Journal of Applied Electrochemistry (2020) 50:125–138

https://doi.org/10.1007/s10800-019-01374-3

RESEARCH ARTICLE

Electrochemical formation of silver nanoparticles and their

applications in the reduction and detection of nitrates at neutral pH
Catherine M. Fox1 · Carmel B. Breslin1 

Received: 2 May 2019 / Accepted: 21 November 2019 / Published online: 4 December 2019
© Springer Nature B.V. 2019

Abstract
A glassy carbon electrode modified with silver nanoparticles was employed as a nitrate sensor to give a calibration curve
with a sensitivity of 2.6 μA μM−1 cm−2 and a LOD of 4.1 μM N ­ O3− at a neutral pH. The calibration curve was generated
using rotating disc voltammetry coupled with constant potential amperometry, giving efficient diffusion of the nitrate to the
surface. Reasonably good selectivity for nitrate was observed in the presence of nitrite, chloride and phosphate anions. The
nitrate diffusion coefficient was estimated as 1.41 × 10−5 to 1.73 × 10−5 cm2 s−1 using a combination of cyclic voltammetry
and rotating disc voltammetry, while the rate constant for the nitrate reduction reaction was estimated as 0.11 cm s−1. Some
deviations from the Randles–Sevick and Levich equations were seen at higher scan rates, consistent with the slow kinetics
and nitrate adsorption. While stable silver nanoparticles were electrochemically formed in the solution phase and incor-
porated within a hydrogel matrix, the best approach in forming the nitrate sensor was the direct electrodeposition of silver
nanoparticles at glassy carbon at − 0.50 V versus Ag|Ag+ following a 60-min seeding period at the open-circuit potential.
Graphic abstract

0.3

0.3 -
NO3

0.2
Current/mA cm-2

0.2

0.1 -
e
0.1

0.0
0.00 0.02 0.04 0.06 0.08 0.10 0.12
[NO3-]/mM

Keywords  Silver nanoparticles · Nitrate sensor · Nitrate reduction · Electrochemical synthesis · Nitrite · Hydrogel

1 Introduction
* Carmel B. Breslin
Carmel.Breslin@mu.ie
Nitrogen is an essential and important element for plant life,
giving higher plant yields with the application of nitrogen-
1
Department of Chemistry, Maynooth University, Maynooth, containing fertilisers [1]. As population growth continues
Co. Kildare, Ireland

