Somayeh Tajik1, Hadi Beitollahi2, Rahman Hosseinzadeh3, Abbas Aghaei Afshar4, Rajender S Varma5, Ho Won Jang6, Mohammadreza Shokouhimehr6. 1. Research Center for Tropical and Infectious Diseases, Kerman University of Medical Sciences, Kerman 7617934111, Iran. 2. Environment Department, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman 7631818356, Iran. 3. Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar 47416-1467, Iran. 4. Research Center for Tropical and Infectious Diseases, Kerman University of Medical Sciences, Kerman 1234, Iran. 5. Regional Center of Advanced Technologies and Materials, Palacky University, Š lechtitelů 27, 783 71 Olomouc, Czech Republic. 6. Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea.
Abstract
The electrocatalytic performance of carbon paste electrode (CPE) modified with ferrocene-derivative (ethyl2-(4-ferrocenyl[1,2,3]triazol-1-yl)acetate), ionic liquid (n-hexyl-3-methylimidazolium hexafluorophosphate), and CoS2-carbon nanotube nanocomposite (EFTA/IL/CoS2-CNT/CPE) was investigated for the electrocatalytic detection of hydrazine. CoS2-CNT nanocomposite was characterized by field emission scanning electron microscopy, X-ray powder diffraction, and transmission electron microscopy. According to the results of cyclic voltammetry, the EFTA/IL/CoS2-CNT-integrated CPE has been accompanied by greater catalytic activities for hydrazine oxidation compared to the other electrodes in phosphate buffer solution at a pH 7.0 as a result of the synergistic impact of fused ferrocene-derivative, IL, and nanocomposite. The sensor responded linearly with increasing concentration of hydrazine from 0.03 to 500.0 μM with a higher sensitivity (0.073 μA μM-1) and lower limit of detection (LOD, 0.015 μM). Furthermore, reasonable reproducibility, lengthy stability, and excellent selectivity were also attained for the proposed sensor. Finally, EFTA/IL/CoS2-CNT/CPE was applied for the detection of hydrazine in water samples, and good recoveries varied from 96.7 to 103.0%.
The electrocatalytic performance of carbon paste electrode (CPE) modified with ferrocene-derivative (ethyl2-(4-ferrocenyl[1,2,3]triazol-1-yl)acetate), ionic liquid (n-hexyl-3-methylimidazolium hexafluorophosphate), and CoS2-carbon nanotube nanocomposite (EFTA/IL/CoS2-CNT/CPE) was investigated for the electrocatalytic detection of hydrazine. CoS2-CNT nanocomposite was characterized by field emission scanning electron microscopy, X-ray powder diffraction, and transmission electron microscopy. According to the results of cyclic voltammetry, the EFTA/IL/CoS2-CNT-integrated CPE has been accompanied by greater catalytic activities for hydrazine oxidation compared to the other electrodes in phosphate buffer solution at a pH 7.0 as a result of the synergistic impact of fused ferrocene-derivative, IL, and nanocomposite. The sensor responded linearly with increasing concentration of hydrazine from 0.03 to 500.0 μM with a higher sensitivity (0.073 μA μM-1) and lower limit of detection (LOD, 0.015 μM). Furthermore, reasonable reproducibility, lengthy stability, and excellent selectivity were also attained for the proposed sensor. Finally, EFTA/IL/CoS2-CNT/CPE was applied for the detection of hydrazine in water samples, and good recoveries varied from 96.7 to 103.0%.
