Sensors and Actuators B 263 (2018) 237–247

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Sensors and Actuators B: Chemical

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

Correlating surface growth of nanoporous gold with electrodeposition

parameters to optimize amperometric sensing of nitrite
Abhishek Kumar ∗ , Josué M. Gonçalves, Anandhakumar Sukeri, Koiti Araki,
Mauro Bertotti ∗
Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, 05508-000 São Paulo, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Nanoporous gold (NPG) films were electrodeposited on a gold substrate and the generated platform was
Received 13 November 2017 used for amperometric determination of nitrite. The electrochemical characterization of different NPG
Received in revised form 14 February 2018 surfaces showed that the electrocatalytic activity concerning the nitrite anodic oxidation is strongly mod-
Accepted 16 February 2018
ulated by changes in the electrodeposition parameters. Microstructural analysis using scanning electron
Available online 20 February 2018
microscopy, profilometry and X-ray diffraction revealed changes in the deposited layers, following a
unique growth mechanism strongly dependent on applied potential and electrodeposition time. Accord-
Keywords:
ingly, more negative potentials resulted in changes in morphology from highly branched standing flakes
Nanoporous gold
Amperometric sensors
to flat dense surfaces, whereas higher electrodeposition times led to the evolution of nanodendrites. NPG
Electrodeposition electrodes prepared by electrodeposition at −4 V for 100 s were selected as the best platform for nitrite
Food quality-control determinations at 0.77 V. Evaluation of sensing characteristics demonstrated the sensor exhibits a very
Thin films fast response time (<4 s), a detection limit of 10 nM and two linear ranges (1–110 ␮M and 110–2000 ␮M)
Electrochemistry with sensitivity values found to be 0.02 ␮A ␮M−1 cm−2 and 0.012 ␮A ␮M−1 cm−2 , respectively. Other ana-
lytical properties such as reproducibility, selectivity and long term stability were also investigated and
the results showed the fabricated sensor has favorable features for detection of nitrite in real samples, as
demonstrated in experiments involving successful nitrite determinations in meat and lake water samples.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Nitrite is a ubiquitous pollutant in modern society as it has
adverse implications on human health and surrounding environ-
ment. In particular, because of the excessive use as preservative
in meat, processed foods and beverages, nitrite can pose a seri-
ous health risk [1]. Excess nitrite in our body can interact with
hemoglobin forming methaemoglobin by oxidizing ferrous iron
(Fe2+ ) into ferric state (Fe3+ ), which inhibits the ability of blood
to transport oxygen, a condition described as methaemoglobi-
naemia [2]. Besides, nitrite can combine with amines and form
N-nitrosamines, which are carcinogenic compounds as mentioned
by the International Association for Research on Cancer (IARC) [3].
According to the World Health Organization (WHO), the permitted
level of nitrite in drinking water should not exceed 0.9 ppm [4]. The
United State Food and Drug Administration (USFDA) standard for
the allowed limit of nitrite in processed meat is 200 ppm [5]. Tak-
∗ Corresponding author.
E-mail addresses: abkumar@iq.usp.br (A. Kumar), mbertott@iq.usp.br
(M. Bertotti).
ing these guidelines into account, methods for sensitive detection
and quantification of nitrite become an imperative task. Normative
methods for nitrite determination are mainly based on spectropho-
tometry [6,7], chemiluminescence [8], chromatography [9,10] and
electrophoresis [11]. Although these methods are highly sensitive
and selective, there are limitations intrinsic to the measurement
techniques, restricting their wide scale and real-time applications.
Different exploratory approaches have been continuously pro-
posed to overcome the challenges of conventional methods. Among
them, electrochemical methods are a logical choice because of the
electroactive nature of nitrite. Moreover, cost-effectiveness, ease
of operation, large linear range and competitive detection perfor-
mance in comparison to normative modes [12] make them more
attractive.
The electrochemical detection of nitrite can be achieved by oxi-
dation as well as by reduction, but the later remains a less preferred
choice because of interference from dissolved oxygen and nitrate.
In researches reported so far, different types of electrodes have
been used, but the sensitivity towards nitrite is marred by high
overpotential and low current on bare electrode surfaces. Such
problems can be alleviated by modifying the working electrode

