Electrochimica Acta 323 (2019) 134821

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

Zeolitic-imidazolate-framework-derived Co@Co3O4 embedded into

iron, nitrogen, sulfur Co-doped reduced graphene oxide as efficient
electrocatalysts for overall water splitting and zinc-air batteries
Junke Zhu, Wenmao Tu**, Ziyu Bai, Hongfei Pan, Pengxia Ji, Heng Zhang, Zhao Deng,
Haining Zhang*
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Nr. 122 Luoshi Rd., Wuhan, 430070,
China

a r t i c l e i n f o a b s t r a c t

Article history: Rational design and fabrication of nonprecious metallic multifunctional catalysts with superior perfor-
Received 6 July 2019 mance are crucial for energy-related electrochemical devices. Herein, we report the synthesis and
Received in revised form electrochemical properties of a sandwich-like Co@Co3O4 embedded into Fe, N, S co-doped reduced
26 August 2019
graphene oxide (Co@Co3O4/FeNS-RGO) nanocomposite catalyst. The designed Co@Co3O4/FeNS-RGO
Accepted 3 September 2019
Available online 4 September 2019
catalyst is synthesized by pyrolysis of one-pot solvothermal method-induced nano-zeolitic imidazolate
framework (ZIF)/graphene oxide nanocomposite using dimethylsulfoxide as both the solvent and sulfur
source. The synthesized catalyst exhibits the outstanding electrocatalytic activity in basic media for
Keywords:
Solvothermal synthesis
oxygen reduction reaction and oxygen evolution reactions, which outperforms the commercial Pt/C and
Electrocatalysis IrO2 catalysts, respectively. In addition, the synthesized catalyst also shows a promising electrocatalytic
Oxygen-involved reaction activity towards hydrogen evolution reaction. The performance of the thus-assembled zinc-battery and
Zinc-air battery the overall water-splitting device reveals that the synthesized Co@Co3O4/FeNS-RGO can be practically
Water splitting applied in energy-related electrochemical devices with great activity and stability.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
There is no doubt that the over exploitation of fossil energy
results in the unprecedented global energy crisis and environ-
mental pollution. Development of clean and renewable energy
sources has thus attracted considerable attention to address the
existing energy and environmental issues. Of various technologies
developed, electrochemical energy conversion and storage devices
including fuel cells and metal-air batteries have been recognized as
the most practical and viable alternative to the depleting fossil
energy resources because of their high energy density and low
emission level [1,2]. For electrochemical energy conversion and
storage devices, oxygen reduction reaction (ORR), oxygen evolution
reaction (OER), and hydrogen evolution reaction (HER) are three
crucial electrochemical reactions. For example, ORR is an essential
* Corresponding author.
** Corresponding author.
E-mail addresses: tuwm@whut.edu.cn (W. Tu), haining.zhang@whu.edu.cn
(H. Zhang).
step for fuel cell and both ORR and OER have been considered as
two significant processes in metal-air batteries [2e4]. Both OER and
HER are essential in the electrochemical water-splitting process to
produce hydrogen that is the carrier of hydrogen energy [5,6]. In
spite of the efficient electrocatalytic activity, the high price and the
scarce resources of the commercially noble metal-based electro-
catalysts such as Pt/C, IrO2, and RuO2 hinder their widespread ap-
plications [7,8].
Recently, transition metal (TM) nanoparticles embedded into
graphene-based materials have been widely recognized as prom-
ising candidates for electrocatalysts. With the combination of active
TM nanoparticles (such as Fe, Co, Ni) and graphene-based mate-
rials, the composites possess higher electrical conductivity,
improved stability and superior synergistic effects on electro-
catalysis [9,10]. Furthermore, both theoretical calculation and
experimental results revealed that the introduction of heteroatoms
including N, S, P into carbon material could increase the active sites
and accelerate the electron transport from metal nanoparticles to
carbon-based materials. Zeolitic imidazolate frameworks (ZIFs),
which are constructed from tetrahedrally coordinated TM ions

