Nano Energy 31 (2017) 541550

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Nano Energy
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NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes as a MARK

highly ecient bifunctional electrocatalyst for rechargeable zinc-air
batteries

Xiaopeng Hana,c, Xiaoyu Wua, Cheng Zhonga,b, , Yida Denga, Naiqin Zhaoa,b, Wenbin Hua,b,
a
Tianjin Key Laboratory of Composite and Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China
b
Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of Education), Tianjin University, Tianjin 300072, China
c
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China

A R T I C L E I N F O A BS T RAC T

Keywords: The commercial development of metal-air batteries with remarkably high theoretical energy output is largely
Metal-air batteries limited by the scarcity of low-cost and highly stable electrocatalysts with activities for oxygen reduction reaction
Nanocomposite (ORR) and oxygen evolution reaction (OER) comparable to precious metals and their alloys. Herein, a new
Metal sulde inorganic-nanocarbon coupled hybrid, homogeneous NiCo2S4 nanocrystals anchored on nitrogen-doped carbon
Nitrogen-doped carbon nanotubes
nanotubes (NiCo2S4/N-CNT), has been developed as an extremely ecient bifunctional catalyst to promote the
Bifunctional electrocatalysis
sluggish ORR and OER kinetics for advanced rechargeable zinc-air battery. It is found that the highest activity is
obtained by tailoring the crystal size of NiCo2S4 in the hybrid through tuning the construction of metal-
ammonia complexes. The optimized NiCo2S4/N-CNT nanocomposite exhibits extraordinary bifunctional
activity through half reaction testing, displaying comparable ORR activity to state-of-the-art carbon supported
platinum (Pt/C) and superior OER capability to RuO2 as well as much better durability. The resulting battery
performance in generative Zn-air system further conrms its superb eective bi-functionality for catalyzing dual
ORR and OER. Compared with those of well-known commercial Pt/C and RuO2, the synergetic NiCo2S4/N-CNT
hybrid enables signicantly reduced charge-discharge polarization (~0.63 V), enlarged energy eciency
(~67.2%) and prolonged cyclability up to 150 cycles at 10 mA cm2. The tremendously enhanced electro-
chemical behaviors arise from favorable factors including small sized, homogenous dispersed novel NiCo2S4
nanocrystals and coupling interaction between sulde spinels and underlying N-doped CNT network, which not
only provides ecient electron transfer pathway but also alters the electronic structure, thus facilitating the
oxygen electrocatalysis during the discharge-charge processes.

1. Introduction Otherwise, the insucient durability of these noble metal-based cata-

Rechargeable metal-air batteries have received increasing attention
owing to their prominent advantages including drastically high energy
density (510 folds than current lithium-ion batteries), cost eective,
safe and environmental compatibility [1,2]. The intrinsic sluggish
kinetics of oxygen reduction reaction (ORR) and oxygen evolution
reaction (OER) occurred on the air cathode is one of the major technical
obstacles, resulting in large battery overpotential, limited practical
energy density and poor reversibility of oxygen chemistry [35]. At
present, precious metals (e.g., Pt, Ru, and Ir) and their alloys are
recognized to possess the best oxygen electrocatalytic activities, however,
their prohibitive price and rare availability bring great challenges for the
widespread practical implementation of metal-air batteries [69].
lysts still need further improvement owning to the dissolution, Ostwald
ripening, and aggregation of active species in prolonged cycle period
[1013]. More importantly, it is extremely dicult to exploit one
electrocatalyst with satisfactory activities for both ORR and the rever-
sible OER [14]. Thus, it is urgently imperative to design and develop
earth-abundant, corrosion-resistant and highly active bifunctional elec-
trocatalysts for dual ORR and OER to build next generation rechargeable
metal-air batteries.
Among precious-metal-free alternatives, rst-row transition metal
chalcogenides have been extensively investigated as ORR and OER
catalysts owning to their advantages of high abundant resources, low
cost and considerable activity [1521]. Among them, cobalt suldes
(e.g., Co3S4, Co9S8, Co1xS etc.) have attracted particular attention for

Corresponding author at: Tianjin Key Laboratory of Composite and Functional Materials, School of Material Science and Engineering, Tianjin University, Tianjin 300072, China.
E-mail addresses: cheng.zhong@tju.edu.cn (C. Zhong), wbhu@tju.edu.cn (W. Hu).

