Sensors and Actuators B 236 (2016) 311317

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Determination of nitrite in tap water: A comparative study between

cerium, titanium and selenium dioxide doped reduced graphene
oxide modied glassy carbon electrodes
Dalibor M. Stankovic a, , Eda Mehmeti b , Janez Zavasnik c , Kurt Kalcher b
a

Innovation center of the Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, Serbia
Institute of ChemistryAnalytical Chemistry, Karl-Franzens University Graz, A-8010 Graz, Austria
c
Center for Electron Microscopy and Microanalysis, Jozef Stefan Institute, Ljubljana, Slovenia
b

a r t i c l e

i n f o

Article history:
Received 3 December 2015
Received in revised form 27 May 2016
Accepted 1 June 2016
Available online 2 June 2016
Keywords:
Cerium dioxide
Titanium dioxide
Selenium dioxide
Reduced graphene oxide
Nitrite ion

a b s t r a c t
In this work, a comparative study between three different novel synthesized materials, cerium, titanium and selenium dioxide doped reduced graphene oxide, was done toward detection of nitrite in tap
water. It was found that best response and analytical performance were achieved with acerium dioxide
reduced graphene oxide modied glassy carbon electrode. The materials were synthesized and characterized with transmission electron microscopy (TEM), electrochemical impedance spectroscopy and
UVvis spectroscopy. The prepared electrode has a wide linear range from 0.7 to 385 M witha detection
of 0.18 M using amperometric detection. Various parameters were optimized and the sensor was successfully applied for the nitrite ion quantication in tap water samples. Inclusion of different dopants in
the graphene structure for novel materials to modify solid electrodes was found to enhance the catalytic
effect toward nitrite detection.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Nitrite salts of different metals are naturally present in environment, natural water and in food. Nitrites have found wide
application in various industries. In food production nitrites are
usually used as food preservative (E250) and in others elds of
industry nitrites are used for inhibition of corrosion processes in
big water industrial units [14]. These salts are present in the soil,
sometimes in high quantity, which can cause their presence in
high level in natural waters [3]. The potential metabolites of nitrite
could be N-nitroso compounds, which possess carcinogenic effect
[46]. Nitrites also can cause different health implications such as
gastric and nasopharyngeal problems when people are seriously
exposed [79]. Due to these facts a development of a fast, simple,
cost-effective, selective and sensitive method for its quantication
is very important. Numerous methods have been reported in the
literature dealing with nitrites quantication, such as spectrophotometric methods [10,11], ow methods [12], chemiluminescence
[13] as well as electroanalytical methods [4,1422].

Corresponding author.

E-mail address: dalibors@chem.bg.ac.rs (D.M. Stankovic).

http://dx.doi.org/10.1016/j.snb.2016.06.018
0925-4005/ 2016 Elsevier B.V. All rights reserved.

Electroanalytical methods offer all advantages of one analytical procedure to be promising for quantication of species present
in the environment. Different solid electrodes, now widely used,
are manufactured from materials such as platinum, silver, gold and
different types of carbon. However, they possess some disadvantages such as passivation of the surface and notable background
currents, and due to these facts in recent years chemically modied electrodes are still gaining ground in electroanalysis [2325].
A proper selection of the electrode material can strongly improve
important parameters for the electroanalytical procedure, such as
sensitivity, selectivity and background current.
Recently the application of reduced graphene oxide decorated
with differentnanomaterials has been reported for the detection
of various analytes from the environment, food and biological
uids [16,2528].Titanium dioxide in combination with reduced
graphene oxide and copper was reported by Hasan et al. for the photoelectrochemical reduction of CO2 [29], as well as for dopamine
sensing [30]. Due to date, there is no data about possible application
of cerium dioxide and selenium dioxide doped reduced graphene
oxide.
In this study, we aimed to investigate theapplication of novel
synthesized materials based on reduced graphene oxide for the
quantication of nitrite in water.The introductionof different oxide
materials in the reduced graphene oxide structure showed to

