Synthetic Metals 220 (2016) 14–19

Contents lists available at ScienceDirect

Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Poly(3,4-ethylenedioxythiophene) nanorods/graphene oxide

nanocomposite as a new electrode material for the selective
electrochemical detection of mercury (II)
Yinxiu Zuoa,b,1, Jingkun Xua,1, Xiaofei Zhua , Xuemin Duana,* , Limin Lub,* , Yansha Gaoa ,
Huakun Xinga , Taotao Yanga , Guo Yea , Yongfang Yub
a
Shool of Pharmacy, Jiangxi Science and Technology Normal University, Nanchang 330013, PR China
b
College of Science, Jiangxi Agricultural University, Nanchang 330045, PR China

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

Article history:
Received 7 January 2016 Development of selective methods for the detection of mercury (Hg2+) has received tremendous
Received in revised form 17 May 2016 attention in modern chemical research due to its health hazard and persistence in environment. In this
Accepted 20 May 2016 paper, the electrochemical determination of Hg2+ at trace level based on poly(3,4-ethylenedioxythio-
Available online xxx phene) nanorods/graphene oxide nanocomposite modified glassy carbon electrode (PEDOT/GO/GCE) is
reported. PEDOT/GO nanocomposite has been proposed via a simple liquid–liquid interfacial
Keywords: polymerization approach. Scanning electron microscopy (SEM) and transmission electron microscope
Poly(3,4-ethylenedioxythiophene) (TEM) were employed to characterize the morphology and structure of the as-prepared PEDOT/GO. The
Graphene oxide
results revealed that PEDOT with a nanorods-like structure anchored on the surface of GO nanosheets,
Interfacial polymerization
which could enhance the electro-active sites of the nanocomposite. Differential pulse stripping
Electrochemical detection
Mercury ions voltammetry (DPSV) was applied to determine low concentrations of Hg2+ on PEDOT/GO/GCE.
Experimental conditions, including accumulation time, pH values and deposition potential were
optimized. In optimal conditions, a good linear relationship was found between peak currents and the
concentration of Hg2+ in 10.0 nM-3.0 mM range. The detection limit was estimated to be 2.78 nM at a
signal-to-noise ratio of 3. Finally, the applicability for Hg2+ determination in tap water samples was
successfully demonstrated.
ã 2016 Elsevier B.V. All rights reserved.

1. Introduction performance of solid electrode was greatly enhanced through

Toxic heavy metal in the environment is a growing threat to
humanity. Among them, mercury pollution has attracted extensive
attention because of its health hazard, accumulative and persis-
tence character in living organisms and environment [1,2]. Thus,
developing a high sensitivity, ease use and low cost method for Hg2
+
determination is necessary. Differential pulse stripping voltam-
metry (DPSV) has been deemed as a sensitive detection technology
for trace-level heavy metals as it involves unique accumulation/
preconcentration of analyte species contained in the solutions, and
then improve the detection sensitivity [3,4]. Moreover, the
* Corresponding authors.
E-mail addresses: duanxuemin@126.com (X. Duan), lulimin816@hotmail.com
(L. Lu).
1
These authors contributed equally to this work and should be considered co-
first authors.
the usage of chemically modified electrode.
Recently, graphene oxide (GO) has aroused increasingly
interests in fabricating various electrochemical sensors and
biosensor because of the similar structure to graphene [5,6].
Unlike graphene, there are plenty of oxygen-containing groups on
the graphene oxide (GO) sheet, which allows it disperse easily in
water and some other solvents [7]. Besides, the functional groups
on GO sheets can prevent carbon sheets from restacking and
agglomeration, and act as the combining sites for graphene-based
composite. In order to make full use of the advantages and
compensate for the poor conductivity of GO, several nanomaterials
are employed to combine with GO to form novel conducting
composites for various applications [8,9].
Recently, conducting polymer/GO nanocomposite have
attracted tremendous attentions and become a research focus,
because they possess both excellent properties of conducting
polymers and GO, such as high electric conductivity, long term

http://dx.doi.org/10.1016/j.synthmet.2016.05.022
0379-6779/ã 2016 Elsevier B.V. All rights reserved.
