Research Article
ChemistrySelect doi.org/10.1002/slct.202202271
Electrochemical Sensor for the Anti-tuberculosis Drug
Rifampicin on CuO@rGO-Nanocomposite-Modified GCE by
Voltammetry Techniques
Pinky Sagar,[a] Monika Srivastava,[b] and Sanjay K. Srivastava*[a]
Reduced-graphene-oxide layers (rGO) offer extremely subtle
transducer thin-films and can be unified in interdigital micro-
electrodes for various purposes. Understanding the functions
and nature of rGO specially bio-compatibility, we can use this
as potent-tool for the detection of antibiotic-drug Rifampicin
(RFP) in standard/pharmaceutical samples. Herein, we synthe-
size CuO@rGO nano-composite and explored its potency for
the preparation of electrochemically-active-electrodes. Cata-
lytic-activity of as-synthesized CuO@rGO nano-composite is
checked in 1.0 mM of Fe2 + /3 + solutions and found to be more
Introduction
Rifampicin (3-[(4-methyl-1-piperazinyl)imino] methyl rifamycin) is
the first-line considered drug among anti-tuberculosis drugs,
and is used to treat mycobacterium tuberculosis infection (MB-
TBI) often, but can be used to treat human immunodeficiency
virus (HIV) and Hansen disease also.Tuberculosis is known as a
transferrable bacterial infection which may affect numerous
organs of body such as lungs, kidneys or brain. RFP is also used
to treat infection caused by neisseria meningitides. Neisseria is a
bacterium that can cause serious infection in throats or noses
known as meningitis.[1] Prior to encountering bacteria, the
concentration of anti-bacterial infection drug plays a vital
role.[2] The excess dose of RFP is toxic and can lead to various
side effects such as immunological disturbances, allergic rashes,
nausea and hepatotoxicity. Besides, sustained consumption
(60–180 days) of RFP often develops drug resistance, and as
result fosters death despite curable disease. So, an adequate
dose of RFP should be determined and it is highly recom-
mended to trace the level of antibiotic drugs particularly RFP in
biological and pharmaceutical samples.[3]
Graphene is a well-known innovation with unique 2D
carbon structure accompanying large surface specific area,
[a] P. Sagar, Prof. S. K. Srivastava
Department of Physics, Institute of Science,
Banaras Hindu University,
Varanasi 221005, India
Tel.: + 91- 9454233138
E-mail: sanjay_itbhu@bhu.ac.in
[b] Dr. M. Srivastava
School of Materials Science & Technology,
Indian Institute of Technology (BHU),
Varanasi 221005, India
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202202271
ChemistrySelect 2022, 7, e202202271 (1 of 13)
www.chemistryselect.org
than three times higher current as compared to bare, rGO or
CuO modified GCE. Subsequently, modified electrodes are used
to detect RFP via two-techniques (differential-pulse voltamme-
try viz. DPV and cyclic-voltammetry viz. CV) in three-ways
simultaneously. The CuO@rGO-modified-GCE (CuO@rGO/GCE)
exhibits remarkable sensitivity with very low-detection-limit of
5–11 nM and long term-usage, which is far-better than other
reported works. Non-interfering ability in existence of several
body-interferents exposes that CuO@rGO/GCE could be an
effective/ beneficial contrivance for the detection of RFP.
thermal, mechanical and electrical properties and it has been
well-thought-out for several applications like nano-sensors,
hydrogen storage, charge storing devices, nano-electronics
etc.[4] Until today, there have been innumerable ways to
prepare graphene including mechanical exfoliation, chemical
vapour deposition, epitaxial growth, etc.[5] Prior to practical
application, rGO has dragged vast attention and used specially
because of its low cost-large production. rGO is indeed a
graphene like structure with comparatively good conductivity
than graphene oxide (GO). Also, it contains lesser number of
oxygen rich functional groups than that of GO.On the other
hand, presence of hydroxyl, carboxyl and epoxy groups in rGO
shows its stability in the aqueous solutions, which enhances
the electrochemical performance of rGO.[6] Hydrophilicity,
control over the oxygen-rich-functional groups and cost-
effective production of rGO make it demanding material for
various applications. However, pristine rGO does not show
remarkable response in some aspects. Metal organic-framework
(MOF) have grabbed a wide attention of scientific community
nowadays.[7] MOF is the emerging field of organic and inorganic
materials that involve metallic compounds and organic func-
tional substances. Materials based on MOF play significant role
in the electrochemical bio-sensors.[8] Until now, various meth-
ods have been developed and applied to improve the perform-
ance of organic materials; rGO such as rGO/carbon nano tube,[9]
rGO/noble metal particle,[10] rGO/metal oxide,[11] rGO/metal
sulfide,[12] rGO/polymer.[13] Combined effects of metal oxides
and rGO have been proven in many fields, such as bio-sensors,
supercapacitors, field emitters etc. Incorporation of metal
oxides to rGO poses the outstanding properties and results in
some specific aspects. So far, various kind of metal oxides have
been embraced to improve the performance of rGO, for
instance, Fe3O4,[14] Fe2O3,[15] NiO,[16] Cu2O,[17] ZnO,[18] Co3O4,[19]
SnO2[20] and CuO etc.[21]
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ChemistrySelect doi.org/10.1002/slct.202202271
CuO is a p-type semiconductor substance with band gap
1.2 eV along with a high surface specific area, excellent
electrical conductivity, low oxidation potential, adjustable sur-
face morphology, proven electrochemical efficiency.[22] Mean-
while, CuO is an interesting material for the electrochemical
applications because of its high electro catalytic properties, low
cost, and chemical stability. Moreover, it has been observed
that inclusion of second material could enhance the effective
cost, electro-catalytic efficiency, lower the oxidation potential
and would increase the aspect ratio. Therefore, incorporation of