Hydrazine enjoys a multitude of industrial deployments
today, although
in the 1960s, it found predominant application as one of the propellants
for spacecrafts and rockets.[1] However,
it presently contributes significantly to industries and is utilized
as corrosion inhibitor, catalyst, reducing agent, blowing agents,
and so forth. Moreover, its derivatives find widespread usage in the
agriculture sector as one of the insecticides. In addition, numerous
hydrazine-based drugs exist in the pharmaceutical sector. Nonetheless,
it suffers from detrimental impacts on the terrestrial as well as
aquatic organisms so that the prolonged exposures to it at lower concentration
can seriously hurt the respiratory system, livers, skin, kidneys,
central nervous system (CNS), cardiovascular system, and the human
DNA.[2] In addition, hydrazine has been listed
as a carcinogen by the US Environmental Protection Agency,[3] thus making its accurate determination imperative.Some analytical techniques have been applied to detect hydrazine,
including luminescence,[4] spectrophotometry,[5] capillary electrophoresis,[6] spectrofluorimetry,[7] high-performance
liquid chromatography (HPLC),[8] flow-injection
analysis,[9] and gas chromatography-mass
spectrometry.[10] These methods have proven
to be sensitive and accurate, but their higher costs, usage of larger
amounts of the environmentally unfriendly solvents, longer working
time, the necessity of laborious pretreatment, etc. limit their application.[11] In addition, electrochemical techniques have
a widespread utilization in analytical chemistry due to the simplified
preparation process, faster responses, affordability, higher sensitivity
and selectivity, and feasible miniaturization.[12−16] Consequently, they have been extensively utilized
for the determination of hydrazine.[17−24]Nevertheless, larger oxidation overpotential
as well as poorer voltammetric response over the conventional bare
electrode (unmodified electrode) surface has been considered as one
of the prime challenges for detecting analytes directly and sensitively.
The other problem pertaining to the analyte direct oxidation at bare
electrode has been proposed; electrode surface passivation through
an oxide film is created at the high anodic potential. Hence, in the
electrochemistry field, modifying the electrodes has been considered
as the special and prime phase that allows solving or diminishing
the above problems.[25−31] Consequently, it is
of high importance to choose substances to modify electrodes for fabricating
an electrochemical sensor with enhanced performance and sensitivity.Considering the accelerated advances in nanoscience, nanomaterials
have garnered immense attention for creating newer electrochemical
sensors due to their very good electrical conductivity, larger surface
areas, and acceptable biocompatibility.[32−35] For example, transition-metalsulfides are proposed as one of the active nanomaterials due to their
prominent features appropriate for uses in catalysis, energy, and
so forth. Particularly, cobalt disulfide (CoS2) is one
of the potent materials for electrode modification due to its higher
catalytic abilities.[36,37] Furthermore, conductivity for
sulfides is commonly greater than the corresponding oxides because
of their abilities to facilitate the transfer of electrons;[38] additional advantages include higher active-edge
position and larger specific surface area for CoS2.[39,40] To enhance the electronic conductivity and electrochemical performance
of CoS2, the combination of CoS2 with carbon
nanomaterials is a useful strategy;[41,42] CNTs are often
deployed to fabricate the composite substances for the new electrode
modifiers because of their excellent mechanical features, acceptable
physical features, wider potential window, and increased catalytic
activities.[43,44]Ferrocene and the respective
derivatives have been proposed as one of the classes of electron mediators
with very good redox electroactivities and improved electron-rich
sandwich-type structure because of their reversible redox behavior
of ferrocene to ferrocene+.[45] Moreover, faster transfer of electron as well as two-state redox
stability have been considered the other promising electrochemical
feature displayed by Ferrocene and the similar compounds, making them
very good mediators.[46,47]Ionic liquids (ILs) are
the stable salts comprising organic or inorganic anion and organic
cation and can be maintained in a liquid state within a broad range
of temperatures.[48] They possess very good
chemicophysical features like acceptable solvating features, high
chemical and thermal stabilities, nonflammability, very little vapor
pressure, higher conductivity, and wider electrochemical windows.[49] As green solvents, ILs are attractive and effective
pasting binders rather than nonconductive organic binders to procure
the carbon composite electrodes.[50−52]Thus, the strategy presented here is based
on the combination of ferrocene-derivative, IL, and CoS2-CNT nanocomposite to design a new voltammetric sensor for the electrochemical
determination of hydrazine. The electrochemical studies revealed that
this new sensor has an excellent electrocatalytic activity to oxidize
hydrazine with numerous benefits like operational simplicity, higher
sensitivity, prolonged stability, good reproducibility, and remarkable
selectivity. Furthermore, the introduced electrochemical sensor has
been substantially utilized for the detection of hydrazine in various
water specimens.