13
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126
to increase and the demand for food intensifies, greater
amounts of nitrogen-containing fertilisers are used. Nitro-
gen normally exists as nitrates in fertilisers, and in this form
it is soluble and leaches from the soil into water systems.
Eventually, it escapes into drinking water. It is well known
that nitrates have significant health risks and have harmful
effects on ecosystems. In particular, when nitrates are pre-
sent with phosphates, eutrophication occurs and this depletes
the dissolved oxygen content in the water, causing detrimen-
tal effects on the life that is supported in ecosystems. Fur-
thermore, ­NH4+, which is bound to the soil through electro-
static attractions with the clay, which is negatively charged,
is readily converted to nitrate by microbes [2]. Nitrates and
other nitrogen-containing compounds that are easily con-
verted to nitrates are also produced from various industrial
processes and from road traffic. As a result, Environmental
Protection Agencies have set Maximum Contamination Lev-
els for nitrates. The European Communities Drinking Water
Regulations 2000 set nitrate levels at 50 ppm (0.80 mM)
while in the US, it is even lower at 10 ppm (0.16 mM).
It is no surprise that there is considerable interest in the
monitoring of nitrates and the development of nitrate sen-
sors. Various methods have been developed and reported
and these include spectrophotometry [3, 4], chromatogra-
phy [5, 6], chemiluminescence [7], capillary electrophore-
sis [8], fluorimetry [9] and electrochemistry [10–17]. Each
analytical approach has merits, but also has a number of
disadvantages and these include the need to derivatise the
nitrate or nitrite, initial sample preparation and separation,
interference, mainly from chloride, and specialised equip-
ment, which makes the analysis more expensive [18]. In
terms of electrochemical detection, the relatively low cost
and portability of the sensor and equipment are attractive,
but the electrochemical detection of nitrates at unmodified
electrodes, such as platinum, gold or copper, is limited due
to selectivity and sensitivity issues and the slow kinetics
of the nitrate reduction reaction [18]. Some of these issues
can be addressed by employing metal nanoparticles. The
nanoparticles have the potential to give higher catalytic
efficiency, have a higher surface area and are promising in
electroanalysis for a number of different molecules [19, 20].
Two approaches can be used to modify an electrode with
nanoparticles: electrodeposition or drop-casting the synthe-
sised nanoparticles onto the substrate. However, the adher-
ence of the synthesised particles drop-cast onto the substrate
electrode may be an issue, particularly in terms of long-term
stability. Nanoparticles are normally formed using chemical
synthesis, and many of these synthetic routes use harsh reac-
tion conditions combined with organic solvents and toxic
reducing reagents [21, 22], although in recent times there is
more focus on developing green synthetic approaches.
In this study, silver nanoparticles were formed in an aque-
ous solution using an electrochemical approach and also
13
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Journal of Applied Electrochemistry (2020) 50:125–138
electrodeposited directly at the substrate electrode, eliminat-
ing the need for reducing agents and a non-aqueous solvent
system. For comparative purposes, the electrochemically
generated nanoparticles were drop-cast onto the substrate
and also dispersed in a hydrogel matrix formed at the sub-
strate. These modified electrodes were then used to reduce
nitrates and their performance as a nitrate sensor at neutral
pH was evaluated. Silver was chosen, as nanostructured sil-
ver electrodes have been shown to reduce nitrates in neutral
solutions [23, 24], while, in many studies, acidic conditions
are employed [25, 26] or alkaline conditions are used [27]
requiring pH adjustments before analysis. For example,
Jiang et al. [24] electrodeposited zinc onto a silver electrode
and subsequently removed the zinc using anodic dissolu-
tion to give a nanostructured silver layer that enabled the
detection of nitrates in neutral solution, whereas Zhad and
Lai [23] electrodeposited leaf- and branch-like structures of
silver and used the modified nanostructures to detect nitrates
without any pH adjustments.
2 Experimental
2.1 Chemicals, electrodes and equipment
All chemicals were obtained from Sigma-Aldrich and the
electrodes were purchased from Goodfellow Metals. Glassy
carbon (GC) (99.99%, 3 mm diameter) and bulk silver rods
(99.99%, 2 mm diameter) were encased in Teflon using
epoxy resin. The electrical contact was achieved using a
copper wire, which was threaded to one end of the elec-
trode and this section was then encased in resin. The exposed
surfaces were polished to a smooth finish with successively
finer grades (from 300 to 1200 grit) of lubricated silicon
carbide paper, rinsed and sonicated in deionised water
between each grade. Using Buehler MetaDi Monocrystalline
Diamond suspensions with particle sizes between 30 and
1 µm, a mirror finish was achieved. Platinum sheets (99.9%,
1 × 5 cm length × width) were employed to form the silver
nanoparticles in solution. These sheets were polished using
a Metaserve Universal polisher with water-lubricated sili-
con carbide paper to a 1200 grit grade. The electrochemical
experiments were carried out using a Solartron (Model SI
1287) potentiostat and a Princeton Applied Research Model
636 ring-disc electrode system. UV–Vis spectroscopy was
performed with a Varian Cary 50 UV–Vis spectrometer and
scanning electron microscopy (SEM) and energy-dispersive
X-ray (EDX) analyses were performed on a Hitachi SEM
model S-3200N which was fitted with an Oxford instruments
EDX system with a Penta FET Precision INCA X-act detec-
tor. FTIR spectra were recorded on a Perkin Elmer system
using KBR discs.
Journal of Applied Electrochemistry (2020) 50:125–138 127
2.2 Formation of the silver nanoparticles
The silver nanoparticles were formed using two approaches;
direct electrodeposition onto glassy carbon and electrofor-
mation in the solution phase protected with PVP (poly(N-
vinylpyrrolidone). For direct electrodeposition, the silver
nanoparticles were formed at a glassy carbon electrode in
a three-electrode cell, with a silver reference electrode and
a platinum counter electrode in 1.0 mM A ­ gClO4 in 0.1 M
­LiClO4. Initially, an oxidative pulse, 1.0 V for 15 min in
0.1 M ­LiClO4, was applied to remove any intercalated sil-
ver from the previous experiment. Then, the electrode was
immersed in the silver-containing solution at the open-circuit
potential for 60 min and this was followed by a single-pulse
electrodeposition step to deposit the silver nanoparticles.
The PVP-protected silver nanoparticles generated in
solution were formed using a three-electrode cell, with two
platinum sheets, serving as the working and counter elec-
trodes and a silver wire as a pseudo-reference electrode.
The solution consisted of 5.0 mM A ­ gNO3, 0.1 M K ­ NO3
and 423.75 g dm−3 PVP to give a ratio of ­Ag+:PVP of 75:1.
The electrolysis was carried out under constant agitation at
fixed potentials between − 1.0 and− 6.0 V versus Ag|Ag+.
The potential of the silver pseudo-reference electrode was
checked against a saturated calomel reference electrode,
before and after the experiments and no significant potential
drift was observed.
2.3 Formation and characterisation of the nitrate
sensors
Nitrate sensors were fabricated using the electrodeposited
silver nanoparticles and the PVP-protected solution phase
silver nanoparticles. For the silver nanoparticle-modified
GC electrode, the size, density and surface area of the elec-
trodeposited nanoparticles were estimated using Image J
software (US NIH), from 10 random sites on each sample.
As the particles are viewed as 2D circles, with an area of
πr2 rather than the hemispherical shape that they most likely
adopt with an area of 2πr2, the data were adjusted. The sur-
face area of the silver nanoparticles deposited onto the GC
electrode was also estimated using lead underpotential depo-
sition using 10 mM ­PbCl2 in 0.1 M HCl and by the reduction
of surface oxides.
The PVP-protected silver nanoparticles were formed at
a glassy carbon electrode by drop-casting the PVP-pro-
tected silver nanoparticle solution onto the electrode and
then the electrode was air-dried until all the solvent was
evaporated. They were also protected in a polyacrylamide
hydrogel composite. This composite was prepared by dis-
solving the acrylamide monomer and N,N′-methylene-bis-
acrylamide (MBA) in 10 mL of water, under a nitrogen
atmosphere. The aqueous and deoxygenated PVP-protected
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
silver nanoparticle solution (10 mL) was then added. Poly-
merisation was initiated using freshly prepared ammonium
persulphate and tetramethylethylenediamine (TEMED),
which were added with vigorous mechanical stirring. A
1-mm diameter electrode was immobilised in the hydrogel
by suspending the wire in a 5-mm diameter straw, with a
plastic plug at the end. The gel solution was then poured
into the straw and gelation was allowed to occur. Once set,
the plug was removed and the gel was released. The hydro-
gel-modified electrodes were then suspended in deoxygen-
ated deionised water and maintained in the dark for 24 h to
extract any unreacted chemicals.
2.4 Electrochemical detection of nitrate
The modified electrodes were first cycled in the background
electrolyte, 0.1 M L
­ iClO4, between − 0.2 and − 1.6 V versus
SCE for 30 cycles and then transferred to the various con-
centrations of nitrate (­ KNO3 in 0.1 M L ­ iClO4) and cycled
at 50 mV s−1 until a near steady state was reached (about
30 cycles). Constant potential amperometry using a rotat-
ing disc was employed to generate a calibration curve. A
saturated calomel electrode was employed as the reference
in the three-electrode cell and all solutions were deoxygen-
ated with nitrogen.
3 Results and discussion
A GC electrode was used as the substrate to support the
silver nanoparticles as it does not facilitate the reduction
of nitrates and therefore the nitrate signal can be attributed
to the silver particles. For comparison purposes, the sil-
ver nanoparticles were electrodeposited directly at the GC
electrode and drop-cast onto the surface of the electrode.
The electrochemically synthesised nanoparticles were also
dispersed in a hydrogel which was formed around a wire
electrode, with a view to protecting the nanoparticles from
escaping to the environment.
3.1 Electrochemical formation of silver
nanoparticles in solution
It is well known that poly(N-vinylpyrrolidone) (PVP)
can be employed as a protecting agent in the formation
of silver nanoparticles [28, 29]. The nanoparticles were
formed at different applied potentials to generate nano-
particles with a narrow size distribution. A typical cur-
rent–time transient recorded at a fixed potential of − 1.5 V
versus Ag|Ag+ is presented in Fig. 1a, where reduction of
­Ag+ is evident with a reduction current of approximately
0.15 A after about 200 s where near steady-state currents
are achieved. As evident in Fig. 1b, higher steady-state
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128 Journal of Applied Electrochemistry (2020) 50:125–138

