Carbon 144 (2019) 492e499

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Designed synthesis of cobalt nanoparticles embedded carbon

nanocages as bifunctional electrocatalysts for oxygen evolution and
reduction
Ya-Nan Hou a, Zongbin Zhao a, *, Han Zhang a, Changtai Zhao a, Xuguang Liu b,
Yongchao Tang a, Zhanming Gao c, Xuzhen Wang a, d, Jieshan Qiu a, **
a
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Liaoning Key Laboratory for Energy Materials and Chemical Engineering, Dalian
University of Technology, Dalian, 116024, Liaoning, PR China
b
Key Lab of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan, 030024, PR China
c
Chemistry Analysis& Research Centre, Faculty of Chemical, Environmental& Biological Science and Technology, Dalian University of Technology, Dalian,
116024, PR China
d
School of Chemistry, Dalian University of Technology, Dalian, 116024, PR China

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

Article history: The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are fundamental for many
Received 3 October 2018 renewable energy conversion and storage technologies. Developing economic and durable bifunctional
Received in revised form ORR and OER electrocatalysts as substitute for noble-metal based catalysts, are urgently expected to
2 December 2018
reduce the industrial cost. Herein, a strategy towards synthesizing cobalt nanoparticles embedded N-
Accepted 15 December 2018
Available online 15 December 2018
doped carbon hollow nanocages (Co@NPC-H) by ion exchanging is reported. The Co@NPC-H nanocage
structures integrate the high activity of heteroatoms doped catalytic active sites with the hollow
structure for high exposure ratio of the active sites, exhibiting superior electroctalytic performance to
noble-metal catalyst for both ORR and OER with the application potential of 860 mV when used as
bifunctional catalyst, much smaller than other reported electrocatalysts, making Co@NPC-H a promising
candidate as efficient air electrode in Zn-air batteries.
© 2018 Published by Elsevier Ltd.

1. Introduction improved overall potential and significant reduction of emissions

During the process of society evolution from traditional fossil
fuel dominant to renewable energy rise, electrochemical methods
work a lot in clean energy produce and utilization [1]. Among the
electrochemical methods, electrochemical reduction and oxidation
process, such as the oxygen evolution reaction (OER) and oxygen
reduction reaction (ORR), provides an efficient, economical and
clean means to realize the energy utilization by dissociating water
into oxygen and then reducing oxygen back to water [2e5]. These
two O2 reactions work in a variety of energy storage and conversion
devices, such as rechargeable metal (Zn or Li)-air batteries and fuel
cells [6e8]. Such reversible electrochemical devices exhibite a se-
ries of merits such as the high theoretical specific capacity,
* Corresponding author.
** Corresponding author.
E-mail addresses: zbzhao@dlut.edu.cn (Z. Zhao), jqiu@dlut.edu.cn (J. Qiu).
over traditional fossil fuel [9,10]. However, during the practical
application of unitized regenerative and rechargeable devices, one
of the obstacle to realize high energy conversion efficiency is the
sluggish kinetics of ORR and OER, which is influenced by the
electron/proton transfer, leading to not only a high over-potential
but low round-trip efficiency [2,11]. Thus, the development of
economic and sustainable electrocatalysts with high activity as
bifunctional catalyst to fulfill the demands in practical use is highly
desirable.
Up to now, the efficient electrocatalysts for ORR or OER are
mainly recognized as the noble metal catalysts such as Pt-, Ru-, and
Ir-based materials [12e17]. However, Pt and Pt-based alloys
exhibite high efficient electrocatalytic activity for ORR but poor for
OER, and, Ru, Ir and their oxides exhibit an absolutely contrarily
electrocatalytic performance. Moreover, their supply scarcity, high
cost and inferior durability become an obstacle to realize the large-
scale commercialization [18e24]. Thus, successfully designing and
realizing the bifunctional active sites in a single catalyst efficient for

https://doi.org/10.1016/j.carbon.2018.12.053
0008-6223/© 2018 Published by Elsevier Ltd.
 Y.-N. Hou et al. / Carbon 144 (2019) 492e499
both ORR and OER as the substitutes for noble metal electro-
catalysts in a facile and economical method is still in great urgency
[25e30]. Recent investigations demonstrate that transitional metal
(or metal oxide, sulfide, etc.)/N-doped carbon hybrids (M-N-C,
M ¼ Fe, Co, Ni, etc.) hold great potential to be the alternate to
replace noble metal catalysts in pH-universal medium [31e33].
