Process Safety and Environmental Protection 168 (2022) 77–87

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Construction of graphene oxide wrapped gadolinium vanadate

nanocomposites as an efficient electrocatalyst for the amperometric sensing
of sulfadiazine
Selvarasu Maheshwaran a, Ramachandran Balaji a, Shen-Ming Chen a, *,
Elayappan Tamilalagan a, Narendhar Chandrasekar b, Selvarajan Ethiraj c, Melvin S. Samuel d
a
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 106, Taiwan, ROC
b
Department of BioNano Technology, Gachon University, Seongnam 13120, Gyeonggi, Republic of Korea
c
Department of Genetic Engineering, School of Bioengineering, College of Engineering, SRM Institute of Science and Technology, Chennai, Tamil Nadu, India
d
Department of Material Science and Engineering, University of Wisconsin-Milwaukee, Milwaukee, WI, USA

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

Keywords: Ultrasensitive detection of antibiotic molecules is fast becoming a vital field of research in recent years. In this
Rare-earth metal vanadate research article, we hydrothermally developed a pellet-shaped nanomaterial based on rare-earth metal vanadate
Graphene Oxide (GdVO4) and they are made of composites with graphene oxide (GO). The surface morphology studies through
Sulfadiazine
microscopes confirm the effective formation of pellet and sheet-like architectures of GdVO4 and GO. The syn­
electrochemical sensor
biological and environmental analysis
thesized nanocomposites are probed for the electrochemical detection of antibiotic sulfadiazine (SLZ). The
electrochemical detection performance is investigated through cyclic voltammetry (CV), electrochemical
impedance spectroscopy (EIS), and i-t amperometry analysis. The primary composite of GdVO4 @GO displayed
superior selectivity and sensitivity to GdVO4 and GO. Through i-t amperometry analysis, enhanced sensitivity of
1.3009 µA µM− 1 cm− 2 and a limit of detection of 3.1 nM for SLZ detection are achieved. In order to validate the
fabricated SLZ sensor, we tested them in real-world biological and environmental samples like human blood
serum, river and waste water samples. The GdVO4 @GO-based sensor performed remarkably well with good
selectivity for SLZ.

1. Introduction
In recent years, the medical and pharmaceutical fields have widely
consumed sulfonamide-dependent drugs. In particular, sulfadiazine
(SLZ) is the most commonly used sulfonamide based antibacterial agent
to control infections in animals and humans (Sakthivel et al., 2019b;
Vilian et al., 2022a). Having said that, after consumption the inappro­
priate disposal procedure of SLZ is major root cause of environmental
pollution towards sustainable ecosystem. If human comes to contact
with SLZ exceeding the permissible limit it unlocks series of health
hazards like damage to genes, develops antibiotic resistance, severe
damage to liver, and elevates the overall toxic level in system (Vinoth
et al., 2021a). Advised and maximum recommended level for SLZ in the
China for its aquatic environment is 0.014 – 0.28 µg/L (Kokulnathan
et al., 2020). The permissible limit for SLZ in the milk is about 0.07 ppm
as per the international standards. Considering these facts, it is vital to
create an easy and rapid sensor to effectively detect the SLZ in trace level
concentrations under real world conditions (Vilian et al., 2022b). Until
now, many traditional sensing techniques has been reported for SLZ
detection which uses gas/liquid chromatography, UV-Visible spec­
trometry, fluorescence spectrometry, electrophoresis etc., (Altunok
et al., 2016; Errayess et al., 2017; Wen et al., 2011). Due to enhanced
detection limit, low cost and broad linear range, the electrochemical
sensor has gathered tremendous attention in last few years. With respect
to electrochemical sensor, design and fabrication of electrode material
(electrocatalyst) for analysis is of prime importance.
Lanthanide (Ln) doped inorganic material enjoys a crucial part in our
everyday life mainly due to their interesting physical/chemical prop­
erties and structural arrangement (Rahman et al., 2020, 2021). Espe­
cially their electrical and optical property are admired in wide range of
applications (Akilarasan et al., 2020; Maheshwaran et al., 2021a; Zhang
et al., 2018). Ln doped materials are predominantly used in display

* Corresponding author.
E-mail address: smchen78@ms15.hinet.net (S.-M. Chen).

