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A porous Co(OH)2 material derived from a MOF

template and its superior energy storage
Cite this: J. Mater. Chem. A, 2015, 3,
20658 performance for supercapacitors†
Zifeng Wang, Yushan Liu,* Chengwei Gao, Hao Jiang and Jianmin Zhang*

Received 24th June 2015
Accepted 2nd September 2015
DOI: 10.1039/c5ta04663g
www.rsc.org/MaterialsA
A novel method was explored to synthesize Co(OH)2 using a Co-based metal–organic framework (MOF) as
a template via a solid–solid conversion process in alkali solution. The MOF-derived Co(OH)2 was proved to
have a loose and mesoporous structure, which can provide good electrolyte penetration, shorten the ion
transfer distance, and increase the contact area of the MOF-derived Co(OH)2 and electrolyte. As a result,
the as-made Co(OH)2 exhibits superior electrochemical properties with high specific capacitance
(604.5 F g
1 at a current density of 0.1 A g
1), excellent rate capability, and good cycling performance.
The facile and eco-friendly nature of the strategy give it potential to be extended to other metal
hydroxides with excellent electrochemical performances.

precursors and sacricial templates to prepare metal oxides,16–18

Introduction
The boom of electronic devices and lack of fossil fuel resources
have pushed an urgent demand for better energy storage
systems. Therefore, supercapacitors have been drawing a large
amount of attention due to their high power density, splendid
rate performance and long cycle life. So far, a great diversity of
materials has been widely investigated as supercapacitor elec-
trodes, such as carbon materials,1 graphene-based compos-
ites,2,3 conducting polymers,4 metal oxides5 and metal
hydroxides.6 Among the materials mentioned above, metal
oxides and hydroxides (MnO2, Co3O4, Fe3O4, RuO2, Co(OH)2,
Ni(OH)2, etc.) are regarded as remarkable pseudocapacitor
materials due to their high theoretical specic capacitance.
Therefore, Co(OH)2 is a promising candidate as a super-
capacitor electrode material due to its high theoretical specic
capacitance (3458 F g
1), layered structure, low cost and envi-
ronmental friendly physicochemical features.7,8
Metal–organic frameworks (MOFs) are novel porous mate-
rials with structures that are controllable by changing the metal
ions, organic bridging ligands and reaction conditions.9 MOFs
with high specic surface area, adjustable pore size and
different topological structures are destined to be promising
materials for gas storage,10 sensors,11 catalysis,12 separation13,14
and energy storage.15 Recently, MOFs have also been used as
College of Chemistry and Molecular Engineering, Zhengzhou University, 100 Science
Road, Zhengzhou 450001, P. R. China. E-mail: zhjm@zzu.edu.cn; liuyushan@zzu.
edu.cn
† Electronic supplementary information (ESI) available: PXRD patterns of the
as-synthesized and simulated Co-BPDC-MOF, Nyquist plot of EIS data of the
MOF-derived Co(OH)2 electrode, and the equivalent Randles circuit. See DOI:
10.1039/c5ta04663g
metal suldes19 and porous carbon materials.20,21 The func-
tional materials derived from MOF templates/precursors have
been summarized by Xu in an early review.22 These obtained
materials have been proven to retain their porous structures,
maintain their open diffusion channels and have excellent
properties. For example, Sun et al. prepared magnetic nano-
porous carbon materials from MOFs, which were applied
successfully to glycomics analysis.21 Kong et al. reported a MOF-
derived N-doped and Co-nanoparticle-embedded carbon mate-
rial as a highly active non-precious metal catalyst for the oxygen
reduction reaction.23 Wu et al. fabricated 3D hollow cobalt sul-
des@porous carbon polyhedra/carbon nanotube hybrids for
high-performance lithium-ion batteries.19 Meng et al. synthe-
sized porous Co3O4 materials by solid-state thermolysis of a Co-
MOF crystal, which showed superior energy storage perfor-
mance for supercapacitors.16 Li et al. obtained mesoporous
nanostructured Co3O4 from a Co-MOF for use as an anode
material in lithium-ion batteries with good electrochemical
performance.17 As earlier studies have reported, cobalt
hydroxide is mainly prepared by a hydrothermal method,24 so
template method25 and electrodeposition method.26 Herein, we
developed a novel and facile method to fabricate porous
Co(OH)2 materials via a solid–solid conversion process using a
Co-MOF as a template and source of cobalt.