the second phase would significantly increase the electro-
chemical performance of the CuO.[23] Recently, Wang et al.
investigated non-enzymatic glucose detection with CuO/Au
nano-particle.[24] Chen et al. sensed room temperature NO2 via
CuO nanorods functionalised with Au nanoparticles.[25] The
integration of noble metal nano particles significantly improved
the electrochemical properties as well as effective cost. There-
by, it is demand to find a better alternate to include another
phase which is economically affordable and could improve the
performance in the desired aspect. Earlier, the few applications
of rGO/CuO have been documented. In 2014, Wang et al.
reported urchin-like CuO modified by rGO synthesized via
microwave assisted hydrothermal route. The composite was
then used to fabricate humidity sensor and assured the
relatively good performance in terms of response time and
value.[26] Lohar et al. reported electrochemical behaviour of rGO
nano-sheets and CuO nano crystals synthesized via modified
hummers method. rGO/CuO nanopellets then utilised for the
fabrication of flexible supercapacitor, non-enzymatic hydrogen
peroxide and glucose detection.[22] However, the CuO@rGO/
GCE based electrochemical sensor for the detection of anti-
tuberculosis drug RFP is still unexplored.
In this work, we introduced robust and cost effective CuO
nanoparticles supported on reduced graphene oxide layers for
the nano-molar detection of RFP for the very first time. The
incorporation of CuO nanoparticles to rGO layers was inves-
tigated experimentally with the help of various characterisation
tools including X-ray diffraction (XRD) and Raman spectroscopy,
Transmission electron microscopy (TEM), Field emission scan-
ning electron microscope (FESEM) and Electron Dispersive X-
ray diffraction (EDX) mapping. Also, we studied the surface
chemistry of the CuO@rGO via X-ray photo-electron spectro-
scopy (XPS) and Fourier transform infra-red (FT-IR) spectro-
scopy. Electrochemical impedance spectroscopy (EIS) analysis
was carried out to investigate the fundamental nature of
CuO@rGO/GCE for the electrochemical applications, which
unveils that the addition of CuO to the rGO enhances the
conductivity and improves the electron transfer performance of
the CuO@rGO. Also, electrochemical testings (DPV and CV)
revealed that CuO@rGO have remarkable recognition capability
towards RFP in phosphate buffer solution (PBS) at pH = 7.4).
Thereafter, DPV and CV measurements were taken for the
detection of RFP in PBS (pH = 7.4) and a sensing mechanism
waselucidated.
ChemistrySelect 2022, 7, e202202271 (2 of 13)
Results and Discussion
Characterizations of CuO@rGO
To investigate valence states and chemical composition (sur-
face chemistry) of CuO@rGO nano-composites, XPS was used,
as shown in Figure 1. In the core-level XPS profile of CuO@rGO
nano-composites Cu (Copper), C (carbon) and O (Oxygen)
elements are present (Figure 1a). The energy bands at 933.4
and 934.6 eV are attributed to 2p1/2, while energy bands at
953.2 and 954.5 eV are assigned to 2p3/2 for CuO confirming the
presence of Cu2 +. Besides, some other peaks are appeared in
core-level XPS of CuO at 941.1, 942.2, 944.1 and 962.5 eV. These
peaks are assigned to strong satellite signals for CuO for 3d
electronic configuration (Figure 1b).[7a,27] In the core-level of C
1s spectrum (Figure 1c), the peaks appeared at 284.6, 285.0,
285.4, 286.4 and 287.9 eV evident the presence of C O, C C C-
OH, C=O and O C=O groups, respectively.[26,28] This results
unveiled the interaction of carbon-atoms with oxygen-atoms in
form of epoxide (C O), hydroxyl (C OH) and carbonyl (C=O/
O C=O) functional groups. Also, existence of non-oxygen
containing functional group (C C) indicates the graphitic
structure of the rGO. Figure 1d shows the XPS spectrum of O
1s. The energy bands located at 529.8, 530.2, 531.8 and
533.0 eV agree the presence of metallic-O bonds, OH, C O,
and C=O groups, respectively.[7a,22] These peaks resemble the
binding of oxygen atoms via double bond to aromatic carbons
(C=O), single bond to carbon groups (C O), single bond to
metals (metallic-O) and presence of hydroxyl group.
Raman spectroscopy is a pronounced technique to inves-
tigate the structure and defect of the samples. Figure 2
represents the Raman spectra of rGO, CuO and CuO@rGO
nano-composites. Raman spectrum of rGO (Figure 2a) displays
the two prominent peaks at 1347 and 1590 cm 1, which
correspond to defective (D) and graphitic (G) bands of
carbon.[26,27b, 29] It is well known that the D-bands in Raman
spectrum arise due to the breakdown of the translational
symmetry in the graphitic planes. This is known as A1g
symmetry originated from the zonal boundaries of phonons.
Another band identified as G-band is appeared owing to first-
order-scattering. This band signifies the E2g symmetry which is
related to Brillouin zone of sp2 lattices in graphitic planes.[30]
The defect level indicator ratio (ID/IG) of rGO is found to be 1.08,
which shows the large defect density in the rGO sample.
Moreover, Figure 2b shows the Raman spectrum CuO@rGO
nano-composite, where circled region depicts the signal for
inclusion of CuO to rGO layers. The D and G bands
corresponding to rGO in CuO@rGO nano-composite shifted
towards higher wavenumber when compared with Figure 2a
with the difference of ∼ 5 cm 1. Also, the value of ID/IG
decreased to 1.06 attributing to formation of CuO NPs on the
graphitic sites.[29b,31] A zoomed section of Figure 2b is shown in
inset corresponding to CuO, which comprises two peaks
positioned at 289, 614 cm 1conformingthe Ag and 2Bg vibra-
tional modes of CuO.[26] An additional peaks arises at 521 cm 1
due to Si/SiO2 substrate.
The crystal structure of CuO, rGO and CuO@rGO nano-
composites was studied by XRD analysis. The XRD profile of
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ChemistrySelect doi.org/10.1002/slct.202202271

