Carbon 208 (2023) 410–420

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Carbon
journal homepage: www.elsevier.com/locate/carbon

In-situ growth of MoS2 nanosheets on g-C3N4 nanotube: A novel

electrochemical sensing platform for vanillin determination in food samples
Raja Nehru a, b, Chiu-Wen Chen a, b, **, Cheng-Di Dong a, b, *
a
Sustainable Environment Research Center, National Kaohsiung University of Science and Technology, Kaohsiung City, 81157, Taiwan
b
Department of Marine Environmental Engineering, National Kaohsiung University of Science and Technology, Kaohsiung City, 81157, Taiwan

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

Keywords: The molybdenum disulfide (MoS2) based nanomaterials show outstanding catalytic performance in many elec­
Electrocatalyst trochemical sensing applications with improved catalytic and electrochemical properties. Novel electrocatalyst
Composite developments and their application for food additives monitoring are of significant interest. In this work, we
Cost effective
have developed a novel synthesis protocol for graphitic carbon nitride nanotubes decorated MoS2 composite (g-
Food additives
Electrochemical sensor
C3N4 NTs@MoS2) using the hydrothermal method and evaluated its electrochemical sensing performance to­
wards vanillin (VN) determination. The electrochemical sensor was accomplished at various electrolytes and
optimized parameters to get an enhanced current signal for VN detection. Under the optimized conditions, the
sensor obtained wide linear ranges (0.005-458.9 µM), low limit of detection (LOD, 4 nM), and excellent sensi­
tivity (3.48 μA μM− 1 cm− 2) using differential pulse voltammetry (DPV). Moreover, the practical applicability of
the developed sensor was also successfully evaluated in food samples with an excellent recovery rate.

1. Introduction
Vanillin (VN, 4-hydroxy-3-methoxy benzaldehyde) is one of the
influential flavoring materials employed as a flavoring agent in food,
beverages, perfumes, pharmaceutical products, etc. [1]. Moreover, the
VN has been acting as a smell additive and attracting most food products
(such as cookies, chocolate, etc.) in everyday life, which can give a
positive and pleasant emotional experience with anti-epilepsy and
anti-anxiety effects [2]. The VN intake is beneficial for heart and anemia
patients in limited dosage. However, the overdosage of VN (above 10
mg kg− 1) can trigger potential health issues such as headaches, vomit­
ing, and nausea and affects the kidney and liver [3]. So, there is a need
for a simple, robust, and cost-effective method for VN accurate detec­
tion. Up to now, different analytical methods have been reported for VN
estimation that includes high-performance liquid chromatography
(HPLC) [4–6], spectrophotometry [7], gas chromatography-mass spec­
trometry (GC-MS) [8], fluorescence [9], capillary electrophoresis [10],
and electroanalysis [11,12]. These methods are time-consuming,
high-cost, complicated instrumentations, and require skilled operators.
In recent years, electrochemical methods have attracted considerable
interest with the advantages of simple operation, high sensitivity, and
excellent selectivity [13]. However, the electrochemical quantification
of VN is restricted by electrode surface fouling over glassy carbon
electrodes (GCE). Chemically modified electrodes (CME) by employing
is one way to overcome this issue. In this regard, nanomaterials have
been used as an electrocatalyst to explore VN determination [2,14–16].
The modified electrode surface is a crucial factor for the limit of
detection (LOD), sensitivity, and selectivity toward the electrochemical
determination of VN. Therefore, the new electrode modifiers are of
significant interest for reliable and accurate VN sensors.
As we know, for electrochemical sensing applications, graphene
oxide (GO), reduced graphene oxide (rGO), multiwalled carbon nano­
tubes (MWCNT), carbon black (CB), and graphitic carbon nitride (g-
C3N4) electrocatalysts are showing great interest. For example, Jinyun
Peng et al. reported the graphene-based electrochemical sensor for
vanillin detection with a LOD of 5.6*10− 8 mol L− 1 [17]. Moreover,
Mahsa Tabrizi et al. reported the rGO/Fe3O4 nanocomposite for VN
determination, the observed results showing good concentration ranges
(1.0 nM–250 μM) with good stability and recovery (99.25–103.11%)
[18]. LydiaTaouri et al. explored the fullerene-MWCNT nanostructure

* Corresponding author. Sustainable Environment Research Center, National Kaohsiung University of Science and Technology, Kaohsiung City, 81157, Taiwan.
** Corresponding author. Department of Marine Environmental Engineering, National Kaohsiung University of Science and Technology, Kaohsiung City, 81157,
Taiwan.
E-mail addresses: nrajache@nkust.edu.tw (R. Nehru), cwchen@nkust.edu.tw (C.-W. Chen), cddong@nkust.edu.tw (C.-D. Dong).

https://doi.org/10.1016/j.carbon.2023.03.053
Received 18 November 2022; Received in revised form 10 March 2023; Accepted 23 March 2023
Available online 2 April 2023
0008-6223/© 2023 Elsevier Ltd. All rights reserved.
