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Bio-inspired FeN5 moieties anchored on a three-

Cite this: J. Mater. Chem. A, 2018, 6,
dimensional graphene aerogel to improve oxygen
18488 reduction catalytic performance†
Jianshe Huang,a Qingqing Lu,ab Xiao Maab and Xiurong Yang *a

Transition-metal-coordinated nitrogen-doped carbon (M-N-C) materials have been regarded as the most
promising oxygen reduction reaction (ORR) catalysts. However, the ambiguity of the exact active sites
seriously hampered the understanding of the structure–performance correlation and the further activity
improvement of M-N-C catalysts. Herein, we designed and synthesized a three-dimensional graphene
aerogel (GA) supported FeN5 composite with an explicit five-coordinated Fe–N bond. In this composite,
pyridine groups were covalently grafted on the graphene surface to anchor iron phthalocyanine (FePc)
molecules (FePc/AP-GA). The ORR performance of this catalyst showed a half-wave potential of
0.035 V
(vs. Hg/HgO) in an alkaline electrolyte, which surpassed those of the benchmark Pt/C and most pyrolyzed
or non-pyrolyzed nonprecious metal catalysts. Additionally, the FePc/AP-GA composite also exhibited
a high kinetic current density of 20.01 mA cm
2 at
0.1 V, good durability, and high tolerance to methanol
poisoning effects. X-ray absorption spectroscopy results revealed that the five-coordinated Fe–N bond
Received 5th July 2018
Accepted 4th September 2018
dominated in the FePc/AP-GA composite with an elongated bond length. This geometric and electronic
structure of the iron atom in the FePc/AP-GA composite is believed to facilitate the adsorption of O2 and
DOI: 10.1039/c8ta06455e
intermediates and thus to enhance ORR activity and durability. Our results provided a promising target
rsc.li/materials-a active site for the rational design of highly efficient M-N-C catalysts for fuel cells and metal–air batteries.

and heteroatom-doped carbon materials.3,6–13 Among these

1. Introduction
The sluggish kinetics of the cathodic oxygen reduction reaction
(ORR) is one of the major limiting factors for developing cost-
effective fuel cells and metal–air batteries.1–3 The Pt nano-
particles supported on carbon black (Pt/C) catalyst has long
been regarded as the best electrocatalyst for the ORR,4 although
Pt nanoparticles are prone to dissolution, aggregation, and
poisoning under fuel cell conditions. Furthermore, the high
cost and scarcity of Pt have limited its large-scale application in
fuel cells, especially for it accounts for over 55% of the cost of
a fuel-cell stack.5 Therefore, numerous efforts have been dedi-
cated to reducing the Pt consumption or completely
substituting for Pt in ORR catalysts. One of the efficient strat-
egies is to develop earth-abundant substitutes for Pt catalysts.
To date, various nonprecious metal catalysts (NPMCs) have
been widely investigated, including transition metal carbides,
nitrides, oxides, chalcogenides, and phosphides, as well as
transition-metal-coordinated nitrogen-doped carbon (M-N-C)
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, Changchun, 130022, Jilin, China. E-mail:
xryang@ciac.ac.cn
b
University of Chinese Academy of Sciences, Beijing, 100049, China
† Electronic supplementary information (ESI) available.
10.1039/c8ta06455e
materials, M-N-C catalysts have been regarded as the most
promising class of NPMCs for the ORR.14 In particular, most of
the M-N-C catalysts exhibit an ORR activity comparable to or
even better than that of Pt/C in alkaline solution, but their
performance is inferior to that of Pt/C in acid medium,2,6
demonstrating the great promising prospects of M-N-C catalysts
in anion exchange membrane fuel cells.15,16 For M-N-C catalysts
free of metal-based crystalline phases, it is commonly accepted
that the MNx structures are the most active catalytic sites, but
the exact active site structure has not yet been explicitly iden-
tied.17 In previous reports, both ex situ and in situ character-
izations using microscopic and spectroscopic techniques have
identied the FeN4 structure as the active site for pyrolyzed Fe–
N–C catalysts.18–22 However, the ve-coordinated FeNx sites with
an axial ligand were also theoretically and experimentally
proved to signicantly promote the ORR activity.23–30 Addition-
ally, FeN6 31,32 and FeN2 33 congurations were also regarded as
the active centers in some specic Fe–N–C catalysts. Due to the
complexity of the formed moieties aer the heat-treatment
process, it is very difficult to identify the exact active sites of
this type of catalyst. Therefore, to prepare materials containing
explicit catalytic sites and to correlate the structure–perfor-
mance relationship would be signicantly important for the
See DOI:
rational design of M-N-C catalysts.