https://doi.org/10.1016/j.electacta.2019.134821
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
2 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821
linked by N- contained organic imidazole units, would transfer into
the N-doped carbon after pyrolysis [11]. For example, Wu et al.
fabricated a reduced graphene oxideeCo3O4 yolk-shell nanocage
composite through a precipitation reaction with subsequent calci-
nation and hydrothermal treatment and the resulted catalyst which
exhibited an excellent OER performance in alkaline condition [12].
However, ZIFs-derived TM nanoparticles embedded into graphene-
based composites with co-doped heteroatoms remains largely
unexplored.
In this work, we report the synthesis of cobalt@cobalt oxide
embedded iron, nitrogen, sulfur co-doped reduced graphene oxide
(Co@Co3O4/FeNS-RGO) nanocomposites by pyrolysis of self-
assembled iron impregnated ZIF-67 and graphene oxide (Fe/ZIF-
67/GO) precursor. The Fe/ZIF-67/GO precursor was synthesized
through a simple and efficient DMSO solvothermal approach in
which DMSO as a sulfur-containing organic solvent plays a crucial
role in the growth of MOF particles and can be decomposed slightly
to sulfides. The Fe3þ together with the sulfides were encapsulated
into the framework of Fe/ZIF-67/GO precursor. The thus-
synthesized sandwich-like Co@Co3O4/FeNS-RGO composite mate-
rial exhibited remarkable electrocatalytic activity for ORR, OER, and
HER as well.
2. Experimental section
2.1. Synthesis of Co@Co3O4/NS-RGO
ZIF-67/GO composite was fabricated by an efficient dimethyl
sulfoxide (DMSO) solvothermal method. Graphene oxide (GO) was
prepared through chemical exfoliation of graphite using a modified
Hummers’ method [13]. Typically, 120 mg GO and 6.7 g 2-
methylimidazole was dispersed with 120 ml DMSO under ultra-
phonic treatment for 2 h. 2 mmol cobalt acetate tetrahydrate was
dissolved in 5 ml DMSO and the clear purple solution was slowly
added into the former solution under stirring at 25  C. The mixture
was transferred into 100 ml Teflon-lined autoclave and held at
140  C for 24 h. After cooling down naturally to room temperature,
the product was collected by centrifugation with ethanol and water
in sequence, followed by freeze-dying for 24 h. The obtained ZIF-
67/GO was annealed at 800  C for 2 h in N2 atmosphere and the
resulted black powder was denoted as Co@Co3O4/NS-RGO. For
comparison, samples were also synthesized using the same pro-
cedure without the addition of ZIF-67 and GO, denoted as RGO and
CoPC, respectively.
2.2. Synthesis of Co@Co3O4/FeNS- RGO
Co@Co3O4/FeNS-RGO was prepared by similar synthesis pro-
cedure to Co@Co3O4/NS-RGO. In brief, 120 mg GO and 6.7 g 2-
methylimidazole was dispersed with 120 ml DMSO solution.
Another 5 ml DMSO solution contained 1.9 mmol cobalt acetate
tetrahydrate and 0.1 mmol Iron (III) nitrate nonahydrate was added
into the former mixture under stirring. The total molar amount of
(Co þ Fe) was fixed to be 2 mmol. The mixture was transferred into
100 ml Teflon-lined autoclave and held at 140  C for 24 h. After
washing with ethanol and water, the freeze-drying product was
calcined at 800  C for 2 h in N2 atmosphere. The resulted powder
which denoted as Co@Co3O4/FeNS-RGO was preserved for further
analysis.
2.3. Material characterization
The morphology of nano-sandwich-like Co@Co3O4/FeNS-RGO
composites was characterized by FETEM (JEM2100-HR, Japan) and
FESEM (Zeiss Ultra Plus, Germany). PXRD patterns were recorded
on a D8 Advance (Brook, Germany). Raman spectra were studied by
an InVia Laser Raman Spectrometer (Renishaw, England). XPS tests
were performed on an ESCALAB 250Xi (Thermo Fisher, America).
Elemental analysis (Vario EL cube, German) and Inductively
Coupled Plasma-Optical Emission Spectra (Prodigy 7, America)
were recorded to investigated the element contents of samples.
2.4. Electrochemical measurements
All the electrochemical tests were carried out in a three-
electrode system on CHI 660E electrochemical workstation (CH
Instruments, Chenhua). For the fabrication of the working elec-
trode, 6 mg catalyst and 20 mL Nafion (5 wt%) were dispensed in
980 mL isopropanol and sonicated to get some homogeneous ink. A
