Analytica Chimica Acta 852 (2014) 45–54

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Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

Ultrasensitive and simultaneous detection of heavy metal ions based

on three-dimensional graphene-carbon nanotubes hybrid electrode
materials
Hui Huang a , Ting Chen a , Xiuyu Liu b , Houyi Ma a, *
a
Key Laboratory for Colloid and Interface Chemistry of State Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan
250100, China
b
Shandong Academy of Sciences, Jinan 250114, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Three-dimensional graphene-
MWCNTs nanocomposites were pre-
pared.

Graphene-MWCNTs based electro-
chemical sensor was used to detect
heavy metal ions for the first time.

The proposed sensor was certified
capable for real sample with satis-
factory results.

A R T I C L E I N F O A B S T R A C T

Article history: A green and facile method was developed to prepare a novel hybrid nanocomposite that consisted of
Received 24 June 2014 one-dimensional multi-walled carbon nanotubes (MWCNTs) and two-dimensional graphene oxide (GO)
Received in revised form 2 September 2014 sheets. The as-prepared three-dimensional GO–MWCNTs hybrid nanocomposites exhibit excellent
Accepted 9 September 2014
water-solubility owing to the high hydrophilicity of GO components; meanwhile, a certain amount of
Available online 16 September 2014
MWCNTs loaded on the surface of GO sheets through p–p interaction seem to be “dissolved” in water.
Moreover, the graphene(G)-MWCNTs nanocomposites with excellent conductivity were obtained
Keywords:
conveniently by the direct electrochemical reduction of GO–MWCNTs nanocomposites. Seeing that there
Graphene-carbon nanotubes hybrid
Heavy metal ions
is a good synergistic effect between MWCNTs and graphene components in enhancing preconcentration
Differential pulse anodic stripping efficiency of metal ions and accelerating electron transfer rate at G-MWCNTs/electrolyte interface, the
voltammetry G-MWCNTs nanocomposites possess fast, simultaneous and sensitive detection performance for trace
Detection amounts of heavy metal ions. The electrochemical results demonstrate that the G-MWCNTs
nanocomposites can act as a kind of practical sensing material to simultaneously determine Pb2+ and
Cd2+ ions in terms of anodic stripping voltammetry (ASV). The linear calibration plots for Pb2+ and Cd2+
ranged from 0.5 mg L1 to 30 mg L1. The detection limits were determined to be 0.2 mg L1 (S/N = 3) for
Pb2+ and 0.1 mg L1 (S/N = 3) for Cd2+ in the case of a deposition time of 180 s. It is worth mentioning that
the G-MWCNTs modified electrodes were successfully applied to the simultaneous detection of Cd2+ and
Pb2+ ions in real electroplating effluent samples containing lots of surface active impurities, showing a
good application prospect in the determination of trace amounts of heavy metals.
ã 2014 Elsevier B.V. All rights reserved.

1. Introduction

* Corresponding author. Tel.: +86 531 88364959; fax: +86 531 88564464. The environmental pollution caused by heavy metal ions has
E-mail addresses: hyma@sdu.edu.cn, hyma414@gmail.com (H. Ma). already become serious problems that influence the survival

