i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0

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Core-shell structured metal organic framework

materials derived cobalt/ironenitrogen Co-doped
carbon electrocatalysts for efficient oxygen
reduction

Zhiyuan Guo, Shaoming Liu, Xiao Hu*, Jie Song, Ke Xu, Qing Ye, Guizhi Xu,
Zhanfeng Deng
State Key Laboratory of Advanced Transmission Technology, Global Energy Interconnection Research Institute
Limited Company, Beijing 102209, China

highlights

ZIF-8@Fe,Co-ZIF composite precursor was controllably synthesized.

The catalyst had a porous structure and highly dispersed active sites.

The catalyst exhibited excellent ORR activity in alkaline electrolyte.

article info abstract

Article history: Homogeneous dispersion of active sites and abundant pore structure for non-precious
Received 19 May 2020 metal electrocatalysts are favorable for the oxygen reduction reaction (ORR) activity.
Received in revised form Herein, a nitrogen-doped carbon core supported CoFe alloy-nitrogen co-doped carbon shell
13 November 2020 nanopolyhedron (NC@CoFe,NeCNP) electrocatalyst, which has rich pore structure and
Accepted 23 November 2020 uniformly distributed active sites, is prepared through a facile thermal conversion of a ZIF-
Available online 2 February 2021 8 core and Fe,Co-ZIF shell composite precursor (ZIF-8@Fe,Co-ZIF) without any post-
treatments. The existence of ZIF-8 core can maintain the structure of the ZIF-8@Fe,Co-
Keywords: ZIF composite controllable, avoiding the damage to the pore structure for fast mass
Oxygen reduction reaction transfer during pyrolysis. Meanwhile, the bi-metal iron and cobalt co-doping shell is more
Electrocatalyst conducive for uniform dispersion of CoFe alloy particles than single one due to the interval
Core-shell structure effects, which can create various active sites and efficiently promote the ORR activity. As
Uniform dispersion expected, the optimal NC@CoFe,NeCNP electrocatalyst exhibits an excellent catalytic ac-
One-step pyrolysis tivity with a high onset potential and half-wave potential (0.970 V and 0.865 V) compared to
commercial Pt/C (0.934 V and 0.846 V). The kinetic current density of NC@CoFe,NeCNP
reached to 7.99 mA cm2, which is higher than Pt/C (5.14 mA cm2) at 0.85 V. Furthermore,
the NC@CoFe,NeCNP electrocatalyst demonstrates better electrochemical stability and
anti-poisoning ability.
© 2020 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.

* Corresponding author.
E-mail address: [email protected] (X. Hu).
https://doi.org/10.1016/j.ijhydene.2020.11.210
0360-3199/© 2020 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.
9342 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0

