Electrochimica Acta 151 (2015) 126–133

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Nitrogen-doped graphene-silver nanodendrites for the non-enzymatic

detection of hydrogen peroxide
M.T. Tajabadi a , W.J. Basirun a,d, F. Lorestani a , R. Zakaria b , S. Baradaran c , Y.M. Amin b ,
M.R. Mahmoudian a , M. Rezayi a , M. Sookhakian a,b, *
a
Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
b
Department of Physics, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
c
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia
d
Nanotechnology & Catalysis Research Centre, Institute of Postgraduate Studies, University Malaya, 50603 Kuala Lumpur, Malaysia

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

Article history: An organic-metal hybrid film based on nitrogen-doped graphene-silver nanodendrites (Ag-NG) was
Received 25 June 2014 fabricated on an indium tin oxide (ITO) electrode using a simple electrophoretic and electrochemical
Received in revised form 5 November 2014 sequential deposition approach. The microwave-assisted method was utilized for the synthesis of
Accepted 5 November 2014
nitrogen-doped graphene. This method involves a three-step process consisting of graphite oxidation,
Available online 7 November 2014
exfoliation, and finally chemical reduction with the use of hydrazine as the reducing agent, which leads to
the simultaneous reduction of graphene oxide and production of nitrogen-doped graphene. The
Keywords:
morphology and structure of the as-fabricated electrode were determined by X-ray diffraction, field
Silver nanodendrite
N-graphene
emission electron microscopy and transmission electron microscopy. The as-prepared Ag-NG-modified
electrodeposition ITO electrode exhibited superior electrocatalytic activity toward hydrogen peroxide (H2O2) reduction,
Hydrogen peroxide with a wide linear detection range of 100 mM to 80 mM (r = 0.9989) and a detection limit of 0.26 mM with
electrophoretic deposition a signal-to-noise ratio of 3. Furthermore, the fabricated non-enzymatic H2O2 electrochemical sensor
exhibited excellent stability and reproducibility.
ã 2014 Elsevier Ltd. All rights reserved.

1. Introduction Therefore, to improve the sensitivity of non-enzymatic sensors,

In recent years, there has been considerable interest in
hydrogen peroxide (H2O2) detection due to its wide range of
applications, such as in food production (as a disinfecting agent),
the textile industry (as a bleaching agent), fuel cell devices (as an
energy storage site), chemical synthesis (as an active reagent) and
even in many oxidative biological reactions (as an essential
mediator) [1]. The methods for H2O2 detection include chemilu-
minescence, fluorescence, titration, chromatography, and electro-
chemistry, among others. Of these detection methods, the use of
electrochemical sensors has proven to be a simple and effective
approach, and these sensors have been widely used due to their
high sensitivity, good selectivity and easy operation [2]. Further-
more, in comparison to enzymatic detection, electrochemical
sensors based on the non-enzymatic technique possess the
advantages of low cost, high stability and good reproducibility.
* Corresponding author. Tel.: +603 79675330; fax: +603 79675330.
E-mail address: m.sokhakian@gmail.com (M. Sookhakian).
simple metal nanoparticles, such as Pt [3], Au [4] and Pd [5], with
extraordinary electrocatalytic activities have been utilized to
modified electrodes for the detection of H2O2.
It is well known that silver (Ag) nanostructures have good
catalytic activity toward H2O2 reduction, and they have been
widely developed for enzymeless-based H2O2 sensors. Consider-
able effort has recently been focused on designing Ag nano-
structures with various morphologies, such as nanowires [6],
nanobars [7], nanobelts [8] and multiple twinned structures [9]. Of
these different morphologies, nanodendritic structures composed
of trunks and multiple hierarchical symmetrical branches have
attracted substantial research interest due to their unique optical,
electronic and catalytic properties [10]. It can be observed that
silver nanodendrites (Ag NDs) can form porous structures on the
surfaces of electrodes due to the high surface area compare of Ag
nanoparticles (Ag NPs), which can form a dense film on the
electrode surface [11]. Therefore, Ag NDs exhibit better catalytic
performance than do Ag NPs. A number of different methods have
been employed to prepare Ag nanostructures, such as electro-
chemical deposition [12], thermal evaporation [13], chemical

