Microporous and Mesoporous Materials 309 (2020) 110583

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Microporous and Mesoporous Materials

journal homepage: http://www.elsevier.com/locate/micromeso

MWCNT/zirconia porous composite applied as electrochemical sensor for

determination of methyl parathion
Karine dos Santos Caetano a, Danielle Santos da Rosa a, Tânia Mara Pizzolato a,
Pamela Andrea Mantey dos Santos c, Ruth Hinrichs b, Edilson Valmir Benvenutti a,
Silvio Luis Pereira Dias a, Leliz Ticona Arenas a, Tania Maria Haas Costa a, *
a
Instituto de Química, Universidade Federal do Rio Grande do Sul -UFRGS, CP 15003, CEP 91501-970, Porto Alegre, RS, Brazil
b
Instituto de Geociências, Universidade Federal do Rio Grande do Sul- UFRGS, CP 15001, CEP 91501-970, Porto Alegre, RS, Brazil
c
Departamento de Física, Universidade Federal de Santa Maria UFSM, CEP 97105-900, Santa Maria, RS, Brazil

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

Keywords: A selective, sensitive, quickly responsive and simple sensor for methyl parathion (MP) detection was developed
Carbon paste electrode using a composite based on a nearly 45% by weight of highly dispersed multiwalled carbon nanotubes (MWCNT)
Cyclic voltammetry in a zirconia matrix, synthesized by sol-gel method. The composite MWCNT/zirconia showed a mesoporous
Multiwalled carbon nanotubes
nature, presenting a high surface area of 135 m2 g− 1, where morphology and texture of MWCNT were preserved.
Zirconia matrix
Organophosphate pesticide detection
The modified carbon paste electrode, obtained with this porous composite, presented an electroactive area of 7.4
mm2, showing a good response for MP detection. The electrochemical parameters for MP were obtained by
differential pulse voltammetry (DPV) with detection limit of 9.0 × 10− 9 mol L− 1 and sensitivity of 1.475 μA
μmol− 1 L in a linear interval of 19.9 × 10− 6 at 176.8 × 10− 6 mol L− 1. The electrode presented good selectivity in
the presence of different interferences; it also showed good repeatability with RDS 0.91% for 13 cycles and
reproducibility with RSD 14.2% in measurements. The sensing platform was tested in an ethanolic soybean
extract with addition of methyl parathion at concentrations of 160; 180 and 200 × 10− 6 mol L− 1. The recoveries
varied from 102 to 113%, and the relative standard deviation was 5.2%. The developed sensor demonstrated to
be adequate for its utilization in the determination of methyl parathion with the purpose to ensure food safety.

1. Introduction magnetic resonance spectroscopy. However, they are expensive

Pesticides are widely used in agriculture as they offer benefits such as
increased quality and production. Organophosphate pesticides (OP)
represent 70% of these substances and they have been used for several
decades in the control of domestic pests and in agriculture. The most
used OPs are paraoxon, parathion, diazinon, chlorpyrifos, malathion,
coumaphos, fenitrothion, cyanophos and methyl parathion [1]. How­
ever, these organophosphates can be harmful to humans and animals as
they can contaminate water sources and even processed foods. The OPs,
such as methyl parathion (MP) affect proteins like the acetylcholines­
terase, which plays an important role in both the peripheral and the
central nervous system [2].
The analytical methods for the detection of these pesticides are
liquid, gas or thin layer chromatography, colorimetry, capillary elec­
trophoresis, enzyme-linked immunosorbent assays and nuclear
methods and require high-purity grade materials (solvents, columns,
vials, filters), they are also time-consuming and need well trained ana­
lysts [3,4]. Therefore, there is a great interest in finding other techniques
that can analyze OP quickly, reliably and economically. The electroan­
alytical methods are a good alternative because they are speedy,
low-cost, simple, potentially portable, easy-to-use [5] and constitute a
good solution to replace expensive instrumentation [1,6,7]. Therefore,
although there are many applications of the electrochemical techniques,
studies are still necessary to enhance their performance.
Several electrochemical sensors for MP detection, obtained from
different materials, have been proposed and applied to voltammetric
and amperometric techniques. Among them, there are those based on
carbon allotropic forms. Functionalized MWCNT were used properly to
modify glassy carbon electrodes (GCE) [8]. Kumar et al. [7] used a GCE
modified with acetylcholinesterase immobilized on semiconducting

* Corresponding author.
E-mail address: taniaha@iq.ufrgs.br (T.M.H. Costa).

