Electrochimica Acta 55 (2010) 7182–7187

Contents lists available at ScienceDirect

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

An unusual H2 O2 electrochemical sensor based on Ni(OH)2 nanoplates

grown on Cu substrate
Aixia Gu a,c , Guangfeng Wang a,c , Jing Gu a , Xiaojun Zhang a,b,∗ , Bin Fang a,c,∗
a
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, PR China
b
Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu 241000, PR China
c
Anhui Key Laboratory of Chem-Biosensing, Anhui Normal University, Wuhu 241000, PR China

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

Article history: In this work, Ni(OH)2 nanoplates grown on the Cu substrate were synthesized and characterized by scan-
Received 22 May 2010 ning electron microscopy (SEM), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy
Received in revised form 7 July 2010 (XPS). Then a novel Cu–Ni(OH)2 modified glass carbon electrode (Cu–Ni(OH)2 /GCE) was fabricated and
Accepted 7 July 2010
evaluated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and typical amper-
Available online 15 July 2010
ometric response (i–t) method. Exhilaratingly, the Cu–Ni(OH)2 /GCE shows significant electrocatalytic
activity toward the reduction of H2 O2 . At an applied potential of −0.1 V, the sensor produces an ultrahigh
Keywords:
sensitivity of 408.1 ␮A mM−1 with a low detection limit of 1.5 ␮M (S/N = 3). The response time of the
Cu–Ni(OH)2
Nanocomposites
proposed electrode was less than 5 s. What’s more, the proposed sensor displays excellent selectivity,
Electocatalysis good stability, and satisfying repeatability.
Amperometric sensor © 2010 Elsevier Ltd. All rights reserved.
H2 O2

1. Introduction Recently, some multidimensional nanomaterials have been pre-

At present, nanomaterial-modified glass carbon electrodes can
significantly improve their analytical performance [1,2]. Numerous
excellent materials have been applied to many analytical appli-
cations, such as carbon nanotubes [3], transition metal oxides
[4], prussian blue [5], conducting polymers [6], and carbon nan-
otubes/prussian blue nanocomposites [7].
Nickel hydroxide (Ni(OH)2 ), as one of the most important tran-
sition metal hydroxides, has been widely used as positive electrode
active materials in alkaline rechargeable Ni-based batteries [8]. It
is well known that layered double hydroxide (LDH) is well-defined
layered structure, which is widely applied as electrochemical
sensor materials [9,10]. Hexagonal ␤-Ni(OH)2 possesses similar
layered structure to LDH. Unfortunately, synthesizing LDH is quite
difficult and the fabrication of some LDH modified electrodes is very
complicated and time-consuming [11]. Hence, we consider that ␤-
Ni(OH)2 may be a substitute for LDH as electrochemical sensor
materials. However, there are few reports about electrochemical
sensors based on Ni(OH)2 [12].
∗ Corresponding authors at: College of Chemistry and Materials Science, Anhui
Normal University, Wuhu 241000, PR China. Tel.: +86 0553 3869302;
fax: +86 0553 3869303.
E-mail addresses: zhangxiaojun173@yahoo.com.cn (X. Zhang),
binfang 47@yahoo.com.cn (B. Fang).
pared by material scientists. Attaching these nanostructures onto
certain support makes the resultant products be feasibility in some
special applications, thus more and more attention has been paid to
the research field [13]. Our group has successfully constructed elec-
trochemical sensors based on Cu–CuO and Cu–Ag2 O nanomaterials.
The satisfying properties of these sensors have been acquired. It is
estimated that the improved electrochemical performance might
be due to the electric Cu substrate [14,15]. Considering the poten-
tial of Ni(OH)2 as electrochemical sensor materials, inspired by our
previous work, we prepared Ni(OH)2 nanoplates grown on Cu sub-
strate to fabricate a new electrochemical sensor.
It is no doubt that hydrogen peroxide (H2 O2 ) is a useful com-
pound widely used in modern medicine, environmental control,
and various branches of industry. Up to now, there have been
considerable interests in the accurate determination of H2 O2 . Elec-
trochemical sensing of H2 O2 has been a vigorous alternative to
spectrophotometric [16,17] and chemiluminescence techniques
[18,19] for H2 O2 detection, owing to its low cost, high sensitiv-
ity, ease of operation, and high efficiency [9,20,21]. In the past
few decades, a number of excellent reports have focused on the
electrochemical determination of H2 O2 utilizing metal [22], carbon
nanotubes [3], layered double hydroxide [11], prussian blue [5], and
conducting polymers [6] modified electrodes. However, to the best
of our knowledge, there are no reports about the detection of H2 O2
using the Cu–Ni(OH)2 nanocomposites modified electrodes.
In this paper, we present the fabrication of a H2 O2 amperomet-
ric sensor based on Cu–Ni(OH)2 nanocomposites. The proposed