http://dx.doi.org/10.1016/j.aca.2014.09.010
0003-2670/ ã 2014 Elsevier B.V. All rights reserved.
46 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
environment of human beings and other creatures. Therefore, it is
essential to construct rapid, sensitive, simple, low-cost and
portable monitoring devices, with the aim of achieving the
on-site, real-time and on-line determination of trace amounts of
heavy metals [1–3]. Anodic stripping voltammetry (ASV), as a
simple and sensitive electroanalytical method, has been proved to
be very effective for the analysis of trace concentrations of heavy
metal ions in aqueous solutions [4–6]. Besides the advantages of
high detection sensitivity, small sample consumption, simple
operation, low cost and practical convenience, a distinct advantage
of ASV over atomic absorption spectroscopy (AAS) method is its
ability to detect several metal ions simultaneously. Seeing that the
working electrode plays a critical role in carrying out the stripping
analyses, an ideal working electrode should have multiple
functions, including effective preconcentration, selective reaction
surface, good repeatability and low background current over a
wide potential range [7–9]. However, the commonly used hanging
mercury drop electrodes (HMDE) [10] or thin mercury film
electrodes (TMFE) [11] pose great risks to the environment and
human health, much attention has been focused on how to
construct high performance sensing electrodes made from
environmental friendly “green materials”. In recent years,
carbon-based nanostructural materials, especially graphene
[12–15] and carbon nanotubes (CNTs) [16,17], have received
increased interest in the electrochemical detection of heavy
metals, due to their environmental safety, fast electron transfer
rate, unique structural characteristics and physico-chemical
properties. For example, Hwang et al. reported a bismuth-modified
screen-printed CNTs electrode for the simultaneous detection of
Zn2+, Cd2+, Pb2+ ions, with the linear range of 2–100 mg L1 [18]. Yu
et al. developed a glucose and pyrene residues modified GO sensor
with the detection limit of 0.1 nM, in which the glucose residue
works as the adsorption sites for heavy metal ions and the pyrene
residue non-covalently binds to the graphene surface by p bond
[19]. In particular, Wang et al. reported that amination-based GO
was applied to the determination of lead ions, with the detection
limit down to 0.1 pM; however, toxic Hg was used in the
enrichment step of heavy metal ions [20]. Although CNTs and
the reduced graphene oxides (rGOs) have respective advantages,
together they work better than either one does alone when they
are used to design carbon-based sensing electrodes for detecting
heavy metal ions. Thus, the combination of graphene and MWCNTs
enables the resulting hybrid nanocomposites to act as an ideal
electrode material for the fabrication of environmentally friendly
sensing electrodes [21–23].
It is generally believed that graphene, a one-atom-thick layer
of graphite, possesses excellent conductivity, high electron
transfer rate and very large surface area [24,25]. However, these
properties are strongly dependent on the preparation process of
graphene sheets. In fact, for the rGO obtained by the reduction of
GO sheets that are synthesized through the well-known
Hummers method [26], its electrical conductivity and specific
surface area are usually much lower than the theoretical expected
values owing to the excessive defects originated from chemical
oxidation process and the clustering caused by intensive p–p
interaction. Instead, the main superiority of the as-prepared rGO
is its strong hydrophilicity because some surface functional
groups may be preserved after the reduction of GO, which enable
rGO to strongly adsorb metal ions [27]. In contrast to the rGO,
CNTs can be produced in large batch by floating catalyst chemical
vapor deposition (FC-CVD), carbon arc methods, or laser
evaporation [28,29]. The as-prepared CNTs own excellent
electrical conductivity because the FC-CVD method avoids the
excessive oxidation of carbon surfaces. However, CNTs primary
deficiency is that there are only a few functional groups on its
surface, such as  COOH,  CQO and  OH, making this kind of
carbon material highly hydrophobic. Consequently, unmodified
CNTs are unable to chelate metal ions in aqueous solutions and
can not work as good electrode materials for the ASV analyses
[30].
As mentioned above, seeing that rGO or CNT has its own
advantages and disadvantages, we tend to use two-dimensional
(2D) GO nanosheets and one-dimensional (1D) MWCNTs to
fabricate a type of G-MWCNTs hybrid nanocomposites with
excellent conductivity and good water-solubility. In this way, the
effective combination of two carbon nanostructures can not only
make full use of respective advantages but also make up respective
deficiencies. In this paper, we developed a simple and green
method to fabricate three-dimensional (3D) G-MWCNTs nano-
composites. Thus, hydrophilic GO components may load CNTs
through p–p interaction, making a certain amount of CNTs be
“dissolved” in water, and the presence of CNTs components not
only greatly enhances the conductivity of the nanocomposites but
also suppresses to some degree the aggregation between GO
nanosheets. Moreover, the hydrophilic hybrid nanocomposites are
able to adsorb heavy metal ions from aqueous solution due to the
rich chelating groups. These advantages make the G-MWCNTs
nanocomposites be an ideal sensing nanomaterial suitable for the
electrochemical detection or preconcentration of trace amounts of
heavy metal ions, as illustrated by Scheme 1.
2. Experimental
2.1. Reagents
Natural graphite powder (325 mesh) was purchased from Alfa
Aesar. MWCNTs (purity: >95 wt.%; O.D.: 20–30 nm; length:
0.5–2 mm) produced by the CVD method were obtained from
Chengdu Organic Chemicals Co. Ltd. (Chengdu, China). Nafion
(5 wt.% in lower aliphatic alcohols) was obtained from
Sigma–Aldrich and diluted to 1 wt.% by ethanol before use.
Working solutions containing Zn2+, Cd2+, Pb2+, Cu2+ and Bi3+ ions
were prepared by diluting high concentration standard stock
solutions that were purchased from Aladdin (Shanghai, China). A
0.1 M HAc-NaAc buffer solution (pH 4.5) was prepared by mixing
appropriate amounts of CH3COOH and CH3COONa and served as a
supporting electrolyte during the analysis of metal ions. Ultrapure
water (18 MV cm) was used throughout the experiments. All