R. Nehru et al.
Fig. 1. PXRD patterns and FT-IR spectra of g-C3N4 NTs, MoS2 NS, and g-C3N4 NTs@MoS2 (a and b), hexagonal structure of MoS2 with the space group of P63/mmc
(c). (A colour version of this figure can be viewed online.)
for VN detection, the observed result revealed that low LOD (3.4 × 10− 8
mol L− 1), good stability, and repeatability [19]. Moreover, the g-C3N4
also shows great interest in vanillin detection (Li Fu et al.) [20]. The
reported results show low LOD (4 nM) with a linear range of 20 nM to 10
μM, respectively. However, the recent reports suggest that carbon-based
materials are significant interest and are highly suitable electrocatalyst
to construct the electrochemical sensor with the help of novel transition
metal dichalcogenides (TMC). Molybdenum disulfide (MoS2) is related
to the metal dichalcogenide group (MX2, where M = Mo, W, and X = S,
Se) is widely used for different applications consisting of active covalent
bonds in the form of Mo–S with weak Van Der Waals attractions. The
MoS2 unique property displays excellence in different field including,
water splitting [21], photocatalytic hydrogen evolution [22], photo­
catalyst [23], electrocatalysis [24], gas sensor [25] and electrochemical
(bio)sensors [26], respectively. However, the potential design of nano­
structured materials shows a great interest in developing significant
electrode material constructions to increase the conductivity in the
electrode/electrolyte prosses, such includes MoS2 nanoflowers [27],
nanorods [28], nanosheets [29], nanowires [30], nanospheres [31] and
hydride nanostructures [28], respectively. Recently, Dinesh et al.
designed the MoS2 nanosheets decorated on multiwalled carbon nano­
tubes for electrochemical hydrogen evolution in 0.5 M H2SO4, which
showed good sensitivity (1.67 μA/μM/cm2), stability, selectivity, and
low overpotential (211 mV), respectively [32]. Pranjala Tiwari et al.
reported the Self-standing MoS2/CNT and MnO2/CNT one-dimensional
core-shell for supercapacitor applications, which offers 0.34 F cm− 2
and 6.5 F cm− 3, respectively. Additionally, Zhang et al. reported the
MoS2 nanosheets grown on TiO2 nanowire arrays using glucose assisted
hydrothermal method, which offers good specific capacity, cycling sta­
bility, and excellent performance in lithium-ion batteries [33]. Herein,
the addition of glucose helps to grow the MoS2 nanosheets on different
carbon-based materials and is beneficial as a better electrode material
for various electrochemical applications. In recent years, the metal-free
semiconducting material of g-C3N4 showing great interest in water
splitting and CO2 reduction [34], photocatalytic pollutant degradation
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[35], sensing [36], optoelectronics [37] and gas sensing applications
[38], respectively. However, the g-C3N4 could be a challenging electrode
material with unsatisfactory performance because of poor conductivity
and considerable contact resistance. Moreover, the intrinsic structure of
g-C3N4 can provide more metal coordination sites during the electro­
catalytic process. The above limitations suggest that different structural
or appropriate modifications can improve the electrocatalytic activity of
g-C3N4.
In this study, we developed a new type of g-C3N4 nanotubes (NTs)
decorated with uniform MoS2 nanosheets with the help of glucose via a
hydrothermal method with the attention of cost-effective, significant
structural futures and highly active electrocatalyst toward effective VN
detection. Ultimately, the developed g-C3N4 NTs@MoS2 composite
shows interesting structural features and excellent electrochemical
characteristics, confirming successful fabrication. Here, the proposed g-
C3N4 NTs@MoS2 composite improved with electrical conductivity and
specific surface area because of the large number of MoS2 nanosheets
combined over g-C3N4 NTs with their synergistic effect. On this basis, a
novel electrochemical sensing platform was developed using g-C3N4
NTs@MoS2 composite over a glassy carbon electrode (GCE) for VN
detection and reported for the first time. The results confirm that the g-
C3N4 NTs@MoS2 composite can offer a more satisfactory catalytic ac­
tivity, cycle stability, and low detection limit (LOD) than other VN
electrochemical sensors. Nevertheless, the developed electrode shows
significant sensing performance in VN determination in commercial
food samples with appreciable recoveries.
2. Experimental section
2.1. Chemicals and reagents
Melamine (≥99.0%), thiourea (CH4N2S), Sodium molybdate dihy­
drate (Na2MoO4.2H2O, ≥99.5%), glucose (C₆H₁₂O₆) and Vanillin
(C8H8O3) were obtained from Sigma Aldrich. The electrolyte utilized
throughout the experiment was phosphate buffer (PB). This works
R. Nehru et al.
Fig. 2. Schematic illustration picture for stepwise g-C3N4 NTs@MoS2 composite preparation, TEM images of g-C3N4 NTs (b–c), MoS2 NS (d–e), g-C3N4 NTs@MoS2
composite (f–h), HR-TEM image and inverse FFT of g-C3N4 NTs@MoS2 composite (i–j), and EDX images of g-C3N4 NTs@MoS2 composite (k). (A colour version of this
figure can be viewed online.)
experimental and electrolyte preparation water is ultrapure water (Milli-
Q, 18.2 MΩ/cm), and all other chemicals and reagents were of analytical
reagent grade.
2.2. Characterizations and electrochemical measurements
The morphology and elemental characteristics were analyzed using
scanning electron microscopy (SEM, HITACHI S3000H) and trans­
mission electron microscopy (TEM – JEOL JEM-2100) with energy
dispersive X-ray spectroscopy (EDX-probe). XPS measurements were
carried out with a Kratos Axis Ultra spectrometer using 1486.6 eV
focused monochromatized Al Kα radiation (hν). The electrochemical
characteristics and analytical performance have accomplished by
employing AUTO LAB PGSTAT302 N (Metrohm) with the three-
electrode system. All experiments were carried out at room temperature.
