nanomaterials

Article
Electrodeposition of Silver Nanoparticles on Indium-Doped Tin
Oxide Using Hydrogel Electrolyte for Hydrogen
Peroxide Sensing
Jihyeon Kim 1 , Byung-Kwon Kim 2, * and Kyungsoon Park 1, *

1 Department of Chemistry and Cosmetics, Jeju National University, Jeju 690-756, Republic of Korea
2 Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 03760, Republic of Korea
* Correspondence: [email protected] (B.-K.K.); [email protected] (K.P.); Tel.: +82-2-3277-6578 (B.-K.K.);
+82-64-754-3545 (K.P.); Fax: +82-2-3277-2385 (B.-K.K.); +82-64-756-3561 (K.P.)

Abstract: Nanoparticles are used in various fields, including fuel cells, energy conversion devices,
and sensors, because of their large surface area and excellent catalytic properties. Although various
methods of synthesizing nanoparticles are available, the most popular is the solution-phase reduction
of metal ions. Electrodeposition is a method of reducing metal ions in solution and is widely used
because of its various advantages. In this study, Ag nanoparticles with a narrow size distribution were
evenly dispersed on the surface of an electrode by applying electrodeposition in an agarose hydrogel
medium instead of in solution, confirming the feasibility of Ag deposition in agarose hydrogel, even
at a lower reduction potential than that in solution. These results are attributed to the electrolyte
effect owing to the hydrophilic backbone of the agarose hydrogel and the gel effect, which reduces
unexpected convection. H2 O2 was detected by using the Ag nanoparticles synthesized in agarose
hydrogel, and the limit of detection for H2 O2 was found to be 4.82 µM, with a dynamic range of
1–500 µM. The nanoparticle synthesis platform proposed in this study is expected to be actively used
for the synthesis of other metal/nonmetal nanoparticles.

Keywords: silver nanoparticle; electrodeposition; hydrogel; electrochemical H2 O2 sensing

Citation: Kim, J.; Kim, B.-K.; Park, K.

Electrodeposition of Silver
1. Introduction
Nanoparticles on Indium-Doped Tin
Oxide Using Hydrogel Electrolyte for Nanostructured metals deposited on diverse substrates have played a pivotal role
Hydrogen Peroxide Sensing. in the development of technological applications, including microelectronics [1,2], sens-
Nanomaterials 2023, 13, 48. https:// ing [3,4], electroplating [5], energy storage [6,7], and the enhancement of Raman scat-
doi.org/10.3390/nano13010048 tering [8] and electrocatalysis [9,10]. Metal nanoparticles have a high surface-to-volume
ratio, with the capability to interact with target molecules, good electrical and catalytic
Academic Editor: Rosario Pereiro
properties, and a large number of active sites [11]. The properties of metal nanoparticles
Received: 16 November 2022 differ from those of the corresponding bulk materials. Among the various strategies for
Revised: 13 December 2022 fabricating nanocomposites, electrochemical deposition is a practical alternative to gaseous
Accepted: 20 December 2022 phase deposition under vacuum, such as vapor deposition, sputtering, chemical vapor
Published: 22 December 2022 deposition [12,13], and in the solution phase, such as printing and dip-coating [14,15].
Electrochemical techniques can be used as not only facile methods for fabricating metal
nanoparticles, but also versatile analytical tools for manipulating the electrochemical behav-
Copyright: © 2022 by the authors.
ior. The potential applied to the working electrode and the duration can affect important
Licensee MDPI, Basel, Switzerland.
properties of nanoparticles, such as the size, density, morphology, and electrocatalytic
This article is an open access article
effects [16].
distributed under the terms and Aqueous electrolytes are typically used in conventional electrodeposition processes;
conditions of the Creative Commons however, they have some limitations, including gas evolution, the need for complexing
Attribution (CC BY) license (https:// agents, water pollution in industrial use, and irregular deposition caused by natural
creativecommons.org/licenses/by/ convection for long-term electrolysis [17,18]. To overcome the limitations of aqueous
4.0/). solvents, several alternative media, such as organic solvents or ionic liquids, have been

Nanomaterials 2023, 13, 48. https://doi.org/10.3390/nano13010048 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2023, 13, 48 2 of 14

used, but the toxicity, volatility, and poor solubility of simple metal salts are the major
barriers to their application [19–22].
A hydrogel is a three-dimensional (3D) network comprising a hydrophilic func-
tional group of polymer chains, which can imbibe a large amount of water without
dissolving [23,24]. The unique structures and properties of hydrogels provide useful ap-
plications in many research areas, including tissue engineering [25], drug delivery [26,27],
biosensors [28], and energy storage and conversion fields [29]. Agarose is a widely used
material among various types of hydrogels because it is inexpensive, non-toxic, and easy
to synthesize and has high structural flexibility. Agarose is a linear polysaccharide con-
sisting of 1,3-linked β-D-galactopyranose and 1,4-linked 3,4-anhydro-α-L-galactopyranose
repeating units [30]. Recently, Hwang et al. used a hydrogel pen (HYPER) for the electrode-
position of platinum between pyramid-shaped agarose and a gold substrate by controlling
the contact area [31]. We also reported the mass transport properties of solutes on the
agarose interface, which precluded the effect of natural convection on the long-term elec-
trochemistry [32].
The selective, rapid, and quantitative determination of hydrogen peroxide (H2 O2 )
has attracted considerable attention because of the essential role of this compound in
the food [33], pharmaceutical [34], clinical [35], cosmetic [36], and biochemical indus-
tries [37]. Various analytical methods have been employed to trace H2 O2 , including
chromatography [38], fluorescence [39], chemiluminescence [40], and electrochemical meth-
ods [41,42]. Among these techniques, electrochemical analysis is the most suitable owing
to its speed, low detection limit, simple instrumentation, and real-time measurement capa-
bilities. Electrochemical detection of H2 O2 is commonly based on the use of enzymes as
signal transducers [43]. Although enzyme-based sensors have an ultra-low detection limit
for analytes, their application to H2 O2 is limited because of their inherent poor stability,
which causes denaturation. Moreover, the catalytic activity and selectivity for H2 O2 are
significantly reduced by other interfering substances with similar detection potentials, such
as dopamine, uric acid, catecholamine, and ascorbic acid. Because of these disadvantages
of enzyme-based electrochemical sensing for H2 O2 , metal nanoparticles are prospectively
good alternatives for replacing enzyme transducers owing to their outstanding conductivity,
long-term stability, and excellent electrocatalytic activity [41,44].
Herein, we report a simple method for the electrodeposition of Ag nanoparticles on
indium tin oxide (ITO) by using agarose hydrogel media. Agarose-based Ag deposition
exhibits numerous desirable characteristics, such as well-dispersed and uniform particles
and adjustable properties, compared with the conventional solution-phase process. Elec-
trodeposition is a versatile method of controlling the shape and size of metal nanoparticles
on a conducting surface by adjusting the preparation conditions [45,46]. Therefore, the size
of the Ag nanoparticles can be controlled by adjusting the deposition time without any
interference (i.e., natural convection), as confirmed by performing field-emission scanning
electron microscopy (FE-SEM) analysis of the particle morphology. Metal nanoparticles are
considered the most promising alternatives to enzymes for electrochemical detection [47].
In this study, the electrocatalytic activity of Ag nanoparticles for H2 O2 sensing is evaluated
using an electrochemical method. Many methods of fabricating metal nanoparticles in bulk
solutions are known and widely used; however, hydrogel-based methods of synthesizing
nanocomposites have rarely been studied. Therefore, our approach is expected to be a good
candidate for the synthesis of various types of metal nanoparticles. The electrochemical
setup for Ag deposition and H2 O2 sensing using agarose hydrogel are depicted in Scheme 1.
 Nanomaterials
Nanomaterials 13,13,
2023,
2023, 48 PEER REVIEW
x FOR 3 of3 14
of 13

Scheme 1. Schematic of cell configuration for the electrodeposition of Ag nanoparticles on ITO and
Scheme 1. Schematic of cell configuration for the electrodeposition of Ag nanoparticles on ITO and
H2O2 sensing.
H2 O2 sensing.

