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Solvothermal synthesis and electrochemical properties of 3D flower-like iron
phthalocyanine hierarchical nanostructure
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Jingbo Mu,b Changlu Shao,*a Zengcai Guo,b Mingyi Zhang,a Zhenyi Zhang,a Peng Zhang,a Bin Chen*b
and Yichun Liua
Received 16th June 2011, Accepted 19th September 2011
DOI: 10.1039/c1nr10627a

In the present work, a highly uniform three-dimensional flower-like 2,9,16,23-tetra-

nitrophthalocyanine iron (TNFePc) hierarchical nanostructure has been successfully obtained by
a facile ethylene glycol solvothermal synthetic route. The as-obtained product was characterized by
mass spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron
microscopy (TEM), IR spectroscopy, UV-vis spectroscopy, and Brunauer–Emmett–Teller analysis.
The results showed that the flower-like hierarchical nanostructure was made up of numerous two-
dimensional nanoplates with a thickness of about 50 nm. Electrochemical measurements revealed that
the TNFePc hierarchical nanostructure exhibited excellent capacitance behavior, which could be
ascribed to the ultrahigh surface area and large pore volume. Finally, a possible mechanism for the
formation of three-dimensional flower-like TNFePc was suggested.

1. Introduction
Phthalocyanines (Pcs) and their derivatives are excellent organic
semiconductors and they have potential applications in field
effect transistors,1,2 xerography,3 photoswitches,4 laser recording
materials,5 photovoltaic cells,6,7 and electrochemical sensors.8,9
Among them, the electrochemistry usages of metal-
lophthalocyanines (MPcs) have been the focus of numerous
investigations from their superior electron transfer capacities,10
which are due to the interaction between the phthalocyanine ring
and the metal center. Recently, some results have demonstrated
that MPcs have potential applications in electrochemical
capacitors.11,12 Electrochemical capacitors, known as promising
energy storage devices, have gained considerable attention over
the past decade because of their higher power density and longer
cycle life than secondary batteries and their higher energy density
compared to conventional electrical double-layer capacitors.
On the other hand, since electrochemical capacitors are inter-
facial devices, the structure and morphology are strongly related
to the electrochemical properties of the electrode material.13
Recently, low-dimensional nanostructured materials, such as
1D,14 or 2D15 nanoscale materials and the hierarchical assembly of
1D or 2D nanoscale building blocks into 3D superstructures,
which could provide high surface-to-volume ratio and short
diffusion path lengths for ions, have stimulated great interest for
the next generation of supercapacitors.16,17 Over recent years, the
fabrication of low dimensional MPc structures has proven to be
a very promising research area, such as organic vapor-phase
deposition to prepare a one dimensional structure of MPcs,18,19
electrochemical methods to prepare a two-dimensional self-
organization of MPcs based on Au templates,20 and the solvent
diffusion method to prepare MPcs nanofibers and micro-tubes.11
However, either the requirement for equipment is high or the
yields are low by these methods, which greatly minimizes the
applications of MPcs. Therefore, a simple method with high yields
is a new focus for the fabrication of these nanostructured MPcs.
Recently, the solvothermal method has been considered one of the
promising new routes due to its low growth temperature, potential
for scaled-up fabrication, and many adjustable parameters that
allow control of the final size and morphology of the MPcs.21,22
To the best of our knowledge, there are no reports on the
synthesis of TNFePc with a hierarchical nanostructure. Herein,
for the first time we report the fabrication of a 3D flower-like
TNFePc hierarchical nanostructure constructed from 2D nano-
plates via a simple template-free and reproducible solvothermal
method. The electrochemical properties are also investigated in
detail. Finally, a possible mechanism for the formation of the 3D
flower-like TNFePc hierarchical nanostructure is suggested.