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Carbon 208 (2023) 410–420
2.3. Synthesis of g-C3N4 NTs@MoS2 composite
The g-C3N4 NTs has prepared by hydrothermal method. In detail, the
8g of melamine was dispersed with 50 mL of deionized (DI) water and
allowed for continuous stirring for 20 min. Afterward, the solution
mixture was heated in a Teflon-lined hydrothermal autoclave at 200 ◦ C
for 16 h. After the centrifugation, the white powder obtained after
vacuum dried at 60 ◦ C for 6 h and then placed in a tubular furnace at
550 ◦ C for 3 h with a ramping rate of 5 ◦ C/min to get the g-C3N4 NTs. The
100 mg of g-C3N4 NTs dispersed in 35 mL of DI water, and then 0.05 M of
glucose was introduced to the above solution and sonicated for 20 s.
Afterward, the 0.3 g of Sodium molybdate dihydrate and 0.6 g of thio­
urea were added and stirred well with continued stirring for 5 min.
Finally, the solution mixture was transferred into the Teflon-lined hy­
drothermal autoclave and heated at 200 ◦ C for 24 h. The received yield
R. Nehru et al.
Fig. 3. XPS survey spectrum of g-C3N4 NTs@MoS2 composite (a) and high-resolution XPS spectrum of Mo 3d (b), S 2p (c), N 1s (d), and C 1s (e) for g-C3N4
NTs@MoS2 composite. (A colour version of this figure can be viewed online.)
was washed several times with DI water and vacuum dried at 60 ◦ C to
obtain a g-C3N4 NTs@MoS2 composite. The pristine MoS2 nanosheets
also were prepared using the same method without g-C3N4 NTs for
comparison.
2.4. Fabrications of g-C3N4 NTs@MoS2 modified electrode surfaces
According to our previous study, the glassy carbon electrode (GC)
has been pre-treated with aluminum oxide (Al2O3, rain size of 0.3 μm)
powder to get mirror-like surfaces. 2.0 mg of g-C3N4 NTs@MoS2 com­
posite was added into 1.0 mL of DI water and dispersed via ultra­
sonication for 30 min to obtain a stable black suspension. Then, 6.0 μL of
g-C3N4 NTs@MoS2 composite was drop cast onto the GCE surfaces
(0.071 cm2) and dried at room temperature. The prepared electrode, g-
C3N4 NTs@MoS2/GCE, was rinsed with DI water before use. A similar
procedure prepared the g-C3N4 NTs and MoS2 modified GCE for the
comparison study.
3. Results and discussions
3.1. Physicochemical characterizations of the materials
The PXRD patterns of the samples as displayed in Fig. 1a. In detail,
Fig. 1a (black line) shows the XRD patterns of g-C3N4 NTs with two
distinctive peaks at 13.4◦ and 27.6◦ , related to the (100) and (002) plane
of g-C3N4 and confirmed with the standard JCPDS No. 87–1526 [39,40].
Fig. 1a (red line) shows the XRD patterns of MoS2 NS synthesized using a
hydrothermal method and confirmed to be a hexagonal structure of
MoS2 with the space group of P63/mmc indexed with the diffraction
patterns at 16.6◦ (002), 32.7◦ (101), 43.1◦ (103), 49.3◦ (105), 57.5◦ (110),
and 68.7◦ (210) by JCPDS No 37–1492 [41]. Fig. 1c shows the MoS2
crystal structures belonging to the space group of P63/mmc with a unit
cell a = b = 3.190 Å and c = 14.879 Å and α = 90⁰, β = 90⁰ and υ = 120⁰
unit cell parameters, respectively. The individual S–Mo–S unit com­
prises [MoS6] octahedra sharing edges; no Mo–Mo clustering exists.
Further, the composition of MoS2 NS decorated g-C3N4 NTs were char­
acterized by PXRD, as shown in Fig. 1a (blue line). The g-C3N4
NTs@MoS2 composite has different diffraction patterns combined with
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the additional strong peak of g-C3N4 NTs at 27.6◦ , related to the (002)
plane and good agreement with the JCPDS No. 87–1526. The observed
results confirm the successful composition of g-C3N4 NTs@MoS2. Fig. 1b
shows the FT-IR spectra of the prepared samples of g-C3N4 NTs (red
line), MoS2 NS (blue line), and g-C3N4 NTs@MoS2 composite (green
line) to investigate the functional groups. The FT-IR spectra of g-C3N4
NTs (red line) show the two characteristic peaks at 806 cm− 1 and 884
cm− 1 conform to the breathing modes of tri-s-triazine ring units [42,43].
The peaks at 1252–1627 cm− 1 are due to the CN heterocycles stretching
vibrations. In detail, the characteristics peaks exist at 1249, 1317, 1417,
1466 cm− 1, and 1571 to 1637 cm− 1 related to C–N and C– – N bonds [44].
In addition, additional peaks existing in the range from 3047 to 3585
cm− 1 are related to the N–H and O–H stretching vibrations [45,46].
