMOF-3-

Fig. 6. (A) Current-time chronoamperometric durability test (relative decrease of the current with time)of 1%Fe/IRMOF-3-900 and commercial 20% Pt/C at +0.80 V vs RHE in
O2-saturated 0.1 M NaOH solution. The rotation speed was 900 rpm. Inset shows the chronoamperometric curves at +0.80 V in an O2-saturated aqueous solution of 0.1 M
NaOH + 0.5 M methanol. The rotation speed was also 900 rpm. (B) LSV curves before and after the electrode was stored in the electrolyte solution for 5000 cycles.
60 H. Sun et al. / Electrochimica Acta 205 (2016) 53–61
900 catalyst (black curves) only exhibited about 7 mV down-shift
(black curves) in the half-wave potential. However, the commercial
20% Pt/C catalyst (red curves) showed about 44 mV down-shift. The
much enhanced durability of 1%Fe/IRMOF-3-900 might be
attributed to the 3D structure of the mesoporous carbon sphere
promoted the transport of electrolyte ions, oxygen, and water.
Furthermore, the mesoporous structure of the catalyst might also
stabilize the active sites in the catalyst.
4. Conclusions
In the current communication, we report a novel and high
active non-precious metal ORR catalyst of 1%Fe/IRMOF-3-900 de-
rived from IRMOF-3. The results demonstrated that this 1%Fe/
IRMOF-3-900 can yield limiting current density of 4.6 mA cm2,
kinetic current density of 4.5 mA cm2 at 0.88 V, half wave
potential of 0.88 V and onset potential of 1.02 V, demonstrating
the superior ORR activity for many MOF-derived catalysts reported
so far, also, presented much high stability, illustrating that the as-
prepared 1%Fe/IRMOF-3-900 catalyst is very promising for ORR in
an alkaline solution with competitive performance to those of Fe/
N/C non-precious metal ORR catalysts. The excellent ORR perform-
ances of the 1%Fe/IRMOF-3-900 catalyst have been attributed to
the well-defined cubic morphology of the IRMOF-3 by 1% Fe
doping, which could provide high surface area and large total
porevolume, high N content and high density of electrocatalytic
active N-species. The study has thrown a new insight in the
exploration of high active non-precious ORR catalyst for fuel cell
applications.
Acknowledgements
The authors acknowledge the financial supports from the NSFC
(Nos. 21173269,91127040, 21573286), the Ministry of Science and
Technology of China (No. 2011BAK15B05), Science Foundation of
China University of Petroleum, Beijing (No.2462014YJRC003) and
State key laboratory of physical chemistry of solid surfaces, Xiamen
University (No. 201406), and specialized Research Fund for the
Doctoral Program of Higher Education (20130007110003).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.electacta.2016.
04.037.
Supporting information is available for SEM images of 1% Fe/
IRMOF-3, 5% Fe/IRMOF-3, 10% Fe/IRMOF-3, 5% Fe/IRMOF-3-
900 and 10% Fe/IRMOF-3-900, TEM images of 5% Fe/IRMOF-3-
900 and 10% Fe/IRMOF-3-900, XPS spectra of Feof as-prepared
three products,summary of BET surface area, the electron transfer
number, onset potential, half-wave potential and limiting current
density for some other Fe/N/C catalysts and MOF-derived electro-
catalysts reported recently.
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