https://doi.org/10.1016/j.micromeso.2020.110583
Received 28 May 2020; Received in revised form 17 August 2020; Accepted 19 August 2020
Available online 25 August 2020
1387-1811/© 2020 Elsevier Inc. All rights reserved.
K.S. Caetano et al.
single-walled carbon nanotubes. Xu et al. [9] developed a biosensor,
using single-walled carbon nanotubes decorated with gold nanoparticles
to modify a gold electrode. Yue et al. [10] constructed a sensor based on
carbon nanotubes grown on carbon paper. Song et al. [11] used a GCE
modified by nano-TiO2 and graphene composite film to construct a
sensor. Wu et al. [12] developed a GCE using molecularly imprinted film
containing MWCNT decorated with functionalized gold nanoparticles.
Dong et al. [13] reported an electrochemical sensor developed by using
modified GCE with a nanocomposite based on MWCNT–CeO2–Au.
The interest in the application of carbon nanotubes (CNT) in elec­
trochemical sensors is due to their good electrochemical durability and
higher performance in electrical conductivity [13]. Moreover, MWCNT
present good chemical and thermal stability, excellent mechanical
properties, good textural properties such as large specific surface area
and high pore volume, forming a network structure [10,14] that im­
proves the performance of the electrodes.
Metal oxides are also attracting interest when it comes to develop
modified electrochemical sensors [2,15–19], since their physicochem­
ical properties promote improvements in the performance of the elec­
trodes. Zirconia is desirable due to its chemical inertness, non-toxicity
and thermal stability [2]. Other advantages of zirconia are the presence
of basic and acidic surface active sites; it has abundant surface oxygen
defects, which exist in the crystalline phases and are formed after heat
treatment at temperatures above 400 ◦ C. Besides, the zirconia presents
good ion exchange capacity and allows functionalities that are desirable
in catalyzed electron transfer processes. Some of these characteristics
will be important according to the type of electrode to be prepared.
Zirconia also has strong affinity for organophosphorus pesticides
providing sensors with high selectivity and sensitivity [20–22].
The sol-gel method, which is easy-to-handle at ambient conditions,
allows to prepare a composite of MWCNT and zirconia, in which the
components are well dispersed and form a composite with adequate
morphology, combining the interesting characteristics of both, and
presenting desirable properties to be applied in the preparation of
electrodes [23].
Most of the works mentioned before developed the sensors by using a
glassy carbon electrode (GC). Although they have presented satisfactory
performance, the preparation of the GC electrodes requires time-
consuming procedures and modifications with multiple processes. Be­
sides, they have to be cleaned and polished for repeated use [10]. On the
other hand, the use of modified carbon paste electrodes for organo­
phosphorus pesticides determination has been promising, mainly as a
result of their high reproducibility. In this context, a modified carbon
paste electrode (CPE) was chosen to be studied since it presents ad­
vantages such as easy preparation, low-cost, improved selectivity and
sensitivity in the determination of specific analytes and also allows low
background current in a wide potential range [24]. Thus, in this work an
electrochemical sensor was developed by using a composite as a starting
material, which was obtained by sol-gel method and containing a high
percentage of multi walled carbon nanotubes dispersed in a zirconia
matrix. This sensor should be able to detect and evaluate the methyl
parathion in aqueous buffer solutions and in ethanolic soybean extract,
having in mind the importance of MP detection in food safety.
2. Experimental methods
2.1. Materials and reagents
The reagents used were: MWCNT Baytubes C150P (Bayer, Germany),
zirconium (IV) propoxide in 1-propanol (Sigma-Aldrich, USA, 70%),
acetyl acetone (Sigma-Aldrich, Germany, 99%), stearic acid (Dinâmica,
Brazil, 95%), ammonium hydroxide (Dinâmica, Brazil, 28–30%),
parathion-methyl (Sigma-Aldrich, Germany), ethanol (Emsure Merk,
Germany, 99.9%), dichloromethane (Merk, Germany, 99.5%), potas­
sium chloride (Emsure Merk, Germany, 99.5%). All cited reagents are of
analytical grade and were used without any purification. Britton-
2
Microporous and Mesoporous Materials 309 (2020) 110583
Robinson buffer solution (BR) (0.1 mol L− 1, pH 4.0) was made from
acetic acid (Dinâmica, Brazil, 99.7%), hydrochloric acid (Emsure Merk,
Germany, 37%) and boric acid (Neon, Brazil, 99.5%). Distilled water
was used for the preparation of all aqueous solutions.
2.2. Synthesis of MWCNT/zirconia composite
The composite MWCNT/zirconia, which was devised to have about
50% by weight of MWCNT, was prepared by sol-gel method according to
a process adapted from Almeida et al. [25]. Firstly, 100 mL of 10 g L− 1
ammonium stearate aqueous solution was prepared. In sequence, 10 mL
of this solution was used to disperse 1.35 g of MWCNT. This mixture was
ultrasonicated for 10 h at room temperature to disperse the carbon
nanotubes. When preparing the composite, 5.0 mL of zirconium
n-propoxide and 2.0 mL of acetylacetone were added to 10 mL of
MWCNT/ammonium stearate water dispersion, at room temperature
and under stirring. The condensation and drying of the composite
occurred at ambient conditions, left standing over a week. The xerogel
composite MWCNT/zirconia formed was ground, washed with ethanol
and vacuum dried.
2.3. Elemental analysis (CHN)
PerkinElmer MCHNS/O, 2400 equipment was used and approxi­
mately 2.0 mg of sample were used in the analysis.
2.4. Thermogravimetric analysis (TGA)
MWCNT/zirconia composite and Bayer pure nanotubes (Baytubes)
were subjected to thermogravimetric analysis using a TGA-50 analyzer
(Shimadzu, Japan). The samples were heat treated from ambient tem­
perature to 900 ◦ C at a rate of 20 ◦ C min− 1 in an inert atmosphere using
nitrogen as the purge gas.
2.5. Raman spectroscopy
The Raman spectra were obtained for the MWCNT/zirconia com­
posite using a Horiba Jobin-Yvon iH30 Helium–Neon laser spectrometer
with a wavelength of 632 nm and a nominal power of 10 mW and liquid
nitrogen-cooled CCD.
2.6. EDX obtained by SEM
The elemental analysis EDX was carried out using a JEOL LV5800
SEM microscope. The sample was compacted as disks (4.6 ton cm− 2).
2.7. X-ray diffraction (XRD)
X-ray diffraction was performed in a Siemens D500 diffractometer
using Cu-Kα (α = 0.154056 nm) radiation with θ/2θ geometry with 2θ
ranging from 10◦ to 90◦ .
2.8. Transmission electron microscopy (TEM)
Images were taken from the MET JEOL - JEM 1200 EXII equipment
operating at a voltage of 80 kV. The MWCNT/zirconia composite sus­
pension was obtained by dispersing the sample in isopropyl alcohol by
means of an ultrasonic bath for 5 min. Then, 1 drop of this dispersion