Fig. 1b (blue line) shows the FT-IR spectra of the MoS2 nanosheets
observed at 601 and 930 cm− 1, related to the Mo–S and S–S bond for­
mation. Compared with MoS2 NS, the peak of g-C3N4 NTs@MoS2 com­
posite at 811 cm− 1 shifts slightly to a higher wavenumber, suggesting
that g-C3N4 NTs strong interaction with MoS2 NS due to the glucose. The
observed results demonstrate the successful formation of g-C3N4
NTs@MoS2 composite. Fig. 2a shows the schematic illustration of the
g-C3N4 NTs@MoS2 composite formation. Herein, the g-C3N4 NTs ob­
tained via a hydrothermal method, and then the glucose was introduced
to the nanotube surfaces for the nuclei formation and in-situ growth of
MoS2 nanosheets. Specifically, the Mo6+ ion can be complex with the
pyridine-like nitrogen atoms in the heptazine unit of g-C3N4 NTs, and
these Mo ions can further act as reaction sites to form MoS2 nuclei with
the help of glucose.
As a result, the successful formation of g-C3N4 NTs@MoS2 composite
of nanotubes decorated layered structural futures. Fig. 2 b and c show
the low and high magnification TEM images of g-C3N4 NTs on smooth
surfaces with a diameter of 200 nm. Fig. 2d and e shows the low and high
magnification TEM images of MoS2 nanosheets, revealing the coexis­
tence of few-layer nanosheets folded and tangled together. The image in
Figs. S1a–b shows the HR-TEM images of MoS2 nanosheets were well-
stacked and exhibited parallel lines related to the MoS2 layers. The
inset figures show the Inverse Fast Fourier transform (IFFT) image and
profile of MoS2 layers with the interplanar distance of 0.528 and 0.213
nm, respectively, which is related to the (100) and (121) planes of MoS2
R. Nehru et al.
layers. Figs. S1c–d shows the TEM image and energy dispersive spectra
(EDS) of MoS2, which confirms the stoichiometry of Mo and S elemental
presence (Fig. S1). The TEM image of the g-C3N4 NTs@MoS2 composite
was analyzed using TEM. Fig. 2f and g shows the low and high magni­
fications of TEM images of g-C3N4 NTs@MoS2 composite, revealing that
the g-C3N4 NTs well decorated by MoS2 nanosheets. Fig. 2h shows the
edge surfaces of the g-C3N4 NTs@MoS2 composite, indicating that the
MoS2 layers are folded and tangled over g-C3N4 NTs. Fig. S2 shows the
TEM images of g-C3N4 NTs@MoS2 composite of layered MoS2 with
interlayer spacing distances of 0.908 nm and 0.6712 nm, respectively.
The standard interlayer spacing of 2H-type MoS2 is 0.62 nm. However,
the demonstrated g-C3N4 NTs@MoS2 composite of the MoS2 layer has
extended to the interlayer during the composite formation, which could
be more favorable for electron transfer rate with improved capability.
Fig. 2i HR-TEM image (inset: IFFT image) of g-C3N4 NTs@MoS2 com­
posite and the layered MoS2 observed the line intensity profile of the
inverse FFT interplanar distances of 0.286 nm (Fig. 2j), respectively,
which is related to the (101) plane of MoS2. Further, the g-C3N4
NTs@MoS2 composite was analyzed using EDX, which confirms the
composition of Mo, S, N, and C elemental presence without any impu­
rities (Fig. 2k). 3i HR-TEM image (inset: IFFT image) of g-C3N4
NTs@MoS2 composite and the layered MoS2 observed the interplanar
distances of 0.286 nm, which is related to the (101) plane of MoS2.
The chemical composition and state of g-C3N4 NTs@MoS2 composite
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Carbon 208 (2023) 410–420
Fig. 4. EIS Nyquist plots and CVs results of bare GCE,
g-C3N4 NTs/GCE, MoS2 NS/GCE, and g-C3N4
NTs@MoS2/GCE in 0.01 M KCl and 5.0 mM con­
taining [Fe(CN)6]3-/4- (a and b), the CVs different scan
rates (20–300 mV/s) redox responses of g-C3N4
NTs@MoS2/GCE in 0.01 M KCl and 5.0 mM con­
taining [Fe(CN)6]3-/4- probe (c), corresponding cur­
rent vs. (scan rate)1/2 (V s− 1)1/2 (d), CVs different
scan rate (20–300 mV/s) oxidation peak current re­
sults of bare GCE, g-C3N4 NTs/GCE, MoS2 NS/GCE,
and g-C3N4 NTs@MoS2/GCE in redox probe electro­
lyte (e) and corresponding electrochemical active
surface area of different electrodes (f). (A colour
version of this figure can be viewed online.)
and their presence of Mo, O, N, and C were determined using XPS
analysis (Fig. 3a–e). The binding energy of the g-C3N4 NTs@MoS2
composite survey spectrum was displayed in Fig. 3a with distinct peak
positions at 37.8 eV (Mo 4p), 162.3 eV (S 2p), 233.4 eV (Mo 3d), 284.3
eV (C 1s) and 396.8 eV (N 1s) revealing that the contribution and ex­
istence of g-C3N4 NTs and MoS2 NS. The Mo high-resolution XPS char­
acteristic deconvolutes into five individual peaks. The two peaks
centered at 229.5 and 233.1 eV are associated with the binding energies
of Mo4+ 3d5/2, respectively. Moreover, the peak at 230.9 eV and 234.5
eV are related to the Mo 3d3/2 of Mo4+, respectively. In addition, the
weak XPS spectra of the S 2s peak obeyed at 226.9 eV. Fig. 3c shows the
XPS spectra of S 2s with two deconvoluted peaks at 162.6 eV and 163.9
eV, related to the S 2p 3/2 and S 2p 1/2, respectively. Fig. 3d shows the
XPS spectra of N 1s spectra with three peaks at 396.7 eV, 399.4 eV, and
402.4 eV, corresponding to the C– – N–C, N–C3, and C–N–H, respectively
[47], and the XPS spectra of C 1s spectra shows the two peaks at 285.0
eV and 286.2 eV corresponds to the C–C and N–C– – N (Fig. 3e), respec­
tively [21]. The analysis confirms the successful formation of MoS2 NS
over g-C3N4 NTs.