Among currently reported strategies, direct pyrolysis of zeolitic
imidazolate frameworks (ZIFs), which are constructed by the co-
ordinated bonds between atomically dispersed central metal (Co,
Zn, Fe, etc.) and imidazole based organic linkers, provides an effi-
cient approach for producing nanostructured M-N-C hybrid cata-
lysts [34e38].
Most recently, ZIF-67, which consists of inorganic cobalt cation
and organic 2-methylimizazole ligands, has become one of the
most typical candidate precursor for preparing N, Co-dual doped
nanocarbon materials. However, the electrocatalytic activity of bulk
carbons synthesized by directly pyrolyzing ZIF-67 nanocrystals
often suffer from the irreversible collapse of the tunnels, fusion of
the carbon skeleton and aggregation of cobalt nanoparticles, lead-
ing to the insufficient active surface and limited charge transfer. To
address these issues, the performance of ZIF-67 derived electro-
catalysts could be improved by rational structural engineering
design. In this regard, hollow nanostructures are of great interests
due to their low density, large surface area, multiple interfaces, and
reduced diffusion lengths for mass transport, which endows them
with better catalytic activities than their corresponding bulk
counterparts [35,39e41].
In this investigation, we demonstrated a method of synthesizing
hollow carbon nanocubes with cobalt embedded into the N-doped
porous carbon shells (Co@NPC-H) by directly pyrolyzing hollow
ZIF-67 nanocubes (ZIF-H). The ZIF-H is precisely synthesized from
Co3[Co(CN)6]2 nanocubes in aqueous solution via the induction of
n-butylamine. The as-prepared Co@NPC-H is used as the electro-
catalyst for ORR and OER. Interestingly, the resulting Co@NPC-H
exhibits more excellent stability, competitive catalytic activity
and superior methanol tolerance compared to the noble metal-
based catalysts.
2. Experimental section
2.1. Sample preparation
2.1.1. Synthesis of Co3[Co(CN)6]2 nanocubes
The Co3[Co(CN)6]2 nanocubes were synthesized by a reported
method [42]. An aqueous solution (20 mL) of 175 mg of Co(N-
O3)2$6H2O and 265 mg sodium citrate was added into an aqueous
solution (20 mL) of 132 mg of K3[Co(CN)6] slowly and regularly by
using a syringe to form Co3[Co(CN)6]2 nanocubes. After stirring at
room temperature for 24 h, the products were collected by centri-
fugation and washed by water, and finally dried up.
2.1.2. Synthesis of ZIF-67 nanocrystals
The ZIF-67 nanocrystals were synthesized by a reported method
[37]. Two methanolic solutions were prepared by dissolving
Co(NO3)2$6H2O (582 mg, 2 mmol) and 2-methylimidazole (656 mg,
8 mmol) in 50 mL of methanol, respectively. Then, methanolic so-
lution of 2-methylimidazole was poured into Co(NO3)2$6H2O so-
lution rapidly under stirring and aged for 24 h at room temperature.
The precipitate was washed by methanol for several times before
dried at room temperature overnight finally.
2.1.3. Synthesis of ZIF-H and ZIF-S
20 mg of Co3[Co(CN)6]2 nanocubes were dispersed in 10 mL
deionized water with ultrasonic for 5 min. 2.61 g of 2-
methylimidazole and 32 mL of n-butylamine were dissolved in
493
10 mL deionized water. Subsequently, the pink colored dispersion
of Co3[Co(CN)6]2 nanocubes were poured into the solution of 2-
methylimidazole and n-butylamine. The resulting mixture was
transferred into a Telflon-lined stainless steel autoclave with a ca-
pacity of 50 mL. The autoclave was sealed and heated at 75  C for
12 h. After cooling down to room temperature, washing with water
for several times and drying at 60  C for 12 h, the ZIF-H was
obtained.
For comparison, sample with solid structure was also prepared
in the similar method but without adding n-butylamine (denoted
as ZIF-S).
2.1.4. Synthesis of Co@NPC-H, Co@NPC, Co@NPC-ZIF and Co@NPC-
CoCN
The Co@NPC-H was prepared by direct carbonization of the as
synthesized ZIF-H nanoparticles.