 Y. Zuo et al. / Synthetic Metals 220 (2016) 14–19
environmental stability, good electrochemical activity and
biocompatibility of conducting polymers [10], as well as unique
electrical and chemical properties of GO [11,12]. Among various
conducting polymers, PEDOT, a new polythiophene derivate, has
the merits of excellent environmental stability, low band gap,
excellent electrochemical activity, high electric conductivity, and
transparency in the doped state [13,14]. Synergistic properties like
enhanced properties in electrochemical cyclability and electrical
conductivity have shown based on PEDOT and GO composite, and
there are many good potential applications in many fields such as
energy storage, supercapacitors or electrochemical sensors and
biosensors for the detection of certain special substances. PEDOT/
GO nanocomposite were usually prepared by a noncovalent
mixing/adsorption route, in situ polymerization or electrodeposi-
tion techniques [15–17]. However, these methods generally yield
insoluble powders, and moreover, these composites showed
irregular structures, resulting in a decrease in the electrocatalytic
activity of the resulting composite.
Very recently, our group and Sun group have reported simple
liquid–liquid interfacial polymerization for the preparation of high
quality PEDOT/GO nanocomposite [18,19]. The obtained PEDOT/GO
nanocomposite exhibited good catalytic activity toward the
oxidation of rutin and nitrite due to the plenty of electro-active
sites of the nanocomposite. However, to the best of our knowledge,
electrochemical determination of heavy metal ions using PEDOT/
GO has not been reported. In this work, PEDOT/GO composite was
proposed via liquid/liquid interfacial polymerization, in which
EDOT monomer and GO were dispersed in organic phase and water
phase, respectively. It was found that such PEDOT/GO nano-
composite showed excellent catalytic activity toward Hg2+, leading
to a selective sensor for the detection of Hg2+. The detection limit
was calculated to be 2.78 nM with linear range 10.0 nM to 3.0 mM,
which is well below to previous report [20–25].
2. Experimental
2.1. Chemicals and reagents
Hg2+ stock solution was prepared by dissolving HgCl2 into
doubly deionized water with different concentrations. Acetate
buffer solution (ABS, 0.1 M, different pH) was obtained by mixing a
certain amount of 0.1 M CH3COOH and 0.1 M CH3COONa. GO was
received from Nanjing Xianfeng Nanomaterials Technology Co.,
Ltd. (Nanjing, China), 3,4-ethylenedioxythiophene (EDOT) was
received from Sigma-Aldrich. HgCl2 was purchased from Shanghai
Scheme 1. Schematic illustration for preparation of PEDOT/GO/GCE and electrochemical determination of Hg2+.
15
Vita Chemical Plant, China. Chloroform (CHCl3) and ferric chloride
(FeCl3) were received from Shanghai Chemical Co. Ltd. (Shanghai,
China). and CH3COONa and CH3COOH were purchased from
Aldrich. All these regents were received in analytical grade and
used without further purification. Doubly deionized water was
used in the whole experiments.
2.2. Apparatus
Transmission electron microscope (TEM) images were obtained
from JEM-3010 transmission electron microscope (JEOL Co., Ltd.,
Japan). Scanning electron microscopy (SEM) images were obtained
from Hitachi S–3000 N scanning electron microscope. The
electrochemical measurements were carried out on a CHI660D
electrochemical workstation (Shanghai, China) with conventional
three-electrode system. A bare glassy carbon electrode (GCE,
K = 3 mm) or modified GCE was used as the working electrode, a
platinum foil electrode as the counter electrode and a saturated
calomel electrode (SCE) as the reference electrode.
2.3. Preparation of the PEDOT/GO nanocomposite
The PEDOT/GO nanocomposite was prepared according to our
previous report [18]. To be briefly, 1 mL GO dispersion aqueous
(0.5 mg mL
1) was added with 1 mL FeCl3 (1 M) as oxidant. After
10 min sonication procedure, the above solution was slowly added
into 2 mL of EDOT solution in CHCl3 (25 mg mL
1) and an interface
was produced in the middle of two layers. The received mixture
was kept at 50  C under static conditions. The upper layer mixture
was centrifuged after 12 h reaction and the obtained precipitate
was washed with distilled water and ethanol a couple of times. The
obtained nanocomposite was collected for further experiments
(Scheme 1).