In this work, we chose the Co-BPDC-MOF as a template
because of its convenient synthesis process (simply mixing the
cobalt salt aqueous solution and organic ligand aqueous solu-
tion at room temperature) and utilized a facile transformation
in alkali solution to synthesize the porous Co(OH)2 materials
(Scheme 1). The transformation of the MOF in this process is
supposed to generate pores and open diffusion channels, and
was demonstrated by the transmission electron microscopy

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Scheme 1 Schematic illustration of the formation process for MOF-
derived Co(OH)2.
observation of a porous structure. This structure is favorable for
improving charge transfer and transportation efficiency. From
the electrochemical evaluation, the MOF-derived Co(OH)2
exhibits a superior performance with a specic capacitance of
604.5 F g
1 at 0.1 A g
1.
Results and discussion
The FTIR spectra of Co-BPDC-MOF, MOF-derived Co(OH)2, and
Co(OH)2 prepared via precipitation method were measured at
ambient temperature (Fig. 1a). It can be found the characteristic
peaks of the organic groups of the Co-BPDC-MOF appear in the
FTIR spectrum, while these ligand peaks reduce or disappear in
Fig. 1 (a) FT-IR spectra of Co-BPDC-MOF, MOF-derived Co(OH)2,
and Co(OH)2 prepared via precipitation method. (b) TG curve of the
MOF-derived Co(OH)2 in synthetic air. (c) PXRD pattern of the MOF-
derived Co(OH)2. (d) N2 adsorption–desorption isotherm of the MOF-
derived Co(OH)2. The insets are the pore-size distribution from BJH
calculation based on the absorption branch of the corresponding
isotherm (left) and the Horvath–Kawazoe differential pore volume plot
(right). (e) Full XPS spectrum of the MOF-derived Co(OH)2 and (f) the
elemental spectrum of Co 2p.
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the spectrum of the MOF-derived Co(OH)2, conrming the
transformation of Co-BPDC-MOF. Moreover, a narrow band in
the region of 3631 cm
1, which corresponds to the nO–H
stretching of the OH groups in the brucite-like structure,27 ari-
ses in the FTIR spectrum of the MOF-derived Co(OH)2 demon-
strating the formation of Co(OH)2. That is to say, carboxyl
organic ligands were replaced by hydroxide ions in the
construction of Co-BPDC-MOF in NaOH solution resulting in
Co(OH)2. This phenomenon was also reported by Miles et al. in
a previous article,28 which demonstrated the conformal trans-
formation of MOF-71 in LiOH electrolyte for use as an electrode
material for supercapacitors. In consideration of this conver-
sion process, cyclic utilization of the ligands can be realized by
merely adjusting the pH value of the mother liquor since the
organic ligands cannot be destroyed during the process. Only
the cobalt salt and NaOH are consumed in the whole synthesis
process, making this method more eco-friendly and promising
for application than pyrolysis. On the other hand, the wide
shallow peak located at 2250 cm
1 to 1250 cm
1 shows the
remnants of the organic ligand in the as-made Co(OH)2,
attributed to residues of the Co-MOF in the core of the bigger
particles.
The thermal behaviour and mass percentage of Co(OH)2 in
the MOF-derived Co(OH)2 sample were investigated by ther-
mogravimetric (TG) analysis in synthetic air from 30 to 1100  C
(Fig. 1b). The sample lost 15.58% of its original weight when the
temperature was increased from room temperature to about 450

C, attributed to the elimination of bound water molecules,
pyrolysis of Co(OH)2 to Co3O4, and decomposition of the
residual organic ligands. The slight weight loss (5.39%) above
920  C corresponds to the thermal decomposition of Co3O4 to
CoO.17,29 According to the law of conservation of mass, the
conversion rate of the Co-BPDC-MOF to MOF-derived Co(OH)2
reaches as high as 98%.