other chemicals used were of analytical reagent grade or better,
and were used without further purification.
2.2. Apparatus
Differential pulse anodic stripping voltammetry (DPASV) and
cyclic voltammetry (CV) were performed in a three-electrode cell
made of quartz beaker with a CHI750D electrochemical worksta-
tion (Chenhua Instruments, China). All potentials presented in this
paper were measured with respect to the SCE. The solutions were
deoxygenated by bubbling with high-purity nitrogen for at least
10 min prior to each experiment. Tapping-mode atomic force
microscopy (AFM, NanoScope IIIA, Digital Instruments) was
performed to examine the surface morphology on the Si/SiO2
substrate. Raman spectrum was obtained with an Ocean Optics
QE65000 Raman system (laser wavelength 785 nm and laser focus
size about 158 mm); all the spectra were baseline-corrected and
calibrated with respect to the Raman mode of Si at 520.7 cm1.
UV–vis adsorption spectroscopy and transmission electron
microscopy (TEM) measurements were obtained using a Hitachi
U-4100 spectrophotometer and a JEOL JEM-1011 TEM with an
acceleration voltage of 100 kV, respectively.
 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
Scheme 1. Schematic diagram for the synthesis of GO–MWCNTs hybrid nanomaterials and their application as novel electrode materials which are applicable to the
electrochemical detection of heavy metal ions by means of ASV method. Inset shows the digital photos for the GO, MWCNTs and GO–MWCNTs solutions, respectively.
2.3. Preparation of GO–MWCNTs nanocomposites
Prior to use, MWCNTs were treated with mixed acids (volume
ratio of 1:3 of concentrated HNO3 to concentrated H2SO4) for about
4 h followed by filtering, rinsing with water and drying in proper
order. This process is known as the segmentation and carboxyla-
tion of MWCNTs [31]. 1.0 mg mL1 MWCNTs dispersion was
prepared by ultrasonication for 1 h. Even so, the obtained
dispersion was not stable since most MWCNTs were hydrophobic.
GO nanosheets were obtained by 1 h ultrasonic exfoliation of
graphite oxides, which were produced by the oxidative treatment
of natural graphite based on the modified Hummer’s method
[32,33]. The as-prepared homogeneous GO hydrosol (1.0 mg mL1)
was brown in color. Afterwards, 10 mL of MWCNTs dispersion and
10 mL of GO hydrosol were mixed together and the resulting
mixture was further treated with ultrasonication for 2 h. Excessive
MWCNTs were removed by centrifugation at 5000 rpm and the
unreacted GO was separated at 12,500 rpm. The obtained sediment
was dried at 50  C in vacuum drying oven, forming the
GO–MWCNTs hybrid composites that can be stably dispersed in
aqueous phase for several months.
2.4. Fabrication of graphene-MWCNTs-Nafion composite film
Ultrasonic agitation (1 h) was used to disperse the
GO–MWCNTs nanocomposites into water to produce 0.5 mg mL1
GO–MWCNTs colloid. Before use, a bare glassy carbon electrode
(GCE) was polished carefully with 1.0 mm, 0.3 mm and 0.05 mm
alumina slurry, respectively, and washed ultrasonically with water,
ethanol and ultrapure water in sequence. Then, the GCE was
scanned between 0 and 2.0 V in 0.5 M H2SO4 at 100 mV s1 for
47
50 cycles to remove possible contaminations. Subsequently, an
aliquot of 5 mL of the colloid was cast on the GCE surface, and then
the solvent was evaporated under an infrared lamp. Finally, 5 mL of
Nafion solution was deposited on the electrode to improve film
stability and anions-resistant permselectivity. In this way, the GO/
MWCNTs/Nafion/GCE was thus obtained. For comparison, GO/GCE,
MWCNTs/GCE electrodes were also prepared using the same
procedures.
2.5. Procedure for electrochemical testing
The electrochemical tests were performed in a quartz beaker
containing a three-electrode setup at room temperature. Herein,
the modified GCE (the diameter of 5 mm) worked as the working
electrode, a saturated calomel electrode (SCE) as the reference
electrode and a platinum plate as counter electrode, with 60 mL of
0.1 M HAc–NaAc buffer solution (pH 4.5) as the electrolyte. For
differential pulse anodic stripping voltammetry (DPASV) test, a
modified electrode (GO/MWCNTs/Nafion/GCE) was immersed
into the electrolyte containing Bi3+ (500 mg L1) and other metal
ions under strong stirring to allow trace amounts of heavy metal
ions to be preconcentrated at the modified GCE electrode. The
deposition potential was chosen as 1.4 V and the preaccumu-
lation time was 180 s. After the preconcentration, the potential
was held at 1.4 V for 10 s under the static condition, followed by
a positive-going DPV scan (with a step increment of 5 mV,
amplitude of 50 mV, and pulse period of 0.2 s) from 1.4 V to
0.4 V. Prior to the next analysis, a preconditioning step (60 s at
0.4 V in stirred solution) was carried out in order to remove
residual metal ions on the surface of working electrode. For the
analysis of practical samples, 54 mL of electroplating effluent and
48 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
6 mL of 1.0 M acetate buffer (pH 4.5) were fully mixed, and
the resulting mixed solution served as the electrolytic solution.
The electroplating effluent was filtered with 0.22 mm membrane
before carrying out an electrochemical test.
3. Results and discussion
3.1. Characterizations of morphology and electronic structure of
GO–MWCNTs nanocomposites
GO can be dissolved in water, forming a brownish-yellow
hydrosol with high stability, as the picture of the leftmost bottle in
Scheme 1 shows. Due to the excellent hydrophilicity associated
with rich carboxyl and hydroxyl groups, the GO hydrosol remained
stable even after centrifuging at 12,000 rpm for 30 min. Instead, the
pristine MWCNTs tended to form precipitates because of the high
hydrophobicity and the strong Van der Waals force between
MWCNTs, as evidenced by the second bottle on the left shown in
Scheme 1. However, it is noteworthy that, after being fully mixed
and further treated according to our proposed method, the
as-obtained GO–MWCNTs hybrid nanocomposites displayed good
hydrophilicity and could be stably stored in an aqueous solution for
several months at room temperature, without resulting in any
precipitation (see the rightmost bottle in Scheme 1). Moreover, the
G-MWCNTs hybrid nanocomposites prepared via the direct
electrochemical reduction of the GO–MWCNTs materials in
aqueous solutions combine the conductivity of CNTs with the