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D.M. Stankovic et al. / Sensors and Actuators B 236 (2016) 311317

improve its characteristics especially with respect tosensitivity and

selectivity. Important parameters for the analytical procedure have
been optimized and successfully applied for nitrite ion detection in
tap water.
2. Experimental
2.1. Reagents
Highly pure water (resistivity >18 M cm, MilliQ, Millipore) was
used for the preparation of all solution used in this study. Analytical grade reagents were used. They were obtained from Sigma
Aldrich (if not stated otherwise) and used as received without
further purication. Britton-Robinson buffer solution (BRBS) was
prepared by mixing boric acid, acetic acid and phosphoric acid in
the concentration of 0.04 M. Graphene oxide was purchased from
ACS Materials.
2.2. Apparatus
All electrochemical measurements were done with a potentiostat/galvanostat (Autolab PGSTAT 302N, Metrohm Autolab B.V.,
The Netherlands) controlled by the corresponding electrochemical
software (Nova 1.9). The electrochemical cell with a total volume
of 10 mL was equipped with a glassy carbon (GC) working electrode (plain or modied), an Ag/AgCl (saturated KCl, all potentials
reported in this paper are referred versus this electrode) as the reference and a Pt wire as the counter electrode. All measurements
were done at an ambient temperature. The pH of the BRBS was
adjusted with 0.5 M sodium hydroxide using an Orion pH meter
(model 1230) equipped with a combined glass electrode. UVvis
absorption spectra were recorded by using a VARIAN spectrophotometer in the wavelength range from 200 to 800 nm.The structure
and chemistry of the samples were studied using a 200-kV transmission electron microscope (TEM; JEM-2100, Jeol Inc.) equipped
with a LaB6 lament and an energy-dispersive X-ray spectrometer
(EDS). The micrographs were recorded with a high-resolution slowscan CCD camera (Orius DC1000, Gatan Inc.). Powdered synthesized
samples were dispersed in DMF, while GO was dispersed in water,
and transferred onto commercially available Cu grids (200 mesh Cu
holey carbon, SPI Supplies/Structure Probe, Inc.).
For cyclic voltammetry the potential was swept in the range of
01.5 V at the scan rate of 50 mV/s (if not stated otherwise) and this
was used for selection of pH of the supporting electrolyte as well
as for the investigation of the nature of the electrochemical reaction at the new electrode surface. For detection of nitrite ion as an
electrochemical technique, amperometry was selected. All amperograms were recorded at a constant potential of +1.0 V, which is
selected from previous measurements. The limit of detection (LOD)
was calculated according the equation:
LOD = 3 xintercept /slope.

2.3. Synthesis of the electrode materials

Novel materials were synthesized by modifyingthe previously
described procedures for synthesis of similar materials [2628].
According to these procedures the metal oxide is produced in situ
on the surface of graphene oxide, followed by reduction of such
hybrids. In the procedure here the metal oxides were directly
added to a solution containing graphene oxide and such hybrids
were reduced by glucose and Zn foils. All three selected doping
materials for reduced graphene were tetravalent oxides of metals,
titanium, cerium and selenium, abbreviated as TiOrGo, CeOrGo and
SeOrGo, respectively. In 5.0 mL of graphene oxide suspension with

Fig 1. Electrochemical response in absence (dotted line) and presence (solid lines)
of 1 mM of nitrite ion at various modied GC electrode in BRBS at pH 4.2, scan rate
50 mV/s.

