Chemical Engineering Journal 299 (2016) 150155

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Chemical Engineering Journal

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

An electrochemical sensor based on phytic acid functionalized

polypyrrole/graphene oxide nanocomposites for simultaneous
determination of Cd(II) and Pb(II)
Hongxiu Dai, Nan Wang, Donglei Wang, Houyi Ma , Meng Lin
Key Laboratory for Colloid and Interface Chemistry of State Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China

h i g h l i g h t s

PPy/GO nanocomposites were simply and rapidly prepared by in situ polymerization.

The PPy/GO nanocomposites were functionalized with PA by electrostatic attraction.

The PA/PPy/GO modified electrode exhibited a high sensitivity for Cd(II) and Pb(II) detection.

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

Article history: An electrochemical sensor was developed for detecting heavy metal ions by using a phytic acid function-
Received 23 February 2016 alized polypyrrole (PPy)/graphene oxide (GO) modified electrode. PPy/GO nanocomposites were synthe-
Received in revised form 12 April 2016 sized by in situ chemical oxidation polymerization. The PPy/GO nanocomposites were functionalized with
Accepted 16 April 2016
phytic acid (PA) molecules by electrostatic attraction. The structural features of the fabricated nanocom-
Available online 22 April 2016
posites were confirmed by transmission electron microscopy (TEM), attenuated total reflection infrared
(ATR-IR) spectroscopy and Raman spectroscopy. The PA/PPy/GO modified electrode exhibited high elec-
Keywords:
trochemical conductivity, and produced a remarkable increase in peak current compared with the PPy/
Phytic acid
Polypyrrole
GO and PA/GO modified electrodes. The developed sensor was used for the electrochemical analysis of
Graphene oxide various trace metal ions by differential pulse voltammetry (DPV). The modified electrode demonstrated
Electrochemical detection to measure Cd(II) and Pb(II) with a linear working range of 5150 lg/L. This work demonstrated a simple,
Heavy metal ions rapid and high performing electrochemical strategy for high-sensitivity detection of heavy metal ions.
2016 Elsevier B.V. All rights reserved.

1. Introduction of sensors; therefore to improve electrochemical behaviors of the

The discharge of heavy metals ions into the natural environ-
ment has become a serious problem with the improvement of liv-
ing standards [1]. Electrochemical detection of heavy metal ions
presented several advantages such as simplicity, accurateness,
inexpensive, prominent sensitivity, high stability and high selectiv-
ity for the application of the health care, food industry, agriculture,
environment, and other fields [2,3]. Differential pulse anodic strip-
ping voltammetry (DPASV) has been widely deemed to a forceful
technique for the detection of heavy metal ions due to an effective
preconcentration process followed by electrochemical dissolution
test of the accumulated heavy metal ions [4]. Electrode materials
play important roles to enhance the determination performance
Corresponding authors.
E-mail addresses: hyma@sdu.edu.cn (H. Ma), mlin@sdu.edu.cn (M. Lin).
electrode materials is a focus of research for electrochemical sen-
sors [5].
Since the first created conductive polyacetylene in 1970s, con-
jugated conducting polymers (e.g., polyacetylene, polypyrrole and
polyaniline) have received increasing attentions from biosensor,
electroluminescent materials, supercapacitors, and so on [6,7].
PPy, one of the most significant conducting polymers, presented
several advantages such as easy synthesis, stability, inexpensive
and relatively high conductivity [8,9]. However, PPy usually suffer
from serious aggregation resulting from the intermolecular inter-
action and contained the defects of poor dispersion and machin-
ability [10]. One way to conquer these drawbacks is to deposit
PPy on a carbon-based material [11,12]. Owing to the high specific
surface area, chemical stability, high p-conjugation and hydrophi-
lic properties, GO can offer an excellent electrode platform for
adsorbing other molecules [13,14]. PPy, the presence of p bond