http://dx.doi.org/10.1016/j.electacta.2014.11.031
0013-4686/ ã 2014 Elsevier Ltd. All rights reserved.
 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133
vapor deposition [14] and the template approach [15], but
electrochemical deposition is a relatively simple and versatile
technique for this purpose.
In contrast, graphene is a single sheet of two-dimensional sp2-
hybridized carbon nanosheets arranged in a honeycomb lattice.
Graphene has recently attracted considerable attention due to its
extraordinary physical and chemical properties, such as its high
surface area, high thermal conductivity, high chemical stability and
rapid charge carrier mobility [16,17]. Many theoretical and
experimental studies have demonstrated that the chemical doping
of graphene with foreign atoms such as nitrogen, boron, chlorine,
phosphorus, fluorine, hydrogen, and sulfur is a promising approach
to further modulate and tailor its electronic properties, to manipu-
late its surface chemistry and to introduce a considerable number of
defects into the graphene lattice [18,19]. Among these elements,
nitrogen is considered an excellent dopant for graphene due to its
comparable atomic size and valence electrons. Furthermore, strong
valence bonds can be formed between the nitrogen lone pair
electrons and the graphene p-electron system. Therefore, nitrogen
doping can induce the creation of a band gap in the graphene energy
levels, which is accompanied by the transformation of graphene to
an n-type semiconductor. This process leads to a significant increase
in the electron conductivity, spin density and charge distribution of
the carbon atoms, which lead to the formation of an activation region
on the graphene surface [20] that increases its ability to bind guest
molecules. Compared to other active inorganic compounds such as
Prussian blue [21] and conductive polymers-metal nanocomposites
such as Polyaniline-Palladium nanocomposites [22], N-graphene not
only has excellent electrocatalytic activity and biocompability, but
also has the advantage of large surface area, which is useful for
adsorption of more Ag NDs on the surface of N-graphene by p-p
stacking. This is very important for improving the sensitivity of H2O2
detection. Various methods, such as chemical vapor deposition, laser
ablation, and ammonia plasma treatment [23], have been used to
synthesize nitrogen-doped graphene (N-graphene); however, these
methods involve high energy consumption.
In this work, N-graphene was electrophoretically deposited
(EPD) on an indium tin oxide (ITO) electrode. Ag NDs were
deposited as a second layer via electrochemical deposition. The
N-graphene was synthesized using a microwave-assisted method
that consists of a three-step process of graphite oxidation,
exfoliation, and finally chemical reduction with the use of
hydrazine as a reducing agent at low temperature. This approach
could simultaneously realize the reduction of graphene oxide
(GO) and its doping with nitrogen atoms. Furthermore, micro-
wave irradiation is a rapid and highly efficient method for
transferring energy into the reaction system. The as-fabricated Ag
NDs-N-graphene-modified ITO electrode (Ag-NG) was utilized as
a non-enzymatic H2O2 sensor and exhibited high stability,
excellent reproducibility and good electrocatalytic activity for
the rapid detection of H2O2 over a wide linear range from 100 mM
to 80 mM.
2. Experimental methods
2.1. Chemical reagents
All chemicals (NaH2PO4, Na2HPO4, H2O2 (30 wt%) and AgNO3)
were purchased from Merck Co. and were of analytical grade and
used without further purification. Double-distilled water (resis-
tance = 18.3 MV) was used in all experimental procedures.
Phosphate-buffered saline (PBS) solution was prepared by mixing
stock solutions of NaH2PO4 and Na2HPO4. Each experimental
detection of H2O2 was performed using a freshly prepared solution.
All experiments were conducted at ambient temperature.
127
2.2. Synthesis of N-graphene and graphene via the microwave-assisted
method
N-graphene was synthesized using a simple method that
employed GO as a starting material. The Hummers method was
used to synthesize the GO [17]. The exfoliation process consisted of
sonicating the graphite oxide dispersion (0.2 mg mL
1) in an
ultrasonic bath for 30 min to obtain a yellow-brown dispersion.
The chemical reduction reaction was initiated by adding 0.8 mL of
hydrazine to the 30 mL GO dispersion. Subsequently, the product
was irradiated under the high power mode in a microwave oven for
5 min to obtain a stable black dispersion of N-graphene sheets. The
lower density N-graphene suspension was collected from the
solution by centrifuging and was dried at 50  C. Graphene was