partial hydrophilicity of GO, and own the strong ability to catch
metal ions through coordination reactions. Therefore, G-MWCNTs
hybrid nanomaterials are expected to be promising sensing
electrode materials for the ASV analyses, including DPASV, as
shown in Scheme 1.
The morphology and microstructure of as-prepared
GO–MWCNTs nanocomposites were investigated using TEM and
AFM. Fig. 1a shows that MWCNTs are dispersed well on the GO
nanosheets, presenting in the form of individual fibers, with the
length of 0.5–2 mm. Meanwhile, the GO sheets display large and
unfolded planes. Even though the brownish black dispersion was
centrifuged at 8000 rpm for 30 min, no obvious precipitate was
observed. Besides, a very strong sonication did not cause the
dispersion to separate into upper and lower phases, thereby
demonstrating the good water-solubility and the strong stability of
the present GO–MWCNTs nanocomposites. The AFM image shown
in Fig. 1b shows that the GO film is nearly composed of a single
layer of GO sheet, with the average thickness of 2 nm and the
planar size of ~1 mm. It is believed that the combination of 2D GO
sheets and 1D MWCNTs creates an interconnected framework, in
which the aggregation tendency between the MWCNTs is
effectively inhibited [34]. The presence of MWCNTs can greatly
enhance the conductivity of the hybrid nanocomposites and also
make the GO plane unfold, whereas, the GO components can give
the hybrid an important property to capture metal ions in aqueous
phase [35].
The electronic structure of carbon materials can be captured
with Raman spectroscopy, which is a fast and convincing
nondestructive tool to identify ordered and disordered crystal
structure of carbon [36]. The Raman spectra of carbon materials
have been reported to show the characteristic peaks at ~1350
cm1 (D band), 1580 cm1 (G band) and 2700 cm1 (2D band, also
labelled as G0 band), respectively [36]. D band is the defect peak
near 1350 cm1, which reflects the randomness of graphite layers,
such as amorphous carbon or specific vibrations at the edges
(e.g. oxides or CQC groups that appear only at the edges). G band
is usually assigned to the characteristic band of E2g phonon of C sp2
atoms, representing the symmetry and degree of crystallization of
carbon materials. And 2D band near 2700 cm1 originates from
two-phonon inelastic scattering. Fig. 2 shows the full (a) and local
enlarged (b) Raman spectra of MWCNTs, GO and GO–MWCNTs
hybrid samples, respectively. The Raman spectrum of MWCNTs
exhibits a strong D band at 1321.0 cm1, a moderate G band at
1574.7 cm1, and a weak 2D band at 2648.6 cm1, respectively. The
previous study shows that the D band of CNTs appears in the form
of weak peak [37]. The apparent difference in the peak intensity of
D band indicates the existence of more structural defects in the
as-prepared MWCNTs, possibly caused by using intense ultrasonic
waves, strong acid oxidization and the shorter MWCNTs. In order to
obtain high performance electrode materials with the larger
specific surface area, we purchased short-length MWCNTs and
further shortened their length by means of a 4 h acid treating
process. It is found that the shorter nanotubes tend to migrate in
water and are easy to incorporate with GO. As for the Raman
spectrum of GO, the intensity of D band is approximately equal to
that of G band. Obviously, the G band of GO is much higher in
intensity than G band of MWCNTs. However, as compared with
MWCNTs, the spectrum of GO shows a very weak and broadened
2D peak, implying that there exist considerable defects in the
resulting GO films. The results are in basic agreement with the
previous report [35]. For GO–MWCNTs hybrid materials, although
the strong D and G bands are observed, their peak positions are
shifted to the lower frequency as compared to those corresponding
to D and G bands of GO. It is observed more clearly from the
enlarged D and G bands (Fig. 2b) that, the D band is red-shifted by
1.1 cm1 while the G band is red-shifted by 11.4 cm1, which should
be due to the introduction of MWCNTs. In particular, it is
interesting to point out that the 2D band of the GO–MWCNTs
nanomaterials disappears. The significant changes in the intensity
of 2D band reveal that: (i) new structural defects were created in
the GO–MWCNTs nanocomposites, (ii) the combination of 1D CNTs
with 2D graphene sheets generated 3D carbon networks to some
extent. It is worth noting that, the ratios of the peak area of D to
that of G band (ID/IG), in the order from low to high, are GO
(ID/IG = 1.1), GO–MWCNTs (ID/IG = 1.2), and MWCNTs (ID/IG = 1.7),
suggesting that the GO and MWCNTs co-exist in the composites
and also confirming a fact that the GO–MWCNTs hybrid was
synthesized successfully.
The morphological characterizations and Raman spectra have
demonstrated that GO has been successfully mixed with MWCNTs,
but we want to understand how the two individual materials
interact with each other. In order to have a better understanding of
the problem, we measured UV–vis spectra of MWCNTs, GO and
GO–MWCNTs suspensions since the UV–vis spectrum is very
helpful for analyzing conjugated compounds and aromatic
compounds [22]. It is seen from Fig. 3 that the UV–vis spectrum
of GO exhibits two characteristic absorption peaks: a strong peak
in the region between 220 nm and 230 nm is assigned to the p–p*
transition of C C bonds, and a shoulder peak located around
300 nm is associated with the n–p* transition of carbonyl groups.
But for the MWCNTs after being treated with strong acid, a broad
and weak absorption peak at 225 nm related to p–p* transition
is observed. According to the relevant report [23], the UV–vis
spectrum of MWCNTs solution usually exhibits an unconspicuous
absorption peak related to its insolubility. However, herein the
weak absorption should originate from the small proportion
of water-soluble MWCNTs since the hydrophilicity has been
improved after acid treatment. Interestingly, except the peaks
located in 220–230 nm and at 300 nm, a new absorption peak can
be observed at 205 nm in the spectrum of GO–MWCNTs, which is
ascribed to the p–p covalent attractions between the basal plane
of GO and the nanowall of MWCNTs. In addition, the p–p*
transition was red-shifted by about 10 nm. This result is in
accordance with the result reported by Zhang’s group [23]. Thus, it
is concluded that the interaction between MWCNTs and GO in the
 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54 49