certain amount of the catalyst ink was drop-casted on the glassy
carbon electrode and dried at room temperature (catalyst loading,
0.3 mgcm2). All the working electrodes were activated by accel-
erated cycle voltammetry (CV) process until the curve stabilizes.
The measured potential was converted against the reversible
hydrogen electrode (RHE).
For ORR, glassy carbon (GC) rotating disk electrode (RDE) and
graphite rod served as working electrode and counter electrode,
respectively, as well as the reference electrode was Ag/AgCl (satu-
rated KCl). CV tests were performed in both oxygen (O2)/nitrogen
(N2) saturated 0.1 molL-1 KOH at 10 mVs1. Linear sweep voltam-
metry (LSV) and Chronoamperometric i-t tests were performed in
O2-saturated environment at the speed rate of 1600 rpm. The po-
larization curves at different rotating speeds (from 400 to
2000 rpm) were studied to figure out the numbers of electrons
transferred (n), which is calculated by Koutecky-Levich equation
[14]. For comparison, A potential at which current density exceeds a
threshold value of 0.1 mAcm2 was defined as onset potential
(Eonset) [6].
For both OER and HER, GC working electrode, graphite rod
counter electrode and Hg/HgO (filled with 1 molL-1 KOH) reference
electrode were used in 1 molL-1 KOH electrolyte. LSV tests were
performed with a scan rate of 5 mVs1 and all the potentials in the
polarization curves here were iR corrected. Electrochemical
impedance spectroscope (EIS) was carried out in a frequency
ranging from 50 kHz to 0.01 Hz with an amplitude of 5 mV. All the
Tafel slopes were obtained from the corresponding LSV curves.
To prepared liquid Zn-air battery, Zn plate was used as anode
and carbon paper loading Co@Co3O4/FeNS-RGO catalyst (1
mgcm2) was used as the air electrode. In addition, a solution of 6
molL-1 KOH and 0.2 molL-1 zinc acetate was used as electrolyte. For
the all-solid-state Zneair batteries, Zn plate and Co@ Co3O4/FeNS-
RGO have been used as anode and cathode, respectively. The solid
electrolyte was fabricated as follow: 3g PVA (Mw, 144000) was
added to 30 ml H2O under stirring at 90  C for 1 h, and the trans-
parent gel was cooled down naturally to room temperature. 3 ml
electrolyte solution (6 molL-1 KOH, 0.2 molL-1 zinc acetate) was
added to the formed gel under stirring, and the mixture was poured
onto an evaporating dish and frozen in a freezer. After thawing at
room temperature, the gel electrolyte was dried at 65  C.
The overall water splitting tests were performed in two-
electrode (3 mm GC electrode) system and measured in 1 molL-1
KOH electrolyte. The catalysts on both anode and cathode were
Co@Co3O4/FeNS-RGO, and the catalyst loading is 0.3 mgcm2.
Long-term performance was carried out at 1.7 V for at least 10 h.
3. Results and discussion
The designed sandwich-like catalyst Co@Co3O4/FeNS-RGO was
synthesized by pyrolysis of pre-formed Fe/ZIF-67/GO by a simple
solvothermal method using DMSO as solvent, as schematically
 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821
illustrated in Scheme 1. The ZIF-67 nanoparticles were encapsu-
lated between surfaces of GO layers, which were further transferred
into the RGO-metal nanoparticles-RGO structure. Furthermore, the
nitrogen-atoms from imidazole moieties were also expected to be
doped into the RGO layers as observed in literatures [15e17]. The
flakes of GO were partly reduced during the solvothermal process
and they were further reduced completely into reduced graphene
oxide (RGO) during the pyrolysis process [15,18]. In addition, Fe3þ
were reduced to Fe2þ by the generated carbon at high temperature
and the complexation between iron ions and N-atoms was con-
structed in the doped carbon-based materials [19]. Moreover, the
pyrolysis of nanosized ZIF-67 particles can provide N-doped carbon
and can result in the homogeneous dispersion of Co@Co3O4 on the
layers of RGO.
Powder X-ray diffraction (PXRD) measurements were per-
formed to determine the crystallinity of ZIF-67, ZIF-67/GO, and Fe/
ZIF-67/GO (Fig. S1 in Supporting Information). The XRD pattern of
the as-prepared ZIF-67 matches well with the simulated one and
the characteristic diffraction peaks are consistent with those of the