(a) -0.10
currents are achieved at lower applied potentials and this
gives rise to the production of larger amounts of silver
nanoparticles. At these potentials, the reduction of H­ + and
-0.15
water occurs at the platinum substrate and these redox
reactions will contribute to the measured current. As the
-0.20 solutions were agitated continuously, variations in the
interfacial pH will be limited. The current remains low
Current/A

-0.25
until potentials exceeding − 1.0  V versus Ag|Ag + are
applied, while the current becomes limited by mass trans-
port effects as the potential is varied from − 2.0 to − 4.0 V
-0.30
versus Ag|Ag+. The concentration ratio of A ­ g+ to PVP,
the applied potential, electrodeposition period and charge
-0.35 were varied to obtain the optimised conditions to generate
0 100 200 300 a narrow size distribution of particles with good repro-
Time/s ducibility. The optimised conditions involved a solution
of 0.1 M K­ NO3, 0.05 M A ­ gNO3 and 423.75 g dm−3 PVP,
(b) 0.00
while an electrochemical pulse of − 6.0 V versus Ag|Ag+
-0.05 was applied until a charge of 180 C was reached.
The concentration, stability and size dispersion of the
-0.10
nanoparticles generated were monitored using UV–Vis
-0.15 spectroscopy. The UV–Vis spectra of three separate solu-
Current/A

tions of PVP-protected silver nanoparticles generated

-0.20
using the optimised conditions are shown in Fig. 1c. The
-0.25 reproducibility is impressive given the competing H ­ + and
water reduction reactions. Furthermore, the nanoparticles
-0.30
appear stable with little evidence of particle agglomera-
-0.35 tion and this is clearly evident from the spectrum recorded
-8 -6 -4 -2 0 following 1 month, as shown in Fig. 1c. There is only a
Potenal/V small change in the absorbance, indicating very good sta-
bility. Furthermore, the bandwidth is narrow indicating a
small size distribution. The protective properties of the
(c) 1.0 PVP are illustrated in Fig. 2a, where FTIR spectra for PVP
and PVP-protected silver nanoparticles are compared. The
0.8 carbonyl stretch is seen at 1663 cm−1 for pure PVP, but
is red shifted to 1656 cm−1 for the PVP-protected silver
nanoparticles, as the coordination of silver with the PVP
Absorbance

0.6
weakens the > C=O bond. This interaction between the
PVP and silver nanoparticles prevents agglomeration of
0.4
the electrochemically formed silver nanoparticles.
These electrosynthesised silver nanoparticles were
0.2
incorporated into a polyacrylamide gel (PAAm). Typically,
gelation times for this system were 15–20 min using the
0.0 conditions summarised in Table 1; however, in the pres-
200 300 400 500 600 ence of the silver nanoparticles, instantaneous gelation
Wavelength/nm was observed. The amounts of APS and TEMED were
reduced to control the gelation period, as illustrated in
Fig. 1  a Current–time curve recoded during the formation of silver Table 1. Similar effects have been observed with a silver
nanoparticles generated at − 1.5 V versus Ag|Ag+ in 0.05 M ­AgNO3, electrode [30] and A ­ g+ [31] and this has been attributed
0.1 M ­KNO3 and 423.75 g dm−3 PVP, b steady-state current recorded
during the formation of the nanoparticles as a function of the applied to the generation of radicals from the dissociation of per-
potential. c UV–Vis spectra of the formed nanoparticles red line, grey sulphate in the presence of silver. The SEM micrograph of
line initially and blue line after 1 month. (Color figure online) the dried composite is shown in Fig. 2b. The surface shows
a globular-like morphology.