a concentration of 1 mg/ml (this suspension was ultra-sonicated

for 3 h before use) a 2.3 104 M of metal oxide was added and
ultra-sonicated for more 2 h. After that 50 mL of glucose solution (2000 ppm) were added together with Zn foils and heated
for 30 min at 75 C with continuous stirring. After cooling the suspension to room temperature followed by removal of Zn foils the
obtained material was collected by centrifugation, washed three
times with water and dried. For comparison the reduced graphene
oxide without dopant (metal oxide) was prepared following same
procedure.
2.4. Preparation of the modied electrodes
The obtained crude materials were weighed, suspended in DMF
(dimethylformamide) to a of 8 mg/ml and ultra-sonicated for 1 h. It
was found that this concentration provides best response for nitrite
oxidation (data not shown) and was used in all further experiments. The surface of glassy carbon electrode was polished with
0.3 and 0.05 m alumina powder, washed with water and sonicated for 10 min in nitric acid followed by washing with water.
Then 10 L of the suspension was pipetted on the electrode surface and dried at room temperature. Before use, the suspensions
were ultra-sonicated for 12 h. Hand mixing or vortexing did not
provide satisfactory results.
3. Results and discussions
3.1. Electrochemical behavior of the modied electrodes
The cyclic voltammograms of nitrite in BRBS at pH 4.2 show
that highest current was obtained cerium dioxide/reduced graphite
oxide(CeOrGo, Fig. 1). The increase in the current obtained with
CeOrGo, calculated after background current subtraction is around
100%in comparison with rGo and SeOrGo, and around 30% compared to TiOrGo. From Fig. 1, it can be concluded that the other
electrodes do not show well-dened and oval-shaped peaks for the
nitrite oxidation. These results can be correlated with UVvis spectra of all materials which are presented in Fig. 2A. It is obvious that
whenSeO2 was used as a dopant there is no change in the absorption
spectra in comparison with reduced graphene oxide. In case of titanium and cerium dioxide doping a high decrease inthe visible part
of spectra is observed, which is attributed to the presence of dopant
in material structure. A strong decrease of absorbance is correlated
with inclusion of metal oxides inthe reduced graphene structure

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313

Fig. 2. A) UVvis spectra of the nanomaterials. Inset gure present solutions obtained after synthesis of nanomaterials; B) Impedance plots of () CeO2 rGO, () rGO, ()
SeO2 rGO, () TiO2 rGO and () graphene oxide modied GC electrodes for 1 mM [Fe(CN)6 ]3/4 in 1.0 M KCl.

Fig. 3. TEM micrographs; a) reduced graphene oxide in DMF (left) and graphene oxide in water (right) showing increased contrast due to scattering of electrons on increased
thickness due to folding; SAED patterns show identical crystallography. b) Reduced graphene oxide in DMF with well-developed tetragonal CeO2 nano-particles, evenly
distributed over graphene foil. c) Reduced graphene oxide in DMF with scarce SeO2 particles. SAED pattern indicate agglomerates of larger single-crystal grains. d) Reduced
graphene oxide in DMF with TiO2 nano-particles, well-distributed over graphene sheets. SAED pattern corresponds to a mixture of anatase with minor amount of rutile.

[2628]. From the color of the synthesized materials (inset of Fig. 2)

it can be concluded that in the presence of selenium dioxide the
reduction process is occur toward reduction of selenium dioxide
rather then graphene oxide, and the color of the nal solution is
yellow-brown, similar to the starting color of the graphene oxide
suspension. A brown-red color on the Zn foils leads to the same
conclusions (data not shown). Selection of the appropriate metal
oxide and its incorporation in the reduced graphene oxide structure
increases its activities as it is shown in Fig. 1. The electrochemical
impedance spectroscopy (EIS) was employed to depict the surface
features of the modied electrode using the redox probe 1 mM

[Fe(CN)6 ]3/4 containing 0.1 M KCl, in the frequency range

105 0.1 Hz, at potential of 0 V and amplitude of 5 mV, and the result
is shown in Fig. 2B. The Nyquist plot was tted using the Randles equivalent circuit (insert of Fig. 2B). As can be seen from this
gure, the obtained results implied that the charge transfer resistance of the electrode surface decreases and the charge transfer rate
increases upon using the different modied electrodes (Table 1).
These results are indicating that application of reduced graphene
oxide in the composition of the electrode strongly improves the
response of the sensor, which is attributed to the high specic area
of the used materials that helps extraction of the target ions into
the surface of the electrode.