https://doi.org/10.1016/j.psep.2022.09.069
Received 8 July 2022; Received in revised form 19 September 2022; Accepted 26 September 2022
Available online 28 September 2022
0957-5820/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
S. Maheshwaran et al.
Scheme 1. The schematic illustration of the overall synthesis procedure of GdVO4 @GO nanocomposite.
technology, LEDs and sensors as they exhibit high energy conversion
efficiency, high conductivity and high thermal stability (Majeed et al.,
2016). Rare earth orthovanadates referred as REVO4 has recently proven
to be possess excellent host lattices for Ln3+ ions (Akilarasan et al., 2022;
Rabasovic et al., 2018; Vinoth et al., 2021b). This architecture displays
efficient charge transfer process from vanadate groups to Ln ions which
is vital for electrocatalytic activity. Various field of research employs
REVO4 as a catalyst like batteries, supercapacitors, solar cells, gas sen­
sors, and electrochemical sensors (Balaji et al., 2021; Chumha et al.,
2014; Maheshwaran et al., 2022a). Yet, some deficit in crystal structures
of REVO4 results in high resistance and blockage of charge carriers.
These issues serve as a major demerit and also limits the electrochemical
properties. So, numerous attempts are made to solve this issue with
doping of metal/non-metal ions, carbon based and organic compounds.
Of late, carbon-oriented materials like carbon nanotubes (CNT),
graphitic carbon nitride (gC3N4) and graphene oxide (GO) are more
popular for electrocatalytic applications (Akilarasan et al., 2021;
Maheshwaran et al., 2021a, 2022b, 2021b). Amongst them, GO is
preferred choice for the electrode material as it has enhanced conduc­
tivity, high specific surface area and provides ideal support for the
REVO4 (Chaudhary et al., 2021). Therefore, REVO4 @GO is used as an
electrocatalyst for trace level sensing applications.
In this research investigation, we present a modified electrode using
GdVO4 @GO nanocomposite for ultrasensitive electrochemical
Fig. 1. (A) XRD analysis of (a) GdVO4, (b) GO, and (C) GdVO4@GO. (B) Raman spectra of (a) GdVO4, (b) GO, and (C) GdVO4@GO.
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Process Safety and Environmental Protection 168 (2022) 77–87
detection of SLZ. The GdVO4 @GO nanocomposite is synthesized
through hydrothermal process and they are subsequently characterized
to understand its physical properties. The synthesized GdVO4 @GO
nanocomposite modified electrodes are investigated for its electro­
chemical performance using cyclic voltammetry techniques. GdVO4
@GO nanocomposites displayed enhanced catalytic activity resulting in
large surface area and enhanced charge transportation. Upon the
investigation, the GdVO4 @GO nanocomposite based electrochemical
sensor displayed a wide working range (0.02 – 145.5 and 145.5 – 945.5
µM) and good detection limit (3.1 nM). These impressive results are due
to influence of REVO4 as they have superior conductivity especially
when they are coupled with GO. This is one of the primary report for SLZ
sensing using novel GdVO4 @GO nanocomposite based sensor. The
fabricated sensor is also tested for its selectivity and reproducibility. The
real sample performance (biological and environmental samples) of the
GdVO4 @GO nanocomposite modified electrode is also thoroughly
investigated.
2. Experimental section
2.1. Chemicals and reagents
The chemicals used and preparation of buffer are explained and
explained in S1.
S. Maheshwaran et al.
Fig. 2. (A) XPS survey spectrum for GdVO4 @GO nanocomposite and corresponding high-resolution spectrum for (B) Gd, (C) V, (D) O, and (E) C.
2.2. Synthesis of GO
GO is synthesized from pristine graphite powder by the modified
Hummer’s method (Maharana et al., 2017). In brief, 1 g of graphite
powder and 0.5 g of NaNO3, and 25 ml of H2SO4 during the following
stages, the mixture is constantly stirred. KMnO4 is gradually added to
the mixture after 1 hr of stirring and maintained below 20 ºC. The DD