http://dx.doi.org/10.1016/j.nanoen.2016.12.008
Received 11 November 2016; Received in revised form 5 December 2016; Accepted 5 December 2016
Available online 06 December 2016
2211-2855/ 2016 Elsevier Ltd. All rights reserved.
X. Han et al.
application in oxygen electroreduction [2227]. Theoretical calcula-
tions have already predicted that the Co9S8 catalyzed the ORR via a
four-electron transfer pathway, which is similar to Pt surface [28].
However, the experimental performance still lies far behind so far.
Recent research has demonstrated Ni doped Co-S to form thiospinel
compound (i.e., NixCo3xS4) can display enhanced ORR performance in
comparison with binary Co-S composition [26]. Unfortunately, the
moderate OER capability and intrinsic limited electronic conductivity
still need to be overcome in order to meet the practical requirements of
oxygen-related regenerative metal-air technologies.
Downsizing the particles could signicantly contributes to the much
enhanced electrocatalytic eciency owning to resulted higher specic
surface area and increased active surface-atom exposure ratio [29,30],
which can not only oer more interfacial active sites, but also shorten
the mass/electron transfer distance. To compensate the poor electrical
conductivity, the combination of active species and carbonaceous
nanomaterials (e.g., carbon nanotube (CNT) and graphene) has been
proven to be a promising strategy to achieve the resultant hybrids with
excellent electrocatalytic activity and satised stability by virtue of
improved overall conductivity and the coupling synergetic eect
[17,19]. Furthermore, doping heteroatoms (e.g., N, P) into the carbon
framework could further optimizes the surface electronic structure
congurations and the adsorption/desorption behaviors towards oxy-
gen intermediates, thus facilitating the electrocatalytic kinetic pro-
cesses in metal-air chemistries [31,32].
Based on these design principles, we herein demonstrate the
rational design and controllable synthesis of covalent hybrid of
NiCo2S4 nanocrystals homogeneously grown on N-doped multiwall
CNT (designated as NiCo2S4/N-CNT) through a facile two-step meth-
od, which involving a formation of hydrolyzed metal precursors as the
nucleation and then a simple solvothermal crystallization process to
aord the resultant hybrid (Scheme 1). Interestingly, the crystal size of
supported NiCo2S4 spinels can be easily tailored by tuning the
nucleation degree with metal-ammonia coordination. The N-CNT
matrix underlying the crystallized NiCo2S4, oers an electron transfer
framework for active centers, connes the growth size of suldes, and
boosts the oxygen electrochemistry performance through the synergis-
tic interaction between two components. Electrochemical half-cell tests
revealed that the optimized NiCo2S4/N-CNT hybrid exhibited superior
overall catalytic activity than bare NiCo2S4 and N-free CNT supported
NiCo2S4 (designated as NiCo2S4/CNT). Particularly, the NiCo2S4/N-
CNT manifests comparable ORR onset/half-wave potential (0.93 V,
0.80 V) and diusion current density (3 mA cm2) compared to that of
commercial carbon supported Pt (Pt/C, 0.95 V, 0.83 V, 2.95 mA cm2),
accompanied with superior long-term durability. The composite also
renders prominent improvement in OER capability (70 mV lower than
RuO2 to reach 10 mA cm2), rendering excellent bifunctional activity of
about 0.80 V in alkaline medium, comparable to those of highly active
noble-metal, transition-metal and metal-free catalysts reported so far.
The resulting primary Zn-air battery exhibits high discharge peak
Scheme 1. Schematic illustration of the preparation of NiCo2S4/N-CNT nanocomposite.
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Nano Energy 31 (2017) 541550
power density of 147 mW cm2 and energy density of 554.6 Wh kg1.
When employed in real rechargeable Zn-air cells, the NiCo2S4/N-CNT-
based electrode achieves smaller ORR and OER polarization (0.63 V),
higher energy eciency (67.2%) and several times longer operational
life (150 cycles) than those of precious Pt/C (0.90 V, 59.8%, 59 cycles)
and RuO2 (0.79 V, 60.5%, 44 cycles) catalysts at 10 mA cm2, respec-
tively. This study should shed light on exploring potential earth-
abundant candidate alternatives to promote the development of next-
generation rechargeable metal-air batteries technologies.
2. Experimental section
2.1. Material synthesis
A modied Hummers method was adopted to prepare the mildly
oxidized multi-walled CNT. In a typical synthesis, 1 g CNT was added
to 23 mL concentrated H2SO4 and stirred for 20 h at ambient atmo-
sphere. After addition of 400 mg NaNO3 into the mixture, 1 g KMnO4
was then slowly added at 40 C. 3 mL deionized water was added drop
by drop after continuous stirring for 30 min, followed by another
addition of 3 mL deionized water after 5 min. Another 5 min later,
40 mL deionized water was subsequently added. Then after 15 min,
140 mL deionized water together with 10 mL H2O2 (30 wt%) was
added to mixture to terminate the oxidization process. Finally, the
CNT with mildly oxidization state were collected, washed with 5%
hydrochloric acid and water, then lyophilized.
In a typical synthesis of NiCo2S4/N-CNT, 68 mg as-prepared mildly
oxidized CNT were ultrasonically dispersed in 38 mL ethanol and 2 mL
deionized water mixed solvent. Then, 0.3 mmol Co(AC)24H2O and
0.15 mmol Ni(AC)24H2O were dissolved in the above 40 mL suspension
and stirred at 80 C for 2 h in water bath, followed by addition of desired
amount of NH3H2O. After stirring for another 2 h, 0.9 mmol thiourea
was added to the above system. After continuous stirring for 20 h, the
reaction mixture was transferred to a 50 mL autoclave for solvothermal
reaction at 170 C for 3 h. After cooling to room temperature, the
prepared sample was collected by centrifugation and washed with
deionized water and dried by lyophilization overnight. For comparisons,
NiCo2S4/CNT was prepared following similar procedures except without
the addition of NH3H2O and bulk NiCo2S4 particle were synthesized
under the same conditions in the absence of CNT matrix.
2.2. Materials characterization
The phase purity and micro-nanostructured morphologies of the as-
synthesized samples were respectively characterized by powder X-ray
diraction (XRD, Bruker/D8 Advanced with Cu K radiation), eld-
emission scanning electron microscopy (SEM, Hitachi S4800, 30 kV) and
transmission electron microscopy (TEM, JEOL JEM-2100F, 200 kV)
equipped with an energy-dispersive spectrometer (EDS). Raman spectra
were performed using a confocal Raman microscope (DXR, Thermo-
X. Han et al.
Fisher Scientic) at 532 nm excitation from an argon ion laser.
Thermogravimetric tests were conducted in air atmosphere from room
temperature to 850 C with heating rate of 10 C/min using Netzsch
STA449F3 Jupiter analyzer. The Brunauer-Emmett-Teller (BET) specic
surface area was determined by using the N2 adsorption/desorption
isotherms at 77 K on an AutosorbiQ instrument (Quantachrome U.S.)