Typically, ZIF-H powder was placed in a quartz boat and trans-
ferred into the temperature-programmed furnace for an exposure
to nitrogen gas flow at room temperature (30 min) firstly. The py-
rolysis program was performed at 800  C for 1 h with the heating-
rate of 3  C/min. The obtained black powder was washed with
0.5 M H2SO4 at 80  C for 12 h to remove the unstable cobalt species.
After washing with water for several times and drying up for 12 h
the final product was obtained.
For comparison, ZIF-67 nanocrystals derived Co@NPC-ZIF,
Co3[Co(CN)6]2 nanocubes derived Co@NPC-CoCN and ZIF-S
derived Co@NPC were also prepared under the same conduction.
2.2. Characterization
The morphologies of the samples were observed using field
emission scanning electron microscopy (FESEM, FEI Company,
NOVA NanoSEM 450), transmission electron microscopy (TEM, FEI
Tecnai G20, 200 KV) and high-resolution transmission electron
microscopy (HRTEM, FEI Tecnai F30, 300 KV). The X-ray diffraction
(XRD) patterns were recorded on a Rigaku D/max-2400 diffrac-
tometer. The chemical composition was analyzed by X-rays
photoelectron spectroscopy with Al Ka X-rays radiation (XPS,
Thermo ESCALAB250). The content of Co species was measured by
inductively coupled plasma-optical emission spectroscopy (ICP-
OES, Optima2000DV).
2.3. ORR and OER tests
Electrode preparation. As to the working electrode preparation,
4 mg of the sample was dispersed ultrasonically in a mixture of
ethanol (980 mL) and Nafion (20 mL, 5 wt%) to form a uniform sus-
pension. 10 mL of the catalyst ink was then loaded onto a glassy-
carbon electrode (RDE, 5 mm diameter, 0.196 cm2 geometric sur-
face areas) by microsyringe with a mass loading of 0.2 mg cm2 for
all samples including commercial Pt/C (20 wt%, Johnson Matthey)
and RuO2 (Sigma-Aldrich).
Electrochemical text. All electrocatalytic measurements were
performed on a CHI 760D electrochemical workstation using a KOH
aqueous solution saturated with O2 as the electrolyte at room
temperature (25  C). A glassy-carbon rotating disk electrode (RDE,
PINE Research Instrumentation) or a rotating ring-disk electrode
(RRDE, PINE Research Instrumentation) was used as working
electrode while a Pt rod and a KCl saturated solution Ag/AgCl
electrode was employed as counter and reference electrode,
respectively. All potentials was converted to the potential versus
RHE according to Evs RHE ¼ Evs Ag/AgCl þ 0.059 pH þ 0.197 when
measured against an Ag/AgCl electrode in this study.
494 Y.-N. Hou et al. / Carbon 144 (2019) 492e499

3. Results and discussion (denoted as ZIF-S). This is because the n-butylamine, which pos-
sesses the chemical functionality of monodentate ligand, could be
The synthesis strategy of Co@NPC-H is schematically illustrated regarded as a modulation during the deprotonation equilibria and
in Scheme 1. Typically, the preparation involves two steps. In the complex formation [44]. To be more specific, at the beginning of the
first step, the Co3[Co(CN)6]2 nanocubes (denoted as CoCN) firstly reaction, the ion exchange reaction takes place at the solid-liquid
synthesized via sediment between Co2þ and [Co(CN)6]3- in water interface between the surface of CoCN nanocubes and the Hmim
system were functioned as template for the subsequent ionic ex- liquid solution followed the reaction as described by equation (1)
change [43], in which Co(CN)3- 6 was replaced by 2-methylimidazol below [45]:
with the induction of n-butylamine to form a hollow ZIF-67
nanocube (ZIF-H). Then as-obtained ZIF-H was converted to
Co@NPC-H by thermal annealing at high temperature under inert Co3 ½CoðCNÞ6 2 þ 6mim /3CoðmimÞ2 ðsÞ þ 2½CoðCNÞ6 3 ðaqÞ
atmosphere. The obvious color change from pink of CoCN to violet
of ZIF-67 proves the successful synthesis of ZIF-H after ion ex- where mim is the deprotonated 2- methylimidazole (Hmim) and
change (inset digital images in Fig. S1). X-ray diffraction (XRD) Co(mim)2 is the basic structural unit of ZIF-67. During this process,
analysis shows that the diffraction signals of resultant ZIF-H sample the deprotonation of n-butylamine induce more nuclei and accel-
is in good agreement with simulated pattern of ZIF-67 in peak erate the crystallization process, leading to the rapid nucleation and
position and intensity (Fig. 2a). The panoramic pictures taken formation of ZIF-67 layer on the surface of CoCN cubes. In other
(Fig. S1b) by filed-emission scanning electron microscopy (FESEM)
reveals that the as-prepared ZIF-H sample inherits the morphology
of cubes from CoCN (Fig. S1a) with a smooth surface and an average
edge length of z300 nm. No aggregates are observed in the sample.
