Chemical Engineering Journal 395 (2020) 125158

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

FeCo nanoparticles wrapped in N-doped carbon derived from Prussian blue T

analogue and dicyandiamide as efficient oxygen reduction electrocatalysts
for Al-air batteries
Linfang Cuia,b, Mingxing Chena,b, Ge Huoa,b, Xian-Zhu Fua, , Jing-Li Luoa,c,
⁎ ⁎

a
College of Materials Science and Engineering, Shenzhen University, 1066 Xueyuan Ave, Nanshan District, Shenzhen 518055, China
b
Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University,
Shenzhen 518060, China
c
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada

HIGHLIGHTS GRAPHICAL ABSTRACT

• N-doped graphitic carbon embedded

with FeCo nanoparticles has been
FeCo nanoparticles wrapped in N-doped carbon is developed as efficient oxygen reduction electrocatalysts for
Al-air batteries
prepared.
• The PD-800 is an efficient ORR cata-
lyst and comparable with Pt/C.
• Al-air battery for PD-800 surpasses
that of Pt/C catalyst.

ARTICLE INFO ABSTRACT

Keywords: Developing highly active and durable electrocatalysts with low-cost for the oxygen reduction reaction (ORR) is of
FeCo alloy paramount importance for promoting economical and high-performance Al-air batteries. Herein, nitrogen-doped
N-doped carbon carbon decorated with FeCo nanoparticles catalysts is prepared by a low-cost and facile approach employed Prussian
Oxygen reduction reaction blue analogue and dicyandiamide as precursors. The obtained catalyst exhibits remarkable ORR activity with an
Al-air battery
onset potential (0.981 V vs. RHE) and a high half-wave potential (0.848 V vs. RHE), as well as superior stability in
alkaline conditions. The outstanding electrocatalytic performance of electrocatalysts might be resulted from the
hierarchical porous structure and synergetic effect between FeCo alloy and N-doped graphitic carbon species. As a
demonstration, the optimized catalysts are employed as the cathode catalysts in a Al-air battery, which shows re-
markable discharge performance with higher open-circuit voltage of 1.67 V and large power density of
98.62 mW cm−2 which exceeding commercial Pt/C electrocatalysts (1.65 V, 90.81 mW cm−2), and exceptional cycle
stability of 40 h (4 cycles). This work will provide a chance to explore scalable advanced catalysts in Al-air battery.

⁎
Corresponding authors at: College of Materials Science and Engineering, Shenzhen University, 1066 Xueyuan Ave, Nanshan District, Shenzhen 518055, China
(J.L. Luo).
E-mail addresses: xz.fu@szu.edu.cn (X.-Z. Fu), luoj@ualberta.ca (J.-L. Luo).

