Current Applied Physics 17 (2017) 1114e1119

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Current Applied Physics

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

Glassy carbon electrode modified with poly(methyl orange) as an

electrochemical platform for the determination of 4-nitrophenol at
nanomolar levels
Krishnan Giribabu a, b, Yuvaraj Haldorai c, Muruganantham Rethinasabapathy b,
Sung-Chan Jang b, d, Ranganathan Suresh a, Wan-Seob Cho e, Young-Kyu Han c,
Changhyun Roh d, **, Yun Suk Huh b, *, Vengidusamy Narayanan a, ***
a
Department of Inorganic Chemistry, University of Madras, Guindy Maraimalai Campus, Chennai, 600025, India
b
WCSL of Integrated Human Airway-on-a-chip, Department of Biological Engineering, Biohybrid Systems Research Center (BSRC), Inha University, 100,
Inha-ro, Incheon 22212, Republic of Korea
c
Department of Energy and Materials Engineering, Dongguk University-Seoul, 30, Pildong-ro 1-gil, Seoul 04620, Republic of Korea
d
Biotechnology Research Division, Advanced Radiation Technology Institute (ARTI), Korea Atomic Energy Research Institute (KAERI), 29, Geumgu-gil,
Jeongeup-si, Jeonbuk 56212, Republic of Korea
e
Lab of Toxicology, Department of Medicinal Biotechnology, College of Health Sciences, Dong-A University, 37, Nakdong-daero 550 Beon-gil, Busan, 49315,
Republic of Korea

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

Article history: In this study, poly(methyl orange) (PMO) was synthesized by electrodeposition onto a glassy carbon
Received 20 December 2016 electrode (GCE), and the resulting structure was examined for the determination of 4-nitrophenol (4-NP).
Received in revised form Cyclic voltammetry revealed that the PMO-modified GCE (PMO/GCE) exhibited excellent electrocatalytic
14 April 2017
activity for the oxidation of 4-NP in a 0.5-M phosphate buffer solution. In contrast, the bare GCE showed
Accepted 24 April 2017
no oxidation peak. Interestingly, PMO/GCE exhibited an oxidation peak at approximate 0.93 V, and the
Available online 2 May 2017
background current was higher than that of the bare GCE. Furthermore, the developed electrochemical
sensor exhibited a linear relationship with the 4-NP concentration from 600 nM to 10 mM, and the limit
Keywords:
4-Nitrophenol
of detection was 170 nM (signal/noise ¼ 3). The sensor demonstrated excellent selectivity, good stability,
Poly(methyl orange) and reproducibility. It was applied to the determination of 4-NP in water samples by the standard
Electrochemical determination addition method and gave recoveries of 99.2e100.9%.
Differential pulse voltammetry © 2017 Elsevier B.V. All rights reserved.

1. Introduction Phenolic compounds enter natural water bodies in the effluents of

Organic pollutants represent a serious threat to the environ-
ment worldwide and adversely affect human health. Because they
persist for long periods of time, these pollutants have exerted un-
foreseen effects on human health and the environment and can
accumulate and pass from one species to the next through the food
chain [1]. The improper disposal of materials containing these
chemicals leads to problems. Phenols and their derivatives are
considered serious, ubiquitous pollutants in water and soil [1].
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: chroh@kaeri.re.kr (C. Roh), yunsuk.huh@inha.ac.kr (Y.S. Huh),
vnnara@yahoo.co.in (V. Narayanan).
various chemical industries, such as the rubber, dye, pharma,
detergent, resin, paper, and petrochemical industries, which use
these compounds as precursors or intermediates. The water dis-
charged from these industries contains highly toxic substances that
enter human food chains and lead to a variety of disorders ranging
from infertility to death. As a result, these substances are included
in the list of priority pollutants [1]. Among phenolic pollutants,
many nitrophenols (NPs) not only affect the respiratory and central
nervous system but also induce cancer at higher doses. Therefore,
these phenolic industrial effluents must be identified and treated
before being discharged into the environment. Thus, the develop-
ment of reliable techniques for the determination of phenols and
substituted phenols in wastewater is highly important.
Analytical techniques such as spectrophotometry, fluorimetry,
and chromatography [2e7] have been used for the determination

http://dx.doi.org/10.1016/j.cap.2017.04.016
1567-1739/© 2017 Elsevier B.V. All rights reserved.
 K. Giribabu et al. / Current Applied Physics 17 (2017) 1114e1119 1115