Transmission electron microscopy (TEM) images further confirm
the formation of the ZIF-H nanocrystals with a hollow space inside
the cube (Fig. S2a). For comparison, another sample was also syn-
thesized in the same method but in the absence of n-butylamine.
While, TEM images (Fig. S2b) suggest that the samples are poly-
hedron with uniform size of z400 nm but with a solid nature

Fig. 2. a) XRD patterns of ZIF-H and Co@NPC-H; b) XPS full scan, c) N 1s XPS spectrum
Scheme 1. Schematic illustration for the synthesis of Co@NPC-H. and d) Co 2p XPS spectrum of Co@NPC-H.

Fig. 1. (a, b) FESEM images and (d, e) TEM images of Co@NPC-H; (c) HRTEM image, (f) FESEM image and the corresponding elemental mapping of Co@NPC-H.
 Y.-N. Hou et al. / Carbon 144 (2019) 492e499
words, the n-butylamine acts as a molecular “inducer” and “fixer”,
which induce the high concentration of ZIF-67 nuclei and then fix
them onto the surface of CoCN cubes, furthermore preventing the
cubic morphology from collapsing [44,46]. At the same time, the
[Co(CN)6]3- ions generated in the internal surface diffused outward.
During this ion exchange process, the CoCN cubes are consumed
gradually implemented on the extensional growth and internal
dissolution, eventually evolved into ZIF-67 hollow nanoboxes (ZIF-
H). While, in case of without n-butylamine, the protonated Hmim
coordinate with Co(II) ion and form the complexes [Co(Hmim)n].
These complexes exist in the form of ion and dissociate in the so-
lution freely, not only reduce the rate of nucleation and crystalli-
zation but also regrow into solid cubes with an edge length of z
400 nm (Fig. S2b).
In order to clarify the role of n-butylamine during the growth of
ZIF-H, ZIF-67 nanocrystals were also prepared in a modified
method as reported previously [37]. TEM images (Fig. S2c) reveale
that the ZIF-NC consist of uniform rhombic dodecahedrons and the
average edge length is about 200 nm. The ZIF-H, ZIF-S, ZIF-NC and
Co3[Co(CN)6]2 nanocubes are then used to thermal treatment in
flowing inert N2 at 800  C at a ramp rate of 3  C min1, the resulted
hybrid were treated by H2SO4 solution to move away the unstable
Co nanoparticles. As shown in the images of FESEM, well-defined
hollow space are inherited successfully from ZIF-H after decom-
position and carbonization treatment (Fig. 1a and b). Because of the
growth of ZIF-67 layer, the edges and corners of CoCN were
destroyed slightly, the average edge length of the particles is
reduced to z200 nm due to the shrinkage to denser carbon-based
composites. TEM examinations furthermore identify the presence
of hollow structure and a carbon shell with the thickness of
z30 nm (Fig. 1d). High resolution transmission electron micro-
scopy (HRTEM) analysis demonstrated the occurrence of graphitic
carbon similar to “onion” layer encapsulating the Co nanoparticles,
leading by the catalytic graphitization of Co nanoparticles from
amorphous carbon at high temperature (Fig. 1c) [35,47,48]. The
dense graphitic carbon sheath protected Co nanoparticles from
acidic/alkali etching during the catalytic process, retaining the ac-
tivity of active site and enhance the stability of the catalyst. While,
the product of ZIF-S, ZIF-NC and ZIF-CoCN aggregated severely into
the bulk carbon (Fig. S3), preventing the utilization of electro-
catalytic active sites during the ORR.