with a 6 h outgas at 80 C. X-ray photoelectron spectroscopy (XPS) results
were collected on a Perkin Elmer PHI 1600 ESCA system.
2.3. Electrochemical measurements
The electrochemical performance was tested using a three-electrode
system comprising a platinum foil counter electrode, a saturated
calomel reference electrode and a catalyst-modied rotating ring-disk
glass-carbon working electrode (disk diameter 5.61 mm). In a typical
procedures to prepare the working electrode, a mixture of 3 mg
NiCo2S4 and 7 mg carbon powder (Vulcan XC-72) or 10 mg NiCo2S4/
CNT, NiCo2S4/N-CNT was suspended in a mixed solvent containing
0.8 mL deionized water, 0.2 mL ethanol, and 0.14 mL Naon (v/v/v
=4/1/0.7) to form a homogeneous catalyst ink. As for the precious
metal catalysts, 10 mg Pt/C or 3 mg RuO2 mixed with 7 mg carbon
were used. Then 7.0 l of the as-prepared ink was deposited onto the
GC electrode and dried at ambient condition to aord a mass loading of
~ 0.248 mg cm2. The electrolyte (0.1 M KOH) was pre-purged with
high-purity Ar or O2 for at least 30 min before each test and
maintained gas ow until the end of the tests. Electrochemical data
were performed on a IviumStat workstation accompanied with a
rotating system (PHYCHEMI). Before collecting the data, several CV
curves were scanned until the stabilized signals were observed. The
linear sweep voltammetry was scanning at a potential scan rate of
5 mV s1 and the ring potential was constant at 1.3 V vs RHE for ORR.
The ORR polarization curves were subtracted the background currents
in Ar-saturated electrolyte. The OER voltammetry were corrected with
iR-compensation. All the potential were transferred with reference to
standard reversible hydrogen electrode (RHE) according to following
equation: Evs RHE = Evs SCE +0.99 V in 0.1 M KOH [33]. The electro-
chemical surface area was determined by using the in situ method
based on the measurement of electrochemical double layer capacitance
in non-Faradaic potential region. Electrochemical impedance spectra
were measured in a frequency range of 100 kHz100 mHz at a bias
potential of 0.8 V vs. RHE.
The Koutecky-Levich plots can be constructed to analyze the ORR
kinetics with the following equation:
1 1 1 1 1
= + = groups of CNT nanostructure [19]. Afterward, solvothermal treatment
I Ik Id nFAkC 0 0.62nFADO2/3
2
v1/6C 0w1/2
where I, Ik, and Id represent the measured, kinetic, and diusion-
limiting current densities, respectively, n is the transferred electron
number of oxygen reduction, F is the Faraday constant, A is the
geometric electrode area (cm2), k is the rate constant of the reaction,
C0 is the oxygen-saturated concentration in 0.1 M KOH, DO2 is the
oxygen diusion coecient, is the kinetic viscosity of solvent, and
is the rotation rate in unit of rad s1. Thus, the kinetic currents used to
t the tafel curves can be calculated on the basis of following equation:
I Id
Ik =
Id I
For analyzing the RRDE, the percentage of peroxide species and the
electron transfer number (n) were determined using the following
equations:
4NId
n=
NId + Ir
200Ir
HO2 (%) =
NId + Ir
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Nano Energy 31 (2017) 541550
Where Id, Ir, and N correspond respectively to the disk, ring currents,
and current collection eciency of RRDE.
2.4. Zn-air battery assembly
The Zn-air battery was assembled by zinc plate anode, 6.0 M KOH
electrolyte with 0.2 M ZnCl2 dissolved (to ensure the reversible Zn
anode reaction) and air catalysts coated on carbon ber paper as the
cathode. The porous air cathode was prepared by casting catalyst ink of
NiCo2S4/N-CNT or Pt/C (10 mg) or 3 mg RuO2 mixed with 7 mg
Vulcan carbon XC-72 in 1 mL mixture solution of deionized water/
ethanol (volume ratio: 4:1) and 140 l Naon on carbon ber paper
and dried at 100 C for 4 h. The average catalyst loading is about
1.0 mg cm2. The LAND-CT2001A testing devices were used to analyze
the battery discharge/charge performance and cycling reversibility with
oxygen continuously fed to the cathode during the measurements. The
voltage-current polarization data was performed on IviumStat work-
station in oxygen atmosphere. The electrolyte was pre-purged with
high-purity O2 for at least 20 min before each test.
2.5. Li-air battery assembly
The non-aqueous coin-type Li-air cell was fabricated in an argon-
lled glove box (Mikrouna Super 1220/750/900) using a lithium metal
anode, a glass ber separator, and a catalyst-coating oxygen cathode.
1 M LiTFSI (lithium bis-(triuoromethanesulfonyl)-imide) dissolved in
TEGDME (tetraethylene glycol dimethyl ether) is employed as the
electrolyte. The air cathodes were prepared by casting a homogenous
ink of 90 wt% catalyst materials (NiCo2S4/N-CNT) and 10 wt% poly-
vinylidene uoride (PVdF) onto the carbon paper with a catalyst
loading of about 1 mg cm2 and then dried at 110 C in vacuum
overnight. The specic capacity and current density were calculated
based on the amount of the catalyst. The tests were conducted in 1 atm
high-purity oxygen atmosphere.
3. Results and discussion
As schematically illustrated in Scheme 1, the controllable synthesis
of NiCo2S4 nanoparticles supported on N-CNT nanocomposite pro-
ceeds through facile nucleation-crystallization two step strategy after
the CNT pre-oxidation (see experimental section for details). In the
rst nucleation step, the mildly oxidized CNT was reacted with certain
amount of Co(OAc)2, Ni(OAc)2 in an ethanol/water NH4OH mixed
solvent at 80 C to form hydrolyzed metal precursors on the functional
was adopted to simultaneously incorporate N into carbon framework
and crystallize metal suldes on the surface of N-CNT in thiourea
solution, yielding the designed spinel NiCo2S4/N-CNT hybrid. The
interaction between the introduced electronegative oxygen-containing
functional groups, N dopants and the metal cations (i.e. Ni2+, Co2+)
contributes to the homogeneous nucleation and nal anchor of formed
NiCo2S4 nanocrystals [34]. In the powder X-ray diraction (XRD)
proles of the synthesized samples (Fig. 1a), the peaks of NiCo2S4 can
be readily assigned to the spinel NiCo2S4 (Joint Committee on Powder
Diraction Standards, JCPDS card No. 200782, space group: Fd-3 m)
with divalent ions occupying tetrahedral sites and trivalent ions
occupying octahedral sites (Fig. 1b). Compared with pure NiCo2S4,
the broadened XRD diraction peaks of the hybrid indicate the
ultrane size of supported NiCo2S4 nanocrystallines, especially in the
case of NiCo2S4/N-CNT. The presence of CNT in the hybrid is
conrmed by the signicantly increased peak intensity at 2 27,
which originates from the (002) graphitic diraction of carbon
structure (Fig. S1, Supporting Information). This is also veried by
the analysis from Raman spectra. Two characteristic peaks of the D
(1350 cm1) and G band (1590 cm1) were indentied in NiCo2S4/N-
CNT hybrid. The intensity ratio of D/G (ID/IG) are ca. 0.40, 0.95, and
X. Han et al. Nano Energy 31 (2017) 541550

