Electrochimica Acta 85 (2012) 256–262

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

Porous nickel oxide microflowers synthesized by calcination of coordination

microflowers and their applications as glutathione electrochemical sensor
and supercapacitors
Huan Pang a,b,c,∗ , Yunfeng Shi a , Jimin Du a , Yahui Ma a , Guochang Li a , Jing Chen a , Jiangshan Zhang a ,
Honghe Zheng b,∗ , Baiqing Yuan a,∗
a
College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, 455000, Henan, PR China
b
School of Energy, Soochow University, Suzhou, 215006, Jiangsu, PR China
c
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, Jiangsu, PR China

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

Article history: Porous nickel oxide (NiO) microflowers have been successfully synthesized by calcining a coordina-
Received 26 June 2012 tion microflower without any hard template, seed or using soft template. More importantly, porous
Received in revised form 10 August 2012 NiO microflowers have been applied as effective electrochemical sensor of the tripeptide glutathione
Accepted 15 August 2012
(GSH) and electrochemical supercapacitors. The effectively electrochemical GSH sensor of porous NiO
Available online 23 August 2012
microflowers in 0.1 M HAc–NaAc (pH 5.0) solution was the first time evaluated. Moreover, the specific
capacitance of porous NiO microflower was up to 1678.4 F g−1 at current density of 0.625 A g−1 , and
Keywords:
maintained about 99.7% at 6.25 A g−1 after 1000 cycles.
Porous NiO microflowers
Glutathione electrochemical sensor © 2012 Elsevier Ltd. All rights reserved.
Electrochemical supercapacitors

1. Introduction nanomaterials would serve to maximize the performance of using

Thiols are very important to living organisms as they provide
regulatory intracellular and extracellular functions. The tripeptide
glutathione (Glu-Cys-Gly, GSH) is pivotal for reducing oxidative
stress in cells and maintaining redox homeostasis that is cru-
cial for cell growth [1–3]. Electrochemical methods have proven
as very useful for determination of thiols as they are sensitive,
selective, with very good linear range and rapid response times.
The oxidation of thiols on carbon based electrodes exhibits rela-
tively low heterogeneous electron transfer rates. In the past, the
electrode materials used for the determination of thiols consisted
of mercury, edge plane pyrolytic graphite, boron doped diamond
electrode, fullerenes and carbon nanotubes [4–9]. The electro-
catalytic enhancement of biologically related thiol detection was
sought and PtFeNi [10] or PtNiCo [11] catalysts were employed.
Recently, Martin Pumera have successfully discovered that NiO
nanoparticles significantly enhance the signal of glutathione dur-
ing cyclic voltammetry measurements [12,13]. As the development
of nanoscience, precisely control of the morphology of NiO
∗ Corresponding authors at: College of Chemistry and Chemical Engineering,
Anyang Normal University, Anyang, 455000, Henan, PR China.
E-mail addresses: huanpangchem@hotmail.com (H. Pang),
hhzheng@suda.edu.cn (H. Zheng), baiqingyuan1981@126.com (B. Yuan).
inexpensive NiO for enhanced detection of regulatory peptides glu-
tathione.
Transition metal oxides such as ruthenium oxide, manganese
oxide, cobalt oxide, and nickel oxide are qualified to be electro-
chemical capacitor materials. Among these materials, NiO is of
great significance, and the theoretical capacitance of NiO can be
ca. 2573 F g−1 within 0.5 V. With the development of nanoscience,
many groups found that nanomaterials generally exhibit many
size and shape dependent properties, and the specific capacitance
of NiO nanomaterials is depended on the synthesis method and
morphology [14–27]. In particular, there have been considerable
research efforts devoted to the use of nickel oxide for super-
capacitors, due to its good pseudocapacitive behavior, practical
availability, environmentally begin nature and low cost compared
to the state-of-the-art supercapacitor material RuO2 [16–24].
The interaction between metal ions and ligands has been widely
investigated in materials science and chemistry during the past
few decades [28,29]. Recently, a growing number of studies are
now dedicated to the synthesis of nanostructured metal–organic
complexes [30]. Coordination complexes have been used as a
nanostructured precursor to prepare mesoporous metal oxides in
our previous work [31–33]. The coordination complex precursor
always has a micro or nanostructure due to the growth mechanism
of the polymer complex precursor, and such unique nanostruc-
ture may bring on an exciting performance of utility in many