The components of ZIF-H-derived Co@NPC-H could be visual-
ized, including uniformly dispersed carbon, nitrogen and cobalt
elements by elemental mapping (Fig. 1f). The structural character-
istics of Co@NPC-H, Co@NPC, Co@NPC-ZIF and Co@NPC-CoCN are
identified by XRD analysis (Fig. 2a and Fig. S4). Typically, for the
XRD pattern of Co@NPC-H, the sharp signal peak at 2q ¼ 26 cor-
responds to (002) plane of graphitic carbon while the other three
signals at z44 , 51, and 76 should be attributed to the diffraction
from (111), (200), and (220) planes of metallic Co (a ¼ 3.545 Å,
JCPDS No. 15e0806) [35,49,50].
Fig. S4 reveals that ZIF-S derived Co@NPC, ZIF-NC derived
Co@NPC-ZIF and CoCN cubes derived Co@NPC-CoCN show almost
the same XRD patterns with Co and graphitic carbon signals at the
same position, which indicate the similar constitutions of Co@NPC-
H, Co@NPC, Co@NPC-ZIF and Co@NPC-CoCN. The inductively
coupled plasma atomic emission spectrometry (ICP-AES) analyses
identify that the cobalt contents of Co@NPC-H, Co@NPC, Co@NPC-
ZIF and Co@NPC-CoCN are 22.30, 17.58, 27.51 and 66.21 wt%,
respectively, which are coincided with the results of thermogravi-
metric analysis (TGA) (Fig. S5). The chemical compositions are
investigated by X-ray photoelectron spectroscopy (XPS), indicating
the presence of C, N, O, and Co elements in Co@NPC-H (Fig. 2b). The
high-resolution N 1s spectrum gives four signals and proves the
presence of four types of N species, the pyridinic N (z398.4 eV), Co-
495
Nx (z399.3 eV), pyrrolic N (z400.1 eV) and graphitic N
(z401.1 eV) in the nanocages (Fig. 2c) [51e53]. The Co 2p3/2 XPS
spectrum suggests the presence of metallic Co (778.5 eV), Co-Nx
(779.7 eV), CoCxNy/CoOy (780.7 eV), CoxOy (781.9 eV), and Co-
carbonate (Fig. 2d) [51]. As shown in Fig. S6a, the C1s high-
resolution XPS spectrum can be attributed to the presence of sp2-
hydridized carbon (284.5 eV), C-N bonds (285.0 eV) and C¼O bonds
(286.0 eV) [54,55]. Moreover, the identification of C-N bonds could
be regarded as another evidence of the N doping in Co@NPC-H. The
signal of O element can be attributed to the residual oxygen in
carbon framework and the adsorbed oxygen on surface from
environmental atmosphere (Fig. S6b) [54].
The electrocatalytic activities towards ORR of Co@NPC-H are
identified in 0.1 M O2-saturated KOH electrolyte. To reflect the
actual current response of cyclic voltammetry (CV), rotating disk
electrode (RDE), and rotating ring-disk electrode (RRDE) linear
sweep voltammetry (LSV), all the collected curves were modified
by subtracting the value collected under saturated Ar solution. To
demonstrate the superiority of Co@NPC-H in ORR, the performance
of Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN and commercial Pt/C were
also investigated under identical conditions. The ORR performance
was firstly investigated by CV at a scan rate of 10 mV s1. As shown
in Fig. 3a, a significant reduction peak was observed at z0.76 V
versus reversible hydrogen electrode (RHE) in the O2-saturated
solution, while within the same voltage window, only featureless
quasi-rectangular voltammogram is observed in Ar- saturated
electrolyte. To estimate the electocatalytic activities, the CV curves
of Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN and commercial Pt/C were
also tested (Fig. S7a). Notably, the reduction peak position for
Co@NPC-H occurs at 0.76 V, which is closer to that of commercial
Pt/C (0.84 V) than those of Co@NPC, Co@NPC-ZIF and Co@NPC-
CoCN, suggesting the superior electrocatalytic activity of
Co@NPC-H among these catalysts.
In order to gain deeper insight into the catalytic activity and
kinetics, the LSV curves of Co@NPC-H, Co@NPC, Co@NPC-ZIF,
Co@NPC-CoCN and commercial Pt/C are recorded on a rotating
disk electrode (RDE) with a rotation rate of 1600 rpm at a scan
rate of 10 mV s1. As shown in Fig. 3b, the onset potential (Eonset
equals the potential when limited current density reaches
0.20 mA cm2) for Co@NPC-H, Co@NPC, Co@NPC-ZIF and
Co@NPC-CoCN was 0.88, 0.84, 0.83 and 0.82 V versus RHE,
respectively, quite similar to that of commercial Pt/C (0.93 V).