2.2.Experimental
Experimental
2.1.Materials
2.1. Materials
Agarose (Low
Agarose (Low EEO),
EEO), silver
silver nitrate
nitrate(AgNO
(AgNO 3 , 3,97%),
97%),potassium
potassium perchlorate (KClO
perchlorate (KClO
4, 4,
99.9%), and nitric acid (HNO 3 , ~70%) were obtained from Sigma-Aldrich
99.9%), and nitric acid (HNO3, ~70%) were obtained from Sigma-Aldrich (St. Louis, MO,(St. Louis, MO,
USA). Perchloric acid (HClO , 70%) and hydrogen peroxide (H2 O2 , 30%) were purchased
USA). Perchloric acid (HClO44, 70%) and hydrogen peroxide (H 2O2, 30%) were purchased
from Acros Organic and Fisher Chemical, respectively. Silver was electrodeposited on
from Acros Organic and Fisher Chemical, respectively. Silver was electrodeposited on in-
indium tin oxide (ITO)-coated glass (Omniscience, Yongin-si, Republic of Korea, 10 Ω cm−2 −2
dium tin oxide (ITO)-coated glass (Omniscience, Yongin-si, Republic of
sheet resistance). The ITO was cleaned with acetone and isopropanol in an ultrasonic
Korea, 10  cm
sheet
bathresistance). Thedried
for 5 min and ITO was
undercleaned with acetone
a N2 stream. and isopropanol
All chemicals in an used
and reagents ultrasonic
in thisbath
for 5 min and dried under a N stream. All chemicals and reagents used
work were of reagent grade. Water (>18 MΩ·cm) was obtained from a Millipore Milli-Q
2 in this work were
ofpurification
reagent grade. Water
system. (>18 MΩ·cm) was obtained from a Millipore Milli-Q purification
system.
2.2. Preparation of Agarose Hydrogel for Electrochemical Measurement
2.2. Preparation of Agarose
The agarose solutionsHydrogel
(3.2 wt%)for Electrochemical
were prepared in aMeasurement
microwavable cylindrical container
equipped with a sealing
The agarose cap.
solutions The
(3.2 solution
wt%) wereinprepared
the container
in awas heated under
microwavable microwavecon-
cylindrical
(700 W power) until the agarose was completely dissolved. The dissolved solution was
tainer equipped with a sealing cap. The solution in the container was heated under micro-
placed in a vacuum desiccator to remove air bubbles that disrupted the gel. The prepared
wave (700 W power) until the agarose was completely dissolved. The dissolved solution
agarose solution (viscous and transparent) was poured into a glass mold and cooled
was placed in a vacuum desiccator to remove air bubbles that disrupted the gel. The pre-
slowly in a humidity-controlled chamber. The solidified agarose was cut into the desired
pared
sizes,agarose solution
carefully (viscous
separated andglass
from the transparent)
mold, andwas poured
stored into a glass
in distilled mold
water. and cooled
Before the
slowly in a humidity-controlled
electrochemical measurements, the chamber.
agarose The
gels solidified agarose
were immersed was
in an cut into
aqueous the desired
solution of
sizes,
redox molecules and a supporting electrolyte for 12 h to achieve complete equilibrium. For the
carefully separated from the glass mold, and stored in distilled water. Before
electrochemical measurements,
the electrochemical measurements, theaagarose gels were
redox material immersed
containing in an
agarose aqueous
gel solution
was installed in of
redox molecules
a homemade cell.and a supporting electrolyte for 12 h to achieve complete equilibrium.
For the electrochemical measurements, a redox material containing agarose gel was in-
2.3. Electrochemical
stalled in a homemade and FE-SEM
cell. Measurement
Electrochemical measurements were performed in a conventional three-electrode
cell using a CHI 601e
2.3. Electrochemical andpotentiostat (CH Instruments, Austin, TX, USA). Indium tin oxide
FE-SEM Measurement
(ITO; 2.5 × 2.5 cm) was used as the working electrode, and a Pt wire and Ag/AgCl wire
Electrochemical measurements were performed in a conventional three-electrode cell
were used as the counter electrode and quasi-reference electrode, respectively, and were
using a CHI inside
positioned 601e potentiostat
the agarose (CHgel. AInstruments,
homemade Austin, TX, USA).
cell equipped with Indium tinpress
a vertical oxide (ITO;
was
2.5 × 2.5 cm) was used as the working electrode, and a Pt wire and Ag/AgCl
used to ensure conformal contact between the agarose hydrogel and ITO electrode. The wire were
used as the
surface counter electrode
morphology and quasi-reference
of the electrodeposited Ag on ITO electrode, respectively,
was characterized and FE-SEM
by using were posi-
tioned insideMIRA
(TESCAN, the agarose gel.WD
III, 15 kV, A homemade cell equipped
= 9.9~10.3 mm) which waswith a vertical
equipped withpress wasfor
detector used
toimaging
ensure conformal
of secondarycontact between
electron. the agarose
Additionally, thehydrogel
chemical and ITO electrode.
composition The surface
were analyzed
by the FE-SEM
morphology of equipped with energy dispersive
the electrodeposited Ag on ITO spectrometry (EDS, Oxford
was characterized by Instruments,
using FE-SEM
Oxford, UK).
(TESCAN, MIRA III, 15 kV, WD = 9.9~10.3 mm) which was equipped with detector for
imaging of secondary electron. Additionally, the chemical composition were analyzed by
the FE-SEM equipped with energy dispersive spectrometry (EDS, Oxford Instruments,
Oxford, UK).
 Nanomaterials 2023, 13, x FOR PEER REVIEW 4 of 13
Nanomaterials 2023, 13, 48 4 of 14

2.4. Electrodeposition of Ag on ITO and Electrochemical H2O2 Reduction

2.4. Electrodeposition of Ag on ITO and Electrochemical H2 O2 Reduction
The electrochemical deposition of Ag on ITO is potentiostatically similar to that in
The electrochemical deposition of Ag on ITO is potentiostatically similar to that in
the aforementioned cell configuration. Agarose gel was immersed in a mixture of 1 mM
the aforementioned cell configuration. Agarose gel was immersed in a mixture of 1 mM
AgNO,3, 55 mM
AgNO mM KClO
KClO4,, and 1 mM HClO4 as a soaking solution which was adjusted to pH
3 4 and 1 mM HClO4 as a soaking solution which was adjusted to
pH 4 (see Figure S1 in the SupplementaryMaterials).
4 (see Figure S1 in the Supplementary Materials).Cyclic
Cyclicvoltammetry
voltammetry (CV)
(CV) scans were
scans were
recorded in the range of 0.4 to −0.5 V at a scan rate of 50 mV/s. Chronoamperometry
recorded in the range of 0.4 to −0.5 V at a scan rate of 50 mV/s. Chronoamperometry (CA)
for Ag deposition was performed by applying −0.35 V (vs. Ag/AgCl
(CA) for Ag deposition was performed by applying −0.35 V (vs. Ag/AgCl quasi-referencequasi-reference elec-
trode (QRE)) to the ITO working electrode in contact with the agarose hydrogel.
electrode (QRE)) to the ITO working electrode in contact with the agarose hydrogel. To To ensure
a conformal
ensure contact,contact,
a conformal constantconstant
pressurepressure
was applied betweenbetween
was applied agarose hydrogel and ITO
agarose hydrogel
by home-made press machine. The electrocatalytic effect of Ag
and ITO by home-made press machine. The electrocatalytic effect of Ag on ITO (Ag on ITO (Ag deposition
time: 10 s, time:
deposition Figure10S2) for H2OS2)
s, Figure 2 detection was determined by performing CV and chrono-
for H2 O2 detection was determined by performing CV
coulometry (CC) in an electrochemical
and chronocoulometry (CC) in an electrochemical buffer (EB; 0.1 M(EB;
buffer phosphate buffer and
0.1 M phosphate 700 mM
buffer and
NaCl; pH 7.4) with different concentrations of
700 mM NaCl; pH 7.4) with different concentrations of H O .H 2O2.
2 2