Fig. 1. (a) XRD proles of synthesized NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT samples. (b) Crystal structure of spinel NiCo2S4. (c-e) SEM and TEM images of NiCo2S4/N-CNT.
Inset in (e) displays the FFT patterns of a single nanocrystalline. (f) Elemental mapping of NiCo2S4/N-CNT.

0.87 for pristine CNT, oxidized CNT, and NiCo2S4/N-CNT (Fig. S2),
suggesting that the abundant vacancies are introduced in graphitic
lattice after the oxidization treatment while the N dopants are
embedded in the defect sites of the carbon net in NiCo2S4/N-CNT
hybrid. Otherwise, the low integrated area ratios of sp3 to sp2 (Asp3/
Asp2 =0.19, 0.15, and 0.18, respectively) are indicator of sp2 hybridiza-
tion type carbon atoms in the synthesized samples.
Fig. 1c presents the eld-emission scanning electron microscopy
(SEM) image of NiCo2S4/N-CNT nanocomposite, which inherits the
typical morphology of CNT with average diameter of 100 nm (Fig. S1).
Transmission electron microscopy (TEM) image (Fig. 1d) clearly
reveals that uniform NiCo2S4 nanocrystals are homogenously dispersed
on N-doped CNT nanoarchitecture matrix without obvious detachment
and aggregation. It is found that the crystal size can be signicantly
aected by dierent amounts of NH3H2O in the reaction system. The
mass-average nanocrystalline size in NiCo2S4/N-CNT is about 15.4 nm
when adding 0.5 mL and increased to 28.7and 46.2 nm when using
0.25 and 0 mL NH3H2O, respectively (Fig. 2a-c). Unless stated, the
NiCo2S4/N-CNT in the following section refers to the hybrid with
nanocrystal size of 15.4 nm. The reason is that N-groups can serve as
favorable anchor sites for sulde nanocrystals owing to the coordina-
tion eect with Ni2+, Co2+ cations, leading to a smaller NiCo2S4
crystalline size with higher degree of nucleation on N-CNT than on
N-free CNT [33,35]. The size dierence is also consistent with the
broadened extent of XRD peaks. What's more, the particle size
dramatically grows to be several hundred nanometers and aggregates
severely without the support of CNT (Fig. 2d). The clear lattice fringes
with neighboring interlayer distances of 0.29 and 0.34 nm in high-
resolution TEM (Fig. 1e) are consistent with the spacing of (311) and
(220) planes in spinel NiCo2S4. The well-dened points in correspond-
ing fast Fourier transform (FFT) diraction pattern (inset in Fig. 1e)
coincides with the Bragg diraction of cubic crystal structural symme-
try of NiCo2S4. The energy dispersive spectroscopy (EDS) elemental
mapping demonstrates the homogeneous dispersion of various ele-
ments including C, N, Ni, Co, and S in the NiCo2S4/N-CNT hybrid
(Fig. 1f), conrming the uniform distribution of NiCo2S4 deposited on
the nitrogen-doped carbon matrix. EDS results further revealed that
the atomic ratio of Ni: Co: S is approximately 1:2:4, again conrming

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Fig. 2. TEM images of NiCo2S4/N-CNT with NH3H2O adding amount of 0.5 (a), 0.25 (b) and 0 mL (c). (d) SEM image of bare NiCo2S4. Inset in (a-c) shows the particle size
distribution.