Figure 1. XPS profile of CuO@rGO nano-composites (a) XPS wide, (b) Cu 2p, (c) C 1s and (d) O 1s.

Figure 2. Raman spectra of (a) rGO and (b) CuO@rGO.

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CuO (Figure 3a) shows prominent peaks at 32.46, 35.47, 38.71,
48.73, 53.44, 58.28 and 61.5° corresponding to the lattice
planes (110), (002), (111), (222), (020), (113) and (311),
respectively (JCPDS card no. 05–0667).[22,27b, 29b] All the peaks
resemble the monoclinic phase of CuO. Likewise, rGO shows
the reflection peaks at 28.29 and 40.85° corresponding to (002)
and (100) plane as displayed in (Figure 3b).[26] The observance
of peak at 28.29 confirms the successful formation of rGO from
graphite[32], which resembles the Raman spectroscopy analysis
of rGO. In the XRD profile of CuO@rGO nano-composite, no
obvious change has been observed for CuO and rGO diffraction
peaks. In addition, for CuO, lower intensity in XRD peaks were
observed owing to diminished crystallinity when compared to
Figure 3a. It can be endorsed to the presence of oxygen rich
functional moieties over the graphene layers (as discussed in
XPS analysis) which retards the crystallinity, and diffusion in
CuO nanoparticles.[33]
The morphology of CuO,rGO and CuO@rGO was inves-
tigated by TEM as shown in Figure 4. Figure 4a, b and c show
the TEM image of the CuO, rGO and CuO@rGO, respectively
portraying the nano particle, layered and well-dispersed
Figure 3. XRD profiles of (a) CuO(powder) (b) rGO (deposited on Si/SiO2 substrate), and (c) CuO@rGO composite (deposited on Si/SiO2 substrate).
Scheme 1. Schematic sketch of the electrochemical oxidation of antibiotic Rifampicin drug over CuO@rGO/GCE.
ChemistrySelect 2022, 7, e202202271 (4 of 13)
samples. High resolution TEM (HRTEM) images of the CuO, rGO
and CuO@rGO at 20 nm resolution has been shown in Fig-
ure 4d, e and f, respectively. The interplaner distance of CuO
(0.25 nm)[34] and rGO (0.35 nm)[35] is in good agreement of XRD
and corroborate the (110) and (002) plane, respectively. Further,
Figure 4g, h and I parade the selected area electron diffraction
(SAED) patterns of CuO, rGO and CuO@rGO. The indexing in
SAED ring patterns matched well with XRD data and clearly
indicates the formation of CuO@rGOnano-composite.
Further, EDS has been carried out to analyse the elemental
composition of the CuO@rGO nanoparticles. Figure 5 indicates
the presence of C (wt. 72 %), O (wt. 20.21 %) and Cu (wt. 7.79 %)
elements which can be clearly seen in EDS mapping (Figure S1)
also. FESEM study demonstrates the presence of rectangle and
square shaped CuO nano-particles embed into graphene layers
(Figure 5 inset). It has been found that the CuO dispersed well
and average size found to be 17–50 nm of its crystallites. Also,
image of the CuO@rGO reveal the excellent layer formation in
rGO with CuO nanoparticles. EDS analysis is in good agreement
of the XPS and XRD studies.
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ChemistrySelect doi.org/10.1002/slct.202202271

Figure 4. TEM images of (a) CuO, (b) rGO, (c) CuO@rGO composite, HRTEM images of (d) CuO, (e) rGO, (f) CuO@rGO nano-composite and SAED patterns of (g)
CuO, (h) rGO, (i) CuO@rGO nano-composite.

