Polymer 242 (2022) 124593

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Simultaneous analysis of catechol and hydroquinone by polymelamine/

CNT with dual-template molecular imprinting technology
Chao Hu , Haiping Huang *, Han Sun , Yu Yan , Fang Xu, Jinsheng Liao
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, School of Chemistry and Chemical Engineering, Jiangxi University of Science and
Technology, Ganzhou, 341000, PR China

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

Keywords: Dual-template molecularly imprinted polymer/carbon nanotubes/grassy carbon electrode (MIP/CNTs/GCE) was
Molecularly imprinted polymer constructed by electropolymerizing a layer of bimolecular imprinted film with melamine (Mel) as functional
Carbon nanotubes monomer, hydroquinone (HQ) and catechol (CC) as template molecules on CNTs modified GCE. The
Polymelamine
morphology, structure and electrochemical properties of MIP/CNTs/GCE were characterized by scanning elec­
Catechol
Hydroquinone
tron microscopy, Fourier transform infrared spectroscopy and electrochemical technology, respectively. The
experimental parameters for the construction of sensor were optimized in detail, which includes the reagent
molar ratio, the electropolymerization cycles, the elution time and the pH value of the electrolyte. Under the
optimal conditions, the simultaneous detection of HQ and CC was realized via cyclic voltammetry (CV) and
differential pulsed voltammetry (DPV). Compared with CNTs/GCE, molecularly imprinted membrane can
significantly enhance its response current to HQ and CC. At the same time, both the linear range of HQ and CC
measured by DPV are 10–100 μM, with the detection limits of 3.1 μM and 3.5 μM, respectively. The electrode also
owned good reproducibility and stability. Finally, MIP/CNTs/GCE was successfully utilized for the detection of
HQ and CC in river water.

1. Introduction [12–15]. Owing to these properties, it is been applied in many fields

Catechol (CC) and hydroquinone (HQ), which are isomers of dihy­
droxybenzene [1,2], are commonly used in dyes, pharmaceuticals,
cosmetics, antioxidants, pesticides and rubber industries. However, they
may cause different diseases such as cancer [3]. In the United States and
the European Union, their low degradability and high toxicity make
them be officially treated as pollutants in the ecosystem [4]. Therefore,
precise detection of their contents becomes extremely important. Drawn
from the commonly employed analytical technologies like optical
spectrum and chromatogram, electrochemical technology becomes
more popular for sensitivity, rapidity, simplicity [5–8]. Nevertheless,
the main problem is the similar structure of these two phenolic isomers
endows with the similar electrochemical behaviors. Therefore, the
exploration of new material for the modification of the electrode still
remains a big challenge for the purpose of simultaneous determination
of HQ and CC [9–11].
As a widely used carbon-based nanomaterial, carbon nanotubes
(CNTs) have the characteristics of large specific surface area, excellent
electrical conductivity, outstanding mechanical strength and toughness
ranging from electrode modified materials, catalyst supports to other
composite materials [16]. In recent years, many scholars have devel­
oped many unique modified electrodes using CNTs as decorated mate­
rials. These electrodes exhibit good electrocatalytic activity in different
redox reactions [17,18].
As a widely employed analysis technology, molecularly imprinted
polymer (MIP) has specific recognition sites which are complementary
to the template molecule in shape, size or functional group. This can be
utilized for selectively recognition and adsorption of target molecules
[19]. To analysis two targets in one polymer, dual -template imprinting
strategy is proposed by using dual-target as the templates [20]. The
commonly employed polymers are conductive polymers [21,22].
Because of their relatively high conductivity and ease of synthesis
[23–26], conductive polymers such as polythiophene, polypyrrole,
polymelamine (PMel), polyaniline and their derivatives are widely
employed in MIP applications. Among these polymers and the relative
monomers, melamine is a cyanamide trimer with three amino groups.
These functional groups can provide plenty of active sites during the
accumulative process. Compared with other materials, the π electrons in

* Corresponding author.
E-mail address: huanghp@jxust.edu.cn (H. Huang).