H2O (50 ml) is added dropwise manner into the mixture in order to
dilute the mixture. After sometime, dark green color solution is obtained
which indicates the successful formation of GO. Then 100 ml of DD H2O
is added followed by the addition of 10 ml of H2O2 and stirred for about
10 min. During the addition of H2O2, the excess manganate is removed.
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Process Safety and Environmental Protection 168 (2022) 77–87
The graphene oxide deposit is collected by centrifuging and repeated
washing with DD H2O until pH-7 is reached. After drying the obtained
precipitate, graphene oxide sheets are obtained.
2.3. Synthesis of GdVO4 @GO nanocomposite
The GdVO4 @GO nanocomposite is prepared by a facile hydrother­
mal method, 0.4 g of Gd(NO3)30.6 H2O and 0.8 g of NH4VO3 are dis­
solved in 40 ml DD H2O and stirred for over 15 min in a magnetic stirrer
to get a homogenous mixture. Subsequently, 1 g of NaOH in 10 ml of DD
H2O is added to the homogenous mixture and continued stirring. After
that 5 mg of GO is added to the mixture and stirred for about 30 min.
S. Maheshwaran et al.
Fig. 3. FE-SEM images of (a) GdVO4, (b) GO, (C-D) GdVO4 @GO nanocomposite.
Then the solution is transferred into a Teflon-lined autoclave and kept at
180 ºC for 12 hr. After completing the reaction, the autoclave is allowed
to reach ambient temperature. Then the obtained precipitate is washed
several times with DD H2O and ethanol and the collected precipitate is
dried at 50 ºC for 24 hr. The dried sample is ground and named GdVO4
@GO nanocomposite and used for further characterization and elec­
trochemical process. The same procedure is followed for the synthesis of
GdVO4 without adding GO. The schematic illustration of the overall
synthesis procedure of GdVO4 @GO was shown in Scheme 1.
3. Results and discussion
3.1. Crystal structure and Raman investigations
The XRD spectra of as-synthesized GdVO4 @GO have been exhibited
in Fig. 1 A. The XRD pattern of GdVO4 indicates the existence of
tetragonal crystal structure (JCPDS: 01–086–0996). The peaks detected
at 18.6, 24.6, 31.0, 33.2, 35.1, 37.7, 40.0, 44.6, 47.6, 49.1, 57.0, 61.8,
and 64.0 º in the XRD pattern of GdVO4 are ascribed to the (101), (200),
(211), (112), (220), (202), (301), (103), (321), (312), (420), (332), and
(323) tetragonal planes of GdVO4 shown in Fig. 1 A (a). All the peaks in
Fig. 1 A (c) are observed in the nanocomposite (GdVO4 @GO) as same as
in GdVO4, there is no obvious impurity peak which suggests the pure
tetragonal phase formation of GdVO4 @GO composite. Whereas for GO
in Fig. 1 A (b) the peak at 12.5 º corresponds to the (001) plane
demonstrating the existence of GO in the as-synthesized GdVO4 @GO
nanocomposite (Maharana et al., 2017). Fig. 1 A (c) shows the XRD
pattern of GdVO4 @GO nanocomposite which is similar to that of GdVO4
due to effective interaction between the GdVO4 and GO.
The molecular vibration and symmetry of the crystal structure of
GdVO4 @GO are scrutinized by Raman spectra in Fig. 1B. In the Raman
spectra of GdVO4 in Fig. 1B (a), the peaks observed at 155.1, 296.1, and
421.5 are appearing due to the symmetrical stretching vibration (He
et al., 2020). The sharp peak at 296.1 and 421.5 is attributed to the
asymmetric stretching vibrations of (VO4)3- respectively. The peak at
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Process Safety and Environmental Protection 168 (2022) 77–87
854 is attributed to the asymmetric stretching vibration of (VO4)3-,
whereas the peak at 906.5 is attributed to the symmetric stretching vi­
bration of (VO4)3-. Fig. 1B (b) demonstrates the Raman spectra of GO in
the range of 1200–1800 cm− 1. The D band at 1373 cm− 1 indicates de­
fects or disorders in the hexagonal graphene sheet. The G band at
1619 cm− 1 is caused by the stretching of C-C bonds in graphitic mate­
rials (Aadil et al., 2016). The intensities of the D band and G band ratio
(ID/IG) are used to calculate the disorder degree of GO, whereas the
calculated ID/IG value found to be 0.84 and 0.87 corresponds to GO and