Experimental
Section
Apparatus and
Chemicals
An Autolab potentiostat/galvanostat (PGSTAT 302N,
Eco-Chemie; the Netherlands) has been employed to make the electrochemical
measurements. General Purpose Electrochemical System (GPES) software
has been applied for controlling the testing condition. In addition,
a conventional three-electrode cell has been utilized at 25 ±
1 °C, with a platinum wire, EFTA/IL/CoS2-CNT/CPE,
and Ag/AgCl/KCl (3.0 M) electrodes the as auxiliary, working, and
reference electrodes, respectively. Finally, a Metrohm 710 pH meter
has been used to measure the pH.Hydrazine and other used reagents
were of analytical grade. Merck (Darmstadt, Germany) supplied these
materials. Ethyl2-(4-ferrocenyl[1,2,3]triazol-1-yl)acetate was synthesized
in our laboratory as reported previously.[53] In addition, ortho-phosphoric acid as well as the respective salts
(KH2PO4, K2HPO4, and K3PO4) with a pH ranging between 2.0 and 9.0 has
been utilized to procure buffer solution. The CoS2-CNTs
nanocomposite was prepared according to the description outlined earlier.[54]
Preparation of CoS2-CNT and Electrode
Commercialized
CNT (Sigma-Aldrich) and CoS2 (Sigma-Aldrich) were mixed
in a weight ratio of 5:2 by ball-milling with zirconia balls for 14
h to produce CoS2-CNT. EFTA/IL/CoS2-CNT/CPE
was prepared via dissolution of 0.01 g of ferrocene-derivative in
3 mL of diethyl ether and subsequently a pestle and mortar were used
to grind into 0.94 g of graphite powder and 0.05 g of CoS2-CNT nanocomposite. In the next step, 0.6 mL of paraffin and 0.3
mL of IL were poured into the obtained mixture and blended for 15
min until a uniformly moist paste was obtained. Next, this paste was
packed at the bottom of a glass tube (3.4 mm i.d. and 10 cm in length)
and a copper wire was placed on the carbon paste, to establish the
electrical contact. To compare our results, controls were prepared
by similar protocols such as ferrocene-derivative modified CPE (EFTA/CPE)
without CoS2-CNT and IL, CoS2-CNT-modified CPE
(CoS2-CNT/CPE) without ferrocene-derivative and IL, and
unmodified CPE in the absence of ferrocene-derivative, IL, and CoS2-CNT.The surface areas of the EFTA/IL/CoS2-CNT/CPE and the bare CPE were obtained by cyclic voltammetry (CV)
using 1 mM K3Fe(CN)6 at different scan rates.
Using the Randles–Sevcik formula[55] for EFTA/IL/CoS2-CNT/CPE, the electrode surface was found
to be 0.306 cm2, which was ∼3.4 times greater than
bare CPE.
Preparation
of the Real Samples
According to the research design, we
utilized various samples of water, river water, drinking water, and
tap water (from the laboratory) as the real samples. The water samples
were filtered three times prior to the analysis and varying amounts
of hydrazine was added into the water samples for subsequent standard
analysis method.
Results and Discussion
Characterization of the CoS2-CNT Nanocomposite
The field emission scanning electron microscopy (FESEM) images
of
CoS2 and CNT are shown in Figure a–c; CNT had ∼5 nm diameter
size and CoS2 nanoparticles (NPs) show ∼100 nm diameter
size, which could be confirmed with transmission electron microscopy
(TEM) studies. The X-ray powder diffraction (XRD) results confirmed
a single phase for the CoS2-CNT nanocomposite (Figure ). After the ball-milling
process for the mixed CoS2 and CNTs, CoS2 NPs
were trapped in the CNTs cluster. This sponge-like structure was favorable
for the easier diffusion of ionic liquid electrolyte in a cathode
material, making CoS2 more accessible as active sites (Figure ). As demonstrated
in Figure S1 of the Supporting Information,
the Brunauer–Emmett–Teller surface area of the CoS2-CNT nanocomposite was measured to be 168 m2 g–1.
Figure 1
FESEM images of (a) CoS2 NPs. SEM
images of (b) low and (c) magnified CoS2-CNT nanocomposite.
Figure 2
XRD pattern for the CoS2-CNT nanocomposite.