Hence, in this context, we prepared a nitrogen-doped car-

Introduction bon core supported CoFe alloy-nitrogen co-doped carbon shell
nanopolyhedron (NC@CoFe,NeCNP) electrocatalyst through a
Excessive consumption of the limited fossil fuel and conse- facile thermal conversion of a ZIF-8 core supported Fe,Co-ZIF
quent environmental pollution problems have been getting shell composite precursor (ZIF-8@Fe,Co-ZIF). During the py-
worse in the last couple of years, the key to which lied in the 
rolysis of 950  C (Zn boiling point: 908 C), the core ZIF-8 not
development of green energy storage and conversion tech- only acts as a support to guarantee structural integrity and
nology [1e5]. Hydrogen technologies consist of water elec- inhibits the collapse of structure, but creates abundant pore
trolysers [6,7], metaleair batteries [8,9] and fuel cells [10,11], structure for fast mass transfer by the generated Zn gas.
have been drawing more attentions due to their competitive Simultaneously, bi-metal iron and cobalt co-doping shell is
advantages of zero emission, high efficiency and durability. more conducive to uniform dispersion of metal particles than
Especially, the fuel cell shows great application prospect in single one due to the interval effect, which could create
mobile and stationary power generation. However, Oxygen various active sites consist of Fe-Nx or Co-Nx and efficiently
reduction reaction (ORR) has a higher energy barrier and a promote the oxygen reduction activity. By regulating the
slower kinetics in the cathode of fuel cells [12e14], thus effi- molar ratio of shell metal to nuclear metal (Fe,Co/Zn), and
cient electrocatalyst should be explored to reduce the over- shell metal Fe to Co (Fe/Co), the NC@CoFe,NeCNP could be
potential and improve the ORR activity. Up to now, platinum obtained with high N content, large specific surface area,
(Pt) and Pt-based catalysts [15e17] are the state of the art abundant pore structure, uniformly dispersed metal particles
owing to their higher catalytic activity. However, the high cost and excellent electrochemical activity. As expected, the
and inferior stability have become major constraints on the NC@CoFe,NeCNP with Fe,Co/Zn ¼ 0.1 and Fe/Co ¼ 1/1
large scale applications. Thus, the alternative catalysts with exhibited excellent electrochemical activity with a higher
lower price arouse wide interests and attract more explora- half-potential of 0.865 V than that of Pt/C (0.846 V) in the
tion. Nowadays, Pt-free catalysts including alloys [18], metal alkaline solution.
oxides [19], sulfides [20], carbides [21], and heteroatoms doped
carbon materials [22] have attracted more attentions. Among
the catalysts, carbon-based catalysts with transition metal Experimental sections
and heteroatoms (especially N atom) doped (TM-N-C, TM ¼ Fe,
Co, Ni, etc.) have been widely regarded as most promising Synthesis of ZIF-8 precursor
substitutes for Pt-based catalysts because of their low cost and
high activity [23,24]. Although great achievements have been In the synthesis of ZIF-8 precursor, Zn(NO3)2$6H2O (5.45 mmol,
made by the TM-N-C catalyst derived from metal salt and 1.62 g) and 2-Methylimidazole (MeIm, 12.8 mmol, 1.052 g) were
nitrogen-carbon complex, there are still some problems uniformly distributed in the methanol (40 mL) respectively.
remained, such as severe agglomeration of metal particles, Then, the above were evenly mixed under the stirring condi-
the collapse of pore structure and low utilization of active sites tion for 2 min, followed by standing for 12 h at room tem-
and so on [25]. perature. As a result, the white powder was obtained by
The metal-organic frameworks (MOFs), formed by the co- suction filtration, washing and drying process.
ordination of metal ions and nitrogen-containing ligands on
the condition of no carbon source, have emerged as a pre- Synthesis of ZIF-8@Fe,Co-ZIF precursor
cursor for synthesizing the TM-N-C catalyst due to diverse
structural topologies, ultrahigh specific surface area, and In the synthesis of ZIF-8@Fe,Co-ZIF, ZIF-8 (160 mg) dissolved
adjustable composition [26]. A large number of reports [27,28] in N2-saturated methanol (160 mL) was first prepared by ul-
have shown that the catalysts derived from MOFs could trasonic dispersion. Afterward, 20 mL N2-saturated methanol
inherit the excellent characteristics for ORR, such as large with FeSO4$7H2O (0.3 mmol, 83.4 mg) and Co(NO3)2$6H2O
specific surface area, rich nitrogen or TM-N content. In this (0.3 mmol, 87.3 mg) was injected in the radius flask under
case, more than 20 thousand MOFs have been investigated, continuously stirring and followed was the addition of 10 mL
which consist of single MOF [29], double MOF [30], core-shell methanol with MeIm (9.6 mmol, 788.2 mg) in the same way.
structural MOF [31], heteroatom doped MOF [32], and tem- The solution would keep for 12 h at room temperature on the
plate or carbon source supported MOF [33] and so on. How- condition of continuous N2 injection and stirring. As a result,
ever, it has proved that most carbon electrocatalysts always the purple powder was obtained by suction filtration, washing
face the pore structure collapses under high temperature py- and drying process. All the solution system was simulta-
rolysis, causing the active sites to be buried [34], And then, it is neously purged N2 gas to control an O2-free environment,
not conducive to the rapid mass transfer of the reactants to inhibiting the oxidation of Fe2þ to Fe3þ.
the active sites, further decreasing the catalytic activity. The contrast Fe,Co-ZIF precursor was prepared in the
Meanwhile, the intermediate states of different reactions (eg. similar method. Co(NO3)2$6H2O (1.5 mmol, 437 mg) and
OH*, OOH*) have a linear relationship with intrinsic adsorp- FeSO4$7H2O (1.5 mmol, 417 mg) with Fe/Co of 1/1 and MeIm
tion energy, and single active site cannot achieve the optimal (48 mmol, 3.941 g) were dissolved into 160 mL N2-saturated
thermodynamic equilibrium of multiple reaction intermedi- methanol, respectively. Then, the above solution was evenly
ate states, which makes it difficult to optimize the catalyst mixed for 12 h at room temperature on the condition of
performance [35]. continuous N2 injection and stirring. As a result, the purple
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0 9343