3.3.Results
Resultsand
andDiscussion
Discussion
Thescanning
The scanningelectron
electron microscopy
microscopy (SEM)
(SEM) images
images showshow
the the morphology
morphology of bare
of the the bare
ITO
ITO electrode before and after three CV cycles. The bare ITO electrode showed
electrode before and after three CV cycles. The bare ITO electrode showed densely attached densely
attached
grains grains
with with crystalline
crystalline particles particles of approximately
of approximately 30 nm in 30 diameter
nm in diameter
(Figure(Figure 1b).
1b). This
This structure
structure imparted
imparted highlyhighly conductive
conductive properties
properties to thetoITO
the surface.
ITO surface. Figure
Figure 1c shows
1c shows the
the SEM
SEM micrograph
micrograph afterafter
threethree CV cycles,
CV cycles, in which
in which the the
ITOITO surface
surface remained
remained stable
stable with-
without
outdamage
any any damage caused
caused by ITOby reduction
ITO reduction or oxygen
or oxygen evolution.
evolution.

Figure 1. Three cycles of CVs for bare ITO electrode (a) in a solution of 1 mM HClO4 and 5 mM
Figure 1. Three cycles of CVs for bare ITO electrode (a) in a solution of 1 mM HClO4 and 5 mM
KClO4 (scan rate, v = 100 mV/s). SEM image of bare ITO (b) before and (c) after three cycles of CV.
KClO4 (scan rate, v = 100 mV/s). SEM image of bare ITO (b) before and (c) after three cycles of CV.
 light (90% transmittance), it is known that electrochemically reduced ITO electrodes turn
dark brown in color and are less conductive [48,49]. To prevent this reduction, the ITO
electrode was evaluated by employing CV to check its stability within the potential win-
dows for the electrodeposition of silver. Figure 1a shows that ITO was stable in the sup-
Nanomaterials 2023, 13, 48 porting electrolyte over the potential range of +1.3 V to −0.7 V. ITO was reduced at5 aofpo- 14
tential more negative than −0.7 V, and oxygen evolution was initiated at a potential more
positive than +1.3 V.
The electrochemical process of silver deposition on the ITO substrate was studied
ITO was used as the working electrode for the electrodeposition of Ag nanoparticles.
using CV in solution and agarose hydrogel (Figure 2). In the solution (Figure 2a), two
Although ITO has low electrical resistivity (~10−4 Ω·cm) with high transparency to UV-vis
distinct peaks related to the reduction of silver ions and the oxidation of silver previously
light (>90% transmittance), it is known that electrochemically reduced ITO electrodes
deposited on the ITO surface are observed. The sharp increase in the cathodic current at
turn dark brown in color and are less conductive [48,49]. To prevent this reduction, the
−0.2 V is an indication of an increase in silver nucleation and particle growth, reaching the
ITO electrode was evaluated by employing2 CV to check its stability within the potential
cathodic peak current (Ipc) of −176 mA/cm at −0.376 V. The reaction related to the peak
windows for the electrodeposition of silver. Figure 1a shows that ITO was stable in the
current (Ipc) is indicated by Equation (1):
supporting electrolyte over the potential range of +1.3 V to −0.7 V. ITO was reduced at
a potential more negative than −0.7 V, Ag and e− → evolution
+ +oxygen Ag was initiated at a potential (1)
more positive than +1.3 V.
Theelectrochemical
The deposition potential between
process metal
of silver ions andonthe
deposition theforeign substratewas
ITO substrate is generally
studied
higher than that between the same metal particles due to crystallographic
using CV in solution and agarose hydrogel (Figure 2). In the solution (Figure 2a), two substrate-metal
misfit, peaks
distinct exceptrelated
in the case
to theofreduction
underpotential deposition
of silver [17].
ions and the Therefore,
oxidation the deposition
of silver previously of
Ag + on the ITO electrode was more negative than the formal potential of Ag+/Ag. How-
deposited on the ITO surface are observed. The sharp increase in the cathodic current at
−ever,
0.2 Vduring the positive
is an indication scan,
of an the oxidation
increase of silver began
in silver nucleation from the
and particle same silver
growth, reachingsurface
the
that had already been deposited onto the ITO
2 surface. Owing to the difference
cathodic peak current (Ipc ) of −176 mA/cm at −0.376 V. The reaction related to the peak in the dep-
osition(Iand
current stripping potentials, a crossover between the cathodic and anodic current
pc ) is indicated by Equation (1):
traces occurred. Therefore, crossover is another method of forming metal nuclei on the
electrode [50]. Ag+ + e− → Ag (1)

Figure2.2.CVs
Figure CVsofofsilver
silverredox
redoxprocess
processon
onITO
ITOelectrode
electrode(a)
(a)ininsolution
solutionand
and(b)
(b)ininagarose
agarosehydrogel,
hydrogel,
both containing 2 mM AgNO 3, 1 mM HClO4, and 5 mM KClO4. The dotted line represents the back-
both containing 2 mM AgNO3 , 1 mM HClO4 , and 5 mM KClO4 . The dotted line represents the
ground signal without AgNO3. Scan rate: 50 mV/s.
background signal without AgNO3 . Scan rate: 50 mV/s.

The deposition potential between metal ions and the foreign substrate is generally
higher than that between the same metal particles due to crystallographic substrate-metal
misfit, except in the case of underpotential deposition [17]. Therefore, the deposition of Ag+
on the ITO electrode was more negative than the formal potential of Ag+ /Ag. However,
during the positive scan, the oxidation of silver began from the same silver surface that had
already been deposited onto the ITO surface. Owing to the difference in the deposition and
stripping potentials, a crossover between the cathodic and anodic current traces occurred.
Therefore, crossover is another method of forming metal nuclei on the electrode [50].
Nanomaterials 2023,
Nanomaterials 13,13,
2023, 48x FOR PEER REVIEW 6 6of
of 13
14

Figure
Figure2b 2bshows
showsthe thecyclic
cyclicvoltammogram
voltammogram for for the
the electrochemical
electrochemical deposition
deposition of of Ag
Ag
ononthetheITO
ITOsubstrate
substrateininthetheagarose
agarosehydrogel.
hydrogel. From
From thethe electrochemical
electrochemical analysis,
analysis, itit was
was
confirmed
confirmedthat thatthe
theagarose
agarosehydrogel
hydrogelwaswasnot
notadsorbed
adsorbed on on the
the surface
surface ofof the
the synthesized
synthesized
Ag nanoparticles. (see Figure S3 in the Supplementary Materials).
Ag nanoparticles. (see Figure S3 in the Supplementary Materials). The CV The CV profile
profile was
was
similar to that in solution, but presented different onset potentials for silver
similar to that in solution, but presented different onset potentials for silver deposition. deposition.
The
Thedecrease
decreaseininboth
boththe
thecathodic
cathodicandandanodic
anodicoverpotentials
overpotentials compared
compared to to those
those inin solution
solution
suggests
suggeststhatthatsilver
silver deposition
deposition in in agarose
agaroseisismore
morefavorable
favorable than
than in in solution,
solution, which
which is
is as-
assumed
sumed to to be
be due
due toto the
the higher
higher interaction
interaction and
and stabilization
stabilization between
between charged
charged silver
silver ions
ions
and
andthethehydrophilic
hydrophilicmoieties
moietiesofofthetheagarose
agarosepolymer
polymerbackbone.
backbone.
ToToconfirm
confirm the mass transport properties of silver ions
the mass transport properties of silver ions in
in the
the agarose media, the
agarose media, the CV
CV
ofofthe silver deposition process was measured by varying the scan
the silver deposition process was measured by varying the scan rate in the agarose rate in the agarose
hydrogel.
hydrogel.As Asshown
shownininFigure
Figure3a,3a,the
thecathodic
cathodic and
and anodic
anodic currents
currents both
both increased
increased as as the
the
scan rate increased from 5 to 100
scan rate increased from 5 to 100 mV/s. mV/s.

