Surfaces and Interfaces 16 (2019) 108–113

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Surfaces and Interfaces

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Highly sensitive fipronil pesticide detection on ilmenite (FeO.TiO2)-carbon T

paste composite electrode
⁎
Muhammad Nurdina, , Owink Agung Prabowoa, Zul Arhamb, Dwiprayogo Wibowoc,
⁎
Maulidiyah Maulidiyaha, Siti Khatijah Md Saadd, Akrajas Ali Umard,
a
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Halu Oleo, Jl. H.E.A. Mokodompit Kampus Baru Anduonohu, Kendari 93232 –
Southeast Sulawesi, Indonesia
b
Department of Mathematics and Natural Sciences, Institut Agama Islam Negeri (IAIN), Jl. Sultan Qaimuddin No.17, Kendari 93563 – Southeast Sulawesi, Indonesia
c
Department of Environmental Engineering, Faculty of Engineering, Universitas Muhammadiyah Kendari, Jl. K.H. Ahmad Dahlan No. 10, Kendari 93127 – Southeast
Sulawesi, Indonesia
d
Institute of Microengineering and Nanoelectronics, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Ilmenite (FeO.TiO2) has been widely known as an excellent catalyst in antimicrobial activity, chemical oxygen
CPE demand (COD) sensing, photocatalysis and photoelectrocatalysis. Here we report the role of ilmenite in elec-
FeO.TiO2 trochemical detection of fipronil pesticide using ilmenite modified carbon paste electrode. It was found that the
Voltammetry ilmenite effectively enhanced the electrochemical sensing of CPE electrode towards the presence of fipronil
Fipronil
pesticide compound in 1.0 M MgSO4 electrolyte solution with a strong anodic current (160 µA) at the oxidation
Pesticide
potential of −0.4 V, which is related to the electron releasing from the compound. The limit of the detection
(LOD) and Horwitz Ratio (HR) values were calculated to be as low as 0.0012 μM and 0.173%. The electrode also
demonstrates high stability with life-time usage can be up to 24 days of repeated used. The new ilmenite-CPE
electrode is also able to detect the presence of fipronil under a high concentration of Cu2+ ion, inferring a high
selectivity property. The electrode preparation and the sensing characterization will be discussed in details.

1. Introduction
Fipronil is a group of pyrazole phenyl that has been widely used as
insecticide which acts by attacking the nervous system, paralyzing or
killing the target organisms [1,2]. It has recently been used to control
the formation of adult pest and larvae, such as beetles, cockroaches,
flies, mosquitoes, ants, and termites, and has been found to be more
effective in eradicating insects that are resistant to other pesticides
[2,3]. Therefore fipronil pesticide has been widely used in agriculture
industry, particularly crops and poultry as well as bee farm [4–11].
While the use of pesticide may improve the productivity of the agri-
culture, its residue has been well known to contaminate soil, air and
water [12,13]. The presence of fipronil has also been detected in
poultry and dairy product such as chicken meat, eggs and cow milk that
has been exposed to the fipronil contaminated environment
[4,6,8,9,14]. Due to these widespread contaminations of fipronil, the
human being will be severely exposed to the possibility of health risk
such as nervonal system and blood biochemistry [5,15–17]. For that
reason, the effort to limit the usage of fipronil pesticide and at the same
time to develop devices that can detect the trace presence of it in the
environment is highly demanded.
In general, the detection of fipronil was carried out using a chro-
matographic technique, such as thin layer chromatography (TLC)
method, high performance liquid chromatograph (HPLC) and gas
chromatography-mass spectrometry (GC-MS) technique [18–21].
Normal in chromatography technique, the process is complicated that
involved lengthy sample preparation and refinement, longer analysis
time and vulnerable to measurement error [22]. Recently, the im-
plementation of Raman microscopy and surface enhanced Raman
scattering technique in fipronil detection were also reported. These
methods provide rapid detection of fipronil in shorter time; however
these methods involved costly equipment and setup [4,5]. Hence, a
simple and effective technique for fipronil detection should be con-
tinuously demonstrated.
The voltammetry method is considered as the most potential ap-
proach for chemical species detection due to its high accuracy and
stability via current control [23]. A combination with a high perfor-
mance working electrode, high sensing sensitivity towards wide range

⁎
Corresponding authors.
E-mail addresses: mnurdin06@yahoo.com (M. Nurdin), akrajas@ukm.edu.my (A.A. Umar).