prepared using the same procedure but with the absence of the
hydrazine solution.
2.3. EPD of N-graphene-modified and graphene-modified ITO
electrodes
The experimental set-up for the EPD of N-graphene-modified
ITO and graphene-modified ITO electrodes is reported elsewhere
[17]. Two milligrams of the as-synthesized N-graphene was
dispersed in 40 mL of isopropyl alcohol under sonication for
5 min to obtain a homogeneous suspension (0.05 mg L
1). The
suspension was adjusted to pH 3 with a dilute HCl solution before
EPD. ITO glass substrates with an area of 10 mm  20 mm were
immersed in a 5% HF solution for a few minutes to remove the
native oxide layer, followed by washing in acetone and distilled
water before being vertically immersed into the suspension. The
linear distance between the two electrodes was maintained at
10 mm. The DC potential and deposition time were set at 20 V and
5 min, respectively, during the EPD to form an N-graphene-
modified ITO electrode film. The freshly coated film was dried at
50  C in an oven to remove the excess solvent from the EPD process.
2.4. Electrochemical deposition of Ag NDs
The electrochemical deposition of Ag NDs was performed in a
three-electrode electrochemical cell by chronoamperometry at
-0.6 V with respect to an Ag/AgCl reference electrode. The N-
graphene-modified ITO electrode (with an active area of 1 cm2)
was used as the working electrode, and a platinum foil with an area
of 2 cm2 was used as the counter electrode. The solution contained
40 mM Ag(NH3)2OH, which was prepared by adding ammonia
(1 wt%) to a 50 mM silver nitrate solution until complete
dissolution of the precipitates. Distilled water at a volume ratio
of 1:12 (Ag(NH3)2OH: water) was subsequently added for the
chronoamperometric deposition of the Ag NDs-N-graphene-
modified ITO electrode for 10 min. The final product (Ag-NG)
was washed with distilled water and dried at 50  C in a
conventional oven. The same procedure was used for the
electrochemical deposition of the Ag NDs-graphene modified-
ITO electrode (Ag-G).
2.5. Characterization
The crystal structures of the products were characterized using
an automated X-ray powder diffractometer (XRD, PANalytical‘s
Empyrean) with monochromated CuKa radiation (l=1.54056 Å).
The particle sizes and structural characteristics of the as-
synthesized products were determined using a transmission
electron microscope (TEM-FEIG-4020, 500 kV) and a high-resolu-
tion field emission scanning electron microscope (FESEM-Hitachi
SU8000). The samples were ultrasonicated in distilled water before
128 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133
Fig. 1. (a) XRD patterns of bare ITO electrode, bare GO, and graphene-modified and
N-graphene-modified ITO electrodes; (b) XRD patterns of the Ag-G-modified and
Ag-NG-modified ITO electrodes.
Fig. 2. (a) FESEM image of N-graphene on an ITO substrate after EPD; (b) and (c) low- and high-magnification FESEM images of the Ag NDs coated on the N-graphene-
modified ITO electrode after electrochemical deposition.
the TEM and FE-SEM characterizations. X-ray photoelectron
spectroscopy (XPS) analysis was carried out using an ESCALAB
MK II X-ray photoelectron spectrometer with Mg as the excitation
source. Raman spectroscopy was performed using a Renishaw
Invia Raman Microscope instrument with laser excitation
(l = 514 nm). Electrochemical measurements were performed with
a potentiostat/galvanostat (Autolab PGSTAT30) from Ecochemie
(Netherlands).
3. Results and discussion
3.1. Crystal structures
Fig. 1(a) presents the X-ray diffractograms of GO and of the
graphene-modified and N-graphene-modified ITO electrodes after
EPD. An intense and sharp diffraction peak for GO appears at
2u = 9.8 , which is attributed to the (001) lattice plane, corre-
sponding to an interlayer d-spacing of 0.90 nm between the
stacked GO nanosheets [16]. As a comparison, after the microwave
irradiation of GO, the diffractogram shows the disappearance of
this strong peak and the appearance of a (002) peak at 2u = 32.62
and 31.58 , corresponding to d-spacings of 0.27 and 0.28 nm for
graphene and N-graphene, respectively [24,25]. This result
suggests that the GO was reduced to graphene sheets during
the microwave-assisted process, with the removal of the functional
groups. Moreover, the downshift of the (002) peak from graphene
to N-graphene indicates that the interlayer spacing in N-graphene
was enhanced as a result of the nitrogen doping. The crystal
structures of the Ag-G-modified and Ag-NG-modified ITO electro-
des at -0.6 V after 30 min of electrochemical deposition are
 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133 129