https://doi.org/10.1016/j.snb.2018.02.125
0925-4005/© 2018 Elsevier B.V. All rights reserved.
238 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247
surface with a suitable electrocatalyst. A wide range of materi-
als have been investigated as electrode modifiers to facilitate the
electron transfer process involving nitrite, including N-4 macrocy-
cles like metalloporphyrins and metallophthalocyanines [13,14],
organic polymers[15], metals and their oxides [16,17]. Nanomate-
rials have also been used for the fabrication of attractive platforms
for nitrite sensing, including metal nanoparticles [18,19], carbon
nanomaterials [20] and hybrid nanocomposites [21]. These mod-
ified electrodes have shown high sensitivity (detection limit in
the ␮M range), large linear range and good selectivity for nitrite
determination. In the same direction, our endeavor is to improve
further different sensing characteristics by using nanoporous gold
as a novel platform.
The electrochemical deposition of nanoporous gold on a solid
substrate has been an intensive area of research in recent years.
Such facile technique offers a fine control over the growth and
nucleation mechanism, which determines the grain size and the
morphology of the deposited NPG, which in turn strongly influ-
ences its electrochemical activity. Among the methods investigated
so far to synthesize NPG, dealloying [22,23] and Dynamic Hydro-
gen Bubble Template (DHBT) [24,25] approaches have drawn a lot
of attention. DHBT assisted growth implies synchronous evolution
of hydrogen and reduction/deposition of metal ions in solution on
the working electrode surface. The size and the rate of evolution of
hydrogen bubbles can provide a dynamic template for depositing
metal atoms thus generating porous materials with 3-D nanoar-
chitectures. In particular, parameters such as deposition potential
and time strongly influence porosity, grain size and density of the
films [26], consequently altering the electrochemical interaction
with targeted analytes. In fact, better suited platforms for sensor
applications can be generated by optimizing the electrodeposition
parameters.
Accordingly, a systematic study was performed in the present
work to fabricate NPG modified gold electrodes using the DHBT
method, which were subsequently tested for the electrooxidation
of nitrite. The NPG sensor giving optimum performance was identi-
fied by intercomparison of the electrocatalytic role. Microstructural
and surface characterizations of different NPG surfaces were carried
out to understand the evolution of nanostructures on chang-
ing electrodeposition parameters and their implication on nitrite
oxidation. The modified electrode exhibiting optimized electro-
catalytic activity was employed as a sensor for the amperometric
determination of nitrite. Different quantitative sensing character-
istics as well as analytical properties were thoroughly analyzed and
compared with those of previously reported electrochemical sen-
sors. Finally, the proposed sensor was applied to determine nitrite
in real samples. The novelty of this work comes at first with the
selection of DHBT assisted growth of NPG for generation of a new
platform for nitrite analysis, with substantial improvement in ana-
lytical performance. Secondly, efforts have been made to interlink
electrodeposition parameters, growth mechanism and electrocat-
alytic activity.
2. Experimental section
2.1. Materials
All the chemicals used in this study were of analytical grade and
used without any further purification. Solutions used throughout
the work were prepared with Milli-Q ultrapure water (resistiv-
ity ∼ 18 M cm). NaNO2 , Phosphate Buffer Saline (PBS) tablets,
HAuCl4 . 3H2 O and H2 SO4 were purchased from Sigma-Aldrich, ACS
reagent. PBS solutions at pH ∼ 7.4 were prepared by dissolving one
tablet into 200 mL water. 0.1 M NaNO2 stock solution was prepared
in PBS solution.
2.2. Electrochemical setup
All electrochemical experiments were performed in a PGSTAT-
128N Autolab Metrohm equipment interfaced with Nova 11.1
software. A conventional three-electrode cell was constructed
including gold, Ag/AgCl (sat. KCl) and platinum as working, refer-
ence and counter electrodes, respectively. The working electrode
used was a commercial gold disk electrode purchased from
Metrohm Autolab. The geometric area of the working electrode was
0.070 cm2 . After each experiment, the gold electrode was cleaned
by polishing with alumina slurry (0.05 ␮m) and sonication for
10 min. All electrochemical experiments were carried out at room
temperature.
2.3. Preparation of nanoporous gold
Nanoporous gold was electrodeposited at a fixed applied
potential in a three-electrode cell using a strongly stirred 5 mM
AuCl4 − solution in 0.5 M H2 SO4 . Evolution of current during each
electrodeposition was continuously monitored, which remained
approximately constant at a given applied potential. All electrode-
positions were performed at open atmosphere in the absence of
external gas bubbling and at room temperature. Two sets of exper-
iments were carried out: a) NPGs were electrodeposited at applied