Figure3.3.(a)
(a)CVs
CVsofofITO
ITOelectrode
electrodeininagarose
agarosehydrogel
hydrogelcontaining
containing22mM
mMAgNO
AgNO3,, 11 mM
mM HClO
HClO4,, and
Figure 3 4 and
5 mM KClO4 depending on scan rate. (b) Plots of cathodic peak current (Ipc) vs. square root of the
5 mM KClO4 depending on scan rate. (b) Plots of cathodic peak current (Ipc ) vs. square root of the
scan rate (v) and (c) dependence of peak potential, Epc, vs. log v in 4.8 wt% of agarose hydrogel.
scan rate (v) and (c) dependence of peak potential, Epc , vs. log v in 4.8 wt% of agarose hydrogel.
 Nanomaterials 2023, 13, x FOR PEER REVIEW 7 of 13

Nanomaterials 2023, 13, 48 7 of 14

A linear relationship between the cathodic peak current (Ipc) and square root of the
scan rate (v) was observed for the silver deposition process (Figure 3b). Linearity is gen-
A linear
erally relationship
observed between thereactions
in electrochemical cathodicin peak current
which the (Ipc ) and
mass square root
transport of themole-
of redox scan
rate
cules(v)iswas observed
mostly for the
governed silver
by the deposition
diffusion process
process (Figure 3b).
[51]. Therefore, theLinearity
main factor is generally
affecting
observed in electrochemical
mass transfer reactions
in agarose hydrogels in whichwhereas
is diffusion, the mass transport
other factors of redox
(i.e., molecules
convection and
ismigration)
mostly governed by the diffusion process [51]. Therefore,
are not worth considering at normal scan rates [32]. the main factor affecting
mass transfer
Figure 3cinshows
agarosethehydrogels
change in is the
diffusion,
cathodicwhereas other factors
peak potential (Epc) (i.e., convection
according to theand
log
migration) are not worth considering at normal scan rates [32].
(scan rate, v) for the electrodeposition of silver on ITO in agarose hydrogel. The coefficient
Figuretransfer
of charge 3c shows(α) the change in
is calculated tothe cathodic
be 0.38 at roompeak potential (298
temperature (Epc )K)according
by using to the
Equa-
log
tion(scan rate, v) for the electrodeposition of silver on ITO in agarose hydrogel. The
(2) [52,53]:
coefficient of charge transfer (α) is calculated to be 0.38 at room temperature (298 K) by
using Equation (2) [52,53]: │Ep – Ep/2│ = 1.857RT/αnF (2)
where R is the gas constant, T |E p-E
is the p/2 | = 1.857RT/αnF
absolute temperature, α is the charge-transfer coeffi- (2)
cient,Rnisisthe
where thegasnumber of electrons
constant, in the rate-determining
T is the absolute temperature, α isstep, and F is the Faraday
the charge-transfer con-
coefficient,
stant.
n is the number of electrons in the rate-determining step, and F is the Faraday constant.
Silverwas
Silver waselectrodeposited
electrodepositedon onthetheITO
ITOelectrode
electrodeunder undertwo twoconditions:
conditions: in in solution
solution
andagarose
and agarose hydrogel.
hydrogel. FigureFigure4a4ashow show thethe
SEMSEMimages
images of the
of Ag
thedeposits formed
Ag deposits at −0.35
formed at
−V0.35(vs.VAg/AgCl
(vs. Ag/AgCl QRE) QRE)
over 10 overs in10solution, demonstrating
s in solution, demonstrating a broad range range
a broad of sizes of (refer
sizes
Figures
(refer S4a and
Figures S4aS5a andinS5a
the in
Supplementary
the Supplementary Materials) and irregular
Materials) shapes. shapes.
and irregular This suggestsThis
that controlling the morphology or distribution of the deposited
suggests that controlling the morphology or distribution of the deposited nanoparticles nanoparticles is difficult
isindifficult
the solution
in thephase,
solution which
phase, is assumed to be caused
which is assumed to bebycaused
uncontrollable mass transport
by uncontrollable mass
properties
transport (i.e., natural
properties (i.e.,convection). Ag deposition
natural convection). in the agarose
Ag deposition hydrogelhydrogel
in the agarose (refer Figures
(refer
S4b andS4b
Figures S5bandin the
S5bSupplementary
in the SupplementaryMaterials) afforded
Materials) nanoparticles
afforded with a regular
nanoparticles shape,
with a regular
whichwhich
shape, were well were-distributed laterallylaterally
well-distributed compared to those obtained
compared to those via solution-phase
obtained via solution-elec-
trodeposition
phase (Figure 4b).
electrodeposition Additionally,
(Figure the total amount
4b). Additionally, the total of amount
Ag nanoparticles on ITO was
of Ag nanoparticles
onapproximately 7.265 × 10−12 7.265
ITO was approximately mol/cm × 210 −12 mol/cm
using 2 using anodic
anodic stripping voltammetry
stripping(see Figure S6 in
voltammetry
theFigure
(see Supplementary Materials). We assumed
S6 in the Supplementary Materials).thatWetheassumed
interactionthatbetween the Ag+ between
the interaction ions and
theAg
the +
hydrophilic
ions and polymer networkpolymer
the hydrophilic of the hydrogel
network can reduce
of the natural
hydrogel canconvection
reduce natural [32],
which causes
convection [32],irregular
which causestransport of the
irregular solute to
transport of the
the electrode
solute to thesurface. The surface.
electrode transport of
The
transport
metal ions of to
metal ions to thesurface
the electrode electrode surfacefor
is crucial is the
crucial for the electrodeposition
electrodeposition of metal
of metal nanoparti-
nanoparticles.
cles. The poreThe pore structure
structure of the agarose
of the agarose hydrogelhydrogel
could becould be controlled
controlled by varying
by varying its con-
itscentration.
concentration.
FromFrom these these results,
results, the agarose
the agarose hydrogel
hydrogel appeared
appeared not only
not only to beto be a good
a good tem-
template, but also a well-controllable reaction medium for the electrochemical
plate, but also a well-controllable reaction medium for the electrochemical deposition of deposition
ofmetal
metalnanoparticles.
nanoparticles.

Figure4.4. SEM
Figure SEM images
images of
of silver
silverclusters
clusterselectrodeposited onon
electrodeposited ITO electrode
ITO (a) (a)
electrode in solution, (b) in
in solution, (b)aga-
in
rose hydrogel (3.2 wt%) from a solution containing 1 mM AgNO3, 1 mM HClO4, and 5 mM KClO4.
agarose hydrogel (3.2 wt%) from a solution containing 1 mM AgNO3 , 1 mM HClO4 , and 5 mM
Electrodeposition was performed at −0.35 V (vs. Ag/AgCl quasi-reference electrode (QRE)) for 10 s.
KClO4 . Electrodeposition was performed at −0.35 V (vs. Ag/AgCl quasi-reference electrode (QRE))
for 10 s.