Furthermore, at the potential of 0.0 V, Co@NPC-H exhibits a
comparable kinetic limiting current density (Jk)
of 5.20 mA cm2 with that of commercial Pt/C (5.00 mA cm2)
at the potential of 0.0 V, but much superior to those of Co@NPC,
Co@NPC-ZIF and Co@NPC-CoCN (4.41, 4.44
and 4.05 mA cm2 respectively). Meanwhile, Co@NPC-H has the
most positive half potential (E1/2) at 0.77 V (vs 0.76 V of Co@NPC,
vs 0.75 V of Co@NPC-ZIF and vs 0.72 V of Co@NPC-CoCN), which
is very close to that of commercial Pt/C (0.81 V). According to the
LSV curves, the calculated Tafel Slope (Fig. 3c) of Co@NPC-H
(33.2 mV dec1) is much smaller than those of Co@NPC
(35.5 mV dec1), Co@NPC-ZIF (36.6 mV dec1), Co@NPC-CoCN
(49.1 mV dec1) and even commercial Pt/C (46.0 mV dec1) at
low over-potential, indicating the superior ORR kinetics of
Co@NPC-H and the advantage of hollow nanostructures for
electrocatalytic activity.
The wide current plateau at the range of 0.7e0.0 V represents a
diffusion-controlled process, corresponding to the efficient four
electron-dominated ORR pathway [55]. To furthermore uncover
the reaction pathway of catalyst Co@NPC-H, RRDE LSV technology
is applied to detect the yield of peroxide intermediate (HO 2 ) and
electron transfer number per oxygen molecular (n) during the
process of ORR. As it is shown in Fig. 3d, the LSV curve of Co@NPC-
496 Y.-N. Hou et al. / Carbon 144 (2019) 492e499

H catalyst still shows an comparable Jk of 1.3 mA to that of Pt/C
(1.2 mA) at 0.0 V, which is much higher than that of Co@NPC
(1.1 mA), Co@NPC-ZIF (1.1 mA) and Co@NPC-CoCN (1.1 mA) cata-
lyst. The electron transfer number per oxygen molecule (n) and
peroxide yield are calculated according to the RRDE LSV curves, as
it is shown in Fig. 3e and f, the Co@NPC-H has a smaller peroxide
yield than those of Co@NPC, Co@NPC-ZIF and Co@NPC-CoCN,
demonstrating a high electrocatalytic selectivity of Co@NPC-H
catalyst [56e58]. In particular, during the catalytic process, the
Co@NPC-H catalyst exhibited a peroxide yield below 15% with a
high electron transfer number above 3.70 over the potential
ranges of 0.0 Ve0.7 V, approximating to that of commercial Pt/C
(peroxide yield is below 5.6% and electron transfer number is
3.96). The electron transfer number and kinetic limiting current
density (Jk) for ORR of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-
CoCN and commercial Pt/C are furthermore determined according
to the LSV curves (Fig. S8, Supporting Information) calculated by
the KoutechyeLevich (KeL) equation. The good parallel linearity
of KeL plots of Co@NPC-H from 0.6 to 0.2 V, suggesting a first-
order reaction kinetics for ORR. Notably, the slope of KeL plots
of Co@NPC-H is very similar with those of commercial Pt/C,
manifesting a close n of Co@NPC-H to that of commercial Pt/C,
which is determined to be z 4.0, indicating the in situ formation
of OH in alkaline electrolyte [59,60]. To further investigate the
superiority of the hollow structure, the apparent electrochemical
surface areas (ECSA) of Co@NPC-H, Co@NPC, Co@NPC-ZIF and
Co@NPC-CoCN are compared by measuring their double-layer
capacitance (Cdl), which could be used to investigate the specific
activity [18,61,62]. Their corresponding CV curves without Faradic
responses are shown in Fig. S9 (Supporting Information).The Cdl
value was estimated by the linear slope of the fitting line that was
plotted by capacitive currents versus scan rates. The Cs value is
adopted as z0.04 mF cm2 [35]. As it is shown in Fig. 3g, the
Co@NPC-H possesses the high specific activities of 8.92 mF cm2,
higher than those of Co@NPC (4.18 mF cm2), Co@NPC-ZIF
(7.76 mF cm2) and Co@NPC-CoCN (5.27 mF cm2), revealing the
superiosity of hollow nanostructure on ORR.