Figure 3
TEM images of the CoS2-CNT nanocomposite in
different magnifications.
FESEM images of (a) CoS2 NPs. SEM
images of (b) low and (c) magnified CoS2-CNT nanocomposite.XRD pattern for the CoS2-CNT nanocomposite.TEM images of the CoS2-CNT nanocomposite in
different magnifications.
Electrochemical Behavior
of Hydrazine on EFTA/IL/CoS2-CNT/CPE
The electrochemical
behavior of hydrazine depends upon the pH value
of the aqueous solution. On the one hand, optimizing the solution
pH is crucial for obtaining hydrazine electrocatalytic oxidation.
Hence, electrochemical behaviors of hydrazine were examined in 0.1
M phosphate buffer solution (PBS) at distinct pH values (2.0 <
pH < 9.0) at the EFTA/IL/CoS2-CNT/CPE surface using
the CV method. Analyses revealed higher favorability of hydrazine
electrocatalytic oxidation at the EFTA/IL/CoS2-CNT/CPE
surface at neutral conditions in comparison to the basic or acidic
media (Figure ). Finally,
we selected pH 7.0 as an optimal value to electrocatalyze hydrazine
oxidation at the EFTA/IL/CoS2-CNT/CPE surface.
Figure 4
Plot of Ip vs pH obtained
from DPVs of EFTA/IL/CoS2-CNT/CPE in a solution containing
200.0 μM of hydrazine
in 0.1 PBS with different pHs (2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0,
and 9.0).
Plot of Ip vs pH obtained
from DPVs of EFTA/IL/CoS2-CNT/CPE in a solution containing
200.0 μM of hydrazine
in 0.1 PBS with different pHs (2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0,
and 9.0).The
CV responses for electrochemical oxidation of 200.0 μM hydrazine
at the unmodified CPE (curve b), IL/CPE (d), CoS2-CNT/CPE
(curve e), EFTA/CPE (curve f), EFTA/IL/CPE (curve g), and EFTA/IL/CoS2-CNT/CPE (curve h) are shown in Figure ; the potential of the anodic peak is ∼860
mV for hydrazine oxidation over the surface of bare CPE (curve b)
and IL/CPE (d), and 330 mV over the EFTA/IL/CoS2-CNT/CPE
surface (curve f). Considering the aforementioned curves, the potential
peak observed for hydrazine oxidation over the surface of the modified
electrode shifts is 530 mV to the negative values in comparison to
the surface of the bare electrode. With regard to the hydrazine oxidation
on the EFTA/CPE (curve f), EFTA/IL/CPE (curve g), and EFTA/IL/CoS2-CNT/CPE (curve h) surfaces, we observed an increase in the
anodic peak current on the EFTA/IL/CoS2-CNT/CPE surface
compared to that in EFTA/CPE and EFTA/IL/CPE, demonstrating an augmentation
in the peak current through the introduction of both IL and CoS2-CNT nanocomposite in the modification of CPE. In addition,
several advantages could be found for IL/CPE including faster electron
transfer, appropriate antifouling features, high conductivity, and
IL catalytic nature.
Figure 5
CVs of (a)
bare CPE in 0.1 M PBS (pH 7.0); (b) as (a) in 200.0 μM hydrazine;
(c) as (a) at the surface of EFTA/IL/CoS2-CNT/CPE; (d)
as (b) at the surface of IL/CPE; (e) as (b) at the surface of CoS2-CNT/CPE; (f) as (b) at the surface of EFTA/CPE; (g) as (b)
at the surface of EFTA/IL/CPE; and (h) as (b) at the surface of EFTA/IL/CoS2-CNT/CPE. In all cases, the scan rate was 10 mV s–1.