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.08.057
 H. Pang et al. / Electrochimica Acta 85 (2012) 256–262
Fig. 1. (a) XRD patterns of coordination microflowers, NiO microflowers; (b) TG curve of coordination microflowers; (c) SEM image of coordination microflowers; (d–f) SEM
image of NiO microflowers; (g) TEM image of NiO microflowers; (h) HRTEM image and SAED.
fields [31–37]. More importantly, when calcining the nanostruc-
tured precursor, there were a large number of gases releasing from
decomposed organic ligands and new pores were generated, finally
resulting in a novel porous structure. This ‘precursor method’ needs
no template. More importantly, the decomposition products have
both retained micro/nano structures and generated porous struc-
tures [31–34].
In this study, a microflower structured coordination com-
plex precursor was successfully synthesized in aqueous solution
under room temperature conditions. More importantly, by con-
trolling the calcination condition, we have easily obtained porous
NiO microflowers. Unlike conventional approaches for preparing
porous inorganic structures, this method avoids the subsequent
to complicated work up procedure for the removal of the hard
template, seed or using soft template. Electrochemical sensor tests
of GSH have revealed that the prepared porous NiO microflower
material has significantly enhanced the signal of glutathione during
cyclic voltammetry measurements, and show good linear depend-
ence and high sensitivity to GSH concentration changes as GSH
sensors. Moreover, porous NiO microflower material also can be
used as electrochemical supercapacitor, which has a large specific
capacitance (1678.4 F g−1 at 0.625 A g−1 ), good rate capability and
extremely excellent cycling property (maintained about 99.7% at
6.25 A g−1 after 1000 cycles).
257
2. Experimental
2.1. Chemicals
All the chemicals used in our experiments were of analytical
reagent grade and were directly used without further purifica-
tion. l-glutathione and isonicotinic acid were purchased from
Sigma–Aldrich. Nickeldinitrate hexahydrate was purchased from
Sinopharm Chemical Reagent Co., Ltd, China; KOH and NaOH were
purchased from Shanghai Chemical Reagents Company; Deionized
18 M cm water (Milli-Q reagent water system, Millipore, Bedford,
MA) was used to prepare all aqueous solutions. Unless otherwise
noted, 0.1 M HAc–NaAc buffer (pH 5.0) was used as the supporting
electrolyte solution for electrochemical measurements.
2.2. Materials preparation
In a typical synthesis, firstly, 0.147 g isonicotinic acid, 0.054 g
NaOH, 8.00 g H2 O and 50.0 mL alcohol were mixed together and
were stirred for 1 h continuously at room temperature. Secondly,
0.300 g Ni(NO3 )2 was added into the above system. After stirring
for 1 h continuously, a green precipitate could be obtained. The final
product was collected by centrifugation and washed with deionized
water, ethanol several times and then dried in air. Then the products
258 H. Pang et al. / Electrochimica Acta 85 (2012) 256–262

were calcined in the air at 450 ◦ C for 440 min. The heating-up rate
was 1 ◦ C/min.

2.3. Electrochemical sensor electrode preparation

Bare carbon paste electrode (B-CPE), 1.8 mm diameter, was

prepared using graphite powder, liquid paraffin, with a ratio of
75:25 (w/w); NiO-carbon paste electrode (NiO-CPE), 1.8 mm diam-
eter, was prepared using graphite powder, liquid paraffin, and NiO
microflowers with a ratio of 74:25:1 (w/w). The electrochemical
cell was assembled with a conventional three-electrode system:
a Ag/AgCl/KCl (saturated) reference electrode and a platinum coil
as an auxiliary electrode. 0.1 M HAc–NaAc (pH 5.0) was used for
determination of glutathione.