was added to the carbon-coated copper grid and dried at room
temperature.
2.9. N2 adsorption and desorption isotherms
N2 adsorption and desorption isotherms were obtained at liquid ni­
trogen temperature (77 K), using the Tristar II 3020 Krypton Micro­
meritics equipment. The sample was heated at 393 K for 10 h under
K.S. Caetano et al.
vacuum. The specific surface area was obtained by the BET multipoint
technique and the pore size distribution was calculated by the BJH
method.
2.10. Electrochemical measurements
The paste for the CPE was made by using the composite MWCNT/
zirconia according to the following procedure: 15 mg of composite and
6 μL of mineral oil were placed in an agate crucible for homogenization.
A portion of the paste was put in a Teflon cylinder containing a cylin­
drical hole with 1 mm depth and 3 mm diameter. The geometric area
was calculated as 7.1 mm2. This set was put in a glass tube fused to a 5
mm diameter platinum disk, which was connected to an external device
by a conducting wire.
This modified CPE was characterized by cyclic voltammetry (CV) by
using a three-electrode system, in which a platinum wire was used as
counter electrode, a saturated calomel electrode (SCE) was used as
reference electrode and the modified CPE was used as working elec­
trode. An aqueous solution containing the iron redox pair potassium
ferrocyanide/ferricyanide 0.001 mol L− 1 and KCl 0.5 mol L− 1, was used
as support electrolyte. Measurements were performed at room temper­
ature, and cyclic voltammograms were performed at different scan rates
(5–300 mV s− 1). A potential range of − 0.2 to 0.6 V was adopted for these
measurements.
The differential pulse voltammetry (DPV) and the CV techniques
were used for the analysis of the pesticide MP. Firstly, buffer and pH
tests were carried out and the Britton-Robinson (BR) at pH 4 was
applied. The measurements were performed in an electrochemical cell
containing 10 mL of 0.1 mol L− 1 BR buffer with KCl 0.1 mol L− 1. A
pesticide ethanolic stock solution 0.01 mol L− 1 was prepared. At each
stock solution addition, the system was stirred for 15 s and left standing
for 60 s before the readings. The applied potential range was 0.5 to − 0.7
V, pulse time 110 × 10− 3 s, pulse amplitude 100 mV, and scan rate 0.02
V s− 1 for the DPV measurements.
2.11. Interference analysis
The cations and anions Cu2+, Cl− , Mg2+, SO2− 4 , Na , Ni
+ 2+
and the
nitroaromatic compound ρ-NPP were tested as interferences in the
presence of a 10 mL solution containing 49.8 μmol L− 1 of MP. A 10 μL
aliquot of each interference at a concentration of 0.1 mol L− 1 was added
immediately after the addition and reading of the MP, resulting in a
concentration of 94 μmol L− 1.
2.12. Soybean sample preparation
Shelled soybean samples were purchased from a local supermarket.
10 g of soybeans were crushed with 10 mL of dichloromethane. Subse­
quently, this solution was filtered with 0.45 mm membrane filters. The
filtrates were evaporated, then 2 mL of ethanol were added. A stock
solution of MP (0.01 mol L− 1) was prepared from the latter solution.
Stock solution aliquots of 20 μL were added in a cell containing 10 mL of
BR buffer solution, pH 4, attaining concentrations of 160; 180 and 200
× 10− 6 mol L− 1 of MP in the soybeans extracts that were used for the
analyses. A blank solution without MP was also prepared according to
the same procedure.
3. Results and discussion
3.1. Structural and textural characterization of the MWCNT/zirconia
composite
The obtained MWCNT/zirconia composite was characterized by
CHN Elemental Analysis and the result showed that 44.6% of carbon was
incorporated. The presence of 1.6% hydrogen content was also detected.
Thermogravimetric analysis (TGA) provided us information on the
3
Microporous and Mesoporous Materials 309 (2020) 110583
weight loss of MWCNT/zirconia composite and pure Bayer MWCNT
(Baytubes) as the temperature increases. The thermograms obtained are
presented in Fig. 1.
According to Fig. 1, the MWCNT/zirconia composite showed sig­
nificant weight losses during the whole heating process. Between room
temperature and 150 ◦ C there are weight losses related to the humidity
of the analyzed materials. These losses are close to zero for MWCNT,
which presents hydrophobicity, and close to 4% for the MWCNT/zir­
conia sample, thus indicating that the composite became more hydro­
philic. The composite sample, unlike MWCNT, showed greater weight
loss between 150 and 600 ◦ C because it contains the remaining organic
part from the sol-gel moiety. From 250 ◦ C on, the weight loss of this
composite is also related to the dehydroxylation of zirconium hydroxyl
groups formed during the sol-gel process, which is converted into zir­
conium oxide during heating. Even considering all the losses, the residue
is 73.3% of the original weight. On the other hand, MWCNT Baytubes
have more expressive weight loss from 500 ◦ C on, maintaining a residue
of 84.5%, indicating their high thermal stability. Table 1 shows the
percentage of weight loss within certain temperature ranges.
The MWCNT/zirconia composite as well as the pristine MWCNT
were characterized by Raman spectroscopy and the spectra can be
observed in Fig. 2a and in the inset of Fig. 2a, respectively. The obtained
spectrum shown in the inset of Fig. 2a is characteristic of carbon
structures, containing the D band, at ca. 1350 cm− 1, which is related to
defects due to tetrahedral carbon atoms contained in the MWCNT; G
band at ca. 1580 cm− 1 which is ascribed to the vibration of the hexagons
formed by the trigonal carbons of the nanotube structure, and the G′
band at ca. 2680 cm− 1 which represents the harmonic tone of band D.
These same bands are found in the spectrum of MWCNT/zirconia
composite (Fig. 2 a), thus confirming the presence and integrity of the
MWCNT. The spectrum also showed a fluorescence effect caused by the
presence of zirconia. Similar result was obtained by the study of dos
Santos et al. [23] in which materials based on MWCNT incorporated in
zirconia were obtained.
The X-ray diffractograms for the MWCNT/zirconia composite and for
the pristine MWCNT are shown in Fig. 2b and in the inset of Fig. 2b,
respectively. The characteristic peak of MWCNT can be seen near the
angle 2θ = 26◦ in the inset of Fig. 2b; this peak is related to the carbon
graphitic plane 002, The diffractogram of the composite is very similar
to the pristine carbon nanotubes, this is a good indication of its
composition to be majority in MWCNT [23]. No peaks referring to the
zirconia phase were observed, only a halo between 20 and 35◦ , indi­
cating that the zirconia phase is in the amorphous form. This result was
expected since the zirconia was prepared by sol gel method at room
Fig. 1. TGA of MWCNT/zirconia composite and MWCNT (Baytubes).
K.S. Caetano et al. Microporous and Mesoporous Materials 309 (2020) 110583