The influence of the duration of application of the potential (hereinafter, potential

duration) on silver deposition in the agarose hydrogel was determined by varying the
Nanomaterials 2023, 13, x FOR PEER REVIEW 8 of 13

Nanomaterials 2023, 13, 48 The influence of the duration of application of the potential (hereinafter, potential 8 of 14
duration) on silver deposition in the agarose hydrogel was determined by varying the
deposition time using a ITO working electrode. Small metal particles have adjustable
properties (e.g.,
deposition timemagnetic,
using a ITO optical, and electronic)
working electrode.that Smallcanmetal
be tuned based on
particles havetheadjustable
structure,
interparticle density, and particle size. In a typical electrodeposition process,
properties (e.g., magnetic, optical, and electronic) that can be tuned based on the structure, the potential
duration applied to the electrodes influences the nucleation and crystal
interparticle density, and particle size. In a typical electrodeposition process, the potentialgrowth of the
metal nanoparticles [17,46].
duration applied to the electrodes influences the nucleation and crystal growth of the metal
Figure 5 shows
nanoparticles [17,46].the SEM micrograph of the Ag-deposited ITO electrode surface when
a potential
Figure of −0.35 the
5 shows V against the Ag/AgCl
SEM micrograph QRE
of the is applied for
Ag-deposited ITOdurations
electrodeof 0.5 towhen
surface 10 s in a
the silver-containing agarose hydrogel. The SEM images show marked
potential of −0.35 V against the Ag/AgCl QRE is applied for durations of 0.5 to 10 s in thedifferences in the
size and morphology
silver-containing agaroseof the particles
hydrogel. Thewith
SEMan increasing
images show deposition time. As in
marked differences shown
the size in
Figure 5a, after electrodeposition of 1.0 mM AgNO for 0.5 s, silver deposits
and morphology of the particles with an increasing deposition time. As shown in Figure 5a,
3 with a diam-
eter less
after than 100 nm areofobtained.
electrodeposition 1.0 mM AgNOThis indicates that the onset of silver nucleation occurs
3 for 0.5 s, silver deposits with a diameter less
earlier
than 100than
nm0.5
ares.obtained.
AlthoughThis uneven, at longer
indicates deposition
that the onset of times, the size of occurs
silver nucleation the silver de-
earlier
posits0.5
than increases owinguneven,
s. Although to the aggregation of small clusters
at longer deposition (Figures
times, the 5a–f).
size of Precisedeposits
the silver control
of the sizeowing
increases and morphology is beyond
to the aggregation of the scope
small of this
clusters work, 5a–f).
(Figure and the well-controlled
Precise control offab- the
rication of electrodeposited nanoparticles is still a challenging technique
size and morphology is beyond the scope of this work, and the well-controlled fabrication that depends on
various parameters. Nonetheless, Ag nanomaterials of various sizes
of electrodeposited nanoparticles is still a challenging technique that depends on various were successfully
fabricated onNonetheless,
parameters. the ITO electrode surface in agarose
Ag nanomaterials hydrogel
of various sizesby controlling
were the deposition
successfully fabricated
time.
on the ITO electrode surface in agarose hydrogel by controlling the deposition time.

Figure 5.
Figure 5. SEM
SEM micrographs
micrographs of of silver
silver nanoparticles
nanoparticles deposited
deposited on
on ITO
ITO electrode
electrode in
in agarose
agarose hydrogel
hydrogel
containing 1 mM AgNO3 at a potential of −0.35 V at deposition times of (a) 0.5 s, (b) 1.0 s, (c) 1.5 s,
containing 1 mM AgNO3 at a potential of −0.35 V at deposition times of (a) 0.5 s, (b) 1.0 s, (c) 1.5 s,
(d) 2.0 s, (e) 5.0 s, and (f) 10.0 s.
(d) 2.0 s, (e) 5.0 s, and (f) 10.0 s.

Silver particles
Silver particles are
are known
known totoact
actas
aselectrocatalysts
electrocatalystsfor
forHHO
2O2 reduction [52]. H2O2 is
2 2 reduction [52]. H2 O2 is
reduced on the electrode via the following mechanism [54]:
reduced on the electrode via the following mechanism [54]:
H2O2 (aq)+ e− → OHads + OH− (aq) (3)
H2 O2 (aq) + e− → OHads + OH− (aq) (3)
OHads + e− → OH− (aq) (4)
OHads + e− → OH− (aq) (4)
The net reduction of H2O2 in solution is given as
The net reduction of H2 O2 in solution is given as

H2 O 2 (aq) + 2e− → 2OH− (aq) (5)

Nanomaterials 2023,
Nanomaterials 13, 13,
2023, 48 x FOR PEER REVIEW 9 of 13 9 of 14

To confirm the electrocatalytic H2O2 (aq) properties

+ 2e− → 2OH of− (aq)
the prepared Ag nanostructures, (5) the
electroreduction of H2 O2 was characterized by employing CV within the stable potential
To confirm the electrocatalytic properties of the prepared Ag nanostructures, the
range of the ITO
electroreduction of Helectrode in a deaerated 0.1 M phosphate-buffered solution (pH 7.4)
2O2 was characterized by employing CV within the stable potential
containing 1.0 mM
range of the ITO electrodeH O
2 in , at a scan rate
2 a deaerated of phosphate-buffered
0.1 M 100 mV/s (Figuresolution 6a). The current
(pH response of
7.4) con-
the bare ITO electrode (black line)
taining 1.0 mM H2O2, at a scan rate of 100 mV/s for H O is small, indicating negligible
2 2 (Figure 6a). The current response of the electrocatalytic
activity.
bare ITOIn the absence
electrode (black ofline)H2for
O2H(blue dottedindicating
2O2 is small, line), even the ITO
negligible electrode modified
electrocatalytic ac- with
tivity. In the absence of H O (blue dotted line), even the ITO electrode modified
Ag nanoparticles exhibits a weak current, similar to that of bare ITO without H2 O2 . In both
2 2 with Ag
nanoparticles
cases, the H2 Oexhibits a weak current, similar to that of bare ITO without H2O2. In both
2 reduction signals are negligible. However, the strongest catalytic reduction
cases, the H 2O2 reduction signals are negligible. However, the strongest catalytic reduction
current is observed for the Ag-modified ITO electrode in the presence of H2 O2 at −0.6 V
current is observed for the Ag-modified ITO electrode in the presence of H2O2 at −0.6 V
vs. Ag/AgCl QRE. This suggests that H2 O2 can be reduced only on the Ag surface of the
vs. Ag/AgCl QRE. This suggests that H2O2 can be reduced only on the Ag surface of the
ITO electrode, and the Ag-ITO electrode possesses excellent electrocatalytic capability for
ITO electrode, and the Ag-ITO electrode possesses excellent electrocatalytic capability for
HH22O reduction.
O22reduction.

Figure 6.
Figure 6. (a)
(a)CVs
CVsobtained
obtainedwith barebare
with ITO ITO
(black(black
line) and ITO
line) electrode
and modified modified
ITO electrode with Ag nanopar-
with Ag nanopar-
ticles in the presence (red line) or absence of 1.0 mM H2O2 (blue dotted line) in phosphate buffer
ticles in the presence (red line) or absence of 1.0 mM H O
2 2
(pH 7.4). Scan rate: 100 mV/s. (b) CCs obtained at −0.6 V in phosphate
(blue dotted line) in phosphate buffer
buffer (pH 7.4) containing
(pH 7.4). Scan rate: 100 mV/s. (b) CCs obtained at −0.6 V in phosphate buffer (pH 7.4) containing
various concentrations (1, 10, 50, 100, 200, 300, and 500 µM) of H2 O2 . (c) Calibration plot for the
charge values at 5 s in panel (b). The error bars represent the standard deviation (SD) of three
independent measurements. All data were corrected by the mean value of the double layer charging
current determined from five measurements at zero concentration of H2 O2 . The dotted line shows
three times the SD of the charging current obtained at zero concentration of H2 O2 . Ag deposition
condition: potential of −0.35 V (vs. Ag/AgCl QRE) for 10.0 s.
Nanomaterials 2023, 13, 48 10 of 14

To investigate the analytical application of the modified electrode for H2 O2 sensing,

chronocoulograms were acquired for the Ag-modified ITO electrodes using different con-
centrations of H2 O2 (Figure 6b). In chronocoulometry (CC) [55], the integrated current
at a given period of time is used as the sensing signal. These signals show superior re-
producibility over those obtained by using potential sweep techniques such as CV. The
capacitive charging current, as the background level in CV, can be a major obstacle in
electrochemical sensing, whereas the effect of the capacitive charging current in CC can be
sufficiently reduced by the integration process under sufficiently long-term measurements.
The typical charge-time response is proportional to the H2 O2 concentration in the range
of 1.0–500 µM. The mean charge value at 5.0 s in the absence of H2 O2 is 10.7 µC, and the
standard deviation (SD) is 0.65 µC. Figure 6c shows the calibration plot for the charge data
obtained at 5.0 s presented in Figure 6b. The estimated limit of detection (LOD) using
Equation (6) for this sensing platform is ca. 4.83 µM.