Table 1. Recovery assessment followed by standard addition procedure.

Amount of RFP from capsule Amount of standard RFP drug spiked Total RFP in sample Total RFP found Percentage %
(μM) (μM) (μM) (μM) recovery RSD
(n = 3)

4 10 9.69 96.96 1.79

5 11 11.32 102.90 0.05
6 7 13 13.21 101.61 0.45
8 14 14.32 102.28 0.04

The vibrational (FT-IR) spectroscopy unveils the interaction
between rGO and CuO as shown in Figure S2. FT-IR spectro-
scopy was performed on all three samples prior to justify the
nano-composite formation. A broad peak is observed in range
of ∼ 459–626 cm 1in CuO which corresponds to Cu O bonds.
Absorption peaks around ∼ 1096 and ∼ 1385 cm 1 are arisen
attributed to C-OH stretching and C O-H bending in rGO.
Addition of CuO to rGO decreased the intensity of C-OH
stretching and C O-H bending in rGO which demonstrates the
successfully attachment CuO at rGO edges. A low intensity
absorption band occurred at ∼ 828 cm 1 due to the presence of
epoxide vibration and –COOH group. Which exists in rGO and

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Figure 5. EDS spectrum and FESEM image (inset) of CuO@rGO composite.

Table 2. Comparison of similar electrochemical RFP sensor.

Electrode Method Linear Range (μM) LOD[a] (μM) Matrix Ref.

C-Dots@Cu2FeO4/CPE SWV 0.07–8.0 0.022 B R Buffer (pH = 7) [41]

MWCNTs-CoTHPP/GC LSV 0.01–5000 0.008 Acetate Buffer (pH = 4.7) [42]
PMel-Aunano/GCE CV 0.08–15.00 0.03 PBS (pH = 7) [1b]
MWCNTs-Mo2C/GCE CV 0.5–74 0.045 PBS (pH = 7) [43]
MWNT/GCE DPV 0.04–10 0.0075 Acetate Buffer (pH = 3.5) [2]
SWV 0.04–10 0.0113
Co en -q/Fe3O4NPs/MWCNTs/GCE CV 2–20 0.032, 0.413 PBS (pH = 7.5) [44]
DPV 0.05–35 0.005 PBS (pH = 7.4) Present
CuO@rGO/GCE CV(Oxi.[b] ) 0.05–35 0.006 Work
CV(Red.[c] ) 0.05–29 0.008
DPV 0.05–25.5 0.006 Pharmaceutical formulation (pH = 7.4) Present
CuO@rGO/GCE CV(Oxi.) 0.05–35 0.007 Work
CV(Red.) 0.05 – 29 0.011

[a] Limit of detection.[b] Oxidation.[c] Reduction.

Scheme 2. Mechanism of action of RFP during electrochemical process.

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Figure 6. (a) CV of (i) bare, (ii) rGO modified, (iii) CuO modified and (iv) CuO@rGO/GCE in 1 mM K3[Fe(CN)6] prepared in 0.1 M KCl solution, (b) DPV of (i) & (ii)
bare GCE in absence and presence of RFP, (iii) & (iv) CuO@rGO/GCE in absence and presence of 15 RFP in 0.1 M PBS (pH = 7.4) (c) CV of (i) & (ii) bare GCE in
absence and presence of RFP, (iii) & (iv) CuO@rGO/GCE in absence and presence of 15 μM RFP in 0.1 M PBS (pH = 7.4) (d) Nyquist plot of (i) & (ii) bare GCE in
absence and presence of RFP, (iii) & (iv) CuO@rGO/GCE in absence and presence of 15 μM RFP in 1 mM K3[Fe(CN)6] in 0.1 M KCl (e) fitted equivalent circuit
diagram for electrochemical impedance spectroscopic measurement.

CuO@rGO nano-composite but absent in CuO. Prominent peaks

located at ∼ 1635 and ∼ 3441 cm 1 are assigned to C=O
stretching vibration of the carboxylic group and OH stretching
vibration, respectively, which is present in all three samples
rGO, CuO and CuO@rGO nano-composite.[22,32b, 36]
Electrochemical characterizations of CuO@rGO
Prior to the detection RFP on the best suitable electrode, the
electrochemical response of the bare GCE with rGO, CuO and
CuO@rGO/GCE nano-composite modified GCE was seen in
1 mM K3[Fe(CN)6] prepared in 0.1 M KCl solution as shown in
Figure 6a. K3[Fe(CN)6] was considered owing to its electron
transfer characteristics. It facilitates non-bonded electron

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Figure 7. (a) CV response, (b) anodic (black line) and cathodic (red line) current vs. square root of scan rate plot for bare GCE, (c) CV response and (d) anodic
(black line) and cathodic (red line) current vs. square root of scan rate plot for CuO@rGO/GCE 0.1 M PBS (pH = 7.4).