https://doi.org/10.1016/j.cej.2020.125158
Received 11 February 2020; Received in revised form 1 April 2020; Accepted 18 April 2020
Available online 23 April 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
L. Cui, et al.
1. Introduction
Recently, Al-air batteries (AABs) have been evidenced as a pro-
mising choice to meet ever-growing energy demands, due to their
merits of higher theoretical voltage and energy density, excellent se-
curity and stability in operation [1,2]. Moreover, aluminum is earth-
abundance, low costs, recyclable as well as environmental metal com-
pared with the noble metal and its materials [3]. Nevertheless, the
performance and efficiency of AABs are still hindered by the intrinsic
sluggish kinetics of oxygen reduction reactions (ORR) at cathode [4].
Thus, it is imperative to explore cost-effective ORR catalysts with en-
hanced activity and improved durability for boosting applications of Al-
air batteries. As of today, the noble metal (Pt) and Pt-based materials
are still considered to be the benchmark and most efficient catalysts for
catalyzing ORR, but their exorbitant price and poor stability seriously
obstruct prevailing applications [5–7]. In this regard, it is therefore
urgent to develop inexpensive and scalable ORR catalysts with high-
efficiency as an alternative for noble metal materials.
Tremendous efforts have been devoted to developing non-precious
metal catalysts including carbonaceous materials doped with heteroa-
toms (i.e. N, P, S, B, F) [4,8], transition metals and their derivations
(such as oxides, carbides, nitrides, sulphides and phosphides) [9,10], as
well as transition metal-N-doped carbon (M−N−C) [11–13]. There-
into, three-dimensional (3-d) earth-abundant transition metals (i.e. Fe,
Co, Ni) have recently emerged as a new family of materials toward the
ORR with high activity and stability, rendering the great potential for
diverse catalytic environmental [14,15]. Especially, large numbers of
research groups have exploited intermetallic alloys of the transition
metals, FeCo [16–19], FeNi [20], and NiCo [15,21,22] for ORR cata-
lysts, which are contributed to new integrate functionalities formed by
intermetallic interactions between individual metals. However, elec-
trocatalytic ORR in basic/acidic medium toward is precluded by the
self-aggregation and poor stability. The carbon shell coating has been
regarded as an effective way to protect alloys from aggregation and
degradation when alloys are subjected to ORR, because carbon coating
can effectively isolate alloys from the electrolyte solutions [18,19]. The
carbon coating doped with nitrogen (N), and N-doped carbonaceous
materials have also been confirmed as a promising ORR catalyst. The
insertion of N dopants into the carbonaceous materials display sig-
nificant improvement of catalysts’ conductivity and electronic affinity
of the carbon matrix, resulting in an enhancement in electrocatalyst
activity and producing more active sites [8,22]. Moreover, there are
synergetic effects between N-doped carbon materials and transition
metals, which can enhance ORR catalytic activity greatly by modifying
the local electronic structure and optimizing the intermediate adsorp-
tion. For example, FeCo alloy nanoparticles assembled in the Nitrogen-
doped carbon nanofibers exhibits superior bifunctional activities to-
ward ORR and OER in KOH solution [23]. CoNi nanoparticles em-
bedded in the N-doped carbon tubes could improve ORR and OER
performance in all the pH-dependence media [21]. However, the cur-
rent non-precious metal catalysts still show undesirable intrinsic ac-
tivities, and thus lead to their activities are inferior compared with
commercial Pt/C. There is still a long way to develop the non-precious
metal catalysts to be competitive in the family of ORR electrocatalysts,
because of their undesirable intrinsic activities and durability.
The well-organized metal–organic frameworks (MOFs) have been
regarded as an attract platform for the fabrication of porous carbon-
based materials because of the coexistence of abundant nitrogen species
and various transition metals, as well as porous structure, which en-
dows its deprived hybrid composites with abundant of N-C or M−N−C
active sites for electrocatalysis [24]. As a class of MOFs, Prussian blue
analog (PBA) has recently stood out as a promising precursors for
preparation of the porous carbon frameworks [25–27]. However, in-
ferior electrical conductivity and loss of nitrogen caused by carboni-
zation greatly restrict their electrocatalytic activity.
Herein, we adopt dicyandiamide (DCDA) as secondary carbon and
2
Chemical Engineering Journal 395 (2020) 125158
nitrogen source to tune the structure and N dopant of the MOF-derived
porous carbon, a highly porous framework of N-doped graphitic carbon
with FeCo nanoparticles encapsulated are synthesized by the thermal-
treatment of the mixture of DCDA and Prussian blue analog Fe3[Co
(CN)6]2 in Ar atmosphere. The resultant Fe3[Co(CN)6]2/DCDA com-
posite derived catalysts have an unique hierarchical micro-/meso-
porous structures. The integration of the architecture with abundant
FeCo species and N-doped graphitic carbon active sites enables the
catalyst excellent ORR activity and long-term durability in alkaline
electrolyte, and dramatically higher than most of reported MOFs de-
rived catalysts. The equipped Al-air battery as the cathode catalysts
exhibits an outstanding discharge performance, even outperforming the
Pt/C catalyst. This work may afford an alternative methodology for the
rational design of highly efficient catalysts based on alloy nanoparticles
encapsulated with carbon shell, and it is rewarding to develop these
catalysts for their application in metal-air batteries.
2. Experimental section
2.1. Preparation of catalyst
All purchased chemicals were of analytical grade and used as re-
ceived. Deionized (DI) water with a resistivity of 18.2 MΩ cm was used
for all experiments. In this work, a Prussian blue analogue (PBA) Fe3[Co
(CN)6]2 was prepared by a chemical precipitation reaction between
FeSO4·7H2O (Sigma–Aldrich) and K3[Co(CN)6]2 (Beijing J&K Co., Ltd.,
China) in aqueous solution of polyvinylpyrrolidone (PVP, average MW
58000, Aladdin Co., China). The desired product was referred to as
FeCo-PBA. The approach for FeCo-PBA was prepared according to the
previously reported literatures [28,29], except for some little mod-
ification. In a typical procedure, 0.005 mol of K3[Co(CN)6]2 was dis-
solved in 40 mL DI water containing 1.5 g of PVP. Then 50 mL of
FeSO4·7H2O (9 mM) was added dropwise into the premixed solution
under magnetic stirring, followed by stirring for another 30 min and
aged at room temperature for 24 h. The precipitates were collected after
several centrifuge-wash with deionized (DI) water and ethanol cycles,
and finally dried in vacuum drier at 40 °C for 24 h.
To prepare the FeCo-PBA/dicyandiamide (DCDA) composite, the as-
synthesized FeCo-PBA were mixed with DCDA according to the mass
ratio of 1:10 and grinded for 20 min. Then, the homogeneous precursor
was placed into a crucible under the nitrogen atmosphere, and annealed
at a designated temperature (600, 700, 800 and 900 °C) for 2 h with a
rate of 5 °C min−1. To remove the unstable and inactive species, the
obtained carbonized products were immersed in 0.5 M H2SO4 aqueous
solution for 24 h in room temperature. Subsequently, the products were
washed with DI water until pH = 7, and then dried at 60 °C for 24 h.
The finial products were designated as PD-T, where T refers to the
annealing temperature. To confirm the vital effect of DCDA, the fabri-
cation of pure FeCo-PBA (marked as PA-800) was also studied under the
identical conditions as PD-800.
2.2. Material characterizations
Wide-angle X-ray diffraction (XRD) patterns were collected using X-
ray diffractometer (Bruker D8 Advance) at 50 kV and 360 mA with Cu-
Kɑ radiation (λ = 1.54178 Å). Field-emission scanning electron mi-
croscope (FESEM, SU-70) and Field-emission transmission electron
microscope (FEI Tecnai G2 F20) were employed to characterize the
morphologies of the samples, and Raman spectrum of the samples were
carried out on a RENIDHAW invia instrument with a 532 nm excitation
laser source. X-ray photoelectron spectroscopy (XPS, ESCALAB 250XI,
Thermo Scientific) was employed to analyze the elemental composi-
tions and chemical states of elements of sample surface, and C 1s
(284.8 eV) was employed as a reference to calibrate all binding energies
for samples. Specific surface areas and pore size distributions of the
catalysts were analyzed using Brunauer-Emmett-Teller (BET, 3FIex),
L. Cui, et al.
Barrett-Joyner-Halenda (BJH) methods was used. Ahead of testing, all
catalysts were degassed in a vacuum overnight at 60 °C. Inductively
coupled plasma optical emission spectroscopy (ICP-OES) was con-
ducted on PerkinElmer 8300.
2.3. Electrochemical characterizations
The electrochemical activities of all the as-synthesized catalysts
were conducted in a conventional three-electrode system on a CHI 760E
workstation (Shanghai Chenhua, China) at 25 ± 1 °C. Glassy carbon
(GC) electrode (5 mm diameter, area of 0.196 cm2), Pt foil (2 × 2 cm2
square) and Ag/AgCl-3.5 M electrode were employed as the working
electrode, counter electrode, and reference electrode, respectively.
Ahead of using, GC electrode was polished with 0.3 μm and 0.05 μm
alumina slurry in turn, and then was rinsed with DI water and dried at
room temperature. The catalyst ink was prepared in the following: 4 mg
of the catalyst was dispersed in 1 mL solution of 2:1 v/v ethanol/
deionized water mixed solvent with 20 μL of 5 wt% Nafion (Sigma-
Aldrich), and subsequently ultrasonicated for 30 min to form a homo-
geneous suspension. Then, 20 μL of suspension was carefully dropped
onto the GC rotating disc electrode (RDE) to yield a loading of
~0.4 mg cm−2. For comparison, 20 wt% Pt/C (Alfa Aesar) ink was
formed like other catalyst inks with a similar procedure, and the
loading was 0.1 mg cm−2 for Pt/C. Prior to the ORR measurements, the
electrolyte was purged with N2/O2 for approximately 30 min. The
cyclic voltammetry (CV) curves were tested in N2/O2-saturated 0.1 M
KOH with a scan rate of 10 mV s−1. LSV tests were measured using the
RDE in O2-saturated 0.1 M KOH solution at a sweep rate of 10 mV s−1
with different electrode rotation rates from 100 to 2025 rpm, and the
potential range from 0.2 to −0.8 V (vs. Ag/AgCl). Long-time and me-
thanol crossover measurements were conducted in O2-saturated solu-
tion under a rotating speed of 1600 rpm. For the anti-methanol tests,
the current was recorded when 3.0 M methanol was added into the
electrolyte at 400 s. All measurements initially versus Ag/AgCl and
were normalized to reversible hydrogen electrode (RHE) according to
the following formula:
ERHE = E(Ag/AgCl) + 0.197 + 0.059 × pH (1)
For the ORR, electrochemical impedance spectroscopy (EIS) was
tested in O2-saturated 0.1 M KOH electrolyte at an amplitude of 10 mV
with varying frequency from 0.01 Hz to 1000 kHz. The Tafel curves
were obtained by fitting the LSV linear portions of the polarization plots
according to the equation:
= a+ blog |j| (2)
where a and b are constant and depend on specific catalysts and con-
ditions, and j is the current density.
The kinetic current density (Jk), known as mass-transport correction
for different rotating disk electrodes, is determined based on the fol-
lowing formula [30,31]:
J*JL
Jk =
JL J (3)
where J is the experimentally measured current density, and JL is the
obtained diffusion limited current density.
The electron transfer number (n) and kinetic current density (Jk) for
3
Chemical Engineering Journal 395 (2020) 125158
a typical ORR are calculated from the Koutecky-Levich equations:
1 1 1 1 1
= + = +
J Jk JL Jk B 2
1
(4)
2
- 1
B = 0.62nFC0 D03 6 (5)
Here, J, Jk and JL are the measured current density, kinetic current
density and diffusion limit current density, respectively. ω is the an-
gular rate of the disc in rpm and n is the electron transfer number, F is
Faraday constant (F = 96485C mol−1). C0 and D0 are the bulk con-
centration (1.2 × 10−6 mol cm−3) and diffusion coefficient
(1.9 × 10−5 cm2 s−1) of O2 in 0.1 M KOH solution, υ is the kinetic
viscosity (υ = 0.01 cm2 s−1). It’s noted that the coefficient 0.2 is
adopted when the rotation speed is presented in rpm.
To further understand of the ORR catalyzed by the as-synthesized
samples, the overall number of transfer electrons (n) and the yield of
H2O2 in ORR process can be evaluated on the base of rotating ring-disc
electrode (RRDE) using the following formulas:
IR
H2 O2 (%) = 200 ×
N
ID + IR
N (6)
ID
N= 4 ×
ID + IR /N (7)
in which IR and ID represent the ring current and the Faradaic current
densities at the disc, N is the current collecting efficiency of the Pt ring
and determined to be 0.37.
2.4. Al-air battery evaluation
To explore the potential of the as-synthesized materials in metal-air
battery applications, Al-air batteries were performed in a configuration
of homemade electrochemical cell, where Al foil was employed as
anode and 4.0 M KOH as electrolyte. As for the cathode, which con-
taining of a conductive current collector(Nickel foams), a gas diffusion
layer (Teflon-coated carbon fiber paper, catalyst loading 1.0 mg cm−2)
and a catalyst layer (as-synthesized catalyst, PVDF and carbon black
with a mass ratio of 3:4:7). Subsequently, the homogeneous electro-
catalyst slurry is uniformly loaded on a Ni foam with an area of
1 × 1 cm2. Prior to electrochemical testing, the above components are
pressed under 2 MPa pressure for 1 min, and then, drying it at 60 °C for
12 h to remove the solvent. All Al-air batteries test is conducted on a
CHI 760E electrochemical workstation at room temperature. The spe-
cific capacity can be calculated using the following equation:
Specific capacity = It/ m
where I is the discharging current (A), t is the discharging time (s) and
Δm is the weight loss of the anode (g).
3. Results and discussion
3.1. Catalyst preparation and characterization
The synthetic strategy of FeCo alloy nanoparticles encapsulated in
N-doped graphitic carbon is described in the experimental section and
schematically illustrated in Fig. 1. First, uniform Fe/Co-PBA nanocubes
Fig. 1. Schematic illustration of the preparation
of the PD-T catalyst.
L. Cui, et al. Chemical Engineering Journal 395 (2020) 125158