2.4. Preparation of the modified electrode
Prior to modification, GCE was polished with chamois leather
containing 0.05 mM alumina slurry, subsequently, the electrode
was rinsed with doubly distilled water, absolute ethanol and
doubly distilled water in an ultrasonic bath for 5 min each wash.
Then the drop-coating technique was used to fabricate electro-
chemical sensor by dropping an aliquot of 5 mL of the mixture on
the surface of GCE. After that, the drying step was performed under
an IR heat lamp. The obtained modified electrode was called as
PEDOT/GO/GCE.
16 Y. Zuo et al. / Synthetic Metals 220 (2016) 14–19
Fig. 1. SEM images of GO (A) and PEDOT/GO (B). TEM image (C) of the PEDOT/GO.
2.5. Differential pulse stripping voltammetric measurement of Hg2+ at
the modified electrodes
The differential pulse stripping voltammetry (DPSV) was
conducted in 0.1 M acetate buffer solution (ABS) (pH 5.0) in the
range from
0.1 V to + 0.5 V with optimized parameters: accumu-
lation time: 360 s, deposition potential:
0.2 V, amplitude: 50 mV,
potential step: 4 mV. Prior to the next determination, the modified
electrode was cleaned for 200 s at 0.6 V in ABS (pH 5.0). The results,
such as experimental conditions, optimized parameters, and
calibration curve, were subject to statistical analysis and were
presented as the mean  SD (standard deviation).
3. Result and discussion
3.1. Characterization of PEDOT/GO nanocomposite
SEM and TEM were used to investigate the surface morphology
and structure of PEDOT/GO nanocomposite. As can be observed
from the SEM image of GO (shown in Fig. 1A), it manifests
homogeneous, flexible and wrinkled sheets. For the PEDOT/GO
(shown in Fig. 1B), it can be seen that lots of PEDOT nanorods with
uniformly distributed on the surface of GO. The carboxyl, hydroxyl
and epoxide on the surface and edges on GO functioned as
recognition site to attract PEDOT [26–28]. The TEM image of
PEDOT/GO (shown in Fig. 1C) further showed the diameters and
lengths of PEDOT nanorods were in the range of 20–30 nm and
100–200 nm, respectively.
The detailed information of impedance changes after modifi-
cation was given through the electrochemical impedance spec-
troscopy (EIS) in 5 mM Fe(CN)63
/4
containing 0.1 M KCl.
Generally, the semicircle diameter at higher frequencies represents
Fig. 2. EIS of bare GCE (a), GO/GCE (b), PEDOT/GCE (c) and PEDOT/GO/GCE (d) in
5.0 mM K3Fe(CN)6/K4Fe(CN)6 (1:1) containing 0.1 M KCl.
the electron transfer resistance (Ret), and the linear part at lower
frequencies corresponds to the diffusion process [29]. As shown in
Fig. 2, the Ret value corresponding to the bare GCE was about 280 V
(a). When GO was modified onto the GCE (b), the semicircle
dramatically increased relative to the bare GCE (a), indicating a
high electron transfer resistance existed. However, compared with
bare GCE (a), the semicircle of PEDOT/GCE (c) decreased
distinctively, suggesting faster electron transfer kinetics of [Fe
(CN)6]3
/4
on the electrode surface. Furthermore, it can be seen
that the Ret value of PEDOT/GO/GCE (d) was between PEDOT/GCE
and GO/GCE, suggesting that PEDOT was successfully combined
with GO.
3.2. Electrochemical behaviors of Hg2+ at various electrodes
The electrochemical behaviors of Hg2+ on bare GCE (a), GO/GCE
(b), PEDOT/GCE (c) and PEDOT/GO/GCE (d) were investigated in
0.1 M ABS. As shown in Fig. 3, no obvious signal was observed on
GCE. While, weak peaks were observed on GO/GCE and PEDOT/GCE
at 0.17 V and 0.25 V, respectively, which were ascribed to absorbing
ability of carboxylic and hydroxyl on GO surface [30,31], and high
electric conductivity of PEDOT [32,33]. By contrast, a sharp peak
with increased current can be observed on PEDOT/GO/GCE at
0.18 V, which might be ascribed to the synergistic activity of PEDOT
(high electric conductivity) and GO (excellent catalytic activity)
and the large surface area of nanocomposite.