3.2. Electrochemical behavior of the modified electrodes
The electrochemical impedance spectroscopy (EIS) measurements
conducted in the 100 kHz to 0.0001 Hz frequency range in the presence
R. Nehru et al.
Fig. 6. Oxidation mechanism of VN over modified electrodes. (A colour version of this figure can be viewed online.)
of 0.1 M KCl and 5.0 mM [Fe(CN)6]3− /4− electrode-electrolyte redox
probe interface on GCE unmodified, g-C3N4 NTs/GCE, MoS2 NS/GCE,
and g-C3N4 NTs@MoS2/GCE to examine the charge-transfer (Rct)
characteristics (Fig. 4a). The Nyquist plots of small semicircle observed
for g-C3N4 NTs@MoS2/GCE (Rct = 16.30 Ω), which was highly com­
parable with that of the unmodified GCE (Rct = 327.95 Ω) and modified
electrodes of g-C3N4 NTs (Rct = 41.53 Ω) and MoS2 NS (Rct = 17.46 Ω),
respectively. Fig. 4b shows the electron transfer rate responses of GCE
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Carbon 208 (2023) 410–420
Fig. 5. CV results of bare GCE, g-C3N4 NTs/GCE,
MoS2 NS/GCE, and g-C3N4 NTs@MoS2/GCE in the
presence of VN (200 μM) at 0.05 M PB (pH-3.0) in the
scan rate of 50 mV/s and the corresponding anodic
peak current responses (a and b), CV results of
different scan rates (20–300 mV/s) in the presence of
VN (200 μM) and the corresponding oxidation peak
current vs. (scan rate)1/2 (V s− 1)1/2 (c and d), CV re­
sults of g-C3N4 NTs@MoS2/GCE in 0.05 M PB with
different pHs (pH 3.0–9.0) in the presence of VN at
50 mV/s and the corresponding oxidation peak cur­
rent differences (e and f). (A colour version of this
figure can be viewed online.)
unmodified, g-C3N4 NTs/GCE, MoS2 NS/GCE, and g-C3N4 NTs@MoS2/
GCE using a CV technique in the potential window of − 0.3 to 0.6 V at
0.1 M KCl, and 5.0 mM [Fe(CN)6]3-/4-. Herein, the well-defined redox
behavior with the peak-to-peak current (Ipa/Ipc) ratio of 1.33 obeyed on
g-C3N4 NTs@MoS2/GCE, comparable with bare GCE (1.160). Moreover,
the surface modification strategy plays a significant role that helps to
increase the electron transfer rate on different electrocatalyst-modified
GCE in the 0.1 M KCl and 5.0 mM [Fe(CN)6]3− /4− containing
R. Nehru et al.
Fig. 7. Schematic illustration picture of carrier-assisted g-C3N4 NTs@MoS2/GCE for VN detection in electrochemical sensing platform (a), DPV results for g-C3N4
NTs@MoS2 composite modified GCE in 0.05 M PB (pH 3.0) containing VN different concentrations (b), and corresponding linear current responses vs. concentration
of VN (c). (A colour version of this figure can be viewed online.)
electrode-electrolyte redox probe. Herein, g-C3N4 NTs@MoS2/GCE
shows a well-defined significant redox peak current with enhancement
responses observed compared to the unmodified GCE. Fig. S3a-c and
Fig. 4c show the CVs results of various scan rates (20–300 mV/s) on bare
GCE, g-C3N4 NTs/GCE, MoS2 NS/GCE, and g-C3N4 NTs@MoS2/GCE has
performed at 0.1 M KCl and 5.0 mM [Fe(CN)6]3− /4− containing
electrode-electrolyte redox probe.
Fig. 4c displays that the hybrid catalyst of g-C3N4 NTs@MoS2 boos­
ted the electron transfer rate over GCE in the electrode/electrolyte
system at different scan rates (20–300 mV/s) in the electrolyte redox
probe. The corresponding Ipa (R2 = 0.9988) and Ipc (R2 = 0.9986) re­
sults of g-C3N4 NTs@MoS2/GCE different scan rates (20–300 mV/s)
have displayed in Fig. 4d. From the observed results of Fig. S3 (a-c) and
Fig. 4c, the electrochemically active surface area (A) of different elec­
trodes such as bare GCE, g-C3N4 NTs/GCE, MoS2 NS/GCE and g-C3N4
NTs@MoS2/GCE has calculated to be 0.0754, 0.0757, 0.1497, 0.2763
cm2 using the Randles Sevcik equation (Equation (1)) and compared in
Fig. 4e and f [48–50]. The obtained results indicate that while
comparing to unmodified GCE, the developed g-C3N4 NTs@MoS2 com­
posite modified GCE shows a significant interest in this research to
improve the electrode active surface area, novel mass electron transport,
electrical conductivity, and rapid charge transfer capability.
ip = 2.69 ∗ 105 n1/2 A D1/2 C ϑ1/2 (1)
Where ip is the peak current (A); n is the number of electron transfer, A is
the electrochemical active area (cm2), D is the diffusion coefficient (cm2
s− 1), C is the concentration of the electroactive species (mol/cm3), and
ϑ1/2 is the different scan rate (Vs− 1).