18488 | J. Mater. Chem. A, 2018, 6, 18488–18497 This journal is © The Royal Society of Chemistry 2018

Paper
Reminiscent of biological systems, heme-based enzymes
catalyze diverse important metabolic transformations that
require the binding and activation of dioxygen. In these
enzymes, the central iron ion not only coordinates with four
nitrogen atoms on the porphyrin cycle but also usually has an
axial ligand (histidine, cystine, etc.).34 The axial ligand can
provide an extra electron “push” effect, thus controlling the
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heme redox potential and stability of the reaction intermedi-
ates, further modulating the O–O bond cleavage reactivity.34,35 A
prime example is cytochrome c oxidase (CcO), which catalyzes
the O2 reduction reaction to power its proton-pumping func-
tion.36 The catalytic site of CcO is a binuclear heme–copper
center, where the high spin heme iron coordinates with ve
nitrogen atoms (FeN5) (Fig. S1†). Inspired by the high efficiency
of these enzymes, numerous attempts have been focused on
developing biomimetic molecular catalysts37 or heterogeneous
catalysts27–29,38,39 with an FeN5 conguration for the ORR. Both
the experimental results and DFT calculations demonstrated
that, compared with FeN4 structures, the axial ligand signi-
cantly changed the geometric and electronic structure of the Fe
center in the FeN5 conguration, resulting in greatly enhanced
ORR performance.27,29 Encouraged by these research studies, we
developed a moderate synthesis approach for three-
dimensional (3D) graphene aerogel (GA) supported FeN5
moieties for the ORR, where pyridine groups were covalently
graed on the graphene surface to anchor iron phthalocyanine
(FePc) molecules (FePc/AP-GA), which mimic the active site of
O2-activating heme-based enzymes. Combined with the large
specic area and excellent conductivity of the GA, this FePc/AP-
GA catalyst showed superior ORR activity and durability
compared to the commercial Pt/C catalyst under alkaline
conditions.
2. Experimental section
2.1 Synthesis of 4-aminopyridine functionalized GO (AP-GO)
Graphene oxide (GO) was prepared from natural graphite akes
(Alfa Aesar) according to a modied Hummers' method.40,41 The
as-prepared GO was ultrasonically dispersed in deionized (DI)
water to form a 2 mg mL
1 homogeneous suspension. Pyridine-
functionalized GO was synthesized by an epoxide ring-opening
reaction between GO and 4-aminopyridine (4-AP).42,43 Briey,
the GO solution (10 mL) was pipetted into a ask, and 4-AP
(0.1 g) was added and stirred for 30 min. Then ammonia solu-
tion (0.2 mL, 28%) was added to the suspension and heated at
90  C for 4 h under vigorous stirring. Aer cooling down to
room temperature, the suspension was centrifuged and washed
with DI water and ethanol to completely remove the residual 4-
AP and bases. The resulting AP-GO was re-dispersed in 10 mL DI
water to form a homogeneous brownish black solution for
subsequent reaction.
2.2 Synthesis of FePc/AP-GA
The FePc/AP-GA composite was prepared by a one-step hydro-
thermal method. FePc loading and the formation of a 3D gra-
phene hydrogel were simultaneously achieved in this process.
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In a typical synthesis, FePc in tetrahydrofuran (1 mL,
2 mg mL
1) and sodium ascorbate aqueous solution (0.5 mL,
1.0 M) were added to the AP-GO dispersion. The resulting
homogeneous mixture was sealed in a Teon-lined autoclave
and maintained at 100  C for 2 h. The autoclave was naturally
cooled to room temperature, and the as-formed graphene
hydrogel was taken out with tweezers and dipped in DI water for
2 days to remove residues and weakly adsorbed FePc. Finally,
the hydrogel was freeze-dried to obtain FePc/AP-GA.
For comparison, reduced graphene aerogel (GA) and AP-GA
were prepared under the same conditions with GO or AP-GO
as the starting material. FePc and AP-GA were also physically
mixed with a ratio of 1 : 10 (m : m), and the mixture was ground
in a mortar for over 20 min. The resulting composite was named
FePc + AP-GA.
2.3 Materials characterization
The material morphology was examined using a eld-emission