Powder X-ray diffraction (PXRD) analyses were carried out to
determine the formation of the Co-BPDC-MOF and MOF-
derived Co(OH)2. All reections in the as-prepared Co-BPDC-
MOF are in good agreement with the simulated pattern
(Fig. S1†). As shown in Fig. 1c, all the diffraction peaks of the
MOF-derived Co(OH)2 can be assigned to the standard JCPDS
card no. 00-001-0357, proving the formation of Co(OH)2 from
the Co-BPDC-MOF. Moreover, the broad diffraction peaks with
low intensity reveal the polycrystalline structure of the MOF-
derived Co(OH)2.
Nitrogen adsorption–desorption isotherms at 77 K were
measured to study the porous structure of the MOF-derived
Co(OH)2 material. The adsorption–desorption hysteresis loop in
Fig. 1d reveals the mesoporous characteristic of the Co(OH)2
material. In addition, the H3 type hysteresis loop indicates the
slit and wedge shape pores stacked between lamella, which can
be further proved by the TEM image (Fig. 2b). The BET specic
surface area was measured to be 92.4 m2 g
1. The adsorption
average pore width was measured to be 10.7 nm (le inset of
Fig. 1d). Furthermore, the MOF-derived Co(OH)2 material also
has a microporous structure (right inset of Fig. 1d). The MOF-
derived Co(OH)2 was further characterized using X-ray photo-
electron spectroscopy (XPS) measurements (as shown in Fig. 1e
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Fig. 2 (a)–(c) TEM images, (d) HRTEM image (inset is the selected area
electron diffraction pattern), (e) SEM image, and (f) EDS image of the
MOF-derived Co(OH)2.
and f). The binding energies of the Co 2p3/2 and Co 2p1/2 states
are located at 780.2 and 795.3 eV, respectively, and are assigned
to the spin-orbital states of Co(II), corresponding to the previous
literature.30,31
Fig. 2a–d show the transmission electron microscopy (TEM)
and high-resolution transmission electron microscopy
(HRTEM) images. From Fig. 2a and b, it can be observed that
thin Co(OH)2 sheets of various sizes heap up irregularly to
build a crushed-ice like structure. The loose structure and slit
pores provide open channels for the transportation of ions and
enlarge the contact area between the Co(OH)2 material and
electrolyte, which is supposed to endow materials with an
enhanced pseudocapacitive performance. As shown in Fig. 2c,
there are many pores penetrating the thin Co(OH)2 sheets.
These correspond to the microporous structure in the BET
test. Fig. 2d (HRTEM image) exhibits the lattice fringes with d-
spacings of 0.438 nm corresponding to the standard JCPDS
card no. 00-001-0357. The corresponding selected area elec-
tron diffraction (SAED) pattern (shown in the inset of Fig. 2d)
shows multiple diffraction circles, indicating the poly-
crystalline feature of the MOF-derived Co(OH)2, which is in
agreement with the PXRD result. The SEM image (Fig. 2e)
20660 | J. Mater. Chem. A, 2015, 3, 20658–20663
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displays the thin Co(OH)2 sheets building up in a loose
structure, which agrees with the TEM results. Fig. 2f shows the
EDS image of the MOF-derived Co(OH)2. The mass percentage
of C decreases to 8.91% compared with 45.70% in the
Co-BPDC-MOF (Fig. S2b†), suggesting the transformation of
Co-BPDC-MOF to Co(OH)2.