Fig. 3. (a and b) TEM images of Ag NDs deposited on an N-graphene-modified ITO electrode (the inset (b) is the TEM image of an individual Ag ND).

illustrated in Fig. 1 (b). The remaining peaks at 2u values of 38.115 ,

44.229 , 64.443 and 77.397 can be indexed to the (111), (200),
(220) and (311) lattice planes, respectively, of the cubic structure of
electrodeposited Ag (JCPDS card no. 01–087-0597), with the lattice
constant a = b = c = 4.086 Å. Moreover, the appearance of the high
intensity peak of the (111) plane indicates dendritic growth along
the (111) plane of cubic silver. The ratios of the peak intensities of
(111)/(200) and (111)/(220) of Ag-NG are 3.16 and 6.25, respec-
tively, and are higher than the conventional values viz. 2.5 and 4.0.
This result is due to the formation of a non-spherical morphology
of Ag [26].

3.2. Morphology and chemical composition

Fig. 2(a)shows an FESEM image of the N-graphene-modified ITO

electrode before the deposition of Ag NDs. As shown, the surface of
the N-graphene thin film is highly smooth, while the typical wrinkles
and ripple-like features are slightly visible. A representative FESEM
image of AG NDs are shown in Fig. 2(b), which demonstrates a well
ordered dendritic nanostructure. Figs. 2(c) and (d) present the FESEM
images of the electrochemically deposited Ag NDs on the N-
graphene-modified-ITO electrode. Fig. 2 (c) clearly shows that the as-
deposited Ag NDs are uniformly embedded in the N-graphene
surface; however, a number of Ag NDs protrude from the edges of the
N-graphene sheets. Furthermore, the higher magnification FESEM
image in Fig. 2(d) clearly reveals the presence of small gaps between
the individual Ag NDs and N-graphene nanosheets. This porous
structure could facilitate gas diffusion and ionic transport for
enhancing the electrochemical reduction of H2O2. Further investi-
gation of the composite morphology was performed using TEM. Fig. 4. The Raman spectra of GO, graphene and N-graphene.
130 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133
Figs. 3(a) and (b) present TEM images of the Ag-NG composite
after its removal from the ITO electrode by ultrasonication. As can
be seen, the N-graphene sheets show crumpled silk veil waves due
to the local stress induced by the loss of oxygen and the
introduction of nitrogen in the N-graphene structure. Moreover,
Fig. 3(b) clearly shows that the as-fabricated Ag-NG composite
electrode consists of a large amount of dendritic structures.
Furthermore, the Fig. 3(c) and (d) present a representative TEM
image of Ag NDs. As shown, the individual Ag ND has an elegant
two-dimensional dendritic structure with long trunks and
uniformly arranged parallel branches. The side branches are
symmetric and form an angle of approximately 70 . th the trunk.
Moreover, the diameters of the trunk and the side branches are
approximately 1 mm and 400 nm, respectively.
Raman spectroscopy is a powerful technique for investigating
the structural and electronic properties of carbon compounds.
Fig. 4 shows the Raman spectra of pristine GO and of the Ag-G-
modified and Ag-NG-modified ITO electrodes, where the D, G and
2D bands are centered at approximately 1359, 1587 and 2681 cm
1,
respectively. In addition to these three peaks, the Ag-NG-modified
ITO electrode presents a weak D0 band located at 1628 cm
1 [27].
The G band arises from the in-plane bond stretching of the C-C sp2
bond, whereas the D and D0 bands (activated by inter-valley and
intra-valley double-resonant Raman process, respectively) are
associated with the various types of defects, such as vacancy-like