CVs of (a)
bare CPE in 0.1 M PBS (pH 7.0); (b) as (a) in 200.0 μM hydrazine;
(c) as (a) at the surface of EFTA/IL/CoS2-CNT/CPE; (d)
as (b) at the surface of IL/CPE; (e) as (b) at the surface of CoS2-CNT/CPE; (f) as (b) at the surface of EFTA/CPE; (g) as (b)
at the surface of EFTA/IL/CPE; and (h) as (b) at the surface of EFTA/IL/CoS2-CNT/CPE. In all cases, the scan rate was 10 mV s–1.It is evident that even in the absence
of hydrazine, a well-behaved redox reaction at EFTA/IL/CoS2-CNT/CPE in 0.1 M PBS (pH = 7.0) occurs (Figure curve c); however, in the presence of 200.0
μM hydrazine at EFTA/IL/CoS2-CNT/CPE (curve f), a
noticeable increase in the anodic peak current is observed. According
to these results, we suggest an EC′ catalytic mechanism[55] for the electrochemical oxidation of hydrazine
at EFTA/IL/CoS2-CNT/CPE, as depicted in Scheme . It has been proposed that
in a catalytic reaction, hydrazine is oxidized by the oxidized form
of EFTA which is produced during an electrochemical reaction at the
electrode surface.
Scheme 1
Electrocatalytic
Oxidation of Hydrazine at EFTA/IL8-/CoS2-CNT/CPE
Effect of Scan Rate on
the Results
LSV has been utilized
to study the impacts of the scan rates on the electrocatalytic oxidation
of hydrazine over the modified electrode surface. Figure shows that by enhancing the
scan rate, the oxidation peak potential shifts to a more positive
potential, which reflects the kinetic limitation of the electrochemical
reaction. Additionally, the peak height (Ip) plot versus square of
the scan rate root (ν1/2) displayed the linear range
between 5 and 200 mV s–1, showing that at sufficient
overpotential, the oxidation procedure was controlled by diffusion
rather than the surface, as shown in Figure inset (A). Moreover, the plot of the scan
rate-normalized current (Ip/ν1/2) vs the scan rate obviously showed a specific form of a typical
electrocatalytic procedure as depicted in Figure inset (B).[55]
Figure 6
Linear sweep voltammograms
(LSVs) of EFTA/IL/CoS2-CNT/CPE 0.1 M PBS (pH 7.0) containing
250.0 μM hydrazine at various scan rates of (a–h) 5,
10, 15, 30, 70, 100, 150, and 200 mV s–1, respectively.
Insets: (A) variation of anodic peak current with the square root
of scan rate and (B) variation of scan rate-normalized current (Ip/ν1/2) with scan rate.
Linear sweep voltammograms
(LSVs) of EFTA/IL/CoS2-CNT/CPE 0.1 M PBS (pH 7.0) containing
250.0 μM hydrazine at various scan rates of (a–h) 5,
10, 15, 30, 70, 100, 150, and 200 mV s–1, respectively.
Insets: (A) variation of anodic peak current with the square root
of scan rate and (B) variation of scan rate-normalized current (Ip/ν1/2) with scan rate.In the next step, the Tafel plot that corresponded to the LSV curve
with the increased sharpness at 5 mV s–1 scan rate
is depicted in Figure . Moreover, the number of electrons involved in the rate-determining
step may be approximated according to the Tafel slope under a rapid
deprotonation step of hydrazine. This Tafel slope has been specified
as 0.2166 V, revealing that the rate-determining step contains one
electron in the electrode procedure, considering 0.72 for charge-transfer
coefficient (α).
Figure 7
LSV (at 5 mV s–1) of the electrode in 0.1 M PBS
(pH = 7.0) containing 250.0 μM
hydrazine. The points are the data used in the Tafel plot (inset).
LSV (at 5 mV s–1) of the electrode in 0.1 M PBS
(pH = 7.0) containing 250.0 μM
hydrazine. The points are the data used in the Tafel plot (inset).
Chronoamperometric Analysis
According to the research
design, chronoamperometric measurement of hydrazine has been accomplished
using a modified electrode by setting the working electrode potential
at 380 mV for diverse concentrations of hydrazine in the PBS at a
pH 7.0, as shown in Figure . Moreover, the current seen for an electroactive moiety in
the electrochemical reactions with the mass transport limitation can
be described by the Cottrell equation.[55]here D and Cb are the diffusion coefficients (cm2 s–1) and the bulk concentration (mol cm–3), respectively.