Fig. 3. (a) Ni 2p, (b) Co 2p XPS spectra of synthesized NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT. (c) S 2p, and (d) N 1 s of NiCo2S4/N-CNT.

the formation of spinel NiCo2S4 phase (Fig. S3). The weight amount of thermogravimetric analysis (TGA) in air (Fig. S4), respectively. The
suldes are measured to be about 55.4 wt% and 53.8 wt% in the Brunauer-Emmett-Teller (BET) specic surface area of NiCo2S4/N-
synthesized NiCo2S4/CNT and NiCo2S4/N-CNT nanocomposites by CNT hybrid is determined to be 73.14 m2 g1 by N2 adsorption/

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Fig. 4. (a) Cyclic Voltammograms of NiCo2S4, NiCo2S4/CNT, and NiCo2S4/N-CNT in O2-saturated 0.1 M KOH at 25 mV s1. (b) Linear voltammograms of NiCo2S4, NiCo2S4/CNT,
NiCo2S4/N-CNT, and Pt/C measured using RRDEs at 5 mV s1. (c) Corresponding percentage of peroxide (solid line) and electron transfer number (dotted line) at various potentials. (d)
K-L plots at 0.5 V. (e) Tafel plots determined from the corresponding voltammetry data. (f) Dependence of current densities as a function of scan rates at 0.8 V.

desorption measurements (Fig. S5). The type-IV isotherm with H3-

Table 1 type hysteresis loop indicates that mesopores and macropores both
Summary of electrocatalytic performance of prepared catalysts in this worka. exist in the hybrid (also see inset in Fig. S5), which can promote the
Catalyst Eonset (V) Ehalf (V) Is (mA Ik (mA Im (mA n E
catalytic reaction by providing more exposed active sites and enough
cm2) cm2) mg1) (Ej=10- tri-phase contact area to facilitate oxygen transportation and electro-
Ehalf) lyte permeation.
X-ray photoelectron spectroscopy (XPS) was performed to gain
NiCo2S4 0.77 0.64 2.16 0.03 8.71 3.37 1.04
insight into the elemental compositions and chemical oxidation states
NiCo2S4/ 0.84 0.69 2.66 0.17 10.71 3.65 0.94
CNT of NiCo2S4 compound and the interaction with carbon nanotube
NiCo2S4/ 0.93 0.80 3.00 3.20 12.10 3.82 0.80 (Fig. 3). The XPS survey spectra of NiCo2S4, NiCo2S4/CNT, and
N-CNT NiCo2S4/N-CNT reveal the presence of Ni, Co, and S with desired
Pt/C 0.95 0.83 2.95 6.90 11.90 3.90
stoichiometric ratio, in consistent with the EDS analysis (Fig. S6). In
a the Ni 2p XPS spectra (Fig. 3a), two spin-orbit doublets and two
Eonset is the onset potential, Ehalf is the half-wave potential, Is is the specic current,
Ik is the kinetic current density at 0.8 V, Im is the mass current density, E is the shakeup satellites (denoted as Sat.) are best tted by using a Gaussian
variance metric between OER current density of 10 mA cm2 and Ehalf. Is, Im, and n tting method, corresponding to characteristic peaks of Ni2+ and Ni3+.
correspond to the values at 0.5 V. The rotation rate is 400 rpm. The Co 2p spectra (Fig. 3b) can be deconvoluted into six species,

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X. Han et al. Nano Energy 31 (2017) 541550

Fig. 5. (a) Chronoamperometric curves of NiCo2S4/N-CNT hybrid and Pt/C at 0.8 V vs RHE in O2-saturated 0.1 M KOH. (b) Cyclic Voltammograms of NiCo2S4/N-CNT with prolonged
cycles at 400 rpm at a scanning rate of 200 mV s1. (c) Electrocatalytic OER activity of the synthesized catalysts and the counterpart Pt/C and RuO2. (d) Comparison of OER and ORR
bifunctional activities of samples in this work with representative electrocatalysts in references. The dotted lines show the E at constant values.

Fig. 6. (a) A schematic conguration of Zn-air batteries. (b) Polarization curves and corresponding power densities of NiCo2S4/N-CNT and Pt/C-based cathodes.

including pairs of tting peaks for Co2+ and Co3+, and their shakeup
satellites, respectively. These results suggest that the coexistence of
mixed valence of Ni2+, Ni3+, Co2+, and Co3+ in prepared products, in
accordance with the reports for NiCo2S4 in literatures [36,37].
Particularly, the Ni and Co 2p peaks of the composite shifted positively
to higher binding energy as compared with that of neat NiCo2S4 as a
result of the migration of metal electron cloud induced by the strong
electronegativity of doped N and O species on N-CNT surface,
demonstrating strong covalent coupling between the spinel and
nanocarbon substrate [17,30]. The intimate hybridization interaction
renders the nanocomposite highly conductive and electrochemical
active, favoring the enhancement of electrocatalytic capability
[17,19]. Fig. 3c shows the core-level spectrum of the S 2p region in
NiCo2S4/N-CNT hybrid, which can be deconvoluted into four peaks
along with one shake-up satellite peak. The peaks centered at 163.1
and 161.8 eV are assigned to S 2p1/2 and S 2p3/2, respectively. Another
tting peak at 163.8 eV is a typical signal of a metal-sulfur bond, while
the component peak located at 162.6 eV is an indicator of the presence
of sulfur ions (S2-) in a low coordination state on the surface [36,38].
The successful incorporation of N into CNT framework in NiCo2S4/N-
CNT was proved by N signal (Fig. S6). The detected substantial N
content is about 4.68 at% and four types of N conguration are