3.3. Electrochemical behaviours of VN at different electrodes
The electrochemical behavior of VN (200 μM) analyzed at bare GCE,
g-C3N4 NTs/GCE, MoS2 NS/GCE, and g-C3N4 NTs@MoS2/GCE using CV,
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in the potential window of 0.3–1.3 V with the scan rate of 50 mV/s in the
0.05 M PB (pH 3.0) (Fig. 5). In Fig. 5a, bare GCE detects the VN at 0.944
V with diminished current responses of 4.520 μA, low electrical con­
ductivity, and high overpotential due to an insufficient oxidation pro­
cess. After modifications with the g-C3N4 NTs over GCE, the VN
detection obeyed at 0.898 V with an improved current response (5.383
μA) and sharp peaks displayed with the on-site potential of 0.822 V,
respectively. Moreover, the MoS2/GCE shows a significant peak current
(21.085 μA) improvement with an enhanced VN detection signal in the
electrode/electrolyte interfaces in contrast to the bare GCE and g-C3N4
NTs/GCE. Moreover, the MoS2 NS is a very active adsorbing of VN
during the electrochemical process and shows ~4.664 times higher than
bare GCE. The MoS2 NS has improved with g-C3N4 NTs for VN detection
with enhanced stability and effectiveness on peak current responses
(25.19 μA) in the electrode/electrolyte system. Among other electrodes,
g-C3N4 NTs@MoS2/GCE enhanced the effectiveness of VN detection due
to the MoS2 NS decorated over g-C3N4 NTs. Herein, 200 μM of VN over g-
C3N4 NTs@MoS2 modified GCE shows the strong oxidation peak with an
on-site potential of 0.8493 V, attributed to the irreversible oxidation of
VN, as illustrated in Fig. 6. Moreover, due to the synergistic effect, the
MoS2 and g-C3N4 NTs composite improved the dispersion ability and
electrical conductivity, passive electron transfer rate, and better elec­
trical conductivity towards VN determination. However, the peak po­
tential shifted slightly towards the positive side compared to g-C3N4
NTs, and MoS2 NSs modified GCE, which could be related to the glucose-
assisted g-C3N4 NTs@MoS2 composite activity in 0.05 M PB at 50 mV/s.
The overall peak current improvements of different electrodes as
compared in Fig. 5b.
Fig. 5c shows the influence of different scan rates on the g-C3N4
NTs@MoS2/GCE for VN electrochemical behavior in the 0.05 M PB
electrolyte system. As expected, with the increases in scan rate ranging
from 20 to 300 mV/s, the oxidation peak potential shifted slightly to­
ward positive directions, and the current intensities increased. The
corresponding oxidation peak current (Ipa) responses vs. (scan rate)1/2
R. Nehru et al. Carbon 208 (2023) 410–420

Table 1 (VN) at 50 mV/s (Fig. 5e). The CVs results of VN show a gradual
Carbon and nanomaterials-supported electrochemical VN sensors. decrease of the oxidation peak current of VN from pH 3.0 to 9.0 over g-
Electrodes Method Linear range Sensitivity LOD Ref. C3N4 NTs@MoS2/GCE (Fig. 5e). Fig. 5f shows the VN anodic peak cur­
(μM) (μA μM− 1. (M) rent responses and peak potential shift differences of different pHs at g-
cm− 2) C3N4 NTs@MoS2/GCE. Herein, the 3.0 (PB) pH shows a strong oxidation
AuPd-Gr/GCE DPV 10–40.0 – 20 × [53] peak current compared to the other PB electrolytes in the modified
10− 9 electrode surfaces. In addition, the peak oxidation potential of VN shifts
CeO2-ErGO/GCE SDLSV 0.04–20.0, – 10 × [54] linearly to a more negative side with increasing pHs, which demon­
20–100.0 10− 9
MIP-SWNTs- DPV 0.4–8.0, 178.0 200 [55]
strates the involvement of hydrogen ions (H+) in an electrolyte solution
COOH/GCE 10–140.0 × during the electro-oxidation process for VN. The linear relationship
10− 9 between the pHs and peak oxidation potential of VN follows the linear
MWNTs- DPV 0.2–10.0 1.22 100 [56] regression equation: Epa (V) vs. Ag/AgCl = − 0.0583 [pH] + 1.1453 and
PDA@MIP/ ×
R2 = 0.9442 (Fig. S5). The obtained results revealed that the slope value
SWNTs- 10− 9
COOH/GCE is near the theoretical value (− 59.0 mV/pH) of the Nernst equation [51,
Poly(GA)/ DPV 0.50–13.0 3.19 12 × [57] 52] and confirms that the electrochemical behavior of VN shows an
(MWCNTs-GT) 10− 9 equal number of electrons and protons. The observed results revealed
CPS that pH 3.0 shows good electrochemical behavior for VN detection;
CB/SPCE DPV 0.1–495.0 0.10 39 × [58]
10− 9
therefore, we utilized pH 3.0 for further electrochemical measurements
MoS2/PANI/g- DPV 4.6–103.0 8.50 43 × [59] hereafter.