Figure 8
Chronoamperograms obtained
at EFTA/IL/CoS2-CNT/CPE in 0.1 M PBS (pH 7.0) for different
concentrations of hydrazine: (a–f) 0, 0.1, 0.3, 0.6, 1.0, and
2.0 mM hydrazine. Insets: (A) Cottrell plot for the data from the
chronoamperograms, (B) plot of the slope of the straight lines against
hydrazine concentration and (C) dependence of IC/IL on t1/2 derived from the chronoamperogram data.
Chronoamperograms obtained
at EFTA/IL/CoS2-CNT/CPE in 0.1 M PBS (pH 7.0) for different
concentrations of hydrazine: (a–f) 0, 0.1, 0.3, 0.6, 1.0, and
2.0 mM hydrazine. Insets: (A) Cottrell plot for the data from the
chronoamperograms, (B) plot of the slope of the straight lines against
hydrazine concentration and (C) dependence of IC/IL on t1/2 derived from the chronoamperogram data.We drew experimental outputs of I vs t–1/2 with the most acceptable
fits for diverse hydrazine concentrations, as shown in Figure , inset (A). In the next step,
the slopes of the straight lines have been drawn on the opposite of
hydrazine concentration (Figure , inset B). Considering the final slopes as well as
the Cottrell equation, D mean value was found to be 2.1 × 10–6 cm2 s–1. Additionally,
it is possible to evaluate the catalytic rate constant (k) with chronoamperometry for hydrazine reaction at EFTA/IL/CoS2-CNT/CPE regarding Galus’s equation.[56]where IC is the
hydrazine
catalytic current at EFTA/IL/CoS2-CNT/CPE, IL is the limiting current in the absence of hydrazine.
γ = kCbt is the
error function argument (Cb implies hydrazine
bulk concentration). In case of a greater value of γ than 2,
error function becomes 4. Hence, eq is shortened aswhere t is the time spent. According to eq , the slope of IC/IL versus t1/2 at a given concentration of hydrazine has been utilized for computing
k for the catalytic process. Based on the final slopes shown in Figure , inset (C), k for hydrazine reaction at EFTA/IL/CoS2-CNT/CPE
was obtained as 2.8 × 103 M–1 s–1.
Calibration Plot and Limit
of Detection
In this step, differential
pulse voltammetry (DPV) has been applied for determining the hydrazine
content with different concentration gradients at a pH 7.0 (initial
potential = 0.1 V, end potential = 0.53 V, step potential = 0.001
V, amplitude = 0.02 V). According to Figure , the association of the peak current of
hydrazine with its concentrations is linear in the range 0.03–500.0
μM. The linear equation is as follows: y =
0.073x + 3.4261, the correlation coefficient is 0.9996.
Figure 9
DPVs of EFTA/IL/CoS2-CNT/CPE in 0.1 M PBS (pH 7.0) containing
different concentrations
of hydrazine: 0.03, 1.0, 5.0, 10.0, 30.0, 50.0, 75.0, 100.0, 150.0,
200.0, 250.0, 300.0, 350.0, 400.0, 450.0, and 500.0 μM of hydrazine,
respectively. The inset: the peak current plot as the function of
hydrazine concentrations in ranges from 0.03 to 500.0 μM.
DPVs of EFTA/IL/CoS2-CNT/CPE in 0.1 M PBS (pH 7.0) containing
different concentrations
of hydrazine: 0.03, 1.0, 5.0, 10.0, 30.0, 50.0, 75.0, 100.0, 150.0,
200.0, 250.0, 300.0, 350.0, 400.0, 450.0, and 500.0 μM of hydrazine,
respectively. The inset: the peak current plot as the function of
hydrazine concentrations in ranges from 0.03 to 500.0 μM.In addition, the detection limit, Cm, of hydrazine was obtained using the following equationIn the above equation, m is the slope of the calibration plot (0.073 μA μM–1) and sb is the standard
deviation of the blank response, which is obtained from 20 replicate
measurements of the blank solution. The detection limit is 0.015 μM.
The comparison of the results for the detection of hydrazine with
different modified electrodes in the literature is listed in Table .