https://doi.org/10.1016/j.surfin.2019.05.008
Received 8 January 2019; Received in revised form 7 May 2019; Accepted 22 May 2019
Available online 23 May 2019
2468-0230/ © 2019 Elsevier B.V. All rights reserved.
M. Nurdin, et al.
Fig. 1. XRD spectrum (A) and SEM micrograph (B-C) of ilmenite-CPE nanocomposite. D is EDX spectrum for the ilmenite sample.
organic chemical species could be obtained [24]. Here we report a
highly sensitive detection of fipronil using working electrode that
composed of ilmenite and carbon paste electrode. Ilmenite is a com-
posite of anatase TiO2 and FeO. In recent study, we found that the
composite of TiO2 with carbon paste has shown a remarkable perfor-
mance as an electrode for detection of cypermethrin and phenol de-
tection [25,26]. In this study, we found that the ilmenite plays a key
role in the sensing sensitivity where it increases with the increasing of
ilmenite concentration and maximum at 0.1 μM. At this condition the
fipronil existence in supporting electrolyte as low as 0.0012 μM can be
easily detected as demonstrated by a high anodic current at the oxi-
dation potential of fipronil over this electrode. The electrode also shows
remarkable stability with significantly low sensitivity variation
(0.173% RSD) over 9 days repeated measurement. The ilmenite CPE
composite electrode should find potential applications as an early
pesticide detection system.
2. Experimental
2.1. Synthesis and characterization of ilmenit (FeO.TiO2)
The ilmenite was synthesized by a two-steps preparation approach,
i.e., (i) TiO2 and (ii) ilmenite synthesis. TiO2 nanostructure was pre-
pared by a controlled hydrolysis method [27] using 4.0 mL titanium
tetra-isopropoxide (TTIP) in 0.5 mL acetylacetone and 15 mL ethanol
99%. Immediately, a solution containing 15 mL ethanol 99%, 2.0 mL
distilled water and 1.0 mL of 0.1 M acetic acid was then added to the
reaction. The reaction was then refluxed by using magnetic stirrer for
3 h at 50 °C. After that Fe(NO3)3 (1.0 mL 0.5 M) was then injected to the
reaction to produce ilmenite sol. Subsequently, the sol was evaporated
at room temperature for 48 h in order to forming a sol-gel. Finally the
sol-gel was annealed in air at 80 °C for 30 min. The entire chemicals
used in this experiment were purchased from Merck (Germany) and
used without any purification process.
The phase crystallinity of ilmenite sol-gel was then characterized by
x-ray diffraction (XRD) spectroscopy using Shimadzu 6000 (Japan)
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Surfaces and Interfaces 16 (2019) 108–113
XRD spectrometer. The morphology of the ilmenite nanostructures was
examined by scanning electron microscopy (SEM) using HITACHI
SU3500 (Japan) SEM apparatus. Elemental analysis was carried out via
the electron energy dispersive spectroscopy (EDS) using EDX apparatus
equipped in the SEM system.
2.2. The preparation of ilmenite-CPE nanocomposites working electrode
The ilmenite-CPE was prepared by mixing the FeO.TiO2 of weight of
0.05 g with 0.7 g graphite. The mixed compound was then grinded to
form fine powder and sieved using 200 mesh stainless steel. After that
0.3 g liquid paraffin was added into the powder and stirred at tem-
perature of 80 °C for approximately 30 min. Homogenous ilmenite-CPE
paste was then obtained from this processed. Finally, the composite
electrode was prepared by pouring the composite paste into a glass
mould (diameter ca. 4.0 mm) that mounted onto the end of a copper
wire connector. The composite paste was then pressed to solidify and
then polished until flat and shiny using a sand paper 2000. The thick-
ness of the composite electrode is approximately 0.5 mm.
2.3. Fipronil detection
The detection of fipronil using the ilmenite-CPE nanocomposite
electrode was carried out using three electrode cyclic voltammetry (CV)
method. In typical process, the detection of fipronil was performed in
an electrolyte system of 25.0 mL of 1.0 M MgSO4 (Merck) solution
containing fipronil in a glass container as an electrochemical cell.
Electrochemical performance was investigated at a scan rate from 0.02
to 0.2 Vs−1 in a potential windows of +0.8 to −0.8 V.
3. Results and discussion
3.1. Characterization of ilmenite electrode
The phase crystallinity of the prepared ilmenite nanostructure was
verified and confirmed using XRD technique. The result is shown in
M. Nurdin, et al. Surfaces and Interfaces 16 (2019) 108–113