were synthesized as precursor through coprecipitation method in the

solution of PVP. Then, the desired PD-T was obtained by pyrolyzing the
mixture of solid Fe/Co-PBA nanocubes with DCDA at elevated tem-
perature under Ar atmosphere. DCDA is usually added as a precursor
for pyrolysis, and it can serve as the in situ template to produce the
layered graphitic nitride, which can regarded as a sacrificial template
for producing graphite materials [32].
As depicted in Fig. 2a and b, Fe/Co-PBA shows cubic morphology
and uniform size, its size is ca. 600–900 nm, and its pattern was con-
firmed by XRD result in Fig. 2c. After the carbonization treatment of the
mixture of the Fe/Co-PBA and DCDA at desired temperature, the
morphology and their network structure are preserved, along with a
slight size shrinkage (Fig. 2d and e), and the EDS mappings confirm that
C, Co, N, Fe, S are uniformly dispersed in the whole carbon matrix for
PD-800 (Fig. S1). There are no obvious differences in morphology and
size among these samples with different carbonation temperature
treatments in the hybrid (Fig. S2 and Fig. S3). Similar XRD patterns
(Figs. 2f and S4) of these PD-T and PA-800 samples are observed with
three main peaks centered at 44.9°, 65.3° and 82.6° for (1 1 0), (2 0 0)
and (2 1 1) planes, which correspond to the FeCo alloy (JCPDS No. 49-
1567), respectively. A distinct peak at approximately 26° for (0 0 2)
plane belonging to the graphitic carbon is detected in all samples,
confirming that the highly graphitized carbon is obtained in the cata- Fig. 3. (a) TEM and (b) HRTEM images of PD-800 (inset in (b) SAED pattern of
lysts. Also, Fe3C (assigned by &) is observed in PD-800 and PD-900, PD-800). (c) N2 adsorption–desorption isotherm and (d) pore size distribution
indicating that Fe3C alloy is formed in the hybrid catalysts. The ratio of curve of PD-800.
FeCo and Fe3C is 9.75 measured by the ICP-OES technique. The ex-
cellent ORR activity thus might be ascribed to the active sites for FeCo carbon shell. These results indicate the formation of FeCo nanoparticles
nanoparticles, N-doped graphitic carbon and Fe3C [23,33]. within the N-doped carbon layer and confirmed by the above-discussed
The microstructure of PD-800 catalyst is further observed by TEM XRD patterns (Fig. S5a and b). In addition, the FeCo nanoparticles size
and HRTEM. The black portion shown in TEM image is assignable to the for PD-900 (~25 nm) is larger than PD-800, and then the decreased
alloy particles wrapped by several graphitic carbon layers with a electrocatalytic activity for the PD-900. The select area electron dif-
0.34 nm lattice fringe (Fig. 3a). {Ma, 2019 #217}{Ma, 2019 #217} fraction (SAED) pattern (inset in Fig. 3a) reveals that the crystalline
Based on the analysis of HRTEM (Fig. 3b), the size of the FeCo alloy nature of the as-prepared PD-800. In order to analyze the specific sur-
nanoparticles are approximately 20 nm. Furthermore, FeCo alloy na- face area and porous structure, N2 adsorption/desorption measure-
noparticles with the lattice spacing of 0.202 nm, corresponding to the ments are carried out on the catalysts (Figs. 3c and S5c), which displays
(1 1 0) lattice fringe, which clearly demonstrates that the PD-800 a type-IV isotherm with a distinct hysteresis loop at a higher pressure
composite is constructed by FeCo alloy nanoparticles encapsulated by range from 0.4 to 1.0, representing the coexistence of micropores and
N-doped graphitic carbon shell (inset in Fig. 3b). In comparison, the PD- mesopores, which will provide more reactive active sites and hence
900 also resulted in similar FeCo alloy nanoparticles embedded by

Fig. 2. SEM images of (a, b) FeCo-PBA. (c) XRD patterns of the as-prepared Fe3[Co(CN)6]2. SEM images of (d, e) PD-800. (f) XRD patterns of PD-T samples.