LOD = 3Sb /m (6)

where Sb is the SD of the blank and m is the slope of the corresponding calibration curve
(refer Figure S7 in the Supplementary Materials) [56]. To confirm the selectivity of our
sensor system, amperometric i-t response was obtained in the presence of interference
molecule such as nitrate, glucose, and ascorbic acid (refer Figure S8 in the Supplementary
Materials). These results reveal that the developed hydrogel-based Ag-ITO sensor exhibits
excellent performance in terms of high sensitivity and selectivity as well as low detection
limit, comparable to those of other non-enzymatic H2 O2 sensors (see Table 1).

Table 1. Comparison of various non-enzymatic H2 O2 sensors based on nanomaterials.

Dynamic Range
Sensor Type LOD (µM) Ref.
(mM)
Cu NPs@GCE 3.4 8–70 [57]
Co3 O4 NWs@rGO 2.4 0.015–0.675 [58]
Ag-mSiO2 NPs@GCE 3.00 0.004–10 [44]
Crod @Ag-Ps 67 0.5–5.0 [59]
AuNPs-NH2 /Cu-
1.2 0.005–0.85 [60]
MOF/GCE
Ni/Ag@C 10 0.03–17 [61]
AgNPs@rGO@PANI 0.05 0.00001–1 [62]
AuCu alloy NPs 10.93 0.05–10 [63]
Ag NPs@ITO 4.83 0.001–0.5 This work
NP—nanoparticle, GCE—glassy carbon electrode, NW—nanowire, rGO—reduced graphene oxide, MOF—metal-
organic framework, PANI—polyanlinie, MWCNT—multi-walled carbon nanotube.

4. Conclusions
In this study, we successfully deposited Ag nanoparticles on an ITO electrode in
agarose hydrogel. Electrodeposition of Ag nanoparticles in agarose hydrogels has the
following advantages over deposition in solution: (1) nanoparticles can be deposited with
relatively mild reduction potentials; (2) nanoparticles are evenly dispersed and deposited
on the electrode surface; (3) the sizes of the synthesized nanoparticles are relatively homo-
geneous. These advantages may be attributed to the hydrophilic backbone of the agarose
hydrogel and the minimization of unexpected convection. Ag nanoparticles synthesized in
agarose hydrogel, as a solid electrolyte, showed good sensing ability for H2 O2 . The LOD of
our sensing platform for H2 O2 detection was 4.83 µM, with a dynamic range of 1–500 µM.
The LOD and dynamic range were extremely low compared with those observed in several
recent studies. The proposed method for nanoparticle electrosynthesis in agarose hydrogel
is not limited to Ag. Agarose hydrogels can be actively used for the synthesis of various
metal and non-metal nanoparticles and are expected to be used as important nanoparticles
or nanocatalyst synthetic media.
Nanomaterials 2023, 13, 48 11 of 14

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/nano13010048/s1, Figure S1: Cyclic voltammetry of silver depo-
sition on ITO using agarose hydrogel (3.2 wt%) as function of pH in 2 mM AgNO3 , 1 mM HClO4 ,
and 5 mM KClO4 . pH was adjusted by HNO3 . Scan rate: 10 mV/s; Figure S2: The calibration plot
for the H2 O2 oxidation charge values of chronocoulograms obtained at −0.6 V according to the Ag
deposition time. The H2 O2 sensing experiment conducted in 0.1 M phosphate buffer (pH 7.4) and
700 mM NaCl with 300 µM H2 O2 . The error bars represent the three independent measurements;
Linear sweep voltammetry (LSV) with bare ITO (black line) and electrodeposition of Ag on ITO
in solution (blue line), in agarose hydrogel (red line) from a solution containing 1 mM H2 O2 in
phosphate buffer (pH 7.4). Electrodeposition was performed at −0.35 V (vs. Ag/AgCl QRE) for
5 s. The indicated numbers are each onset potential; Figure S4: The size distribution histograms
for silver nanoparticles deposited on ITO in solution (a), in agarose hydrogel (b); Figure S5: SEM
micrographs of ITO surface upon electrodeposition of silver (a) in solution, (b) in agarose hydrogel at
both ×50 k magnification; Figure S6: Anodic stripping voltammetry curve on silver nanoparticles
electrodeposited on ITO prepared the same as in Figure 4b; Figure S7: Calibration plot for the charge
values at 5 s in Figure 6b against the concentration of H2 O2 ; Figure S8: Amperometric responses of
Ag nanoparticles modified ITO in Ar-saturated phosphate buffer (pH 7.4) with addition of 0.5 mM
interference molecules (ascorbic acid, glucose, nitrate) and 0.5 mM H2 O2 .
Author Contributions: Conceptualization, B.-K.K. and K.P.; methodology, J.K. and K.P.; software, J.K.,
B.-K.K. and K.P.; validation, J.K., B.-K.K. and K.P.; formal analysis, B.-K.K. and K.P.; investigation, J.K.
and K.P.; resource, B.-K.K. and K.P.; writing—original draft preparation, K.P.; writing—review and
editing, B.-K.K. and K.P.; supervision, K.P.; project administration, B.-K.K. and K.P.; funding acquisi-
tion, B.-K.K. and K.P. All authors have read and agreed to the published version of the manuscript.
Funding: K.P. acknowledges the support from the Basic Science Research Program of the Research In-
stitute for Basic Sciences (RIBS) of Jeju National University through the National Research Foundation
of Korea (NRF), funded by the Ministry of Education (2019R1A6A1A10072987). This research was
also supported by the Basic Science Research Program through the National Research Foundation of
Korea (NRF), funded by the Ministry of Education (NRF-2022R1I1A3072996). B.K. was supported
by the Basic Science Research Program through the National Research Foundation of Korea (NRF),
funded by the Ministry of Education (2021R1A6A1A10039823) and the National Research Foundation
(NRF) of Korea, funded by the Ministry of Science and ICT (NRF-2021R1A2C4002069).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We sincerely appreciate the editor and reviewer to improve our work by con-
structive comments.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Liu, Q.; Chen, D.; Kang, Z. One-step electrodeposition process to fabricate corrosion-resistant superhydrophobic surface on
magnesium alloy. ACS Appl. Mater. Interfaces 2015, 7, 1859–1867. [CrossRef] [PubMed]
2. Zhao, M.; Balachandran, R.; Patterson, Z.; Gouk, R.; Verhaverbeke, S.; Shadman, F.; Keswani, M. Contactless bottom-up
electrodeposition of nickel for 3D integrated circuits. RSC Adv. 2015, 5, 45291–45299. [CrossRef]
3. Qiu, Z.; Tang, D. Nanostructure-based photoelectrochemical sensing platforms for biomedical applications. J. Mater. Chem. B
2020, 8, 2541–2561. [CrossRef] [PubMed]
4. Ravindran, A.; Chandran, P.; Khan, S.S. Biofunctionalized silver nanoparticles: Advances and prospects. Colloids Surf. B
Biointerfaces 2013, 105, 342–352. [CrossRef] [PubMed]
5. Sun, X.; Zhang, X.; Ma, Q.; Guan, X.; Wang, W.; Luo, J. Revisiting the Electroplating Process for Lithium-Metal Anodes for
Lithium-Metal Batteries. Angew. Chem. Int. Ed. Engl. 2020, 59, 6665–6674. [CrossRef]
6. Arico, A.C.; Bruce, P.; Scrosati, B.; Tarascon, J.-M.; Schalkwijk, W.V. Nanostructured materials for advanced energy conversion
and storage devices. Nat. Mater. 2005, 4, 366–377. [CrossRef]
Nanomaterials 2023, 13, 48 12 of 14