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D.M. Stankovic et al. / Sensors and Actuators B 236 (2016) 311317

Table 1
Results obtained from EIS measurements.
Element/Value

GO

rGO

CeO2 rGO

TiO2 rGO

SeO2 rGO

R1
WoR
WoT
WoP
Rct
C

180
269000
6.65
0.588
105
3,7E-7

1000
225000
6.6
0.394
1000
3,11E-7

1000
180000
8.8
0.405
48
6,2E-7

150
120000
12
0.405
100,5
6E-7

480
100000
80.5
0.305
4500
4,65E-7

The results obtained for the electrocatalytic effect exerted by

the studied materials toward nitrite oxidation can be associated
to the Ce4+ which is a very strong oxidant. Since the oxidation of
nitrite ion takes place at a more positive potential than the oxidation of Ce3+ to corresponding Ce4+ , the most probable pathway is a
chemical oxidation of nitrite by Ce(IV) which in turn is reduced to
Ce(III). This is also in accordance with a report describing the direct
titrimetric determination of nitrite with Ce(IV) [31]. Consequently
the trivalent cerium is electrochemically oxidized to its tetravalent
state again. As the aim of this work is to investigate the applicability
of the materials under consideration for nitrite quantication, from
all results, it can be concluded that CeOrGo modied GC electrode
presents promising material and for further studies this electrode
was used.
In the TEM images (Fig. 3) the thin layers of graphene are stable
under electron beam; but the thin individual layers are transparent
and can beseenonly in strong defocus or when folded (Fig. 3a, right
image). The presence of metal-oxide particles, mixed with reduced
graphene oxide, was conrmed by EDS analysis while their crystal structure was identied by selected-area electron diffraction
(SAED) patterns. Investigation of the graphene samples doped with
SeO2 revealed up to 100 nm large irregularly shaped monocrystals
and agglomerations, scarcely distributed on graphene sheets, while
TiO2 and CeO2 particles were 530 nm in size, with well-developed
crystal faces. The discrepancy of the SeO2 -doped sample from the
othersconrmsits different behavior during synthesis of the metaloxide particles already, which is also in accordance with UVvis
results.

3.2. Effect of pH and different scan rates toward nitrite oxidation

at CeOrGo modied GC electrode
When novel materials are involved as new electrode modiers,
in the current case CeOrGo, for the quantication of selected compounds, optimization of various experimental conditions presents
an important part which strongly inuences the nal electroanalytical characteristics. Selection of appropriate pH of BRBS was done
in a pH range from 2.4 to 6.0, as it is shown in Fig. 4. It can be concluded that the best analytical response, taking in account the peak
current as well as the peak shape, was found for the pH value of
3.4. A further increase of the pH causes a broadening of the peak
and a slight decrease of the peak current. Also, from these measurements it is obvious that with this electrode linear dependence in
the studied pH range was not observed as an indication of no proton
participating in the oxidation reaction of nitrite ion. The pH of 3.3
represents the equilibrium dissociation constant (pKa ) of HNO2 , so
this can explained these obtained results.
At the selected pH, the electrochemical behavior of nitrite was
studied with CV at a CeOrGo modied GC electrode with scan
rates from 10 to 300 mV/s. The representative voltammograms
are shown in Fig. 5.It is obvious that the peak current gradually
increased with increasing of the scan rate in this range, and this
dependence possesses satisfactory linearity for a plot ofpeak cur-

Fig. 4. Cyclic voltammogramsin theabsence (dotted line) and presence (solid lines)
of 1 mM of nitrite ion at aCeOrGo modied GC electrode in different pH of BRBS.
Scan rate 50 mV/s.