Fig. 1A. By referencing the XRD spectrum to the JCPDS file no. 96-900-
6336, it is confirmed that the samples is ilmenite. Therefore, the dif-
fraction peaks at 2θ of 23.80, 35.07, 42.76 and 48.90° can be assigned
to Bragg plane of (012), (110), (113) and (024), respectively. By con-
sidering the nature of peak intensity, the ilmenite grown using this
synthetic method is a hexagonal structure with a polycrystalline phase
[28]. Beside the ilmenite phase, the anatase phase of TiO2 was also
observed in the spectrum. It is represented by the appearance of dif-
fraction peak at 2θ of 25.60, 37.44, 48.10, 54.96, 55.06, 62.69 and
70.31° that is well-matched with the standard diffraction of JCPDS file
no. 21–1272 [29,30], which are associated with the Bragg plane of
(101), (200), (004), (105), (211), (204) and (220), respectively.
Next, we performed FESEM characterization to investigate the sur-
face morphology of ilmenite. As can be seen from the Fig. 1B, at lower
magnification, it is understood that the ilmenite is constructed by
homogeneous and compact nanostructures with the absence of large
grain structure. At higher magnification (see Fig. 1C), the detailed
structure of ilmenite can be seen clearly, where the ilmenite is com-
posed of nanospherical-like structure with size of ca. 20 nm. EDX ana-
lysis further confirmed that the successful insertion of Fe in the ilmenite
nanostructures. Fig. 1D reveals the EDX spectrum for the ilmenite na-
nostructures that indicates the typical elements in the nanostructures,
such as Fe, O and Ti, and their composition were detected as high as
2.18, 41.94 and 55.89%, respectively.

3.2. Electrochemical behavior of fipronil over FeO.TiO2/CPE

To evaluate the ilmenite-CPE electrochemical behavior, first we

prepared the nanocomposites of ilmenite-CPE and investigate its mi-
croscopic structure by FESEM analysis. The FESEM results are shown in
Fig. 2A and B. From the figure, it can be seen that the structures of the
nanocomposites of ilmenite-CPE have expanded and become bigger in
size compared to the nanostructures size of ilmenite as previously dis-
cussed in Fig. 1B. It is believed that the changes in nanocomposites Fig. 3. (A) Typical voltammogram of the electrode in MgSO4 supporting elec-
structures were due to the incorporation of graphite in large weight trode in the absence (curve a) and in the presence (b) of 1.0 μM fipronil. Scan
rate is 0.3 V/s. (B) The schematic oxidation of fipronil.
percentage compared to the ilmenite, causing the graphite nano-
particles to dominate the structures. Thus, it is worth to claim that
successful incorporation of the nanocomposites of ilmenite-CPE into the higher cyclic voltammetry activity will be achieved from the samples.
CPE matrix has been achieved. Fig. 2A and B also depicts that with the Prior to applying the electrode in the fipronil detection, we examine
incorporation of the ilmenite into the CPE matrix, the porosity of the the effect of ilmenite concentration on the electrochemical properties of
electrode was also increase compared to the pristine ilmenite samples the nanocomposite electrode by evaluating the voltammetric response
(see Fig. 1B). The increase in porosity may help facilitates the charge of the electrode in 1 M K3[Fe(CN)6] solution. The result is shown in
transfer and carrier mobility of the material [29,31,32] for improved Fig. 1. As the figure reveals, the voltammetric response of the electrode,
electrochemical properties of the ilmenite-CPE. Thus, we expect that respect to the redox reaction of the electrolyte, is observed only if the

Fig. 2. (A-B) Field-emission scanning electron microscopy image of ilmenite-CPE electrode. (C) Voltammogram ilmenite-CPE nanocomposite electrode with different
ilmenite concentration, i.e. 0.01 (b), 0.05 (c) and (0.10 (d), in 1 M K3[Fe(CN)6 solution. Curve a is voltammogram for pristine CPE electrode.

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M. Nurdin, et al. Surfaces and Interfaces 16 (2019) 108–113