Table 1
Performance
Comparison Study of the Purposed Electrochemical Sensor with Previously
Published Articles for the Detection of Hydrazine
It is well known that interference
examinations have been conducted
for understanding the effectiveness of the outputs to analyze hydrazine
via the presence of diverse organic compounds and inorganic ions.
Based on the common definition, the ratio of the interfering species
concentration to the hydrazine refers to the tolerance limit, resulting
in a relative error of <±5.0%. The possible interference has
been examined by adding diverse ions and biological compounds such
as Na+, Cl–, K+, NO3–, Ag+, Pb2+, glucose, sucrose,
urea, and uric acid to PBS at a pH 7.0 in the presence of 50.0 μM
hydrazine. It was found that the addition of these interfering species
did not show any considerable impact on the hydrazineDPV signal.
Hence, this modified electrode exhibited acceptable selectivity to
detect hydrazine.
Reproducibility and Stability
of EFTA/IL/CoS2-CNT/CPE
In this section, the reproducibility
of the modified electrode
was examined using five different sensors (EFTA/IL/CoS2-CNT/CPE) that were fabricated in the same condition containing 30.0
μM hydrazine by CV. The relative standard deviation (RSD) value
for this compound was found to be 2.6%. This RSD value for the analysis
of hydrazine reflects that the EFTA/IL/CoS2-CNT/CPE displayed
good reproducibility property.For checking our sensor stability,
we kept the recommended sensor within the pH equal to 7.0 in the PBS
for 2 weeks to test THE EFTA/IL/CoS2-CNT/CPE stability
and, consequently, we recorded the CV of the solution consisting of
30.0 μM hydrazine to be compared to the CV observed prior to
immersion. The oxidation peak of hydrazine did not change and in comparison
to earlier responses to the current showed a less than 2.7% reduction
in signal, reflecting acceptable stability of EFTA/IL/CoS2-CNT/CPE.
Real
Sample Analysis
According to the research design, the as-proposed
EFTA/IL/CoS2-CNT/CPE has been utilized to detect hydrazine
in the water samples by the standard addition procedure. Moreover, Table reports the content
as well as the recoveries of hydrazine. As shown in the table, recoveries
were in the range from 96.7–103.0% with the relative standard
deviation (RSD) of <3.6%. These results confirmed the ability of
EFTA/IL/CoS2-CNT/CPE as a sensitive sensor for hydrazine
analysis in the water specimens.
Table 2
Determination of Hydrazine in Water Samplesa
sample
spiked
found
recovery (%)
R.S.D.
(%)
0
5.0
4.9
98.0
3.5
drinking water
7.5
7.6
101.3
2.1
10.0
10.3
103.0
1.9
12.5
12.3
98.4
2.8
0
5.0
5.1
102.0
2.6
tap water
6.0
5.9
98.3
3.0
7.0
7.1
101.4
2.1
8.0
7.8
97.5
1.9
0
4.0
4.1
102.5
1.7
River Water
6.0
5.8
96.7
3.6
8.0
8.1
101.2
2.4
10.0
9.9
99.0
2.5
All the concentrations
are expressed in μM (n = 5).
All the concentrations
are expressed in μM (n = 5).
Conclusions
The performance of a ferrocene-derivative
compound as a mediator/IL/CoS2-CNT nanocomposite modified
CPE was developed for the electrochemical sensing of oxidation of
hydrazine. Ferrocene-derivative, IL, and CoS2-CNT nanocomposite
as modifiers displayed stronger catalytic features. Hence, on the
resultant EFTA/IL/CoS2-CNT/CPE, the anodic overpotential
of hydrazine oxidation decreased; however, the oxidation peak current
considerably improved. The fabricated sensing electrode displayed
a linear range within 0.03–500.0 μM hydrazine having
a detection limit of 0.015 μM and a sensitivity value of 0.073
μA μM–1. Moreover, the hydrazine sensor
exhibited acceptable reproducibility, long-term stability, and excellent
selectivity. EFTA/IL/CoS2-CNT/CPE has excellent accuracy
in recovering hydrazine analysis in water samples. Therefore, the
fabricated EFTA/IL/CoS2-CNT/CPE with prominent electrochemical
features could be considered as one of a potent, reliable, and competitive
candidates to detect diverse analytes.