Figure 8. (a) DPV response of CuO@rGO/GCE upon addition of various concentration of RFP (b) corresponding calibration plot in 0.1 M PBS (pH = 7.4).

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Figure 9. (a) DPV response of CuO@rGO/GCE upon addition of various concentration of RFP-capsule (b) corresponding calibration plot in 0.1 M PBS (pH = 7.4).
Figure 10. (a) Interference study of CuO@rGO/GCE for the detection of RFP in presence of various biological compound (ratio 1 : 10) and (b) Stability assessment
in presence of RFP in 0.1 M PBS (pH = 7.4).
relocation through the electrode surface to the Fe metal via
hexacyano-ligands. When the redox behaviour was compared
for the bare GCE with rGO, CuO and CuO@rGO nano-composite
modified GCE, the difference of redox potential decreases after
modification of electrode surface due to the diffusion con-
trolled process. This data well corroborated EIS measurement
which will be discussed later. In case of CuO@rGO/GCE, there
was more than 3 times enhancement in current when
compared to bare, rGO and CuO modified GCE. The reason
behind it could be enhanced catalytic turnover of as prepared
nano-composite as a result of the synergistic effect between
CuO and rGO. Next, the voltammetric response of the drug;
RFP was observed opting DPV at fixed 15 μM concentration in
0.1 M PBS (pH = 7.4). It is evident from Figure 6b, the bare GCE
has efficiency to oxidize the RFP at potential 0.433 V, and
CuO@rGO/GCE sense the RFP at lower potential 0.422 V with
much higher current value with prominent peak. This assess-
ChemistrySelect 2022, 7, e202202271 (9 of 13)
ment suggests that CuO@rGO nano-composite has high
electro-catalytic activity, enhanced conductivity, large specific-
surface-area and abundance of nano-scale-level interfacial
bindings, which allows fast electron exchange between GCE
and RFP. Henceforth, to validate, similar experiment was
performed with the help of CV technique under the same
conditions as DPV (cf. Figure 6c). Interestingly, similar results
were obtained as in case of DPV. RFP got oxidise at
considerably lower potential (0.43 V) on CuO@rGO/GCE than on
bare GCE (0.51 V). Also, the electrochemical response of RFP on
CuO@rGO/GCE was optimised at different pH values and found
that pH = 7.4 is best suitable for further electrochemical sensing
studies. These findings compel to investigate comparative
charge transfer behaviour between reference electrode (RE)
and, the vicinity of bare and modified electrodes (usually called
working electrode, WE) by Electrochemical impedance spectro-
scopy (EIS) technique. Impedance of bare and modified electro-
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des were measured within frequency range 10 mHz–10 KHz at
OCP (open circuit potential) along with AC amplitude of 5 mV
at ∼ 27 °C. EIS analysis was opted to explore the interfacial
properties and fundamental behaviour of bare GCE and
CuO@rGO/GCE. Figure 6d shows the Nyquist plot of the bare
and modified GCE without and with15 μM RFP using 1 mM
K3[Fe(CN)6] redox probe. The inset shows the zoomed part of
bare GCE without and with RFP. In general interpretation,
appearance of semicircle linked with straight line along with its
bending towards Z’-axis indicates the impedance to charge-
transfer (between the WE and RE), and diffusion-controlled-
process with mass transfer in the proximity of WE.[37] On the
other hand, in the high frequency range, inclination of straight
line towards Z’’-axis directs about more charge accumulation
on working electrode as compared to its counter ones.[38] From
Figure 6d, curve (i) and (ii) represent bare GCE without and
with RFP, respectively. For Bare GCE (curve i), in lower
frequency range, there is resistance to charge transfer.
However, after addition of drug, charge accumulates on the
electrode surface which signifies pseudo capacitive behavior
(curve ii). Moreover, in the Figure 6d, curve (iii) and curve (iv)
represent EIS plot for CuO@rGO/GCE without and with RFP.
Curve (iii) is more inclined towards Z’’-axis as compared to
curve (i) showing more charge transfer on the electrode surface
and favours diffusion-controlled-dominated phenomenon. For
curve (iv), inclination towards Z’-axis represents the develop-
ment of resistance. This shows that some active sites on the
CuO@rGO/GCE is now covered by analyte moiety. EIS results
were further authenticated by fitting of Nyquist plot using a
simple equivalent circuit, shown in Figure 6e, where Rs
represents solution resistance, Q denotes charge distribution
due to inhomogeneous surface of electrode, R1 was the
resistance created due to inhomogeneous surface and W was
Warburg. Individual fitted EIS spectrum are shown in Figure S3.
However, C and R2 denoted double layer capacitance and
resistance developed on the surface of GCE, respectively.
Detailed information was extracted from the circuit fitting
using ZSimpWin 3.21 software with above mentioned circuit
and shown in Table S1. From the values shown in table, it was
evident that when RFP was added over bare GCE, value of R2