7. Pomerantseva, E.; Bonaccorso, F.; Feng, X.; Cui, Y.; Gogotsi, Y. Energy storage: The future enabled by nanomaterials. Science 2019,
366, 6468. [CrossRef]
8. Ren, B.; Liu, G.K.; Lian, X.B.; Yang, Z.L.; Tian, Z.Q. Raman spectroscopy on transition metals. Anal. Bioanal. Chem. 2007, 388,
29–45. [CrossRef]
9. Ma, M.; Trzesniewski, B.J.; Xie, J.; Smith, W.A. Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on
Oxide-Derived Nanostructured Silver Electrocatalysts. Angew. Chem. Int. Ed. Engl. 2016, 55, 9748–9752. [CrossRef]
10. Liu, H.; Park, J.; Chen, Y.; Qiu, Y.; Cheng, Y.; Srivastava, K.; Gu, S.; Shanks, B.H.; Roling, L.T.; Li, W. Electrocatalytic Nitrate
Reduction on Oxide-Derived Silver with Tunable Selectivity to Nitrite and Ammonia. ACS Catal. 2021, 11, 8431–8442. [CrossRef]
11. Jamkhande, P.G.; Ghule, N.W.; Bamer, A.H.; Kalaskar, M.G. Metal nanoparticles synthesis: An overview on methods of
preparation, advantages and disadvantages, and applications. J. Drug Deliv. Sci. Technol. 2019, 53, 101174. [CrossRef]
12. Cioffi, N.; Colaianni, L.; Ieva, E.; Pilolli, R.; Ditaranto, N.; Angione, M.D.; Cotrone, S.; Buchholt, K.; Spetz, A.L.; Sabbatini, L.; et al.
Electrosynthesis and characterization of gold nanoparticles for electronic capacitance sensing of pollutants. Electrochim. Acta 2011,
56, 3713–3720. [CrossRef]
13. Caschera, D.; Federici, F.; Zane, D.; Focanti, F.; Curulli, A.; Padeletti, G. Gold nanoparticles modified GC electrodes: Electrochemi-
cal behaviour dependence of different neurotransmitters and molecules of biological interest on the particles size and shape. J.
Nanopart. Res. 2009, 11, 1925–1936. [CrossRef]
14. Baig, N.; Kammakakam, I.; Falath, W. Nanomaterials: A review of synthesis methods, properties, recent progress, and challenges.
Mater. Adv. 2021, 2, 1821–1871. [CrossRef]
15. Abbott, A.P.; Griffith, J.; Nandhra, S.; O’Connor, C.; Postlethwaite, S.; Ryder, K.S.; Smith, E.L. Sustained electroless deposition of
metallic silver from a choline chloride-based ionic liquid. Surf. Coat. Technol. 2008, 202, 2033–2039. [CrossRef]
16. Pei, A.; Zheng, G.; Shi, F.; Li, Y.; Cui, Y. Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal. Nano Lett. 2017, 17,
1132–1139. [CrossRef] [PubMed]
17. Grujicic, D.; Pesic, B. Electrodeposition of copper: The nucleation mechanisms. Electrochim. Acta 2002, 47, 2901–2912. [CrossRef]
18. Park, K.; Kim, E.; Park, J.H.; Hwang, S. Influence of an active vibration isolator and electrochemical cell design on electrochemical
measurements to minimize natural convection. Electrochem. Commun. 2017, 82, 93–97. [CrossRef]
19. Suryanto, B.H.R.; Gunawan, C.A.; Lu, X.; Zhao, C. Tuning the electrodeposition parameters of silver to yield micro/nano
structures from room temperature protic ionic liquids. Electrochim. Acta 2012, 81, 98–105.
20. Kazeminezhad, I.; Barnes, A.C.; Holbrey, J.D.; Seddon, K.R.; Schwarzacher, W. Templated electrodeposition of silver nanowires in
a nanoporous polycarbonate membrane from a nonaqueous ionic liquid electrolyte. Appl. Phys. A 2007, 86, 373–375. [CrossRef]
21. Simka, W.; Puszczyk, D.; Nawrat, G. Electrodeposition of metals from non-aqueous solutions. Electrochim. Acta 2009, 54,
5307–5319. [CrossRef]
22. Abbott, A.P.; El Ttaib, K.; Frisch, G.; Ryder, K.S.; Weston, D. The electrodeposition of silver composites using deep eutectic
solvents. Phys. Chem. Chem. Phys. 2012, 14, 2443–2449. [CrossRef] [PubMed]
23. Mahinroosta, M.; Jomeh Farsangi, Z.; Allahverdi, A.; Shakoori, Z. Hydrogels as intelligent materials: A brief review of synthesis,
properties and applications. Mater. Today Chem. 2018, 8, 42–55. [CrossRef]
24. Herrmann, A.; Haag, R.; Schedler, U. Hydrogels and Their Role in Biosensing Applications. Adv. Healthc. Mater. 2021, 10, e2100062.
[CrossRef]
25. Tang, J.D.; Mura, C.; Lampe, K.J. Stimuli-Responsive, Pentapeptide, Nanofiber Hydrogel for Tissue Engineering. J. Am. Chem. Soc.
2019, 141, 4886–4899. [CrossRef]
26. Vashist, A.; Vashist, A.; Gupta, Y.K.; Ahmad, S. Recent advances in hydrogel based drug delivery systems for the human body. J.
Mater. Chem. B 2014, 2, 147–166. [CrossRef]
27. Dreiss, C.A. Hydrogel design strategies for drug delivery. Curr. Opin. Colloid Interface Sci. 2020, 48, 1–17. [CrossRef]
28. Khajouei, S.; Ravan, H.; Ebrahimi, A. DNA hydrogel-empowered biosensing. Adv. Colloid Interface Sci. 2020, 275, 102060.
[CrossRef]
29. Xu, W.; Huang, L.-B.; Wong, M.-C.; Chen, L.; Bai, G.; Hao, J. Environmentally Friendly Hydrogel-Based Triboelectric Nanogenera-
tors for Versatile Energy Harvesting and Self-Powered Sensors. Adv. Energy Mater. 2017, 7, 1601529. [CrossRef]
30. Pernodet, N.; Maaloum, M.; Tinland, B. Pore size of agarose gels by atomic force microscopy. Electrophoresis 1997, 18, 55–58.
[CrossRef]
31. Kang, H.; Hwang, S.; Kwak, J. A hydrogel pen for electrochemical reaction and its applications for 3D printing. Nanoscale 2015, 7,
994–1001. [CrossRef]
32. Kim, B.-K.; Park, K. Mass Transport Properties and Influence of Natural Convection for Voltammetry at the Agarose Hydrogel
Interface. J. Electrochem. Sci. Technol. 2022, 13, 347–353. [CrossRef]
33. Juven, B.J.; Pierson, M.D. Antibacterial Effects of Hydrogen Peroxide and Methods for Its Detection and Quantitationt. J. Food
Prot. 1996, 59, 1233–1241. [CrossRef] [PubMed]
34. Wang, J.; Lin, Y.; Chen, L. Organic-phase biosensors for monitoring phenol and hydrogen peroxide in pharmaceutical antibacterial
products. Analyst 1993, 118, 277–280. [CrossRef] [PubMed]
Nanomaterials 2023, 13, 48 13 of 14