2.4. Electrochemical supercapacitor electrode preparation

The working electrodes were prepared as follows: The electrode

material was prepared according to the following steps. The mix-
ture containing 80 wt.% NiO, 15 wt.% acetylene black and 5 wt.%
polytetrafluoroethylene (PTFE) were well mixed, and then were
pressed onto nickel grid (1.2 × 107 Pa) that serves as a current col-
lector (surface is 1 cm2 ). The typical mass load of electrode material
is 5 mg. The electrochemical measurements were carried out by
an electrochemical analyzer system, CHI660D (Chenhua, Shanghai,
China)
2.5. Characterization
The morphology of as-prepared samples was observed by a JEOL
JSM-6701F field-emission scanning electron microscope (FE-SEM)
at an acceleration voltage of 5.0 kV. The phase analyses of the
Fig. 2. Brunauer–Emmett–Teller measurements of NiO microflowers; correspond-
ing Barrett–Joyner–Halenda pore size distribution curve in inset of it.
samples were performed by X-ray diffraction (XRD) on a Ultima
III with Cu K␣ radiation ( = 1.5418 Å). Transmission electron
microscopy (TEM) image and HRTEM image were captured on the
JEM-2100 microscopy at an acceleration voltage of 200 kV.
The electrochemical supercapacitor measurements were car-
ried out by an electrochemical analyzer system, CHI660D (Chenhua,
Shanghai, China) in a three-compartment cell with a platinum plate
counter electrode, a saturated calomel electrode (SCE), reference
electrode and a working electrode. The electrolyte was a 3.0 M KOH
aqueous solution. And electrochemical impedance spectroscopy

Fig. 3. (a) Cyclic voltammetry measurements of GSH solutions, pH 5.0; (b) Cyclic voltammograms at NiO-CPE in 3 mM GSH solutions with different pHs. (c) The amperometric
responses at 0.4 V of the NiO-CPE electrode with successive increments of the GSH concentration from 10 ␮M to 0.62 mM, pH 5.0; (d) the amperometric responses at 0.4 V
of the NiO-CPE electrode with successive increments of the GSH concentration from 0.6 to 3.6 mM, pH 5.0.
 H. Pang et al. / Electrochimica Acta 85 (2012) 256–262 259

(EIS) measurements were conducted at open circuit voltage in the

frequency range of 100 kHz to 0.01 Hz with AC voltage amplitude
of 5 mV using PARSTAT 2273.

3. Results and discussion

3.1. Thermal behavior, crystal structure and morphology of

coordination microflowers, porous NiO microflowers

A green precursor can be obtained by mixing Ni(NO3 )2 and

isonicotinic acid alkaline alcohol solution. And then the coordi-
nation of isonicotinic acid and Ni2+ can self-assemble into novel
microflowers in alkaline alcohol solution. TG curve of coordination
microflowers is shown in Fig. 1a, from which it is seen that coordi-
nation microflowers have two weight loss steps and ends at 400 ◦ C.
An XRD pattern of the precursor is shown in Fig. 1b which shows
the good crystallinity of precursors. A SEM image of the precursor
is shown in Fig. 1c, in which we can see the size of microflower
precursor is about 10 ␮m.
Fig. 1d–f shows the morphologies of the products after heated
treatment at 450 ◦ C. Fig. 1b presents the XRD pattern of the heated
product, which perfectly fits with the standard spectrum of NiO
(JCPDS no.47-1049). From Fig. 1d and e, the microflower struc-
ture has been maintained with 10 ␮m. However there are some
differences on the surface of NiO microflower, which shows rough
surface with many small NiO nanoparticles with 20–30 nm in Fig. 1f.
The rough surface might be caused by the decomposed coordi-
nation microflowers. And this is reasonable because during the
thermal decomposition the remarkable shrinkage would occur as
generating gases (such as COx , N2 , or H2 O). The picture in Fig. 1g
shows TEM image of porous NiO microflowers, in which many
nanopores within 5 nm have been formed by NiO nanoparticles.
The crystalline nature of porous NiO microflowers were also con-
Fig. 4. (a) Cyclic voltammetry curves of porous NiO microflowers electrodes at dif-
firmed by a high resolution HRTEM image in Fig. 1h, which displays
ferent scan rates; (b) the specific capacitances of porous NiO microflowers electrodes
clear lattices of the NiO crystal. calculated according to the CV curves at different scan rates.