In O2-saturated alkali media, the Co@NPC-H catalyst exhibits
superior durability and methanol sustainability in comparison with
Pt/C catalyst. The cycling experiment was evacuated using a chro-
noamperometric measurement in alkali media. The currentetime
(iet) curve for Co@NPC-H delivers almost no current loss after
35 h durability test, demonstrating a higher stability than com-
mercial Pt/C (Fig. 3h). And the Co nanoparticles structure could still
be maintained after the durability test (Fig. S10, Supporting Infor-
mation), indicating the structure stability. However, the i-t curve of
commercial Pt/C catalyst exhibited a current loss with only 79.6%
current retention just after 7 h durability test. Furthermore, the
methanol tolerance of Co@NPC-H was determined by adding
methanol into the electrolyte. As it is shown in Fig. 3i, a very slight
fluctuation in the current density could be observed of Co@NPC-H
after the addition of 1 M methanol, however, the i-t curve of the
commercial Pt/C catalyst shows a “waterfall-like” current loss due
to the methanol oxidation of Pt particles. This result suggest that
Co@NPC-H exhibites much better methanol sustainability toward
ORR. In addition, the performance towards ORR of Co@NPC-H,
Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN and commercial Pt/C are
also texted in acid medium. The results reveal that the Co@NPC-H

Fig. 3. Electrocatalytic performance evaluation of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN and commercial Pt/C in O2-saturated 0.1 M KOH solution. a) CV curves of
Co@NPC-H catalysts in KOH solution saturated by Ar or O2 at a scan rate of 10 mV s1; b) ORR polarization curves and (c) Tafel plots of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-
CoCN and commercial Pt/C catalysts at a rotation rate of 1600 rpm at a scan rate of 10 mV s1; d) RRDE and LSV curves, e and f) corresponding electron transfer number and peroxide
yield at different potential of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN and commercial Pt/C; g) Plots of the current density at 0.915 V vs. the scan rate to determine the
double layer capacitance (Cdl); h) chronoamperometric responses of Co@NPC-H (at 0.6 V, 1600 rpm) in 0.1 M KOH solution with sequential injection of saturated O2 and i) 1 M MeOH
at 300 s.
 Y.-N. Hou et al. / Carbon 144 (2019) 492e499 497

Fig. 4. IR-corrected OER polarization curves a) and Tafel plots derived from the OER polarization curves b) of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN, Pt/C, and RuO2
catalysts in O2-saturated 1 M KOH solution at a scan rate of 10 mV s1 at 1600 rpm; c) IR-corrected polarization curves of Co@NPC-H, Co@NPC, Co@NPC-ZIF, Co@NPC-CoCN, Pt/C, and
RuO2 catalysts, which are tested by using the three-electrode system in the full OER/ORR region in O2-saturated 0.1 M KOH solution. Inset: Digital image of a LED panel lighted by
four Zn-air batteries in series; d) A comparison on the DE of the recently reported bifunctional catalysts; e) Schematic of the Zn-air battery; f) Galvanostatic charge-discharge cycling
performance of rechargeable Zn-air batteries with Co@NPC-H and Pt/C þ RuO2 catalysts at a current density of 10 mA cm2.

catalyst also exhibit much lower onset over-potential (0.71 V) than
those of Co@NPC (0.63 V), Co@NPC-ZIF (0.62 V) and Co@NPC- CoCN
(0.68 V) electrodes, revealing a high ORR electrocatalytic activity in
acidic electrolyte (Fig. S11a). The electron transfer number of
Co@NPC-H in acid media calculated by the KoutechyeLevich (KeL)
equation is 3.89e3.76, which is very closed to that of the com-
mercial Pt/C (4.00) (Fig. S11b). The KeL plots of Co@NPC-H exhibit
good parallel linearity from 0.10 to 0.35 V and exhibit a very similar
slope with those of commercial Pt/C (Fig. S11c). Co@NPC-H also
shows superior stability and methanol endurance to commercial
Pt/C catalysts (Fig. S11d).