https://doi.org/10.1016/j.polymer.2022.124593
Received 14 December 2021; Received in revised form 13 January 2022; Accepted 25 January 2022
Available online 29 January 2022
0032-3861/© 2022 Published by Elsevier Ltd.
C. Hu et al.
Scheme 1. The whole fabricating steps and diagrammatic illustration for the MIPs preparation and detection process.
N-rich PMel can facilely interact with the target analyte [27,28].
Therefore, PMel attracts much attention as a favorable candidate in the
field of MIP.
Herein, PMel was first electrodeposited on the surface of CNT
modified GCE via electrochemical polymerization with melamine as
precursor monomer. PMel, CC and HQ were simultaneously electro­
deposited on the electrode surface, and then the CC and HQ molecules
were eluted to leave imprinted holes to form the prepared MIP electrode.
The simultaneous electrochemical determination of CC and HQ by dual-
template MIP technology was realized with good performance. The
whole schematic illustration is displayed in Scheme 1.
2. Experimental
2.1. Reagents and apparatus
Melamine was provided from Aladdin (Shanghai China). Chitosan
was gained from Sigma-Aldrich (Shanghai China). MWCNTs were got
from XFNANO Materials Tech Co., Ltd (Nanjing China). Resorcinol, CC,
HQ and other reagents were all received from Sinopharm Chemical
Reagent Co. Ltd (Shanghai, China).
Scanning electron microscopy (SEM) image was obtained on
MLA650F FEI (USA). Fourier transform infrared spectroscopy (FTIR)
was operated on Bruker ALPHA spectrometer (German) in the wave
number range of 500–4000 cm− 1 with KBr as pellet. All electrochemical
results were obtained on Chenhua electrochemical workstation (CHI
660D, Shanghai China).
Fig. 1. CVs of bare GCE in 0.5 M H2SO4 electrolyte containing melamine alone (A), and containing melamine, CC and HQ (B).
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Polymer 242 (2022) 124593
2.2. Preparation of MIP-modified electrodes
Firstly, the raw CNTs was acidulated in 100 mL mixed acid solution
(V(98% concentrated sulfuric acid): V(68% concentrated nitric acid) =
3:1) under reflux with magnetic stirring at 90 ◦ C for 4h [29]. The acid
pre-treated CNTs were collected for future use.
The GCE was polished with aluminum oxide powder (1.0 mm and
0.3 mm). The pre-treated CNTs were dispersed in water (2 mg in 2 mL)
and sonicated 15 min to form a uniform dispersion. To fabricate the
CNTs/GCE, 10 μL of the dispersion was dropped onto the GCE surface
and allowed to dry naturally.
For preparation of MIP sensor, CNTs/GCE was electrochemical
polymerized in 0.5 M H2SO4 electrolyte containing CC (1 mM), HQ (1
mM) and melamine (5 mM) from 0–1.0 V (vs. SCE) for 30 cycles using
cyclic voltammetry (CV) at 50 mV s− 1. After polymerization, the elec­
trode was immersed in ethanol/water solution (1:1, v/v) for 5 min to
remove two template molecules from the polymer film, so as to obtain
the final MIP/CNTs/GCE sensor. The similar process was used to prepare
NIP/CNTs/GCE (NIP for non-imprinted polymer) without HQ and CC in
0.5 M H2SO4 electrolyte.
3. Results and discussion
3.1. MIPs electropolymerization
CV is employed to actualize the electrochemical polymerization
process of MIP and NIP electrodes, as shown in Fig. 1. Due to the mel­
amine polymer film formed by electrochemical polymerization on the
electrode surface, the current gradually decreases as the number of
scanning cycles augments. As shown in Fig. 1A, the current peaks
C. Hu et al. Polymer 242 (2022) 124593

Fig. 2. A and B for SEM images of MIP/CNTs before (A) and after elution (B), C for FTIR spectra of melamine monomer (a), NIP (b), MIP (before elution, c) and MIP
(after elution, d).

Fig. 3. CVs MIP/CNTs/GCE in 0.2 M KCl +2.0 mM [Fe(CN)6]3-/4- solution at scan rate range of 10–150 mV s− 1
(A) and the corresponding linear curves between the
anode/cathode peak current vs. the scan rate (B).

appeared at ~0.3 V is attributed to the formation of polymelamine,
which is consistent with the literature [28]. In the existence of CC and
HQ, the CV in Fig. 1B emerges two sharp redox peaks, which belong to
the redox reaction of CC and HQ, respectively. This indicates that CC and
HQ molecules are co-polymerized with the functional monomer mel­
amine during the polymerization process.
3.2. Morphologic characterization
For more direct observation of the synthesized polymer film, SEM
was used to study the surface of modified electrode at different stages,
which are shown in Fig. 2A and B. When melamine, HQ and CC are
electrochemical co-polymerized onto the CNTs/GCE, the electrode
conductivity is decreased due to the poor conductivity of the polymer.
Therefore, only a fuzzy layer on the surface is observed in Fig. 2A.
However, after the MIP electrode was immersed into ethanol/water
solution, a porous morphology for the modified electrode surface can be
observed, as shown in Fig. 2B. This is attributed to the fact that the
template molecules of HQ and CC are eluted from the polymer, resulting
to the porous structure. This result indicates that the template molecules
have been successfully eluted from the MIP membrane.
In order to further confirm the successful formation of polymers and
the elution of template molecules from MIP, FTIR technology is
employed to characterize the different states of the polymer. FTIR
spectra of the different polymer states are shown in Fig. 2C. Firstly, the
FTIR spectrum of melamine monomer is exhibited in curve a Fig. 2C. The
peaks at 3470 and 3330 cm− 1 are assigned to the N–H asymmetric and
symmetric stretching vibrations, respectively. The peaks at 1653 and
1554 cm− 1 are due to the characteristic amine II and III bonds of mel­
amine. After being electrochemical polymerized (curve b in Fig. 2C), the
peaks related to the N–H stretching vibrations at 3100–3500 cm− 1 are
merged into one single peak at 3439 cm− 1, suggesting the successful
polymerization of melamine. When HQ and CC are co-polymerized with
melamine (curve c in Fig. 2C), new peaks at 600 and 1200 cm− 1 are
emerged, which belongs to the characteristic peaks of HQ and CC.
However, these peaks are disappeared after elution in ethanol/water