In order to study the electrochemical performance of the
MOF-derived Co(OH)2, cyclic voltammetry (CV) and galvano-
static charge–discharge (GCD) tests were carried out with a
three-electrode cell in 6 M KOH. Fig. 3a shows the CV curves of the
MOF-derived Co(OH)2 at various scan rates from 1 to 100 mV s
1
with a potential range of
0.2 to 0.4 V. The CV curves exhibit a
typical pseudocapacitive performance with clearly observable
redox peaks which correspond to the conversion between
different cobalt oxidation states according to previous
reports:6,32
Co(OH)2 + OH
4 CoOOH + H2O + e
(1)
CoOOH + OH
4 CoO2 + H2O + e
(2)
Fig. 3b shows the galvanostatic charge–discharge (GCD)
curves at various current densities of 0.1, 0.2, 0.5, 1, 2, 5 and 10
A g
1. The sloped potential plateaus which appear in Fig. 3b are
attributed to typically faradaic reactions, matching well to the
redox peaks in the CV curves in Fig. 3a. The nearly symmetric
potential–time curves imply a high charge–discharge coulombic
efficiency. The specic capacitance of the MOF-derived Co(OH)2
electrode at a current density of 0.1 A g
1 is as high as 604.5 F g
1.
The specic capacitances calculated from the charge–discharge
curves at 0.5 A g
1, 1 A g
1, and 5 A g
1 are 559.8 F g
1, 531.8 F g
1,
and 454.6 F g
1, respectively (shown in Fig. 3c).
Fig. 3 (a) CV curves of the MOF-derived Co(OH)2 in 6 M KOH elec-
trolyte at different scan rates. (b) Galvanostatic charge–discharge
(GCD) curves of the MOF-derived Co(OH)2 at different current
densities. (c) The corresponding specific capacitance at current
densities from 0.1 to 10 A g
1. (d) Cycle performance of the MOF-
derived Co(OH)2 at a current density of 2 A g
1.
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These values are much higher than those of Co(OH)2 prepared

via a precipitation method (127.3 F g
1 at 1 A g
1, as shown in
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Fig. S3†) and another control experiment (86.2 F g
1 at 1 A g
1, as

shown in Fig. S4†) which uses a mixture of Co(NO3)2$6H2O and
Na2(bpdc) in place of Co-BPDC-MOF as the precursor. Further-
more, the specic capacitance of the MOF-derived Co(OH)2 is
higher than those obtained via a facile precipitation method (429
F g
1 at 1 A g
1 reported by Wang et al.32) and a so template
method (351 F g
1 at 1 A g
1 reported by Tang et al.,33 325 F g
1 at
1.33 A g
1 reported by Yuan et al.,25 and 166.7 F g
1 at 1 A g
1
reported by Tan et al.24), as shown in ESI Table S1.† Moreover, the
MOF-derived Co(OH)2 exhibits excellent rate capability. The
specic capacitance remains at 430.9 F g
1 even at a relatively
high current density of 10 A g
1, which is about 71% of its
specic capacitance at 0.1 A g
1 current density.
The cycle life performance of the MOF-derived Co(OH)2
material was examined using GCD cycling at a current density of
2 A g
1. As shown in Fig. 3d, the specic capacitance drops by
15.5% in the rst 200 cycles then decreases slightly. Aer 2000
charge–discharge cycles, the specic capacitance retention is
70%. TEM images of the MOF-derived Co(OH)2 materials aer
2000 cycles show no apparent morphology and structure
changes (Fig. S5, ESI†). This means that the capacitance loss
Fig. 4 (a) CV curves of AC and the MOF-derived Co(OH)2 at a scan
might be ascribed to the peeling off of the active material from rate of 50 mV s
1. (b) CV curves at different scan rates, (c) GCD curves
the substrate or dissolution of the active material into the at different current densities, (d) the Ragone plot, and (e) cycle
electrolyte.34 To study the transport characteristics of the charge performance at a current density of 1 A g
1 of the MOF-derived
carrier within the MOF-derived Co(OH)2 electrode, electro- Co(OH)2//AC asymmetric supercapacitor.