Table 1 alone, has a surface area of 196 ± 5 m2 g− 1 [27]. These results of textural
Percentage mass loss of MWCNT/zirconia samples. properties, which showed the presence of micro and mesoporosity of the
Sample Weight loss (%) Residue MWCNT/zirconia composite, as well as the high surface area, make this
(%) kind of materials eligible for their application as electrodes, because
25 C–150 C
◦ ◦
150 C–600 C
◦ ◦
600 C–900 C
◦ ◦
they facilitate the diffusional process of the analytes, improving the
MWCNT/ 4.0 19.0 3.8 73.3 electrode response.
zirconia
MWCNT 0.0 4.5 11.0 84.5
Baytubes 3.2. Electrochemical characterization of MWCNT/zirconia composite in
K3[Fe(CN)6]/K4[Fe(CN)6] probe solution

temperature and did not suffer any thermal treatment that could induce
The redox behavior of probe solution using the MWCNT/zirconia
crystallization.
modified CPE was evaluated by cyclic voltammetry (CV) in a 0.001 mol
The TEM images (Fig. 3a and b) in conventional transmission mode
L− 1 K3[Fe(CN)6]/K4[Fe(CN)6] solution containing 0.5 mol L− 1 of KCl
provides morphology details of the MWCNT/zirconia composite. It is
and the voltammogram is shown in Fig. 6a. The anodic peak at 0.292 V
possible to observe that the integrity of the MWCNT is physically and
vs SCE and the cathodic peak at 0.158 V vs SCE attributed to redox
morphologically preserved. The dark and apparently amorphous mate­
behavior of the Fe (II)/Fe (III) system were observed. The separation of
rial, in the middle of the entangled MWCNT, is interpreted as the zir­
peaks (ΔEp) was 0.134 V vs SCE, whose value is higher than the ideal
conia matrix, considering that the zirconium has a high atomic number
ΔEp value, which is 0.059 V. This behavior is typical of a quasi-revers­
and, therefore, appears dark in conventional TEM. The images confirm
ible process, thus indicating resistance of electron transfer on the elec­
that the nanotubes are present in large volumetric proportions, suffi­
trode surface [29,30]. In relation to the intensity of anodic (ipa) and
cient to provide continuous paths that allow electrical conductivity. In
cathodic (ipc) peaks, the ipa/ipc ratio value, which is close to 1, indicates
this composite the zirconia fraction provides support for the MWCNT.
good reversibility [29,31].
Fig. 4a shows a SEM backscattered electron image (BEI) of the
The cyclic voltammograms at different scan rates from 5 to 300
MWCNT/zirconia composite, in which dark and light areas form
mVs− 1 and the ratio between ipa, ipc and square root of scan rate (v1/2)
micrometric domains. The contrast of BEI is opposite to the TEM
are shown in Fig. 6b and in the inset of Fig. 6b, respectively. A slight
contrast, and regions with higher atomic numbers are bright. The EDX
increase in the peak separation, which is proportional to the scan rate
spectra of areas 1 and 2 (Fig. 4b and c, respectively) indicate that the
increase, was detected for the modified CPE, suggesting that the process
dark area 1 is rich in carbon (and poor in Zr), while the bright area 2 is
involved in the electrode/solution interface is quasi-reversible. In
rich in zirconium (and poor in carbon).
addition, the CVs of MWCNT/zirconia electrode showed a linear ratio
Textural analysis using nitrogen adsorption and desorption iso­
between the square root of the scan rate and the anodic and cathodic
therms of the MWCNT/zirconia composite is shown in Fig. 5 and the
BJH pore size distribution curve is shown in the inset of Fig. 5. In the
isotherm shown in Fig. 5, it is possible to observe an increase in the
amount of adsorbed nitrogen at relative pressure P/Po above 0.8, and
also the presence of hysteresis, whose behavior is typical of mesoporous
materials containing large pores. The BJH pore size distribution curve,
presented in the inset of Fig. 5, shows a bimodal distribution. The pore
region with diameter below 5 nm with a peak at 2.3 nm is related to the
pores that are formed by the mouth of the CNT tubes and the mesopore
region with diameter between 10 and 50 nm, with maximum at 30 nm, is
due to the entanglement of these tubes [26], as observed by TEM. This
bimodal pore size distribution is typical of MWCNT and it was main­
tained in the composite [27,28]. This composite presents the surface
area value of 135 ± 5 m2 g− 1 and pore volume of 0.469 cm3 g− 1. This
significant porosity can be explained by the presence of a high volu­ Fig. 3. Images of transmission electron microscopy of MWCNT/zirconia com­
metric amount of MWCNT in the composite, which, when considered posite in different magnifications. (a) 200kx and (b) 100kx.