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X. Han et al.
Fig. 7. (a) Discharge/recharge proles of rechargeable Zn-air cells based on NiCo2S4/N-CNT, Pt/C and RuO2 cathode with duration of 400 s per cycle at 10 mA cm2. Inset shows a LED
light lit by assembled Zn-air battery. (b) 1st and 150th discharge/charge curves of NiCo2S4/N-CNT electrode. (c) Voltage-current polarization data of the NiCo2S4/N-CNT, Pt/C and
RuO2 catalyst.
identied in the high-resolution N 1 s spectrum (Fig. 3d), correspond-
ing to pyridinic N (398.6 eV, 52.72%), pyrrolic N (399.6 eV, 26.27%),
graphitic N (400.8 eV, 9.48%), and oxidized N (402.4 eV, 11.52%),
respectively. The positive peak shift is also pronounced for N species
due to the strong interaction of C-N-transition metal [17]. These XPS
results demonstrate the successful formation of NiCo2S4 crystallo-
graphic phase with mixed metal valence and the strong covalent
coupling between sulde spinels and the underlying N-doped carbon
nanostructure within NiCo2S4/N-CNT hybrid.
Half-cell testing was employed to assess the ORR and OER
activities of synthesized compounds in alkaline electrolyte via a tri-
electrode conguration. Fig. 4a shows the typical cyclic voltammo-
grams (CVs) in 0.1 M KOH saturated with high-purity Ar (dotted line)
or O2 (solid line). For NiCo2S4/N-CNT, the cathodic peak potential
located at 0.78 V, more positive than that of NiCo2S4/CNT (0.70 V) and
bare NiCo2S4 (0.68 V). Thus, the NiCo2S4/N-CNT attains the better
ORR catalytic activity, which is further conrmed by the results
determined from rotating ring-disk electrode (RRDE). Fig. 4b displays
the linear sweeping voltammograms at a potential scanning rate of
5 mV s1 under rotating speed of 400 round per minute (rpm). The
disk currents reect ORR electrocatalysis (currents are negligible in Ar-
saturated electrolyte, Fig. S7) while the ring currents are relevant to the
oxidation of generated intermediate peroxide species. Compared to
bulk NiCo2S4 (optimal additive conductive carbon amount is found to
be 70 wt%, Fig. S8), the nanocomposites exhibit lower overpotential,
higher half-wave potential and larger reduction current. As for the two
hybrids, the NiCo2S4/N-CNT is catalytically more active than NiCo2S4/
CNT, enabling an enhancement of onset and half-wave potential by 90
and 110 mV, respectively, and a 12.8% enlarged limiting current
density (Table 1). The activity gradually decreases as the size of
supported NiCo2S4 nanocrystals increased mainly due to reduced
active surface-atom exposure ratio (Fig. S9) [29]. Remarkably, the
548
Nano Energy 31 (2017) 541550
ORR performance derived by NiCo2S4/N-CNT hybrid is closer to that
of commercial Pt/C in terms of onset/half-wave potential and reduc-
tion current. The electrochemical parameters of NiCo2S4/N-CNT is
comparable to the reported activities based on precious metal-free
catalysts [15,16,2226,29,30].
The ORR catalytic activity was further assessed by the calculated
electron transfer number (n) and generated peroxide percentage from
the RRDE plots. As illustrated in Fig. 4c, the monitored n is above ~3.8
and peroxide percentage is below ~10% for NiCo2S4/N-CNT nanocom-
posite over the potential range of 0.230.83 V, much better than the
other two comparatives. Similar to Pt/C, the NiCo2S4/N-CNT hybrid
catalyzed the ORR via an apparent 4e pathway, consistent with the
determination from the Koutecky-Levich curves constructed at dier-
ent rotation rates (Fig. 4d). Higher n and lower peroxide yield again
suggest the enhancement of ORR kinetic properties due to the
combination of NiCo2S4 nanocrystals and conductive CNT substrate.
Superior ORR performance of NiCo2S4/N-CNT is also gleaned from the
much smaller Tafel slopes at lower overpotentials and larger kinetic
currents (Fig. 4e) than those measured over NiCo2S4 and NiCo2S4/CNT
counterparts. Since the electrochemical active surface areas are calcu-
lated to be 25.5, 62.5, 76.0 m2 g1 for NiCo2S4, NiCo2S4/CNT and
NiCo2S4/N-CNT based on the linear correlation of current density
versus the scan rate (Fig. 4f and S10) in double-layer capacitance
dominated potential region, the order of catalytic activities can be thus
easily understood. Moreover, electrochemical impedance spectroscopy
measurements reveal that a much lower charge transfer resistance is
demonstrated on NiCo2S4/N-CNT than those on pure NiCo2S4 and
NiCo2S4/CNT (Fig. S11), further indicating faster ORR kinetic proper-
ties on N-doped nanocomposite.
Apart from high catalytic activity, the hybrid NiCo2S4/N-CNT
aords satisfactory catalytic durability. After a continuous chronoam-
perometric period of 25 h, the ORR current on NiCo2S4/N-CNT can
X. Han et al. Nano Energy 31 (2017) 541550

Table 2
Comparison of key performance parameters for rechargeable Zn-air batteries extracted from literature.