Fig. 1. (a) A typical low magnification TEM and (b) AFM images of GO–MWCNTs nanocomposites. Here the arrows point to the MWCNTs.

hybrid nanocomposites arises from the covalent interaction

between p–conjugated aromatic rings of both GO and MWCNTs.

3.2. Electrochemical characterization of GO–MWCNTs

nanocomposites

GO–MWCNTs hybrid nanocomposites can be electrochemically

reduced by carrying out repeated potential cycling in the potential
range between 0 V and 1.7 V in the deoxygenized HAc–NaAc (pH
4.5) buffer solution [37]. In the first potential scan, a large
reduction peak appeared at 1.5 V, as shown in Fig. 4a. Herein the
onset potential for the electrochemical reduction was 0.45 V. It is
obvious that the peak is attributed to the reduction of oxygen-
containing functional groups, such as hydroxyl and epoxy groups
produced during the synthetic process of GO via the Hummers
method. The large cathodic peak no longer appeared since the
second voltammetric cycle; meanwhile, the GO–MWCNTs nano-
composites could reach a stable state after three voltammetric
cycles. For comparison, a control experiment was performed using
a GO-modified GCE as the working electrode. As indicated in
Fig. 4b, the onset potential for the electrochemical reduction of GO
was 0.85 V, much more negative than that of the GO–MWCNTs
nanocomposites. Besides, the complete reduction of GO needed
more than 10 voltammetric cycles. These results clearly demon-
strate that the good conductivity of CNTs is very beneficial to the
reduction of GO. CNTs may act as conducting wires that connect