Fig. 4. CVs of various electrode in 2 mM [Fe(CN)6]3-/4- + 0.1 M KCl (A) and in phosphate buffer (0.1 M) containing 0.5 mM HQ + 0.5 mM CC (B). Curve a for bare
GCE, b for CNTs/GCE, c for MIP/CNTs/GCE (not eluted), d for NIP/CNTs/GCE and e for MIP/CNTs/GCE. Scan rate: 50 mV s− 1.

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C. Hu et al.
Fig. 5. The effect of different ratios of functional monomers and template molecules (A), different electropolymerization cycles (B) and different elution time (C) on
the CV peak current response. CVs in PBS (PH = 7) containing 0.5 mM HQ and 0.5 mM CC. Scan rate: 50 mV s− 1.
solution (curve d in Fig. 2C). The emergence and disappearance of HQ/
CC characteristic peaks solidly prove the formation and elution of the
template molecules.
3.3. Electrochemical behaviors of modified electrodes
The electrochemical kinetic behavior of MIP/CNTs/GCE were
investigated by recording the CV responses in 0.1 M KCl aqueous solu­
tion with 2 mM [Fe(CN)6]3-/4-, whose results are shown in Fig. 3A. As the
scan rate increases from 10 to 150 mV s− 1, the anode peak current and
the cathode peak current increase correspondingly. Fig. 3B shows the
linear relationship between the anode/cathode peak current values vs.
the scan rate. For the anode, the linear regression equation is Ip(μA) =
-2.50429 + 2.99865 v (mV⋅s− 1) with R2 = 0.9971. For the cathode, the
linear regression equation is Ip(μA) = 19.243–3.5793 v (mV⋅s− 1) with
R2 = 0.9959. This proves that the electrochemical process on MIP/
CNTs/GCE is surface-controlled process.
The electrochemical behaviors of various modified electrodes were
also checked in the above electrolyte, whose results are shown in
Fig. 4A. Owing to the fact that CNTs have good electrical conductivity,
larger current peak is observed on the electrode loaded with CNTs (curve
b in Fig. 4A) than the bare GCE (curve a in Fig. 4A). When a layer of
melamine, CC and HQ is co-polymerized on the surface of CNTs/GCE to
form the MIP/CNTs/GCE, the peak current is relatively reduced (curve c
in Fig. 4A), which may be due to the poor electric conductivity of the
polymer. The similar phenomenon is observed when only melamine is
electro-polymerized onto the CNTs/GCE to form the NIP/CNTs/GCE
(curve d in Fig. 4A). Nevertheless, after extracting the templates of CC
and HQ from the MIP membrane, the current peak value increases again
(curve e in Fig. 4A). When the template molecules are removed from the
membrane, there are voids in the MIP membrane, which increases the
conductivity of the electrode [11]. These experimental results confirm
that CC and HQ have been embedded in the melamine polymer mem­
brane and could be exterminated from the membrane in the elution
process.
Shown in Fig. 4B is the CV response of various modified electrodes in
the 0.1 M phosphate buffer (PH = 7.0) containing 0.5 mM HQ + 0.5 mM
CC with the scanning rate of 50 mV/s. For the bare GCE, only very weak
redox peaks are observed for CC and HQ (curve a in Fig. 4B). These peaks
current are enlarged with different degrees for CNTs/GCE (curve b in
Fig. 4B), MIP/CNTs/GCE (not eluted, curve c in Fig. 4B) and NIP/CNTs/
GCE (curve d in Fig. 4B). Nevertheless, after being eluted the template
molecules of CC and HQ from the MIP membrane, the CV curve (curve e
in Fig. 4B) shows two well-defined the peaks current. This confirms that
the molecularly imprinted membrane has a good promotion effect to­
wards the electrocatalytic oxidation of CC and HQ, which means that
they can be simultaneous detected in this system.
4
Polymer 242 (2022) 124593
3.4. Parameters optimization for sensor preparation
3.4.1. Optimization of reagent molar ratio
In order to obtain the best experimental condition for the construc­
tion of the MIP electrode so as to improve the performance of the sensor,
different parameters such as monomers ratio, the number of electro­
polymerization cycles and elution time are investigated to study the
effect upon the MIP performance. Firstly, 0.5 M H2SO4 electrolyte with
different molar ratios of template molecules and monomer are employed
for the electropolymerization, where nhydroquinone: ncatechol: nmelamine =
0:0:5, 1:1:5, 2:2:5, 3:3:5, 4:4:5 and 5:5:5 respectively, and the concen­
tration of melamine remains unchanged at 5 mM. The electro­
polymerization was completed in different electrolyte via CV under the
same electrochemical settings of 0–1.0 V at 50 mV s− 1 for 30 cycles. The
effect of different molar ratio upon the sensor performance was studied
by examining the CV responses of each MIP sensor in phosphate buffer
containing two targets (0.5 mM). It can be seen from that Fig. 5A the
maximum current response is obtained when the malor ratio is nhy­
droquinone: ncatechol: nmelamine = 1:1:5. Therefore, this dosage is adopted in
the following experiment.
3.4.2. Optimization of electropolymerization cycles
For the MIP based sensor, the film thickness is a key factor for the
electrochemical response. The thickness is usually controlled by
changing the number of cycles in the electrochemical polymerization
process. Herein, cycles from 20 to 40 with increasement of 5 were used
to synthesize the MIP film. In Fig. 5B, the electrochemical response of
the MIP sensors with different CV cycles was also studied in phosphate
buffer containing two targets (0.5 mM). The peak current reaches the
maximum at 30 cycles. This phenomenon is attributed to the fact that
with smaller number of cycles, fewer active sites are formed on the MIP
film, which causes the lower peak current. However, polymerization
with too many cycles will increase the film thickness, which causes the
template molecules not being completely exterminated from the thick
polymer matrix. This will reduce the number of active sites in the MIP
film. So the number of 30 cycles is chosen as the optimal number for the
electropolymerization process.
3.4.3. Optimization of elution time
For the purpose of studying the influence of the elution time of the
template molecules upon the performance of the MIP sensor, the elec­
trode after electropolymerization was immersed and eluted in ethanol
aqueous solution for a certain time. The CV response of each sensor in
phosphate buffer with two targets (0.5 mM) was recorded in Fig. 5C.
Firstly, the peak current enlarges as the elution time extends. When the
elution time reaches 5 min, the current reaches peak and remains almost
constant in the next elution time, which indicates that the elution is
complete in 5 min. Thus, the elution time is set to 5 min for the con­
struction of the sensor.
C. Hu et al. Polymer 242 (2022) 124593