Fig. 2. (a) Raman spectrum of MWCNT/zirconia composite. Inset Fig. 2 (a): Raman spectrum of pristine MWCNT (b) X-Ray diffractogram of MWCNT/zirconia
composite. Inset of Fig. 2 (b): X-Ray diffractogram of pristine MWCNT.

4
K.S. Caetano et al. Microporous and Mesoporous Materials 309 (2020) 110583

Fig. 4. (a) Backscattered electron image obtained by SEM of MWCNT/zirconia composite. EDX spectra of (b) area 1 (dark) and (c) area 2 (light).

( )
ipc (μA) = − 2, 97 (±0, 13) − 0, 59 ( ± 0, 01)v1/2 mV1/2 s− 1 withR2 = 0.993
(2)
The linear behavior between ipa, ipc and v1/2, suggests that the
oxidation and the reduction of the probe solution in the interface elec­
trode/solution are controlled by diffusion [32,33]. Thus, the electro­
active area of the MWCNT/zirconia electrode can be calculated with
approximation by using Equation (3) of the Randles-Sevcik model [34].

ip = 2.69x105 .n3/2 .A.D01/2 .C. v1/2 (3)

where ip is the peak current (A) at 0.02 V s− 1, n is the number of elec­

trons transferred in the redox process, A is the electroactive area (cm2),
D0 is the diffusion coefficient (6.7 × 10− 6 cm2 s− 1) and C is the con­
centration of the probe solution (1 × 10− 6 mol cm− 3)
Isolating A (electroactive area) from equation (3), the electroactive
area was determined, resulting in 7.4 mm2 for CPE of MWCNT/zirconia
composite, which is comparable to other MWCNT based electrodes [35,
36]. This electroactive area is considered satisfactory for application of
the electrode as sensor [15,37].
Fig. 5. Textural analysis of the MWCNT/zirconia composite: N2 adsorption and
desorption isotherms. Inset Fig. 5: Pore size distribution curve of MWCNT/
3.3. Behavior of MWCNT/zirconia composite as electrochemical sensor
zirconia composite obtained by the BJH method.
for methyl parathion (MP)

peak intensity, as shown in the inset of Fig. 6b and described by Equa­
tions (1) and (2) respectively.
( )
ipa (μA) = 1.37 (±0.24) + 0.92(±0, 02)v1/2 mV1/2 s− 1 withR2 = 0.991 (1)
In order to obtain the best response for MP, when the MWCNT/zir­
conia modified CPE is applied, studies were performed using DPV, in
different buffer solutions (sodium acetate, Britton-Robinson and sodium
phosphate), and different pH values, commonly reported in the

Fig. 6. (a) CV of MWCNT/zirconia modified CPE in the presence of 0,001 mol L− 1 K3[Fe(CN)6]/K4[Fe(CN)6] and 0.5 mol L− 1 of KCl at scan rate 20 mV s− 1. (b) CVs of
MWCNT/zirconia modified CPE varying scan rate from 5 to 300 mV s− 1 in K3[Fe(CN)6]/K4[Fe(CN)6] solution 0.001 mol L− 1. Inset Fig. 6 (b): Linear relationship
between ipa, ipc and v1/2.

