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org Research Article

Two-Dimensional Bimetallic Zn/Fe-Metal-Organic Framework

(MOF)-Derived Porous Carbon Nanosheets with a High Density of
Single/Paired Fe Atoms as High-Performance Oxygen Reduction
Catalysts
Long Zheng, Siyan Yu, Xueyi Lu,* Wenjun Fan, Bin Chi, Yuekun Ye, Xiudong Shi, Jianhuang Zeng,
Xiuhua Li, and Shijun Liao*
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sı Supporting Information

ABSTRACT: Developing efficient non-precious-metal catalysts to accelerate

the sluggish oxygen reduction reaction (ORR) is highly desired but remains a
great challenge. Herein, using 2D bimetallic Zn/Fe-MOF as the precursor
and g-C3N4 as the nitrogen source and stabilizer, porous carbon nanosheets
doped with large amounts of single/paired Fe atoms (3.89 wt %) and N
(10.28 wt %) are successfully prepared. It is found that the addition of g-
C3N4 plays a key role in achieving a high loading of Fe single/paired atoms,
and the 2D nanosheet structure gives the materials a high surface area and
highly porous structure, resulting in outstanding ORR catalytic activity in
both alkaline and acidic solutions. Our optimal sample achieved half-wave
potentials in alkaline and acid media of up to 0.86 and 0.79 V (vs reversible
hydrogen electrode (RHE)), respectively, values 20 mV higher than a
commercial Pt/C catalyst in an alkaline medium and only 60 mV lower than
Pt/C in an acidic medium. Moreover, its ORR durability was superior to that of commercial Pt/C in both electrolytes. We found
that almost all the doped Fe in the sample existed as single or paired atoms coordinated with N. This work may provide an effective
strategy for preparing high-performance catalysts bearing single/paired atoms by using MOFs as precursors.
KEYWORDS: non-precious-metal catalyst, single/paired atoms, metal−organic framework (MOF), oxygen reduction reaction (ORR),
2D materials

■ INTRODUCTION
Fuel cells are considered promising electric power sources,
because of their high energy densities, zero emissions, and
superior energy-conversion efficiency.1 However, the intrinsi-
cally sluggish kinetics of the oxygen reduction reaction (ORR)
require high loads of Pt catalyst at the cathode, so the scarcity
and expense of Pt continue to impede the widespread
application of fuel cell technology.2,3 Consequently, there is an
urgent need to develop noble-metal-free catalysts, especially
low-cost carbon-based catalysts, as alternatives to Pt/C
catalysts.4−8
Previous reports have revealed that single/paired non-noble
atoms doped into carbon is one of the most promising
categories of non-precious-metal catalysts, performing very
well for the ORR.9,10 However, low active-site density keeps
the performance of single-atom-doped catalysts too low for
use in fuel cells, especially their cathode performance in the
membrane electron assemblies (MEAs) of proton-exchange
membrane (PEMFCs) fuel cells.11 Therefore, it is necessary to
enhance the density of single/paired atom sites on the
catalyst’s limited surface area to achieve better perform-
ance.12,13
It has recently been found that the well-defined pore
structures and tunable chemical composition of metal−organic
frameworks (MOFs) make them ideal precursors for
preparing atomically dispersed M−N−C catalysts.14,15 Chen
et al. used the microporous structure of ZIF-8 to separate and
encapsulate the metal precursor Fe(acac)3.16 The confinement
effect of the pore structure effectively prevented the
aggregation of Fe atoms during pyrolysis. Zhang et al. used
Fe ions to partially replace Zn when preparing 3D Zn/Fe
bimetallic metal−organic frameworks (BMOFs).17 Zn2+ can
serve as a “fence” to increase the distance between Fe3+ atoms
Received: December 19, 2019
Accepted: March 10, 2020
Published: March 10, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.9b22577

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Figure 1. Schematic illustration of the preparation of Fe/N-PCNs: (a) self-assembly, (b) mixing the MOF precursor and g-C3N4, and (c)
pyrolysis.
and prevent its agglomeration during pyrolysis. However, the
mass loadings of single Fe atoms in most MOF-derived
catalysts are still low.18 Furthermore, because of the high-
temperature required for pyrolysis, the N content in MOF-
derived carbon catalysts is also too low, because most of the
nitrogen is lost during pyrolysis, limiting the formation of
porphyrinic-N (Por-N4) moieties to form Fe−N4.19,20 Hence,
it is still a great challenge to achieve a high N-doping level,
especial high porphyrinic-N content, in MOF-derived M−N-C
catalyst to improve the loading of single-atom dispersed Fe−
N4.