defects and sp3 defects, that can be produced by oxidation and
hydrogenation, grain boundary edges, domain boundaries and
electron doping [27]. Notably, although both the D and D0 bands are
activated by defects, the nature of these defects differs. Nitrogen
doping in the graphene lattice leads to the presence of a D0 band in
the Raman spectrum of Ag-NG. The presence of a D band in the
Raman spectra of both Ag-G and Ag-NG indicates that the densities
of defects in these samples are similar due to the introduction of
vacancies during the microwave-assisted process.
In contrast, the intensity of the 2D band (activated by a two-
phonon double-resonant Raman process) is reciprocal to the
electron-hole scattering rate [28]. Moreover, the intensity ratios of
the D to G band (ID/IG) in GO and in the Ag-G-modified and Ag-NG-
modified ITO electrodes are 0.61, 0.74 and 0.79, respectively,
Fig. 5. (a) XPS spectrum of GO and N-graphene; (b) the high-resolution C1s spectrum of GO; (c) and (d) the high-resolution C1s and N1s spectra of N-graphene.
indicating an increase in the density of defects in graphene and N-
graphene after the microwave-assisted reaction and nitrogen
doping. However, the intensity of the 2D band in pristine GO is
higher than that in the Ag-G-modified and Ag-NG-modified ITO
electrodes; thus, the intensity ratio of the 2D to G band (I2D/IG)
decreases from 0.28 for GO to 0.19 and 0.17 for Ag-G and Ag-NG,
respectively, which is further support for the increase in the defect
density and successful reduction of GO. Note that the intensity of
the 2D band is reciprocal to the electron-hole scattering rate. Thus,
nitrogen doping creates defects in the graphene lattice, which
leads to an increase in electron-hole scattering and a decrease in
the 2D band intensity.
To further investigate the chemical composition and nitrogen
content in N-graphene, X-ray photoelectron spectra (XPS) are
presented in Fig. 5. The wide-scan spectra of GO reveals the
presence of carbon and oxygen, and the presence of nitrogen in N-
graphene clearly indicates that nitrogen was successfully doped
into the graphene lattice during the reduction of GO. The spectrum
of GO exhibits the C1s peak at 283.2 eV and the O1s peak at
531.6 eV [20]. The calculated C:O atomic ratio is approximately
0.69. However, after the microwave-assisted reduction with
hydrazine, the intensity of the O1s peak significantly decreased
and the C:O atomic ratio reached 3.31, indicating a successful
reduction of GO. Moreover, the N1s peak at 400 eV is clearly
observed in the N-graphene spectrum with a N:C atomic ratio of
0.17. The oxygen functionalities on the surface of GO and N-
graphene are identified by deconvoluting the C1s peak into three
different regions. As shown in Fig. 5b, the high-resolution C1s
spectra of GO can be deconvoluted into two different strong peaks
at 284.6 and 286.9 eV, which are assigned to C-C epoxide and C-O
hydroxyl groups, respectively[20], and the weak peak at 288.8 eV is
attributed to the O-C&9552;O bond of GO [20]. In addition, the C1s
spectrum of N-graphene exhibits the same oxygen groups as for
GO, but with a considerable decrease in the intensity of the
oxygenated carbons (C-O and O-C&9552;O) in the higher energy
region (286–290 eV) after the microwave-assisted process in the
presence of hydrazine, confirming the effective recovery of the
p-electron system of graphene, as shown in Fig. 5c [20].
Deconvolution of the N1s peak of N-graphene can provide detailed
 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133 131