3.3. Optimization of experimental conditions
With the purpose of achieving high sensitivity for trace Hg2+
detection with PEDOT/GO/GCE, various experimental conditions,
including accumulation time, pH and deposition potential were
Fig. 3. DPSV curves at the bare GCE (a), GO/GCE (b) PEDOT/GCE (c) PEDOT/GO/GCE
(d) in the presence of 3.0 mM Hg2+ in 0.1 M ABS (pH 5.0). Deposition potential:

0.2 V, accumulation time: 360 s, pulse amplitude: 50 mV, pulse width: 50 ms.
 Y. Zuo et al. / Synthetic Metals 220 (2016) 14–19
optimized. The electrochemical analysis includes three steps: (i)
accumulation process; (ii) electrochemical reductive process; (iii)
electrochemical oxidative process [34]:
(i) adsorption process:
PEDOT/GO/GCE + Hg(II) (solution) ! PEDOT/GO/GCE Hg(II) (sur-
face)
(ii) electrochemical reductive process:
PEDOT/GO/GCE Hg(II) (surface) + 2e
! PEDOT/GO/GCE Hg(0)
(surface)
(iii) electrochemical oxidative process:
PEDOT/GO/GCE Hg(0) (surface) ! PEDOT/GO/GCE + Hg(II) (solu-
tion) + 2e

3.3.1. Optimization of accumulation time
The amount of the Hg2+ absorbed on the surface of modified
electrode was affected by accumulation time. Therefore, in order to
improve the detection sensitivity, the influence of accumulation
time on the peak current in
0.2 V was investigated. As it shown in
Fig. 4, the accumulation time was studied from 60 s to 500 s. Peak
currents of Hg2+ increased sharply with time increasing before
360 s. With the accumulation time further increased, the peak
current increased slowly, indicating that 360 s is relatively
sufficient to reach saturation on PEDOT/GO/GCE. Thus, 360 s was
selected to be the optimal accumulation time for Hg2+ detection.
3.3.2. Optimization of pH
As the effect of pH is vital to achieve high sensitivity, the effect
of pH on the voltammetric response was investigated in the pH
range from 3.0 to 6.0. As can be observed in Fig. 5, the stripping
peak currents of Hg2+ increased with pH value ranging from 3.0 to
5.0. While, the peak current was decreased with the further
increase of pH value. The decrease of peak current under pH 5.0
might be due to the competitive binding of proton ion and Hg2+ to
the combining groups on the surface of PEDOT/GO, The decrease
over the pH 5.0 was attributed to the hydrolysis of Hg2+ [35].
Therefore, pH 5.0 was selected as the optimal pH in this work.
3.3.3. Optimization of deposition potential
The effect of deposition potential is very essential to achieve
high sensitivity. Thus, the effect of deposition potential was
investigated by applying varying potential. As can be observed in
Fig. 6, the peak currents increased and reached a maximum at
potential
0.2 V with deposition potential shifts from 0.2 V to
Fig. 4. DPSV carried out on the PEDOT/GO/GCE in the presence of 5.0 mM Hg2+ in
0.1 M ABS of different accumulation time (pH 4.5, deposition potential:
0.2 V).
17
Fig. 5. DPSV carried out on the PEDOT/GO/GCE in the presence of 5.0 mM Hg2+ in
0.1 M ABS with different pH (deposition potential:
0.2 V, accumulation time:
360 s).

0.2 V. However, the peak currents decreased with deposition
potential varying from
0.2 V to
0.4 V, and decreased slightly
with the potential shifted from
0.4 V to
0.5 V. The decreased
peak currents might be attributed to the fact that PEDOT was
partially de-doped. [36–40]. PEDOT has good electronic conduc-
tivity in its doped state. The higher doping level can result in higher
electrical conductivity of PEDOT [41–43]. However, the degree of
doping level decreased when negative deposition potential was
applied, leading to a decreased conductivity. So,
0.2 V was the
optimal accumulation potential for the Hg2+ detection.