scanning electron microscope (PHILIPS XL-30 ESEM) with an
accelerating voltage of 20 kV and a transmission electron
microscope (TEM) equipped with an energy dispersive X-ray
spectrometer (EDS) (JEM-2100F, JEOL, Japan) operating at
200 kV. Fourier transform infrared (FT-IR) spectra were ob-
tained using a VERTEX 70 FT-IR spectrophotometer (Bruker,
Germany). X-ray diffraction (XRD) patterns were acquired on
a D8 ADVANCE diffractometer (Bruker, Germany) with Cu Ka
radiation (l ¼ 1.5418 Å). XPS measurements were performed on
an ESCALABMK II X-ray photoelectron spectrometer using Al Ka
radiation as the excitation source. The binding energies were
calibrated based on the graphite C 1s peak at 284.6 eV. Nitrogen
adsorption/desorption analysis was performed on an Autosorb
iQ Station 2 (Quantachrome, USA) at liquid N2 temperature. The
iron content in the prepared catalysts was determined by
inductively coupled plasma optical emission spectroscopy (ICP-
OES, Thermo Fisher Scientic). Fe K-edge X-ray absorption ne
structure spectra of FePc, Fe2O3, and the as-prepared catalysts
were recorded at the 1W1B station in Beijing Synchrotron
Radiation Facility (BSRF) at 2.5 GeV. Fe foil was used for energy
calibration. The obtained X-ray absorption ne structure spec-
troscopy (XAFS) data were analyzed according to the standard
procedures using the ARTEMIS module implemented in the
IFEFFIT soware package.
2.4 Electrochemical measurements
Electrochemical tests were carried out on a CHI760e electro-
chemical analyzer (Chenhua Instrument, China) by using
a typical three-electrode setup, with a graphite rod as the
counter electrode and a Hg/HgO electrode as the reference
electrode. All the reported potentials are versus the Hg/HgO
reference electrode unless otherwise stated. An AFMSRCE
rotator (Pine Research Instrumentation, USA) was used to
control the rotation speed. All the electrochemical measure-
ments were performed at 25  1  C. A rotating disk electrode
(RDE, glassy carbon, 5 mm OD) and a rotating ring-disk elec-
trode (RRDE, 5.61 mm OD glassy carbon disk, 0.1866 cm2 Pt
ring, 320 mm gap) were used as the substrate electrodes, and the
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Journal of Materials Chemistry A
RRDE collection coefficient at the Pt ring was 0.37. Before use,
the electrode was polished to a mirror nish with alumina
slurry and cleaned by ultrasonication in DI water and acetone.
The Pt ring electrode was activated through cyclic voltammetry
(CV) in 0.5 M H2SO4 solution from
0.2 to 1.3 V (vs. Ag/AgCl) at
a scan rate of 100 mV s
1 for 25 cycles. The catalyst ink was
prepared by ultrasonically dispersing 5.0 mg of the synthesized
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catalyst or commercial 20 wt% Pt/C catalyst (HiSPEC® 3000,
Alfa Aesar) in a solution containing 980 mL ethanol and 20 mL
Naon (5 wt%, Aldrich). The suspension was sonicated for
1 hour to obtain a homogeneous dispersion. A certain volume of
the catalyst ink was dropped onto the glassy carbon disk of the
substrate electrode and dried in air. For the synthesized cata-
lysts, the catalyst loading is 404.0 mg cm
2. For the Pt/C catalyst,
the Pt loading is 20.2 mgPt cm
2. Before the electrochemical
measurements, highly puried N2 or O2 was bubbled into 0.1 M
KOH electrolyte for at least 30 min. A ow of gas was maintained
over the electrolyte during the electrochemical tests. The cata-
lyst lm coated electrode was rst activated by repeated cycling
of the potential between 0.4 V and
0.8 V in N2-saturated 0.1 M
KOH solution for 50 cycles. ORR activity was characterized by
using CV and linear sweep voltammetry (LSV) techniques. The
detailed experimental process, and the calculation of electron
transfer number (n) and kinetic current density (jk) are shown in
the ESI.†
The accelerated stability tests (ASTs) were carried out by
continuous potential cycling in O2-saturated 0.1 M KOH solu-
tion between
0.35 V and 0.15 V with a scan rate of 50 mV s
1.
Aer 6000 cycles, the ORR polarization curves were recorded in
O2-saturated 0.1 M KOH solution. The ORR stability was also
investigated by chronoamperometry at a constant potential of