http://dx.doi.org/10.1016/j.cej.2016.04.083
1385-8947/ 2016 Elsevier B.V. All rights reserved.
 H. Dai et al. / Chemical Engineering Journal 299 (2016) 150155
on the pyrrole ring, can be adsorbed on the surface of the GO by the
pp stacking interactions, hydrogen bond and van der Waals inter-
actions [15]. Nanocomposites based on PPy and GO have displayed
synergistic properties like enhancement in electrical conductivity
and dispersibility of the conducting polymer [16]. Recently, in
most of the instances preparation of PPy/GO nanocomposites are
done by in situ polymerization technique that equably mixing pyr-
role monomer and GO, and the PPy/graphene composites were
simply and rapidly synthesized by using GO as a chemical oxidant
at a temperature over 90 C [17,18]. The method did not introduce
impurities, but it needed a high temperature. Bose et al. [19]
reported that PPy/graphene nanocomposites were fabricated via
in situ polymerization followed by chemical reduction using hydra-
zine monohydrate at the room temperature. However, the PPy/GO
nanocomposites cannot satisfy various requirements. Synergistic
properties between the disparate components could improve the
performance of the materials. In order to expand the application
range, the functional materials (e.g. metal oxides and biomole-
cules) combine with the PPy/GO nanocomposites should be highly
expected [20,21].
Due to the significant properties, such as biocompatible, non-
toxic and environment friendly, interest in the electroanalytical
application of phytic acid modified electrodes has surged [22,23].
Herein, we report an electrochemical metal ions sensor based on
a phytic acid functionalized PPy/GO nanocomposites modified
electrode (Scheme 1). PPy/GO nanocomposites were simply and
rapidly prepared by in situ polymerization with the ferric chloride.
Phytic acid was adsorbed on the surface of PPy/GO nanocomposites
by electrostatic attraction. The presence of PA and PPy on the elec-
trode surface could enhance the electrochemical activity of the
electrode, and the results showed that the PA/PPy/GO nanocom-
posite modified electrode offered a remarkable electrochemical
response for the detection of Cd(II) and Pb(II) in aqueous solution.
2. Experimental
2.1. Reagents and apparatus
Pyrrole (Py, 98%) was purchased from Sinopharm Chemical
Reagent Co. Ltd and was distilled and kept in a refrigerator at
4 C. Nafion solution (5 wt%), phytic acid (PA, 90%) and standard
solutions of metal ions were purchased from Aladdin (Shanghai,
China). All chemicals were of reagent grade and used without fur-
ther purification. A 0.1 M acetic acidsodium acetate (HAc/NaAc)
buffer solution (pH 4.5) containing 300 lg/L Bi(III) served as a sup-
porting electrolyte during the analysis of metal ions. Ultrapure
water (P18 MX cm) was used throughout the experiments, and
all solutions were freshly prepared.
Scheme 1. Schematic diagram for the synthesis of the PA/PPy/GO nanocomposites and the electrochemical detection of heavy metal ions.
151
Electrochemical measurements that included differential pulse
voltammetry (DPV) and cyclic voltammetry (CV) were performed
on a CHI760C workstation (Chenhua Instruments, China) with a
conventional three-electrode system. Attenuated total reflection
infrared (ATR-IR, Thermo Nicolet, USA) spectroscopy and Raman
spectroscopy (QE65000) were used to confirm the structural mod-
ification of the electrode. The morphology of the nanocomposites
was characterized by transmission electron microscope (TEM,
JEM-2100).
2.2. Preparation of the PA/PPy/GO nanocomposites
GO was fabricated according to the Hummers method by the
exfoliation of natural graphite [24,25]. As-purified GO nanosheets
were dispersed in water giving a yellow-brown dispersion with a
concentration of 0.5 mg/mL. Then 30 lL of pyrrole was added into
a 40 mL GO solution by magnetic stirring for more than 1 h. Subse-
quently, 20 mL oxidation agent solution containing 0.32 g FeCl3-
6H2O added into the mixture. After stirring for 4 h at 04 C, the
resulting sample was filtered and washed with ethyl alcohol and
deionized water, and dried at 45 C for 12 h under vacuum. In order
to obtain PA/PPy/GO nanocomposites, the PPy/GO nanocomposites
(5 mg) were dispersed into 5 mL 0.01 M PA solution and sonicated
for 2 h to form a stable PA/PPy/GO nanocomposites suspension. For
comparison, the pure PPy and PA/PPy nanocomposites were pre-
pared by using same processes without GO.
2.3. Fabrication of the sensor and electrochemical measurements
Prior to use, a bare glassy carbon electrode (GCE, diameter:
5 mm) was polished with 1.0 lm, 0.3 lm and 0.05 lm alumina
slurry, respectively, and washed ultrasonically with deionized
water, ethanol and ultrapure water in sequence. Then, the GCE
was scanned by CV between 0.3 V and 1.5 V in 0.5 M H2SO4 at
100 mV/s for 40 cycles. Subsequently, 10 lL of the PA/PPy/GO
nanocomposites dispersion was dropped onto the surface of GCE,
and dried under an infrared lamp. In order to improve the stability
of the PA/PPy/GO film, 5 lL of Nafion solution (1%) was coated on
the modified electrode.
The electrochemical measurements were performed in a three-
electrode cell with a modified electrode as the working electrode, a
saturated calomel electrode (SCE) as the reference electrode, and a
Pt plate with a surface area of 1 cm2 as the counter electrode. For
pre-concentration step, the PA/PPy/GO nanocomposites modified
electrode was immersed into a 0.1 M HAc/NaAc buffer solution
containing various concentration of metal ions (Cd(II), Pb(II)), and
then accumulation and reduction of metal ions into metal under
a constant potential at 1.2 V for 200 s. Then, the electrochemical
152 H. Dai et al. / Chemical Engineering Journal 299 (2016) 150155