3.4. Electrochemical determination of Hg2+
Under the optimized conditions, DPSV was used for the
electrochemical detection of Hg2+ at different concentrations on
the PEDOT/GO/GCE. From Fig. 7, it can be observed that the well-
defined peak currents increased linearly with the increased
concentration of Hg2+ in the range from 10.0 nM to 3.0 mM and
the corresponding linear regression equation was represented as y
(mA) = 6.7445 x + 0.0432 with the correlation coefficients of 0.9978
(inset of Fig. 7). The detection limit for Hg2+ was calculated to be
2.78 nM. Thus, the PEDOT/GO/GCE method exhibited a wide
concentration range with a low detection limit for the detection of
Hg2+.
Fig. 6. DPSV carried out on the PEDOT/GO/GCE in the presence of 5.0 mM Hg2+ in
0.1 M ABS with different deposition potential (pH 5.0, accumulation time: 360 s).
18 Y. Zuo et al. / Synthetic Metals 220 (2016) 14–19
Fig. 7. DPSV responses of the PEDOT/GO/GCE for the detection of different
concentrations of Hg2+ (from a to m are 10 nM, 30 nM, 60 nM, 90 nM, 150 nM,
0.3 mM, 0.5 mM, 0.7 mM, 0.9 mM, 1.5 mM, 2.0 mM, 2.5 mM, 3.0 mM) in 0.1 M ABS (pH
5.0); Insert: The corresponding linear calibration plots of stripping peak currents for
Hg2+.
3.5. Interference study, reproducibility and stability
The interferences which may compete with Hg2+ on the surface
of the modified electrode during deposition, were investigated to
evaluate the selectivity of PEDOT/GO/GCE to Hg2+. In this
experiment, 3.0 mM Hg2+ and 50-fold concentration interference
ions, including Mn2+, Ca2+, Pb2+, Co2+, Mg2+, Cu2+, Ni2+ and Zn2+
were used. As can be seen from Fig. 8, these potential co-exist ions
did not interfere significantly during Hg2+ determination and these
ions did not show any stripping peaks in the potential window,
even though the stripping peak potential of Cu2+ is close to that of
Hg2+. These indicated good selectivity of Hg2+ with the existance of
potential interference and confirmed its practicability in real
sample analysis. The good selectivity of the modified electrode is
largely attributed to the fact that Hg2+ has high affinity for the
“soft” donor sulfur in thiophene rings of PEDOT [44,45].
Reproducibility is an important parameter for precise analytical
measurements, hence, 3.0 mM Hg2+ was successively measured for
30 times under identical conditions. The relative standard
deviation (RSD) was calculated to be 4.68%, which indicated the
good reproducibility of the proposed method. Also, to evaluate the
long-term stability of PEDOT/GO/GCE, it was stored in the air at
Fig. 8. Effect of interference ions on the electrochemical stripping signals of 3.0 mM
Hg2+ at PEDOT/GO/GCE. Electrochemical stripping signals (1, 2, and 3) of 3.0 mM Hg2
+
at the same PEDOT/GO/GCE after the investigation for interference.
Table 1
Recovery measurements of the Hg2+ in the tap water samples using the modified
electrode (n = 3).
Samples Hg (II) (nM) Recovery (%) RSD (%)
Added Found
Tap water 1 10 9.7 97.0 2.3
Tap water 2 30 29.6 98.7 2.5
Tap water 3 50 51.4 102.8 1.4
room temperature and used for detection of Hg2+ daily over
consecutive 4 weeks. The results indicated the changes of signal
current were less than 6.4% for Hg2+, which confirmed its excellent
long-term stability.
3.6. Real sample analysis
For the evaluation of its applicability in real sample is necessary,
the fabricated PEDOT/GO/GCE was used for the determination of
Hg2+ in tap water samples. The real samples were diluted with
0.2 M ABS (pH 5.0) in a ratio of 1:1. No obvious signals were
observed during experiment procedure. Subsequently, after
standard Hg2+ solutions with different concentrations were added
to pretreated samples, well-defined stripping peaks can be
observed in the potential window. As can be seen from Table 1,
the recoveries in the range from 97.0% to 102.8% were obtained,
indicated that the present electrode could be efficiently applied for
Hg2+ detection in real samples.