0.2 V and a rotation rate of 900 rpm. Methanol tolerance tests
were conducted with chronoamperometric measurements in
O2-saturated 0.1 M KOH at
0.3 V and 900 rpm, followed by the
addition of 0.5 M methanol.
3. Results and discussion
The synthesis of FePc/AP-GA composites is schematically illus-
trated in Fig. 1a. In this approach, 4-aminopyridine (4-AP) was
rst covalently anchored onto the graphene oxide (GO) surface
to form 4-AP functionalized GO (AP-GO), through a nucleophilic
ring-opening reaction between the amine group of 4-AP and the
epoxy groups of GO.42,43 The bifunctional linker of 4-AP termi-
nates in the pyridine moiety, which can be used to coordinate
with FePc molecules via a strong coordination bond between
the pyridine group and FePc.44,45 Therefore, the axial coordi-
nated FePc composites mimic the active sites of natural heme-
based enzymes. Cao et al.27 and Wei et al.28 synthesized similar
pyridine and imidazole group graed carbon nanotubes using
a diazonium reaction, which were subsequently used to anchor
FePc and iron porphyrin molecules, respectively. Recently,
similar pyridine-containing molecules were also used as axial
ligands to tune the ORR activity of FePc.46,47 Compared with
their methods, the present synthetic process is more moderate
without harsh reaction conditions. The reduction of GO and the
formation of a 3D graphene hydrogel and FePc/AP complexes
18490 | J. Mater. Chem. A, 2018, 6, 18488–18497
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were accomplished in a low temperature hydrothermal reaction
via a reduction induced solution self-assembly process.48
Finally, the hydrogel was freeze-dried to obtain FePc/AP-GA
composites.
The morphology of the as-prepared FePc/AP-GA composites
was investigated by electron microscopy. The SEM image reveals
a 3D hierarchical porous graphene framework with the pore size
ranging from hundreds of nanometers to several micrometers
(Fig. 1b). The graphene sheets in the 3D framework are highly
interconnected, which prevents them from restacking. Even
aer long-period ultrasonic dispersion, the graphene sheets
still interlocked together and maintained highly corrugated
structures (Fig. 1c). Different from previously reported FePc/
graphene materials,49–52 no FePc aggregate or particle could be
observed in our material, indicating that FePc molecules are
highly dispersed on the graphene sheets. The unique structure
of the GA not only greatly enlarged the surface area but also
facilitated the decoration of FePc molecules on both sides of the
graphene sheets.53 Nitrogen adsorption–desorption analysis
revealed that the FePc/AP-GA showed a Brunauer–Emmett–
Teller (BET) surface area of 719.4 m2 g
1 and a pore volume of
1.033 cm3 g
1, both of which are higher than those of GO
(135.8 m2 g
1 and 0.485 cm3 g
1) (Fig. S2†). Barrett–Joyner–
Halenda (BJH) pore size distribution centered in the range of
2–10 nm, which was ascribed to the mesopores formed between
the neighboring stacked graphene nanosheets. The porous
structure and high surface area were expected to allow the
reactant/product to transfer to and from the active sites, and
then to enhance the catalytic performance.
The functional groups present in the starting materials and
the resulting products were initially investigated by Fourier
transform infrared (FTIR) spectroscopy (Fig. 2). Strong vibration
peaks of GO appear at 1057, 1227, 1622 and 1730 cm
1, which
correspond to the stretching vibrations of C–O–C (epoxy group),
C–OH, skeletal ring, and C]O species, respectively.38 For 4-AP,
the FTIR spectrum is identical to that reported in the Spectral
Database for Organic Compounds (AIST, Japan). The peak at
991 cm
1 is attributed to the breathing mode of the pyridine
ring, and the peak at 1271 cm
1 is due to the C–NH2 stretching
mode.54 The peaks observed in the range of 1300–1600 cm
1 are
ascribed to the pyridine ring stretching vibrations.55 In the
spectrum of AP-GO, the vibration of C–O–C at 1057 cm
1 is
signicantly reduced, indicating that the epoxy bonds are
broken in the reaction process. Simultaneously, the ngerprint
bands of the pyridine group (ring breathing at 991 cm
1 and
C–C stretching at 1364, 1527 and 1588 cm
1), C–N stretching in
the –C–NH–C– group at 1254 cm
1, and N–H scissoring at
1648 cm
1 are also observed.43,54,55 These results prove that the
4-AP molecules have been covalently immobilized on the GO
surface via a nucleophilic ring-opening reaction. For FePc, the
FTIR spectrum is in good agreement with that reported previ-
ously.56 The IR bands present in the spectrum of FePc are also
observed in the spectrum of FePc/AP-GA composites but with
slightly modied frequencies. The bands at 1214 cm
1 and
1604 cm
1 could be attributed to the axially coordinated pyri-
dine.57 In addition, the shi of the pyridine ring breathing
mode from 991 to 1015 cm
1 also reects the strong
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Fig. 1 (a) Fabrication process of the 3D FePc/AP-GA composites. (b) SEM and (c) TEM images of FePc/AP-GA. (d) Typical STEM image and
corresponding elemental mapping images of FePc/AP-GA.
coordination bond between the iron atom in FePc and the
nitrogen atom in pyridine.54,58 These results indicated that the
FePc molecules have been anchored on the graphene surface via
the coordination interaction of the 4-AP linker at the axial
position.
The composition of FePc/AP-GA was investigated using
scanning transmission electron microscopy coupled with