3.2. Brunauer–Emmett–Teller (BET) measurements of porous NiO

microflowers
To gain further insight into the porous structure and size
distribution of NiO microflowers, BET measurements were per-
formed to examine its specific structural properties. The porous
NiO microflowers show a distinct hysteresis in the larger range
ca. 0.5–1.0 P/P0 in Fig. 2, indicating the presence of mesopores
possibly formed by porous stacking of component nanoparticles
[38,39]. The BET surface area of NiO microflowers (62.7 m2 g−1 ) is
making an efficient contact of the microflowers with GSH molec-
ular or the electrolyte. The corresponding Barrett–Joyner–Halenda
(BJH) pore size distribution curve in inset of Fig. 2 shows that the
pore size is uniform, within the range of the mesopores (5–10 nm).
These porous microflowers structures do not only offer high sur-
face areas, but provide small molecular and electrolyte accesses.
The morphology of microflowers might offer a stable structure
for redox reactions of GSH or ion intercalated/extracted into/out,
which might improve the electron transfers and cycle life of the
electrode [40–44].
3.3. Porous NiO microflowers as electrochemical sensor of GSH
We proposed the possible electrochemical oxidation of l-
glutathione (GSH) proceeds as follows: 2GSH − 2e− − 2H → 2 GSSG
[13,45,46]. Fig. 3a shows cyclic voltammetry measurements at the
B-CPE electrode and NiO-CPE electrode. It can be seen that GSH
shows no redox peak at the B-CPE electrode in the GSH solution
with the concentration as high as 5 mM GSH in 0.1 M HAc–NaAc (pH
5.0) solution. There are also no redox peaks at NiO-CPE electrode in
0.1 M HAc–NaAc (pH 5.0) solution. It is clear that a strong peak at
NiO-CPE electrode can be seen in 5 mM GSH in 0.1 M HAc–NaAc (pH
5.0) solution, which means good electrochemical response of GSH
and the redox reaction of GSH on the surface of NiO-CPE electrode
has happened. What is more, we have also tested cyclic voltam-
mograms at NiO-CPE in GSH solutions with different pHs in Fig. 3b,
it was clear that 0.1 M HAc–NaAc (pH 5.0) solution is the best one
for electrochemical GSH sensor of NiO-CPE electrodes.
Fig. 3c shows the amperometric responses at 0.4 V of the NiO-
CPE electrode with successive increments of the GSH concentration
from 10 ␮M to 0.62 mM. The current signals increase rapidly and
sensitively after each addition of GSH, which gives a good lin-
ear dependence (correlation coefficient, R = 0.9918). This linear
dependence between the amperometric response and the GSH
concentration can also be found in the high GSH concentration
in the range of 0.6–3.6 mM with R = 0.9931 as shown in Fig. 3d.
These results indicate that the NiO-CPE electrode sensor has a good
sensitivity and detection concentration range for GSH. This phe-
nomenon might be caused by many connecting pores of porous NiO
microflowers based on the TEM images in Fig. 1 and BET results in
Fig. 2, which have more channels or pores to let the small molec-
ular go through easily and can enhance the travelling speed of the
electron, and thus bring the high electrochemical response of GSH.
And we also found the same electrochemical behavior of other
thiol compounds – Cysteine. From cyclic voltammograms at NiO-
CPE in serials of Cysteine (Cys) solutions, pH 5.0, ESI Fig. 1, it is clear
that the NiO-CPE electrode could detect Cys and the peak current
increased as the increasing concentration of Cys solution. The pos-
sible interference for the detection of GSH at the NiO-CPE electrode
260 H. Pang et al. / Electrochimica Acta 85 (2012) 256–262