was increased evidencing that some surface was covered by
the drug. Similar increment in R2 was observed when RFP was
added over modified electrode. However, if we compare bare
and modified GCE, we can observe significant increment in Q
value, i. e. charge distribution was more over modified GCE.
Finally, the quality of this fitting was checked by χ2, that was
low enough to rely and confirmed the goodness of fitting.
These results were in good agreement as per previous
explanation of EIS and also with results of CV and specifies that
CuO@rGO modified GCE possess excellent performance and
showed efficient electrical communication at the electrode
surface. Such behaviour was also evidenced later (see Figure 7a
and 7c).
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Effect of Scan Rate
Effect of scan rate on RFP detection was examined over bare
GCE and CuO@rGO/GCE in 0.1 M PBS (pH = 7.4) in the presence
of 15 μM RFP for the potential range 0.1 to 0.9 V. Figure 7
indicates that the CuO@rGO/GCE exhibits the good electro-
catalytic activity and current keep on increasing when CV
measurement were taken at 10–250 mV/s scan rates, however,
there is no noticeable change in the shape of CV (Figure 7a and
c). An apparent variation in current demonstrates appropriate
rate proficiency of CuO@rGO/GCE. Moreover, with the upsurge
of scan rate, the location of oxidation peaks unavoidably moves
towards positive value of x-axis and location of reduction peaks
shifts in the negative direction of x-axis. Further, Figure 7b and
d display the calibration plot for “current” vs. “square root of
scan rate” obtained from Figure 7a and c, respectively. This
analysis evidences that the anodic (black line) and cathodic
peak (red line) currents are directly proportional to the square
root of the scan rate following the Randles Sevcik equation
(eqn. (1)), and confirm the oxidation and reduction of RFP to be
diffusion-controlled-process as already discussed in Fig-
ure 6d.[39]
ip ¼ 2:69 � 105 � n3=2 � A � C � D1=2 � n1=2 (1)
Where, ip ; n; A; C; D and n represent peak current, number
of electrons exchanging, electroactive surface area of the GCE
(cm2), concentration, diffusion coefficient (7.6 × 10 6 cm2 s 1)
and scan rate, respectively.
Further, in order to calculate electrochemical active surface
area (EAS), CV was performed in 1.0 mM K3Fe(CN)6/K4Fe-
(CN)6 (test solution) in 0.1 M KCl, at different sweep rates for
bare GCE and CuO@rGO/GCE.[40] The value of EAS was
calculated by using eqn. (1). The area of the electrode surface
designated as A, was calculated from the slope of the plot of Ip
vs. ν1/2.The calculated value of EAS of the bare GCE and
CuO@rGO/GCE was found to be 0.354 and 0.463 cm2 respec-
tively.
Besides, Figure S4 displays the linear relation between Ea
(peak potential) and logarithm of scan rate. Using Laviron’s
equation (eqn. (2)), number of electron participating in the
redox reaction was analysed as ∼ 2 which is in good agreement
of previously reported data.
0
2:303 RT RTKs
Ea ¼ E0 log þ
ð1 aÞnF ð1 aÞnF
(2)
2:303 RT
logn
ð1 aÞnF
Where, Ea, E0’, R, T represent peak potential, formal
potential, gas constant (8.314 J/mol K) and temperature (K),
respectively. While, Ks, α, n, ν, F indicates standard rate
coefficient, charge transfer coefficient, number of electron
involved in the reaction, scan rate and Faraday constant
(9.6445 × 104 C/mol), respectively.
© 2022 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202202271
Effect of pH
The effect of the pH of the supporting electrolyte on the
potential value and peak current was investigated on CuO@r-
GO/GCE in 0.1 M PBS with different pH values Figure S5a. As
shown in Figure S5b and 7c, the peak current and potential
both rely on pH of the electrolyte, and the value of peak
potential decreased continuously for the pH ranging from 8.0
to 4.0. The linear equation (eqn. (3)) corresponding to peak
potential and pH of electrolyte is articulated as follows:
E ðVÞ ¼ 0:053pH þ 0:82; R2 ¼ 0:99
The slope of the linear equation demonstrates that the
oxidation and reduction reaction of the RFP on CuO@rGO/GCE
is isoelectronic and isoprotonic.[41] Also, the peak current was
observed maximum for pH = 7.4 as shown in Figure S5c.
Therefore, all the sensing measurement were performed for
pH = 7.4 of the PBS.
Sensing of Rifampicin
The DPV and CV responses (both oxidation and reduction)
were tested via CuO@rGO/GCE with different concentrations of
RFP varying from 0.05 to 44 μM for potential window 0.3 to
0.7 V as shown in Figure 8 and Figure S6 for standard drug. It
has been observed that upon increasing the concentration of
RFP (from 0.05 to ∼ 35 μM), the anodic peak current enhanced
(Figure 8a). After addition of ∼ 35 μM of RFP the anodic peak
current started bending slowly towards the potential axis which
can be attributed to the less availability of active sites for
charge transfer (Figure 8b). The addition of the high concen-
tration of the RFP showed a visible impact on the DPV signals
as shown in Figure 8a and b. A schematic illustration of