of NPs. Among these methods, electrochemical methods have been

determined to be reliable because of their simple instrumentation,
high sensitivity, and cost effectiveness. Electrochemical methods
constitute a group of analytical techniques based on two pathways:
reduction and oxidation. A variety of reduction-based methods has
been reported in the literature [8e11]. However, to date, very few
studies have focused on the oxidative determination of 4-NP
[12,13]. The advantage of oxidative determination is that, unlike
reductive determination, no prerequisite procedure is needed to
analyze 4-NP. In electroanalytical studies, conducting polymers are
used to detect analytes rapidly because of their ease of polymeri-
zation. Electrochemical polymerization is generally achieved by
oxidizing monomers under an external potential [14]. Recently,
Reddy et al. reported the electrochemical polymerization of methyl
orange (MO) for the detection of L-dopa [15]. Although poly(methyl
orange) (PMO) has been used in various applications, few studies Fig. 1. CV curve of MO electropolymerization: 0.1-mM MO, 0.05-M PBS, 30 cycles
from 0.6 to þ1.2 V versus SCE at 50 mV s1.
have investigated its application for the electrochemical detection
of analytes. Indeed, previously, no attempt was made to utilize PMO
for the electrochemical detection of 4-NP. potential range from 0.6 to þ1.2 V for 20 cycles. Fig. 1 illustrates
In the present study, we reported the electropolymerization of the CV analysis of MO polymerization on the GCE in 0.1-M PBS (pH
MO on the surface of a glassy carbon electrode (GCE) using cyclic 7). The CV curve shows oxidation and reduction peaks in the given
voltammetry (CV) and the application of the resulting structure for potential ranges from 0.7 to 0.6 V and from 0.16 to 0.02 V, respec-
the electroanalytical determination of 4-NP. The PMO-modified tively. The peak observed in the potential range of 0.7 to 0.6 V is
GCE (PMO/GCE) exhibited a limit of detection (LOD) of 170 nM, related to the oxidation of MO, whereas the other peak
the linear response from 600 nM to 12 mM, improved better anti- (0.16e0.02 V) is attributed to the formation of PMO. During the
interference ability, and good sensitivity. electrochemical process, the number of CV cycles gradually
decreased as the cycle time increased.
2. Experimental A plausible electropolymerization mechanism is shown in
Scheme 1 and is consistent with the existing literature [15]. The
2.1. Materials eNme2 group of MO can bind to the GCE because of the adsorptive
nature of the electrode surface.
4-NP and MO were purchased from Sigma-Aldrich. All other Fig. 2a shows the CV curves of PMO/GCE at different pH values.
chemicals were of analytical grade and used as received unless The voltammetric profiles collected from 0.2e0.8 V display
otherwise specified. reversible oxidation and reduction peaks. As shown in Fig. 2a, the
redox peaks disappeared as the pH increased from 3 to 11, and the
2.2. Fabrication of PMO/GCE oxidation peak current decreased as the proton concentration
decreased. Thus, the optimal pH was in the range of 3e5. When the
Prior to electrochemical polymerization, the GCE was polished electrolyte pH value is over 5 or below 3, it may affect the sensi-
using 1-mm, 0.3-mm, and 0.05-mm alumina slurries in sequence; tivity and conductivity of PMO at the electrode surface. The
washed ultrasonically in ethanol and deionized water for 10 min, morphological analysis of PMO/GCE was performed using scanning
and dried at room temperature. The electrode pretreatment was
performed as described in our previous report [16]. The electro-
deposition of PMO onto the GCE was conducted at a scan rate of
50 mV s1 in the given potential range from þ0.6 to þ1.2 V versus a
saturated calomel electrode (SCE) for 30 CV cycles in 0.1-M phos-
phate buffer solution (PBS) containing 0.1-mM MO. After electro-
deposition, the electrode was thoroughly washed with deionized
water.

2.3. Electrochemical measurements

A three-electrode system (CHI 1103A electrochemical worksta-

tion) was used to evaluate the electrochemical performance of
PMO/GCE. The electrochemical performance of the catalyst-
modified GCE was evaluated by CV and differential pulse voltam-
metry (DPV) in 0.1-M PBS (pH 5). PMO/GCE was used as the
working electrode, and a Pt wire electrode was used as the counter
electrode. All potentials were measured versus an SCE. DPV ex-
periments were conducted at a scan rate of 50 mV s1 in the range
of 0.4 to 0.4 V with a pulse amplitude of 0.025 V and a pulse in-
terval of 0.05 s.