0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.07.023
 A. Gu et al. / Electrochimica Acta 55 (2010) 7182–7187
electrode shows an ultrahigh current sensitivity of 408.1 ␮A mM−1 .
To our great surprise, the current sensitivity is increased to 16
times as compared with that of our previous report [12]. The
proposed sensor is also highly selective to the target analyte.
The Cu–Ni(OH)2 nanocomposites can be potentially used in some
novel electrochemical sensors and other electronic devices.
2. Experimental
2.1. Chemicals and apparatus
NiCl2 ·6H2 O, NaOH and Cu foil were purchased from the
Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). Nafion
was purchased from Sigma–Aldrich. Phosphate buffer solution
(PBS, pH 7.0, 0.05 M) was prepared by varying the ratio of KH2 PO4
to K2 HPO4 . All chemicals are analytical grade and used as received
without any further purification. Millipore water was used in all
experiments.
X-ray powder diffraction (XRD) patterns of the as-prepared
material were recorded on a Shimadzu XRD-6000 employing a
scanning rate of 0.05◦ s−1 with the 2 range from 10◦ to 80◦ ,
with high-intensity Cu KR radiation () 0.154178 nm. X-ray pho-
toelectron spectroscopy (XPS) data were acquired on a Thermo
ESCALAB 250 X-ray photoelectron spectrometer with an Al K␣
excitation source (1486.6 eV). Field-emission scanning electron
microscopy (FESEM) images were obtained using Hitachi S-4800
SEM (operated at 10 kV). Electrochemical impedance spectroscopy
(EIS), cyclic voltammetry (CV), and amperometric experiments
were performed on a model CHI 660B electrochemical analyzer
(CHI, Instruments, Shanghai, China) coupled to a computer.
2.2. Synthetic procedures
The synthesis procedure of Cu–Ni(OH)2 nanocomposites is sim-
ilar to the former report [15]. A Cu foil (1.5 cm × 1.5 cm × 0.25 cm)
was cleaned from a consecutive ultrasonication in acetone, ethanol
and distilled water. In a typical procedure, NiCl2 ·6H2 O was dis-
solved into 20 mL distilled water to give a green transparent
solution with [Ni2+ ] = 0.2 M, then 20 mL NaOH solution (0.4 M) was
added under stirring. Light green Ni(OH)2 suspension was obtained.
Finally, the suspension was transformed into a 60 mL Teflon-lined
autoclave with the prepared Cu substrate being immersed. After
that the autoclave was sealed and maintained at 180 ◦ C for 8 h,
and then cooled naturally to room temperature. The green precip-
itate scraped from the Cu substrate was washed with ethanol and
distilled water for several times before characterizations.
2.3. Construction of the modified electrodes
Glass carbon electrode (GCE) (3 mm in diameter) was cleaned
according to the literature [7]. The fabrication of Cu–Ni(OH)2 mod-
ified electrode was described as follows: Cu–Ni(OH)2 nanocompos-
ites were dispersed into 1 mL distilled water to give homogeneous
dispersions (1 mg mL−1 ) under bath sonication. After dropping
10 ␮L of the mixture onto the prepared electrode surface, the elec-
trode was dried at room temperature. Finally, 5 ␮L Nafion (0.1%,
v/v) was cast onto the surface and allowed to dry for 24 h to form
a uniform structure. The same process was applied to prepare
the Ni(OH)2 modified electrode. These resulting electrodes were
defined as Cu–Ni(OH)2 /GCE, Ni(OH)2 /GCE, respectively.
2.4. Electrochemical measurements
All electrochemical experiments were conducted using a three-
electrode system: a Cu–Ni(OH)2 /GCE or Ni(OH)2 /GCE as working
7183
electrode, saturated calomel electrode (SCE) as reference electrode
and platinum wire as auxiliary electrode. All potentials in this paper
were referenced to the SCE. EIS was obtained at different electrodes