Another proposed strategy for enhancing ORR activity is to
lower the dimension of the catalysts from three-dimensional
(3D) to two-dimensional (2D).21,22 Compared with their 3D
counterparts, 2D porous carbon nanosheets have a tendency
to expose more active sites to reactants and decrease diffusion
resistance, which is beneficial for promoting the utilization
efficiency of the catalytic sites and enhancing power
densities.23 Usually, 2D porous carbon nanosheets are
prepared by templating methods that use metal oxides or
graphene oxide as the templates.24 However, the process of
synthesizing and removing the template is complex and
tedious, so a template-free method is desirable.
Here, we describe developing a catalyst based on 2D porous
carbon nanosheets, with a high loading of single/paired Fe
atoms (∼3.89 wt %) and high N content (∼10.28 wt %), by
using 2D bimetallic Zn/Fe-MOF as the precursor and g-C3N4
as the nitrogen source/single Fe atom promoter. As expected,
the catalyst showed excellent durability and activity toward the
ORR in both alkaline and acidic media, with a half-wave
potential of 0.86 V (vs reversible hydrogen electrode (RHE))
under alkaline conditions, which is superior to commercial Pt/
C (0.84 V(vs RHE)), and a half-wave potential of 0.79 V (vs
RHE) in an acidic medium, close to that of commercial Pt/C.
Importantly, we found that the addition of g-C3N4 played a
crucial role in achieving the catalyst’s high single/paired Fe
atom loading and high N content by achieving high
porphyrinic-N content of the catalyst.
■
EXPERIMENTAL SECTIONS
Synthesis of 2D Bimetallic Zn/Fe-MOF. A typical synthesis
followed previously reported steps,25 with some modifications. In a
150-mL glass vial, 1,4,5,8-naphthalenetetracarboxylic anhydride (60
mg) was added to 100 mL of deionized water and dissolved with 18
mg of sodium hydroxide (NaOH). The solution then was stirred at
40 °C for 8 h until it became clear. After that, 20 mL of deionized
water was used to dissolve 150 mg of Zn(NO3)2·6H2O, and 2 mg of
FeSO4·7H2O was added to that solution. The glass vial then was
capped and the resulting mixture was stirred at 60 °C for 24 h.
Subsequently, the precursor was centrifuged to isolate, washed 3
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times with deionized water, and then dried under vacuum for 24h at
80 °C. Thirty milligrams (30 mg) of Zn/Fe-MOF could be obtained
after the hydrothermal reaction.
For comparison, the synthetic procedures of Zn-MOF and Fe-
MOF were as same as that of bimetallic Zn/Fe-MOF but without
adding FeSO4·7H2O or Zn (NO3)2·6H2O.
Synthesis of g-C3N4. Urea (10 g) was placed in a porcelain
crucible (50 mL) with a lid, then heated in a muffle furnace from 25
°C to 550 °C at a heating rate of 5 °C min−1; the temperature then
was held at 550 °C for 4 h. After the muffle furnace was cooled to
room temperature, g-C3N4 was obtained.26
Preparation of Catalysts. Bimetallic Zn/Fe-MOF (100 mg) was
mixed with g-C3N4 (300 mg) to form Zn/Fe-MOF@g-C3N4, yielding
g-C3N4/Zn/Fe-MOF in a ratio of 3:1. After uniform grinding, the
mixed precursor (∼400 mg) was pyrolyzed under an argon
atmosphere from 25 °C to different temperatures (850, 950, 1050
°C) at a heating rate of 5 °C min−1, then held at the highest
temperature for 1 h. The final catalysts were named as Fe/N-PCNsT,
where T was the pyrolysis temperature. (For the sake of simplicity,
the optimal sample, Fe/N-PCNs950, was also denoted simply as Fe/
N-PCNs.)