C3N4@GCE 10− 9 Fig. S6 (a-d) shows the different concentrations (0–200 μM) of VN
SnO2-CPB/GCE DPV 0.10–100, – 20 × [60] performed in the presence of 0.05 M PB (pH-3.0) at 50 mV/s over un­
100–500.0 10− 9
modified GCE and g-C3N4 NTs, MoS2 NS, and g-C3N4 NTs@MoS2 com­
CuO@SiO2/GCE DPV 0.05–1.2, 2.88 53 × [61]
6.2–111.2 10− 9 posite modified GCE using cyclic voltammetry (CVs). Fig. S6e shows the
CuS–H/GCE DPV 0.1–46.5 0.85 53 × [26] corresponding linear plots of different electrodes with the linear
10− 9 regression equation of Ipa (μA) = 0.0173 (μM) + 1.11 (R2 = 0.9963) for
MoS2-CNFs/GCE i-t 0.3–135.0 – 150 [2] bare GCE, Ipa (μA) = 0.0208 (μM) + 1.275 (R2 = 0.9944) for g-C3N4
NTs/GCE, Ipa (μA) = 0.0488 (μM) + 11.603 (R2 = 0.9805) for MoS2 NS/
×
10− 9
C3N4/GCE DPV 0.02–10, – 4.0 × [20] GCE, and Ipa (μA) = 0.057 (μM) + 13.9 (R2 = 0.9921) for g-C3N4
15–200 10− 9 NTs@MoS2/GCE, respectively. The observed results revealed that the
MoS2/ DPV 6–86.6 – 43 × [52] corresponding peak current of VN linearly increased while increasing
PANI@GO/ 10− 9
the different concentrations and demonstrated the current was directly
GCE
MoS2/PANI/f- DPV 3.6–125 – 21 × [62] proportional to the VN. However, the g-C3N4 NTs@MoS2/GCE shows
MWCNTs/GCE 10− 9 the highest VN oxidation peak current responses compared to the other
g-C3N4 DPV 0.005–458.9 3.48 4.0 × This electrode, which is related to the fast electron rate, thus boosted by g-
NTs@MoS2/ 10− 9 work C3N4 NTs and MoS2 sheets through GCE surfaces. Therefore, the g-C3N4
GCE
NTs@MoS2/GCE was analyzed to identify the catalytic performance and
quantitative determination of VN using the differential pulse voltam­
(Vs− 1)1/2 with an R2 value of 0.9903 (Fig. 5d), respectively. According to metric (DPV) technique. Under the optimized conditions of start po­
the regression equation: Ipa = 28.419 + 11.831 (R2 = 0.9903), the VN tential: 0.3 V, stop potential: 1.3 V, step: 0.03 V, modulation amplitude:
oxidation over g-C3N4 NTs@MoS2/GCE followed by an adsorption- 0.025 V, modulation time: 0.05 s, and interval time: 2 s, the g-C3N4
controlled process. Moreover, the oxidation peak potentials (Epa, V) NTs@MoS2/GCE was subjected to quantitative analysis using the DPV
VN slightly shift with different scan rates (20–300 mV/s), and Fig. S4 technique. Before exploring the VN sensing using the DPV technique, the
shows the Epa and lnv relationship following in equation (2) [15]. GCE electrode surface was well-polished and modified according to the
( ) ( ) ( ) fabrication process as given experimental section (2.4). Fig. 7a shows
Ep = E0 +
RT
ln
RTk⁰
+
RT
lnv (2) the schematic illustration of a stepwise electrode preparation using the
αnF αnF αnF as-proposed electrocatalyst of g-C3N4 NTs@MoS2 composite and direc­
tion toward VN detection using the electrochemical approach with a
Where: Ep is the peak potential, E0 is the formal potential, T is the
three-electrode system in 0.05 M PB electrolyte. Fig. 7b shows the well-
temperature (298.15 K), R is the universal gas constant (8.314 J/(K
defined oxidation peaks observed over GCE-modified g-C3N4
mol)), n is the number of transferred electrons of the oxidation of VN, F
NTs@MoS2 composite with different concentrations of VN additions
is the Faraday constant (96485C/mol), k0 is the heterogeneous rate
ranging from 0.005 to 3.9 and 33.89–458.9 μM, respectively. The LOD
constant, and v is the scan rate (V/s). According to equation (2), the plot
and LOQ were calculated based on the previously reported literature and
of Ep vs. ln n shows an excellent linear relationship with the R2 of 0.9802
found to be 4.0 × 10− 9 M, 16 × 10− 9 M, and 155 × 10− 9 M, 518 × 10− 9
(Fig. S4), respectively. Herein, the slope value of Ep vs. ln n allows
M, with the linear regression equations Ipa1 (μA) = 0.2458c (μM) +
calculating the αn value by assuming a value of α equal to 0.5. The value
0.5472 (R2 = 0.9992), and Ipa2 (μA) = 0.0079c (μM) + 2.0924 (R2 =
of n as estimated for VN is ~2; therefore, VN involves a two-electron and
0.9822), respectively (Fig. 7c).
two-proton reaction, as demonstrated in Fig. 6 [1,13].