GdVO4 @GO. According to the ID/IG results, the ratio of GdVO4 @GO
was higher than that of GO which reveals the integration of GdVO4 and
GO. In Fig. 1B (c), the GO peaks are obtained along with the GdVO4
nanocomposite, confirm the successful formation of GdVO4 @GO
nanocomposite.
3.2. XPS analysis of GdVO4 @GO nanocomposites
The chemical composition of elements in the GdVO4 @GO nano­
composite is investigated by XPS analysis. The XPS spectra of GdVO4
@GO is shown in Fig. 2 A. The survey spectra confirm the presence of
Gd, V, O, and C elements in the GdVO4 @GO nanocomposite. The core
level spectra of Gd 4d associated with two characteristics peaks 4d3/2
and 4d5/2 correspond to the binding energy of 152.19 and 147.7 eV
respectively shown in Fig. 2B (Mariyappan et al., 2022). The XPS spectra
of V 2p show peaks centered at 521.9 and 523.7 eV attributed to 2p1/2
and a broad peak at 516.6 eV which corresponds to 2p3/2 respectively in
Fig. 2 C (Kim et al., 2017). The two deconvoluted peaks are shown in
Fig. 2D at 532.01 and 529.4 eV in O 1 s spectra correspond to
metal-oxygen bond (M-O) and adsorbed oxygen by hydroxyl function­
alities (M-OH), respectively (Sriram et al., 2021). The peaks at 287.9,
285.9, and 284.1 eV correspond to O-C– – O, C-OH, and C-C respectively,
which are the characteristic peaks of C 1 S depicted in Fig. 2E (Johra and
Jung, 2015). Hence, these results confirm the successful formation of
GdVO4 @GO nanocomposite.
S. Maheshwaran et al.
Fig. 4. TEM images of (A-C) GdVO4 @GO, (D) Lattice fringes of GdVO4 @GO, (E) SAED pattern of GdVO4 @GO, (F) TEM survey elemental mapping images GdVO4
@GO, (G) Gd distribution, (H) V distribution, (I) O distribution, and (J) Carbon distribution.
3.3. Surface morphology investigations
Surface morphology of GdVO4, GO and GdVO4 @GO are observed by
FE-SEM. Fig. 3A shows the pellet-like structure of GdVO4 which is
randomly distributed and not uniform in size. The FESEM image of GO
clearly shows the wrinkled sheet-like structure of GO in Fig. 3B. The
FESEM image of GdVO4 @GO is depicted in Fig. 3C-D, in which the
GdVO4 pellets are uniformly distributed over the GO sheets. Whereas,
the GdVO4 pellets are extensively covered over the GO sheets. The
FESEM images demonstrates the successful formation of GdVO4 @GO, in
which the incorporation of GdVO4 and GO would be favorable to
improve the electrocatalytic property of the nanocomposite.
To describe the morphology of the hydrothermally synthesized
nanocomposite GdVO4 @GO, TEM analysis is performed. The Fig. 4A-C
displays the TEM images of GdVO4 @GO which confirms the pellet-like
structure of GdVO4 distributed randomly over the GO sheets. GdVO4
pellet is well wrapped with the thin layer of GO sheets. Both the FE-SEM
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Process Safety and Environmental Protection 168 (2022) 77–87
and TEM images show consistent morphology which reveals the suc­
cessful formation of GdVO4 @GO nanocomposite. Fig. 4D shows the
lattice fringes of the GdVO4 @GO from which the D-spacing is calculated
to be 0.357 and 0.124 nm. The Fig. 4E shows the SAED pattern of the
GdVO4 @GO nanocomposite. Elemental mapping of GdVO4 @GO
nanocomposite in Fig. 4F Survey, Fig. 4G-J distribution of Gd, V, O, and
C which confirms the even distribution of elements. The EDS spectra of
GdVO4 @GO nanocomposite are depicted in Fig. S1. The well-wrapped
GdVO4 pellets over the GO sheets provide more active sites due to the
synergetic effect between the GO sheets and the GdVO4 pellets, hence it
is expected to be used for the electrochemical sensor detection of SLZ.
3.4. Electrochemical Impedance Spectroscopy (EIS) studies
To demonstrate the electrocatalytic and charge transfer ability of
different modified electrodes, we have performed EIS investigation. The
EIS studies are done under 0.1 M KCl which contains 5 mM of [Fe
S. Maheshwaran et al.
Fig. 5. (A) EIS studies of (a) bare GCE, (b) GO/GCE, (c) GdVO4/GCE and GdVO4 @GO/GCE. (B) Cyclic Voltammetry responses recorded for (a) bare GCE, (b) GO/