For comparison, N-PCNs, Fe-PCNs, and Fe-bulk/N-PCNs were
prepared by the same procedures but with different precursors, Zn-
MOF@g-C3N4, Zn/Fe-MOF, and Fe-MOF@g-C3N4, respectively.
Materials Characterization. Scanning electron microscopy
(SEM) was conducted on a Merlin field-emission SEM system
(Carl Zeiss). Transmission electron microscopy (TEM) was
recorded on a JEM-2100 TEM system (JEOL, Japan) operating at
120 kV. Thermogravimetric analysis (TGA) was performed on a TA
SDT Q600 thermal analyzer (TA Instruments, Inc., USA), heating
from 30 °C to 1000 °C under a N2 flow at a rate of 5 °C min−1.
Powder X-ray diffraction (XRD) patterns were obtained on a TD-
3500 powder diffractometer (Tongda, China) operating at 30 kV and
20 mA current with Cu Kα radiation sources. Raman analysis was
recorded on a LabRAM Aramis Raman spectrometer (HJY, France).
ESCALAB 250 X-ray photoelectron spectroscope (Thermo-VG
Scientific, USA) was used to investigate the surface valence state of
the samples. 57Fe Mössbauer spectra was tested at room temperature
with a Topologic 500A spectrometer (MFD-500AV, Japan). The
specific surface area and pore size distributions were analyzed by a
Micromeritics Tristar II 3020 adsorption analyzer (Micromeritics,
USA).
Electrocatalytic Testing. The electrocatalytic performance of
the catalysts was evaluated on the Ivium electrochemical workstation
at 25 °C with a standard three-electrode system. A glassy carbon
electrode (GC, 0.196 cm−2) and Pt wire served as the working and
counter electrodes, respectively. Ag/AgCl (3 M NaCl solution) and
Hg/HgO (1 M KOH solution) served as the reference electrodes in
0.1 M HClO4 and 0.1 M KOH, respectively. The commercial 20
wt % Pt/C catalyst was purchased from Johnson Matthey (UK)
Company.
The samples were prepared as follows. Five milligrams (5 mg) of
catalyst powder was mixed with 1 mL of Nafion/ethanol (0.25 wt %
Nafion), further under sonication for 40 min to form homogeneous
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Figure 2. (a, b) SEM images of the precursor Zn/Fe-MOF (panel (a)) and the Fe/N-PCNs catalyst (panel (b)); (c, d) HAAD-STEM image of
Fe/N-PCNs (panel (c)) and an enlarged image of the square highlighted in panel (c) (panel (d)); (e) TEM image, along with C, N, and Fe EDS
mapping images for Fe/N-PCNs. Panel (f) shows an enlarged TEM image.
catalyst inks. Next, dropping the catalyst ink (20 μL) on the working
electrode, and drying the electrode under infrared lamp. The loading
of the sample was ∼0.5 mg cm−2. Cyclic voltammetry (CV) was
conducted in O2- or N2-saturated alkaline and acid electrolytes with a
sweep rate of 10 mV s−1, and RDE tests were measured at different
rotation rates, from 900 rpm to 2500 rpm. The Koutecky−Levich
(K−L) equation was used to calculate the electron transfer number:
J −1 = Jk−1 + (0.62nFCD2/3γ −1/6ω1/2)−1
where J is the measured disk current density and Jk is the kinetic
current density; n is the electron transfer number; F is the Faraday
constant; C and D represent the concentration and diffusion
coefficient of O2 in the electrolytes, respectively; γ is the kinetic
viscosity of the electrolyte; and ω represents the disk rotation rate.
Durability testing of Fe/N-PCNs and Pt/C used the chronoam-
perometric technique and was measured at 0.62 V for 20 000 s in an
O2-saturated alkaline and acid electrolyte (rotation rate = 900 rpm).