Fig. 6. CVs of MIP/CNTs/GCE in phosphate buffer (0.1 M) with 0.5 mM HQ and 0.5 mM CC at different pH 4.0–8.0 (A), and the corresponding linear relationship of
potential vs. pH (B) and current vs. pH (C).

Fig. 7. DPVs of MIP/CNTs/GCE in phosphate buffer (0.1 M, pH = 7.0). (A) containing 70 μM HQ and 10–100 μM CC, (C) containing 50 μM CC and 10–100 μM HQ.
(B) and (D) are the calibration plots of peak current vs. concentration of CC and HQ.

3.4.4. Optimization of pH
The pH value of the electrolyte is also another important parameter
for the electrochemical reaction. To study the influence of pH value on
MIP sensor performance, the CV behaviors in different pH values were
tested. The whole results (4.0–8.0 pH value) are exhibited in Fig. 6A.
With the increase of pH value, the potential of oxidation peaks for CC
and HQ considerably switch to the negative direction. Fig. 6B shows the
linear relationship of pH value vs. oxidation peak potential. For HQ, the
linear regression equation is Ep(V) = 0.5968–0.066 pH with R2 =
0.9971. For CC, the linear regression equation is Ep(V) = 0.6988–0.066
pH with R2 = 0.99736. The ratio of m/n (the number of protons and
electrons involved in the reaction) for the CC and HQ oxidation process
is both equal to 1.1. This confirms the number of protons involved in the
reaction is approximately equivalent to the electrons. The diversification
of peak current along with pH value is shown in Fig. 6C. Both the
oxidation peak current of CC and HQ increases with the enlargement of
pH and gets the top at pH = 7.0. Accordingly, the pH value of 7.0 is
employed for the next detection.
3.5. Determination performance of the sensor
For the determination of these two targets, the DPV signal was

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C. Hu et al. Polymer 242 (2022) 124593

Fig. 8. DPVs (A) of MIP/CNTs/GCE in phosphate buffer (0.1 M, pH = 7.0) with different concentrations of CC and HQ from 10 to 100 μM. (B) and (C) show the
calibration plots of peak current vs. concentration of CC and HQ.