in 0.1 M KCl containing 5 mM K3 [Fe(CN)6 ]/K4 [Fe(CN)6 ] (1:1). Elec-
trochemical catalytic behaviors of different electrodes toward H2 O2
reduction were characterized by CV in 7.0 PBS at a scan rate of
50 mV s−1 . The Cu–Ni(OH)2 /GCE was evaluated as a H2 O2 sensor at
a desired potential. The amperometric curves were obtained after
adding a certain concentration of H2 O2 under vigorous stirring.
3. Results and discussion
3.1. Characterization of the product
The composition of the as-synthesized product was verified by
powder X-ray diffraction (XRD). As shown in Fig. 1A, except for the
three peaks attributable to metallic Cu ((1 1 1), (2 0 0) (2 2 0)), all
reflections such as (0 0 1), (1 0 0), (1 0 1), (1 0 2) can be indexed as
hexagonal ␤-Ni(OH)2 with the lattice parameters a = 3.128 å and
c = 4.605 å. The results are in good accordance with the standard
values (JCPDS 14-117). No peaks of ␣-Ni(OH)2 or NiO are detected,
indicating that pure product was generated under our experimental
conditions.
The component of product was further characterized by XPS
technique, as indicated in Fig. 1B–D. The curve in Fig. 1D shows the
typical peak of Cu2p3/2 and Cu2p1/2 . In Fig. 1D one can see the exis-
tence of Cu (0) and Cu (II). The Cu (0) may be attributed to metallic
Cu and the Cu (II) may be ascribed to CuO, which resulted from the
surface oxidation of the product.
Fig. 2a and b exhibits the overall morphology of Ni(OH)2
nanoplates vertically aligned on the Cu substrate. One can see that
a large amount of densely packed Ni(OH)2 nanoplates are aligned
on the surface of the Cu substrate (Fig. 2a). It can be found from
Fig. 2b that the Ni(OH)2 nanoplates are hexagonal plates with
the thickness of 20–60 nm and side length of 200–600 nm. The
Ni(OH)2 nanoplate arrays on the conductive substrates provide
unique structures for construction of electrodes, which is in favor
of the application as electrochemical sensors. For comparison, we
provided the SEM images of Ni(OH)2 nanoplates (Fig. 2c and d). It
is clear to see that the Ni(OH)2 nanoplates are random stacked, not
orderly or densely stacked. The difference in structure may result
in the difference in electrochemical characters.
3.2. Electrochemical characterization of the modified electrodes
EIS was applied to monitor the whole procedure in preparation
of modified electrodes, which could provide useful information for
the changes of the surface modification [23], and the EIS results are
presented in Fig. 3. The resulting Nyquist plot consists two parts:
one is a semicircular region, which is characteristic of the high
frequency domain; the other is a linear portion, the characteris-
tic of low frequency region, controlled by electron transfer process.
The diameter of the semicircle corresponds to the electron trans-
fer resistance (Rct) at the electrode. In EIS, the bare GCE exhibits
an almost straight line, which implies the characteristic of a dif-
fuse limiting step of the electrochemical processes (Fig. 3a). After
Cu–Ni(OH)2 nanocomposites being cast on the bare GCE, the semi-
circle increases, which indicates that the nanomaterials have been
attached to the electrode surface (curve b). However, comparing
with Ni(OH)2 /GCE (curve c), the EIS of Cu–Ni(OH)2 /GCE is smaller,
indicating that the Cu substrate in the center of Ni(OH)2 nanoplates
facilitates the electron transfer (ET) between electrode and redox
probe.
The scan rate effect was investigated in the range of
50–500 mV s−1 at Cu–Ni(OH)2 /GCE in 7.0 PBS. The peak current
7184 A. Gu et al. / Electrochimica Acta 55 (2010) 7182–7187