a
Center for Advanced Optoelectronic Functional Materials Research, Key
Laboratory of UV Light-Emitting Materials and Technology of Ministry 2. Experimental section
of Education, Northeast Normal University, 5268 Renmin Street,
Changchun, 130024, People’s Republic of China. E-mail: clshao@nenu. 2.1 Materials
edu.cn; Tel: +8643185098803
b
Department of Chemistry, Northeast Normal University, 5268 Renmin 4-Nitrophthalonitrile (>98%) was purchased from Shijiazhuang
Street, Changchun, 130024, People’s Republic of China Alpha Chemical Co. Ltd. FeCl2$4H2O, ammonium molybdate,

5126 | Nanoscale, 2011, 3, 5126–5131 This journal is ª The Royal Society of Chemistry 2011

and ethylene glycol were all commercially available and used
without further purification.
2.2 Preparation of the flower-like iron phthalocyanine
hierarchical nanostructure
In a typical preparation, 4-nitrophthalonitrile (0.9 mmol),
FeCl2$4H2O (0.225 mmol), and ammonium molybdate (5.0 mg)
were added into 15 mL of ethylene glycol. The mixture was
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stirred vigorously for 30 min and then sealed in a Teflon lined
stainless-steel autoclave. The autoclave was maintained at 160
C
for 24 h, and then cooled to room temperature naturally. The
obtained precipitates were washed with distilled water and
ethanol, separately, then dried at 60
C for 8 h. The results of the
mass spectrum of the products were: MS (TOF): m/z required,
748.42 [M+]; found, 748.2 [M+].
2.3 Measurements
Mass spectroscopy was carried out on an LDI-1700 MALDI-
TOF MS spectrometer. Scanning electron microscopy (SEM,
XL-30 ESEM FEG, Micro FEI Philips) was used to characterize
the morphologies of the products. Transmission electron
microscopy (TEM) images were acquired using a JEOL JEM-
2100 (acceleration voltage of 200 kV). UV-vis spectroscopy was
recorded on a Cary 500 UV-vis-NIR spectrophotometer. Fourier
transform infrared (FT-IR) spectroscopy was performed on
Magna 560 FT-IR spectrometer with a resolution of 1 cm1.
Nitrogen porosimetry was performed on a Micromeritics ASAP
2010 instrument. The surface area was calculated using the
Brunauer–Emmett–Teller (BET) equation. The pore size distri-
bution was calculated using the Barrett–Joyner–Halenda (BJH)
model based on a nitrogen desorption isotherm.
2.4 Electrochemical measurements
The as-prepared TNFePc hierarchical nanostructure and a pol-
yvinylidene fluoride binder were mixed in a mass ratio of 95 : 5
and dispersed in ethanol. Then the resulting mixture was coated
onto the nickel foam current collector with a spatula, which was
followed by drying at 90
C for 12 h in a vacuum oven. The
electrical conductivity measurements were made using a standard
four-probe dc method at room temperature (Keithley 2400). For
the four-point probe test, a fixed current is injected into the
substrate through the two outer probes and a voltage was
measured between the two inner probes. Then the conductivity
value was determined by taking the reciprocal of the resistivity.
The data were represented by mean measurement values from at
least 5 trials for the sample. The mean conductivity was
measured to be 3.5  108 S cm1. The cyclic voltammetry
measurements were performed in a typical three-electrode setup.
The prepared electrode was used as the working electrode. A
platinum wire served as the counter electrode and a saturated
calomel electrode (SCE) was used as the reference electrode. The
cyclic voltammograms were recorded from 0–0.6 V at scan rates
of 5, 10, 20, 50, and 100 mV s1. The capacitance studies were
carried out in 40 ml ethanol with 0.4 ml trifluoroacetate acid
electrolyte. The charge–discharge tests were performed using
a potentiostat/galvanostat (Wuhan Land Electronic Co., Ltd.).
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3. Results and discussion
3.1 Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) images of the TNFePc flower-like
hierarchical nanostructure
The morphologies of the as-synthesized products under sol-
vothermal treatment at 160
C for 24 h were examined by SEM.
A large number of uniform flower-like hierarchical nano-
structures of TNFePc with an average diameter of 2 mm can be
clearly observed in Fig. 1a. No single nanoplate could be found,
showing that almost all of the nanoplates had been self-assem-
bled into a flower-like hierarchical nanostructure. It indicated
a high yield of these flower-like hierarchical nanostructures.