GCE, (c) GdVO4/GCE and GdVO4 @GO/GCE. (C) Electrochemical kinetic studies: Varying scan rate data ranging from (a to o = 20–300 mVs− 1) using GdVO4 @GO
/GCE in 5 mM [Fe(CN)6]3-/4- under 0.1 M KCl conditions. (D) Linear graph plotted between Ipc/Ipa against (Vs− 1)1/2.
(CN)6]3-/4- and operating frequency ranges are 0.1–100 KHz (constant
current = 10 mV). The Fig. 5 A (a) reveals the Nyquist EIS plot for bare
GCE, Fig. 5 A (b) shows the plot for GO modified GCE, Fig. 5 A (c) shows
the plot for GdVO4 modified GCE and Finally, the Fig. 5 A (d) shows the
GdVO4 @GO modified GCE. The corresponding Randles circuit model is
drawn as an inset in Fig. 5 A. In the circuit model, the Rct indicates the
charge transfer resistance, Rs stands for electrolyte resistance, Cdl de­
notes double layer capacitance and Rw denotes Warburg impedance.
The bare GCE (Fig. 5 A (a)) has displayed a large semicircle arc at high
frequencies which means their electron transfer rate is low and limited.
Similarly, when the GCE electrode is reinforced with GO, GdVO4 and
GdVO4 @GO, the diameter of semicircle arc is significantly decreased
which denotes the high electron transfer ability of material with low
resistance. Especially, the GdVO4 @GO composite displayed a very less
resistance indicating the superior charge transfer ability. Through the
help of Nyquist plots, Rct values are estimated as follows, Rct for bare
GCE is 379.4 Ω, Rct for GO/GCE is 249.4 Ω, Rct of GdVO4 is 191.03 Ω
and Rct of GdVO4 @GO is 120.2 Ω. The low resistance witnessed from
GdVO4 @GO nanocomposite is mainly credited to the crystal arrange­
ment of GdVO4. The host lattice arrangement of GdVO4 aids in rapid
charge transfer between the material in composite and ultimately
providing high conductivity.
3.5. Electrochemical kinetic investigation using GdVO4 @GO modified
GCE
Electrochemical capability of catalytic combinations of GdVO4 @GO
nanocomposites are intensively studied under [Fe(CN)6]3-/4- conditions.
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Process Safety and Environmental Protection 168 (2022) 77–87
The Fig. 5B. shows the CV current responses obtained for bare GCE (a),
GO/GCE (b), GdVO4/GCE (c) and GdVO4 @GO/GCE (d) in the elec­
trochemical environment containing [Fe(CN)6]3-/4- (5 mM). The steady
scan rate of 0.05 Vs− 1 is kept for electrochemical kinetic studies.
Investigation reveals GdVO4 @GO/GCE has superior redox current
response in comparison to other modified GCE (GO/GCE, GdVO4/GCE
and bare GCE). An impressive anodic to cathodic separation of peak
potential (ΔEp) is observed for GdVO4 @GO/GCE during the analysis.
This is a vital parameter indicating the enhanced electrocatalytic nature
of GdVO4 @GO/GCE. The estimated ΔEp values for bare GCE is 0.188 V,
GO/GCE is 0.155 V, GdVO4/GCE is 0.127 V and GdVO4 @GO/GCE is
0.097 V. So, it is apparent that the GdVO4 @GO/GCE displayed a high
redox peak current than other modified electrodes. In the [Fe(CN)6]3-/4-
(5 mM) conditions, a reversible electrochemical reaction is witnessed
for GdVO4 @GO/GCE as its current response is in close proximity to 1.
Periodically, the operating scan rates are increased from 20 m to
300 mVs− 1 and its respective CV signals are recorded using GdVO4
@GO/GCE. They are displayed in Fig. 5 C. Good linearity in surface area
of GdVO4 @GO/GCE is seen corresponding to positive/negative peak
potentials. It is shown in Fig. 5D. The sustained increase in redox peak
current is mainly due to the charge diffusion polarization phenomenon.
The Randles-Sevcik (Eq. 1) is adopted to estimate the surface area of all
the modified electrodes used in the investigation.
Ip = 2⋅69 ×105 n3/2 AD1/2Cv1/ (1)
In the Eq. 1., n represents number of electrons involved, D is for
diffusion coefficient, v1/2 stands for square root of scan rate, the Ip de­
notes the peak current. The surface area (A) is calculated through by the
S. Maheshwaran et al. Process Safety and Environmental Protection 168 (2022) 77–87