reported result [20], indicating the successful formation of porous
framework using DMSO as solvent. No obvious change was
observed for the XRD patterns of ZIF-67/GO and Fe/ZIF-67/GO,
suggesting that the introduction of low-content Fe3þ (3.93 wt%)
cannot affect the crystallization of ZIF-67 particles significantly. The
corresponding field emission scanning electron microscopy
(FESEM) images (Fig. S2) also confirms that there is no obvious
morphological change with the introduction of iron ions. Further-
more, the average size of the formed ZIF-67 particles is observed to
be 70e100 nm that is much smaller than that of most reported ZIF-
67 particles synthesized using other solvent, including methanol
(300 nm-2 mm) and H2O (300 nm-1.7 mm) [21e23]. In addition, the
images of field emission transmission electron microscopy (FETEM)
clearly shows that the formed ZIF-67 particles were embedded into
the sheets of GO (Fig. S3).
The Fe/ZIF-67/GO composite was further calcined at 800  C in N2
atmosphere to form sandwich-like Co@Co3O4/FeNS-RGO (Fig. 1 and
Fig. S4). It is evident that the typical framework of ZIF-67 collapses
and Co-based nanoparticles (about 12 nm in diameter) are homo-
geneous encapsulated into the sheets of RGO during the pyrolysis
process, as displayed in FETEM images (Fig. 1a and b). The high-
density accessible active sites may boost charge transfer from the
Scheme 1. Schematic illustration of the synthetic process of sandwich-like Co@Co3O4/FeNS-RGO.
3
conductive support (RGO) to catalyst surfaces, implying the
intrinsic electrocatalytic activity [24]. Moreover, the high-
resolution FETEM images (Fig. 1c) revealed that the crystalline
Co@Co3O4 nanoparticles with a core@shell nanostructure are
embedded in the carbon matrix. The lattice fringe of the inner core
observed from high-resolution FETEM image (Fig. 1d) is 0.204 nm
corresponding to the (111) plane of metallic Co whereas the lattice
fringe of outside shell is 0.245 nm that matches well with (311)
plane of Co3O4 [25]. The core-shell structure was also observed for
samples of Co@Co3O4/NS-RGO (Fig. S5) and CoPC (Fig. S6), attrib-
uting to the thermal decomposition of cobalt acetate tetrahydrate
into Co3O4 as also observed in literatures [26e28]. Energy disper-
sive spectroscopy (EDS) elemental mapping results (Fig. 1e and
Fig. S7) indicate that C, N, O, S, Fe, Co elements of Co@Co3O4/FeNS-
RGO are well-distributed in the entire nanoarchitecture, suggesting
the uniformly doping of N, S, Fe in carbon matrix.
The PXRD patterns were measured to further illustrate the
chemical composition of Co@Co3O4 phase. As displayed in Fig. 2a,
all the tested samples Co@Co3O4/FeNS-RGO, Co@Co3O4/NS-RGO,
and CoPC, have three main diffraction peaks at 44.2 , 51.5 and
75.8 corresponding to (111), (200) and (220) plane of crystalline
cobalt (JCPDS 89e7093), respectively, implying the successful
reduction of Co2þ to metallic state during the pyrolysis process [29].
Several weak diffraction peaks observed are indexed to Co3O4
(JCPDS 89e1093) and CoN (JCPDS 83e0831). In addition, the
introduction of Fe3þ doesn't change the crystalline structure of the
composite material as evidenced by the characteristic peaks at the
same angles, possibly due to the low content of the doped Fe atoms.
The structural features of Co@Co3O4/FeNS-RGO are further inves-
tigated by Raman spectroscopy, as shown in Fig. 2b. Both the D
band (1337 cm1) and G band (1596 cm1) are clearly observed,
matching the defective C atoms and crystallized graphitic C atoms,
respectively. The intensity ratio of ID/IG is applied to identify the
degree of disordered carbon structure [29]. The measured ID/IG
ratio of Co@Co3O4/FeNS-RGO is 1.18, higher than that of Co@Co3O4/
NS-RGO (1.11) and RGO (1.09), indicating that there are more de-
fects in Co@Co3O4/FeNS-RGO. The generated defects, owing to the
incorporation of heteroatoms into RGO layers, may provide more
active sites for mass transport in electrochemical reaction [30]. In
addition, three weak Raman absorption bands were observed at
471 cm1, 512 cm1 and 672 cm1, corresponding to the Eg, F2g and
4 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821