Fig. 5. Cyclicvoltammograms obtained for 1 mM of nitrite ion at a CeOrGo modied

GC electrode with scan rates of 10, 25, 50, 75, 100, 150, 200 and 300 mV/s in BRBS
at pH 3.4; the inset represents the plot of current versus square root of scan rate.

rent versus square root of scan rate (inset of Fig. 5), where the
corresponding linear equation can be expressed as
I(A) = 6.737 + 1.279 v1/2 (mV/s)1/2 , R 2 = 0.988.
According these ndings it can be stated that the electrocatalytic oxidation of nitrite on the surface of the modied electrode
is controlled by diffusion.
3.3. Amperometric response of nitrite ion on CeOrGo modied GC
electrode
Amperometric detection was selected for the quantication of
nitrite ion due to its characteristics which lies in selectivity, sensitivity and simplicity. Amperometric measurements were done at
aconstant potential, which was selected from previous measurements, at a value of +1.0 V in BRBS at pH 3.4. Fig. 6A shows a typical
amperogram obtained for different concentrations of nitrite. A
corresponding calibration curve was constructed by plotting theoxidation peak current against the concentration of nitrite (Fig. 6B). It
was found that the modied electrode gives a linear response in a
wide range of concentration from 0.7 to 385 M with corresponding regression equation
2.3(A) = (0.0756 0.0003)c(M) + (0.5183 0.0487)

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315

Fig. 6. A) Amperogram of nitrite registered with a CeOrGo modied GC electrode at a potential of +1 V in BRBS at pH 3.4; B) Calibration curve obtained plotting obtained
current versus concentration of nitrite ion.

The calculated regression coefcient, R2 , for this study was

equal to 0.9994, which conrms our hypothesis that proposed electrode possess excellent possibilities toward nitrite ion oxidation.
The limit of detection was estimated as 0.18 M. If we compare
the LOD for a glassy carbon electrode modied only with reduced
graphene oxide it was estimated as 1.4 M.Thus it is clear that the
use of CeO2 as a dopant in rGo strongly enhances its characteristics,
as it is already shown with the cyclic voltammetric experiments.
Table 2 shows a comparison of LOD values obtained by different
electrode materials. The corresponding value of the CeOrGo modied GC electrode is lower or comparable with those previously
reported in the literature [1422], again conrming that the novel
synthesized material represents a promising alternative for other
electrode materials.
The repeatability, expressed as relative standard deviation (RSD)
of the 8 replicative measurements, with the same electrode, was
determined for 2, 25 and 250 M of nitrite and shows values of 3.8,
2.7 and 1.4%, respectively. The reproducibility, also expressed as
RSDs, for these concentrations with ve separately prepared electrodes was estimated to be 4.2, 2.9 and 2.2%, respectively. Also,
intra- and inter-day studies were done during ve days using the
same concentrations of nitrite ion. Forboth parameters RSD values
of the peak currents were lower than 4%. From all these results it can
be clearly conrmed that the present material posseses excellent
characteristics for application in electroanalysis.

3.4. Interferences studies

The selectivity of the analytical procedures belongs to the group
of important parameters for its consideration to the application in
the analysis of samples. The electrochemical response of the sensor was investigated in the presence of most common cations and
anions present in water which may cause interferences in the determination of nitrite. Fig. 7 presents an amperogram recorded with a
CeOrGo modied GC electrode with addition of the analyte and of
selected interferences. For each of the tested species it was considered that they strongly interfere if they provoked current changes
more than 10%. It can be seen that almost all of tested interferences
do not cause an electrochemical response in 200-fold excess. However, the presence of sulte causes anincrease in peak current. It
was found that the tolerance level, which did not cause a change in
the peak current was evaluated to be 10-fold excessfor sulte. Such
a concentration level of sulte is not expected in tap water. From
these studies it is obvious that the proposed method provides satisfactory selectivity and can be successfully applied for water sample
analysis.
3.5. Analytical application
In order to investigate the capability for practical application
of the proposed analytical method with the modied electrode the
concentration of nitrite was determined in three different tap water

Table 2
Methods for the voltammetric and amperometricdetermination of nitrites.
Electrode