Air catalyst Mass loading Zn electrode Voltage polarization Cycling condition Stability Reference
(mg cm2) electrolyte

NiCo2S4/N-CNT 1.0 Zn foil 0.63 V @ j=10 mA cm2; 10 mA cm2, 400 s per 150 cycles; polarization This work
6 M KOH + 0.2 0.80 V @ j=20 mA cm2 cycle period increased 0.06 V at the
ZnCl2 end

MnO2/CNT composite 0.5 Zn plate ~1.1 V @ j=10 mA cm2 ~8 mA cm2, 600 s per 50 cycles; polarization Electrochim. Acta, 69
6 M KOH cycle period increased ~0.4 V at the (2012) 295300.
end

Co3O4/MnO2 2.0 Zn plate ~0.80 V @ j=10 mA cm2 15 mA cm2, 420 s per 60 cycles; polarization Nanoscale, 5 (2013)
6 M KOH cycle period increased ~0.3 V at the 46574661.
end

LaNiO3/N-CNT 0.72 Zn plate ~1.2 V @ j=20 mA cm2 ~17.6 mA cm2, 600 s 75 cycles; polarization Nano Lett., 12 (2012)
6 M KOH per cycle period increased 0.10.2 V at 19461952.
the end

CoO/N-CNT + NiFe 1.0/5.0 Zn foil ~0.69 V @ j=10 mA cm2 10 mA cm2, 200 s per 60 cycles; negligible Nat. Commun., 4 (2013)
LDH 6 M KOH + cycle period voltage change at the 1805.
0.2 M Zn(AC)2 end

a-MnO2-LaNiO3/CNTs Zn foil 0.746 V @ j=20 mA cm2 20 mA cm2, 600 s per 75 cycles; polarization RSC Adv., 4 (2014)
6 M KOH + cycle period increased ~0.11 V at the 4608446092.
0.4 M ZnO end

Nanostructured Zn plate 0.70 V @ j=20 mA cm2 ~20 mA cm2, 300 s per 50 cycles; polarization Nanoscale, 6 (2014)
NiCo2O4 6 M KOH cycle period increased ~0.2 V at the 31733181.
end

CoMn2O4/N-rGO Zn plate ~0.7 V @ j=10 mA cm2 20 mA cm2, 300 s per 100 cycles; polarization Electrochem. Commun.,
6 M KOH cycle period increased ~0.2 V at the 41 (2014) 5963.
end

Co3O4 nanodisks 1.50 Zn plate ~0.9 V @ j= 10 mA cm2; ~17.6 mA cm2, 600 s 60 cycles; negligible Electrochem. Commun.,
6 M KOH ~1.1 V @ j=20 mA cm2 per cycle period voltage change at the 43 (2014) 109112.
end

La2NiO4 Zn powder ~0.8 V @ j=20 mA cm2 ~25 mA cm2, 150 s per 20 cycles; polarization ACS Appl. Mater.
6 M KOH cycle period increased 0.4 V at the Interfaces, 5 (2013)
end 99029907.

LaNiO3/rGO 10.1 mg Zn plate ~0.8 V @ j=10 mA cm2; ~25 mA cm2, 3600 s per 97 cycles; negligible RSC Adv., 6 (2016)
6 M KOH ~0.98 V @ j=25 mA cm2 cycle period voltage change at the 8638686394.
end