Fig. 1. (A) XRD pattern of Cu–Ni(OH)2 nanocomposites. (B–D) XPS analysis of Ni(OH)2 nanoplates (B) and Cu–Ni(OH)2 nanocomposites (C and D).

Fig. 2. SEM images of Cu–Ni(OH)2 nanocomposites (a and b) and Ni(OH)2 nanoplates (c and d).
 A. Gu et al. / Electrochimica Acta 55 (2010) 7182–7187
Fig. 3. EIS obtained at (a) a bare GCE, (b) Cu–Ni(OH)2 /GCE and (c) Ni(OH)2 /GCE in
0.1 M KCl containing 5 mM K3 [Fe(CN)6 ]/K4 [Fe(CN)6 ] (1:1).
varies linearly with the scan rate, ipa (␮A) = 9.77804 + 0.1251v
(r = 0.996), showing a typical electron transfer-controlled redox
process.
3.3. Electrochemical performance toward H2 O2 reduction at the
Cu–Ni(OH)2 /GCE
In order to evaluate the electrocatalytic activity of the
Cu–Ni(OH)2 /GCE toward the H2 O2 reduction, we conducted the
following experiments. Firstly, Ni(OH)2 /GCE and bare GCE were
tested by CV in the absence and presence of 0.5 mM H2 O2 , respec-
tively (Fig. 4A and B). It can be seen that there was no response
for H2 O2 reduction at the bare GCE, as curves 1 and 2 shown in
Fig. 4A (or curves a and b in Fig. 4B). Under the same experimen-
tal conditions, the reduction of H2 O2 at Ni(OH)2 /GCE demonstrates
increased background current, but no distinct difference is found
between the absence and presence of H2 O2 at the Ni(OH)2 /GCE
(curves 3 and 4 of Fig. 4A). However, for Cu–Ni(OH)2 /GCE, the peak
current increases obviously after the same quantum of H2 O2 being
added into the PBS (curve d of Fig. 4B). As shown in Fig. 4B curve
d, the current sensitivity is about 12.7 × 10−5 A with 0.5 mM H2 O2
being added into the solution. The current sensitivity increases to
27 × 10−5 A with H2 O2 concentration increasing to 1.0 mM, which
may be applied as the quantitative analysis (Fig. 4B curve e).
3.4. Amperometric performance of the Cu–Ni(OH)2 /GCE
Fig. 5A shows the typical amperometric responses of
Cu–Ni(OH)2 /GCE (a) and Ni(OH)2 /GCE (b) upon the successive
addition of H2 O2 into continuous stirring pH 7.0 PBS. The operating
potential was −0.1 V. For the Ni(OH)2 /GCE (curve b), a detectable
but comparatively small current response is observed with the
addition of H2 O2 . In contrast, the Cu–Ni(OH)2 /GCE responds
sensitively to the changes of H2 O2 concentration, reaching a
steady-state signal within 5 s. The corresponding calibration plots
for the two amperometric response curves were shown in Fig. 5B.
The amperometric response of Cu–Ni(OH)2 /GCE and H2 O2 (curve
a) is much more sensitive than that of Ni(OH)2 /GCE and H2 O2
(carve b). The sensitivity on Cu–Ni(OH)2 /GCE is 408.1 ␮A mM−1 ,
which is16.5 times that of on Ni(OH)2 /GCE. The obtained sen-
sitivity is much higher than those of previous reports [24–28].
Under the optimized experimental parameters, the developed
Cu–Ni(OH)2 /GCE shows a linear response within the H2 O2 con-
centrations range among 5–145 ␮M with a correlation coefficient
of 0.996. The detection limit is determined to be 1.5 ␮M (S/N = 3).
7185
Fig. 4. CV images for different electrodes in 7.0 PBS at various concentrations of
H2 O2 : curves 1 and 2 (or curves a and b) for bare GCE in the absence and presence of
0.5 mM H2 O2 , respectively (A or B); curves 3 and 4 for Ni(OH)2 /GCE in the absence
and presence of 0.5 mM H2 O2 , respectively (A); curves c, d and e for Cu–Ni(OH)2 /GCE
with 0, 0.5, 1.0 mM of H2 O2 , respectively (B). The scan rate was 50 mV s−1 .
Based on above phenomena, it confirmed that the Cu–Ni(OH)2
nanocomposites have higher catalysis on H2 O2 reduction than
Ni(OH)2 nanoplates. This may be a direct result of the special struc-
ture of the Cu–Ni(OH)2 nanocomposites. Because the aspect ratio of
the densely packed Cu–Ni(OH)2 nanocomposites is larger than that
of the Ni(OH)2 nanoplates, which can favor electron transfer better.
To attest it, we measured the electrochemical active surface (EAS)
of the two electrodes at 30 ◦ C in 0.1 M NaOH by CV. According to
Ref. [29], the peaks in the potential region −800 mV < E < −500 mV
on the CV curve are associated with the hydrogen adsorption pro-
cess in the anodic scan. The EAS is calculated according to Eq. (1)
[30]:
4.76QH
EAS = (1)
[MO]
where QH denotes the Coulombic charge for hydrogen desorption