4. Conclusions
In summary, liquid–liquid interfacial polymerization method
for preparing a PEDOT/GO hybrid nanocomposite modified
electrode was proposed and the modified electrode was used
for highly selective electrochemical sensing of Hg2+. SEM and TEM
images demonstrated that PEDOT with a nanorods-like structure
was attached on the surface of GO sheets, which could provide
many electro-active sites. The GCE modified with PEDOT/GO
showed high electrocatalytical activity toward Hg2+ and exhibited
good selectivity, wide liner range and good long-term stability. The
proposed method was also successfully applied to detect Hg2+ in
tap water samples.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (51272096 and 51302117), the Natural Science Foundation of
Jiangxi Province (20122BAB216011 and 20151BAB203018), the
Science and Technology Landing Plan of Universities in Jiangxi
province (KJLD12081 and KJLD14069), State Key Laboratory of
Chemical Biosensing & Chemometrics (2015010), Postdoctoral
Science Foundation of China (2014M551857 and 2015T80688) and
Postdoctoral Science Foundation of Jiangxi Province (2014KY14)
for their financial support of this work.
References
[1] E.M. Nolan, S.J. Lippard, Tools and tactics for the optical detection of mercuric
ion, Chem. Rev. 108 (2008) 3443–3480.
[2] B. Ceken, M. Kandaz, A. Koca, Electrochemical metal-ion sensors based on a
novel manganese phthalocyanine complex, Synthetic Met. 162 (2012)
1524–1530.
[3] D.W. Pan, Y.E. Wang, Z.P. Chen, T.T. Lou, W. Qin, Nanomaterial/ionophore-based
electrode for anodic stripping voltammetric determination of lead: an
electrochemical sensing platform toward heavy metals, Anal. Chem. 81 (2009)
5088–5094.
[4] P. Salaun, C.M.G. van den Berg, Voltammetric detection of mercury and copper
in seawater using a gold microwire electrode, Anal. Chem. 78 (2006)
5052–5060.
 Y. Zuo et al. / Synthetic Metals 220 (2016) 14–19
[5] H.L. Wang, Q.L. Hao, X.J. Yang, L.D. Lu, X. Wang, Graphene oxide doped
polyaniline for supercapacitors, Electrochem. Commun. 11 (2009) 1158–1161.
[6] Y. Liu, D.S. Yu, C.Z. Zeng, C. Miao, L.M. Dai, Biocompatible graphene oxide-
based glucose biosensors, Langmuir 26 (2010) 6158–6160.
[7] S. Stankovich, R.D. Piner, X. Chen, N. Wu, S.T. Nguyen, R.S. Ruoff, Stable aqueous
dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite
oxide in the presence of poly(sodium 4-styrenesulfonate), J. Mater. Chem. 16
(2006) 155–158.
[8] Z. Yang, J. Xiao, J.Y. Wan, Z.G. Liu, T.T. Cao, W.J. Zhang, H.X. Wang, Graphene
oxide/carbon dot composite: a new photoelectrode material for photocurrent
response enhancement, Phys. Chem. Chem. Phys. 17 (2015) 32283–32288.
[9] Q. Zhang, D.M. Zhang, Y.L. Lu, G. Xu, Y. Yao, S. Li, Q.J. Liu, Label-free amino acid
detection based on nanocomposites of graphene oxide hybridized with gold
nanoparticles, Biosens. Bioelectron. 77 (2016) 963–970.
[10] A.M. Nardes, M. Kemerink, R.A.J. Janssen, J.A.M. Bastiaansen, N.M.M. Kiggen, B.
M.W. Langeveld, A.J.J.M. Van Breemen, M.M. de Kok, Microscopic
understanding of the anisotropic conductivity of PEDOT:PSS thin films, Adv.
Mater. 19 (2007) 1196–1200.
[11] J.H. Li, D.Z. Kuang, Y.L. Feng, F.X. Zhang, Z.F. Xu, M.Q. Liu, A graphene oxide-
based electrochemical sensor for sensitive determination of 4-nitrophenol, J.
Hazard. Mater. 201 (2012) 250–259.
[12] Y.W. Zhu, S. Murali, W.W. Cai, X.S. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Graphene
and graphene oxide: synthesis, properties, and applications, Adv. Mater. 22
(2010) 3906–3924.