Fig. 1. FETEM images of Co@Co3O4/FeNS-RGO with different resolution as indicated by the scale bars of 200 nm (a), 50 nm (b), 10 nm (c), and 5 nm (d). e) The corresponding element
maps showing images of HAADF: the distribution of C (red), N (orange), O (white), S (yellow), Co (blue), and Fe (green) with the scale bars of 100 nm. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)

Fig. 2. a) XRD patterns of CoPC, Co@Co3O4/NS-RGO and Co@Co3O4/FeNS-RGO. b) Raman spectroscopy of Co@Co3O4/FeNS-RGO, Co@Co3O4/NS-RGO and RGO.

A1g vibration modes of Co3O4, respectively, which agrees with the
XRD results [31,32].
X-ray photoelectron spectroscopy (XPS) measurements were
performed to investigate the surface chemical environments of the
according elements of Co@Co3O4/FeNS-RGO. Apart from C 1s
(285 eV) and N 1s (400 eV) peaks, the observed Co 2p (780 eV), Fe
2p (715 eV), and S 2p (163 eV) peaks suggest the co-existence of Co,
Fe, and S in the nitrogen-doped carbon materials (Fig. 3a and
Fig. S8). In addition, the successful doping of N- and S-atoms was
also confirmed by the particular peak located at 285.6 eV in the
deconvoluted C 1s spectrum (Fig. 3b) [33]. Deconvolution results of
high-resolution N 1s spectrum (Fig. 3c) revealed the appearance of
pyridinic-N (398.4 eV), pyrrolic-N (400.0 eV), graphitic-N
(400.9 eV), oxidized-N (402.7 eV) and metal-bonded nitrogen (M-
N, 397.4 eV) [34]. Moreover, the pyridinic-N and M-N contribute to
49.5% of the overall doped nitrogen atoms, suggesting that the
synthesized composite materials may exhibit promising catalytic
activity for ORR and OER since pyridinic-N and M-N have been
recognized as active sites for ORR and OER [35,36]. In the high-
resolution Co 2p spectrum (Fig. 3d), the deconvoluted peaks
778.5, 779.8, and 780.3 eV, corresponding to Co0, Co 2p3/2, and Co
2p1/2, suggest the presence of metallic Co and Co3O4 [37]. As shown
in Fig. 3e, the high-resolution Fe 2p spectrum clearly evidences the
three chemical environments for Fe atoms, and the Fe 2p3/2 peak
occurring at 711.3 eV reconfirmed the presence of FeeNeC species
[38].
Bulk elemental analysis and inductively coupled plasma (ICP)
analysis was applied to determine the elemental contents, as listed
in Table S1. Apart from C (38.2 wt%) and Co (42.9 wt%), the contents
of N, Fe, and S were determined to be 3.5, 3.9, and 2.2 wt%,
respectively. The content of doped S atoms in Co@Co3O4/FeNS-RGO
(2.2 wt%) is even higher than that of doped S atoms in Co@Co3O4/
NS-RGO (1.2 wt%), suggesting that the strong bonding interaction
between Fe ions and sulfur species can cause the higher content of S
 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821 5

Fig. 3. a) XPS Survey spectrum of Co@Co3O4/FeNS-RGO and its corresponding high-resolution XPS spectrum of b) C1s, c) N1s, d) Co2p and e) Fe2p.