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Journal of Applied Electrochemistry (2020) 50:125–138 129

(a) (b)
65

% Transmission 55

45

35

25

15

5
4000 3500 3000 2500 2000 1500 1000 500 8 µm
Wave number /cm-1

Fig. 2  a FTIR spectra of pure PVP (top trace) and PVP-protected silver nanoparticles (bottom trace) b SEM micrographs of the surface of the
dried PAAm-PVP-Ag nanoparticle discs. (Color figure online)

Table 1  Reagents for the synthesis of polyacrylamide-PVP and and then the cleaned silver electrode was immersed in the
the polyacrylamide-PVP silver nanoparticle composites, PVP silver-containing solution for 60 min under open-circuit con-
(423.75 g dm−3) and APS (1% solution)
ditions, prior to the application of the reduction potentials.
Hydrogel AAm MBA PVP APS TEMED The open-circuit potential in the silver-containing solution
/g /g /mL /μL /μL is shown in Fig. 3a, where it is evident that potentials of
PAAm-PVP 4.0 0.175 10 400 10 approximately − 0.05 V Ag|Ag+ are reached and these are
PAAm-PVP-Ag 4.0 0.175 10 300 5 sufficient to deposit silver from the solution. The presence
of deposited silver was confirmed using stripping voltam-
mograms. A typical stripping voltammogram is shown in the
3.2 Electrochemical formation of silver inset in Fig. 3a. The stripping peak at about 0.20 V versus
nanoparticles at the GC electrode SCE shows that indeed a small amount of silver was depos-
ited under open-circuit conditions. The reproducibility was
The silver nanoparticles were deposited directly at the glassy significantly improved using this cleaning and immersion
carbon electrode using a single-pulse method, at applied routine. For example, stripping voltammograms recorded
potentials between − 0.25 and − 1.0 V versus Ag|Ag+. A following the deposition of the silver nanoparticles but with-
cleaning pulse at 1.0 V versus SCE was employed initially out this pretreatment step are shown in Fig. 3b, where it is

(a) 10
(b) 0.3
0.8
Current density/ mA cm-2

5
Current/µA

0
0.2
0.5
Potenal/V

-5
0.1
0.3 -10
-0.6 -0.3 0.0 0.3 0.6 0.9 1.2
Potenal/V
0.0 0.0

-0.3 -0.1
0 2500 5000 7500 -0.6 -0.3 0.0 0.3 0.6 0.9 1.2
Time/s Potenal/V

Fig. 3  a Open-circuit transient of a GC electrode immersed in Stripping voltammograms recorded in 0.1  M L ­ iClO4 at a GC elec-
1.0  mM ­AgClO4 in 0.1  M L ­ iClO4, inset shows the corresponding trode modified with silver nanoparticles deposited at − 0.5  V versus
stripping voltammogram recorded in 0.1 M L ­ iClO4 at 50 mV s−1. b Ag|Ag+, but without a cleaning and nucleation step

13

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130
clearly evident that different amounts of silver are deposited.
This cleaning and immersion step enables seeding which
gives rise to stable nucleation sites at which the nanopar-
ticles can be formed, increasing the reproducibility, giving
near identical stripping voltammograms with less than a 1%
variation in the peak currents.
The current–time transients recorded at potentials of
− 0.25 V, − 0.50 V, − 0.75 V and − 1.0 V versus Ag|Ag+ for
50 s are shown in Fig. 4. A reduction current is obtained on
application of the potential and this current decays as the
deposition period is increased. Higher currents are obtained
for deposition as the potential is varied from − 0.25 V to
− 1.0 V versus Ag|Ag+. The corresponding stripping vol-
tammograms are presented in the inset of Fig. 4. The strip-
ping peaks are similar for deposition at − 0.50 V and − 0.75
versus Ag|Ag+; however, the quantity of silver deposited is
much lower at − 0.25 V versus Ag|Ag+, and the stripping
peak is also slightly lower for the silver deposited at − 1.0 V
versus Ag|Ag+. This is probably connected with the compet-
ing ­H+ ion and water reduction reactions which occur at this
high overpotential.
Figure 5 shows the SEM micrograph of the resulting GC
surface when potentials of − 0.50 V, − 0.75 V and − 1.0 V
versus Ag|Ag+ are applied for 50 s in the silver-containing
solution. While the number of particles is similar at the dep-
osition potentials, the particles generated at − 0.50 V versus
Ag|Ag+ have the narrowest size distribution and most of the
particles have diameters lower than 75 nm. At this potential,
there is a high density of silver particles deposited on the
surface as the potential allows nucleation to occur during
the entire pulse, but the potential is not sufficiently low to
facilitate rapid growth and consequently there are few larger
particles. Flower-like deposits were seen at − 0.25 V versus
Ag|Ag+ (data not shown), varying from 1 to 2 μm in size,
0.00
-0.05
0.20
0.15
Current/mA
Current /mA
0.10
-0.10 0.05
0.00
-0.15 -0.05
-0.6
-0.20
0 10 20 30
Time/s
Fig. 4  Current–time transients and corresponding stripping vol-
tammograms (inset) for the formation of silver particles using
a single pulse at green line − 0.25  V, black line − 0.50  V, blue line
− 0.75 V and red line − 1.0 V versus Ag/Ag+. (Color figure online)
13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
Journal of Applied Electrochemistry (2020) 50:125–138
and there was no evidence of any smaller silver deposits
on the surface. At these low potentials, which are close to
the onset of silver deposition, the silver ions preferentially
deposit at the more stable silver deposits rather than at new
nucleation sites, giving rise to a few large deposits.
The surface area of the silver deposits was estimated
using the charge associated with silver oxides, under poten-
tial deposition of lead and Image J software. Data are shown
in Fig. 6 for the method employed using silver oxides. In
this approach, the charge associated with the reduction
of the surface oxides which are generated in the forward
sweep is measured as a function of the inversion potential.
The voltammograms recorded for the bulk silver electrode
cycled to various inversion potentials in 0.1 M L ­ iClO4 are
presented in Fig. 6a while the corresponding charge plot
is shown in the inset. The reduction peak at approximately
0.35 V versus SCE corresponds to the reduction of the sil-
ver oxides, and this peak becomes progressively larger as
the inversion potential is increased. Two linear regions are
evident in the charge plot. The linear region which is seen at
the lower potentials is related to the reduction of the silver
oxide/hydroxide monolayer. The electroactive surface area
can be calculated using the charge computed at the intersec-
tion point [32, 33]. The reduction charge was computed as
1.14 × 10−5 C and given that a monolayer of AgOH/Ag2O
consumes approximately 2.10 C ­m−2 [34], the real surface
area was calculated as 0.0542 cm2 for the 2 mm silver elec-
trode, Table 2, to give a roughness factor of 1.73. Similar
data were recorded with the silver nanoparticles, deposited at
− 0.50 V versus Ag|Ag+ for 50 s at the GC electrode, Fig. 6b.
Again, the silver oxide/hydroxide reduction peak is clearly
evident, but with the silver nanoparticles, this reduction wave
appears at a slightly lower potential of 0.28 V versus SCE.
As the applied potential is cycled to higher upper potential
limits, the peak current increases initially, but then begins
to decrease as the silver nanoparticles are dissolved at the
higher applied potentials and the silver ions diffuse from the
surface. Two linear regions are seen and the reduction charge
of 1.53 × 10−5 C, computed at the point of inflection (at
approximately 340 mV), gives a calculated real surface area
of 0.0729 cm2, Table 2. The surface area was also computed
using the underpotential deposition of lead and Image J soft-
ware and these data are summarised in Table 2. Good agree-
ment is obtained between the different methods employed to
0.0 0.6 1.2 estimate the surface area. There is a factor of approximately
Potenal/V
1.3 between the surface area of the bulk silver and the elec-
trodeposited silver nanoparticles at − 0.5 V versus ­Ag+|Ag
40 50
for 50 s. All currents recorded in the detection of nitrates
were normalised using a real surface area of 0.0543 cm2 for
bulk silver and 0.0729 cm2 for the silver-modified GC elec-
trode. In this way, the increased area of the silver nanoparti-
cles can be accounted for, enabling the true catalytic activity
of the nanoparticles in the detection of nitrates to be obtained.
Journal of Applied Electrochemistry (2020) 50:125–138 131