Table 1
Comparison of the sensor performance.
Sensor Method Linear range Detection limit Ref.

CC (μM) HQ (μM) CC (μM) HQ (μM)

NiO/MWCNT/GCE DPV 7.4–56 7.4–56 0.015 0.039 [30]

PNRa/MCPEb DPV 10–100 20–120 6.4 4.9 [31]
(CMWNTs-NHCH2CH2NH)6/GCE DPV 5–80 10–120 1.0 2.3 [32]
AuNP/SGc/GCE DPV 5–100 5–100 2.0 1.0 [33]
RGOd-MWCNTs/GC DPV 5.5–540 8–391 1.8 2.6 [34]
polarized GCE CV 10–300 10–300 3.99 3.57 [35]
MIP/MWCNTs/GCE DPV 10–100 10–100 3.5 3.1 This work
a
PNR: poly (neutral red).
b
MCPE: modified carbon paste electrode.
c
SG: sulfonated graphene.
d
RGO: reduced graphene oxide.

recorded in the electrolyte containing two targets. First, employ

different concentrations of one substance for DPV detection while keep
the concentration of the other substance unchanged. Fig. 7A is the DPV
response measured in 70 μM HQ and CC concentration ranging from 10
to 100 μM. Fig. 7C is the DPV response measured in 50 μM CC and HQ
concentration ranging from 10 to 100 μM. In Fig. 7A, the peak current
for oxidation process increases in proportion to the increase in CC
concentration, while the peak current of 70 μM HQ remains almost
unchanged. This shows that the presence of HQ will not interfere with
CC detection. The analogous tendency is noted in Fig. 7C for HQ
detection. Fig. 7B and D are the curves of the oxidation peak current
versus the concentration of target, respectively. The corresponding
equations are listed below:

Ip (μA) = − 0.444 + 0.119 cHQ (μM), R2 = 0.995.

Ip (μA) = − 0.716 + 0.129 cCC (μM), R2 = 0.996.

The DPV response of sensor upon changing the concentration of HQ

and CC synchronously were also detected (in Fig. 8A). When the con­
centrations of these two targets increase from 10 μM to 100 μM at the
same time, there are two obvious oxidation peaks that do not interfere
with each other in DPV response. Both the oxidation peaks current in­
creases with the increase of target concentration respectively. Fig. 8B Fig. 9. The anti-interference investigation of MIP/CNTs/GCE upon the addition
and C are the linear relationship of the oxidation peak current versus the of different anti-interferences (0.1 mM) in phosphate buffer with HQ (0.1 mM)
concentration of HQ and CC. The linear equations are listed below: and CC (0.1 mM) (pH = 7.0).

Ip (μA) = − 0.793 + 0.113 cHQ (μM), R2 = 0.989;

Ip (μA) = − 0.805 + 0.116 cCC (μM), R2 = 0.994.
The detection limit of HQ and CC is 3.1 μM and 3.5 μM, respectively.
These values are higher than the China environmental quality standard
for residential drinking water, which is 0.002 mg/L.
In order to estimate the behavior of the constructed sensor, Table 1
provides a comparison between the results of MIP/CNTs/GCE in this
system and other published sensors for these two targets determination.
It can be drawn from Table 1 that the 10–100 μM linear range for CC
detection herein is wider than 7.4–56 μM for NiO/MWCNT/GCE [30]
and 5–80 μM for NiO/MWCNT/GCE [32]. 10–100 μM linear range for
HQ detection is comparable to AuNP/SG/GCE [33]. The detection limit
of 3.5 μM for CC detection is lower than 6.4 μM for PNR/MCPE [31] and