Fig. 5. (a) CP curves of porous NiO microflowers electrodes at different current densities; (b) the specific capacitances calculated by the CP curves and current densities of
porous NiO microflowers electrodes; (c) the relationship of the specific energy against specific power for porous NiO microflowers electrodes materials; (d) the relationships
of the specific capacitance against cycling number for porous NiO microflowers electrodes with current density 6.25 A g−1 .

was also investigated. Cyclic voltammograms and differential pulse
voltammograms at NiO-CPE in 3 mM GSH–0.1 mM uric acid were
also tested (ESI Fig. 2), which did not show interferences to GSH
detection at pH 5.0 by DPV method.
It is important that we should consider the suitability of our
approach to analyze ‘real’ samples. The test result of GSH concen-
trations in human plasma is 4.7 mM by our approach, while that of
High Performance Liquid Chromatography (HPLC) is 4.1 mM, indi-
cating it could be used as a practice GSH sensor.
3.4. Porous NiO microflowers as electrochemical supercapacitors
Cyclic voltammetry (CV) was used to evaluate the electro-
chemical properties and quantify the specific capacitance of
as-prepared NiO electrodes. A NiO capacitor in an alkaline solu-
tion relies on charge storage in the electric double layer at the
electrode–electrolyte interface and charge storage in the host
material through redox reactions on the surface and hydroxyl ion
diffusion in the host material [47,48]. Fig. 4a shows CV curves of
porous NiO microflowers at different scan rates. The potential span
is from 0 to 0.50 V (vs. SCE) in 3 wt.% KOH aqueous solution. It is clear
that the redox peaks reveal the Faradaic pseudocapacitive property
of the porous NiO microflowers based on the surface redox mech-
anism of Ni2+ to Ni3+ at the surface of porous NiO microflowers
according to the following equation, NiO + OH− = NiOOH + e− . The
large current densities suggest remarkably large specific capac-
itances of NiO microflowers. Specific capacitance is essential to
the application of supercapacitors and in most cases the most
important factor considered. The specific capacitances of NiO
microflowers are calculated according to the CV curves at different
scan rates and the clear relationships are shown in Fig. 4b. The spe-
cific capacitance of NiO microflowers can reach a surprising value
863 F g−1 at the scan rate of 5 mV s−1 (ESI calculation1). Even though
the specific capacitance of NiO microflowers drops as the scan rate
increases, the specific capacitance is still about 63 F g−1 at the scan
rate of 100 mV s−1 . The drop can be explained by the ion-exchange
mechanism. The OH− needs enough time to transfer between solu-
tions into the surface of porous NiO microflowers in order to be
intercalated/extracted into/out of porous NiO microflowers when
charging/discharging. If the scan rate is low, such as 5 mV s−1 , the
OH− can have enough time to transfer and much more charge trans-
fers than at a high scan rate, which means more charge can be stored
and thus higher specific capacitance. Based on TEM images in Fig. 1
and BET results in Fig. 2, with many connecting pores, materials
such as porous NiO microflowers have more channels to let the ions
go through, which can enhance the travelling speed of the ions and
thus bring the high specific capacitances.
Chronopotentiometry (CP) curves at different current densities
are shown in Fig. 5a. The symmetrical characteristic of charg-
ing/discharging curves is good, which means that the porous NiO
microflowers electrodes with excellent electrochemical capability
and redox process are reversible. The relationships between the
specific capacitances calculated by CP curves and current densities
are given in Fig. 5b (for detailed calculation seen ESI calculation
2). Based on the CP curves, porous NiO microflowers electrodes
have the large specific capacitance and reach 1678 F g−1 at a current
density of 0.625 A g−1 and remain at 856 F g−1 even at 6.25 A g−1 .
Besides the large specific capacitance, another advantage of
supercapacitors is that they have both large power density and
large energy density at the same time. This unique property ensures
 H. Pang et al. / Electrochimica Acta 85 (2012) 256–262