elements in Co@Co3O4/FeNS-RGO, as reported in the literature [39].
To evaluate the multifunctional electrocatalytic properties of the
synthesized Co@Co3O4/FeNS-RGO composite, ORR electrochemical
measurements were first carried out in 0.1 molL-1 KOH electrolyte
with a three-electrode system. For comparison, commercial Pt/C
(20 wt%) was used under the same condition. Fig. S9 shows the
cyclic voltammetry (CV) curves of Co@Co3O4/FeNS-RGO in N2 and
O2-saturated electrolyte. Compared with the sample in N2-satu-
rated electrolyte solution, the clearly observed cathodic peak in O2-
saturated electrolyte solution at 0.85 V versus reversible hydrogen
electrode (RHE) suggests the pronounced electrocatalytic activity of
Co@Co3O4/FeNS-RGO for ORR. Linear sweep voltammetry (LSV)
measurements were performed to further assess the electro-
catalytic activity towards ORR. It should be noted that the LSV
curves were recorded in the three-electrodes system using graphite
rod as counter electrode since it has been reported that the Pt foil is
not suitable as counter electrode due to the possible dissolution of
Pt from the foil surface [40]. Indeed, we compared the LSV curves of
Co@Co3O4/FeNS-RGO using Pt foil or graphite rod as counter elec-
trodes (Fig. S10) and it was found that the half-wave potential using
Pt foil as counter electrode is about 13 mV higher than that using
graphite rod as counter electrode. Fig. 4a displays the LSV curves of
different samples using graphite rod as counter electrodes. It can be
clearly seen that the synthesized Co@Co3O4/FeNS-RGO exhibits the
more positive half-wave potential (E1/2, 0.87 V vs. RHE) compared
with the samples of CoPC (0.83 V), RGO (0.79 V), and commercial
Pt/C catalyst (0.84 V), demonstrating the superior catalytic activity
of Co@Co3O4/FeNS-RGO for ORR. Moreover, the catalytic activity of
the synthesized Co@Co3O4/FeNS-RGO for ORR outperformed many
of the recently reported materials as listed in Table S2. In addition,
the synthesized catalyst of Co@Co3O4/NS-RGO without the doping
of Fe elements displayed comparable ORR activity as evidenced by
the very similar half-wave potentials, indicating that Fe-atoms and
Co-atoms doped in carbon frameworks may play the very similar
role for ORR. From the LSV curves recorded under different rotating
speeds (Fig. S11) and the according KouteckyeLevich plots (Fig. 4b)
[41], the average electron transfer number is calculated to be about
3.9 for Co@Co3O4/FeNS-RGO, suggesting the four-electron-transfer
dominated process for ORR. The great electrocatalytic activity to-
wards ORR for the synthesized catalysts of Co@Co3O4/FeNS-RGO
and Co@Co3O4/NS-RGO can be understood by considering the
synergistic effect of the doped heteroatoms with different elec-
tronegativity (3.04 for N-atom and 2.58 for S-atom) on the
adsorption of Lewis basic oxygen molecules and the core-shell
structure of Co@Co3O4 enhanced electron transport between RGO
and Co@Co3O4 [12,19,42].
Since transition metal was introduced into the catalysts, the
stability of the synthesized materials under electrochemical con-
ditions was investigated by using chronoamperometric tests per-
formed at the potential of 0.4 V (vs RHE). As shown in Fig. 4c, after
10 h operation at 0.4 V (vs. RHE), 96% of the initial current density
was retained for Co@Co3O4/FeNS-RGO, much higher than that of
commercial Pt/C catalyst (86% of initial current density retained)
operated under the same condition, indicating that the synthesized

Figure 4. a) LSV curves of Co@Co3O4/FeNS-RGO (black line), Co@Co3O4/NS-RGO (red line), CoPC (blue line), RGO (orange line), and commercial Pt/C (olive line) for ORR in O2-
saturated 0.1 molL-1 KOH electrolyte. b) Koutecky-Levich (K-L) plots of Co@Co3O4/FeNS-RGO for ORR at different potentials. c) Chronoamperometric responses of Co@Co3O4/FeNS-
RGO and Pt/C at 0.4 V (vs. RHE) in O2-saturated 0.1 molL-1 KOH electrolyte. Electrode rotation speed is 1600 rpm with scan rate of 10 mVs1.
6 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821