powder was obtained by suction filtration, washing and drying diameter size of 1 mm, and Fe,Co-ZIF prepared by a similar
process. method showed irregular morphology with severe structure
damage (Fig. S1), indicating Fe and Co simultaneously replace
Synthesis of NC@CoFe,NeCNP electrocatalyst Zn to prepare the ZIF material was infeasible with the Fe/Co
molar of 1/1. Meanwhile, XRD patterns (Fig. S2) suggested that
The NC@CoFe,NeCNP electrocatalyst was prepared by the the crystal structure of ZIF-8 had a little difference with the
pyrolysis of core-shell structural ZIF-8@Fe,Co-ZIF precursor at Fe,Co-ZIF materials, which suffered severe damage mainly

950  C with a heating speed of 5 C min1 and holding time of due to great lattice expansion or reorganization of chemical
2 h in Ar atmosphere. As a result, the electrocatalyst was bonds [36]. Numerous studies [37,38] have shown that struc-
cooled to home temperature naturally and black power would ture features and active sites of the electrocatalysts are critical
be obtained through a grinding process. Meanwhile, the to catalyst activity, therefore, epitaxial growth of Fe,Co-ZIF on
NeCNP and CoFe,NeCNP was prepared in the same way. ZIF-8 core is a good choice to construct the core-shell struc-
tured ZIF-8@Fe,Co-ZIF with a regular shape and multiple
Materials characterization active sites. It turns out that SEM (Fig. 1a) and TEM images
(Fig. 1b) of ZIF-8@Fe,Co-ZIF precursor has a slightly larger
Scanning electron microscope (SEM) and transmission elec- particle size of 1.1 mm, probable indicating core-shell structure
tron microscope (TEM) was conducted on the FE-JSM-6701F have been formed. Element mapping and EDS (Fig. 1c) further
(JEOL, Japan) and JSM-2100 (JEOL, Japan) to explore the proved the core-shell structured ZIF-8@Fe,Co-ZIF to be formed
morphology, respectively. Energy dispersive spectrometer with Fe, Co element in the shell and Zn in the core. And the N2
(EDS) and high-resolution scanning transmission electron adsorption-desorption test showed the precursor ZIF-
microscopy (HR-STEM) were characterized on the JEM- 8@Fe,Co-ZIF had a large SSA of 1360.3 m2 g1 and a narrow
ARM200F (JEOL, Japan) to analyze the atom and element dis- PSD of 1.7 nm (Fig. S2).
tribution. Thermo-gravimetric was determined on STA7300 The as-prepared NC@CoFe,NeCNP electrocatalyst was ob-
(HITACHI, Japan) to research the pyrolysis process. X-ray tained by directly carbonizing ZIF-8@Fe,Co-ZIF under argon
diffraction (XRD) was detected by D/max-2500 (Rigaku, Japan) atmosphere of 950  C due to the TG analysis (Fig. S3) and the
to explore crystal structure feature. The N2 adsorption and Zn volatility may create abundant tunnel structures. Scheme 1
desorption experiment was identified by MicroActive for ASAP suggested that ZIF-8@Fe,Co-ZIF precursor was converted into
2460 instrument to study the specific surface area (SSA) and CoFe alloy, nitrogen co-doped carbon-based electrocatalyst
pore size distribution (PSD). Raman spectroscopy was ob- during pyrolysis, where the MeIM was adopted as a source of
tained by a confocal microscope (HR800, America) with a carbon and nitrogen doping into the porous carbon matrix. At
632.8 nm laser. X-ray photoelectron spectroscopy (XPS) mea- the same time, Zn2þ will be reduced to form a series of clusters
surement was carried out on the ESCALAB 250xi spectrometer and volatilize at a high temperature of 950  C, and part of Fe2þ
with binding energy alignment of C 1s peak at 284.8 eV. or Co2þ participated in Fe-Nx or Co-Nx active sites, and a small
Inductively coupled plasma-atomic emission spectrometry amount is reduced to CoFe alloy nanoparticles. The XRD
(ICP-AES) was investigated on Penta-ET-X3 instrument to pattern (Fig. 2a) proved the formation of pure phase CoFe alloy
analyze the element content. (PDF#49e1568) nanoparticles in the NC@CoFe,NeCNP elec-
trocatalyst with diffraction peaks located at approximately
Electrochemical measurement 45 , 65 , 83 assignable to the (110), (200), and (220) planes,
however, CoFe,NeCNP exhibited another peak of Co or CoCx
The ORR performance was detected on a work station of ALS/ phase components, which may act as an impurity phase and
DY2323 with three-electrode system at room temperature in weaken the activity of the electrocatalyst. The enlarged XRD
0.1 M KOH solution. Pt wire, saturated calomel electrode (SCE) pattern (Fig. S4) also intuitively illustrates the existence of
and rotating ring-disk electrode (RRDE) coated with electro- CoFe alloy. As shown in the TEM image (Fig. 2b), NC@Co-
catalyst were acted as counter, reference and working elec- Fe,NeCNP inherit the rhombic dodecahedron shape of the
trodes, respectively. The potentials used in the report are all precursor but exhibit a shrinked appearance and uneven
converted into values based on reversible hydrogen electrode surface characteristics, and CoFe alloy nanoparticles
(RHE). The catalyst slurry was firstly conducted by sonicating (approximately 10 nm) existed on the electrocatalyst without
the mixture of the electrocatalyst (5 mg) and Nafion (10 mL, any obvious agglomeration. The CoFe alloy gradually become
5 wt%, Dupont) in ethanol (1.0 mL) until evenly dispersed. And smaller with the increasing of Fe/Co proportion, which all
then, the catalyst slurry is applied dropwise to the working possessed a better dispersibility than that of NC@Co,NeCNP
electrode with 20 mL in total (four times) to ensure the loading derived ZIF-8@ZIF-67 due to the interval effects of Fe (Fig. S5).
of 788 mg cm2. On the contrast, the Pt loading was 20 mg cm2. This result may indicated Fe2þ has a stronger interaction with
N than Co2þ, which in turn causes most Fe2þ to exist in the
form of FeeN instead of separating out to metal particles [36].
Result and discussion Meanwhile, CoFe,NeCNP samples prepared from Fe,Co-ZIF
faced severe aggregation with larger particles of 100 nm
Physical characterization (Fig. S6). This showed that uniform pyrolysis process of Fe,Co-
ZIF shell could be achieved by using ZIF-8 as a support [39].
Homogeneous ZIF-8 precursors with a rhombic dodecahedron The Zn vapor produced by ZIF-8 during pyrolysis might inhibit
structure were synthesized by hydrothermal method with a the aggregation of metal particles and promote uniform
9344 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0