Moreover, the developed detector is relatively simple and low-cost
with high sensitivity (3.48 μA μM− 1 cm− 2). The observed results
3.4. Experimental testing conditions and analytical response of VN in demonstrated that the g-C3N4 NTs@MoS2/GCE showed a wide linear
voltammetry technique range and low LOD compared to most other reported modified elec­
trodes (Table 1) [2,20,26,52–62]. Herein, the enhancement of the
The analytical testing of VN in different pH-supporting electrolytes is electrode sensitivity towards the VN sensor depends on the g-C3N4
necessary because of its evaluation in peak current, peak potential shift, NTs@MoS2 electrocatalyst. However, the relatively low conductivity of
and shape identification. Hence, the VN oxidation has been experi­ g-C3N4 NTs alone not showing good VN oxidation. On the other hand,
mented with different PB in the pH range of 3.0–9.0 and explored over the excellent conductivity and catalytic activity for VN detection led to a
GCE-modified g-C3N4 NTs@MoS2 composite in the presence of 200 μM synergistic coupling effect of g-C3N4 NTs and MoS2 NS. Finally, they

417
R. Nehru et al.
improved the catalytic process for VN oxidation in the electro­
de/electrolyte system. Therefore, compared to the previous reports, our
proposed sensor shows outstanding sensing performance towards VN
with low-cost effects, high surface area, high absorptivity, and combined
catalytic activity of g-C3N4 NTs and MoS2 NS.
3.5. Anti-interference ability and reproducibility
For practical use, the estimation of the proposed g-C3N4 NTs@MoS2
modified GCE selectivity, reproducibility, and stability of the sensor is a
significant factor. Therefore, the experiments were further analyzed
using CV and DPV in the presence of 0.05 M PB electrolyte medium with
VN presence at 50 mV/s. Fig. 8a shows the DPV results for VN with anti-
interfering responses over g-C3N4 NTs@MoS2/GCE in the presence of
different interfering compounds, such as Mn2+ (330 μM), Zn2+(300 μM),
Ni2+ (310 μM), Mg2+ (330 μM), K+ (320 μM), dopamine (DA, 400 μM),
Citric acid (CA, 420 μM), and tartaric acid (TA, 460 μM), respectively.
The corresponding peak current responses, as displayed in Fig. 8b,
reveal that the g-C3N4 NTs@MoS2/GCE sensor is suitable for the selec­
tive detection of VN. Further, the developed sensor allowed for a
reproducibility test using the CV technique. Fig. 8c shows the six
modified electrodes that have experimented with 100 μM of VN in 0.05
M PB at 50 mV/s under the same experimental conditions. As displayed
418
Carbon 208 (2023) 410–420
Fig. 8. DPVs interference profile for g-C3N4
NTs@MoS2/GCE in 0.05 M PB electrolyte medium in
the presence of VN (a), corresponding linear fitting of
anodic peak current (μA) vs. different interfering
compounds (b), CV results of g-C3N4 NTs@MoS2/GCE
of VN sensor reproducibility (c) and corresponding
peak current responses (d), DPVs results for VN
detection in ice-cream samples at g-C3N4 NTs@MoS2/
GCE (e), corresponding linear calibration plots (μA)
vs. concentration (μM) (f). (A colour version of this
figure can be viewed online.)
in Fig. 8d, the corresponding peak current responses show a relative
standard deviation (RSD) of 3.01%, revealing satisfactory reproduc­
ibility for the proposed sensor.
3.6. Determination of VN in food samples
The electrochemical sensing ability of g-C3N4 NTs@MoS2/GCE was
performed in the presence of 0.05 M PB at 50 mV/s using the DPV
technique. To determine the artificial flavoring content of VN in food
products, we have chosen the vanilla ice cream purchased from the local
supermarket in Kaohsiung, Taiwan, for the quantitative analysis. In
detail, the ice cream sample was dispersed with water and stirred for up
to 30 min to get a clear dispersion, which was filtered and diluted with
0.05 M PB solution. Further, the experiment has conducted in the exis­
tence of a VN-flavored food sample (vanilla ice cream) over g-C3N4
NTs@MoS2/GCE with a standard addition method strategy using the
DPV technique. The observed results show (Fig. 8 e and f) good VN re­
coveries in the ice-cream sample and demonstrate that the quantitative
determination of the proposed electrochemical sensor shows real-time
applicability toward VN detection.
R. Nehru et al.
4. Conclusions
In summary, the g-C3N4 NTs@MoS2 modified electrochemical sensor
was investigated with the existence of VN to determine the food additive
in the PB electrolyte medium at 50 mV/s. The g-C3N4 NTs@MoS2/GCE
significantly boosted the characteristic VN oxidation peak current,
demonstrating excellent conductivity, good electrocatalytic activity,
and a large active surface area of the developed electrochemical sensor.
Under the optimized conditions, the developed g-C3N4 NTs@MoS2
composite-based sensor offers a wide linear ranges (0.005-458.9 µM),
low LOD (4 nM), high sensitivity (3.48 μA μM− 1 cm− 2), and selectivity.
The results suggest that the developed sensor can be a potential candi­
date for VN detection and quantification in commercial food products
due to its low-cost effect. Finally, the proposed sensor was also suc­
cessfully applied for VN determination in commercial food products and
shows a satisfying sensing display, which can be a more attractive
strategy for food additives diagnostic research.
CRediT authorship contribution statement
Raja Nehru: Conceptualization, Methodology, Data curation,
Formal analysis, Investigation, Software, Writing – original draft,
Writing – review & editing. Chiu-Wen Chen: Funding acquisition, Re­
sources, Visualization, Supervision, Project administration. Cheng-Di
Dong: Funding acquisition, Resources, Investigation, Visualization,
Supervision, All authors reviewed the manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially funded by the National Science and
Technology (NSTC) of Taiwan (111-2221-E-992-012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.carbon.2023.03.053.
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