potentials of −1 V, −2 V, −3 V and −4 V at a fixed time of 100 s; and
b) at constant applied potential of −4 V varying the deposition time
(100 s, 200 s, 400 s and 600 s). Afterwards, the fabricated NPG mod-
ified gold electrodes were washed with water and dried at room
temperature open to air. In all the electrodepositions, utmost care
was taken to keep the working electrode at exactly the same posi-
tion relative to the rotating magnetic bead. The reference electrode
was positioned close to the working electrode in the electrochem-
ical cell and far from the counter electrode (where gas generation
is expected to occur).
2.4. Structural and optical characterizations
The surface morphology of the NPGs electrodeposited in differ-
ent conditions was investigated using a JEOL JSM-FEG 7401F SEM
equipment. Images were recorded at accelerating voltage of 2 kV
using different magnifications while maintaining a horizontal scan
of the surface. ImageJ software was used to estimate the distribu-
tion of pore sizes, grain boundaries and scaling of the images.
The roughness of NPG samples deposited on gold substrate was
examined by using a Dektak Stylus profilometer on a 2 mm scan
window.
Crystallographic orientation of the deposited layers was
assessed by X-ray diffraction (XRD) performed in a table top Bruker
D2 Phaser X-ray diffractometer equipped with a Cu K␣ source
(␭ = 1.5418 Å), in the 2␪ 30–90◦ window, using a scan step of 0.05◦ .
Purity of the electrodeposited NPG films was ascertained by
performing elemental analysis using Energy Dispersive X-ray Flu-
orescence (EDXRF) spectroscopy with an EDX720 instrument from
Shimadzu, equipped with a X-ray tube with Rh target and a Si(Li)
detector. The instrument was operated at a voltage of 50 kV in a
current range 117–378 ␮A with X-ray collimated with 1 mm colli-
mator and maintained in atmospheric air environment.
UV–vis measurements were carried out using a Hewlett Packard
8453A diode-array spectrophotometer with a 1 nm slit width
and 0.1 nm accuracy. Spectra were recorded in the range of
190–1100 nm using 10 mm quartz cuvette.
2.5. Determination of nitrite
Cyclic voltammetry (CV) was used for the characterization of the
electrochemical behavior of the different NPG electrodes prepared
 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247
in this work. CVs were recorded in 0.5 M H2 SO4 solution, in a poten-
tial range from 0.2 to 1.6 V, at a scan rate of 50 mV s−1 . Studies on the
electrooxidation of nitrite were conducted in a 0.1 M PBS solution
in a potential range from 0 to 0.9 V, at a scan rate of 50 mV s−1 .
Amperometric measurements were carried out to get the cali-
bration curve of the nitrite sensor in the 1 ␮M to 2 mM range, in
continuously stirred solutions. Aliquots of a standardized nitrite
solution were successively added to the electrochemical cell con-
taining PBS after a flat baseline current was reached. The nitrite
content in real samples such as processed meat (purchased from a
local supermarket), lake water (collected from the Ibirapuera Park,
São Paulo city) and tap water was determined by amperometry
using the standard addition method, and the results were validated
by spectrophotometric measurements based on the Griess method
[27]. Briefly, 10 g of meat sample (hot dog and pork sausage) were
crushed and homogenized followed by addition of 12.5 g of satu-
rated borax solution [28]. Then, 300 mL of hot water was added
and the mixture heated in a water bath maintained at 70 ◦ C for
20 min. After cooling, 2.5 mL of a 30% ZnSO4 solution was added
dropwise to precipitate proteins, the upper fattiness removed and
the remaining solution filtered. 100 mL of the filtrate was con-
centrated to 10 mL, transferred to a syringe and passed through a
Glass Fiber/PolyEthylene Terephthalate (GF/PET) 45/25 filter before
carrying out the amperometric and colorimetric analysis. The selec-
tivity of the sensor was further assessed by adding some selected
compounds to the measurement cell at a concentration 50 times
higher than the one of the target analyte.
3. Results and discussion
3.1. Optimization of electrodeposition parameters
3.1.1. Electrochemical characterization of NPG films
The NPG films generated by deposition at −1, −2, −3 and −4 V
for 100 s, and at −4 V for 100, 200, 400 and 600 s on gold elec-
trode surfaces were characterized by cyclic voltammetry in 0.5 M
H2 SO4 solution, in the 0.2–1.6 V range, and scan rate of 50 mV s−1 , as
shown respectively in Fig. 1a and c. Anodic waves characteristic of
the formation of gold oxide were observed in all voltammograms
during the forward scan, whereas metallic gold was regenerated
in the reverse potential scan. The presence of two anodic peaks
for the NPG modified electrode at 1.19 and 1.40 V, respectively,
was attributed to oxidation on gold (110) and (111) surfaces [29],
whereas the additional peak at 1.28 V may suggest the emergence of
a new crystalline plane in electrodes prepared using longer depo-
sitions times, even though polycrystalline gold exhibits only one
peak in the positive potential scan [30,31]. In fact, the nanoporous
structure seems to be strongly dependent on deposition potential