ilmenite is present in the sample. In other word, the pristine CPE does
not show the capability to facilitate redox reaction on the redox species
of the electrolyte solution. The voltammetry response was found to be
optimum when the ilmenite content in the nanocomposite electrode
reached 0.05 g (curve c). At this condition, the oxidation peak for the
redox species is very close to zero potential. It is true that the sample
containing 0.10 g ilmenite give rise to Faradaic current. However, the
oxidation peak is much far from zero, causing the sample less-suitable
for sensitive detection compared to the sample with 0.05 g of ilmenite.
Therefore, it can be pronounced that the sample with ilmenite con-
centration of 0.05 g is optimized and promising for a highly sensitive
electrochemical sensor.
Fig. 3A shows the typical voltammogram of 1.0 μM fipronil in
MgSO4 supporting electrolytes over the ilmenite-CPE electrode (curve
b). As can be seen from the curve, relatively high-anodic current Ipa, i.e.
125 μA, is observed at the electrochemical potential of −0.40 V. Such
significantly high current indicates that the fipronil has facily oxidized
over the ilmenite-CPE electrode and in this case S = O bond might be
removed, releasing two electron and proton into the solution (Fig. 3B).
To our expectance, the supporting electrolyte will not contribute to the
anodic current at the designated potential as no peaks current observed
in the voltammogram (curve a). This result also gives a clear evidence
that the MgSO4 is seemingly suitable for this application as it does not
react with analytes, particularly important at the condition of high
concentration of analytes, and high-stability [33,34]. In addition, ac-
cording to an earlier study, the redox potential of fipronil close to 0 V is
necessary for high-sensitive detection of fipronil [35].
As have been mentioned early, the supporting electrolyte plays a
certain role in successful redox reaction of analyte over a particular
electrode system. Ideal electrolyte, beside not reacting with the analytes
it also should highly conducting, promoting high current for sensitive
detection of analytes [36]. We compared the voltammogram char-
Fig. 4. (A) The voltammograms of 1.0 μM Fipronil in different electrolytes, i.e.
acteristic of fipronil in two different electrolytes, namely NaSO4 and
Na2SO4 1.0 M (curve a), and MgSO4 1.0 M (curve b). (B) Voltammogram of
MgSO4, in order to select a suitable electrolyte for further examining fipronil under different scan rates, i.e. (a) 0.02 V/s, (b) 0.01 V/s, (c) 0.1 V/s,
the electrochemical detection of fipronil. Fig. 4A shows the typical and (d) 0.2 V/s, in MgSO4 supporting electrode.
voltammogram of fipronil in two electrolytes over ilmenite-CPE elec-
trode. As the figure reveals, the MgSO4 generates higher current than
down to the level of 0.0012 μM, which is extremely low compared to
the NaSO4, reflecting the MgSO4 is suitable for high-sensitivity detec-
the allowed concentration of fipronil in the environment.
tion of fipronil (curve b). As also displayed from the figure, the MgSO4
In order to evaluating the stability properties of ilmenite-CPE elec-
does not show redox peaks other than at −0.4 V, further suggesting
trode in the detection of fipronil, we performed two different tests, i.e.
that the MgSO4 does not react with the fipronil. Different result was
(i) direct repeated testing for at least 21 cycles measurements and (ii)
obtained in the NaSO4 electrolyte where besides a low redox current the
repeated testing every three days up to 24 days in a fresh fipronil so-
voltammogram also shows the presence of several redox peaks (curve
lution. Fig. 6A shows the typical voltamograms for fipronil over ilme-
a), inffering the NaSO4 electrolyte reacts to a particular degree with the
nite-CPE electrode under 21 cycles repeated testing. As the figure re-
fipronil. Thus, it is remarked that the MgSO4 should be used for further
veals, the current linearly decreases with the increasing of the cycles. It
study of fipronil detection over the ilmenite-CPE electrode. Fig. 4B
is certainly due to the increasing of diffusion layer thickness during the
shows typical voltammogram of fipronil in MgSO4 under different scan
repeated measurements, limiting the electron transfer from the redox
rate. It is shown that the current increases with the increasing of the
species and electrode surface [37]. Thus, the current decreases. To
scan rate, revealing the reaction involve a diffusion related process. At
extract the stability properties of the electrode, the peak current stan-
low scan rate, thick diffusion layer was formed, limiting the charge
dard deviation (SD) as well as relative standard deviation (%RSD) was
transfer to electrode surface [37]. Meanwhile at high rate, thinner
calculated. The% RSD was obtained based on the SD value result di-
diffusion layer is realized, enabling facile charge transfer process. Thus,
vided by the average current value and multiplied by 100%. This is also
high-current is produced.
called as Horwitz Ratio (HorRat). It was found that the SD value was as
low as 14.85. Because the average peak current value is 85.71 µA, the%
3.3. Detection limit and stability properties
RSD value is calculated to be as low as 0.17%. This %RSD value is far
less than 2%, a level that indicates the electrode has excellent stability
We carried out the detection limit analysis by plotting and de-
properties and become a potential candidate for high-performance fi-
termining the linear region in the anodic current response (Ipa) versus
pronil detection. Similar process is also observed when the electrode
fipronil concentration plot in the range of 1.0 × 10−3 to
was aged and re-used in cyclic voltammetry of fipronil every three days
1.0 × 10−2 μM. The voltammogram of fipronil with different con-
(see Fig. 6B). It was found that the current slowly decreases upon being
centration in 1.0 M MgSO4 is represented in Fig. 5A and its corre-
used after 9 days and then linearly decreases with the increasing of
sponding anodic peaks current versus concentration is shown in Fig. 5B.
aging time. Therefore, on the basis of these results, it can be stated that
As can be seen from the Fig. 5B, the sensing response demonstrates a
the electrode can be used in high-sensitivity up to 9 days of reusage.
remarkably high linearity with R2 value approaching 0.98. On the basis
of the result and the linearity plot, it can be estimated that the de-
tectability of the ilmenite-CPE electrode toward the fipronil can be