electrochemical oxidation of RFP over CuO@rGO/GCE is shown
in Scheme 1. The analysis revealed that as modified GCE
exhibits remarkable sensitivity of 1.42 μA μM 1cm 2 along with
regression coefficient R2 = 0.99. Additionally, the limit of
detection (LOD) and Limit of quantification (LOQ) are found to
be 5.82 nM and 50 nM, respectively. Here, the LOD has been
calculated by opting back-extrapolation of the linear fit line.
Interestingly, we got results in similar order through CV
technique as shown in Figure S 6a, and its both calibration plot
(Figure S 6b for oxidation current and S 6c for reduction
current).Similarly, linear range LOD and sensitivity were found
to be 0.05–35 μM, 6.23 nM and 1.00 μA μM 1cm 2 for oxidation,
and 0.05–29 μM, 8.45 nM and 1.42 μA μM 1cm 2 for reduction
reaction, respectively
Sensing of Rifampicin in Pharmaceutical Formulations
RFP is a potent drug used for the treatment of mycobacterium
tuberculosis infection; therefore, its sensing strategy was also
validated in its pharmaceutical formulations. Thus, electro-
chemical detection of RFP was analysed in pharmaceutical
dosage form with the help of DPV. The Figure 9a clearly
showed the change in anodic peak current upon addition of
ChemistrySelect 2022, 7, e202202271 (11 of 13)
various concentrations of the RFP over the CuO@rGO/GCE
under the similar conditions as previously discussed. As shown
in Figure 9a, the anodic peak current increased for concen-
tration range from 0.05 to 25.5 μM while after 25.5 μM the
increment in peak current is comparatively slower. It might be
due to the reaching of saturation level at the surface of
working electrode. Figure 9b showed the good linearity in the
calibration plot with regression coefficient R2 = 0.99. The
sensitivity, LOD and LOQ were found to be 1.86 μA μM 1cm 2,
6.19 nM and 50 nM, respectively. Further to validate the experi-
ment, we have tested with CV technique and found similar
(3) results when compared to DPV analysis for standard drug
(Figure S7). Hence calculated various parameters via CV
techniques were examined and, linear range, LOD and
sensitivity were calculated as 0.05 to 35 μM, 7.51 nM,
1.14 μA μM 1cm 2 for oxidation and 0.05 to 29 μM, 11.8 nM,
1.28 μA μM 1cm 2 for reduction reaction current, respectively.
Selectivity, Interference and Stability
To test the selectivity of the CuO@rGO/GCE sensor for RFP
detection (15 μM), effect of various interferents that may co-
occur in human body, namely D-glucose, ascorbic acid (AA),
NaCl, creatinine, uric acid (UA), urea, H2O2, glycine and L-
cysteine was examined. The relative changes in anodic peak
currents of RFP oxidation in the suspension of interferents
(concentration 150 μM) were observed and displayed in terms
of percentage as shown in Figure 10a. All the experiments
related to selectivity study were performed in 0.1 M PBS (pH =
7.4) by opting DPV technique. From the observed voltammo-
gram, there was no additional peak for the various interferents
added were found, that can be evidenced from literature. It
was because oxidation potentials of such interferents were not
at the same or nearby potential value as for RFP oxidation. Also
peak current for RFP oxidation was not changed or shifted
much with the addition of such higher concentration of
interferents. At the time of selectivity analysis, the concen-
tration of all the interferents was kept 10 times higher than the
RFP concentration. From Figure 10a, it is evident that CuO@r-
GO/GCE has negligible interference with the RFP, proving
remarkable selectivity of CuO@rGO/GCE for RFP sensor because
proposed sensor was not detecting these interferents at the
oxidation potential of RFP drug during sensing. Henceforth, we
can conclude that the as anticipated electrochemical tracing of
RFP can be employed in biological samples as well.
Prior to investigate the stability of the as suggested
CuO@rGO/GCE towards RFP sensor, the electrode was tested
for one month via DPV technique. Modified electrode were
tested at the interval of 4 days with keeping rest conditions
same and found no leaching from the electrode surface or
potential shift or current change during these repetitions.
Notably, the electrode was found in good condition even after
one month of storage under no special conditions. There was
only 3 % attenuation in the current as shown in the Figure10b.
Therefore, it is evident that the CuO@rGO/GCE can be used for
32 days without any extra ordinary treatment.
© 2022 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202202271
Recovery Study
Lastly, it is highly important to assess the authenticity of the as
proposed RFP sensor in real samples. Purposely, 4 different
amounts of standard RFP were considered and added to the as
prepared solution of commercially available RFP. In the process,
we have opted DPV and collected the data 3 times for each
concentration under pre discussed conditions. The total RFP
content was examined with the help of calibration plot. The
added and found amount of RFP is displayed in Table 1. For all
four concentrations, proposed RFP sensor showed remarkable