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C. Hu et al.
Table 2
Recovery analysis for actual sample detection.
Specimen CC (μM)
Concentration Addition Found Recovery
1 ND* 30.0 30.38 101.3
2 ND 50.0 50.43 100.9
3 ND 70.0 71.8 102.6
* ND for Not Detected.
3.99 μM for polarized GCE [35], similar as the HQ detection. This in­
dicates that the prepared MIP/CNTs/GCE has satisfactory performance
as a new electrochemical sensing platform.
3.6. Anti-interference and reproducibility
As an electrochemical sensor, the ultimate goal is detect the target in
actual sample, which contains many kinds of interference. Therefore, to
study the anti-interference ability of the electrode, the co-existence DPV
response of some common kinds of interference with HQ and CC in
phosphate buffer is carried out. As most components in the waste and
wild water contain metal ions. Therefore, based on the previous re­
porters about the commonly employed interferences, calcium chloride,
sodium chloride, ferric chloride, potassium chloride, resorcinol (RC),
and phenol (ph) are selected for the anti-interference study. As shown in
Fig. 9, after the addition of these interferences (0.1 mM) into the
phosphate buffer containing HQ (0.1 mM) and CC (0.1 mM), the elec­
trochemical signal changes slightly as compared to the independent
detection. This proves that the fabricated electrochemical MIP sensor
owns good selectivity.
In order to study the reproducibility of the electrode, five MIP/CNTs/
GCEs were prepared under the same conditions for simultaneous mea­
surement of these two targets (0.5 mM). The relative standard deviations
(RSD) of the five electrodes were 7.1% and 4.6%, respectively. This
indicates that the prepared electrode owns good reproducibility. The
repeatability is also investigated by using the same MIP sensor to
repeatedly detect these two targets (0.5 mM), the RSD for 5 times
detection were 6.8% and 5.6%, respectively. To test its stability, the
prepared MIP/CNTs/GCE modified electrode was kept at room tem­
perature for two weeks, and then utilized to measure these two targets
(0.5 mM). The signal of HQ and CC maintains 96.4% and 95.3% of the
initial values respectively.
3.7. Actual sample detection
In order to verify the detection ability of the MIP sensor for actual
sample detection, the standard addition method was utilized to deter­
mine these two targets in the local river water. It can be found in Table 2
that the prepared electrochemical sensor has a good recovery rate for the
determination of CC and HQ in actual samples.
4. Conclusion
MIP/CNTs/GCE was constructed and employed for the simultaneous
determination of CC and HQ. The SEM and FTIR characterizations prove
the successful elution of the CC and HQ template molecules from
modified electrode. Under the parallel experiments, the experimental
parameters for the construction of sensor were set to reagent molar ratio
of nhydroquinone: ncatechol: nmelamine = 1:1:5, 30 cycles for the electro­
polymerization process, and 5 min for the elution time. At the pH value
of 7.0, the MIP sensor has a good potential for simultaneous and indi­
vidual determination of these two targets with two well separated
electrochemical oxidation peaks. The results show that the constructed
MIP sensor owns good stability, repeatability and reproducibility. Given
the fact that melamine and CNT are common reactants with pretty
cheapness, and the procession for the sensor construction is easy without
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Polymer 242 (2022) 124593
HQ (μM)
Concentration Addition Found Recovery
ND 30.0 30.9 103.0
ND 50.0 51.7 103.4
ND 70.0 72.5 103.6
complex steps, this work provides an inspiring strategy to expand the
application of MIP in the field of electrochemical sensor.
CRediT authorship contribution statement
Chao Hu: Resources, Writing – original draft, Investigation, Data
curation. Haiping Huang: Validation, Formal analysis, Investigation,
Writing – review & editing, Supervision. Han Sun: Methodology, Vali­
dation, Data curation. Yu Yan: Methodology, Formal analysis. Fang Xu:
Data acquisition and analyses. Jinsheng Liao: Investigation,
Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (Grant Nos. 22061019), the Youth Jinggang Scholars Program
in Jiangxi Province, Qingjiang Excellent Young Talents Program of