Fig. 1 e SEM (a), TEM (b) and EDS and element distribution (c) of core-shell structured ZIF-8@Fe,Co-ZIF precursor.

Scheme 1 e Synthetic routes of the NC@CoFe,NeCNP electrocatalyst for efficient ORR.

dispersion of active sites, probably attributed to the spatial performance. HRTEM in Fig. S7 indicated that NC@Co-
isolation of Zn vapor to the metal particles [40]. The STEM Fe,NeCNP had a graphite carbon structure with the spacing of
element mapping (Fig. 2c) suggested that more C, N, Fe and Co 0.345 nm in C (002) plane and CoFe alloys (110) with a spacing
elements evenly dispersed on the electrocatalyst, which was of 0.202 nm were embedded in the skeleton material to
favorable for the mass transfer of reactants to the Fe-Nx or Co- improve the catalyst conductivity and accelerate the electron
Nx active center, further accelerating the reaction process. As transport of the ORR. The XRD patterns (Fig. S4) of NC@Co-
far as concerned, the electrocatalyst with a higher utilization Fe,NeCNP exhibited a graphite carbon diffraction peak of C
rate of active sites always possess excellent ORR performance, (002) at 26 , which is sharper due to the high degree of
and the highly exposed and uniformly dispersed Fe-Nx or Co- graphitization, as proved by Raman analysis with a lower ID/IG
Nx parts are essential for enhancement of the ORR (Fig. S8).
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Fig. 2 e XRD patterns (a) of NeCNP, CoFe,NeCNP and NC@CoFe,NeCNP electrocatalyst, and TEM (b) and element distribution
(c) of the core-shell structured NC@CoFe,NeCNP electrocatalyst.

Fig. 3 e N2 adsorptionedesorption isotherms (a) and pore size distributions (b) of NeCNP, CoFe,NeCNP, and
NC@CoFe,NeCNP electrocatalyst.