5
K.S. Caetano et al.
literature [11,38,39] for this analyte. Britton-Robinson buffer pH 4
presented the best response for reduction peak, and it was chosen to
perform the MP determination. These results are presented in Fig. S1. to
S3. These evaluations of buffer and pH are very important steps, which
allow to determine the optimal conditions of analyte detection, the
optimal conditions that enable the oxidation/reduction process in the
electrode surface, aiming to obtain the best response of the electrode,
such as the best sensitivity and the lowest detection limit.
The CVs of MWCNT/zirconia modified CPE in the absence and in the
presence of 291.3 × 10− 6 mol L− 1 of MP in BR pH 4 buffer solution are
presented in Fig. 7, curves (A) and (B) respectively. In the absence of MP,
no anodic or cathodic peak current was observed. However, when the
CV, using the MWCNT/zirconia CPE, was performed in the presence of
MP, there is a pair of reversible redox peaks, with oxidation potential at
− 0.04 V and reduction peak at − 0.07 V. These peaks are ascribed to the
two-electron transfer process [15,38] and are related to oxidation and
reduction reactions of hydroxylamine group (-NHOH) and nitrous group
(-NO2) of MP, as shown in the inset of Fig. 7. Besides, in Fig. 7, there is an
intense peak near Epc = -0.5 V, which is related to the reduction re­
actions of the nitro group from MP to hydroxylamine group, as shown in
the inset of Fig. 7.
Peak current measurements as a function of scan rates provide in­
formation about the mechanism at the electrode/solution interface. CVs
of MWCNT/zirconia modified CPE in the presence of MP at different
scan rates (5–300 mV s− 1) are shown in Fig. 8. It is possible to observe
that both anodic and cathodic peak currents increase linearly by
increasing the scan rates, demonstrating that the reaction on the elec­
trode surface is an adsorption-controlled process [40].
In Fig. S4a, a linear ratio between scan rate and the anodic and
cathodic peak intensities obtained for the MWCNT/zirconia modified
CPE in the presence of MP can be observed. The related equations (4)
and (5) are described by:
( )
ipa (μA) = 3.27( ± 0.88) + 0.35 ( ± 0.01)v mVs− 1 with R2 = 0.997 (4)
( )
ipc (μA) = 8.6( ± 0.72) − 0.34( ± 0.01)v mVs− 1 with R2 = 0.989 (5)
In order to confirm which process occurs on the electrode surface,
the relation between log ip and log v was plotted and an example of a
series of experiments is shown in Fig. S4b and the related equations (6)
and (7) are described by:
Fig. 7. CVs of MWCNT/zirconia modified CPE (A) in the absence and (B) in the
presence of 291.3 × 10− 6 mol L− 1 MP in 0.1 mol L− 1 BR buffer solution (pH 4).
Scan rate 20 mV s− 1. Inset Fig. 7: Representation of MP redox reactions.
6
Microporous and Mesoporous Materials 309 (2020) 110583
Fig. 8. CVs of MWCNT/zirconia modified CPE obtained at different scan rates
(5–300 mV s− 1) for modified MWCNT/zirconia CPE in 0.1 mol L− 1 BR buffer,
pH 4 containing 291.3 × 10− 6 mol L− 1 MP.
( )
logipa (μA) = − 0.16( ± 0.03) + 0.88( ± 0.01)logv mVs− 1 with R2 = 0.997
(6)
( )
logipc (μA) = − 0.15 ( ± 0.07) + 0.90 ( ± 0.04)logv mV s− 1 with R2
= 0.989 (7)
According to this model, when the slope of the relations between log
ip and log v present values between 0.5 and 1.0, there is an indication
that the process is controlled by diffusion and adsorption simulta­
neously. A slope value of 0.5 would imply a diffusion-controlled process,
whereas a value of 1.0 indicates that the process is adsorption-controlled
[41,42]. Four series of experiments were performed with different
electrodes in the presence of MP and in similar conditions. The average
slopes, the standard deviations and the coefficients of variation are
presented in sequence. The average slope of log ipa vs log v was 1.01,
with standard deviation 0.09 and the coefficient of variation was 8.9%.
As for the cathodic reaction, the average slope of log ipc vs log v was 1.09
with standard deviation 0.06 and the coefficient of variation was 5.5%.
Considering that the average slope was close to 1, it can be affirmed that
the mechanism of oxidation and reduction of MP is controlled by
adsorption. The MWCNT/zirconia modified CPE is based on a composite
in which the components are dispersed in a micrometer level. Both the
zirconia [22] moiety and the MWCNT [10] present capacity for MP
adsorption.
3.4. Electroanalytical performance for MP by differential pulse
voltammetry
The result of DPV for MP, using the MWCNT/zirconia modified CPE,
is shown in Fig. 9a. Two reduction peaks were seen, one near − 0.5 V and
other near 0.1 V. The MP reduction peak at − 0.5 V (NO2-MP to NHOH-
MP) was selected, since the intensity of this peak was higher when
compared with the MP reduction peak at 0.1 V, as observed. The same
MP reduction peak was also chosen in the study carried out by Govin­
dasamy et al. [5]. Fig. 9a also shows the DPV of MP in the same con­
centration, using a modified CPE without zirconia, using MWCNT alone,
where it is possible to observe that the peaks are less intense and less
defined. This result indicates that the presence of zirconia in the com­
posite enhances markedly the response of the electrode, thus increasing
the intensity of the reduction peaks and shifting the position of peaks
towards more positive values.
The response of the MWCNT/zirconia electrode in relation to MP
K.S. Caetano et al. Microporous and Mesoporous Materials 309 (2020) 110583