Co@Co3O4/FeNS-RGO catalyst has an excellent long-term stability.
We also investigated the electrocatalytic activity of the syn-
thesized samples for oxygen evolution reaction (OER) in 1.0 molL-1
KOH solution, and commercial IrO2 was used for comparison. The
polarization curves (Fig. 5a) show that the overpotential of
Co@Co3O4/FeNS-RGO required to drive a 10 mAcm2 OER current
density is 287 mV that is much lower than that of Co@Co3O4/NS-
RGO (346 mV), CoPC (376 mV), and commercial IrO2 (322 mV).
Furthermore, the synthesized Co@Co3O4/FeNS-RGO catalyst exhibit
better or comparable OER activity (with respect to overpotential at
10 mAcm2 compared with the recently reported MOF-derived
electrocatalysts including Co-N-CNTs [41], Ni@NiS2@S/NeHCC
[42], NixCoyO4/CoeNG [43], and Ni2P/CoN-PCP [44]. The Tafel plots
(Fig. 5b) revealed that the sample of Co@Co3O4/FeNS-RGO has the
smallest Tafel slope of about 69 mVdec1 among all the tested
samples of Co@Co3O4/NS-RGO (94 mVdec1), CoPC (96 mVdec1),
RGO (360 mVdec1), and IrO2 (71 mVdec1), demonstrating the
rapid OER kinetics of Co@Co3O4/FeNS-RGO [43]. From the electro-
chemical impedance spectra (EIS) of the tested samples (Fig. 5c),
the clearly observed small semicircle for Co@Co3O4/FeNS-RGO in-
dicates its great conductivity compared with the other samples. In
addition, the superior long-term stability at the current density of
10 mAcm2 for Co@Co3O4/FeNS-RGO was also confirmed by chro-
noamperometric tests, as shown in Fig. S12.
Apart from the superior ORR and OER activities, the Co@Co3O4/
FeNS-RGO catalyst also displays an impressive HER electrochemical
activity. Polarization curves (Fig. 6a) highlight that the over-
potential of Co@Co3O4/FeNS-RGO to drive a current density of 10
mAcm2 is much lower than those of Co@Co3O4/NS-RGO, CoPC,
RGO, and some other reported catalysts, as listed the detailed
values in Table S2. According to the Sabatier principle, an ideal
electrocatalysts for HER should be capable of strong bond forma-
tion with intermediate H-atoms and should have weak enough
bonding interaction with H2 products [45]. Tafel slope is well
accepted to be a direct indicator of the rate-limiting step for the
arge transfer-involved electrochemical reactions [46]. The Tafel
slope of Co@Co3O4/FeNS-RGO (Fig. 5b) is 111 mVdec1, indicating
that the Volmer reaction is the rate-limiting step of HER process
[47]. The characteristics of charge transfer were further investi-
gated with the EIS plots (Fig. 6c) at the overpotential of 170 mV. The
relatively low resistance suggests that Co@Co3O4/FeNS-RGO may
possess a superior nanoarchitecture improving both the electron
transport and the catalytic kinetics [46]. Furthermore, the time-
dependent current density of Co@Co3O4/FeNS-RGO catalyst for
HER at around 10 mAcm2 slightly degrades within 10 h (Fig. S13),
indicating the promising durability of the resulted Co@Co3O4/FeNS-
RGO catalyst for HER.
We believe that the superior OER and HER activities of
Co@Co3O4/FeNS-GO can be attributed to the co-doping of hetero-
atoms into carbon framework and the sandwich-like architecture
of the synthesized materials. First, the RGO sheets decorated with N
and S atoms may increase the active sites and accelerate the elec-
tron transport, which could enhance the adsorption behavior of
OH or Hþ in alkaline solution, as reported in literatures [42,48,49].
Second, the Co3O4 shell can weaken the OeH bond in the absorbed
OH via electrostatic affinity and lower the thermodynamic barrier
for the formation of intermediate OOHad whereas the metal Co
cores boost the electron transport and the oxidation of Co ions [50].
Third, Co@Co3O4 embedded on RGO sheets is beneficial for the
stability of electrocatalytic process, which as a result of the unique
sandwich-like structure prevents the nanoparticles from being
leached in the alkaline medium [51]. Finally, the introduction of Fe-
atoms can modify the charge density of adjacent Co sites. The
electron transfer from Fe-species to Co atoms can induce a rela-
tively lower oxidation state of Co ions, which in turn boosts the
breakage of the Co-O bond and the release of O2 [39].
Meriting by the excellent ORR and OER electrocatalytic activities
of the Co@Co3O4/FeNS-RGO catalyst, a two-electrode rechargeable
Zn-air battery was assembled. As shown in Fig. 7a and Fig. S14, the
Co@Co3O4/FeNS-RGO electrode exhibits better open-circuit voltage

Fig. 5. a) OER polarization curves, b) Tafel slopes, and c) EIS plots of Co@Co3O4/FeNS-RGO (black line), Co@Co3O4/NS-RGO (red line), CoPC (blue line), RGO (orange line) and
commercial Ir/O2 (olive line) in 1 molL-1 KOH. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

c-
h-

Fig. 6. a) HER polarization curves, b) the corresponding Tafel slopes, and c) EIS plots of Co@Co3O4/FeNS-RGO (black line), Co@Co3O4/NS-RGO (red line), CoPC (blue line), RGO
(orange line) and Pt/C (olive line) in 1 molL-1 KOH. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821 7