(a)
1000

800

Frequency
600

400

200

0
25 50 75 100 150 200
Diameter/nm

2 µm
(b)
1000

800

Frequency
600

400

200

0
25 50 75 100 150 200
Diameter/nm
2 µm

(c)
1000

800
Frequency

600

400

200

0
25 50 75 100 150 200
Diameter/nm

2 µm

Fig. 5  SEM micrographs and size distribution histograms for silver particles deposited on GC by the single-pulse method at a − 0.50  V b
− 0.75 V and c − 1.0 V versus Ag|Ag+ for 50 s

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132 Journal of Applied Electrochemistry (2020) 50:125–138

(a) 0.06
(a) 0.5

Charge/mC
0.0
0.04
0.20 -0.5
0.02 -1.0

Current/mA
0.15
-1.5
0.00
0.10 330 360 390 420 -2.0
Current/mA

Potenal/mV -2.5

0.05
-3.0
0.00 -3.5

-0.05 -4.0
-1.5 -1.2 -0.9 -0.6 -0.3 0.0
-0.10 Poten
al/V
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5
Potenal/V
(b) 1.0

(b) 0.10
0.5
0.08
0.20

Current/mA
0.06
Charge/mC

0.04 0.0
0.15
0.02
0.10 0.00
Current/mA

240 300 360 420 -0.5

0.05 Potenal/mV
0.00 -1.0
-0.2 0.0 0.2 0.4 0.6 0.8
-0.05
Poten
al/V
-0.10
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 Fig. 7  Cyclic voltammograms recorded at 50  mV  s−1 a in 5  mM
Potenal/V ­KNO3 and 0.1  M L ­ iClO4 for bulk silver electrode, with
space electrodeposited silver nanoparticles at GC and with
space GC modified with PVP-protected silver particles b in 10  mM
Fig. 6  Cyclic voltammograms for a a polished silver electrode and ­K3Fe(CN)6 in 0.1 M ­Na2SO4 at platinum, platinum modified
b silver nanoparticles deposited at GC cycled in 0.1  M ­LiClO4 at with polyacrylamide and modified with polyacrylamide contain-
50 mV s−1 to different anodic inversion potentials and corresponding ing PVP-protected silver nanoparticles
reduction charge of silver oxides as a function of inversion potential

­KNO3 in 0.1 M ­LiClO4. A broad peak at approximately

Table 2  Surface area values calculated using different methods − 0.90 V versus SCE is evident for the electrodeposited
Method Surface area/cm2
silver nanoparticles and this corresponds to the irrevers-
ible reduction of the nitrate anions. The reduction of nitrate
Bulk Ag Ag nanoparticles begins at approximately − 0.60 V versus SCE and the cur-
UPD 0.0543 ± 0.005 0.0706 ± 0.007 rent continues to increase until the peak current is observed
Image J – 0.0725 ± 0.006 at − 0.90 V versus SCE. The onset of the water reduction
Ag oxides 0.0542 ± 0.005 0.0729 ± 0.008 reaction is evident at about − 1.4 V versus SCE. There is also
a visible reduction wave at about − 0.38 V versus SCE which
was evident in the background electrolyte. This was attrib-
3.3 Electrochemical detection of nitrate uted to the reduction of surface oxides at the silver-modified
electrode. There was no evidence of nitrate reduction at the
The performance of the silver particles electrodeposited GC substrate, indicating that the broad wave seen in Fig. 7a
directly at GC, the bulk silver electrode and at the GC elec- corresponds to the reduction of nitrate at the silver particles.
trode modified with the PVP-protected silver nanoparticles A similar response, but with a significantly lower peak cur-
is compared in Fig. 7a. The data were recorded in 5.0 mM rent, was observed for the bulk silver electrode, while the