energy-dispersive X-ray spectroscopy (STEM-EDS) and X-ray
photoelectron spectroscopy (XPS). The elemental mappings
reveal that carbon, nitrogen and iron coexist and are uniformly
distributed on the graphene sheets (Fig. 1d). The XPS survey
spectra (Fig. S3†) further showed that nitrogen and iron were
incorporated into the FePc/AP-GA composite. The contents of
nitrogen and iron were found to be 10.23 at% and 0.69 at% in
the nal product, respectively (Table S1†). ICP-OES measure-
ments show that the FePc loading in the FePc/AP-GA composite
is 10.1% (m : m), which is approximately equal to the FePc
content in the precursor suspension (FePc : AP-GA ¼ 1 : 10).
Therefore, the coverage of FePc in the FePc/AP-GA composite
was estimated to be 0.33 monomolecular layer (ML), assuming
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that the lateral dimension of a at-lying FePc molecule is 1.5 
1.5 nm.59,60 The high resolution C1s core level spectrum of GO
could be deconvoluted into three peaks located at 284.6, 286.5,
and 288.1 eV, corresponding to C–C, C–O (hydroxyl and
epoxide), and C]O (carbonyl and carboxylate) groups
(Fig. 3a).43,61 Aer functionalization with 4-AP, an additional
peak at 285.8 eV appeared, which was ascribed to the C–N bond
originating from the pyridine ring and a newly formed C–N
bond by the reaction between 4-AP and epoxy sites of GO.42,62
Concomitantly, the intensity of the C–O and C]O peaks
decreased obviously compared with GO, which is probably due
to the solvent-assisted thermal reduction reaction.48 For FePc/
AP-GA, the oxygenated groups were further reduced in the
hydrothermal process, accompanying the increase of the C–N
bond content from phthalocyanine. The N1s spectrum of AP-GO
(Fig. 3b) was tted to two peaks attributed to pyridinic (398.6 eV)
and amine (399.6 eV) nitrogen atoms,42,62 further conrming
that 4-AP was covalently immobilized on the GO surface. In
contrast, three peaks (398.6, 399.6, and 400.7 eV) could be
identied in the N1s spectrum of FePc/AP-GA, corresponding to
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Fig. 2 FTIR spectra of GO, AP-GO, 4-AP, FePc, and FePc/AP-GA.
the chemical environment of nitrogen atoms bonded to carbon
and iron atoms.49,63 As shown in Fig. 3c, the Fe 2p spectrum of
FePc/AP-GA could be tted to a pair of peaks at 710.4/723.5 eV
for Fe3+, which is different from that of FePc, indicating that the
coordination of the Fe ion with the extra pyridine group leads to
a change of electron density on Fe.27 The XRD patterns (Fig. S4†)
show that GO was reduced to graphene in the preparation
Fig. 3 The high resolution XPS spectra of (a) C1s, (b) N1s, and (c) Fe 2p of FePc/AP-GA and reference materials.
18492 | J. Mater. Chem. A, 2018, 6, 18488–18497
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process and a few-layer graphene stacked framework was
formed. There is not any diffraction peak of iron species,
reecting the molecular state of FePc in the FePc/AP-GA
composite.
To assess the ORR catalytic activity of FePc/AP-GA, cyclic
voltammetry (CV) was rst performed using a conventional
three-electrode electrochemical cell in N2- and O2-saturated
0.1 M KOH solution. As shown in Fig. 4a, the GA and AP-GA
exhibited very poor ORR activity in terms of peak potential
and peak current (Table S2†). However the physically mixed
FePc and AP-GA material (FePc + AP-GA) showed a positive shi
in the peak potential to
0.078 V (vs. Hg/HgO), which is
comparable to that of the benchmark Pt/C catalyst (
0.083 V).
Remarkably, the FePc/AP-GA composite showed a more positive
ORR peak potential (
0.040 V) and higher peak current than the
other tested materials, suggesting the highest ORR activity of
this material and the synergistic effect of FePc and AP-GA in the
composite. To further investigate the ORR electrochemical
performance, we performed rotating ring-disk electrode (RRDE)
voltammetry. Fig. 4b shows the ORR polarization curves of
FePc/AP-GA and the reference materials. In agreement with the
CV results, the pristine GA showed poor catalytic activity with an
onset potential (Eonset) of
0.084 V and a half-wave potential
(E1/2) of
0.233 V. AP-GA showed a slightly improved catalytic
activity compared with GA due to the introduction of pyridine
groups. Compared with GA and AP-GA, the FePc + AP-GA cata-
lyst exhibited greatly improved performance, which is similar to
those of previously reported carbon material-loaded FePc cata-
lysts49,64–66 but is still inferior to that of the Pt/C catalyst (Eonset ¼
0.1 V and E1/2 ¼
0.057 V). Surprisingly, FePc/AP-GA shows the
best activity with an E1/2 of
0.035 V, which is 22 mV more
positive than that of the Pt/C catalyst. FePc/AP-GA also exhibits
the highest diffusion-limiting current density (5.98 mA cm
2 at
0.4 V) and kinetic current density (20.01 mA cm
2 at
0.1 V)
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Fig. 4 Electrochemical characterization of catalysts. (a) CV curves of GA, AP-GA, FePc + AP-GA, FePc/AP-GA, and Pt/C in N2/O2-saturated 0.1 M
KOH with a scan rate of 50 mV s
1. (b) ORR polarization curves of the catalysts in O2-saturated 0.1 M KOH with a scan rate of 10 mV s
1 and
a rotation rate of 1600 rpm. (c) Peroxide species (HO2
) yield and (d) electron transfer number of different catalysts as a function of the electrode
potential. (e) Tafel plots of FePc/AP-GA and Pt/C extracted from (b). The catalyst loading is 0.404 mg cm
2 for NPMCs and 20 mgPt cm
2 for
commercial Pt/C.