Fig. 2. (a) The comparison between Raman spectra of MWCNTs, GO and GO–
MWCNTs. They are scaled to have the same height of the D peak at about 1350 cm1.
(b) Magnification of D band and G band in the wavenumber range from 1200 cm1 Fig. 3. UV–vis absorption spectra of the as-prepared GO (dotted line), MWCNTs
to 1700 cm1. (dashed line) and GO–MWCNTs (solid line) dispersions.
50 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
Fig. 4. The first 10 cyclic voltammograms (CVs) at the scan rate of 50 mV s1 for the electrochemical reduction of GO–MWCNTs modified GCE (a) and GO modified GCE (b) in
0.1 M HAc-NaAc buffer solution (pH 4.5) saturated with nitrogen gas. The initial potential is 0.0 V.
the different GO sheets and accelerate the electron transfer rate
from one GO sheet to another GO sheet, thereby making the GO
components in the hybrid nanocomposites be reduced more easily.
The charge transfer rate at the electrode/solution interface can
be evaluated well by CV [38]. Here we compared the charge-
transfer behavior at the bare GCE and GO-, MWCNTs- and
G-MWCNTs-functionalized GCEs in 0.1 M KCl solution using the
[Fe(CN)6]3/4 couple as a redox probe. The recorded CVs are all
shown in Fig. 5. The CVs of a bare GCE show a quasi-reversible
redox process, with a peak potential difference (DEp) of 80 mV and
a ratio of about 1:1 between anodic and cathodic peak currents,
demonstrating that the GCE was a good reaction interface to the [Fe
(CN)6]3/4 couple [13]. However, for the GO-functionalized GCE,
both the anodic and cathodic peak currents were lowered
considerably, indicating that the charge transfer rate became slow
after the GCE was modified with GO nanomaterials. The reason is
that the poor conductivity of GO slowed the charge-transfer rate
at the modified electrode/solution interface. In contrast, the charge
transfer rates at MWCNTs- and G-MWCNTs-functionalized GCEs
Fig. 5. Cyclic voltammograms (CVs) of modified and unmodified GCEs in 0.1 M KCl
solution containing 5 mM K3Fe(CN)6 + 5 mM K4Fe(CN)6 at a scan rate of 50 mV s1.
had been speeded up in varying degrees, especially at the
G-MWCNTs-functionalized GCE. MWCNTs are able to facilitate
the electron transfer rate due to their high conductivity, without
question. But the reason why the charge transfer rate at the
G-MWCNTs-functionalized GCE is faster should be attributed to
the synergistic effect between graphene and MWCNTs, since the
introduction of CNTs provides a considerable number of electron
transport channels for the [Fe(CN)6]3/4 redox couple.
3.3. Stripping behavior for heavy metal ions
As mentioned above, the high conductivity and rich chelating
groups of the G-MWCNTs make the functionalized GCE compelling
for the electrochemical determination of heavy metal ions. To
enhance the stripping performance of G-MWCNTs-GCE, a bismuth
(Bi) film was in-situ formed on the surface of functionalized
electrode. Bi, known as an environmentally friendly material, is
used in a wide variety of cosmetics and medicines. In the earlier
study carried out by Wang et al. the presence of Bi film was found to
be beneficial to the acquirement of well-defined, single and sharp
stripping peaks for heavy metal ions in contrast to the
conventional Hg electrodes [9]. For this reason, here taking the
electrochemical detection of Pb2+ and Cd2+ ions as a typical
example, we firstly studied the influence of main experimental
variables on the detection sensitivity for acquiring the best
detection results.
The influence of pHs of buffer solutions on the stripping peak
currents was investigated in the pH range between 3.5 and 5.5 by
DPASV. It is seen clearly from Fig. 6a that, the stripping peak
currents were significantly influenced by the pH values of acetate
buffer solutions. A maximum DPASV peak current was observed at
about pH 4.5. The decrease of the currents at the pHs lower than
4.5 can be attributed to the protonation of the hydrophilic groups
on the graphene plane, and the decrease at the pHs higher than
4.5 is due to the hydrolysis of Pb2+ and Cd2+ ions. Thus, pH 4.5 was
chosen as the optimal pH for the analysis.
The influence of the deposition potential on the stripping peak
currents was studied in the potential region between 0.9 V and
1.5 V as shown in Fig. 6b. The more negative the preconcentration
potential, the more easily Pb2+ and Cd2+ ions were reduced, thereby
causing the obvious increase of the stripping peak currents.
 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
Fig. 6. The effects of solution pH (a), preconcentration potential (b), preconcentration time (c), and Bi3+ concentration (d) on the stripping currents of Cd2+ and Pb2+ ions at
Bi/G/MWCNTs/GCE electrode in 0.1 M acetate buffer solution containing 15 mg L1 of Cd2+ and Pb2+ ions.
Fig. 7. DPASV stripping signals for various concentrations (0.5, 5.0, 7.0, 10, 15, 25,
and 30 mg L1 from bottom to top) of Pb2+ and Cd2+ ions on the bismuth and Nafion
films modified G/MWCNTs/GCE. Inset shows the calibration curves of Pb2+ and Cd2+
ions. Supporting electrolyte: 0.1 M acetate buffer (pH 4.5) containing 500 mg L1 Bi3
+
; deposition potential: 1.4 V; deposition time: 180 s; amplitude: 50 mV;
increment potential: 5 mV; quiet time: 10 s.
51
However, when the preconcentration potential was more negative
than 1.3 V, the stripping peak currents decreased because of the
influence of hydrogen evolution reaction (HER). Considering that
the stripping peak potential of Zn was located at 1.3 V, a more
negative preconcentration potential (1.4 V) was selected in this
paper.
We also studied the effect of the deposition time, as shown in
Fig. 6c. It is found that the stripping peak current increased with
the increase of the deposition time. Here the choice of 180 s was a
compromise between reducing practical measurement time and
enhancing high sensitivity.
Finally, we investigated the effect of Bi3+ concentration on the
stripping response in the range of 0–700 mg L1, as shown in
Fig. 6d. As for the influence of Bi3+ ion concentration on the
stripping peak currents of Cd2+ and Pb2+ ions, in the case of using
G-MWCNTs-GCE, the peak currents for both Cd2+ and Pb2+ ions
increased rapidly upon increasing the Bi3+ concentration from
0 mg L1 to 500 mg L1 and then intended to be stable when the Bi3+
concentration was over 500 mg L1. In contrast, in the case of using
bare GCE, the optimal Bi3+ concentration was between 100 and
400 mg L1. This difference in the Bi3+ ion concentration caused by
using different types of working electrodes may be attributed to
the different morphologies and the microstructures of the two
electrodes. As compared with the clean and smooth surface of the
bare GCE, the surface of G-MWCNTs-GCE is covered with the
G-MWCNTs composite film, whose rough and hierarchical
structure provides more active sites for the nucleation of the
52 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54