(Ed ) and depositions times (td ), resulting in enhanced peak currents
as the td increases and the Ed becomes more negative. This can be
attributed to the increasing surface area as the nanoporous struc-
tures build-up, but other factors such as the exposed crystalline
phase also seems to influence significantly the sensitivity towards
nitrite oxidation.
3.1.2. Nitrite sensitivity with changing deposition parameters
The electrochemical activity of different sets of NPG modified
electrodes towards the oxidation of nitrite was investigated by
cyclic voltammetry in a potential range from 0 to 0.9 V in 0.1 M
PBS solution (pH ∼ 7.4). Fig. 1b and d show the CVs recorded with
bare and NPG modified gold electrodes, prepared with increasing
Ed and td , in a 2 mM nitrite solution. The inset of Fig. 1d depicts
the CV of the modified electrode in the absence of nitrite. All mod-
ified electrodes presented an anodic peak close to 0.77 V (except
for td = 600 s), assigned to the oxidation of nitrite to nitrate, with
239
a 100 mV shift in overpotential as compared to the bare gold elec-
trode. Moreover, the oxidation wave is sharper and more intense,
indicating faster electron transfer processes as expected for mod-
ified electrodes with a significant electrocatalytic activity. These
observations clearly indicate that NPG modified electrodes possess
energetically favorable active sites, whose number is dependent
on the deposition parameters (Ed and td ). The small cathodic peak
noticed in Fig. 1d results from the reduction of the gold oxide layer
formed during the oxidation scan, as confirmed by the presence of
a similar peak in the CV recorded in the absence of nitrite, as shown
in the inset of Fig. 1d.
The correlation between changes in peak potential (Ep ) and peak
current (ip ) for different NPG modified electrodes was investigated
in depth by analyzing data from Fig. 1. Accordingly, values for such
parameters were plotted in Fig. 2 as a function of Ed and td . It can
be noticed that peak potential is almost unaffected by varying Ed
and td , except for the longer td (600 s), where Ep was shifted to
more positive potential values. On the other hand, peak currents
were strongly modulated by the electrodeposition parameters. For
instance, an initial decrease and then a linear increase in peak cur-
rent values were observed upon an increase in Ed towards more
negative values. A similar situation was observed for electrodepo-
sition time, i.e., a monotonic exponential increase in peak current
as a function of td . A comprehensive structural and morphological
characterization of fabricated NPG films is presented in the next
section to understand the changes in electrocatalytic properties
with electrodeposition parameters.
A shift in overpotential towards 0 V to get more selectivity and
an enhancement in peak current in order to increase the sensitivity
are among the most desired characteristics of an electrocatalyst.
However, additional features including low capacitive currents are
highly important to ensure low detection limit values, as well as
fast response time and wider range of linear operation. Taking the
limit of detection parameter into account, in spite of exhibiting a 7-
fold enhancement in peak current for nitrite oxidation as compared
to bare gold electrode, the NPG electrode prepared with td = 600 s
is not a suitable choice as supposed at first glance because of the
very high capacitive current associated with its large surface area
[32] (see Fig. 1d). Hence, the NPG fabricated at −4 V for 100 s was
selected as the best platform based on the shift in peak potential,
peak current and relatively low capacitance. Moreover, electrode-
position with lower periods of time consumes less gold from the
precursor solution, which gains significance considering the high
cost of gold.
3.2. Structural characterization of NPG layers
3.2.1. Surface morphology
Changes in morphology of as-deposited NPG on a gold sub-
strate were investigated by SEM. Fig. 3 shows SEM micrographs
of an uncoated gold substrate and different NPG electrode sur-
faces recorded in a wide range of magnifications. Clear differences
in micrometric as well as nanometric structures can be observed
as the Ed becomes more negative, and longer td are employed.
Changes in NPG surface features can even be noticed in less mag-
nified images on a few ␮m scale, as shown in Fig. S1, such as in
surface roughness and porosity. The emergence of a honeycomb
shape, which is a typical feature of films prepared by DHBT elec-
trodeposition method [33,34], can be observed in Fig. S2 for less
magnified SEM images and longer td . The lateral structure of the
deposits was imaged by cross-sectional SEM, as shown in Fig. 4a,
and one can confirm that highly porous microcrystallites with a
range of pore sizes constitute the NPG inner structure.
At low Ed of −1 V, elongated shrub structures popularly known
as Dense Branch Morphology (DBM) [35], characterized by dense
arrays of branches of gold flakes forming a flat circular front grow-
240 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247