Fig. 6. (a) the electrochemical impedance spectra (EIS) of the electrodes at room
temperature; (b) the equivalent circuit for the electrochemical impedance spec-
trum; (c) the phase angles for impedance plots.
the wide use of supercapacitors in many fields which need both
large power density and large energy density. Fig. 5c shows the
relationship of the specific energy against specific power for porous
NiO microflowers electrode materials (ESI calculation 3). From
Fig. 5c, it is easily concluded that porous NiO microflowers elec-
trode has the good performance for both the power density and
the energy density. When its power density is 139.3 W kg−1 , its
energy density is 45.6 W h kg−1 . What is more, when the power
density is 1405.5 W kg−1 , its energy density surprisingly remains
22.1 W h kg−1 . Its large power density and energy density as well
as the large specific capacitance make it as a promising candidate
for the supercapacitor electrode material.
It is also very important for electrode materials to have good
specific capacitance retention. The supercapacitors should work
steadily and safely, which requires the specific capacitance of
electrode materials to change as little as possible. The relation-
ships of the specific capacitance against cycling number of porous
NiO microflowers materials are shown in Fig. 5d. The relationship
261
of porous NiO microflowers shows its excellent specific capaci-
tance retention under large current density 6.25 A g−1 . After 200
continuous charge–discharge cycles, porous NiO microflowers
almost remain the same specific capacitance as its initial value.
More importantly, porous NiO microflowers still retains more
than 99.7% of its specific capacitance after 1000 continuous
charge–discharge cycles. The little drop of specific capacitance
of porous NiO microflowers electrodes possibly results from the
slight collapse of the microflowers structures when the ions are
intercalated/extracted into the microflowers structures.
The electrode kinetics of the as-prepared material electrodes
were estimated by EIS. Fig. 6 shows the EIS of the porous NiO
microflowers electrodes at room temperature and its calculated
curve by ZSimpWin software. The EIS data can be fitted by an
equivalent circuit consisting of a bulk solution resistance Rs , a
charge-transfer Rct , a pseudocapacitive element Cp from the redox
process of NiO, and a constant phase element (CPE) to account
for the double-layer capacitance, as shown in Fig. 6b. The solution
resistance Rs of porous NiO microflowers electrodes was measured
to be 1.8 , while the charge-transfer resistance Rct was calculated
to be 5.6 . This clearly demonstrates the reduced charge transfer
resistance of porous NiO microflowers electrode. In addition, the
charge-transfer resistance Rct , also called Faraday resistance, is a
limiting factor for the specific power of the supercapacitor [47–49].
It is the low Faraday resistance that results in the high specific
power of the porous NiO microflowers electrode. The phase angles
for impedance plots of porous NiO microflowers electrodes and its
calculated curve by ZSimpWin software were observed in Fig. 6c.
These phase angles are nearly to 40◦ in the low frequencies clearly,
which means that the porous structure of NiO microflowers allows
ions or electrolyte transfer to occur quickly.
4. Conclusion
In this paper, porous NiO microflowers structures were suc-
cessfully synthesized by calcination of coordination microflowers
without any template, and its effectively electrochemical GSH
sensor in 0.1 M HAc–NaAc (pH 5.0) solution was the first time
evaluated. The capacitance of porous NiO microflower electrode
was 1678.4 F g−1 at 0.625 A g−1 , good rate capability and extremely
excellent cycling property (maintained about 99.7% at 6.25 A g−1
after 1000 cycles).
Acknowledgments
This work is supported by the National Natural Science
Foundation of China (21201010, 21073129, 21071006), the Depart-
ment of Science and Technology of China for the 863 project
(2009AA03Z225863). Henan Province of Science & Technology
Foundation (122102210253) and the Project of Science & Technol-
ogy of Anyang city.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.electacta.2012.08.057.
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