13

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Journal of Applied Electrochemistry (2020) 50:125–138 133
PVP-protected silver particles formed at the GC electrode
by drop-casting the nanoparticle-containing solution showed
a similar response to the bulk silver electrode. As PVP is
soluble in aqueous solution, the PVP will be largely removed
from the silver particles. Indeed, this was evident on cycling
the electrode in the nitrate solution, with the current increas-
ing on cycling, enabling the adsorption of the nitrate at the
PVP-free silver deposit. However, peak currents similar to
that obtained with the electrodeposited silver nanoparticles
were difficult to obtain with good reproducibility, while
the GC modified with the electrodeposited silver particles
showed very good reproducibility. It is clear that the direct
electrodeposition of the silver nanoparticles at the GC elec-
trode gives currents that are significantly higher and as these
currents are normalised to the real surface area of silver, this
highlights the good catalytic activity of the electrodeposited
silver nanoparticles.
In Fig. 7b, the influence of the polyacrylamide composite
is shown where the electrochemical response of the ferri-
cyanide redox couple is compared for platinum, platinum
modified with the polyacrylamide composite and modified
with the polyacrylamide composite containing the silver
nanoparticles. It is clear from this plot that the redox reac-
tions of the ferricyanide couple are inhibited due to the slow
diffusion of the anions through the polyacrylamide. There is
no increase in the peak currents on adding the silver nano-
particles to the composite, indicating that the particles are
well separated and do not provide a conducting path to the
electrode. Furthermore, there is no evidence for the disso-
lution of the silver nanoparticles which would be expected
at potentials between 0.40 and 0.70 V versus SCE, Fig. 6b,
again consistent with the lack of a conducting network. As
expected, a poor nitrate reduction response was observed
Fig. 8  Steady-state currents
from constant potential amper-
ometry recorded at 2000 rpm
plotted as a function of ­KNO3
concentration recorded at the
Current density/ mA cm-2
silver-modified GC electrode
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
with the peak currents lower than that observed for the bulk
electrode. While this approach may be suitable for larger
nanostructures that provide a conducting path to the sub-
strate, the nanoparticles are too small and well dispersed to
facilitate the reduction of nitrate.
A typical calibration curve is shown in Fig. 8 for the GC
electrode modified with the electrodeposited silver nanopar-
ticles. These data were recorded using rotating disc voltam-
metry at a constant rotation of 2000 rpm and at an applied
potential of − 1.10 V versus SCE. The response time was
within 3 s. A linear response is observed at the lower con-
centrations up to about 0.1 mM ­KNO3. Using the linear cali-
bration curve, R2 = 0.999, the limit of detection was found
to be 4.1 μM ­NO3−. This was obtained using the expression
in Eq. (1) where Cm is the detection limit, Sb is the standard
deviation of the blank response and m is the sensitivity cor-
responding to the slope of the linear calibration curve. The
sensitivity was calculated using the linear calibration curve
as 2.6 μA μM−1 cm−2.
3Sb
Cm = (1)
m
The limit of detection falls well below the maximum
concentration levels set out by the EPA for groundwater
limits of 0.16 mM N ­ O3−. Furthermore, the linear calibra-
tion range, extending up to 0.1 mM nitrate, covers elevated
nitrate concentrations. These data compare very well to
data recently reported for copper nanowires (sensitivity
of 1.375 μA μM−1 and LOD of 1.35 μM) [27], for silver-
modified carbon (sensitivity of 0.07–0.12 nA μM−1 and
LOD of 3.2–5.1 μM) [23] and for copper-modified graphite
(sensitivity of 0.675 μA μM−1 and LOD of 0.59 μM) [35].
0.6
0.5
0.4
Fig 4
0.3
0.2
0.1
0.0
0.00 0.10 0.20 0.30 0.40
[NO3-]/mM
13

134 Journal of Applied Electrochemistry (2020) 50:125–138

The relatively high sensitivity observed in this study can be
linked with the enhanced diffusion at the rotating disc elec-
trode. It also shows that the nanoparticles are stable and not
removed during the rotation of the electrode. Lower sensi-
tivities were obtained using cyclic voltammetry, with values
of 0.53 μA μM−1 ­cm−2 for the silver-modified GC compared
to 0.10 μA μM−1 ­cm−2 for the bulk silver electrode. Linear
plots were also obtained using the charge associated with
the nitrate reduction wave plotted as a function of the nitrate
concentration to give a high sensitivity of 4.3 μC μM−1 ­cm−2
but with a poor LOD value of 16 μM.
The influence of chloride and nitrite as interfering ions is
shown in Figs. 9 and 10. The data presented in Fig. 9a show
the influence of different chloride levels on the peak cur-
rent recorded using cyclic voltammetry in a 5.0 mM nitrate
solution. In the absence of chloride anions, a peak current
of 2.75 mA cm−2 is obtained. It is clear that chloride con-
centrations of about 0.5 mM give rise to a reduction in the
peak current, while further reductions in the peak current are
seen on increasing the chloride concentration. The typical
concentrations of chloride in water/wastewater are between
2.0 and 7.0 mM and at these concentrations, interference is
seen. It is likely that a layer of AgCl is formed on the surface
of the particles. The influence of chloride anions on the peak
potential is shown in Fig. 9b, where a near linear response
between the peak potential and logarithm of the chloride
concentration is evident. The peak potential is lowered as
the chloride concentration is increased indicating that the
reduction of nitrates becomes progressively more difficult.
This is consistent with the formation of AgCl that inhibits
the adsorption of nitrates. Although interference is seen with
the chloride anion, it is possible to estimate the chloride con-
centration using the nitrate reduction peak potential, Fig. 9b.
Consequently, by monitoring both the peak potential and the
peak current, the concentration of chloride can be obtained
and the peak current adjusted to give a reasonably accurate
reading of the nitrate concentration in solutions with high
chloride content. Similar data recorded in the presence of

(a) 3.0 (b)

-0.90
Current density/mA cm-2

2.5
Peak potenal/V

2.0 -0.95

1.5 -1.00
1.0
-1.05
0.5

0.0 -1.10
0 0.1 0.5 2.5 5 25 50 0.01 0.1 1 10 100
[Cl-]/mM [Cl-]/mM

Fig. 9  a Peak currents and b peak potential plotted as a function of the chloride concentration with the nitrate concentration at 5.0 mM