N2 adsorption-desorption test was carried out to check the performance. The as-preferred NC@CoFe,NeCNP electro-
SSA and PSD of NeCNP, CoFe,NeCNP, and NC@CoFe,NeCNP. catalyst showed a rapid adsorption at low pressure and
As the increase of Fe,Co/Zn molar ratio, the SSA exhibited a obvious hysteresis loop at middle pressure (Fig. 3a), which
gradual increasing trend with the larger area of hysteresis indicated the existence of micropores and mesopores,
loops and significant increase in mesoporous content, which respectively. The PSD also suggested that the pore size of the
is beneficial for the promotion of mass transfer efficiency, NC@CoFe,NeCNP catalyst is mainly concentrated at 0e2 and
further enhancing the utilization of active sites and ORR 2e3 nm (Fig. 3b). As expected, the NC@CoFe,NeCNP exhibited
9346 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0

a large SSA of 525.3 m2 g1 with high content micro-SSA of electrocatalyst was explored through the method of element
56.3% and a great pore volume of 0.397 cm3 g1 due to the peak separation. The deconvoluted N 1s [42] spectra of the
abundant porous structure. In contrast, NeCNP derived from NC@CoFe,NeCNP (Fig. 4b) indicated the existence of pyridine
ZIF-8 exhibited a high micropore content with the micro-SSA N (21.8%), pyrrolic N (28.2%), graphitic N (31.6%), and oxidized
of 94.7% and CoFe,NeCNP derived from Fe,Co-ZIF showed a N (18.4%) in the NC@CoFe,NeCNP. The total amount of pyri-
high mesopore content with meso-SSA of 72.6% (Table S1). dine nitrogen and graphite nitrogen reached to 53.4%, which is
These result obviously showed that employing ZIF-8 as the always regarded as a favor for ORR performance [43e46]. The
core to construct coreshell structured ZIF-8@Fe,Co-ZIF is a deconvoluted Fe 2p spectrum [47] suggested the presence of
good choice to build an electrocatalyst with a hierarchically Fe2þ, Fe3þ and shake-up satellite peak in NC@CoFe,NeCNP
microporous and mesoporous structure. The microporous (Fig. 4c) with a higher ratio of Fe2þ (41.3%) than Fe3þ (28.8%),
structure with large SSA was conducive to anchoring Fe-Nx or exhibiting a higher Fe2þ content than NC@CoFe,NeCNP with
Co-Nx active center, and mesopores were favorable for the the Fe/Co ratio of 2/1, and the deconvoluted Co 2p spectrum
efficient mass transport of reactive substances to active center [24] suggested the presence of Co2þ, Co3þ and shake-up sat-
[41]. ellite in NC@CoFe,NeCNP with a higher ratio of Co2þ (48.6%)
XPS measurements showed that the surface of NC@Co- than Co3þ (21.2%) in the Co 2p 3/2 in Fig. 4d, where the Fe2þ or
Fe,NeCNP electrocatalyst contained element compositions of Co2þ were likely to participating in the Fe-Nx or Co-Nx active
C (83.51%), O (9.52%), N (4.62%), Fe (0.99%) and Co (1.36%), center for oxygen reduction [30,48e51].
suggesting the incorporation of Fe, Co and N into the carbon-
based framework derived from ZIF-8@Fe,Co-ZIF precursor Electrochemical performance
(Fig. 4a). The N content of NC@CoFe,NeCNP was gradually
raised until the Fe/Co molar ratio up to 1/1 in the shell (Table The electrochemical activity of NeCNP, CoFe,NeCNP and
S2), which might suggest Fe is easier than Co to combine with NC@CoFe,NeCNP was investigated in Fig. 5aef. Cyclic vol-
N during the carbonization. Excessive Fe/Co molar ratio of 2/1 tammetry (CV) test (Fig. 5a) suggested no redox peak appeared
may lead to N loss (Fig. S9) possibly due to the oxidation of in N2 saturated KOH solution and a strong reduction peak in
Fe2þ to Fe3þ that caused serious damage to crystal structure O2 saturated KOH solution in the range of 0e1.2 V. Further-
and coordination environment, which was not favorable to more, NC@CoFe,NeCNP electrocatalyst exhibited a more
the ORR performance (Fig. S10). It also showed CoFe,NeCNP obvious and positive ORR peak than NeCNP and CoFe,NeCNP
with a significantly lower content of 2.03 at.% than NC@Co- from 0.8 to 0.9 V, indicating a higher ORR performance of
Fe,NeCNP, the severe N content decline of which is mainly NC@CoFe,NeCNP. Linear sweep voltammetry (LSV) test (Fig.
attributed to structural damage during the pyrolysis. Chemi- 5b) confirmed the NC@CoFe,NeCNP possessed an excellent
cal state of N, Fe, Co in the representative NC@CoFe,NeCNP ORR activity with a half potential of 0.865 V, which was higher