among the tested catalysts, which could be attributed to the
favourable oxygen diffusion microenvironment and/or the
exposure of more active sites in the composite material.67 The
ORR performance of the FePc/AP-GA composite is among the
highest reported activities of non-pyrolyzed NPMCs (Table S3†)
and surpasses those of most of the pyrolyzed graphene-based
NPMCs (Table S4†). We also discovered that the ORR onset
potential of FePc/AP-GA is closely correlated with the Fe3+/2+
redox transition (Fig. S5†). This correlation has been widely
observed in unpyrolyzed transition metal macrocycle cata-
lysts68,69 and pyrolyzed Fe–N–C catalysts,20,24,70,71 which can be
accounted for by the redox mechanism. Therefore, the high
ORR activity of FePc/AP-GA was ascribed to the higher Fe3+/2+
redox potential than that in the FePc + AP-GA catalyst, which
may originate from the axial ligand stabilizing Fe2+ active sites
at higher potential.24
The presence of FePc plays a key role in achieving high
electrocatalytic activity. Consequently, the ratio of AP-GO to
FePc (m : m) in the precursor suspension was investigated
(Fig. S6†). It was found that a small portion of FePc (2.5%)
could greatly improve the catalytic activity. The optimal ratio of
AP-GO to FePc was found to be 10 : 1. When the ratio exceeded
4 : 1, a large number of aggregates formed on the graphene
sheets, which blocked the higher activity sites and subsequently
resulted in deteriorated catalytic performance. The effect of
catalyst loading was also studied (Fig. S7†). In the range of 0.1–
0.6 mg cm
2, the catalyst loading showed almost negligible
inuence on the ORR performance, which is related to the high
density active sites and fast mass transport of the 3D FePc/AP-
GA catalyst.72,73 This property is superior to most of the pyro-
lyzed Fe–N–C catalysts, where high catalyst loading was needed
to obtain comparable activity to that of Pt/C and consequently
resulted in unacceptable mass-transport losses.74
The RRDE measurements were also used to study the ORR
catalytic pathway of the composite materials. The measured
peroxide species (HO2
) yields are less than 7% and 4% for
the FePc + AP-GA and FePc/AP-GA catalysts, respectively, in the
potential range of
0.1 to
0.8 V (Fig. 4c). The corresponding
electron-transfer numbers were estimated to be larger than 3.9
in the studied potential range (Fig. 4d). These results indicate
that the catalysts follow the 4e
reduction pathway for the
reduction of oxygen to OH
with high selectivity. In sharp
contrast, the GA and AP-GA showed high HO2
yields (up to
60%), and the calculated electron-transfer numbers are smaller
than 3.0 in the potential range of
0.3 to
0.8 V, suggesting
a dominant 2e
reduction pathway. The high catalytic activity of
the FePc/AP-GA catalyst was also reected by a small Tafel slope
(31 mV dec
1) at low overpotential (Fig. 4e), which is close to the
theoretical value 2.303(2RT/3F) z 40 (R, T and F represent the
molar gas constant, absolute temperature and Faraday constant,
respectively) at room temperature, indicating that the proton-
ation of the adsorbed O2
ions is the rate-determining step.27,75,76
RDE measurements at different rotating speeds were further
carried out to investigate the ORR kinetics and reaction