(a) (b)
0.4 -0.90
Current density/mA cm-2

0.3
Peak Potenal/V

-0.93
0.2

-0.96
0.1

0.0
-0.99
0 0.0001 0.0005 0.001 0.005 0.5
0.0001 0.001 0.01 0.1 1
[NO2-]/mM
[NO2-]/mM

Fig. 10  a Peak currents and b peak potential plotted as a function of the nitrite concentration with the nitrate concentration at 1.0 mM

13

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Journal of Applied Electrochemistry (2020) 50:125–138 135
nitrite are presented in Fig. 10. The concentration of nitrite
was varied from 10 μM to 0.5 mM to reflect the expected
and high concentrations of nitrite in water/wastewater and
the nitrate concentration was reduced to 1.0 mM. At low
nitrite concentrations, there is relatively little interference
from the nitrite anion, with only small changes in the peak
current. On recording cyclic voltammograms in the pres-
ence of nitrite, the reduction of nitrite was seen at around
− 1.12 V versus SCE but with a considerably lower peak
current indicating that silver nanoparticles are a rather poor
surface for the reduction of nitrite (data not shown) and this
is consistent with the data in Fig. 10. At 0.5 mM nitrite, there
is evidence of interference and this may be related to com-
petitive adsorption between the nitrate and nitrite anions,
giving rise to lower nitrate reduction currents. As shown in
Fig. 10b, there are only small changes in the peak potentials
at the low concentrations of nitrite; however, the potential
is about 50 mV lower in the presence of 0.5 mM nitrite.
While interference is seen with the nitrite anion, it is only
evident with the higher concentrations and little interference
is observed at the typical nitrite concentrations expected in
water or wastewater.
In Fig. 11a, the performance of the silver-modified GC
electrode is shown under extended periods of cycling, with
the peak current plotted as a function of cycle number. Ini-
tially, the current increases and this may be related to the
reduction of silver oxides enabling more efficient adsorption
and reduction of nitrate. As the cycles progress the peak
current decreases before eventually reaching a near constant
value of 2.2 mA cm−2. The peak current then remains stable
with only small increases after 800–1000 cycles.
The influence of the solution pH on the nitrate reduction
peak current was evaluated in 5.0 mM ­KNO3 and 0.1 M
­LiClO4. A plot of the peak current as a function of pH is
3.0
Current density /mA cm-2
2.5
2.0
1.5
1.0
0.5
0.0
0 250 500 750
Cycle number
Fig. 11  a Peak current as a function of the cycle number and b
peak current as a function of pH recorded in 5.0  mM ­KNO3 and
0.1 M ­LiClO4 where the open symbols correspond to pH 1.5 (0.1 M
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
shown in Fig. 11b. The pH has little influence between 4.0
and 10.0, but increases considerably in the more acidic solu-
tions. This indicates that adsorbed ­H+ species facilitate the
nitrate reduction but as the pH is increased, hydroxide ions
occupy the active sites and hinder nitrate adsorption [36].
The influence of the supporting electrolyte is also shown in
Fig. 11b, where the plotted pH values (open symbols) repre-
sent different solutions, including ­H2SO4 (pH 1.5), chloride
(pH 8.7), sulphate (pH 5.3), phosphate buffer, PBS, (pH 6.7)
carbonate (pH 11.4) and NaOH (pH 12.6). It is clear from
this plot that the perchlorate anions, which adsorb less than
the other anions, give rise to the highest peak currents. The
nitrate signal in L
­ iClO4 is well defined, stable and reproduc-
ible. It is also evident that a high phosphate concentration
(0.1 M PBS) gives peak currents that are only slightly below
the current obtained with the perchlorate supporting elec-
trolyte and this indicates that interference from phosphates
is minimal.
3.4 Kinetics of the nitrate reduction reaction
Details on the kinetics of the electrochemical reduction of
nitrates at the silver nanoparticle modified GC electrode
were obtained using scan rate studies and rotating disc vol-
tammetry. The silver-modified GC electrode was cycled in
4.0 mM ­KNO3 at scan rates from 5 to 200 mV s−1. The
corresponding data, represented as a Randles–Sevcik plot,
Eq. 2, are shown in Fig. 12a. For slow scan rates below
approximately 70 mV s−1, a linear trend is observed; how-
ever, deviations from linearly are clearly evident at the
higher scan rates. The non-linearity coupled with a non-zero
intercept is consistent with a system which exhibits kinetic
control and this is probably connected with the adsorption
of nitrate, which is time dependent, prior to its reduction.
6.0
5.0
Current density/mA cm-2
4.0
3.0
2.0
1.0
1000
0.0
0 5 10 15
pH
­H2SO4); pH 5.3 (0.1 M ­Na2SO4); pH 6.7 (0.1 M PBS); pH 8.7 (0.1 M
KCl); pH 11.4 (0.1 M ­Na2CO3) and pH 12.6 (0.1 M NaOH)
13

136 Journal of Applied Electrochemistry (2020) 50:125–138

(a) (b)
-880
5
Current density/mA cm-2 -900
4

Peak potenal/mV
-920
3
-940
2
-960
1
-980

0 -1000
0 0.2 0.4 0.6 0.6 0.9 1.2 1.5 1.8 2.1
log (scan rate/mV s-1)