■
RESULTS AND DISCUSSION
Figure 1 shows a schematic diagram of the catalyst
preparation. First, 2D bimetallic Zn/Fe-MOF was synthesized
by the coordination of Fe2+ and Zn2+ with 1,4,5,8-
naphthalenetetracarboxylic without templates. Importantly,
Zn2+ nodes displaced a certain percentage of doped Fe2+
nodes and served as a “fence” to increase the distance between
Fe atoms and avoid the aggregation phenomenon during
pyrolysis. Then, the 2D bimetallic Zn/Fe-MOF precursor was
physically mixed with g-C3N4 as the nitrogen source for the
subsequent pyrolysis procedure; g-C3N4 has a N content of
57.1 at. %, which makes it one of the most nitrogen-rich
materials for this purpose.25 During the pyrolysis procedure, g-
C3N4 gradually decomposed and formed abundant Por-N4
moieties in the MOF-derived carbon nanosheet. After the
decomposition of the organic ligands, the single Fe atom
nodes could be anchored and stabilized by Por-N4 moieties to
form an atomic dispersion of Fe−N4 moieties. The abundant
Fe−N4 sites throughout the 2D porous carbon nanosheets
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gave the catalyst excellent performance toward the ORR in
both acidic and alkaline solutions.
As shown in Figure 2a, our synthesized bimetallic Zn/Fe-
MOF exhibited a 2D nanosheet morphology with a lateral size
of <1 μm and an average thickness of <25 nm. After pyrolysis,
the derived catalyst, Fe/N-PCNs, retained its 2D nanosheet
morphology very well, while the external surface of the
catalyst became much rougher, the thickness of the catalyst
slightly decreased (<20 nm), compared with the precursor,
because of the decomposition of the MOF material during
pyrolysis (see Figure 2b).
We can see from Figures 2c and 2d, as well as Figures S1a
and S1b in the Supporting Information that the doped metal
atoms were highly dispersed in the catalyst as single atoms
and clusters of 2−4 atoms. The high dispersion was confirmed
by the EDX mapping results, shown in Figure 2e; no Fe or Fe
species particles could be observed, and all of the doped
elements (Fe and N) were well-distributed, with high
densities, in the material’s carbon framework.27 The enlarged
TEM image in Figure 2f shows that the material exhibits well-
defined textural pores next to the carbon fibers/bars.
The high density of Fe atoms in the Fe/N-PCNs can be
ascribed to the predesign of 2D bimetallic Zn/Fe-MOF and
the use of g-C3N4, which acted not only as a nitrogen source
(nitriding agent) but also as a stabilizer of the highly dispersed
Fe atoms through the formation of Fe−N4 moieties: (i) the
Zn nodes acted as separators, making the aggregation of Fe
atoms difficult; (ii) the decomposition of g-C3N4 led to the
formation of Por-N4 moieties in the carbon framework, which
was able to anchor single Fe atoms to form Fe−N 4
coordination structures during high-temperature pyrolysis.
Our comparative results support these suppositions: the
sample Fe-PCNs without added g-C3N4 presented many
inorganic Fe nanoparticles when examined via TEM (Figure
S1b), indicating that g-C3N4 prevented Fe agglomeration and
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Figure 3. (a) TGA curves of g-C3N4, Zn/Fe-MOF, and Zn/Fe-MOF@g-C3N4 in N2 as the temperature was increased at a rate of 5 °C min−1;
(b) XRD patterns of Zn/Fe-MOF and Zn-MOF; (c) XRD patterns of N-PCNs, Fe-PCNS, and Fe/N-PCNs; and (d) 57Fe Mössbauer spectrum
of Fe/N-PCNs.

Figure 4. (a, b) N 1s XPS spectra of N-PCNs and Fe/N-PCNs; (c) Fe 2p XPS spectra of Fe-PCNs and Fe/N-PCNs; (d) Raman spectra of N-
PCNs, Fe/N-PCNs, and Fe-PCNs.

promoted the formation of Fe−N4 moieties during high-
temperature pyrolysis.
Figure 3a showed the thermogravimetric analysis (TGA)
curves of Zn/Fe-MOF, g-C3N4, and Zn/Fe-MOF@g-C3N4.
Zn/Fe-MOF started to decompose at 200 °C and completely
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converted to MOF-derived carbon at temperatures above 460
°C. By 680 °C, g-C3N4 was completely decomposed.26 Below
430 °C, the mass of Zn/Fe-MOF@g-C3N 4 gradually
decreased, mainly due to the partial decomposition of Zn/
Fe-MOF; above 430 °C, the mass of Zn/Fe-MOF@g-C3N4
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rapidly decreased, which may have been due to the pyrolysis
of Zn/Fe-MOF and g-C3N4.