35. Lopez-Lazaro, M. Dual role of hydrogen peroxide in cancer: Possible relevance to cancer chemoprevention and therapy. Cancer
Lett. 2007, 252, 1–8. [CrossRef]
36. Bautista, P.; Mohedano, A.F.; Gilarranz, M.A.; Casas, J.A.; Rodriguez, J.J. Application of Fenton oxidation to cosmetic wastewaters
treatment. J. Hazard Mater. 2007, 143, 128–134. [CrossRef]
37. Niethammer, P.; Grabher, C.; Look, A.T.; Mitchison, T.J. A tissue-scale gradient of hydrogen peroxide mediates rapid wound
detection in zebrafish. Nature 2009, 459, 996–999. [CrossRef]
38. Ivanova, A.S.; Merkuleva, A.D.; Andreev, S.V.; Sakharov, K.A. Method for determination of hydrogen peroxide in adulterated
milk using high performance liquid chromatography. Food Chem. 2019, 283, 431–436. [CrossRef]
39. Abo, M.; Urano, Y.; Hanaoka, K.; Terai, T.; Komatsu, T.; Nagano, T. Development of a highly sensitive fluorescence probe for
hydrogen peroxide. J. Am. Chem. Soc. 2011, 133, 10629–10637. [CrossRef]
40. Lee, D.; Khaja, S.; Velasquez-Castano, J.C.; Dasari, M.; Sun, C.; Petros, J.; Taylor, W.R.; Murthy, N. In vivo imaging of hydrogen
peroxide with chemiluminescent nanoparticles. Nat. Mater. 2007, 6, 765–769. [CrossRef]
41. Chen, W.; Cai, S.; Ren, Q.Q.; Wen, W.; Zhao, Y.D. Recent advances in electrochemical sensing for hydrogen peroxide: A review.
Analyst 2012, 137, 49–58. [CrossRef] [PubMed]
42. Luo, Y.; Liu, H.; Rui, Q.; Tian, Y. Detection of Extracellular H2O2 Released from Human Liver Cancer Cells Based on TiO2
Nanoneedles with Enhanced Electron Transfer of Cytochrome c. Anal. Chem. 2009, 81, 3035–3041. [CrossRef]
43. Mao, L.; Osborne, P.G.; Yamamoto, K.; Kato, T. Continuous On-Line Measurement of Cerebral Hydrogen Peroxide Using
Enzyme-Modified Ring-Disk Plastic Carbon Film Electrode. Anal. Chem. 2002, 74, 3684–3689. [CrossRef] [PubMed]
44. Yang, D.; Ni, N.; Cao, L.; Song, X.; Alhamoud, Y.; Yu, G.; Zhao, J.; Zhou, H.B. Silver doped mesoporous silica nanoparticles based
electrochemical enzyme-Less sensor for determination of H2O2 released from live cells. Micromachines 2019, 10, 268. [CrossRef]
[PubMed]
45. Qin, X.; Wang, H.; Wang, X.; Miao, Z.; Fang, Y.; Chen, Q.; Shao, X. Synthesis of dendritic silver nanostructures and their application
in hydrogen peroxide electroreduction. Electrochim. Acta 2011, 56, 3170–3174. [CrossRef]
46. Kim, B.-K.; Seo, D.; Lee, J.Y.; Song, H.; Kwak, J. Electrochemical deposition of Pd nanoparticles on indium-tin oxide electrodes
and their catalytic properties for formic acid oxidation. Electrochem. Commun. 2010, 12, 1442–1445. [CrossRef]
47. Katz, E.; Willner, I.; Wang, J. Electroanalytical and Bioelectroanalytical Systems Based on Metal and Semiconductor Nanoparticles.
Electroanalysis 2004, 16, 19–44. [CrossRef]
48. Liu, L.; Yellinek, S.; Valdinger, I.; Donval, A.; Mandler, D. Important Implications of the Electrochemical Reduction of ITO.
Electrochim. Acta 2015, 176, 1374–1381. [CrossRef]
49. Kim, B.-K.; Lee, J.Y.; Park, J.H.; Kwak, J. Electrochemical detection of dopamine using a bare indium–tin oxide electrode and scan
rate control. J. Electroanal. Chem. 2013, 708, 7–12. [CrossRef]
50. Sandmann, G.; Dietz, H.; Plieth, W. Preparation of silver nanoparticles on ITO surfaces by a double-pulse method. J. Electroanal.
Chem. 2000, 491, 78–86. [CrossRef]
51. Amatore, C.; Szunerits, S.; Thouin, L.; Warkocz, J.-S. The real meaning of Nernst’s steady diffusion layer concept under non-forced
hydrodynamic conditions. A simple model based on Levich’s seminal view of convection. J. Electroanal. Chem. 2001, 500, 62–70.
[CrossRef]
52. Bard, A.J.; Faulkner, L.R. Electrochemical Methods Fundamentals and Applications, 2nd ed.; Wiley: New York, NY, USA, 2000.
53. Su, C.; An, M.; Yang, P.; Gu, H.; Guo, X. Electrochemical behavior of cobalt from 1-butyl-3-methylimidazolium tetrafluoroborate
ionic liquid. Appl. Surf. Sci. 2010, 256, 4888–4893.
54. Meng, F.; Yan, X.; Liu, J.; Gu, J.; Zou, Z. Nanoporous gold as non-enzymatic sensor for hydrogen peroxide. Electrochim. Acta 2011,
56, 4657–4662. [CrossRef]
55. Anson, F.C.; Osteryoung, R.A. Chronocoulometry: A Convenient, Rapid and Reliable Technique for Detection and Determination
of Adsorbed Reactants. J. Chem. Educ. 1983, 60, 293–296. [CrossRef]
56. Harris, D.C.; Lucy, C.A. Quantitative Chemical Analysis, 10th ed.; Freeman and Company: New York, NY, USA, 2022.
57. Sophia, J.; Muralidharan, G. Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper
nanoparticles. Mater. Res. Bull. 2015, 70, 315–320.
58. Kong, L.; Ren, Z.; Zheng, N.; Du, S.; Wu, J.; Tang, J.; Fu, H. Interconnected 1D Co3O4 nanowires on reduced graphene oxide for
enzymeless H2 O2 detection. Nano Res. 2014, 8, 469–480. [CrossRef]
59. Brzózka, A.; Brudzisz, A.; Jeleń, A.; Kozak, M.; Wesół, J.; Iwaniec, M.; Sulka, G.D. A comparative study of electrocatalytic
reduction of hydrogen peroxide at carbon rod electrodes decorated with silver particles. Mater. Sci. Eng. B 2021, 263, 114801.
[CrossRef]
60. Dang, W.; Sun, Y.; Jiao, H.; Xu, L.; Lin, M. AuNPs-NH2 /Cu-MOF modified glassy carbon electrode as enzyme-free electrochemical
sensor detecting H2 O2 . J. Electroanal. Chem. 2020, 856, 113592. [CrossRef]
61. Sheng, Q.; Shen, Y.; Zhang, J.; Zheng, J. Ni doped Ag@C core–shell nanomaterials and their application in electrochemical H2 O2
sensing. Anal. Methods 2017, 9, 163–169.
Nanomaterials 2023, 13, 48 14 of 14

62. Kumar, V.; Gupta, R.K.; Gundampati, R.K.; Singh, D.K.; Mohan, S.; Hasan, S.H.; Malviya, M. Enhanced electron transfer mediated
detection of hydrogen peroxide using a silver nanoparticle-reduced graphene oxide-polyanlilne fabricated electrochemical sensor.
RCS Adv. 2018, 8, 619–631.
63. Ngamaroonchote, A.; Sanguansap, Y.; Wutikhun, T.; Karn-Orachai, K. Highly branched gold–copper nanostructures for non-
enzymatic specific detection of glucose and hydrogen peroxide. Microchim. Acta 2020, 187, 559. [CrossRef] [PubMed]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.