information on the nitrogen functional groups. As shown in Fig. 5d,

the N1s peak can be deconvoluted into three different regions at
398.4, 400.2 and 402.6 eV, which are assigned to three different
types of N-containing groups: pyridinic N, pyrrolic N and oxidized
nitrogen, respectively [20]. Pyridinic N are the N atoms at the edges
of the graphene planes, each of which is bonded to two carbon
atoms and donates one p-electron to the aromatic p-electron
system. Pyrrolic N are the N atoms that are bonded to two carbon
atoms and contribute two p-electrons to the p-electron system,
whereas oxidized nitrogens are the oxidized pyridinic nitrogen
atoms, which are bonded to two carbon atoms and one oxygen
atom.
Nitrogen adsorption-desorption analysis reveals typical Bru-
nauer–Emmett–Teller specific surface areas (SBET) of 462 m2 g
1 for
the Ag-NG electrode, with an average pore size of  32 nm, which is
higher compared to that of the pure N-graphene (316 m2 g
1 and
25 nm) (Fig. 6). This result could be due to the roughened N-
graphene surface with the presence of Ag NDs.

3.3. Enhanced electrocatalytic activity for H2O2 reduction

The electrochemical detection of H2O2 was performed on the

Ag-NG-modified ITO electrode, and Fig. 7(a) presents the cyclic
voltammograms (CVs) of bare ITO, graphene-modified ITO, N-
graphene-modified ITO, Ag NDs-modified ITO and Ag-NG-modi-
fied ITO in N2-saturated 0.1 M PBS at pH 7.2 in the presence of
1.0 mM H2O2. It can be clearly observed that the bare ITO electrode
has the weakest response for the detection of H2O2. In contrast, the
N-graphene-modified ITO electrode exhibits a remarkable catalyt-
Fig. 7. (a) CVs of the bare ITO and graphene-modified, N-graphene-modified and Ag
ic peak current density of approximately 5.6 mA cm
2 at -0.7 V in NG-modified ITO electrodes; (b) CVs of the Ag-NG-modified ITO electrode at
the presence of H2O2, which is considerably higher than that of the different scan rates in N2-saturated PBS (0.1 M, pH 7.2) in the presence of 1 mM
bare ITO, graphene-modified ITO and Ag NDs-modified ITO H2O2.
electrodes. However, the Ag-NG-modified ITO electrode has the
strongest response among the five electrodes, with the lowest and form oxygen-containing groups when exposed to air during
onset reduction potential of -0.40 V and highest current density the microwave-assisted process. Therefore, the structural defects
peak of approximately 7.61 mA cm
2 for H2O2 reduction. This and oxygen-containing groups catalyze the reduction of H2O2.
result demonstrates that both nitrogen doping in the graphene Furthermore, the background current of N-graphene-modified ITO
lattice and the presence of Ag NDs can improve the electrocatalytic is higher than that of Ag NDs-modified ITO electrode which may be
activity of graphene toward H2O2 reduction. Additionally, no attributed to the large surface area of the N-graphene- modified
obvious reduction current is observed for the Ag-NG-modified ITO ITO electrode. It should be noted that the reduction peak current of
electrode in the absence of H2O2. H2O2 at the bare ITO, graphene-modified ITO and N-graphene-
The reason for the enhancement of electrochemical detection of modified ITO is very low compared to the AG NDs-modified ITO
H2O2 by N-graphene compared to graphene may be attributed to electrode. An obvious reduction peak of H2O2 at the Ag NDs-
the increase in structural defects and oxygen-containing groups modified ITO electrode is observed at -0.35 V, which illustrates the
due to the incorporation of nitrogen into the graphene lattice excellent catalytic activity for the reduction of H2O2 by the Ag NDs.
during the microwave-assisted process. As shown in Fig. 2c and However, the reason for the enhanced reduction of H2O2 in Ag-NG
Fig. 4, the microwave-assisted process creates more structural
defects on graphene, which leads to an enhancement in the
amount of unsaturated carbon atoms at the graphene edge sites.
These unsaturated carbon atoms are very reactive toward oxygen

Fig. 6. Nitrogen adsorption-desorption isotherms of Ag-NG and N-graphene (the Fig. 8. Typical amperometric curve of the Ag-NG-modified ITO electrode in N2
inset shows the pore size distribution). saturated PBS (0.1 M, pH 7.2). Inset: calibration curve.
132 M.T. Tajabadi et al. / Electrochimica Acta 151 (2015) 126–133
Table 1
Summary and a comparison of the present work with previous reports in the literature regarding the performance of the H2O2 assays.
Type of electrode Limit of detection (mM)
Ag NPs-NFs/GCE 62
Ag NPs-MWCNT/Au 0.5
Ag NPs-Polypyrrole/GCE 0.57
N-graphene/GCE 0.05
Prussian blue/GCE 100
Polyaniline/Palladium/GCE 2.6
Au/CNT/Polyaniline/GCE 0.4
graphene/Ag/ITO 5 0.1–100
N-graphene-Ag NDs/ITO 0.26
compared to N-graphene could be due to the increase in the
surface area of N-graphene with the presence of Ag NDs. According
to the BET results (Fig. 6), the deposition of Ag NDs on N-graphene
sheets effectively increases the total surface area of N-graphene
accompanied by the formation of large numbers of porous
channels in the Ag-NG composite. Therefore, O2 gas and OH