Figure 3b showed the XRD patterns of bimetallic Zn/Fe-
MOF and Zn-MOF. The patterns were similar, suggesting that
the doped Fe atoms either were incorporated into the Zn-
MOF, partially replaced the Zn, or were atomically dispersed
in the precursor.25 After high-temperature pyrolysis, g-C3N4
(see Figure S2 in the Supporting Information) and the MOF
precursor were not detected in the XRD patterns of the
products (Figure 3c), which was consistent with the TGA
results (Figure 3a). Furthermore, Fe2O3 (Powder Diffraction
File (PDF) No. 39-1346) species peaks were present in the
XRD patterns of Fe-PCNs but not in those of Fe/N-PCNs
and N-PCNs, indicating that g-C3N4 effectively prevented Fe
aggregation during high-temperature pyrolysis, findings also
confirmed by TEM (Figure 2e and Figure S1b). Zn also
played an important role in the atomic dispersion of Fe;
without the addition of Zn2+ in the precursor, even when g-
C3N4 was added, Fe bulk species (Fe2.932O4 (PDF No. 01-
086-1352) and Fe (PDF No. 06-0696)) were observed as Fe-
bulk/N-PCNs (see Figure S3 in the Supporting Information).
X-ray photoelectron spectroscopy (XPS) was performed to
identify the chemical state of the prepared N-PCNs, Fe-PCNs,
and Fe/N-PCNs catalysts (see Figures 4a−c). Trace amounts
of Zn residue in the catalysts could not be detected by the
XPS test, because of the evaporation of Zn atoms. The N
contents of N-PCNs, Fe-PCNs, and Fe/N-PCNs were
estimated to be 10.08, 0, and 10.28 wt %, respectively,
indicating that adding g-C3N4 resulted in high N doping (see
Figure S4 in the Supporting Information, as well as Table 1).
Table 1. Elemental Mass Compositions of N-PCNs, Fe-
PCNs, and Fe/N-PCNs, as Measured by XPS
Composition (wt%)
sample C O N Fe
N-PCNs 82.39 7.53 10.08
Fe-PCNs 90.57 6.44 − 2.99
Fe/N-PCNs 79.56 6.27 10.28
The doped N atoms in N-PCNs could be deconvoluted to
four distinct forms: pyridinic-N, pyrrolic-N, graphitic-N, and
oxidized-N.28 The addition of g-C3N4 seemed to greatly
promote the formation of pyridinic-N (Por-N4), as the
fraction of pyridinic-N in sample N-PCNs reached 43.57%
(see Figure 4a and Table 2). A previous report has shown that
Table 2. Fractions of N Species Present in N-PCNs and Fe/
N-PCNs
Fraction of N Species (%)
sample oxidized-N graphitic-N pyrrolic-N metal-N
N-PCNs 14.30 24.25 17.88 − 43.57
Fe/N-PCNs 8.02 25.98 10.48 29.86
57
Table 3. Fe Mössbauer Fitting Parameters for Fe/N-PCNs
component isomer shift
doublet D1 0.39
doublet D2 0.36
doublet D3 1.25
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four pyridinic-N atoms in a porphyrinic planar architecture
can form Por-N4 moieties, which could have anchored and
stabilized active Fe atoms to form Fe−N4 moieties during
pyrolysis.29 Because of the incorporation of Fe, Fe−Nx forms
could be observed in Fe/N-PCNs (Figure 4b and Table 2),
and the fraction of Fe−Nx moieties in the sample reached
29.86%, indicating that the sample contained an abundance of
Fe−Nx active sites.
The XPS spectra of Fe 2p for Fe-PCNs and Fe/N-PCNs
catalysts are presented in Figure 4c. The spectrum of doped
Fe atoms can be deconvoluted to five distinct forms: the
Fe(III) 2p1/2 peak, the Fe(II) 2p1/2 peak, the Fe(III) 2p3/2
peak, the Fe(III) 2p3/2 peak, and the satellite peak.19 Clearly,
the Fe2+ 2p peak of Fe/N-PCNs shifted toward a lower
binding energy, by ∼1.46 eV, compared with Fe-PCNs. This
negative shift indicates that the electron density of the Fe
atoms was enhanced by the introduction of g-C3N4.30 When
g-C3N4 was not added, Fe atoms coordinated with O atoms to
form Fe2O3 nanoparticles, whereas Fe atoms preferred to
coordinate with N to generate Fe−Nx moieties after g-C3N4
doping. We suppose that the electronegativity of N (3.04) is
lower than that of O (3.44), so the Fe atoms would have lost
fewer electrons around N atoms than O atoms, resulting in a
lower binding energy. The more-negative charge on the metal
centers could have given rise to higher binding energies for O2
molecules, leading to higher ORR activity. Therefore, it is
reasonable to expect that Fe/N-PCNs would deliver much-
higher ORR performance than Fe-PCNs.