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M. Nurdin, et al. Surfaces and Interfaces 16 (2019) 108–113

Fig. 5. (A) Voltammogram of fipronil with different concentration, i.e. (a)
1.0 × 10−3 μM, (b) 3.0 × 10−3 μM (c) 5.0 × 10−3 μM, (d) 7.0 × 10−3 μM, (e)
1.0 × 10−2 μM, over ilmenite-CPE electrode at a scan rate of 0.1 V/s (vs. Ag/
AgCl). (B) Plot of anodic peak current versus concentration.
Fig. 6. (A) The voltammogram of 1.0 μM fipronil in 1.0 M MgSO4 supporting
electrolyte during 21 cycles direct measurement at a scan rate of 0.1 V/s over
ilmenite-CPE electrode. (B) The voltammogram of electrode recorded after
being aged for (a) 1, (b) 3, (c) 6, (d) 9, (e) 12, (f) 15, (g) 18, (h) 21, and (i) 24
days.

3.4. Interference analysis

Due to the existence of Cu2+ ion in excess amount in the environ-

ment [38], it is necessary to evaluate the electrode response to fipronil
in the presence of Cu2+. We conducted the interference analysis by
using CuSO4 as the source of Cu2+ ion by simply adding to the fipronil
in MgSO4 electrolyte solution. The typical voltammograms of fipronil in
the presence of several concentration of Cu2+ ion is shown in Fig. 7.
The result shows that the presence of Cu2+ ion in the fipronil causes a
shifting in the fipronil potential into a more negative direction and the
shifting increases with the increasing of Cu2+ in the reaction. However,
despite the significant shifting in the peak current potential, the fipronil
oxidation is clearly visible, inferring the ilmenite-CPE electrode is ap-
plicable for detecting the fipronil under a condition of high Cu2+ ion
contamination.
Fig. 7. The voltammogram of 1.0 μM fipronil in 1.0 M MgSO4 supporting
4. Conclusions electrolyte in the presence of (a) FIP, (b) 0.1 μM Cu, (c) 0.3 μM Cu, (d) 0.5 μM
Cu, (e) 0.7 μM Cu, and (f) 1.0 μM Cu.
The performance of FeO.TiO2/CPE (ilmenite-CPE) in the electro-
chemical detection of fipronil pesticide has been investigated. It was
general.
found that the electrode exhibits an outstanding performance with
oxidation potential for fipronil close to 0 V, i.e., −0.46 V. Anodic cur-
rent as high as 160 μA has been recorded from 1 μM fipronil in MgSO4 Conflict of interest declaration
electrolyte. Such high anodic current facilitates high sensing sensitivity
with typical limit of detection can go down to the level as low as We, the authors of the paper entitled “Highly sensitive fipronil
0.0012 μM. The electrode also demonstrated high stability property pesticide detection on ilmenite (FeO.TiO2)-carbon paste compo-
with a Horwitz Ratio (HR) value is as low as 0.173%. From the study, site electrode”, declare that we have no any conflict of interest.
we also worthwhile claimed that the ilmenite-CPE electrode is highly
selective as it can detect the presence of fipronil in high Cu2+ ion excess Acknowledgment
background. The ilmenite-CPE electrode should find extensive used
particularly for pesticide sensor and environmental monitoring in We grateful for financial support from Ministry of Research,

112
M. Nurdin, et al.
Technology, and Higher Education of the Republic of Indonesia the
Competency Research Grant No. 056/SP2H/LT/DRP/2018 and on
Sabbatical Leave Program 2018 Award no. 364.5/D2.3/KP/2018. We
also acknowledge Universiti Kebangsaan Malaysia for supporting this
project under GUP-2018-083 and MI-2019-001.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.surfin.2019.05.008.
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