Figure 7. a) Polarization and power density curves of primary Zneair batteries with different catalysts at a scan rate of 5 mVs1. b) chargeedischarge cycling curve of Zneair battery
with the Co@Co3O4/FeNS-RGO at 5 mAcm2; c) Photograph of all-solid-state Zneair battery using Co@Co3O4/FeNS-RGO as air electrodes that measured with a voltammeter; d)
Photograph of a lighted LEDs (3 V) with different color powered by three all-solid-state Zneair batteries interconnected in series.

Figure 8. a) Photograph of two-electrode overall water splitting using Co@Co3O4/FeNS-RGO as catalysts in 1 M KOH electrolyte; b) the corresponding polarization curves (scan rate,
5 mVs1); c) Chronoamperometric response at a constant voltage of 1.67 V.

of 1.45 V and higher power density of 181 mWcm2 than those of
battery assembled from Pt/C catalyst (1.40 V and 121 mWcm2).
The chargeedischarge cycling performance (Fig. 7b) of the
Co@Co3O4/FeNS-RGO-based Zn-air battery investigated at 5
mAcm2 demonstrate that the assembled battery exhibits excellent
stability with 79% of coulombic efficiency after 360 cycles (40 h),
which better than that of Pt/C catalyst (60% of coulombic efficiency
after 200 cycles, Fig. S15). To further meet the needs of practical
applications, all-solid-state Zneair batteries have been investi-
gated. As shown in Fig. 7c, the home-made Zneair battery using
Co@Co3O4/FeNS-RGO as air electrode can generate a high open-
circuit voltage of 1.449 V and light-emit-ting diodes (LEDs) with
blue and red color have been lighted by only three Zneair batteries
in series (Fig. 7d).
We finally applied the synthesized Co@Co3O4/FeNS-RGO cata-
lyst in an overall water splitting device. It is obvious that H2 and O2
bubbles generated from the two GC electrodes (Fig. 8a), respec-
tively, suggesting the successful operation of the devices. LSV curve
(Fig. 8b) reveals that the Co@Co3O4/FeNS-RGO catalyst delivers a
current density of 10 mAcm2 at a cell voltage of 1.65 V, which is
competitive to the other reported non-noble-metal electrocatalysts
such as CoP/NCNHP (at 1.64 V) [52], NiFe/NiCo2O4 (at 1.67 V) [53],
and Ni@N-doped graphene (at 1.60 V) [54]. The durability of the
assembled water electrolyzer was evaluated with chronoampero-
metric measurements, as shown in Fig. 8c. It is evident that the
Co@Co3O4/FeNS-RGO catalyst exhibited an outstanding stability for
overall water splitting.
4. Conclusions
The multifunctional electrocatalyst of Co@Co3O4 nanoparticles
embedded into Fe, N, S co-doped reduced graphene oxide
(Co@Co3O4/FeNS-RGO) was synthesized by pyrolysis of one-step
solvothermal synthesized nano-metal organic framework/
graphite oxide composite using DMSO as both the solvent and
sulfur source. The co-doping of Fe, N, and S atoms with homoge-
neous distribution can accelerate the mass transport and the high
loading of core-shell-structured Co@Co3O4 can lead to an increased
density of accessible active sites for oxygen-involved electro-
catalysis. The thus-designed electrocatalyst of Co@Co3O4/FeNS-
RGO exhibited the excellent electrocatalytic activity for oxygen
reduction and oxygen evolution reactions, which outperformed the
8 J. Zhu et al. / Electrochimica Acta 323 (2019) 134821
commercially available Pt/C and IrO2 catalysts, respectively. The
performance of the assembled zinc-air battery and the overall
water splitting devices demonstrated that the designed material is
a promising, non-precious metal electrocatalysts with great activity
and stability for energy-related electrochemical device
applications.
Acknowledgements
This work was supported by the Natural Science Foundation of
China under grant numbers of 21878239 and 21576216, and
Opening Project of State Key Laboratory of Advanced Technology
for Float Glass (2018KF03).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.134821.
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