Figure 4d shows the Raman spectra of N-PCNs, Fe-PCNs,
and Fe/N-PCNs, which could be fitted to the D-line and the
G-line, centered at 1350 and 1590 cm−1, respectively.31,32 The
D-line is attributed to defects in the graphene layers (e.g.,
vacancies, heteroatom doping, etc.), while the G-line is related
to the structural intensity of the sp2 bonded carbon atoms.33,34
In addition, the peak area values ratio of the D-line and G-line
(ID/IG) can indicate the degree of defects in the catalysts.35
−
Because of the addition of g-C3N4, the widths and areas of the
D-peak in N-PCNs and Fe/N-PCNs obviously increased. The
3.89
ID/IG ratios of Fe/N-PCNs (5.12) and N-PCNs (5.83) is
much higher than that of Fe-PCNs (1.96), indicating that
doping with g-C3N4 may have generated defective sites in the
carbon framework.12,36 However, the ID/IG ratio of Fe/N-
PCNs is lower than that of N-PCNs, suggesting that the
incorporation of Fe improved the graphitization in Fe/N-
PCNs.37
To further investigate the immediate structural and
chemical neighborhood of the Fe atoms, 57Fe Mössbauer
analysis was conducted with Fe/N-PCNs. As shown in Figure
3d, the 57Fe Mössbauer spectra was deconvoluted into three
doublets: a low-spin site (D1), a midspin site (D2), and a
pyridinic-N high-spin site (D3). These can be assigned to molecular FeN4-
like sites with different spin states (see Table 3).38,39 D1 and
25.67 D3 can display higher intrinsic ORR activity than D2 in acidic
media.39 The total content of D1 and D3 in our Fe/N-PCNs
catalyst reached 95.52%, demonstrating that the catalyst had
Q. splitting line width area % assignment
0.99 0.58 43.7 FeIIN4/C
2.47 0.58 4.48 FeII N2+2/C
2.53 1.86 51.79 N−FeII N2+2···Nprot/C
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Figure 5. (a) N2 adsorption and desorption isotherms; (b) pore-size distributions of N-PCNs, Fe-PCNs, and Fe/N-PCNs.

Figure 6. Cyclic voltammetry (CV) curves of Fe/N-PCNs in (a) 0.1 M KOH and (b) 0.1 M HClO4. Linear sweep voltammetry (LSV) ORR
curves of samples in (c) 0.1 M KOH and (d) 0.1 M HClO4. 20 000 s stability test of the Fe/N-PCNs and Pt/C catalysts in (e) 0.1 M KOH and
(f) 0.1 M HClO4.

high ORR activity in the acidic solution. Moreover, no other
Fe-related phases (e.g., Fe, FexC, FexO) were observed,
indicating that the Fe atoms coordinated only coordinated
with N. The result of the 57Fe Mössbauer analysis suggested
that the addition of g-C3N4 promoted the generation of Fe−
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N4 active sites and inhibited the aggregation of Fe species,36
which is quite consistent with the XRD and XPS analysis
results.