recovery approximately 96–102 % and less than 2 % of RSD,
which proves that the CuO@rGO/GCE sensor can be conven-
iently an alternative option for the tracing of RFP in
pharmaceutical formulations.
Fascinatingly, we found our results better and comparable
to other documented electrochemical based RFP sensors as
tabulated in Table 2.
Mechanism
The EAS of the bare and CuO@rGO/GCE (0.354 and 0.463 cm2,
respectively) evidenced that, enlarged electroactive and ad-
sorptive sites rich surface area facilitates the fast electron
transfer which results as substantial increase in anodic as well
as cathodic peak current.[41] Scheme 2 was proposed based on
the DPV as well as CV measurements. Oxidation of RFP was
observed in Figure 8a and b and Figure S 6a and b representing
that Hydroquinone moiety present in RFP was oxidised to its
Quinone form by losing two electrons[1d] and Figure 6a and c
supported reduction process of RFP Quinone to its original
structure (see, Scheme 2). Besides, in Scheme 2, circled part
display the detailed oxidation/reduction sites in the RFP which
takes part during the electrochemical reaction.
Conclusion
An electrochemical biosensor primarily based on oxidation of
RFP over CuO@rGO/GCE was successfully investigated. Our
proposed biosensor showed remarkably good response for the
oxidation as well as reduction of RFP on the surface of
CuO@rGO/GCE when compared to bare GCE via facilitating fast
electron transfer. The as suggested biosensor indicated very
good linear response at lower concentration of the RFP with
efficiently low detection of limit. Here, for the sensing of RFP
over CuO@rGO/GCE, we have chosen two techniques (DPV and
CV) and analysed the results in three ways simultaneously. A
possible reaction mechanism for the RFP oxidation/ reduction
is proposed and facilitated by diffusion dominated process and
is evidenced by electrochemical impedance spectroscopy. The
effect of pH was optimized, which demonstrates the isoelec-
tronic and isoprotonic redox reaction of RFP over CuO@rGO/
GCE along with transfer of ∼ 2 electrons. During the sensing
procedure, the oxidation of RFP to RFP Quinone takes place at
0.43 V with three-fold anodic peak current response in DPV,
when compared to bare GCE. This strong oxidation happens
ChemistrySelect 2022, 7, e202202271 (12 of 13)
probably due to high electroactive surface area of CuO@rGO/
GCE in comparison of bare GCE, 0.354 and 0.463 cm2,
respectively. Notably, it behaves as promising electrode for
electrochemical sensing. Various parameters including LOD,
sensitivity and LOQ related to sensing have been analysed as
5.82 nM, 1.42 μA C 1cm 2, 50 nM and 6.1 nM, 1.86 μA μM 1cm 2,
50 nM for standard and pharmaceutical drug, respectively, via
DPV. The assessment then validated by CV technique and so
parameters (LOD, sensitivity and LOQ) are calculated as
6.23 nM, 1.00 μA C 1cm 2, 50 nM and 7.51 nM,
1 2
1.14 μA μM cm , 50 nM for standard and pharmaceutical
drug, respectively. Noteworthy, the as proposed RFP sensor
also showed reduction of the drug and all the related factors
including LOD, sensitivity and LOQ are assessed as 8.45 nM,
1.42 μA C 1cm 2, 50 nM and 11.8 nM, 1.28 μA μM 1cm 2, 50 nM
intended for standard and pharmaceutical drug, respectively.
The proposed RFP sensor showed astonishing response in real
samples when standard drug spiked with ∼ 97–103 % recovery.
Moreover, effect of various interferents was analysed and found
very good response of RFP even in presence of 10 fold higher
concentrations of many biological compounds. Also, the as
proposed sensor showed remarkably good response even after
∼ one month of fabrication. Therefore, present analysis mani-
fest that the sensor can be practically used for the detection of
RFP in biological and pharmaceutical samples.
Supporting Information Summary
The supplementary information comprises of experimental
section which includes details of reagents and chemicals,
instruments, synthesis of rGO, synthesis of CuO@rGO nano-
composite, modification of electrode and preparation of real
sample. Apart from it, supplementary information contains
graphics of EDS mapping analysis, FT-IR spectroscopy, EIS fitted
plots, Laviron’s plot, CV analysis, effect of pH.
Acknowledgements
S. K. S. acknowledges IoE Scheme for faculty (research grant)
under Development Scheme No.: 6031 for providing financial
support. Pinky Sagar is thankful to DST, New Delhi for providing
INSPIRE Fellowship (DST/INSPIRE/03/2018/000041). Dr. Monika
Srivastava acknowledges DST, New Delhi (SR/WOS-A/CS-52/2018)
for WOS fellowship. Authors convey their thanks to CIF IIT-BHU,
and SATHI-BHU for providing various characterisation facilities.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
© 2022 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202202271
Keywords: Conducting Materials · CuO@rGO Composite ·
Cyclic Voltammetry · Differential Pulse Voltammetry ·
Electrochemical sensor · Rifampicin
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Submitted: June 13, 2022
Accepted: August 4, 2022
© 2022 Wiley-VCH GmbH