4
L. Cui, et al.
improve the efficiency of ORR-related species [6,34].The Brunauer-
Emmet-Teller (BET) specific surface area and pore volume of PD-800
are measured to be 203.41 m2 g−1 and 0.361 cm3 g−1, which are larger
than 164.46 m2 g−1and 0.136 cm3 g−1 for PD-900. A larger specific
surface means a large number of active sites exposed for the catalysts,
resulting in an enhanced electrocatalytic performance. Moreover, a
detailed pore structure analysis (Figs. 3d and S5d) further reveals that
the hierarchical microporous and mesoporous structure, which are re-
sponsible for transporting O2 and electrolyte to the active sites [35].
Furthermore, the mesoporous structure not only facilitates mass
transfer but also leads to the exposure of more active sites [22]. The
unique architecture porous characteristics endows the PD-800 hybrid
with more catalytically active sites, which will facilitate the effective
electron/ion transport during the electrochemical reaction.
Raman spectroscopy is deemed as an effective method to detect the
structure defectiveness and degree of graphitization of samples. It can
be seen clearly that there are two distinct peaks around 1344 and
1572 cm−1 for all the samples, corresponding to D band and G band of
carbon materials, respectively (Figs. 4a and S4b) [36]. The D band is
ascribed to the graphene edges or disordered structure, and accompany
with the defect for its activation [37]. Generally, the intensity ratio of
the D to G band (ID/IG) is used to evaluate the degree of disorder in the
sp2 carbon materials, and a higher value indicates a higher defect de-
gree [38]. Additionally, some reports have revealed that defects of
carbon materials can enhance the electrocatalytic ORR activity
[39–41]. It can be seen from Fig. 4a that the value of ID/IG decreases
from 0.95 (PD-600) to 0.83 (PD-900) with the carbonization tempera-
ture, resulting in a higher degree of graphitization, which thus brings
about an enhancement for electrocatalytic activity of materials [36]. It
is also found that the total nitrogen content decreases from 7.75 at %
(PD-600) to 1.93 at % (PD-900) with increasing pyrolysis temperature
(Table S1), which implies that the number of potential N-based active
sites is diminishing [42]. In addition, the ratio of ID/IG is 0.88 for PD-
800, higher than that of PA-800 (0.83) (Fig. S3b), verifying that the
existence of DCDA can promote the formation of a higher amount of
defect structures carbon matrix, which is beneficial for producing
amount of active sites for electrocatalytic activity of PD-800 [41,43].
Fig. 4. (a) Comparative Raman spectrum of the electrocatalysts. Survey XPS spectrum of the PD-800. (b) High-resolution XPS spectra accompany with the corre-
sponding fitting plots of (c) N 1 s, d) C 1 s, (e) Fe 2p and (f) Co 2p of the PD-800.
5
Chemical Engineering Journal 395 (2020) 125158
X-ray photoelectron spectroscopy (XPS) is an effective method to
detect the chemical compositions and state of samples. The XPS survey
spectrum of all samples directly reveals the existence of C, N, O, S, Co
and Fe elements, indicating that N, Co and Fe heteroatoms have been
successfully doped into the carbon backbone [44]. Moreover, the cor-
responding EDS elemental-mapping images for PD-800 further de-
monstrate the homogenous distribution of C, N, S, Co and Fe elements
throughout the whole carbon architecture (Fig. S1). The presence of O
is possibly due to the incorporation of physic-chemically absorbed
oxygen or the residual oxygen-group in precursor, and the induction of
O atoms can alter the electronic structure of carbon atoms, thus influ-
encing the adsorption of O2 for ORR [41,45]. As for S element in the
sample, which possibly stems from the existence of SO42− affiliated to
samples. During the process of carbonization, the SO42− might be re-
duced and thus resulted in the generation of the element S. As shown in
Table S1, with increasing carbonization temperature from 600 to
900 °C, the contents of Fe, Co, C, N, O, S and the total nitrogen content
decrease obviously, whilst the amount of C increases. Meanwhile, it
should be noted that the pyridine- and pyrrolic-N are predominant for
the PD-T at low temperature, whereas the graphite-N is predominant at
high temperature due to its stability better than the other two N species
under higher temperature, and the results are in good accordance with
the previous report [46]. Notably, compared with the PA-800, the
content of total nitrogen in PD-800 increases and reaches up to 3.23 at
%, suggesting that the decomposition of the FeCo-PBA/DCDA compo-
site and subsequent chemical deposition can improve the content of
doped nitrogen, which likely result in generate amount of N-based ac-
tive sites and promote the ORR of PD-800 [42]. In addition, the high-
resolution N 1s spectra of PD-800 could be divided into five peaks at
398.1 eV (pyridinic -N), 398.9 eV (M (Fe/Co)-Nx), 401.1 eV (graphitic-
N), 399.8 eV (pyrrolic-N) and 402.8 eV (oxidized N), and their relative
percentage are 14.8, 17.5, 33.3, 12.4 and 22%, respectively (Fig. 4c)
[44,47]. This confirms the N dopant is successfully doped into the
carbon matrix. According to the previous reports, these N types except
for the uncertain oxidized N are believed to boost the catalytic activity
towards ORR [48]. The pyridinic N, M (Fe/Co)-Nx and pyrrolic-N are
considered to facilitate the onset potential, while graphitic-N is
L. Cui, et al.
allegedly responsible for the limiting current density by promoting
adsorption of oxygen atoms [44,49,50]. Furthermore, the pyridinic-N
and graphitic-N are considered to facilitate O2 adsorption and sub-
sequent dissociation to form intermediates (such as O* and OH*) in the
ORR process [51]. The high-resolution of C 1s XPS spectra (Fig. 4d) is
observed peaks at 284.5, 286.3, 288.1 and 291.7 eV, which are iden-
tified for CeC, C]N, C]O and Π-Π* bonds in PD-800, confirming that
N has been incorporated into the carbon matrix [17,38,52]. Ad-
ditionally, the C]O bond indicates that substantial oxygen-containing
groups have been successfully decorated on the surface of carbon ske-
leton, which can generate defects in the carbon matrix. The surface
defects on PD-800, regarded as anchoring sites for capturing oxygen
and facilitate the electrocatalytic activity of the material, in agreement
well with Raman result [17]. In order to further confirm the chemical
interaction between nitrogen and metal, the high-resolution of XPS
spectrum Fe 2p of and Co 2p are also studied. For the Fe 2p spectra
(Fig. 4e), the product has six peaks at different binding energy of 707.5,
711.3, 714.9, 720.4, 725.5 and 730.3 eV. The fitting peaks at 711.3 and
725.5 eV are corresponded to Fe2+ 2p3/2 and Fe2+ 2p1/2, while the
peaks at 714.9 and 730.3 eV are assigned to Fe3+ 2p3/2 and Fe3+ 2p1/2,
respectively [4,53]. The deconvolution also displays Fe with zero-va-
lence state (707.5 and 720.4 eV), which are ascribed to metallic iron in
FeCo alloy [54]. Moreover, the peak at 713.4 eV in the Fe 2p spectra
provides evidence of Fe-N interactions [55]. On the other hand, the
peaks centered at 781.6 and 796.4 eV are, respectively, ascribed to Fe
2p3/2 and Fe 2p1/2 [56]. From Fig. 4f, the two peaks at 780.6 and
795.7 eV correspond to Co 2p3/2 and Co 2p1/2, respectively [57]. The
satellite peak (785.2 eV) are also founded in the fitting plot, confirming