anions could be readily transported through these channels while
Ag NDs facilitates the detection of H2O2. Therefore, the Ag-NG
electrode shows the best performance as a H2O2 sensor.
The catalytic activity toward H2O2 reduction was examined by
performing cyclic voltammetry at different scan rates to investi-
gate the sensitivity of the Ag-NG-modified ITO electrode. Fig. 7(b)
shows the CVs of the Ag-NG-modified ITO electrode in a
N2-saturated 0.1 M PBS solution at pH 7.2 with 1 mM H2O2 at
different scan rates; the peak currents increase linearly as the scan
rate increases from 10 to 100 mV s
1. Moreover, the reduction peak
is shifted slightly to negative potentials. This could be assigned to
changes in the electrocatalytic activity and kinetic effect of Ag-NG-
modified ITO surface on the reduction of H2O2. Therefore, the
results illustrate that the electrochemical reduction of H2O2 on the
AG-NG-modified ITO electrode is a surface-controlled process [29].
Fig. 8 presents the amperometric responses of the Ag-NG-modified
ITO electrode in a N2-saturated 0.1 M PBS solution at pH 7.2 with
successive additions of H2O2 at an applied potential of -0.40 V vs.
Ag/AgCl. Well-defined steady-state current responses at the
Ag-NG-modified ITO surface are obtained after each addition of
H2O2, and the maximum current responses are recorded within 2 s,
demonstrating the rapid current response of the electrochemical
sensor. The inset of Fig. 8 shows the calibration curve of the current
and H2O2 concentration. The Ag-NG-modified ITO electrode
displays a linear increase as the concentration increases from
100 mM to 80 mM, with a correlation coefficient of 0.9989 and
detection limit of 0.26 mM at a signal-to-noise ratio of 3. The linear
regression equation can be expressed as I (mA) = 88.47
(mAmM
1cm
2) + 5.348. Moreover, the amperometric response
to 1 mM H2O2 in PBS (0.1 M, pH 7.2) was obtained over a continuous
45 min period. The response of the Ag-NG-modified ITO electrode
remained stable throughout the entire experiment, with only 4.3%,
8.6% and 11.2% decreases in current at 10, 30 and 48 min,
respectively. The reproducibility of the modified electrode was
evaluated by measuring the current response to H2O2 under the
same conditions. The relative standard deviation (RSD) of the
current response to 1 mM H2O2 was 4.1% for 6 successive
determinations. All of these measurements indicate that the Ag-
NG-modified ITO electrode exhibits good stability and reproduc-
ibility for the electrocatalytic reduction of H2O2 and that the
electrochemical performance of this sensor is comparable with
that of sensors based on other materials, as shown in Table 1.
It is worth mentioning that the most important achievement of
this work is the use of ITO as a cheap substrate compared to the
GCE and a facile electrophoretic deposition method for the
Sensitivity(mAmM
1) Linear range (mM) References
0.1–80 [30]
––
1.42 0.05–17 [31]
4.477 0.1–90 [32]
0.005–1.2 [33]
––
60 mAmM
1cm
2 10
5–10 [34]
66 mAmM
1cm
2 0.01–7 [22]
152.29 mAmM
1cm
2 0.22–8.82 [35]
[36]
––
88.47 mAmM
1cm
2 0.1–80 This work
fabrication of the sensor electrodes. Indeed, electrophoretic
deposition can be a substitute for other methods for the
preparation of the sensor substrate from carbon materials,
conductive polymer and other organic materials, in the fabrication
of sensor electrodes based on conductive polymer-metal compos-
ite or other organic-metal composite electrodes.
4. Conclusion
N-graphene nanosheets with N:C atomic ratios of up to
0.17 were successfully synthesized at low temperature using a
simple microwave-assisted process and were grown on ITO using
EPD. In the second step, Ag NDs were deposited on the
N-graphene-modified ITO electrode via electrochemical deposi-
tion for the fabrication of a H2O2 sensor. As an advanced sensor
electrode, the Ag-NG-modified ITO electrode exhibited improved
electrochemical performance compared to pure N-graphene-
modified and graphene-modified ITO electrodes. The improved
electrochemical response is attributed to the enhanced surface
area due to the layered structure of N-graphene and the roughened
surface from the presence of Ag NDs on N-graphene. The response
of the as-fabricated electrochemical sensor was rapid, stable and
reliable with a detection limit of 0.26 mM in the range from 100 mM
to 80 mM.
Acknowledgements
The authors would like to thank MOHE and the University of
Malaya for providing financial assistance for this work under grant
numbers UM.C/HIR/MOHE/ENG/21-(D000021-16001), FP033-
2013A and F000009-21001, and RP005B-13AET.
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