Fig. 6. (A) Current responses recorded using modified electrodes under 50 µM of SLZ. (B) The loading analysis of GdVO4 @GO nanocomposite. (C) Current responses
recorded for GdVO4 @GO/GCE under various pH conditions from 3 to 11. (D) different pH corresponding linear plot of pH vs current response (black) and pH vs
potential (blue).

slope between Ip and v1/2. Further, by applying the Eq. 1., electro­
chemical surface area of GdVO4 @GO/GCE is calculated to be
0.142 cm2. The surface area for other modified electrodes are bare
= 0.078 cm2, GO/GCE = 0.113 cm2 and for GdVO4/GCE = 129 cm2.
Upon comparing all the electrodes, it is evident that GdVO4 @GO/GCE
enjoys a superior electrochemical catalytic activity. The GdVO4 @GO/
GCE is then probed for the electrochemical detection of SLZ. For this
study, the GdVO4 @GO/GCE is operated under the PBS system with
0.1 M concentration at a steady scan rate of 0.05 Vs− 1. The Fig. 6 A.
shows the recorded CV responses for all the modified electrodes (bare
GCE, GO/GCE, GdVO4/GCE, GdVO4 @GO/GCE) in the presence of
50 µM SLZ and 0.1 M PBS pH 7. As expected, the GdVO4 @GO/GCE
displayed highly enhanced oxidation peak current than others (bare
GCE, GO/GCE and GdVO4/GCE).
3.6. Loading and pH optimization studies using GdVO4 @GO/GCE
The anodic or cathodic peak current was influenced by the amount of
catalyst present over the GCE hence the GdVO4 @GO/GCE was opti­
mized. Fig. 6B indicates the plot of the current response Vs GdVO4
@GO/(mg/ml). It is observed that the anodic current increases as the
concentration increases from 2 to 6 (mg)/ml which reveals the active
involvement of GdVO4 @GO in the detection of SLZ. Moreover, in the
higher concentration, the current decreases due to the agglomeration of
particles. In this case, we have chosen 6 mg/ml mixture GdVO4 @GO
loaded GCE for the detection of SLZ. The pH optimization for