that the existence of Co-Nx/C species [36,58]. The Co-Nx groups in
carbon materials are regarded as the active sites, which can boost the
O2 dissociation and desorb H2O during electrochemical processes. No-
tably, the existence of metallic Fe (0) and Co (0) elements further
confirms the formation of FeCo nanoparticles, which is well coincident
with the XRD results. The above discussions further indicate the for-
mation of nitrogen-doped carbon decorated with FeCo nanoparticles.
Fig. 5. (a) LSV curves of the synthesized catalysts in O2-saturated 0.1 M KOH solution with electrode rotating rate of 1600 rpm, and (b) the corresponding Tafel
slopes. (c) Comparative the corresponding half-wave potential (E1/2) and kinetic current density at 0.8 V (Jk@0.8 V) for the samples. (d) The disk current densities
(bottom) and ring densities (top) of different catalysts in O2-saturated 0.1 M KOH recorded on the RRDE. (e) Current-time (i–t) chronoamperometric response for PD-
800 and Pt/C by adding of 3 M methanol after 400 s. (f) ORR chronoamperometric response of PD-800 and Pt/C in O2-saturated 0.1 M KOH with a constant potential
0.7 V (versus RHE) at 1600 rpm.
6
Chemical Engineering Journal 395 (2020) 125158
3.2. ORR catalytic performance
To assess the ORR activities of the as-prepared catalysts, cyclic
voltammetry (CV) measurements is first measured using rotating disk
electrode (RDE) under Ar- and O2-saturated 0.1 M KOH aqueous solu-
tion at a scan rate of 10 mV s−1. All potentials are provided versus RHE.
As illustrated in (Fig. S7), in the case of the Ar-saturated electrolyte, all
the CV curves display a similar feature without any obvious redox peak.
In sharp contrast, a significant oxygen reduction peak is clearly ob-
served at 0.7–0.8 V in the O2-saturated electrolyte, indicating an
oxygen reduction activity for all the samples [59]. Among all the as-
prepared samples, PD-800 shows the most positive reduction peak,
which predicts its best ORR activity. To further confirm the electro-
chemical activity towards ORR, the liner sweep voltammetry (LSV) of
the as-synthesized catalysts (Fig. 5a) are examined at the rotating rate
of 1600 rpm with a sweep rate of 5 mV s−1, the performance of PD-800
is better than its counterparts. Especially, the PD-800 has an onset
potential of 0.981 V, which is more positive than other comparative
catalysts and only 40 mV more negative than that of the commercial Pt/
C (1.02 V), evidencing a higher catalytic activity of PD-800. In addition,
the half-wave potential (E1/2) of PD-800 (0.848 V) is comparable with
that of Pt/C (E1/2 = 0.860 V). By contrast, the PA-800 displays the
lowest activity with a half-wave potential of 0.796 V, which may be due
to the low content of N caused by the absence of DCDA. Taking the
onset and half-wave potentials into consideration, although the PD-800
is inferior to Pt/C, it is comparable with or outperform many transition
metal-based catalysts in alkaline media, and the detailed information is
listed in Table S2. These results exhibit an excellent ORR catalytic ac-
tivity of PD-800, which can be attributed to the comprehensive effects
from the following aspects. (1) Moderate graphitic degree of carbon
framework and N dopant improve the electrical conductivity, accel-
erating electron transport during the reaction of ORR for PD-800. The
better conductivity has been expounded by electrochemical impedance
spectra (EIS) (Fig. S8) in the ORR region at 0.8 V, the charge-transfer
resistance of PD-800 is lower in comparison with other counterparts.
L. Cui, et al.
(2) The multiphase active sites for PD-800 enables it to be employed as
an ORR electrocatalyst, such as FeCo nanoparticles, the metal-N inter-
face coupling center, and abundant N dopant into the carbon matrix,
leading to a synergistic effect for an improved ORR performance. In
addition, the existence of Fe and Co metallic species in catalysts can
significantly enhance the electrical conductivity and then improve
charge transfer during the ORR process. (3) The abundant defects in
PD-800 can significantly enhance the ORR performance. A numerous of
studies have demonstrated that the defects of catalysts can greatly
change the electronic structure and chemical characteristics of material,
resulting in new physical–chemical properties or strong synergy effects
produced. In this work, N-dopants throughout the entire carbon fra-
mework has been evidenced, which can improve the defective degree of
PD-800. (4) The unique hierarchically porous structure enables plen-
tiful active sites provided by numerous N-doped graphitic carbon and
FeCo nanoparticles accessible to the diffusion of O2 and electrolyte
during the reaction. These combined factors together contributed
greatly to the enhanced ORR activity for PD-800 over the comparative
catalysts.
To achieve a better understanding of the reaction mechanism, the
LSV and corresponding Koutecky-Levich (K-L) curves are collected at
various rotating speeds from 100 to 2025 rpm in 0.1 M KOH. For all the
samples, their LSV curves present that the limiting current density are
enhanced gradually with increasing rotation rates (Fig. S9). This
characteristic validated that the process of ORR is kinetically con-
trolled, which is caused by shortening O2 diffusion distance at higher
rotation speeds [44,60]. Moreover, the corresponding K-L plot for PD-
800 exhibits the parallel fitting correlation (Fig. S10), which implies a
first-order reaction kinetics with respect to the dissolved oxygen in
electrolyte and similar electron transfer number (n) for each oxygen
molecule in ORR [61,62]. The n is a vital index to evaluate the ORR
activity of catalyst, the value for PD-800 is calculated to ~4 within the
potential range from 0.3 to 0.7 V according to K-L equation, which is
7
Chemical Engineering Journal 395 (2020) 125158
approach to the theoretical value (n of 4) of Pt/C and higher than that
of PA-800, validating a quasi-four-electron transfer process for PD-800.
Strikingly, the resulting PD-800 possesses a little lower Tafel slope of
95 mV dec−1 than Pt/C (104 mV dec−1), evidencing a fast kinetic re-
lated to the ORR process (Fig. 5b). Furthermore, the kinetic current
density (Jk) results reveal that PD-800 (92.43 mA cm−2) is larger than
that of PA-800 (4.46 mA cm−2), and even far outperforms Pt/C
(9.71 mA cm−2), indicating a faster reaction kinetics and effective
pervasion of reactants for PD-800 catalysts (Fig. 5c).
To further explore the ORR mechanism, we adopt rotating ring-risk
electrode (RRDE) to calculate n and the percentage of H2O2 in the O2-
saturated electrode, and it is considered as the most effective, correct
and convenient method. As depicted in Fig. 5d, it is obviously shown
that the ring current density for PD-800 is far below PA-800, which
further reveals that the introduction of DCDA to PBA is helpful to im-
prove the ORR catalytic performance. Moreover, the n for PD-800 is
above 3.90 in the scanning potential range of 0.178–1.07 V, which is
well coincident with RDE results, further indicating a 4e− electro-
chemistry reaction process. Simultaneously, the amount of H2O2 for PD-
800 in alkaline environments is lower than 10%, while PA-800 exhibits
the lowest n (1.61–3.78 from 0.178 to1.07 V) and the highest H2O2
yields (36.8–73%), indicating that the PD-800 can provide a high ORR
selectivity and efficient 4-electron pathway (Fig. S11).
Apart from the ORR catalytic activity, the durability and methanol