response was measured by DPV with a step increment of 5 mV,

amplitude of 50 mV, and pulse period of 0.2 s from 1.0 V to 0.4 V.

3. Results and discussion

3.1. Preparation of the PA/PPy/GO nanocomposites

3.1.1. TEM images

Fig. 1 illustrates the TEM images of GO, PPy/GO and PA/PPy/GO.
As shown in Fig. 1a irregular sheet-like GO with a crimple and fold
effect can be observed. Due to the excellent rich hydroxyl, carboxyl
and epoxide groups, GO can be easily dissolved in water by the
method of ultrasonic, forming a steady brownish-yellow hydrosol.
Pyrrole monomer can be adsorbed to the surface of GO nanosheets
by the pp aromatic interactions and electrostatic adhesion. After
in situ chemical polymerization by the effect of ferric iron, the PPy
uniformly covered the surface of GO sheets (Fig. 1b). The PPy poly-
merization is an oxidation or doping process, and FeCl3 acts as not
only an oxidizing agent, but also a dopant. The anion (Cl) doped
into the PPy during the process of polymerization in order to bal-
ance the positive charge on the polymer [26]. PA has six phos-
phates groups attached symmetrically to a cyclohexanehexol ring
which is liable to interact with positively charged materials [27].
Through an ultrasonic mixing method, PA molecular could instead
of the Cl doped into the polymer matrix. A darker-colored nano-
sheet of PA/PPy/GO composites displays in Fig. 1c, indicating PA
was well combined with PPy/GO nanocomposites. This conclusion
can be approved by ATR-IR spectroscopy and Raman spectroscopy.
3.1.2. ATR-IR spectroscopy
Fig. 2 shows the ATR-IR spectra of GO, PPy/GO and PA/PPy/GO
films. The ATR-IR spectrum of the GO displays a very wide and
strong intensity of vibration peaks of OAH groups at 3478 cm1,
and the C@O stretching in COOH, C@C stretching, and CAO stretch-
ing in CAOH and CAOAC functional groups are analyzed from the
peaks located at 1726, 1623, 1230 and 1064 cm1, respectively
[16,28]. After polymerization with pyrrole, the peaks at 1623,
1726 and 3478 cm1 resulting from GO are significantly character-
less in the spectrum of PPy/GO. The peaks at 2927 and 2848 cm1
come from the asymmetric stretching and symmetric vibrations of
ACH2 [29], and the peak at 1419 cm1 is primarily due to the CAN
stretching of pyrrole ring [16,17]. This result indicates that the GO
nano-sheets are covered with PPy by in situ polymerization. PA
shows characteristic absorptions at approximately 1643 cm1
(HPO24 characteristic bands of PA) and 997 cm1 (characteristic
band of PO3 4 of PA) [30], and the hydroxyl of PA is observed at
approximately 3274 cm1. The result is in good agreement with
the predicted surface structure of PPy/GO functionalized with PA.
Fig. 2. ATR-IR spectra for the GO; PPy/GO and PA/PPy/GO nanocomposites.
3.1.3. Raman spectroscopy
The Raman spectra of GO, PPy, PPy/GO and PA/PPy/GO are pre-
sented in Fig. 3. As expected, GO exhibits two obvious peaks at
1583 and 1329 cm1, which correspond to the G and D bands from
GO platform, respectively [14]. The Raman spectra of pure GO
shows that the two bands have similar intensity (ID/IG = 1.05) this
implies a high quantity of structural defects due to the oxidation
of graphite [15,16]. For pure PPy, there are two wide bands at
1317 and 1570 cm1 connected with the C@C backbone stretching
and the ring-stretching mode, respectively [17]. The intensity ratio
(ID/IG) of PPy/GO nanocomposites is found to be 1.10 indicates the
combining of PPy exerted little effect on the structure of GO. The
blue shift of the G band at PPy/GO nanocomposites attribute to
the effection of the sp2-bonded carbon vibration by PPy [31]. The
D/G intensity ratio of PA/PPy/GO is calculated as 1.20. Such a result
may be due to the adsorption of the PA on the surface of PPy/GO
film, the structural of PA containing a six-membered ring could
perhaps increase the extent of disordered carbon atoms.
3.2. Electrochemical performance of the modified electrodes
3.2.1. Characterizations of the different electrodes
Fig. 4 shows the DPV responses recorded from 1.0 V to 0.4 V
at the PPy/GO, PA/PPy, PA/GO and PA/PPy/GO modified electrodes
in 0.1 M acetate buffer (pH 4.5) containing 50 lg/L Cd(II) and Pb(II).
There are no appreciable electrochemical features for the PPy/GO
modified electrode while a very slight stripping peak correspond-
ing to the oxidation of captured Pb(II) at 0.64 V was obtained
on the PA/PPy modified electrode. PA consists of six phosphate