More detailed morphologies are displayed in Fig. 1b, which
shows that the flower-like hierarchical nanostructure was made
up of numerous two-dimensional nanoplates with a thickness of
about 50 nm. More importantly, many pores of different diam-
eters were found among the nanoplates in the hierarchical
nanostructure. Further structural characterization of the
TNFePc hierarchical nanostructure was achieved using trans-
mission electron microscopy (TEM). Fig. 1c and d show typical
TEM images of the 3D flower-like hierarchical nanostructure,
revealing that the entire flower was built from thin nanoplates,
which is in accordance with the SEM images. As supercapacitors
are electrochemical capacitors that store charge electrostatically
using the reversible adsorption of ions of the electrolyte onto
active materials that have high accessible specific surface
area,23,24 these nanoplates might improve the electrochemical
properties of TNFePc. The efficacious adsorption of electrolyte
ions was one of the key means to generate high specific capaci-
tance.25 These thin nanoplates could be exposed to the electrolyte
with possibly the highest surface area, and thus the structure
might result in a high specific capacitance. Moreover, all of the
flower-like hierarchical nanostructures maintained their integrity
after vigorous ultrasonic processing during the sample prepara-
tion for TEM measurements, showing the structural stability of
the product.
Fig. 1 FE-SEM images with different magnifications (a,b), TEM image
(c) and HRTEM image (d) of the TNFePc flower-like hierarchical
nanostructure.
Nanoscale, 2011, 3, 5126–5131 | 5127

3.2 UV-vis absorption spectrum
The UV-vis absorption spectrum of TNFePc is shown in Fig. 2,
in which there are two groups of absorption bands at 550–750 nm
and 300–450 nm, respectively. The bands from 550 to 750 nm
were characteristic Q-band absorptions of TNFePc. The Q-band
corresponds to the p–p* transition of the monomer from the
HOMO to the LUMO of the Pc2 ring.26 Furthermore, two
splitting absorption bands were observed around 627 and
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700 nm, which were likely due to the vibronic coupling in the
excited state.22 The band of 300–450 nm should belong to the
typical B-band absorption of TNFePc arising from the deeper
levels to LUMO transition.27
3.3 Fourier transform infrared (FT-IR) spectrum
The FT-IR spectrum of the TNFePc flower-like hierarchical
nanostructure is shown in Fig. 3, with absorption peaks at
1600 cm1, 1320 cm1, 1140 cm1, 908 cm1, 841 cm1, and
760 cm1, which were assigned to the phthalocyanine skeletal
vibration.28 Absorption peaks observed around 1510 cm1,
1090 cm1 and 731 cm1 were assigned to the aromatic phenyl
ring, C–N] stretch vibrations, C–H in-plane bending vibrations
and C–H out-of-plane bending vibrations, respectively.29
3.4 BET surface area and pore size distribution
The TNFePc flower-like hierarchical nanostructure possesses
a porous structure, as revealed by SEM and TEM images
(Fig. 1b and 1d). The porous nature of the product was further
confirmed by measurement of the pore size distribution, which
was obtained by the nitrogen adsorption–desorption isotherm
and Barrett–Joyner–Halenda (BJH) methods on a Mircromer-
itics ASAP 2010 accelerated surface area and porosimetry
system. The typical sorption isotherms and the corresponding
pore size distribution (inset) of the TNFePc 3D flower-like
hierarchical nanostructure are shown in Fig. 4. A typical type IV
isotherm with obvious hysteresis loop (capillary condensation
step) was obtained in the range of 0.41–1.0 P/P0 according to
IUPAC classification. The hysteresis loop proved the existence of
mesopores (2–50 nm) in the product. Accordingly, the pore size
Fig. 2 UV-vis spectrum of the TNFePc flower-like hierarchical nano-
structure. Inset shows the optimized structure of TNFePc.
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Fig. 3 FT-IR spectrum of the TNFePc flower-like hierarchical
nanostructure.
distribution curve displayed a single peak with a maximum at
7.6 nm. Quantitative calculation showed that the BET surface
area of the as-prepared TNFePc flower-like hierarchical nano-
structure was 56.5 m2 g1, and the pore volume was 0.14 cm3 g1.