tolerance of the catalysts are also two vital parameters to determine an
electrocatalyst performance in a practical application [59]. Herein, the
current versus time (i-t) chonoamperometry measurements are carried
out to study the stability of PD-800 and Pt/C toward ORR at a constant
voltage of 0.7 V (versus RHE). In order to evaluate the fuel crossover
effect of PD-800, chronoamperometric responses for catalyzing ORR are
tested (Fig. 5e). Once 1 M methanol (CH3OH) is added into the 0.1 M
KOH electrolyte at 400 s, the current of PD-800 displays a slight change
while Pt/C drops sharply owing to the reaction of methanol poisoning,
Fig. 6. Electrochemical performance of the Al-
air battery with different catalysts as the
cathode in 4 M KOH. (a) Schematic illustration
of the Al-air battery. (b) Open circuit plots. (c)
Al-air batteries discharging polarization
curves and corresponding power density plots
with PD-800, PA-800 and Pt/C as the cathode
catalysts. (d) Specific capacities of the Al-air
batteries using PD-800, PA-800 and Pt/C as
cathodes at the current density of
50 mA cm−2.
L. Cui, et al.
Fig. 7. (a) Galvanostatic discharge plots (30 min for every discharge plateau) at different current densities. (b) The variation in the long-time discharge curves of the
battery with PD-800 as the air electrode with four times replenishing the Al anode and electrolyte.
demonstrating that PD-800 has an excellent immunity to CH3OH in the
practical application. As illustrated in Fig. 5f, after a continuous of
scanning 30 000 s, the PD-800 catalyst retains a superior stability with
approximately 10.5% loss of its initial current density. As a contrast, the
Pt/C fades by 11.9% under the same conditions, illustrating excellent
stability on PD-800 compared to Pt/C. The superior stability and anti-
methanol of PD-800 in comparison to that of the Pt/C reference enables
it an extremely promising material toward ORR in alkaline environ-
ments.
3.3. Application in Al-air batteries
Encouraged by the excellent ORR performance of the PD-800, which
arouse us great interest to investigate its feasibility in practical ap-
plicability, home-made two electrode Al-air batteries are fabricated to
assess the performance of the devices with these as-synthesized cata-
lysts as air cathodes, and paired them with Al foil as the anode in 4 M
KOH, fabricated as shown in Fig. 6a. For comparison, the coupled Pt/C
is also assembled as the air cathode in the same condition. It is evident
from Fig. 6b that the PD-800-based batteries exhibit stable open circuit
voltage of 1.68 V, exceed that of Pt/C (1.65 V) and PA-800 (1.44 V),
which disagree with the above-discussed ORR catalytic behaviors in
three-electrode configurations. The better voltage for PD-800 might be
ascribed to its hierarchical structure and large specific surface area,
which will provide channels for efficient mass-transfer and expose more
active sites (including inner sites) accessible to O2 and electrolyte
[4,63]. The discharge polarization curves in Fig. 6c further reveal the
superior battery behavior based on PD-800 catalyst with N-doped
carbon, which even can compete with that of Pt/C catalysts. Re-
markably, the batteries with the PD-800 catalyst give out a maximum
power density of 98.62 mW cm−2 while the batteries with commercial
Pt/C merely reach 90.81 mW cm−2, and greatly surpassing the PA-800
of 27.94 mW cm−2, implying remarkable output performance of PD-
800.Moreover, when a primary battery setup is adopted, the specific
capacity of the battery with PD-800 is estimated to be 913.41 mAh g−1
based on the Al foil exhausted (Fig. 6d), which is better than those of
Pt/C (883.53 mAh g−1) and PA-800 (793.12 mAh g−1). In addition, the
inferior specific capacity for batteries with Pt/C is possibly due to the
change of the Pt nanoparticles and the carbon corrosion under high
potential [64]. It is worth noting that all the tested three batteries in-
cluding the battery with the Pt/C catalyst exhibit a quite stable voltage
during the whole process of the discharge. Regardless of the above
investigations, the durability of cathode catalysts is the crucial factor to
determine the cycle life of the Al-air batteries, where the aluminum
anode and electrolyte can be replenished while the cathode catalysts
must be kept unchanged.
8
Chemical Engineering Journal 395 (2020) 125158
As presented in Fig. 7a, the dynamic galvanostatic discharge per-
formance of the batteries catalyzed by PD-800 is evaluated at different
discharge current densities from 5 to 280 mA cm−2, in which the vol-
tage decreases accordingly with the continuously increase of the cur-
rent. Meanwhile, for different discharge plateau, which shows ex-
tremely stable discharge behavior, reflecting an outstanding catalytic
durability. Apart from that, to investigate the variation of the voltage in
battery for a long-term stability, the battery with PD-800 is further
underwent four cycles by replenishing the Al foil and electrolyte. The
results are presented in Fig. 7b, the battery of the voltage shows only a
slight drop, further confirming that the superior catalytic stability for
ORR catalyzed with PD-800 catalyst in the Al-air battery, which prob-
ably be contributed to the FeCo alloy encapsulated by the graphitic
layer embedded in the carbon matrix can effectively restrict them from
leaching by the alkaline media during the long-term process. The results
further confirm that the better electrochemical properties for PD-800
catalyst will bring about an enhanced Al-air battery performance [8].
Moreover, the exceptional PD-800-based AABs is also comparable to or
even better than that of reported catalysts in recently literatures (Table
S2), once again verifying its potential application in practical facilities.
Therefore, the PD-800 catalyst has been proven to be a highly pro-
mising/competitive substitute to commercial Pt/C in the practical ap-
plication of the Al-air batteries.
4. Conclusion
An effective approach is developed to synthesize FeCo nanoparticles
encapsulated in N-doped graphitic carbon matrix as highly active ORR
catalysts for Al-air batteries. The electrochemical test delivers out-
standing electrocatalytic activity for PD-800 hybrid catalyst toward
ORR, which is greatly enhanced comparing with that of the PA-800
without adding of DCDA and competitive to Pt/C catalysts. The onset
potential, half-wave potential and transferred electron number of the
ORR on PD-800 are 0.981 V, 0.848 V, and 4.0, respectively. The Al-air
battery assembled by the PD-800 catalyst in alkaline medium even
surpasses the commercial Pt/C, and displays gratifying power density
and excellent long-term stability as the cathode catalysts, evidencing
the potential for practical application. The superb catalytic activity of
the PD-800 can be attributed to the integration combination of unique
hierarchical porous structure, appropriate graphitization degree, FeCo
species, active N-doped carbon, as well as the greatly enhanced electron
transfer between FeCo and the hybrid carbon skeleton, which are
beneficial for the effective exposure of increasing active sites, as well as
fast mass and charge transfer between the electrolyte and catalytic
active sites during the electrochemical reaction. This work will provide
an approach to design high-performance ORR catalysts with cost
L. Cui, et al.