Jiangxi University of Science and Technology, Key Laboratory of Testing
and Tracing of Rare Earth Products for State Market Regulation, and the
Jiangxi Provincial Key Laboratory of Functional Molecular Materials
Chemistry (20212BCD42018).
References
[1] C.M. Kuskur, B.E.K. Swamy, H. Jayadevappa, Poly (naphthol green B) modified
carbon paste electrode sensor for catechol and hydroquinone, J. Electroanal. Chem.
804 (2017) 99–106.
[2] Z. Meng, H. Zhang, J. Zheng, An electrochemical sensor based on titanium oxide-
carbon nanotubes nanocomposite for simultaneous determination of hydroquinone
and catechol, Res. Chem. Intermed. 41 (5) (2015) 3135–3146.
[3] C. Bu, X. Liu, Y. Zhang, L. Li, X. Zhou, X. Lu, A sensor based on the carbon
nanotubes-ionic liquid composite for simultaneous determination of hydroquinone
and catechol, Colloids Surf., B 88 (1) (2011) 292–296.
[4] L.A. Goulart, L.H. Mascaro, GC electrode modified with carbon nanotubes and NiO
for the simultaneous determination of bisphenol A, hydroquinone and catechol,
Electrochim. Acta 196 (2016) 48–55.
[5] Y.X. Liu, Z. Yan, R.Y. Chen, Y.P. Yu, X. Chen, X. Zheng, X.H. Huang, 2,4-
Dichlorophenol removal from water using an electrochemical method improved by
a composite molecularly imprinted membrane/bipolar membrane, J. Hazard
Mater. 377 (2019) 259–266.
[6] N.M.M.A. Edris, J. Abdullah, S. Kamaruzaman, Y. Sulaiman, Voltammetric
determination of hydroquinone, catechol, and resorcinol by using a glassy carbon
electrode modified with electrochemically reduced graphene oxide-poly
(Eriochrome black T) and gold nanoparticles, Microchim. Acta 186 (4) (2019) 261.
[7] H. Ren, Y. Zhang, L. Liu, Y. Li, D. Wang, R. Zhang, W. Zhang, Y. Li, B.-C. Ye,
Synthesis of hollow Mo2C/carbon spheres, and their application to simultaneous
electrochemical detection of hydroquinone, catechol, and resorcinol, Microchim.
Acta 186 (5) (2019) 306.
[8] W.R. Wang, X.X. Wang, N. Cheng, Y.B. Luo, Y.H. Lin, W.T. Xu, D. Du, Recent
advances in nanomaterials-based electrochemical (bio)sensors for pesticides
detection, Trac. Trends Anal. Chem. 132 (2020) 116041.
[9] X. Yuan, D. Yuan, F. Zeng, W. Zou, F. Tzorbatzoglou, P. Tsiakaras, Y. Wang,
Preparation of graphitic mesoporous carbon for the simultaneous detection of
hydroquinone and catechol, Appl. Catal. B Environ. 129 (2013) 367–374.
[10] X. Wang, M. Xi, M. Guo, F. Sheng, G. Xiao, S. Wu, S. Uchiyama, H. Matsuura, An
electrochemically aminated glassy carbon electrode for simultaneous
determination of hydroquinone and catechol, Analyst 141 (3) (2016) 1077–1082.
C. Hu et al.
[11] M. Yu, L. Wu, J. Miao, W. Wei, A. Liu, S. Liu, Titanium dioxide and polypyrrole
molecularly imprinted polymer nanocomposites based electrochemical sensor for
highly selective detection of p-nonylphenol, Anal. Chim. Acta 1080 (2019) 84–94.
[12] T.-W. Chen, X.-N. Yu, S.-J. Liz, Simultaneous determination of dihydroxybenzene
isomers using glass carbon electrode modified with 3D CNT-graphene decorated
with Au nanoparticles, Int. J. Electroanal. Sc. 14 (8) (2019) 7037–7046.
[13] M.M. Barsan, M.E. Ghica, C.M.A. Brett, Electrochemical sensors and biosensors
based on redox polymer/carbon nanotube modified electrodes: a review, Anal.
Chim. Acta 881 (2015) 1–23.
[14] L.T. Yang, B.H. Zhang, B.J. Xu, F.Q. Zhao, B.Z. Zeng, Ionic liquid functionalized 3D
graphene-carbon nanotubes-AuPd nanoparticles-molecularly imprinted copolymer
based paracetamol electrochemical sensor: preparation, characterization and
application, Talanta 224 (2021) 121845.
[15] T.S. Anirudhan, V.S. Athira, V.C. Sekhar, Electrochemical sensing and nano molar
level detection of Bisphenol-A with molecularly imprinted polymer tailored on
multiwalled carbon nanotubes, Polym 146 (2018) 312–320.
[16] T. Alizadeh, S. Nayeri, An enzyme-free sensing platform based on molecularly
imprinted polymer/MWCNT composite for sub-micromolar-level determination of
pyruvic acid as a cancer biomarker, Anal. Bioanal. Chem. 412 (3) (2020) 657–667.
[17] M. Amatatongchai, W. Sroysee, P. Sodkrathok, N. Kesangam, S. Chairam,
P. Jarujamrus, Novel three-Dimensional molecularly imprinted polymer-coated
carbon nanotubes (3D-CNTs@MIP) for selective detection of profenofos in food,
Anal. Chim. Acta 1076 (2019) 64–72.
[18] C.-L. Choong, J.S. Bendall, W.I. Milne, Carbon nanotube array: a new MIP