Fig. 1. CVs of NPG modified electrodes prepared at different Ed and a fixed td (100 s) (a), at fixed Ed (−4 V) and different td (c), and uncoated gold electrode (inset of c) recorded
in a 0.5 M H2 SO4 solution. CVs recorded with the same NPG modified electrodes in a 2 mM nitrite + 0.1 M PBS solution at different Ed and a fixed td (100 s)(b) and at fixed Ed
(−4 V) and different td (d). CV of NPG modified electrode (−4 V for 100 s) in 0.1 M PBS (inset of d). Scan rate = 50 mV s−1 .

Fig. 2. Changes in peak current and peak potential values extracted from CVs recorded with NPG modified electrodes prepared at different Ed (td = 100 s) (a) and td (Ed = −4 V)(b)
in a 2 mM nitrite + 0.1 M PBS solution. Scan rate = 50 mV s−1 .

ing in the axial direction, can be seen. This arrangement makes
the surface highly porous with a wide distribution of micropores
of different sizes. Because of the axial growth of branches, the
surface appears to be very rough with deep surface-height steps.
By increasing the applied potential to more negative values, the
standing branches collapsed and a dense biphasic surface emerged.
A similar transformation in the morphology of gold nanoplates
was previously reported [36]. The predominant phase represents
a highly condensed surface plane over which porous islands were
developed. The black patches on the surface represent dense aggre-
gates of gold, as seen in a magnified image (Fig. S1f). The overall
surface is more compact and less porous, as compared to the one
obtained at −1 V. Further enhancement in the negative Ed to −4 V
led to increase in the number of porous islands on a denser under-
neath layer. Moreover, the porosity of islands and their height tend
to increase as compared to the surface obtained at −2 V. Fig. 3h
and f reveal the reduction in the nanometric grain size and change
in their shape from aggregated square flakes to cauliflowers-like
structures for more negative Ed . Pore sizes of a few nanometers
can be noticed at the grain boundaries. The evolution of hierarchic
micrometric and nanometric structures in NPG with increasing td
time at a constant Ed is obvious when Fig. 3a, d and e are com-
pared. A clear transition in morphology was observed when the
td was increased to 200 s, as the entire surface was covered with
highly porous islands in which the density and sizes of the pores,
as well as their heterogeneity, are much higher in comparison to
the NPG obtained at a lower td (100 s). Further increase in td to
600 s generated new layers over a fully porous film underneath,
with the formation of three-dimensional dendrites on the top sur-
face. These dendrites were well dispersed and presented secondary
and tertiary branching, as shown in Fig. 3g.
3.2.2. Roughness, purity and microstructure of the NPG surfaces
Changes in the surface of NPG electrodes prepared by varying
Ed and td were further examined by surface profilometry measure-
ments, as shown in Fig. 5a and b. It can be noticed that the variation
in surface step heights is much more influenced by td than by Ed .
As indicated in Fig. 5b, the NPG prepared with td = 600 s presents
 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247 241

Fig. 3. SEM images of as-prepared NPG surfaces prepared on gold substrates at applied potentials of −4 V for 100 s (a), −2 V for 100 s (b), −1 V for 100 s (c), −4 V for 200 s (d)
and −4 V for 600 s (e). High magnification images are shown for NPG surfaces prepared at applied potential of −4 V for 100 s (f), −4 V for 600 s (g), −1 V for 100 s (h) and an
uncoated gold substrate (i).