effectiveness and highly durable for the development metal-air battery.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work is financially supported by the National Natural Science
Foundation of China (21975163) and Bureau of Industry and
Information Technology of Shenzhen (201901171518). The authors
sincerely acknowledge the Instrumental Analysis Center of Shenzhen
University (Xili Campus) for HRTEM measurements and analysis and
the Shiyanjia lab (www.shiyanjia.com) for the XPS test.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.125158.
References
[1] G.A. Elia, K. Marquardt, K. Hoeppner, S. Fantini, R. Lin, E. Knipping, W. Peters,
J.F. Drillet, S. Passerini, R.J.A.M. Hahn, An overview and future perspectives of
aluminum batteries, Adv. Mater. 28 (2016) 7564–7579.
[2] M.-C. Lin, M. Gong, B. Lu, Y. Wu, D.-Y. Wang, M. Guan, M. Angell, C. Chen, J. Yang,
B.-J.J.N. Hwang, An ultrafast rechargeable aluminium-ion battery, Nature 520
(2015) 324.
[3] H.G. Schwarz, Aluminum production and energy, in: C.J. Cleveland (Ed.),
Encyclopedia of Energy, Elsevier, New York, 2004, pp. 81–95.
[4] K. Fu, Y. Wang, L. Mao, X. Yang, W. Peng, J. Jin, S. Yang, G. Li, Rational assembly of
hybrid carbon nanotubes grafted on the carbon nanofibers as reliable and robust
bifunctional catalyst for rechargeable zinc-air battery, J. Power Sour. 421 (2019)
68–75.
[5] M.K. Debe, Electrocatalyst approaches and challenges for automotive fuel cells,
Nature 486 (2012) 43–51.
[6] D. Yan, L. Guo, C. Xie, Y. Wang, Y. Li, H. Li, S. Wang, N, P-dual doped carbon with
trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction
reaction, Sci. China Mater. 61 (2018) 679–685.
[7] X.T. Wang, T. Ouyang, L. Wang, J.H. Zhong, Z.Q. Liu, Surface reorganization on
electrochemically-induced Zn-Ni-Co spinel oxides for enhanced oxygen electro-
catalysis, Angew. Chem. Int. Ed. Engl. (2020), https://doi.org/10.1002/anie.
202000690.
[8] S. Chen, L. Zhao, J. Ma, Y. Wang, L. Dai, J. Zhang, Edge-doping modulation of N, P-
codoped porous carbon spheres for high-performance rechargeable Zn-air batteries,
Nano Energy 60 (2019) 536–544.
[9] Y. Wang, J. Li, Z. Wei, Transition-metal-oxide-based catalysts for the oxygen re-
duction reaction, J. Mater. Chem. A 6 (2018) 8194–8209.
[10] H. Tao, S.B. Liu, J.-L. Luo, P. Choi, Q. Liu, Z. Xu, Descriptor of catalytic activity of
metal sulfides for oxygen reduction reaction: a potential indicator for mineral flo-
tation, J. Mater. Chem. A 6 (2018) 9650–9656.
[11] M.M. Hossen, K. Artyushkova, P. Atanassov, A. Serov, Synthesis and characteriza-
tion of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in
alkaline exchange membrane fuel cells, J. Power Sour. 375 (2018) 214–221.
[12] W. Gu, L. Hu, J. Li, E. Wang, Recent advancements in transition metal-nitrogen-
carbon catalysts for oxygen reduction reaction, Electroanalysis 30 (2018)
1217–1228.
[13] Z. Li, L. Wei, W.-J. Jiang, Z. Hu, H. Luo, W. Zhao, T. Xu, W. Wu, M. Wu, J.-S. Hu,
Chemical state of surrounding iron species affects the activity of Fe-Nx for elec-
trocatalytic oxygen reduction, Appl. Catal. B-Environ. 251 (2019) 240–246.
[14] M. Sun, H. Liu, J. Qu, J. Li, Earth-rich transition metal phosphide for energy con-
version and storage, Adv. Energy Mater. 6 (2016) 1600087.
[15] Y. Fu, H.-Y. Yu, C. Jiang, T.-H. Zhang, R. Zhan, X. Li, J.-F. Li, J. Tian, R. Yang, NiCo
alloy nanoparticles decorated on N-doped carbon nanofibers as highly active and
durable oxygen electrocatalyst, Adv. Funct. Mater. 28 (2018) 1705094.
[16] P. Cai, Y. Hong, S. Ci, Z. Wen, In situ integration of CoFe alloy nanoparticles with
nitrogen-doped carbon nanotubes as advanced bifunctional cathode catalysts for
Zn–air batteries, Nanoscale 8 (2016) 20048–20055.
[17] C.-Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z. Hou, F.-Q. Bai, H.-X. Zhang, T.-Y. Ma,
Atomic modulation of FeCo–nitrogen–carbon bifunctional oxygen electrodes for
rechargeable and flexible all-solid-state zinc–air battery, Adv. Energy Mater. 7
(2017) 1602420.
[18] B.K. Barman, K.K. Nanda, CoFe nanoalloys encapsulated in N-doped graphene
layers as a Pt-free multifunctional robust catalyst: elucidating the role of Co-al-
loying and N-doping, ACS Sustain. Chem. Eng. 6 (2018) 12736–12745.
[19] S. Li, W. Chen, H. Pan, Y. Cao, Z. Jiang, X. Tian, X. Hao, T. Maiyalagan, Z.-J. Jiang,
9
Chemical Engineering Journal 395 (2020) 125158
FeCo alloy nanoparticles coated by ultrathin n-doped carbon layer and en-
capsulated in carbon nanotubes as highly efficient bifunctional air electrode for
rechargeable zn-air batteries, ACS Sustainable Chem. Eng. 7 (9) (2019) 8530–8541.
[20] R. Nandan, A. Gautam, K.K. Nanda, Anthocephalus cadamba shaped FeNi en-
capsulated carbon nanostructures for metal–air batteries as a resilient bifunctional
oxygen electrocatalyst, J. Mater. Chem. A 6 (2018) 20411–20420.
[21] J. Ran, X. Guo, P. Liu, S. Peng, X. Gao, D. Gao, Bifunctional catalysts of CoNi na-
noparticle-embedded nitrogen-doped carbon nanotubes for rechargeable Zn–air
batteries, Nanotechnology 30 (2019) 435701.
[22] W. Wan, X. Liu, H. Li, X. Peng, D. Xi, J. Luo, 3D carbon framework-supported CoNi
nanoparticles as bifunctional oxygen electrocatalyst for rechargeable Zn-air bat-
teries, Appl. Catal. B-Environ. 240 (2019) 193–200.
[23] Y.Y. Ma, A. Sumboja, W.J. Zang, S.Y. Yin, S.X. Wang, S.J. Pennycook, Z.K. Kou,
Z.L. Liu, X. Li, J. Wang, Hollow FeCo alloy nanoparticles electrospun in nitrogen-
doped carbon nanofiber enable high performing flexible all-solid-state zinc-air
battery, Sustain. Energy Fuels (2020), https://doi.org/10.1021/acsami.8b14840.
[24] Y.-Z. Chen, C. Wang, Z.-Y. Wu, Y. Xiong, Q. Xu, S.-H. Yu, H.-L. Jiang, From bime-
tallic metal-organic framework to porous carbon: high surface area and multi-
component active dopants for excellent electrocatalysis, Adv. Mater. 27 (2015)
5010–5016.
[25] Z.-Y. Yu, Y. Duan, J.-D. Liu, Y. Chen, X.-K. Liu, W. Liu, T. Ma, Y. Li, X.-S. Zheng,
T. Yao, M.-R. Gao, J.-F. Zhu, B.-J. Ye, S.-H. Yu, Unconventional CN vacancies
suppress iron-leaching in Prussian blue analogue pre-catalyst for boosted oxygen
evolution catalysis, Nat. Commun. 10 (2019) 2799.
[26] M. Khalid, A.M.B. Honorato, H. Varela, L. Dai, Multifunctional electrocatalysts
derived from conducting polymer and metal organic framework complexes, Nano
Energy 45 (2018) 127–135.
[27] M. Zeng, Y. Liu, F. Zhao, K. Nie, N. Han, X. Wang, W. Huang, X. Song, J. Zhong,
Y. Li, Metallic cobalt nanoparticles encapsulated in nitrogen-enriched graphene
shells: its bifunctional electrocatalysis and application in zinc–air batteries, Adv.
Funct. Mater. 26 (2016) 4397–4404.
[28] X. Li, Z. Wang, B. Zhang, A.I. Rykov, M.A. Ahmed, J. Wang, FexCo3-xO4 nanocages
derived from nanoscale metal–organic frameworks for removal of bisphenol A by
activation of peroxymonosulfate, Appl. Catal. B-Environ. 181 (2016) 788–799.
[29] C. Xuan, J. Wang, W. Xia, Z. Peng, Z. Wu, W. Lei, K. Xia, H.L. Xin, D. Wang, Porous
structured Ni-Fe-P nanocubes derived from a prussian blue analogue as an elec-
trocatalyst for efficient overall water splitting, ACS Appl. Mater. Interfaces 9 (2017)
26134–26142.
[30] J. Qian, X. Guo, T. Wang, P. Liu, H. Zhang, D. Gao, Bifunctional porous Co-doped
NiO nanoflowers electrocatalysts for rechargeable zinc-air batteries, Appl. Catal. B-
Environ 250 (2019) 71–77.
[31] O. Ozturk, O.K. Ozdemir, I. Ulusoy, A.S. Ahsen, E. Slavcheva, Effect of Ti sublayer
on the ORR catalytic efficiency of dc magnetron sputtered thin Pt films, Int. J.