[13] F. Jonas, D. Freitag, H. Pielartzik, J.R. Reynolds, Poly(3,4-
ethylenedioxythiophene) and its derivatives: past, present, and future, Adv.
Mater. 12 (2000) 481–494.
[14] H.J. Ahonen, J. Lukkari, J. Kankare, n- and p-doped poly(3,4-
ethylenedioxythiophene): two electronically conducting states of the
polymer, Macromolecules 33 (2000) 6787–6793.
[15] Y. Han, B. Ding, H. Tong, X. Zhang, Capacitance properties of graphite oxide/
poly(3,4-ethylene dioxythiophene) composites, J.Appl. Polym. Sci. 121 (2011)
892–898.
[16] H. Bai, K. Sheng, P. Zhang, C. Li, G. Shi, Graphene oxide/conducting polymer
composite hydrogels, J. Mater. Chem. 21 (2011) 18653–18658.
[17] X.L. Luo, C.L. Weaver, S.S. Tand, X.Y.T. Cui, Pure graphene oxide doped
conducting polymer nanocomposite for bio-interfacing, J. Mater. Chem. B 1
(2013) 1340–1348.
[18] K.X. Zhang, J.K. Xu, X.F. Zhu, L.M. Lu, X.M. Duan, D.F. Hu, L.Q. Dong, H. Sun, Y.S.
Gao, Y. Wu, Poly(3,4-ethylenedioxythiophene) nanorods grown on graphene
oxide sheets as electrochemical sensing platform for rutin, J. Electroanal.
Chem. 739 (2015) 66–72.
[19] S. Liu, J.Q. Tian, L. Wang, Y.L. Luo, X.P. Sun, Production of stable aqueous
dispersion of poly(3,4-ethylenedioxythiophene) nanorods using graphene
oxide as a stabilizing agent and their application for nitrite detection, Analyst
136 (2011) 4898.
[20] P. Kanchana, N. Sudhan, S. Anandhakumar, J. Mathiyarasu, P. Manisankar, C.
Sekar, Electrochemical detection of mercury using biosynthesized
hydroxyapatite nanoparticles modified glassy carbon electrode without
preconcentration, RSC Adv. 5 (2015) 68587–68594.
[21] M. Heitzmann, L. Basaez, F. Brovelli, C. Bucher, D. Limosin, E. Pereira, B.L. Rivas,
G. Royal, E. Saint-Aman, J.C. Moutet, Voltammetric sensing of trace metals at a
poly(pyrrole-malonic acid) film modified carbon electrode, Electroanal 17
(2005) 1970–1976.
[22] I. Cesarino, E.T.G. Cavalheiro, Thiol-Functionalized silica thin film modified
electrode in determination of mercury ions in natural water, Electroanal 20
(2008) 2301–2309.
[23] J. Gong, T. Zhou, D. Song, L. Zhang, X. Hu, Stripping voltammetric detection of
mercury(II) based on a bimetallic Au-Pt inorganic-organic hybrid
nanocomposite modified glassy carbon electrode, Anal. Chem. 82 (2010)
567–573.
19
[24] W. Deng, Y. Tan, Y. Li, Y. Wen, Z. Su, Z. Huang, S. Huang, Y. Meng, Q. Xie, Y. Luo, S.
Yao, Square wave voltammetric determination of Hg(II) using thiol
functionalized chitosan-multiwalled carbon nanotubes nanocomposite film
electrode, Microchim. Acta 169 (2010) 367–373.
[25] Z.Q. Zhao, X. Chen, Q. Yang, J.H. Liu, X.J. Huang, Selective adsorption toward
toxic metal ions results in selective response: electrochemical studies on a
polypyrrole/reduced graphene oxide nanocomposite, Chem. Commun. 48
(2012) 2180–2182.
[26] W. Lei, W.M. Si, Y.J. Xu, Z.Y. Gu, Q.L. Hao, Conducting polymer composites with
graphene for use in chemical sensors and biosensors, Microchim. Acta 181
(2014) 702–722.
[27] S. Chen, J. Zhu, X. Wu, Q. Han, X. Wang, Graphene oxide-MnO2 nanocomposites
for supercapacitors, ACS Nano 4 (2010) 2822–2830.