Fig. 1. TEM images of (a) GO, (b) PPy/GO, (c) PA/PPy/GO nanocomposites.
 H. Dai et al. / Chemical Engineering Journal 299 (2016) 150155
Fig. 3. Raman spectra of GO, PPy, PPy/GO, and PA/PPy/GO nanocomposites.
Fig. 4. DPV of PA/GO, PA/PPy, PPy/GO and PA/PPy/GO modified electrodes in 0.1 M
acetate buffer solution (pH 4.5) containing 50 lg/L Cd(II) and Pb(II). Deposition
potential: 1.2 V, deposition time: 200 s, amplitude: 0.05 V, increment potential:
0.004 V, pulse width: 0.05 s, pulse period: 0.2 s.
groups that have two hydroxyl groups could has a complexation
ability and the functional groups that contain the hydroxyl, car-
boxyl and epoxide groups of GO nano-sheets also can complex
with metal ions. The PPy/GO nanocomposites modified electrode
has no detection signal for the heavy ions presumably due to the
GO nano-sheets covered by PPy. In case of the PA/GO and PA/
PPy/GO modified electrode, the current peaks of Cd(II) and Pb(II)
appeared at 0.88 V at 0.64 V, respectively. The improvement
in stripping peak signals of heavy ions on PA/PPy/GO can be attrib-
uted to two aspects. Firstly, the high surface area of GO and the
excellent electric conductivity of PPy could enhance the electron
transfer during the detection processes. Secondly, number of func-
tional groups with large negative charges on PA and GO is benefi-
cial to improving the adsorption capacity of heavy metal ions. In
consequence, the two aspects synergistic effects can bring about
the accumulation of heavy ions and the increase of the detection
sensitivity of Cd(II) and Pb(II).
3.2.2. pH effect
The acidity of the accumulation solution has a considerable
effect on the electrochemical behavior of heavy metal ions. The
stripping peak currents recorded using PA/PPy/GO modified elec-
trode that was pre-concentrated for a 200 s period with 50 lg/L
153
Cd(II) and Pb(II) in 0.1 M acetate buffer solutions of pH 3.06.0
are shown in Fig. 5. Attributed to the protonation and deprotona-
tion of the hydrophilic groups on PA, the electrochemical responses
of Cd(II) and Pb(II) are low at pH 3.0 and then increase promptly to
reach a maximum value at pH 4.5. Afterwards a notable decrease is
exhibited from 4.5 to 6.0. The reason might be the hydrolysis of Cd
(II) and Pb(II) ions. Thus, pH 4.5 is selected for the electrochemical
measurements throughout experiments.
3.2.3. Analytical performance of the electrochemical sensor
The DPV responses of PA/PPy/GO modified electrode to Cd(II)
and Pb(II) were recorded by varying concentration of the heavy
metal ion in the range from 5 lg/L to 150 lg/L. As shown in Fig. 6a,
the obtained well-defined sharp peaks increased while the concen-
tration of Cd(II) and Pb(II) increased. Fig. 6b displays that the cali-
bration plots were linear over the range 5150 lg/L. The peak
current was proportional to the concentration of heavy metal ions,
and the calibration curves are Ip = 0.18cCd  3.79 (R = 0.992) for Cd
(II) and Ip = 0.27cPb  3.22 (R = 0.995) for Pb(II), respectively. The
limit of detections (S/N = 3) were calculated to be 2.13 lg/L for
Cd(II) and 0.41 lg/L for Pb(II). Numbers of reports for the electro-
chemical detection of Cd(II) and Pb(II) are compared with the pre-
sent work, as listed in Table 1. One can find that the developed
electrochemical sensor had wide linear ranges, which may be
attributed to the synergistic effect of PA, PPy and GO on the depo-
sition of the two metal ions.
3.2.4. Interference study
It was known that during the concentration process in the dif-
ferential pulse anodic stripping voltammetry, interference ions
might co-deposite on electrode with the Cd(II) and Pb(II) metal
ions. The interference study containing 50 lg/L Cd(II) and Pb(II)
metal ions with added interfering ions (K(I), Na(I), Ca(II), Mg(II),
Zn(II), Fe(III)) was performed under the optimized conditions.
The change of the peak currents of Cd(II) and Pb(II) is lower than
10% with added interfering ions as listed in Table 2. When the con-
centration of Cu(II) ions is same to the objective metal ions (50 lg/
L), the peak currents of Cd(II) and Pb(II) were rarely changed. As
expected, the Cd(II) peak current and Pb(II) peak current were
changed more than 30% while the addition of 10-fold Cu(II) ions.
Such interference is similar to that reported for other electrode
as previously reported [32]. Overall, the PA/PPy/GO modified GCE
Fig. 5. The effect of pH on the stripping peak currents of 50 lg/L Cd(II) and Pb(II) at
PA/PPy/GO modified electrodes. Results are presented as mean SD (error bar) of
triplicate experiments. Electrolyte: 0.1 M acetate buffer solution; deposition
potential: 1.2 V, deposition time: 200 s, amplitude: 0.05 V, increment potential:
0.004 V, pulse width: 0.05 s, pulse period: 0.2 s.
154 H. Dai et al. / Chemical Engineering Journal 299 (2016) 150155