Hydrogen Energy 35 (2010) 4466–4473.
[32] X. Li, S. Kurasch, U. Kaiser, M. Antonietti, Synthesis of monolayer-patched graphene
from glucose, Angew. Chem. Int. Ed. Engl. 51 (2012) 9689–9692.
[33] Y. Ma, A. Sumboja, W. Zang, S. Yin, S. Wang, S.J. Pennycook, Z. Kou, Z. Liu, X. Li,
J. Wang, Flexible and wearable all-solid-state al-air battery based on iron carbide
encapsulated in electrospun porous carbon nanofibers, ACS Appl. Mater. Interfaces
11 (2019) 1988–1995.
[34] Y. Ma, A. Sumboja, W. Zang, S. Yin, S. Wang, S.J. Pennycook, Z. Kou, Z. Liu, X. Li,
J. Wang, Flexible and wearable all-solid-state Al–Air battery based on iron carbide
encapsulated in electrospun porous carbon nanofibers, ACS Appl. Mater. Interfaces
11 (2019) 1988–1995.
[35] S.H. Lee, J. Kim, D.Y. Chung, J.M. Yoo, H.S. Lee, M.J. Kim, B.S. Mun, S.G. Kwon, Y.-
E. Sung, T. Hyeon, Design principle of Fe–N–C electrocatalysts: how to optimize
multimodal porous structures? J. Am. Chem. Soc. 141 (2019) 2035–2045.
[36] C. Li, M. Wu, R. Liu, High-performance bifunctional oxygen electrocatalysts for
zinc-air batteries over mesoporous Fe/Co-N-C nanofibers with embedding FeCo
alloy nanoparticles, Appl. Catal. B-Environ. 244 (2019) 150–158.
[37] B. Guo, Q. Liu, E. Chen, H. Zhu, L. Fang, J.R. Gong, Controllable N-doping of
graphene, Nano Lett. 10 (2010) 4975–4980.
[38] M. Wu, Y. Wang, Z. Wei, L. Wang, M. Zhuo, J. Zhang, X. Han, J. Ma, Ternary doped
porous carbon nanofibers with excellent ORR and OER performance for zinc–air
batteries, J. Mater. Chem. A 6 (2018) 10918–10925.
[39] X. Yan, Y. Jia, X. Yao, Defects on carbons for electrocatalytic oxygen reduction,
Chem. Soc. Rev. 47 (2018) 7628–7658.
[40] C. Tang, Q. Zhang, Nanocarbon for oxygen reduction electrocatalysis: dopants,
edges, and defects, Adv. Mater. 29 (2017) 1604103.
[41] J. Tu, J. Wang, H. Zhu, S. Jiao, The molten chlorides for aluminum-graphite re-
chargeable batteries, J. Alloys Compd. 821 (2020), https://doi.org/10.1016/j.
jallcom.2019.153285.
[42] M. Zhang, Q. Dai, H. Zheng, M. Chen, L. Dai, Novel MOF-derived Co@ N-C bi-
functional catalysts for highly efficient zn–air batteries and water splitting, Adv.
Mater. 30 (2018) 1705431.
[43] Z. Zafar, Z.H. Ni, X. Wu, Z.X. Shi, H.Y. Nan, J. Bai, L.T. Sun, Evolution of Raman
spectra in nitrogen doped graphene, Carbon 61 (2013) 57–62.
[44] J. Song, Y. Ren, J. Li, X. Huang, F. Cheng, Y. Tang, H. Wang, Core-shell Co/CoNx@C
nanoparticles enfolded by Co-N doped carbon nanosheets as a highly efficient
electrocatalyst for oxygen reduction reaction, Carbon 138 (2018) 300–308.
[45] H.-F. Wang, C. Tang, B. Wang, B.-Q. Li, X. Cui, Q. Zhang, Defect-rich carbon fiber
electrocatalysts with porous graphene skin for flexible solid-state zinc–air batteries,
Energy Storage Mater. 15 (2018) 124–130.
[46] F. Pan, J. Jin, X. Fu, Q. Liu, J. Zhang, Advanced oxygen reduction electrocatalyst
based on nitrogen-doped graphene derived from edible sugar and urea, ACS Appl.
Mater. Interfaces 5 (2013) 11108–11114.
L. Cui, et al.
[47] X. Han, X. Ling, D. Yu, D. Xie, L. Li, S. Peng, C. Zhong, N. Zhao, Y. Deng, W. Hu,
Atomically dispersed binary co-ni sites in nitrogen-doped hollow carbon nanocubes
for reversible oxygen reduction and evolution, Adv. Mater. 1905622 (2019).
[48] Y. Hou, T. Huang, Z. Wen, S. Mao, S. Cui, J. Chen, Metal−organic framework-
derived nitrogen-doped core-shell-structured porous Fe/Fe3C@ C nanoboxes sup-
ported on graphene sheets for efficient oxygen reduction reactions, Adv. Energy
Mater. 4 (2014) 1400337.
[49] Z. Hu, Z. Zhang, Z. Li, M. Dou, F. Wang, One-step conversion from core–shell me-
tal–organic framework materials to cobalt and nitrogen codoped carbon nanopo-
lyhedra with hierarchically porous structure for highly efficient oxygen reduction,
ACS Appl. Mater. Interfaces 9 (2017) 16109–16116.
[50] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Nitrogen-doped carbon nanotube arrays
with high electrocatalytic activity for oxygen reduction, Science 323 (2009)
760–764.
[51] Z. Sun, Y. Wang, L. Zhang, H. Wu, Y. Jin, Y. Li, Y. Shi, T. Zhu, H. Mao, J. Liu,
C. Xiao, S. Ding, Simultaneously realizing rapid electron transfer and mass transport
in jellyfish-like mott-schottky nanoreactors for oxygen reduction reaction, Adv.
Funct. Mater. 1910482 (2020).
[52] J. Wei, Y. Liang, X. Zhang, G.P. Simon, D. Zhao, J. Zhang, S. Jiang, H. Wang,
Controllable synthesis of mesoporous carbon nanospheres and Fe–N/carbon nano-
spheres as efficient oxygen reduction electrocatalysts, Nanoscale 7 (2015)
6247–6254.
[53] D. Yin, C. Han, X. Bo, J. Liu, L. Guo, Prussian blue analogues derived iron-cobalt
alloy embedded in nitrogen-doped porous carbon nanofibers for efficient oxygen
reduction reaction in both alkaline and acidic solutions, J. Colloid Interf. Sci. 533
(2019) 578–587.
[54] H. Ali-Löytty, M.W. Louie, M.R. Singh, L. Li, H.G. Sanchez Casalongue,
H. Ogasawara, E.J. Crumlin, Z. Liu, A.T. Bell, A. Nilsson, Ambient-pressure XPS
study of a Ni–Fe electrocatalyst for the oxygen evolution reaction, J. Phys. Chem. C
120 (2016) 2247–2253.
[55] X. Fang, L. Jiao, S.H. Yu, H.L. Jiang, Metal-organic framework-derived FeCo-N-
doped hollow porous carbon nanocubes for electrocatalysis in acidic and alkaline
10
Chemical Engineering Journal 395 (2020) 125158
media, ChemSusChem 10 (2017) 3019–3024.
[56] P. Zhou, J. He, Y. Zou, Y. Wang, C. Xie, R. Chen, S. Zang, S. Wang, Single-crystalline
layered double hydroxides with rich defects and hierarchical structure by mild
reduction for enhancing the oxygen evolution reaction, Sci. China Chem. 62 (2019)
1365–1370.
[57] D. Zheng, S. Ci, P. Cai, G. Wang, Z. Wen, Nitrogen-doped carbon nanosheets en-
capsulating cobalt nanoparticle hybrids as high-performance bifunctional electro-
catalysts, ChemElectroChem 6 (2019) 2683–2688.
[58] T. Palaniselvam, V. Kashyap, S.N. Bhange, J.B. Baek, S. Kurungot, Nanoporous
graphene enriched with Fe/Co-N active sites as a promising oxygen reduction
electrocatalyst for anion exchange membrane fuel cells, Adv. Funct. Mater. 26
(2016) 2150–2162.
[59] Q. Niu, J. Guo, B. Chen, J. Nie, X. Guo, G. Ma, Bimetal-organic frameworks/
polymer core-shell nanofibers derived heteroatom-doped carbon materials as elec-
trocatalysts for oxygen reduction reaction, Carbon 114 (2017) 250–260.
[60] M. Kuang, Q. Wang, P. Han, G. Zheng, Cu, co-embedded n-enriched mesoporous
carbon for efficient oxygen reduction and hydrogen evolution reactions, Adv.
Energy Mater. 7 (2017) 1700193.
[61] R. Zhong, Y. Wu, Z. Liang, W. Guo, C. Zhi, C. Qu, S. Gao, B. Zhu, H. Zhang, R. Zou,
Fabricating hierarchically porous and Fe3C-embeded nitrogen-rich carbon nanofi-
bers as exceptional electocatalysts for oxygen reduction, Carbon 142 (2019)
115–122.
[62] Y. Yuan, J. Wang, S. Adimi, H. Shen, T. Thomas, R. Ma, J.P. Attfield, M. Yang,
Zirconium nitride catalysts surpass platinum for oxygen reduction, Nat. Mater. 19
(2020) 282–286.
[63] T. Wang, Z. Kou, S. Mu, J. Liu, D. He, I.S. Amiinu, W. Meng, K. Zhou, Z. Luo,
S. Chaemchuen, 2D Dual‐Metal Zeolitic‐Imidazolate‐Framework‐(ZIF)‐Derived
Bifunctional Air Electrodes with Ultrahigh Electrochemical Properties for
Rechargeable Zinc–Air Batteries, Adv. Funct. Mater. 28 (2018) 1705048.
[64] M. Gao, W. Sheng, Z. Zhuang, Q. Fang, S. Gu, J. Jiang, Y. Yan, Efficient water
oxidation using nanostructured α-nickel-hydroxide as an electrocatalyst, J. Am.
Chem. Soc. 136 (2014) 7077–7084.