Mechanism 1. The schematic representation of electrochemical oxidation mechanism of SLZ on the GdVO4 @GO nanocomposite.

83
S. Maheshwaran et al.
Fig. 7. (A) Obtained CV data for GdVO4 @GO/GCE in the influence of SLZ in varying concentration (a to j = 25–250 µM) under PBS (0.1 M) pH 7 conditions. (B)
Linear plot between [SLZ]/µM against Current (µA). (C) Obtained CV data for GdVO4 @GO/GCE in the presence of 100 µM SLZ at periodically varying scan rates (a to
j = 20–200 mVs− 1). (D) Linear graph between square root of scan rate against obtained current response (µA).
electrochemical detection of SLZ is thoroughly investigated through the
series of CV studies under various pH buffer conditions ranging from 3 to
11 in the influence of 100 µM SLZ. The Fig. 6 C shows the obtained CV
data corresponding to pH from 3 to 11 containing 100 µM SLZ. From the
results we can clearly observe that upon increasing the pH, the peak
potential of SLZ slightly shifted towards the negative potential. This is
mainly due to the activity of proton present in the electrocatalytic
oxidation of SLZ. Amongst all the different pH analyzed, the pH 7 dis­
played a highest peak current (4.06 µA). Therefore, pH 7 is chosen as an
ideal candidate for the electrochemical investigations. The Fig. 6D
shows the different pH corresponding linear plot of pH vs current
response (black) and pH vs potential (blue). The SLZ is electrochemi­
cally oxidized by the irreversible transfer of two protons and two elec­
trons which is illustrated in mechanism 1 (Kokulnathan et al., 2021).
Mechanism 1.
3.7. Electrochemical concentration and sweep rate detection of SLZ using
GdVO4 @GO/GCE
The CV responses are recorded for various concentrations of SLZ
ranging from 25 to 250 µM using GdVO4 @GO/GCE. The electro­
chemical studies are performed under a constant rate of 50 mVs− 1 and in
PBS (0.1 M) pH 7 conditions. The collected CV responses are shown in
Fig. 7 A. It is noteworthy to mention that, upon increasing the concen­
trations of SLZ the oxidation peak current also proportionally increased.
The linearity is shown in Fig. 7B. The correlation coefficient R2 for Ip is
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Process Safety and Environmental Protection 168 (2022) 77–87
estimated to be 0.9954. This undoubtedly proves the fabricated GdVO4
@GO/GCE can be advised for ultrasensitive detection of SLZ. From the
Fig. 7 C, we can understand that the scan rate of CV is directly propor­
tional to oxidation peak current. The linear relationship between the
scan rate and current response is presented in Fig. 7D. This behavior is
seen due to the electrochemical diffusion-controlled process in the
GdVO4 @GO/GCE towards the detection of SLZ.
3.8. Amperometric (i-t) analysis of SLZ on GdVO4 @GO nanocomposite
Amperometric (i-t) analysis is used for the detection of SLZ using a
fabricated GdVO4 @GO nanocomposite sensor. The i-t method is
employed under constant stirring using RRDE (rotating ring disk elec­
trode) in 0.1 M PBS with a working potential of 0.89 V. Fig. 8 A shows
the i-t curve for linear addition concentration of SLZ from 0.02 to 145.5
and 145.5 – 945.5 µM. With increasing concentration of SLZ, the i-t
curve shows a linear and a stepwise increase of current. Fig. 8B shows a
calibration plot for the concentration vs current which has a correlation
coefficient of R2 = 9906 and R2 = 0.9971, respectively. The LOD
calculated from the linear plot is 3.1 nM and the sensitivity is
1.3009 µA µM− 1 cm− 2. Table 1 compares the electrochemical sensor
detection of SLZ on GdVO4 @GO nanocomposite with other related re­
ports. This result shows that the proposed sensor GdVO4 @GO nano­
composite modified GCE is a suitable electrode for SLZ detection.
S. Maheshwaran et al. Process Safety and Environmental Protection 168 (2022) 77–87