3. Results and discussion

Scheme 1. (a) Structure of MO and (b) mechanistic pathway of the electrochemical
Methyl orange was subjected to electropolymerization in the polymerization of MO at the GCE surface.
1116 K. Giribabu et al. / Current Applied Physics 17 (2017) 1114e1119

Fig. 2. (a) CVs of PMO/GCE collected at different pH values (3e11) at 50 mV s1, (b) SEM analysis of PMO/GCE, and (c) magnified SEM image of the PMO surface.

electron microscopy (SEM) (Fig. 2b and c). The SEM results revealed
that PMO formed a fibrous and agglomerated structure on the
electrode surface. The plate-like morphology, which had a thick-
ness of ~200 nm, was interwoven with the agglomerated plates,
revealing that PMO polymerized on the GCE.

3.1. Electrochemical sensing of 4-NP at PMO/GCE

Fig. 3 shows the CV results of 4-NP obtained for the bare GCE
and PMO/GCE. PMO/GCE displays a clear peak at 0.98 V corre-
sponding to the electrooxidation of 4-NP, whereas no peak was
observed using the bare GCE. Furthermore, PMO/GCE shows a
pronounced peak at 0.93 V, which might be attributable to multiple
interactions, such as hydrogen-bonding, electrostatic, dipole, and
p-p interactions, between PMO/GCE and 4-NP (Scheme 2) [17]
causing the electrode to sense the ongoing oxidation of 4-NP at
the electrode surface.
This clear improvement of the oxidation peak with the higher
current response is likely caused by the electronic characteristics
and adsorptive properties of PMO. Indeed, PMO exhibits good
adsorption of 4-NP because of the multiple interactions between
these species, as shown in Scheme 2 [18,19]. which may increase
the oxidation current for 4-NP at PMO/GCE. As predicted, the
oxidation peak current at the PMO/GCE was relatively high, indi-
cating that PMO has a better electrocatalytic activity for the
oxidation of 4-NP than the bare GCE. The observed oxidation po-
tential of 4-NP is consistent with that reported in the literature [20].
Scheme 2. Different types of interaction between 4-NP and PMO at the GCE surface.
3.2. Influence of pH on 4-NP oxidation at the PMO/GCE
The influence of pH on the electrochemical properties of 4-NP at
the PMO/GCE (Fig. 4a) was examined by CV. As shown in Fig. 4b, the
oxidation peak current of 4-NP decreased as the pH increases from
3 to 11. We have observed a lower oxidation peak potential (0.94 V)
and a comparatively higher peak current (4.91 mA) at pH 5. Thus, pH
5 was selected as an optimal pH for our experiment. From pH 6 to
11, the oxidation current decreased gradually. This decrease is
attributed to two factors: At higher pH values, PMO/GCE exhibits a
poor current response because of the passivation of its surface, and
poor mass transport of the ionized 4-NP occurs at the electrode
surface. The plot of pH versus the oxidation potential of 4-NP
(Fig. 4c) clearly explains the dependency of the oxidation poten-
tial of 4-NP on the pH value: As the solution pH changes, the in-
teractions of 4-NP with PMO/GCE change continuously because the
ionizing properties of 4-NP vary as the pH varies. Furthermore, the
maximum current may have been observed at pH 5.0 because of the
effective interaction between PMO and 4-NP. Indeed, the pKa of 4-
NP is 7.15, whereas the pKa of the protonated amino group of MO is
~4.6. At pH 5.0, PMO can interact effectively with 4-NP, leading to
strong molecular interactions between PMO and 4-NP.