[28] C. Xu, X. Wang, J. Zhu, X. Yang, L. Lu, Deposition of Co3O4 nanoparticles onto
exfoliated graphite oxide sheets, J. Mater. Chem. C 18 (2008) 5625–5629.
[29] W. Yan, R. Yang, Y.X. Zhang, L. Wang, J.H. Liu, X.J. Huang, High adsorptive c-
AlOOH(boehmite)@SiO2/Fe3O4 porous magnetic microspheres for detection of
toxic metal ions in drinking water, Chem. Commun. 47 (2011) 11062–11064.
[30] J.J. Shao, W. Lv, Q.H. Yang, Self-assembly of graphene oxide at interfaces, Adv.
Mater. 26 (2014) 5586–5612.
[31] L. Cui, J. Wu, H.X. Ju, Electrochemical sensing of heavy metal ions with
inorganic, organic and bio-materials, Biosens. Bioelectron. 63 (2015) 276–286.
[32] M. Giannetto, G. Mori, F. Terzi, C. Zanardi, R. Seeber, Composite PEDOT/Au
nanoparticles modified electrodes for determination of mercury at trace levels
by anodic stripping voltammetry, Electroanal 23 (2011) 456–462.
[33] H. Shi, C.C. Liu, Q.L. Jiang, J.K. Xu, Effective approaches to improve the electrical
conductivity of PEDOT:PSS: a review, Adv. Electron. Mater. 10 (2015), doi:
http://dx.doi.org/10.1002/aelm.201500017.
[34] A. Chira, B. Bucur, M.P. Bucura, G.L. Radu, Electrode-modified with
nanoparticles composed of 4,40 -bipyridine-silver coordination polymer for
sensitive determination of Hg(II), Cu(II) and Pb(II), N. J. Chem. 38 (2014)
5641–5646.
[35] W.S. Zhou, C.H. Li, C. Sun, X.D. Yang, Simultaneously determination of trace Cd2
+
and Pb2+ based on L-cysteine/graphene modified glassy carbon electrode,
Food Chem. 192 (2016) 351–357.
[36] A. Laforgue, All-textile flexible supercapacitors using electrospun poly(3,4-
ethylenedioxythiophene) nanofibers, J. Power Sour. 196 (2011) 559–564.
[37] X.W. Chen, O. Ingana, Three-step redox in polythiophenes: evidence from
electrochemistry at an ultramicroelectrode, J. Phys. Chem. 100 (1996)
15202–15206.
[38] A.R. Hillmana, S.J. Daisleya, S. Bruckensteinb Kinetics and mechanism of the
electrochemical p-doping of PEDOT, Electrochem. Commun. 9 (2007)
1316–1322.
[39] F. Tran-Van, S. Garreau, G. Louarn, G. Froyerb, C. Chevrot, Fully undoped and
soluble oligo (3,4-ethylenedioxythiophene) s: spectroscopic study and
electrochemical characterization, J. Mater. Chem. 11 (2001) 1378–1382.
[40] A.R. Hillman, S.J. Daisley, S. Bruckenstein, Solvent effects on the electrochemical
p-doping of PEDOT, Phys. Chem. Chem. Phys. 9 (2007) 2379–2388.
[41] T.A. Skotheim, Handbook of Conducting Polymer, Marcel Dekker, New York,
1986.
[42] T.A. Skotheim, R.L. Elsembaumer, J.R. Reynolds, Handbook of Conducting
Polymer, Second Ed, Marcel Dekker, New York, 1998.
[43] H.A.M. van Mullekom, J.A.J.M. Vekemans, E.E. Havinga, E.W. Meijer,
Developments in the chemistry and band gap engineering of donor-acceptor
substituted conjugated polymers, Mater. Sci. Eng.: R: Rep. 32 (2001) 1–40.
[44] H.C. Tai, C. Lim, Computational studies of the coordination stereochemistry
bonding, and metal selectivity of mercury, J. Phys. Chem. A 110 (2006) 452–462.
[45] S. Botasini, G. Heijo, E. Méndez, Toward decentralized analysis of mercury (II)
in real samples. A critical review on nanotechnology-based methodologies,
Anal. Chim. Acta 800 (2013) 1–11.