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A, 2018, 6, 18488–18497 | 18493
 View Article Online

Journal of Materials Chemistry A Paper

pathways of the FePc/AP-GA and reference catalysts. As shown in

Fig. S8,† the linear and parallel Koutecky–Levich (K–L) plots at
different potentials were obtained from the corresponding LSV
curves, implying rst-order reaction kinetics with respect to the
dissolved oxygen. The average electron transfer number per O2
derived from the K–L plots was 4.01, 3.62, and 3.93 for Pt/C, FePc
+ AP-GA, and FePc/AP-GA, respectively. However, the electron
Published on 04 September 2018. Downloaded by Imperial College London Library on 3/24/2022 5:30:11 PM.

transfer number of AP-GA and GA was determined to be 2.38 and

2.30, respectively (Fig. S9†). These results agree well with those of
the RRDE measurements, conrming the 4e
process for the
reduction of O2 on the FePc/AP-GA catalyst.
Apart from the activity, the durability of the catalyst is
another key factor for practical application. We performed an
accelerated stability test (AST) for the FePc/AP-GA catalyst by
cycling the potential between
0.35 and 0.15 V in an O2 atmo-
sphere at a scan rate of 50 mV s
1. Aer 6000 continuous cycles,
E1/2 negatively shis 16 mV (Fig. 5a), which is much smaller
than that of the Pt/C catalyst (56 mV) (Fig. S10†). A long-term
chronoamperometric test was also carried out in an oxygen-
saturated electrolyte at
0.2 V with a rotation rate of 900 rpm
(Fig. S11†). Aer operation for 4 h, the FePc/AP-GA catalyst still
retained 90% of its initial current density, while that for the Pt/C
catalyst declined to 82%, showing the high stability of the FePc/
AP-GA catalyst in the alkaline electrolyte. Comparing the results
obtained by the chronoamperometric test and AST, a larger
current loss was observed for the former. The possible reason
was attributed to the change of O2 concentration and/or the
detachment of the catalyst from the electrode surface during
long periods of rotation. The chronoamperometric response of
the FePc/AP-GA and Pt/C catalysts was also investigated in an
oxygen-saturated electrolyte containing 0.5 M CH3OH (Fig. 5b).
It is striking to note that FePc/AP-GA only shows little uctua- Fig. 5 (a) ORR polarization curves before and after 6000 potential
cycles in O2-saturated 0.1 M KOH solution between
0.35 V and
tion with the addition of methanol, while the response of the Pt/
0.15 V. (b) Chronoamperometric response of FePc/AP-GA and Pt/C in
C catalyst drops by about 30%. These results clearly indicated O2-saturated 0.1 M KOH after the addition of 0.5 M CH3OH.
that the FePc/AP-GA catalyst possesses high durability and
tolerance to methanol poisoning effects, showing its promising
potential for use in direct methanol fuel cells. observed from the rst derivative XANES spectra (Fig. S12†).
X-ray absorption spectroscopy measurements were per- Furthermore, the absorption edge positions of the FePc + AP-GA
formed to investigate the exact coordination environment of Fe and FePc/AP-GA composites are very close to that of the Fe2O3
atoms in the as-prepared composites. As revealed by Fe K-edge reference (Fig. S13†), suggesting the oxidation of Fe atoms in
X-ray absorption near-edge structure (XANES), both FePc/AP-GA these composites, which is consistent with the XPS results. All
and FePc + AP-GA show a similar spectral prole to that of the these results indicated that the loading of FePc onto graphene
reference FePc sample (Fig. 6a), with distinct peak features in sheets greatly changed the local geometric and electronic
the pre-edge region. FePc shows a pre-edge peak at 7118 eV, structure of the central Fe atom, and the changes for FePc/AP-
ascribed to the 1s / 4pz shakedown transition characteristic GA were more prominent than those for FePc + AP-GA. The
for a square-planar conguration of FeN4 with high D4h weakness or even disappearance of the pre-edge peak at
symmetry.19,24,77 For the FePc + AP-GA and FePc/AP-GA 7118 eV is usually observed for pyrolyzed Fe–N–C catalysts,
composites, in addition to the peak at 7118 eV with lower which is attributed to the Fe–N4 moieties embedded in the
normalized intensity, an additional small peak appears at distorted carbon matrix with out-of-plane Fe displace-
7113 eV, which is assigned to the 1s / 3d transition for ment.19,20,24 However, for our non-pyrolyzed FePc-based catalyst,
square-pyramidal iron complexes.78 The intensity of this peak is the Fe atoms are located in an ordered carbon environment.
sensitive to the site symmetry of the iron atom, and an increase Therefore, the transition of the iron atom from in-plane to out-
in its intensity indicates a decrease in the molecular of-plane must be caused by the h axial ligand, in this case the
symmetry.79 Compared with FePc + AP-GA, the peak intensity of pyridine group (Fig. 6c), just like the Naxi–Fe–N4 active sites in
FePc/AP-GA is lower at 7118 eV but is higher at 7113 eV, indi- heme-based enzymes or other biomimetic catalysts.27,28,34
cating the lower molecular symmetry of iron in FePc/AP-GA. However, we cannot completely rule out the physical adsorption
These changes of the pre-edge peak can be more clearly of FePc on graphene sheets due to the presence of the weak pre-