Technique

LOD

Linear range

Reference

ZnO/Pt NPS on MWCNTs

Fe2 O3 @MoS2 nanocomposite
carboxylated graphene oxide/lanthanum
graphite/-cyclodextrin composite
Prussian blue-carbon paste electrode
Gold nanoparticles/MWCNTs
Gold nanoparticles decorated on cobalt porphyrin
Clay/porphyrin
3,6-bis(2-[2sulfanyl-ethylimino-methyl]-4-(4-nitro-phenylazo)phenol)pyridazine coated SiO2@Fe3O4
(L-SCMNPs)
CeOrGo

Differential pulse voltammetry

Amperometry
Amperometry
Amperometry
Amperometry
Square wave voltammetry
Amperometry
Square wave voltammetry
Square wave anodicstrippingvoltammetry

82 nM
1 M
0.07 M
0.26 M
9 M
0.01 M
60 nM
0.5 M
0.625 M

4 107 2 104 M
26370 M
12.75 103 M
0.7 M2.15 mM
251000 M
0.05250 M
0.5 M4.7 mM
1250 M
/

14
15
16
17
18
19
20
21
22

Amperometry

0.18 M

0.7385 M

This work

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D.M. Stankovic et al. / Sensors and Actuators B 236 (2016) 311317

Reference:

Fig. 7. Typical amperogram obtained for nitrite with occasional addition of different
interfering species. The conditions are same as in Fig. 5.
Table 3
Resultsa obtained for determination of nitrite ion in tap water under optimized experimental conditions with CeOrGo modied GC electrode and recovery
experimentsb .
Sample

Found (M)

Added (M)

Found (M)

Recovery(%)

1
2
3

0.00
0.00
0.00

3.00
5.00
7.00

3.10 0.11
5.05 0.17
7.10 0.24

103
101
101

a
b

n=3
recovery was calculated as: NO2 found /NO2 added 100%.

samples. The samples were collected, diluted with supporting electrolyte in ratio 1: 3 (sample/electrolyte) and stored at 4 C before
use. Results were calculated from the calibration curve and recovery experiments were done to examine any matrix inuence. All
results were done in triplicate and mean values from this study are
given in Table 3. The recovery values obtained from these results
and the datafrom all the studiespresented aboveare leading to the
conclusion that the CeOrGo modied GC electrode seems to be
promising for commercial exploitation as a solid electrode for the
determination of nitrite.
4. Conclusions
In this work a comparative study between three novel synthesized materials based on the oxides of tetravalent cerium, titanium
and selenium in combination withreduced graphene oxide was
done for the detection of nitrite ion in tap water samples. The best
analytical response was obtained with a glassy carbon electrode
modied with cerium dioxide-doped reduced graphene oxide.
Materials were characterized with UVvis spectroscopy, electrochemical methods and transmission electron microscopy. Under
optimized operational conditions the proposed sensor possesses
satisfactory selectivity and sensitivity, a low limit of detection
(0.18 M) and a wide linear range from 0.7 to 385 M.
Acknowledgments
This work was supported by the Ministry of Education and
Science of the Republic of Serbia (project No. OI 172030) and
JoinEU-SEE-Penta Erasmus Mundus scholarship. E.M wishes to
acknowledgement Higher KOS Stipendien, nanced by ADA and
MEST and Austrian Agency for International Cooperation in
Education and Research (OeAD-GmbH), Centre for International
Cooperation & Mobility (ICM).

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Biographies
Dr Dalibor M. Stankovic research interest is electroanalytical chemistry and
electrochemistry of bilogical active compounds, application of novel materials
for modication of electrodes and its application in environmental analysis and
biomedical analysis. He is authored and coauthored around 60 publication in this
topic.
Eda Mehmeti is PhD student at the University of Graz, dealing with research in the
eld of chemical sensors and biosensors and application of novel electrode materials
in biomedical application.
Janez Zavasnik is researcher at the Jozef Stefan Institute, Ljubljana, Slovenia.
Research interested is focused on the material characterization and possible application in different elds of chemistry.
Prof. Kurt Kalcher is head of Sensors and electroanalysis group at the University
of Graz. He is authored and coauthored more than 200 publication in the eld on
electroanalytical chemistry, novel materials and biosensors.