chemical impedance spectroscopy (EIS) was used, and the
results are shown in Fig. S6.† The semi-circle in the high-
medium frequency region is related to the charge-transfer in the Fig. 4c presents the GCD curves of the MOF-derived
faradaic reactions, while the straight line refers to the diffusion Co(OH)2//AC asymmetric supercapacitor at various current
of ions in the Co(OH)2 electrode. The impedance data was densities. The charge and discharge curves show a nearly linear
simulated using ZSimpWin soware, and the deviation of each variation with potential and symmetrical distribution, implying
component is less than 5%. The result shows that the internal a good electrochemical reversibility. As shown in ESI Table S2,†
solution resistance is 0.73 U and the charge transfer resistance the specic capacitances of the MOF-derived Co(OH)2//AC asym-
is 0.64 U, indicating a fast electron transfer behaviour. metric supercapacitor are 49.8 F g
1, 41.6 F g
1, and 35.4 F g
1
In order to investigate the electrochemical performance of at 0.2 A g
1, 1 A g
1, and 5 A g
1, respectively. The Ragone plot
the MOF-derived Co(OH)2 for application, an asymmetric of the MOF-derived Co(OH)2//AC supercapacitor is illustrated in
supercapacitor was fabricated with activated carbon (AC) as the Fig. 4d. The energy density of the MOF-derived Co(OH)2//AC
cathode and the MOF-derived Co(OH)2 as the anode. The mass supercapacitor reaches 13.6 W h kg
1 at a power density of
ratio of the AC electrode to the MOF-derived Co(OH)2 electrode 140 W kg
1, which is higher than an AC//AC symmetrical
was decided based on charge balance theory.6 An experiment supercapacitor (<10 W h kg
1).32,35 The long cycling life was
showed that the specic capacitance of AC was 84 F g
1 at a measured using GCD at a current density of 1 A g
1 (as shown in
current density of 2 A g
1, so the optimal mass ratio of the MOF- Fig. 4e). Aer 2000 charge–discharge cycles, the specic
derived Co(OH)2 anode and the AC cathode is 0.27 : 1. capacitance retention is 80%.
Fig. 4a demonstrates the CV curves of the AC and MOF-
derived Co(OH)2 at a scan rate of 50 mV s
1. The AC electrode Conclusions
was measured within a potential window of
1.1 V to 0 V, while
the MOF-derived Co(OH)2 was measured within a potential In summary, a novel method was developed to prepare a
window of
0.2 V to 0.4 V. The CV curve of AC displays a nearly Co(OH)2 material. The MOF-derived Co(OH)2 exhibits superior
rectangular shape, suggesting typical EDLC behaviour, while energy storage performance for supercapacitors with a high
the MOF-derived Co(OH)2 exhibits typical pseudocapacitive specic capacitance (604.5 F g
1 at a current density of 0.1 A g
1),
performance with clearly observed redox peaks. As shown in excellent rate capability, and good cycle stability. The method
Fig. 4b, the shapes of the CV curves of the MOF-derived presented is convenient and accessible due to the simple
Co(OH)2//AC asymmetric supercapacitor at increasing scan synthesis of the Co-BPDC-MOF and facile conversion process.
rates from 5 mV s
1 to 100 mV s
1 do not change, indicating an Moreover, the cyclic utilization of ligands gives this method
excellent rate capability. more potential for application than pyrolysis. Thus the

This journal is © The Royal Society of Chemistry 2015 J. Mater. Chem. A, 2015, 3, 20658–20663 | 20661

Journal of Materials Chemistry A
conversion approach of a MOF template in alkali solution is a
promising method for the synthesis of metal hydroxide-based
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functional materials for various elds.
Experimental
All chemicals are reagent grade and used without further
purication.
Synthesis of Co-BPDC-MOF
The Co-BPDC-MOF was prepared by the method reported in a
previous paper.36 An aqueous solution (10 mL) of Co(NO3)2$6H2O
(0.2910 g, 1 mmol) was immediately added to an aqueous
solution (25 mL) of Na2(bpdc) (0.1431 g, 0.055 mmol). Then, the
obtained pink-white precipitate was washed with de-ionized
water several times.
Synthesis of the MOF-derived Co(OH)2
The obtained Co-BPDC-MOF precipitate was immersed in an
aqueous solution of 2 M NaOH and stirred at room temperature
for 1 h. Then, the products were washed with de-ionized water
to remove the redundant NaOH. Finally, the reddish brown
MOF-derived Co(OH)2 materials were obtained aer drying in a
vacuum oven at 65  C for 12 h.