Fig. 8. (A) (A) The i-t curve response of the addition of different concentrations of SLZ on GdVO4 @GO. (B) The corresponding calibration plot between current and
concentration. (C) The i-t curve response for varying interfering compounds. (D) Stability investigation of GdVO4 @GO.

very reliable for real-world investigations. The fabricated GdVO4 @GO

Table 1 based electrochemical sensor is examined for interference, stability,
The comparison analysis of GdVO4 @GO nanocomposite reinforced electrode reproducibility, and real-world sample analysis. The i-t technique is
with other previously reported electrode material for SLZ drug detection. adopted for the interference study towards SLZ detection. An interfer­
Materials Methods Linear range LOD Reference ence less output current response signals are collected for GdVO4 @GO
(µM) (µM) while periodically introducing 75 µM SLZ into 0.1 M PBS system while
P3MT/GCE SWV 20–3200 4.0 (Msagati and maintaining pH 7. This is shown in Fig. 8 C. In addition to SLZ, the 10
Ngila, 2002) folds of potentially interfering compounds like (b) dopamine, (c)
MoS2/RuS2/ i-t AMP 0.01–598.7 0.004 (Sakthivel et al., glucose, (d) furazolidone, (e) diphenylamine, (f) zinc, (h) uric acid, (i)
GCE 2019a)
tryptophan, (j) flufenamic acid, (k) clioquinol, and (l) ascorbic acid are
GCE SWV 62.7–340 10.90 (Braga et al.,
2010) utilized in the study. From the analysis, the introduced interfering
MWCNTs/GCE CV 10.0–2000 7.10 (Fotouhi et al., compounds expressed very negligible interference in the output
2013) amperometric signal. Furthermore, Fig. 8D depicts the working stability
Hg electrode DPP 2–32 4.90 (Diaz et al., 1996) of the GdVO4 @GO reinforced electrode, which is tested for 1700 s in
SrWO4/SPCE DPV 0.05–235 0.009 (Kokulnathan
et al., 2021)
0.1 M of pH 7 condition containing 75 µM of SLZ. This test confirms that
MWCNTs/ i-t AMP 3.3–3.54 0.21 (Hong and Ma, the as-prepared GdVO4 @GO reinforced electrode has excellent working
OPPF 2013) stability for SLZ detection. In order to investigate the repeatability of
Cu2Sb/SPCE DPV 0.09–818.18 0.07 (Vivekanandan GdVO4 @GO/GCE based SLZ sensor, the CV responses are recorded
et al., 2020)
under 0.1 M PBS system in pH 7 conditions in the presence of 100 µM of
Bi electrode DPV 3.2–97 2.10 (Campestrini
et al., 2010) SLZ. Five separate CV runs are performed and shown in Fig. S2A. It is
GdVO4@GO/ i-t AMP 0.02 – 145.5 0.00319 This work clearly evident from CV response that the fabricated GdVO4 @GO/GCE
GCE 145.5 – 945.5 expressed an incredibly stable current response for electrochemical
detection of SLZ. Identically, the reproducibility of GdVO4 @GO/GCE is
examined in similar conditions in the presence of 100 µM of SLZ and its
3.9. Interference, stability, repeatability, and reproducibility SLZ through
corresponding data is presented in Fig. S2B.
GdVO4 @GO

An interference free and highly reproducible sensor is considered

85
S. Maheshwaran et al.
3.10. Real-world detection of SLZ on GdVO4 @GO nanocomposite
At last, the GdVO4 @GO/GCE is used to analyze the real-world
samples. The real-world samples chosen for analysis are human blood
serum, river and waste water samples. In order to avoid the interference
in the samples, SLZ stock solution is diluted in PBS solution prior to
performing the investigation. The blood serum was obtained from the
Chang-Gung memorial hospital, Taiwan. The river and waste water
samples are obtained from the Xindian river and near Chang-Gung
memorial hospital, Taiwan. Then a desired concentration of SLZ is
spiked into the real-world samples. Spiked samples are directly utilized
for analysis without any further treatment. With the help of DPV anal­
ysis, the real time SLZ detection is carried out. The standard addition
process is adopted to collect the responses from DPV using GdVO4 @GO/
GCE. The recorded results are presented in Table S1. These results
evidently suggest that the fabricated GdVO4 @GO/GCE based electro­
chemical sensor can be recommended for rapid real-world sensing of
various pharmaceutical and environmental pollutants.
4. Conclusion
In brief, GdVO4 @GO nanocomposite are hydrothermally prepared
and employed for electrochemical detection of antibiotic drug SLZ. All
the physical characterizations related to synthesized nanocomposite are
thoroughly investigated. High-surface of the composite structure is a
hugely beneficial for the electrochemical activity. Also, the synergistic
effects occurring in as-prepared GdVO4 @GO nanocomposite enhances
the electrocatalytic properties and helps in SLZ detection. The fabricated
GdVO4 @GO/GCE is probed for SLZ detection though amperometric
analysis and the output responses are highly impressive with good linear
ranges (0.02 – 145.5 and 145.5 – 945.5 µM) and limit of detection
(3.1 nM) for SLZ. Additionally, the GdVO4 @GO/GCE sensor is also
investigated for selectivity, stability, repeatability and reproducibility
and the sensor is proven to be very efficient. GdVO4 @GO/GCE based
electrochemical sensor is then employed for real-world analysis. The
real time samples like human blood serum, river and waste water
samples are used for investigation and very encouraging results are
obtained for GdVO4 @GO/GCE proving the effectiveness.
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 research investigation is supported by The Ministry of Educa­
tion, Taiwan and National Science Council. S. M. Chen, S. Maheswaran
and R. Balaji acknowledge The Ministry of Science and Technology
(MOST), Taiwan for their financial support. The MOST funding number
is MOST 110-2113-M-027-003.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.psep.2022.09.069.
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