at the electrodes (mC cm−2 ) and [MO] represents the nanomateri-
als (Cu–Ni(OH)2 nanocomposites or Ni(OH)2 nanoplates) loading
(mg cm−2 ) on the electrode. The EAS for Cu–Ni(OH)2 /GCE is
35.85 m2 g−1 and for Ni(OH)2 /GCE is 2.39 m2 g−1 . The results show
that the EAS for Cu–Ni(OH)2 nanocomposites is much larger than
that of Ni(OH)2 nanoplates, which is consonant with our estima-
tion. Furthermore, the electric Cu in the center of the Cu–Ni(OH)2
nanocomposites provides more electron transfer passages, so the
electrochemical probe could arrive to the surface of the electrode
more easily [31].
7186 A. Gu et al. / Electrochimica Acta 55 (2010) 7182–7187
Fig. 5. (A) Typical amperometric response of Cu–Ni(OH)2 /GCE (a) and Ni(OH)2 /GCE
(b) to successive injection of H2 O2 at −0.1 V. (B) Calibration curves of H2 O2 concen-
tration at the sensors: (a) for Cu–Ni(OH)2 /GCE and (b) for Ni(OH)2 /GCE.
3.5. Stability, reproducibility and selectivity of the
Cu–Ni(OH)2 /GCE
One of the outstanding advantages of the Cu–Ni(OH)2 /GCE was
the good stability, acceptable reproducibility, and excellent selec-
tivity. After 80 consecutive cyclic scans, the CV at Cu–Ni(OH)2 /GCE
achieved a steady state and kept almost unchanged. The sensor was
stored in a pH 7.0 PBS at 4 ◦ C when was not in use and it retained
about 97% of its initial response to H2 O2 after 15 days. Therefore,
the Cu–Ni(OH)2 nanocomposites showed good stability.
Cu–Ni(OH)2 /GCE showed the relative standard deviation (RSD)
of 3.6% for eight successive assays with 0.5 mM H2 O2 and 2.7%
for four determinations based on four same fabrications of the
modified electrode. Hence the electrode has an acceptable repro-
ducibility.
Here, we investigated the interferences from UA, DA, AA and
l-Cysteine (l-Cys) toward the determination of H2 O2 , which are
common existing interfering species in the physiological samples.
The interfering effect of 0.5 mM UA, 0.1 mM DA, 0.1 mM AA and
0.1 mM l-Cys compared to 0.01 mM H2 O2 was evaluated at the
potential of −0.1 V. As shown in Fig. 6, there is obvious current
response with the addition of 0.01 mM H2 O2 . On the contrary, no
obvious current response is observed with the addition of 0.5 mM
UA, the same instances are received after 0.1 mM DA, 0.1 mM
AA and 0.1 mM l-Cys being consecutively added, demonstrating
the interferences from the interfering species were completely
avoided.
3.6. Mock sample measurements
For possible medical and environmental applications, this H2 O2
sensor was also used to evaluate the feasibility of H2 O2 detection in
Fig. 6. Amperometric response for successive injection of 0.01 mM H2 O2 and inter-
fering species (0.5 mM UA, 0.1 mM DA, 0.1 mM AA and 0.1 mM l-Cys) into 7.0 PBS
with stirring, the working potential was −0.1 V.
Table 1
Results for the determination of H2 O2 in mock solution.
Sample Content (mM) Found (mM) RSD (%) (n = 5) Recovery (%)
1 0.5 0.48 1.18 96
2 1.0 1.02 1.56 102
3 2.0 2.11 2.01 105.5
our mock sample analysis (0.5, 1.0 and 2.0 mM H2 O2 ). The results
obtained as mean from five determinations are shown in Table 1.
It was satisfying.
4. Conclusions
In conclusion, we have synthesized Cu–Ni(OH)2 nanocompos-
ites and applied it as the fast and sensitive H2 O2 sensor material.
The as-prepared Ni(OH)2 nanoplates possess high specific surface
area, especially the high EAS, allowing the free access of analytes
to its surface. Moreover, the Cu substrate has good conductivity,
which provides more electron transport channels, enhancing the
electron transfer reaction between H2 O2 and Ni(OH)2 . All these
features provide a favorable environment for the electrocatalytic
reduction of H2 O2 . The novel Cu–Ni(OH)2 nanocomposites based
sensor demonstrated in this study shows great potential applica-
tions in electrochemical sensor development.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (20675001, 20901003), Anhui Key Laboratory of
Controllable Chemistry Reaction & Material Chemical Engineer-
ing (OFCC0905), the Young Teacher Program of Anhui Normal
University (2009xqnzc19), and the Natural Science Foundation
of Educational Department of Anhui Province (Nos. KJ2008B167,
KJ2009B013Z).
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