Control experiments
1. Synthesis of Co(OH)2 via precipitation method. An
aqueous solution (100 mL) of NaOH (0.4 g, 0.01 mmol) was
immediately added to an aqueous solution (50 mL) of
Co(NO3)2$6H2O (1.455 g, 0.005 mmol) with stirring. Then the
precipitate was washed with de-ionized water and dried at 65  C
for 12 h.
2. Synthesis of Co(OH)2 via a mixture of Co(NO3)2$6H2O
and Na2(bpdc) in place of Co-BPDC-MOF as precursor.
Co(NO3)2$6H2O (0.2910 g, 1 mmol) and Na2(bpdc) (0.1431 g,
0.055 mmol) were each ground. Then the powders were mixed
immediately and added to an aqueous solution of 2 M NaOH
and stirred at room temperature for 1 h. The products were
washed with de-ionized water to remove the redundant NaOH.
Finally, the reddish brown Co(OH)2 materials were obtained
aer drying in a vacuum oven at 65  C for 12 h.
Characterization
Fourier transform infrared (FT-IR) spectroscopic measurements
were conducted using a Bruker IFS 66 V s
1 infrared spec-
trometer. The phase structures of the as-made products were
characterized using X-ray diffraction (XRD, Bruker D8 advance)
with Cu Ka radiation (l ¼ 1.5418  A). Thermogravimetric anal-
ysis (TGA) was carried out using a TA Instrument TGA-2050 at a
scan rate of 10  C min
1 with the temperature ranging from 30
to 1100  C in synthetic air. The specic porous structural
features of the MOF-derived Co(OH)2 were determined using
nitrogen adsorption–desorption on a Micromeritics ASAP 2420
at 77 K. The transmission electron microscopy (TEM) images
were recorded on a JEOL JEM-2010F electron microscope
20662 | J. Mater. Chem. A, 2015, 3, 20658–20663
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(Japan) operating at 200 kV. The powder sample was dispersed
in ethanol in an ultrasonic bath for 5 min, and deposited on a
copper grid covered with a perforated carbon lm. X-ray
photoelectron spectra (XPS) were recorded using a PHI-5702
multi-functional X-ray photoelectron spectrometer using an
X-ray source of Mg Ka. The surface morphology of the products
was investigated using eld emission scanning electron
microscopy equipped with EDS (FE-SEM, JEOL JSM-6700F,
Japan). For the FE-SEM test, the sample was suspended in
ethanol to form a homogeneous slurry. A drop of slurry was
dispersed on an Al sheet. Then the sample was coated with Pt to
increase its electroconductivity.
Electrochemical performance measurements
The electrochemical measurements were carried out using an
electrochemical working station (CHI660E, Shanghai, China)
with a three-electrode cell system at room temperature in 6 M
KOH electrolyte. The working electrode of the MOF-derived
Co(OH)2 was prepared according to the following procedure.
The MOF-derived Co(OH)2 (80 wt%), Super P carbon black
(10 wt%), and polytetra-uoroethylene (PTFE) (10 wt%) were
well mixed in ethanol until a homogeneous black slurry was
formed. The slurry was then laid on a piece of 1 cm2 Ni foam
which was used as a current collector. Then the Ni foam coated
with the MOF-derived Co(OH)2 was dried at 65  C for 12 h.
Finally, the Ni foam was pressed under 1.0 MPa. The mass load
of every electrode was about 2 mg. The cell was constructed with
Ni foam coated with the active material as the working elec-
trode, a saturated calomel electrode (SCE) as the reference
electrode, and Pt as the counter electrode. The AC electrode was
prepared as follows: 90% of HNO3 treated active carbon and
10% of PTFE were mixed in ethanol to form a homogeneous
slurry. The slurry was laid on Ni foam and then the Ni foam was
dried at 65  C for 12 h.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (No. 21373189).
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