platform, Biosens. Bioelectron. 25 (3) (2009) 652–656.
[19] Q. Yang, X.Q. Wu, H.L. Peng, L.W. Fu, X.L. Song, J.H. Li, H. Xiong, L.X. Chen,
Simultaneous phase-inversion and imprinting based sensor for highly sensitive and
selective detection of bisphenol A, Talanta 176 (2018) 595–603.
[20] W.H. Lu, J. Liu, J.H. Li, X.Y. Wang, M. Lv, R. Cui, L.X. Chen, Dual-template
molecularly imprinted polymers for dispersive solid-phase extraction of
fluoroquinolones in water samples coupled with high performance liquid
chromatography, Analyst 144 (2019) 1292–1302.
[21] A. Popov, B. Brasiunas, L. Mikoliunaite, G. Bagdziunas, A. Ramanavicius,
A. Ramanaviciene, Comparative study of polyaniline (PANI), poly(3,4-
ethylenedioxythiophene) (PEDOT) and PANI-PEDOT films electrochemically
deposited on transparent indium thin oxide based electrodes, Polym 172 (2019)
133–141.
[22] H. Wei, C. He, J. Liu, H. Gu, Y. Wang, X. Yan, J. Guo, D. Ding, N.Z. Shen, X. Wang,
S. Wei, Z. Guo, Electropolymerized polypyrrole nanocomposites with cobalt oxide
coated on carbon paper for electrochemical energy storage, Polym 67 (2015)
192–199.
[23] O.S. Ahmad, T.S. Bedwell, C. Esen, A. Garcia-Cruz, S.A. Piletsky, Molecularly
imprinted polymers in electrochemical and optical sensors, Trends Biotechnol. 37
(3) (2019) 294–309.
Polymer 242 (2022) 124593
[24] B. Mostafiz, S.A. Bigdeli, K. Banan, H. Afsharara, D. Hatamabadi, P. Mousavi, C.
M. Hussain, R. Keçili, F. Ghorbani-Bidkorbeh, Molecularly imprinted polymer-
carbon paste electrode (MIP-CPE)-based sensors for the sensitive detection of
organic and inorganic environmental pollutants: a review, TrEAC-Trend, Environ.
Anal. Chem. 32 (2021), e00144.
[25] L.X. Chen, X.Y. Wang, W.H. Lu, X.Q. Wu, J.H. Li, Molecular imprinting:
perspectives and applications, Chem. Soc. Rev. 45 (2016) 2137–2211.
[26] Y. Zhang, Z.Y. Liu, Y.G. Wang, X. Kuang, H.M. Ma, Q. Wei, Directly assembled
electrochemical sensor by combining self-supported CoN nanoarray platform
grown on carbon cloth with molecularly imprinted polymers for the detection of
Tylosin, J. Hazard Mater. 398 (2020) 122778.
[27] J. Li, Y. Li, X. Wei, Molecularly imprinted electrochemical sensors based on the
double-amplification from the electro-catalysis of poly-melamine and the
enzymatic catalysis of HRP for chlortoluron determination, Hua Hsueh Hsueh Pao
70 (17) (2012) 1853–1857.
[28] S. Wu, Z.-Z. Yin, X. Chen, X. Wang, D. Wu, Y. Kong, Electropolymerized melamine
for simultaneous determination of nitrite and tartrazine, Food Chem. 333 (2020)
127532.
[29] A.J.S. Ahammad, T. Akter, A. Al Mamun, T. Islam, M.M. Hasan, M.A. Mamun,
S. Faraezi, F.Z. Monira, J.K. Saha, Cost-effective electrochemical sensor based on
carbon nanotube modified-pencil electrode for the simultaneous determination of
hydroquinone and catechol, J. Electrochem. Soc. 165 (9) (2018) B390–B397.
[30] L.A. Goulart, L.H. Mascaro, GC electrode modified with carbon nanotubes and NiO
for the simultaneous determination of bisphenol A, hydroquinone and catechol,
Electrochim. Acta 196 (2016) 48–55.
[31] T.S.S.K. Naik, B.E.K. Swamy, Modification of carbon paste electrode by
electrochemical polymerization of neutral red and its catalytic capability towards
the simultaneous determination of catechol and hydroquinone: a voltammetric
study, J. Electroanal. Chem. 804 (2017) 78–86.
[32] S.Q. Feng, Y.Y. Zhang, Y.M. Zhong, Y.C. Li, S.X. Li, Simultaneous determination of
hydroquinone and catechol using covalent layer-by-layer self-assembly of
carboxylated-MWNTs, J. Electroanal. Chem. 733 (1) (2014) 1–5.
[33] D.H. Deng, S.J. Li, M.J. Zhang, X.N. Liu, M.M. Zhao, L. Liu, Anti-adsorption
properties of gold nanoparticle/sulfonated graphene composites for simultaneous
determination of dihydroxybenzene isomers, Anal. Methods 5 (2013) 2536–2542.
[34] F. Hu, S. Chen, C. Wang, R. Yuan, D. Yuan, C. Wang, Study on the application of
reduced graphene oxide and multiwall carbon nanotubes hybrid materials for
simultaneous determination of catechol, hydroquinone, p-cresol and nitrite, Anal.
Chim. Acta 724 (2012) 40–46.
[35] H. Zhang, S. Li, F. Zhang, M. Wang, X. Lin, H. Li, Simultaneous detection of
hydroquinone and catechol on electrochemical-activated glassy carbon electrode
by simple anodic and cathodic polarization, J. Solid State Electrochem. 21 (3)
(2017) 735–745.