3.3. Influence of the scan rate

Fig. 3. CV curves of 0.1-mM 4-NP at (a) the PMO/GCE and b) bare GCE in 0.1-M PBS (pH
5) at 50 mV s1. Fig. 5a shows a series of CV results obtained for PMO/GCE in 0.1-
 K. Giribabu et al. / Current Applied Physics 17 (2017) 1114e1119
Fig. 4. (a) CV curves of PMO/GCE at different pH values (3e11), (b) plot of pH versus the oxidation peak current, and (c) plot of pH versus the oxidation peak potential.
Fig. 5. (a) CV curves of PMO/GCE at various scan rates (10e700 mV s1), (b) double logarithmic plot of log(v) versus log(Ipa), and (c) plot of ln(v) versus Epa.
M PBS (pH 5) containing 0.01-mM 4-NP at various scan rates. The
cathodic and anodic peak currents increased as the scan rate
increased from 10 to 700 mV s1, and the peaks shifted toward
more positive and negative potentials, respectively. Thus, the
oxidation/reduction peak separation increased with the scan rate.
As shown in Fig. 5b, the double logarithmic plot of the oxidation
peak current (log(Ipa)) versus the scan rate (log(v)) showed a linear
relationship with a slope of 0.58. These results suggest that the
adsorption process controls the overall reaction kinetics. The rela-
tionship between ln(v) and the oxidation peak potential (Epa) is
presented in Fig. 5c. The Epa increased linearly with log(v), and the
corresponding regression equation was Epa(V) ¼ 0.9330 þ 0.04487
ln(v) (R2 ¼ 0.9918). The relationship between ln(v) and Epa can be
expressed as Eq. (1) [21,22]:
RT RTKs RT
Epa ¼ Eo  ln þ ln v
ð1  aÞnF ð1  aÞnF ð1  aÞnF
where a is the charge transfer coefficient; v is the scan rate in mV
s1; n is the number of electrons transferred; Ks is the electron
transfer rate constant; and R, T, and F have their standard meanings.
The value of a(0.84) was calculated from the slope of Epa versus
ln(v). Substituting the above values into Eq. (1), the Ks for the
electrochemical reaction involving PMO/GCE was calculated to be
0.867 s1.
3.4. Electron and proton transfer numbers
The number of electrons transferred in the oxidation process of
4-NP at the electrode was calculated using Eq. (2) [23]:
1117
nFQ v
ip ¼ (2)
4RT
where ip is the oxidation peak current of 4-NP, n is the number of
electrons; Q is the assumed charge; v is the scan rate (mV s1); and
R, T, and F have their standard meanings. Using Eq. (2), the calcu-
lated n value was 2, which is consistent with the results found in
the literature [24]. The m/n ratio was calculated to be 1.4, where m
corresponds to the number of protons involved in the electro-
chemical process of 4-NP oxidation. According to the above results,
two electrons and three protons were involved in the electro-
chemical oxidation of 4-NP at the PMO/GCE. The electron transfer
process clearly revealed the formation of p-quinonimine and the
involvement of the electrode modifier, PMO.
(1) 3.5. Differential pulse voltammetry
Fig. 6a shows the DPV measurements of PMO/GCE in the pres-
ence of different concentrations of 4-NP in 0.1-M PBS (pH ¼ 5). The
oxidation peak current increased as the 4-NP concentration
increased in the range of 0.6e10 mM. The corresponding linear
regression equation is Ipa (mA) ¼ 0.0819(mM) þ 0.5596 (R2 ¼ 0.9914)
(Fig. 6b). The LOD of 4-NP was determined to be 170 nM. These
results clearly indicate that PMO/GCE has excellent capacity for the
determination of 4-NP. The analytical determination of 4-NP using
PMO/GCE was compared with the results obtained using other
electrodes, and the findings are presented in Table 1.
The electrochemical properties of PMO/GCE imbued this device
with a linear range over which it can be used to sense 4-NP, and the
various interactions between PMO and the analyte resulted in
improved electrocatalytic behavior. Although the electrode
1118 K. Giribabu et al. / Current Applied Physics 17 (2017) 1114e1119

Fig. 6. (a) DPV curves of PMO/GCE with the successive addition of 4-NP in 0.1-M PBS (pH ¼ 5) and (b) plot of the 4-NP concentration versus the oxidation peak current.

Table 1 Table 2
Analytical results obtained using different sensors for the determination of 4-NP. Determination of 4-NP in water samples.