Fig. 6. (a) Electrochemical performance and (b) the corresponding calibration plots of PA/PPy/GO modified electrode towards Cd(II) and Pb(II) at different concentrations
(from a to i: 5, 15, 20, 30, 60, 80, 100, 120, 150 lg/L, respectively). Error bar: n = 3.

Table 1
A comparison of the different methods reported for the detection of Cd(II) and Pb(II).

Electrode Method Deposition time (s) Deposition potential vs. SCE (V) Linear range (lg/L) Refs.
Cd(II) Pb(II)
ABTSMWCNTs DPV 300 1.0 0.535 0.250 [4]
Nafion/PANI-MES SWV 300 1.2 0.120 0.120 [33]
HgBi/SWNTs SWV 300 1.3 0.5130 0.5130 [34]
AuGNCys SWV 800 1.2 0.5040 0.5040 [35]
G/MWCNTs DPV 180 1.4 0.530 0.530 [36]
PA/PPy/GO DPV 200 1.2 5150 5150 This work

ABTS: 2,20 -azinobis(3-ethylbenzothiazoline-6-sulfonate) diammonium salt, MWCNTs: multi-walled carbon nanotubes, PANI-MES: polyaniline-2-mercaptoethanesulfonate,
SWNTs: single-walled carbon nanotubes, AuGNCys: gold nanoparticlegraphenecysteine composite.