18494 | J. Mater. Chem. A, 2018, 6, 18488–18497 This journal is © The Royal Society of Chemistry 2018

Paper
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Fig. 6 (a) XANES spectra and (b) FT-EXAFS of Fe foil, Fe2O3, FePc, FePc
+ AP-GA, and FePc/AP-GA. The vertical dashed lines are provided to
guide the eye. (c) Schematic diagram of the structure of the FePc/AP-
GA composite.
edge peak at 7118 eV and the fact that FePc molecules with the
planar macrocyclic structure easily adsorb on graphene sheets.
The coordination conguration of the iron atom in the FePc/
AP-GA composite was further investigated by using Fourier
transform of Fe K-edge extended X-ray absorption ne structure
(FT-EXAFS) analysis. As shown in Fig. 6b, FePc/AP-GA exhibits
a strong peak at 1.44 Å, which was assigned to the Fe–N/O
coordination.19 The absence of the Fe–Fe peak of bulk Fe at
2.21 Å indicates that FePc retained its intact structure and no
inorganic Fe species were produced in the hydrothermal
process. Curve-tting analysis of FT-EXAFS was performed
using the backscattering path of Fe–N (Fig. S14†). The coordi-
nation number of the Fe–N bond in the FePc/AP-GA composite
was estimated to be 4.7 with a bond length of 2.01 Å, while FePc
+ AP-GA showed a coordination number of 4.2 and a bond
length of 1.98 Å (Table S5†). This result is consistent with that of
XANES analysis, strongly suggesting that the ve-coordinated
Fe–N bond dominated in the FePc/AP-GA composite. There-
fore, it is believed that this geometric and electronic structure of
the ve-coordinated FePc/AP-GA composite is favorable for the
adsorption of O2 and intermediates and thus responsible for the
improved ORR activity and durability.
4. Conclusions
In summary, we successfully prepared an FePc/AP-GA
composite by anchoring FePc molecules onto pyridine
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View Article Online
Journal of Materials Chemistry A
functionalized graphene sheets. The axial pyridine-coordinated
FePc mimics the active site of oxygen-activating heme-based
enzymes. The bio-inspired FePc/AP-GA catalyst demonstrated
higher electrocatalytic activity, durability and methanol toler-
ance for the ORR in alkaline media than the benchmark Pt/C
catalyst. XANES and EXAFS spectra proved the larger iron
atom displacement for FePc/AP-GA in comparison to FePc and
FePc + AP-GA, which is speculated to be responsible for the
enhanced ORR performance. These results suggested that the
FePc/AP-GA catalyst could be a promising candidate for prac-
tical application in fuel cells and metal–air batteries. More
importantly, this research provided a potential highly active site
for the rational design of Fe–N–C catalysts for electrocatalytic
applications.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (No. 21435005 and 21627808), the
Key Research Program of Frontier Sciences, the Chinese
Academy of Sciences (No. QYZDY-SSW-SLH019), and the
Development Project of Science and Technology of Jilin Prov-
ince (No. 20170101195JC).
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