Electrode Detection limit (mM) Reference Sample Added Present methods a

RSD (%) Recovery (%)
106 M 106 M
Hydroxyapatite/GCE 0.6 [18]
GO/GCE 0.020 [25] I 10 9.92 2.85 99.2
Nano-Cu2O/GCE 0.50 [26] II 10 10.02 3.46 100.2
OMCs/GCE 0.1 [27] III 10 10.09 3.69 100.9
Mg(Ni)FeO/CPE 0.2 [28] a
Average of five experiments.
DTD/AgNPs/CPE 0.25 [29]
MWCNT/GCE 0.4 [30]
AgA-PE 0.3 [31]
Silver particles/GCE 0.5 [32] selectivity for 4-NP determination.
PMO/GCE 0.11 Present work

GO: graphene oxide; OMC: ordered mesoporous carbon; DTD: 22-
decahydrodibenzo[h,r][1,4,7,11,15]trioxadiazacyclonanodecine-16,23-dione;
MWCNT: multi-walled carbon nanotube; and AgA-PE: silver amalgam paste
electrode.
materials reported previously exhibited good performance for the
determination of 4-NP, but PMO/GCE exhibited a low LOD for 4-NP,
which is attributable to the synergetic effect of ion-pair formation
and hydrogen bonding between PMO and 4-NP. These results
indicate that PMO/GCE is a suitable electrode material for 4-NP
sensing.
3.6. Stability, reproducibility, and interference
The stability and reproducibility of PMO/GCE were measured to
estimate this material's sensing performance. The stability of the
electrode was examined by detecting 0.1-mM 4-NP on 10 consec-
utive days. Before the analyses, the electrode was stored at 24  C
under vacuum. The sensor showed good electrocatalytic response
and retained approximately 89% of its initial catalytic current after
7 days and 85% after 10 days, indicating this sensor's good storage
stability. In the reproducibility test, three independently fabricated
electrodes were used to detect 4-NP (0.1 mM), and the relative
standard deviation (RSD) was calculated to be 3.1%. This result
clearly demonstrates the acceptable reproducibility of the devel-
oped sensor for 4-NP determination. We also investigated the ef-
fects of various possible interfering materials on the 4-NP sensor. In
this experiment, 100-fold excesses of various common ions, such as
Al3þ, Mg2þ, Kþ, Ni2þ, PO3  2 
4 , NO3 , CO3 , and Cl , did not interfere
with the detection of 4-NP. However, 50-fold excesses of Zn2þ, Fe2þ,
and Cu2þ ions did interfere. Phenol (0.1 mM), 2-NP (0.1 mM), 3-NP
(0.1 mM), 2, 4 diNP (0.1 mM), 4-chlorophenol (0.1 mM), 2-
chlorophenol (0.1 mM), catechol (0.1 mM), and aniline (0.1 mM)
were also added to test for interference. The results revealed that
these materials significantly affected 4-NP sensing at the tested
concentrations. Thus, the developed electrode has outstanding
3.7. Real sample analysis
To conduct a real sample analysis, PMO/GCE was used for the
determination of 4-NP in water samples. The water samples were
collected from different sources within a local city. Before detec-
tion, the water samples were filtered to remove solid impurities. A
standard addition method was used to measure the concentration
of spiked 4-NP. The measurement data are presented in Table 2. The
recoveries ranged from 99.2% to 100.9%, confirming that this sensor
is highly suitable for the determination of 4-NP in water samples.
4. Conclusion
We successfully electrodeposited PMO on a GCE surface and
investigated the resulting structure as an electrode material for 4-
NP sensing. DPV analysis revealed a linear relationship with the
4-NP concentration from 0.6 to 10 mM with an R2 value of 0.9914.
The electrode exhibited a low LOD of 170 nM. This material's high
sensitivity to 4-NP could be attributed to the hydrogen bonding and
ion-pair interactions between the electrode and analyte. The anti-
interference ability results and real sample analysis revealed that
this composite material could be effectively used for the detection
of 4-NP in industrial samples. The present protocol is reliable,
simple, and cost-effective and could be used to develop a new type
of low-cost sensor with high robustness.
Acknowledgements
Dr. K. Giribabu would like to thank the Department of Science
and Technology (DST), Government of India, for providing financial
assistance in the form of an INSPIRE fellowship (Inspire Fellow no:
10226) under the AORC scheme. The authors also acknowledge the
Radiation Fusion Technology Program (2015M2A2A6A020452
62(3)) of the Nuclear Research R&D Program through the National
Research Foundation (NRF) funded by the Ministry of Science, ICT
and Future Planning (MSIP), Korea. This work was supported by
 K. Giribabu et al. / Current Applied Physics 17 (2017) 1114e1119
Inha University WCSL research grant, Korea.
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