Table 1
A comparison of the different methods reported for the detection of Cd2+ and Pb2+.

Analyte Electrode Modifier Method Deposition time (s) Linear range (mg L1) Detection limit (mg L1) Refs.
Cd2+ GCE G/Hg DPASV 500 0.2–15 0.005 [4]
GCE G/Bi DPASV 120 1.5–30 0.02 [6]
Screen printed MWCNTs/Bi DPASV 300 2–100 0.7 [18]
GCE Sn film DPASV 180 10–110 1.1 [41]
GCE G/MWCNTs/Bi DPASV 180 0.5–30 0.1 This work

Pb2+ Screen printed MWCNTs/Bi DPASV 300 2–100 1.3 [18]

GCE Amination of GO/Hg DPASV 180 0.00002–0.01 0.00002 [20]
GCE CN-Polymer DPASV 60 260–58730 165 [42]
GCE Polyaniline/Bi SWASV 120 5.0–30 3.3 [43]
GCE G/MWCNTs/Bi DPASV 180 0.5–30 0.2 This work

SWASV, square wave ASV; CN-Polymer, cyano groups modified Poly(diphenylamine co-2-aminobenzonitrile).

Fig. 8. (a) DPASV stripping signals for Zn2+, Cd2+, Pb2+ and Cu2+ ions with different concentrations (0.5, 5.0, 7.0, 10, 15, 25 and 30 mg L1 from bottom to top) on bismuth and
Nafion films modified G/MWCNTs/GCE. DPASV conditions are identical to those indicated in the caption of Fig. 6. (b) DPASV stripping signals for Zn2+, Cd2+, Pb2+ and Cu2+ ions
with the same concentration (15 mg L1) on bismuth film modified bare GCE and G/MWCNTs/GCE.