Fig. 4 e XPS survey spectra (a), high-resolution N 1s spectra (b), Fe 2p spectrum (c) and Co 2p spectrum (d) of
NC@CoFe,NeCNP.
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Fig. 5 e (a) CV curves of NeCNP, CoFe,NeCNP, NC@CoFe,NeCNP electrocatalysts in N2 and O2-saturated KOH electrolyte. (b)
LSV curves of Pt/C, NeCNP, CoFe,NeCNP and NC@CoFe,NeCNP in O2-saturated KOH electrolyte at 1600 rpm. (c) LSV curves of
NC@CoFe,NeCNP at various rotational speeds (2025 rpm, 1600 rpm, 1225 rpm, 900 rpm, and 625 rpm) and calculated
transferred electrons number according to K-L equation. (d) The corresponding histogram of half wave potential (E1/2) and
kinetic current density (Jk¼0.85) for different electrocatalysts. (e) Corresponding Tafel slopes curves. (f) Comparative electron
transfer number and the H2O2 yield.

Fig. 6 e (a) Chronoamperometric responses for NC@CoFe,NeCNP and Pt/C electrocatalyst at 0.85 V for 10000s in 0.1 M KOH
electrolyte. (b) Chronoamperometric responses for NC@CoFe,NeCNP and Pt/C electrocatalyst at 0.85 V with the injection of
3 M methanol into the KOH electrolyte.

than NeCNP (0.742 V), CoFe,NeCNP(0.841 V) and Pt/C (0.846 V), support played a key role in improving the ORR performance
simultaneously superior to a large number of non-noble metal due to abundant pore structure and evenly dispersed active
oxygen reduction electrocatalysts reported in the literature sites. In addition, the NC@CoFe,NeCNP electrocatalyst
(Table S3). This indicates that NC core derived from ZIF-8 showed a high electron transfer number of 3.97 conducted by
9348 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 9 3 4 1 e9 3 5 0

KL equation (Fig. 5c), showing an excellent four-electron

reduction process compared with Pt/C (n ¼ 4.02, Fig. S11) Acknowledgment
and CoFe,NeCNP (n ¼ 3.79, Fig. S12).
To keep the impression of view more, double histogram This work was supported by State Grid Corporation Technol-
including E1/2 and [email protected] V of NC@CoFe,NeCNP indicated an ogy Support Project: Research on Key Technology of Mem-
excellent ORR performance of 0.865 V and possessed the brane Electrode of Proton Exchange Membrane Fuel Cell
highest Jk of 7.99 mA cm2 at 0.85 V than that of NeCNP Suitable for Variable Load (Contract No.
(0.743 V, 0.18 mA cm2), CoFe,NeCNP (0.847 V, SGGR0000DLJ1800814). The authors acknowledge critical
4.53 mA cm2) and Pt/C (0.846 V, 5.14 mA cm2) in Fig. 5d. The technical services provided by Beijing Zhongkebaice Tech-
Tafel curves (Fig. 5e) showed the NC@CoFe,NeCNP was pro- nology Service Co., Ltd.
vided with a smallest slope of 61 mV dec1 with a fast oxygen
reduction reaction kinetics than NeCNP, CoFe,NeCNP and Pt/
C with a high value of 85 mV dec1, 63 mV dec1and 64 mV Appendix A. Supplementary data
dec1 in a low overpotential region, respectively. ORR selec-
tivity was evaluated by the calculation of H2O2 yield from ring Supplementary data to this article can be found online at
current data, where the results of NC@CoFe,NeCNP exhibited https://doi.org/10.1016/j.ijhydene.2020.11.210.
a lowest H2O2 yield of approximately 10% or less in the po-
tential range from 0.3 to 0.8 V, suggesting an excellent four-
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Declaration of competing interest growth of metal-organic frameworks and their derived
carbon-based network for efficient electrocatalytic oxygen
The authors declare that they have no known competing reduction. Adv Mater 2016;28:2337e44.
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appeared to influence the work reported in this paper.
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