Figure 5 shows the N2 adsorption−desorption profiles of
the three catalysts. The curve of N-PCNs exhibits a typical
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Figure 7. ORR curves of Fe/N-PCNs acquired at different rotation rates in (a) 0.1 M KOH and (b) HClO4; K−L plots on Fe/N-PCNs in (c)
0.1 M KOH and (d) HClO4; transferred electron numbers obtained in (e) 0.1 M KOH and (f) HClO4.
type-I isotherm, while Fe/N-PCNs and Fe-PCNs showed
type-IV isotherms (Figure 5a), indicating that Fe doping
promoted the generation of a mesoporous structure.40 The
surface area of Fe/N-PCNs (864 m2 g−1) was also much
larger than that of N-PCNs (415 m2 g−1) and Fe-PCNs (316
m2 g−1), which suggests that codoping with Fe and N
significantly enhanced the surface area of the catalyst. The
pore-size distributions of the three catalysts further illustrated
that Fe/N-PCNs had a rich, hierarchically mesoporous
structure, whereas micropores dominated N-PCNs (Figure
5b). Fe-PCNs possessed abundant micropores with a few
mesopores. Clearly, Fe doping played a crucial role in the
formation of mesoporous structures, and the addition of g-
C3N4 further increased pore size and surface area by
improving the dispersion of Fe through reacting with Fe
atoms/particles, resulting in larger pore size and surface area
for Fe/N-PCNs, which enhanced the diffusion of oxygen and
electrolytes.26,41
In addition, the specific surface areas of the catalysts were
much larger than that of the Zn/Fe-MOF precursor (47 m2
g−1) (see Figure S5 in the Supporting Information). As the
temperature growing, the low-boiling-point (low-bp) Zn
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atoms (melting point (mp) = 420 °C, bp = 907 °C) can be
evaporated away over 800 °C, leading to the generation of
porous carbon nanosheets with hierarchically microporous
structure and large surface area.42
The ORR performance of Fe/N-PCNs was studied in
alkaline and acidic media. As shown in Figures 6a and 6b, Fe/
N-PCNs exhibited a cathodic oxygen reduction peak at 0.85 V
(vs RHE) in oxygen-saturated 0.1 M KOH solution and at
0.79 V (vs RHE) in oxygen-saturated 0.1 M HClO4 solution,
indicating the catalyst’s high electrocatalytic activity in both
electrolytes.
The high ORR performance of the Fe/N-PCNs catalyst was
further supported by linear sweep voltammetry (LSV). In 0.1
M KOH solution, its half-wave potential reached 0.86 V (vs
RHE), which was higher than the values of N-PCNs, Fe-
PCNs, and Fe-bulk/N-PCNs catalysts and surpassed that of
commercial Pt/C (0.84 V) (see Figure 6c, as well as Figure
S6a in the Supporting Information). Furthermore, its half-
wave potential reached 0.79 V in 0.1 M HClO4, which was
much higher than the values for the other three comparative
samples and only 60 mV lower than that of commercial Pt/C
(see Figure 6d, as well as Figure S6b in the Supporting
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ACS Appl. Mater. Interfaces 2020, 12, 13878−13887
ACS Applied Materials & Interfaces
Information). All these results demonstrate that the predesign
of the Zn/Fe bimetallic precursor and the addition of g-C3N4
significantly promoted the catalyst’s ORR electrocatalytic
activity. In other words, we can ascribe the excellent
electrocatalytic activity of Fe/N-PCNs to several factors: (i)
the abundant atomically dispersed Fe−N4 active sites caused
by the predesign of the Zn/Fe bimetallic precursor and the
addition of g-C3N4; and (ii) the large surface area,
mesoporous structure, and much thinner thickness (ca. 20
nm) resulting from the 2D nanosheets, promoting the mass
diffusion and exposing active sites.23,43 Note that trace
amounts of Zn residue in the final prepared Fe/N-PCNs
catalyst had little effect on ORR performance, based on our
experimental results (see Figures 6c and 6d), although the
existence of Zn in the precursor may help the formation of a
porous structure through the Zn evaporation during pyrolysis.
Compared with other reported 3D morphologies catalysts
with larger specific surface area, our Fe/N-PCNs also shows
remarkable ORR activity (see Tables S1 and S2 in the
Supporting Information). The most important advantage of
the 2D catalyst is its much thinner thickness, compared with
the 3D catalyst, which will make the diffusion of oxygen
molecules and electrolyte molecules much easier, finally
resulting in superior ORR performance.
In addition, the catalyst also exhibited excellent stability, as
shown in Figures 6e and 6f. In an alkaline medium, the
current density of Fe/N-PCNs decreased by only 3.1% after
20 000 s of long-term chronoamperometric measurement,
compared with 19.3% for Pt/C catalyst. In an acidic medium,
Fe/N-PCNs maintained more than 90% of their initial ORR
performance, whereas Pt/C retained only 79.6%.