still maintain > 88.5%, signicantly higher than the case of benchmark
Pt/C (72.8%) (Fig. 5a). The prolonged CVs further conrmed the long-
term catalytic cyclability. After extended 12,000 cycles at 400 rpm, the
shape of the CV curves remains almost unchanged, in a shape contrary
to that of Pt/C (Fig. 5b and S12). The morphology of the NiCo2S4/N-
CNT catalyst is essentially preserved after repeated CV cycles, whereas
the Pt nanoparticles in Pt/C exfoliate and agglomerate severely (Fig.
S13), suggesting remarkable electrochemical robustness of the nano-
composite contributed by rm attachment between the durable CNT
framework and the NiCo2S4 nanocrystallines. Furthermore, in the
context of developing ORR-OER bifunctional catalysts, the NiCo2S4/
N-CNT hybrid exhibits remarkable activity towards catalyzing OER,
rendering an apparently larger OER currents and lower evolution
potential as compared with other catalysts and even the RuO2 (Fig. 5c).
The variance metrics (E= Ej=10-Ehalf), where Ej=10 is the operating
potential to deliver a OER current density of 10 mA cm2 and is related
to a 10% ecient solar fuel synthesis, are traditionally employed to
evaluate the overall oxygen electrode activity and reversibility. The
smaller the E value is, the closer the electrode is to an ideal
reversible oxygen cathode. Accordingly, the NiCo2S4/N-CNT displays
a E value of 0.80 V, lower than that of NiCo2S4 (1.04 V) and
NiCo2S4/CNT (0.94 V) and also comparable to the most active electro-
catalysts reported so far including precious metal (e.g., Pt/C [39], E
=1.16 V; Ir/C [39], E =0.92 V), transition-metal oxides (e.g.,
CaMnO3 microsphere [40], E > 1.14 V; NixOy/N-doped C [41],
E =0.93 V; Co3O4/N-doped C [42], E =1.02 V), and non-metal
materials (e.g., S-doped graphene/CNT [43], E =1.00 V; P-doped g-
C3N4 [44], E =0.94 V) (Fig. 5d). The detailed comparison of key
performance parameters is presented in Table S1. The superb catalytic
activity and reversibility of the hybrid possibly contribute to several
factors: (1) the small size and high dispersed nanocrystallines with
considerable intrinsic catalytic activity facilitate the activation and
dissociation of molecular O2 [45,46]; (2) the enhanced overall electrical
conductivity beneted from the rm contact in the in-situ fabricated
spinel and CNT hybrid; (3) the coupling synergetic eect between the
suldes and the CNT substrate functionalized with nitrogen groups
alters the electron cloud structure and optimizes the adsorption/
desorption behaviors of oxygen-related species, which has been
demonstrated to signicantly favors the oxygen-involved electrocata-
lysis processes [30,33].
The superior bifunctional ORR/OER capability and durability of
NiCo2S4/N-CNT motivated us to investigate its feasibility in realistic
primary and rechargeable Zn-air battery devices. The battery conguration
consisted of a Zn plate as the anode and the prepared NiCo2S4/N-CNT
supported on carbon paper as the air cathode (Fig. 6a and S14). The battery
had an high open-circuit voltage of 1.49 V (Fig. S15) and exhibited a
current density of ~107 mA cm2 at voltage of 1.0 V, which is close to that
of Pt/C (Fig. 6b). The peak power density reached 147 mW cm2 at 0.77 V.

549
X. Han et al.
By normalized to the mass of consumed Zn metal, the specic discharge
capacity of NiCo2S4/N-CNT is 431.1 mAh g1, corresponding to a high
energy density of 554.6 Wh kg1 (Fig. S16). Furthermore, the NiCo2S4/N-
CNT composite enables assembled rechargeable Zn-air battery with lower
discharge/charge overpotential (0.63 V) and exceptional rechargeability
(150 cycles) (Fig. 7a and S17) in sharp comparison with those cells
catalyzed by Pt/C (0.90 V, 59 cycles) and RuO2 ( 0.79V, 44 cycles) at
10 mA cm2. A LED light was continuously lit for more than 12 h by two
series NiCo2S4/N-CNT-based Zn-air batteries (inset in Fig. 7a), indicating
the high capacity density. Otherwise, as shown in Fig. 7b, for NiCo2S4/N-
CNT, the initial overpotential is 0.63 V, corresponding to a round-trip
eciency (discharge end voltage divided by charge end voltage) of 67.2%.
After 150 cycles, the polarization increases to 0.69 V, leading to a voltaic
eciency reduced by only 2.1% (65.1%). In sharp contrast, the voltage gap
of Pt/C and RuO2 shows larger increments after dozens of cycles, implying
their limited rechargeability (Fig. S18). Actually, the rechargeable battery
catalyzed by the composite delivers similar discharge-recharge behaviors to
the present highest-performing ORR electrode of Pt/C and OER electrode
of RuO2 (Fig. 7c), further conrming the excellent bifunctional capability, in
accordance with the results from half-reaction tests. Moreover, when
NiCo2S4/N-CNT-based cell repeatedly discharged/recharged even at
20 mA cm2 for 8 h cycling period (Fig. S19), almost no signicant
degradation can be observed on both the discharge and charge segments.
Otherwise, the spinel composite-based non-aqueous lithium-air cells could
deliver high capacity and considerable cyclability to dozens of cycles (Fig.
S20). These results illustrate the eective applicability of NiCo2S4/N-CNT
as air cathode catalysts for metal-air batteries, especially in the rechargeable
form. The key battery performance parameters presented here are among
the best rechargeable Zn-air system reported in literatures (Table 2). Other
eorts are still underway to address other problems such as the corrosion of
Zn anode and electrolyte carbonation before practical Zn-air batteries are
made.
4. Conclusions
In summary, we have demonstrated controllable synthesis of a new
nanocomposite material-NiCo2S4 nanocrystallines strongly coupled
with nitrogen-doped carbon nanotubes and its employment as electro-
catalyst in both ORR/OER half reactions and practical Zn-air batteries.
The in-situ generated NiCo2S4/N-CNT hybrid manifests excellent
bifunctional activity and long-term stability and reversibility, which
are comparable or even superior to the well-known noble metal
catalysts. The outstanding performance could be attributed to the
homogenous and nanoscaled NiCo2S4 spinel crystallines with remark-
able intrinsic activity and coupling synergism between two components
as well as the N doping CNT altering the surface electron conguration
for oxygen adsorption/activation and providing network for ecient
electron transfer. This study should enlighten the rational design and
controllable synthesis of functional chalcogenides/carbon composites
and highlight their promising application in rechargeable metal-air
batteries and regenerative fuel cells.
Acknowledgements
We thank the nancial support from the National Natural Science
Foundation of China (51602216 and 51472178), National Key
Research and Development Program (2016YFB0700205), and Tianjin
Natural Science Foundation (16JCYBJC17600).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2016.12.008.
550
Nano Energy 31 (2017) 541550
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