bismuth. It is expected that, as the deposition time went on, Bi film
would gradually become thick in a non-uniform growth manner
since the newly formed Bi atoms tended to preferentially deposit
on top of the nuclei already formed. In subsequent analytical tests,
the concentration of Bi3+ ions used to form the Bi film was
controlled at the level of 500 mg L1.
Under the optimized conditions, the DPASV experiments about
the simultaneous determination of Pb2+ and Cd2+ ions were
performed in 0.1 M acetate buffer by using the G-MWCNTs hybrid
modified GCE. The stripping peak currents for different concen-
trations of Pb2+ and Cd2+ ions, together with the calibration plots
for the simultaneous determination, were illustrated in Fig. 7. The
resulting calibration plot (see inset) for Pb2+ is observed to be linear
over the range from 0.5 mg L1 to 30 mg L1. The equation of
calibration curve is y = 0.1914x + 1.6709 (x: concentration/mg L1; y:
current/mA) with the correlation coefficient of R = 0.978. The limit
of detection is determined to be 0.2 mg L1 (S/N = 3) in the case of a
deposition time of 180 s, which is lower than the recommended
value of 10 mg L1 for Pb2+ in drinking water given by the World
Health Organization (WHO). Similarly, the calibration plot for Cd2+
is linear in the concentration range from 0.5 mg L1 to 30 mg L1.
The corresponding equation of calibration curve is y = 0.2358x
+ 2.0457 (x: concentration/mg L1,y: current/mA) with the
correlation coefficient of R = 0.983. The limit of detection is
0.1 mg L1 (S/N = 3) in the case of a deposition time of 180 s, which
is also lower than the guideline value of 3 mg L1 for Cd2+ in
drinking water given by the WHO. Compared to the MWCNTs or
graphene coated Bi film electrodes, the present analytical method
based on the G-MWCNTs functionalized GCE shows better
sensitivity under our laboratory conditions. It should be noted
that the baseline of the stripping peaks obtained using the
functionalized electrode is higher than the previous values
measured with the bare GCE, which should be attributed to the
increase of the electrochemically active surface, together with the
synergistic effect of MWCNTs and graphene [39]. A detailed
comparison between the analytical performances of different
modified electrodes was made (see Table 1). It is clear that the
G/MWCNTs/Bi electrode shows the lower limit of detection than
the MWCNTs/Bi electrode and the wider linear range than the G/Bi
electrode for the detection of Cd2+ and Pb2+ [6,18]. Moreover, our
analytical method is an environmentally friendly method, and the
limits of detection for Cd2+ and Pb2+ ions are both much lower than
the guideline values in drinking water given by the WHO. Although
the detection limit of G/Hg electrode for Cd2+ ion is reported to be
0.005 mg L1 (S/N = 3), an extremely low value [4], the disadvan-
tages of this analytical method include the long deposition time
(500 s) and the toxicity of Hg to human beings.
A significant advantage of the G-MWCNTs functionalized GCE
over other modified electrodes is that several heavy metal ions can be
determined simultaneously. We used the DPASV method to
investigate the feasibility to detect simultaneously trace amounts
of Zn2+, Cd2+, Pb2+ and Cu2+. Fig. 8a shows several groups of DPASV
stripping signals measured in the working solution containing Zn2+,
Cd2+, Pb2+ and Cu2+ ions. The four peaks corresponding to anodic
stripping of Zn2+, Cd2+, Pb2+ and Cu2+ were well resolved and the
corresponding peak currents increased with increasing the
 H. Huang et al. / Analytica Chimica Acta 852 (2014) 45–54
concentration of individual metal ions. Only the stripping peak of Zn2
+
was slightly distorted among four stripping peaks. If comparing the
peak current signals of Cd2+ and Pb2+ shown in Fig. 7 and Fig. 8a, it is
easy to find that the peak current signals of both Cd2+ and Pb2+ are
larger under the coexistence of Cd2+ and Pb2+ ions than under the
coexistence of Cd2+, Pb2+, Zn2+ and Cu2+ ions. This may be attributed
to the interaction effect between different metals.
In order to further show the outstanding advantages of the
G-MWCNTs functionalized GCE in simultaneous determination of
heavy metal ions, the DPASV curves for a bare GCE and a
functionalized GCE measured in the same solution containing
15 mg L1 of Zn2+, Cd2+, Pb2+ and Cu2+ ions were also shown in
Fig. 8b together. On the basis of DPASV results, only two heavy
metal ions, Cd2+ and Pb2+, give very small stripping peaks when
using the bare GCE as the working electrode. In contrast, four heavy
metal ions can be detected simultaneously and accurately by
means of the functionalized GCE, as demonstrated by the four
well-defined stripping peaks.
It should be pointed out that determination of Cu2+ by means of
Bi-film modified electrode remains two problems: (i) the Bi-film has
been already stripped before the appearance of the Cu peak [40], (ii)
the co-deposition phenomenon of different metals resulting from
the intrinsic nature of stripping voltammetry is commonly observed
for most electrodes, including Bi-film electrodes and Hg electrodes.
For instance, the co-deposition of Cu and Zn tends to form Cu-Zn alloy
compounds during electrochemical reduction.
The G-MWCNTs-GCE was also employed for the determination
of Pb2+ and Cd2+ ions in practical samples from electroplating
effluent. The water samples was filtered with a 0.22 mm membrane
(Millipore) filter before use, and then added to 0.1 M acetate buffer
(pH 4.5) containing 500 mg L1 Bi3+ ions. The average recovery for
Pb2+ ions was (98.3  2.6)% and that for Cd2+ ions was (99.1  2.5)%
(here 1.0 mg L1 standard Pb2+ or Cd2+ ions were added). The results
are basically satisfactory, which confirms from one side the
potential application value of the functionalized electrode in
determining trace amounts of heavy metal ions.
4. Conclusions
In conclusion, novel 3D G-MWCNTs hybrid nanocomposites
were fabricated via a simple and green method and their potential
application in the simultaneous determination of several heavy
metal ions were demonstrated. The G-MWCNTs hybrid electrode
materials can be conveniently prepared by means of the direct
electrochemical reduction of its precursors, GO–MWCNTs nano-
composites. As an ideal substitute for the poisonous HMDE and
TMFE electrodes, the G-MWCNTs modified GCE electrode exhibits
the high sensitivity for the electrochemical detection of trace
amounts of Pb2+ and Cd2+ ions, with the lowest detection
concentration of 0.5 mg L1 for Cd2+ and 0.5 mg L1 for Pb2+. In
particular, Zn2+, Cd2+, Pb2+ and Cu2+ ions may be determined
simultaneously by means of the novel modified electrode. The
greatly enhanced detection sensitivity is due to the synergistic
effect between MWCNTs and graphene components in improving
preconcentration efficiency of metal ions and accelerating electron
transfer rate at G-MWCNTs/electrolyte interface.
Acknowledgments
This work was supported by the National Research Foundation
for the Doctoral Program of Higher Education of China
(20120131110009), the National Science Foundation of China
(21373129, 21175059), and the Natural Science Foundation of
Shandong Province (ZR2010BQ029).
53
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