(c) (d) -3
0

Liming current/mA cm-2

-5
-6
Current-1/A-1 cm2
Current/mA

0
-10 -50
-100 -9
-15 -150
-200

-20 -250
0.00 0.10 0.20 0.30
-12

-25 -15
-1.5 -1.2 -0.9 -0.6 -0.3 0.0 0 3 6 9 12 15 18
Potenal/V Rotaon1/2/s-1/2

Fig. 12  a Peak current as a function of the square root of scan rate at green line 400, yellow line 600, grey line 800, black line 1000, red
and b peak potential as a function of the logarithm of scan rate in line 1500 and blue line 2000  rpm, corresponding Koutecky–Levich
4.0 mM ­KNO3, c rotating disc voltammograms recorded at 10 mV s−1 plot (inset) and d Levich plot. (Color figure online)

The diffusion coefficient, D, was estimated using the linear achieved and a value for αn’ of 0.45 was computed using the
region and Eq. (2), where jp is the peak current density, n is gradient. This value is in good agreement with 0.43 which
the number of electrons, D is the diffusion coefficient, ν is was obtained using the shape factor analysis.
the scan rate, Co is the concentration, α is the charge transfer
| | RT
coefficient and n′ is the number of electrons transferred up |Ep − Ep∕2 | = 1.857 (3)
| | F𝛼n�
to and including the rate-determining step.
( ) ( )1∕2 1∕2 1∕2
jp = 2.99 × 105 n 𝛼n� D v Co (2) | dEp | 29.6
| |
| |= (4)
| dlogv |
| | 𝛼n�
The αn′ value was determined using Eq.  (3), where
|Ep − Ep1/2|, corresponding to the shape factor, was measured Using a value of 0.44 for αn′ and Eq. 2, the diffusion coef-
at different scan rates. The shape factor drifts slightly with ficient, D, was calculated as 1.41 × 10−5 ­cm2 ­s−1. This value
scan rate, varying from 107 mV at the lower scan rates to compares well with the diffusion coefficient of 1.31 × 10−5
115 mV at the higher scan rates. An average value of 111 mV ­cm2 ­s−1 obtained for nitrate reduction at a copper electrode
was used for |Ep − Ep1/2| and the value of αn′ was calculated [37], while Gartia reported a value of 8.99 × 10−6 ­cm2 ­s−1 at
as 0.43 with Eq. (3). The αn′ term was also estimated using a silver microelectrode [38], and Reyter et al. [15] obtained
Eq. (4), where Ep is the peak potential, expressed in mV, and values from 1.0 × 10−5 to 2.0 × 10−5 cm2 s−1 at copper elec-
log v is the logarithm of the scan rate. In Fig. 12b, a typical trodes in alkaline solutions.
plot illustrating the relationship between peak potential and Rotating disc voltammetry was employed to monitor
the logarithm of the scan rate is shown. Good linearity is the hydrodynamics of the nitrate reduction reaction. The

13

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Journal of Applied Electrochemistry (2020) 50:125–138 137
modified electrode was cycled in a potential window of
− 0.05 to − 1.45 V versus SCE at different rotation speeds.
The Levich and Koutecky–Levich relationships, Eqs. (5)
and (6), were applied to give insight into the diffusional
and kinetic limitations of the nitrate reduction reaction at
the silver nanoparticles. In these equations, n is the number
of electrons transferred, F is the Faraday constant, A is the
electrode area, v is the kinematic viscosity and C is the con-
centration of nitrate. Figure 12c shows the response of the
silver-modified GC electrode to various rotation speeds. The
voltammograms become more drawn out and the potential
of the limiting current shifts to lower reduction potentials,
from about − 0.91 V at no rotation to − 1.28 V versus SCE
at 2000 rpm. This is indicative of sluggish kinetics where
a larger overpotential is required to facilitate the reaction.
JL = (0.62)nFAD2∕3 𝜔1∕2 v−1∕6 Co (5)
1 1 1 2. van Kessel MAHJ, Speth DR, Albertsen M, Nielsen PH, Op den
J
= +
ik 0.62nFAD2∕3 𝜔1∕2 v−1∕6 C (6)
The Levich plot is shown in Fig. 12d, while the Kout-
ecky–Levich plot is presented in the inset in Fig. 12c. The
Levich plot deviates slightly from linearity at the higher
rotation speeds indicating there is kinetic limitations to
the reaction. Using the slope of the linear portion of the
Levich plot, a diffusion coefficient of 1.65 × 10−5 cm2 s−1
is obtained which is reasonably close to the value obtained
by varying the scan rate (1.41 × 10−5 cm2 s−1), while the
slope of the Koutecky–Levich equation yields a value of
1.73 × 10−5 cm2 s−1. The heterogenous rate constant, k0, was
calculated from the intercept (1/ik) of the Koutecky–Lev-
ich plot and Eq. (7), to give a value of 0.11 cm s−1. This
analysis clearly shows that the nitrate reduction reaction at
the silver nanoparticles is complex with deviations from the
Randles–Sevick and Levich plots.
ik = nFAk0 C (7)
4 Conclusions
On comparing three different methods in the formation
of a silver-modified GC electrode, it was found that the
direct electrodeposition of the nanoparticles from a silver-
containing perchlorate solution provided the best approach
in the design of a nitrate sensor. The reproducible growth
of the silver nanoparticles, with a narrow size dispersion,
was facilitated by immersion of the GC electrode, follow-
ing a cleaning pulse, in the silver-containing solution for
60 min, before deposition of the particles at − 0.50 V ver-
sus Ag|Ag+ for 50 s. The surface area of the silver nano-
particles deposited at the GC electrode was obtained using
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
a combination of recording the charge associated with sur-
face oxides and underpotential deposition of lead and by
estimating the size and coverage using SEM micrographs.
A calibration curve with a sensitivity of 2.6 μA μM−1 ­cm−2
and LOD of 4.1 μM N ­ O3− was obtained for nitrate using
rotating disc voltammetry coupled with constant potential
amperometry. The impressive sensitivity was attributed to
the enhanced diffusion at the rotating disc electrode.
Acknowledgements  This research work was funded by the Irish
Research Council, Ireland.
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