Thus, the TNFePc flower-like hierarchical nanostructure
exhibited a high surface area and might have potential applica-
tion in improving the efficacious adsorption of electrolyte ions.
3.5 Electrochemical measurements
Electrochemical measurements were carried out using coin type
two-electrode supercapacitor cells fabricated in the same way as
in industry. A schematic and pictures of the as-assembled
supercapacitors are shown in Fig. 5a and b, respectively. The
supercapacitor typically consisted of two electrodes, two current
collectors, one porous separator paper and two capacitor shells.
The electrochemical behavior of the supercapacitors was inves-
tigated by cyclic voltammetry and galvanostatic charge–
discharge. Fig. 6a shows the cyclic voltammograms (CVs) of the
TNFePc-based supercapacitor devices with various scan rates in
the range of 0 to 0.6 V. All the curves were almost rectangular in
shape and exhibited mirror-image characteristics within the
Fig. 4 The nitrogen adsorption–desorption isotherm of the TNFePc
flower-like hierarchical nanostructure at 77 K. Inset shows the corre-
sponding BJH pore size distribution curve calculated from the desorption
branch.
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Fig. 5 (a) Schematic diagram of the as-assembled supercapacitor device.
(b) An optical image of an industry-grade coin-shaped supercapacitor
device assembled in this study. (1) Porous separator paper; (2) disk
electrodes pressed onto the Ni foam current collectors; (3) capacitor
shells and (4) coin-type two-electrode cells.
Fig. 6 (a) Cyclic voltammograms (CVs) of the TNFePc flower-like
hierarchical nanostructure electrodes at different scan rates; (b) galva-
nostatic charge–discharge performance of the as-assembled super-
capacitors at different current densities; (c) specific capacitances of the as-
assembled supercapacitors at different current densities; (d) variation of
specific discharge capacitance of the as-assembled supercapacitor with
cycle number at a current density of 300 mA g1 (the inset shows charge–
discharge curves for the first 10 cycles).
measured potential window, suggesting that the samples had
faster charge transfer and cation diffusion.30 Similarly, the
current under the curve was slowly increased by increasing the
scan rate, which indicated that the voltammetric currents were
directly proportional to the scan rate.31 This also reflected the
ideal capacitance behavior of the synthesized TNFePc hierar-
chical nanostructure. The voltammograms did not show redox
peaks of FePcII/III in our experiments. The main reason for this
divergence might be substitution (–NO2) on the peripheral
positions of the phthalocyanine (Pc) rings in our experiments,
which was different from the reported FePc species. According to
the reported literature, substitution had a significant effect on the
redox peaks of their FePcII/III, including the numbers and posi-
tions. In addition, the different electrode designs, synthetic
method, reference electrode, electrolyte, and so forth might also
influence the experiments.32–34 The constant-current charge–
discharge curves of the as-prepared TNFePc hierarchical
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nanostructure at different current densities are shown in Fig. 6b.
The charging/discharging cycling curves have a very symmetric
nature, indicating again that the composite has good electro-
chemical capacitive characteristics. This symmetric nature of the
charging/discharging cycling curves could be maintained even at
a low density of 0.3 A g1. The specific capacitance was evaluated
from the slope of the charge–discharge curves, as shown in
Fig. 6b, according to the equation C ¼ IDt/(mDV), where I is the
applied current and m is the mass of each electrode, and Dt/DV
was calculated from the discharge curve.35 Fig. 6c shows the
dependence of specific capacitance on the discharge current
density for the TNFePc hierarchical nanostructure capacitor.