We investigated the effect of pyrolysis temperature on the
catalyst performance by preparing three samples at 850, 950,
and 1050 °C, and found that 950 °C is the optimal
temperature for attaining the highest ORR electrocatalytic
activity (see Figure S7 in the Supporting Information).
Actually, the effect of temperature has been widely
investigated and reported by other researchers previ-
ously.19,20,44 Their conclusions can be described as follows:
temperatures that are too low are unfavorable to the formation
of high-performance Fe−N active sites and the graphitization
of the carbon materials, and temperatures that are too high
will cause the loss of N and the aggregation of Fe, resulting in
a decrease of the active sites.
To further clarify the ORR electron-transfer pathway for
Fe/N-PCNs, RED test of Fe/N-PCNs was measured at
different rotation speeds, from 900 rpm to 2500 rpm, in an
O2-saturated system (see Figures 7a and 7b). Koutecky−
Levich (K−L) analysis showed that the electron transfer
numbers (n) for Fe/N-PCNs in alkaline and acidic solution
were ∼3.95 and 3.80, respectively, demonstrating that a 4e−
process dominated the ORR in both electrolytes (see Figures
7c−f).
■
CONCLUSION
In conclusion, a 2D bimetallic Zn/Fe-MOF-derived catalyst
featuring porous carbon nanosheets (Fe/N-PCNs) with a high
density of single-atom Fe−N4 sites has been successfully
prepared by using Zn and Fe as the center atoms, and using g-
C3N4 as the nitriding agent and stabilizer of single Fe atoms.
The single-atom dispersion of Fe atoms and the formation of
Fe−N4 sites were evidenced by HAADF−STEM, XPS, and
57
Fe Mössbauer spectra. It was found that the intentionally
13885
www.acsami.org Research Article
added Zn served as a “fence” to prevent the aggregation of Fe
atoms during pyrolysis. Furthermore, the addition of g-C3N4
provided enough N to form abundant Por-N4 moieties in the
MOF-derived carbon, which anchored active Fe atoms at an
elevated temperature. Because of its 2D nanosheet morphol-
ogy, high surface area, mesoporous structure, and high density
of single-atom Fe−N4 sites, Fe/N-PCNs showed superior
ORR electrocatalytic performance in alkaline and acidic
media. This work provides an effective pathway for preparing
high-performance non-precious-metal ORR catalysts for use in
fuel-cell applications.
■
*
ASSOCIATED CONTENT
sı Supporting Information
Supporting Information is about The Supporting Information
is available free of charge at https://pubs.acs.org/doi/
10.1021/acsami.9b22577.
STEM, TEM, XRD, XPS, BET, and LSV analysis results
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Xueyi Lu − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China;
orcid.org/0000-0002-2867-4707; Email: lu.xueyi@
hotmail.com
Shijun Liao − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China;
orcid.org/0000-0003-2481-0377; Email: chsjliao@
scut.edu.cn; Fax: +86 20 87113586
Authors
Long Zheng − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Siyan Yu − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Wenjun Fan − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Bin Chi − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Yuekun Ye − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Xiudong Shi − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Jianhuang Zeng − The Key Laboratory of Fuel Cell Technology
of Guangdong Province & The Key Laboratory of New
https://dx.doi.org/10.1021/acsami.9b22577
ACS Appl. Mater. Interfaces 2020, 12, 13878−13887
ACS Applied Materials & Interfaces
Energy, School of Chemistry and Chemical Engineering, South
China University of Technology, Guangzhou 510641, China;
orcid.org/0000-0002-2243-2299
Xiuhua Li − The Key Laboratory of Fuel Cell Technology of
Guangdong Province & The Key Laboratory of New Energy,
School of Chemistry and Chemical Engineering, South China
University of Technology, Guangzhou 510641, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.9b22577
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (NSFC Project Nos. 21776104 and
21476088), the National Key Research and Development
Program of China (Project Nos. 2016YFB0101201 and
2017YFB0102900), the Guangdong Provincial Department
of Science and Technology (Project No. 2015B010106012),
and the Guangzhou Science, Technology and Innovation
Committee (Project Nos. 2016GJ006 and
201504281614372).
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