Fig. 9. (a) DPVs of MWCNT/zirconia modified CPE and MWCNT modified CPE, both made in BR buffer 0.1 mol L− 1, pH 4 in presence of 99 × 10− 6 mol L− 1 MP. Pulse
time 110 × 10− 3 s, pulse amplitude 100 mV and scan rate 0.02 V s− 1. (b) DPVs of MWCNT/zirconia modified CPE in 0.1 mol L− 1 BR buffer solution pH 4 and 0.1 mol
L− 1 of KCl in different MP concentrations (19.9 × 10− 6 to 176.8 × 10− 6 mol L− 1). Pulse time 110 × 10− 3 s, pulse amplitude 100 mV and scan rate 0.02 V s− 1. Inset
Fig. 9: Linear relation between ipc and MP concentration.

additions at concentrations in the range from 19.9 × 10− 6 mol L− 1 to

Table 2
176.8 × 10− 6 mol L− 1 was verified by DPV in Britton-Robinson buffer
Electrodes applied in MP quantification, for comparison.
solution of 0.1 mol L− 1 and pH 4. The obtained voltammograms are
shown in Fig. 9b and the variation of current intensity as a function of Electrode Linear range (mol L− 1) Detection limit (mol Ref.
L− 1 )
MP concentration is shown in the inset of Fig. 9b. As can be seen in the
inset of Fig. 9b, there is a linear relation between ipc and MP concen­ AB–chitosan film/ 2.0 × 10− 8– 1.0 × 2.0 × 10− 9
[43]
CGE 10− 4
tration in this concentration range, which is described by Equation (8):
Pd/MWCNTs 3.43 × 10− 7 – 4.81 × 1.72 × 10 − 7
[38]
( ) 10− 5
i(μA) = 2.185 + 1.475 [MP] μmolL− 1 with R2 = 0.999 (8)
MWCNTs–PAAM/ 5–2 × 10− 9 2 × 10− 6
[15]
The electrode sensitivity was obtained by the angular coefficient of GCE
MIPs 2.0 × 10− 7 –1.0 × 6.7 × 10− 8
[14]
equation 9, which was 1.475 μA μmol − 1 L. The detection limit (DL)
10− 5
calculated was 9.0 × 10− 9 mol L− 1 using the relation DL = 3 x SDb/ Ag@GNRs/SPCE 0.5 × 10− 9 – 2780 × 0.5 × 10 − 9
[5]
sensitivity and the limit of quantification (LQ) was obtained by the 10− 6
relation, LQ = 10 x SDb/sensitivity, with the result of 0.03 × 10− 3 mol 3.43 × 10− 8– 3.43 × − 9
CNTs/CP 13.4 × 10 [10]
10− 6
L− 1 and SDb is the standard deviation of the blank solution with n = 3.
TiO2/Graphene/GCE 0.002–5.0 × 10− 6 1 × 10− 9
[11]
Table 2 shows a comparison of MWCNT/zirconia modified CPE with 5.0–100 × 10− 6
other electrodes already reported for MP detection. MIP/Au/GCE 0.05–15 × 10− 6 0.01 × 10− 6 [44]
It can be observed that the electrode of this work presented low DL CP5-rGO/GCE 0.001–150 × 10− 6 0.0003 × 10− 6
[6]
when compared with most works, mainly those with electrodes made ZrO2NPs/PEDOT/ 17.2 × 10− 9– 6.86 × 9.61 × 10− 9 [45]
ITO 10− 6
with CNT, indicating that it is highly sensitive at low concentrations. It is
NPG/GCE 0.5–150 × 10− 6 0.02 × 10− 6 [4]
a very interesting result when taking into consideration that the com­ GCE/MWCNTs 1.0 × 10− 7 – 3.4 × 3.3 × 10− 8 [8]
posite is relatively simple and obtained from a low-cost reproducible 10− 5
technique which is sol-gel. The obtained DL is sufficient to detect sub MWCNT/zirconia 19.9–176.8 × 10− 6 9.0 × 10− 9
This
work
lethal concentrations for fish. According to the study by Monteiro [46]
the sub lethal dose for fish is 2 mg L− 1 (6.86 × 10− 6 mol L− 1) and ac­ AB: Acetylene Black.
cording to Machado the lethal concentration is 7 ppm (24 × 10− 6 mol CGE: Glassy Carbon Electrode.
L− 1) [47]. Another factor is that the electrode presented a quick Pd/MWCNTs: Palladium/Multi walled carbon nanotubes.
response, which was achieved just 1 min and 15 s after the electrode PAAM: Poly(acrylamide).
immersion in the MP-containing solution, while some studies present MIPs: Molecularly imprinted polymer.
GNR/SPCE: graphene nanoribbons/screen printed carbon electrode.
responses after a longer immersion time in the MP solution [11,15,39,
CNTs/CP: Carbon nanotubes/Carbon paper.
45].
CP5-rGO: Pillar [5]arene-Reduced graphene.
ZrO2 NPs/PEDOT/ITO: Zirconia nanoparticles/Poly 3,4-ethylenedioxythiophe­
3.5. Repeatability and reproducibility ne/Indium tin oxide
NPG: Nanoporous gold.