The oxygen evolution activities of Co@NPC-H, Co@NPC,
Co@NPC-ZIF, Co@NPC-CoCN, RuO2 and commercial Pt/C are also
evacuated in 1.0 M KOH solution (Fig. 4a). For the Co@NPC-H
electrocatalyst, the current density reaches 10 mA cm2 at the po-
tential (Ej¼10) of 1.58 V, which is comparably favorable to that of
RuO2 (1.57 V), but lower than those of Co@NPC (1.67 V), Co@NPC-
ZIF (1.61 V), Co@NPC-CoCN (1.59 V) and the commercial Pt/C
(1.83 V). Also, Co@NPC-H electrocatalyst exhibits a much lower
Tafel slope (57.0 mV dec1) with respect to RuO2 (78.4 mV dec1),
Co@NPC (96.7 mV dec1), Co@NPC-ZIF (68.2 mV dec1), Co@NPC-
CoCN (63.0 dec1) and Pt/C (90.1 mV dec1) (Fig. 4b), demon-
strating a favorable kinetics in hollow nanostructured electro-
catalyst for OER. According to the LSV curves, the onset potential of
Co@NPC-H is close to that of RuO2 catalyst (1.45 V for Co@NPC-H
and 1.41 V for RuO2).
Because of the excellent exhibition of Co@NPC-H towards both
ORR and OER, the application potential has also been explored by
LSV curve when used as the bifunctional catalyst. The overall ox-
ygen electrode activity is defined by the difference of OER and ORR
metrics (DE ¼ Ej¼10  E1/2)(Fig. 4c). The Co@NPC-H has a DE of
860 mV, much smaller than those of Pt/C (1.16 V) and RuO2 (1.19 V)
and other reported bifunctional catalysts recently (Fig. 4d)
[28,63e67]. The high catalytic activities of cobalt nanoparticles
embedded carbon nanocages are attributed to the synergistic
electron transfer and redistribution between the Co nanoparticles,
the graphitic carbon, and the doped N species [35]. Thus, the
excellent catalytic activity of Co@NPC-H for both ORR and OER
inspired us to construct a home-made Zn-air battery to develop its
potential application. A zinc plate serves as the anode and the
Co@NPC-H electrocatalyst ink loaded on carbon paper is adopted as
the air cathode. The performance of this Zneair battery is tested in
the static ambient atmosphere without external gas providing
(Fig. 4e). The home-made Zn-air battery provides an open-circuit
voltage of 1.38 V (Fig. S12) and four Zneair batteries connected in
series is sufficient to power thirty red light-emitting diodes (inset
in Fig. 4c). The rechargeability of this Zn-air battery used Co@NPC-
H as cathode was also tested by the galvanostatic charging/dis-
charging cycling technology and compared with that of Pt/C þ RuO2
mixture with a same total mass loading (Fig. 4f). At the current
density of 10 mA cm2, the initial potential gap of Co@NPC-H cat-
alysts is 0.77 V, much smaller than that of the Pt/C þ RuO2 mixture
(1.15 V). After 220 min test, the potential gap increased to 0.90 V,
smaller than that of the Pt/C þ RuO2 mixture (1.50 V). This result
reveal the superiority of Co@NPC-H in the case of the oxygen
electrocatalysts in rechargeable Zn-air batteries.
4. Conclusion
In summary, a n-butylamine deprotonation-induced ZIF-67
nanocages and their derived cobalt nanoparticles embedded Co, N-
codoped carbon hollow nanocages (Co@NPC-H) were successfully
prepared in aqueous solution at room temperature. The as-
prepared Co@NPC-H shows excellent electrocatalytic performance
both in the reactions of oxygen evolution and reduction. This is
attributed to the unique Co, N codoped compositions in the carbon
materials, as well as the superiority of the hollow structure, which
affords high surface area, enhances the utilization efficiency of
catalytic active sites, shortens the ion diffusion length, and facili-
tates the charge transfer. This proposed strategy opens up an
498 Y.-N. Hou et al. / Carbon 144 (2019) 492e499
enlightening avenue for the synthesis of MOF derived hollow ar-
chitectures, broadening the application scope of MOFs in the fields
of catalysis, energy conversion and storage devices.
Acknowledgements
The authors acknowledge the financial support of the National
Natural Science Foundation of China (Grant No. 51672033,
U1610105, and U1610255) and the Natural Science Foundation of
Liaoning Province (No. 201602170).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2018.12.053.
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