The specific capacitance of the TNFePc flower-like hierarchical
nanostructure at a current density of 0.3 A g1 was calculated to
be 63 F g1. As the current density increased from 0.3 A g1 to
2 A g1, the specific capacitance of the obtained TNFePc hier-
archical nanostructure electrodes was still 45 F g1 with the
maintenance ratios more than 71% versus its specific capacitance
at 0.3 A g1. It seems not to correspond to its surface area
compared with that of the bulk material. The reason for this
behavior might be the flower-like hierarchical nanostructure of
the obtained TNFePc, which is made up of numerous two-
dimensional nanoplates. In these nanostructured electrode
nanoplates, the distance within the material over which the
electrolyte must transport ions is dramatically smaller compared
with conventional electrodes composed of chemically similar
bulk materials. In addition, when the electrode dimensions
become very small, the high transport rate exceed the rate at
which reactants can be consumed at the surface. Nanostructured
electrode materials show a higher surface area utilization ratio,
and better capabilities and rates than traditional bulk mate-
rials.36,37 All of these properties might lead to its high specific
capacitance. A long cycle life of the supercapacitor is important
for its practical application. In order to examine the cyclability of
the as-obtained TNFePc flower-like hierarchical nanostructure,
a constant current charge–discharge test at a current density of
300 mA g1 of the TNFePc hierarchical nanostructure is shown
in Fig. 6d. As can be seen, the specific capacitance retention of
the as-obtained sample was over 95% after 700 cycles, indicating
its excellent electrochemical stability and cycling performance.
Typical curves of the variation in the potential during the first ten
cycles with cycling time are shown in Fig. 6d (inset). It can be
seen that the discharge curves are approximately linear and
symmetric to their corresponding charge curves, indicating its
good capacitive and reversible behavior.
To reveal the formation process of the flower-like TNFePc
hierarchical nanostructure, we carried out time-dependent
experiments during which samples were collected at different
time intervals. Fig. 7 shows the SEM images of the products that
were obtained at 160
C at different growth stages. At the early
stage, as shown in Fig. 7a, the TNFePc particles with relatively
smooth surface were obtained by solvothermal reaction. When
the reaction time was prolonged from 1 to 3 h, the surfaces of the
particles became rougher, as shown in Fig. 7b. As observed in
Fig. 7c, when the reaction time reached 5 h, nanoplates appeared,
but the nanoplates were very small. Prolonging the reaction time
to 10 h (Fig. 7d) and 24 h (Fig. 7e), the flower-like TNFePc
hierarchical nanostructure was made up of numerous two-
dimensional nanoplates.
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Fig. 7 SEM images of the TNFePc nanostructures obtained at different
reaction times: (a) 1, (b) 3, (c) 5, (d) 10 and (e) 24 h.
Scheme 1 A schematic illustration of the morphological evolution
process of the TNFePc flower-like hierarchical nanostructure.
From our experimental results, we propose a formation
mechanism of the TNFePc flower-like hierarchical nano-
structure. The evolution process is illustrated in Scheme 1. At the
first stage, the precursor is formed, which spontaneously
precipitates to become the nuclei and quickly grows into the
primary particles. Because the surface energy of nanoparticles is
generally high, driven by minimization of surface energy, the new
nuclei in the solution prefer to aggregate to form microspheres
that become the core of the flower-like structure. In the following
stage, the particles orient, agglomerate, and recrystallize on the
surfaces of the spherical structures. In a further crystallization
process, as the growth rates of different crystal facets are
inequable, nanoflakes appear. Finally the continuous growth of
nanoflakes leads to the formation of the ordered TNFePc flower-
like hierarchical nanostructure with prolonged reaction time. It
could be observed that the surface of the petals in the flower-like
structure was very smooth, probably due to Ostwald ripening.38
4. Conclusions
In summary, a highly uniform 3D flower-like TNFePc hierar-
chical nanostructure was successfully synthesized by a facile
solvothermal method. The formation process of the nano-
structure was investigated in detail by time-dependent experi-
ments. Electrochemical studies of the hierarchical nanostructure
of TNFePc flowers shows it has an excellent capacitive perfor-
mance, which could be ascribed to its porous structures and high
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utilization ratio. Overall, the results presented in this work,
together with their interesting morphology, represent a concrete
design for the synthesis of a novel electrode material for capac-
itive energy storage.
Acknowledgements
The present work is supported financially by the National
Natural Science Foundation of China (Nos. 50572014,
50972027) and the Program for New Century Excellent Talents
in University (NCET-05-0322).
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