Repeatability and reproducibility were evaluated for the MWCNT/

zirconia modified CPE. The repeatability test was performed by CV in a
solution containing 99 × 10− 6 mol L− 1 of MP. The same electrode was
used in 13 cycles and the relative standard deviation was 0.91%. After
20 cycles, the deviation increased to 7.6%. For the purpose of evaluating
the reproducibility, DVP technique was used and seven different elec­
trodes were tested in a solution containing 39.8 × 10− 6 mol L− 1 MP. The
relative standard deviation obtained was 14.2%, indicating a good
reproducibility in the preparation of the electrodes.
3.6. Interference studies
As it is intended to apply the manufactured electrode in real samples,
it is very important to evaluate the effect of some ions and nitro aromatic
compounds on MP detection and to test the selectivity of the MWCNT/
zirconia modified CPE. The DPV of MP response at 49.8 × 10− 6 mol L− 1
concentration was tested together with 10 μL of a 0.1 mol L− 1 solution of
Cu2+, Cl− , Mg2+, SO2− 4 , Na , Ni
+ 2+
ions, and nitrophenolic compound

7
K.S. Caetano et al.
ρ-NPP in 10 mL of BR buffer solution. The results indicated a high
selectivity of MWCNT/zirconia composite towards MP, since the MP
peak intensity did not present significant change. Only Mg2+ and SO2− 4 ,
ions showed interference in the MP measurement. These ions, when at
concentration of 94 × 10− 6 mol L− 1, resulted in a 7.8% reduction of MP
peak.
3.7. Application in soybean extract samples
In order to evaluate the electrochemical sensor, the determination of
MP was performed in a soybean sample spiked with MP. Different
concentrations of MP in the soybean samples were used, namely, 160,
180 and 200 × 10− 6 mol L− 1. The recoveries of the measured samples
lay between 102 and 113%, and the relative standard deviation (RSD)
was 5.2%. MP was not detected in blank samples. These results indicate
that this electrode presents potential for the determination of MP in
soybean extract samples.
4. Conclusion
In conclusion, a promising sensor for detecting MP in food was
developed. It was applied in ethanolic soybean extract and showed
satisfactory recovery and repeatability. This quick response sensor, ob­
tained with the modified MWCNT/zirconia CPE, showed high sensitivity
to MP of 1.475 μA μmol− 1 L. The sensor also presented a low limit of
detection, 9.0 × 10− 9 mol L− 1, and good selectivity in the presence of
different interferences. The sensor also showed good repeatability dur­
ing 13 consecutive runs and good reproducibility, with RSD value of
14.2%. The successful figures achieved by this sensor prepared with
porous MWCNT/zirconia composite indicated a good performance.
This performance was based on modified carbon paste electrode
developed from a mesoporous composite based on near 45 wt % of
highly dispersed MWCNT in a zirconia matrix, synthesized by sol-gel
method. The morphology and texture of MWCNT was maintained
affording high surface area, porosity and conductivity to the composite.
Zirconia, in turn, enhances the response of the electrode due to its af­
finity for MP, besides acting as support for the dispersion of the MWCNT.
Due to its important physicochemical characteristics, the composite
is promising for application in the determination of other analytes with
redox properties. Additionally, by using the chemical properties of zir­
conia, the composite can act as support for electroactive species in the
study of specific analytes.
CRediT authorship contribution statement
Karine dos Santos Caetano: Conceptualization, Validation, Inves­
tigation, Formal analysis, Writing - original draft, Writing - review &
editing, Visualization. Danielle Santos da Rosa: Validation, Investi­
gation, Formal analysis. Tânia Mara Pizzolato: Conceptualization,
Methodology, Resources. Pamela Andrea Mantey dos Santos: Meth­
odology, Conceptualization, Investigation. Ruth Hinrichs: Investiga­
tion, Visualization, Resources. Edilson Valmir Benvenutti:
Investigation, Formal analysis, Resources, Funding acquisition, Writing -
review & editing. Silvio Luis Pereira Dias: Resources, Methodology.
Leliz Ticona Arenas: Conceptualization, Methodology, Validation,
Formal analysis, Resources, Writing - original draft, Writing - review &
editing, Visualization, Supervision, Funding acquisition. Tania Maria
Haas Costa: Conceptualization, Methodology, Validation, Resources,
Writing - original draft, Writing - review & editing, Visualization, Su­
pervision, Funding acquisition.
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.
8
Microporous and Mesoporous Materials 309 (2020) 110583
Acknowledgements
We want to acknowledge to the Brazilian agencies: Conselho
Nacional de Desenvolvimento Científico, Tecnológico, Fundação de
Amparo à Pesquisa do Estado do Rio Grande do Sul and Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior. Acknowledgements also
to Centro de Microscopia e Microanálise of UFRGS for providing the
images and to Professor Silvio Buchner, LAPMA UFRGS for Raman
spectra.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2020.110583.
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