Table 3
Table 2 Determination of Cd(II) and Pb(II) in tap water (n = 3).
Interferences of some metal ions (500 lg/L) on the stripping peak currents of 50 lg/L
Cd(II) and Pb(II). Electrolyte: 0.1 M acetate buffer solution (pH 4.5); deposition Analyte Spiked (lg/L) Found (lg/L) Recovery (%) SD (lg/L) RSD (%)
potential: 1.2 V, deposition time: 200 s, amplitude: 0.05 V, increment potential: Cd(II) 50 49 98 0.5 5.1
4 mV, pulse width: 0.05 s, pulse period: 0.2 s. Pb(II) 50 50.5 101 1.2 11.0
Interferences Contribution (%) Contribution (%) SD: standard deviation; RSD: relative standard deviation.
(IpCd(II) = 100%) (IpPb(II) = 100%)
K(I) 2.7 +1.7
Na(I) +1.8 1.0
Ca(II) +5.0 2.3 3.2.6. Analysis of real sample
Mg(II) 1.4 2.5 In order to evaluate the practical application of the PA/PPy/GO
Zn(II) +5.0 +1.3 electrode, it was used to determination of Cd(II) and Pb(II) in real
Fe(III) 4.3 7.0
samples. The tap water samples were collected in the laboratory
Cu(II) (50 lg/L) +6.9 8.7
Cu(II) (500 lg/L) 42.4 31.6 at different times, and the tap water was spiked with a standard
metal ions solution, in order to simulate the metal ions contami-
Ip: peak current.
nated water. The measurement results of the spiked samples were
shown in Table 3. From Table 3, the high recovery percentage
demonstrates that the developed sensor has an excellent capability
for accurate determination of Cd(II) and Pb(II) in water samples.
displayed high selectivity for Cd(II) and Pb(II) in the heavy metal
Besides, the standard deviation (SD) and the relative standard devi-
analysis.
ation (RSD) were in a range of 0.51.2 lg/L and 5.111.0%, indicat-
ing that the prepared electrode could promise for practical
3.2.5. Reproducibility and stability
application for the determination of metal ions in real samples.
The reproducibility of the electrochemical sensor was investi-
gated by DPV, the result was found to be excellent as evidenced
by a relative standard deviation of 4.8% from five different modi- 4. Conclusions
fied electrodes. After measurements, the PA/PPy/GO nanocompos-
ites modified electrode was rinsed and kept in a buffer solution (pH A phytic acid modified electrode based on PPy/GO nanocompos-
4.5) at 4 C, and the electrochemical response of lost only 8.4% of ites was used for the determination of Cd(II) and Pb(II) in the range
the initial response after several weeks, indicating that the modi- of 5150 lg/L. We synthesized PPy/GO nanocomposites using a
fied electrode has a good stability. simple and rapid in situ polymerization method. The functional
 H. Dai et al. / Chemical Engineering Journal 299 (2016) 150155
molecule PA with negative charge was adsorbed on the surface of
the PPy/GO nanocomposites by the electrostatic attraction. The
modification processes were characterized by TEM, ATR-IR and
Raman spectroscopy. The result indicated the pH of the pre-
concentration solution strongly affected the DPV responses. The
electrochemical performance of the PA/PPy/GO nanocomposites
modified electrode, demonstrated for heavy metal ions detection
by DPV in comparison with the other types of modified electrode,
proved that the developed sensor is highly sensitive to detect Cd(II)
and Pb(II). The PA/PPy/GO modified electrode also showed high
reproducibility and stability in an acetic acidsodium acetate buf-
fer solution. With the advent of more functional materials towards
analytes, the presented strategy is likely to offer a potential plat-
form for analysis and treatment of trace amount of environmental
heavy metals.
Acknowledgments
This work was supported by the National Research Foundation
for the Doctoral Program of Higher Education of China
(20120131110009), the Fundamental Research Funds of Shandong
University (2015HW019), and the National Natural Science Foun-
dation of China (21373129).
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