Fig. 4. Cross-sectional SEM image (a) and EDXRF spectrum (b) of as-prepared NPG surfaces prepared on gold substrates at an applied potential of −4 V for 100 s.

very high surface steps with wide gaps, which is a typical feature
of honeycomb-like structures, as observed in SEM images (Fig. S1e
and S2a). The height of the steps can be a good estimate to assess the
depth of the surface pores, which become both bigger and deeper
with increasing td , a characteristic of DHBT deposition. The rough-
ness pattern of surfaces prepared at −1 V shown in Fig. 5a reveals
homogeneous distribution of high and widely separated surface
steps, which is also in agreement with the SEM image (Fig. 3c). The
reduction in surface steps heights at −2 V clearly suggest the for-
mation of a denser film. The non-homogeneous roughness pattern
of the NPG surface developed at −4 V is a result of the growing of
porous islands on a smooth layer, as seen in SEM Image 3a. Hence,
surface topography measurements support the prediction given by
the SEM images. The thickness of the NPG films was estimated by
subtracting average values of surface step heights of bare substrate
and the NPG film, as highlighted in the profilometry pattern shown
in Fig. S3. Resulting values for different NPGs are given in Table 1.
As expected, thicker films were obtained by increasing td . In con-
242 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247

Fig. 5. Surface profile recorded for NPG surfaces with change in Ed at constant td (100 s) (a) and at constant Ed (−4 V) for different td (b). XRD pattern of as-deposited NPG
(Ed = −4 V and td = 600 s) on a gold substrate and the uncoated gold substrate in the range of 10–90◦ using Cu K-␣ X-ray (1.54 A◦ ) (c).

Table 1 Information on the microstructures and crystallographic orien-

Thickness of different NPG films deposited on a gold substrate determined by pro-
tation of the crystallites forming the NPG layers was assessed by
filometry measurements.
XRD studies. Fig. 5c depicts the background corrected XRD pat-
Electrodeposition Electrodeposition Thickness (␮m) tern of as-deposited NPG on a gold substrate compared with XRD
potential (Ed ) Time (td )
of uncoated gold substrate. The sharp diffraction peaks at 38.35◦ ,
−1V 100s 3.27 44.5◦ , 64.5◦ and 77.6◦ correspond to the (111), (200), (220) and
−2 V 100s 1.76 (311) crystallographic planes of a fcc lattice of gold [JCPDS 04-0784]
−4 V 100s 1.51
[38,39], whereas the emergence of the (200), (220) and (311) planes
−4 V 200s 3.94
−4 V 600s 6.44 in NPG is a clear evidence of the formation of gold nanostructures.
Hence, the appearance of additional peaks in CVs recorded with
the NPG modified electrode in H2 SO4 solution (Fig. 1a and c) can be
explained by the presence of gold crystallites exposing new facets
trast, a reverse trend was observed with increasing applied negative to the solution.
potential because of the decrease in grain size [37]. However, the
film obtained at very high potential (−4 V) has non homogeneous 3.2.3. Growth mechanism and implication on nitrite oxidation
topography as a consequence of the increased nucleation rate and Although a detailed assessment of NPG film growth mecha-
more vigorous hydrogen evolution, which can induce higher uncer- nism is beyond the scope of this work, a concise discussion and
tainty in the calculated thickness value. its impact on the electrocatalytic oxidation of nitrite is presented.
EDXRF elemental analysis was conducted as shown in Fig. 4b to The proposed mechanism is based on the already reported the-
determine the purity of as-deposited NPG films. All peaks observed ory of nucleation and growth. At a relatively low Ed of −1 V, the
in the spectrum correspond to the energies of characteristics X- flux of incoming gold ions towards the substrate surface is not so
rays originating from different atomic shells (L and M) of gold. pronounced, as well as the number of active nucleation sites. At
The results of this experiment also confirm the effectiveness of such experimental conditions, nucleation is predominantly instan-
the selected experimental approach towards the development of taneous, i.e., nucleation sites rapidly attain a value that is constant
highly pure NPG films. in time [40,41]. These conditions favor a ballistic growth [42],
 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247 243

Fig. 6. CVs recorded with an NPG modified electrode (green) and a bare gold electrode (black) in 0.1 M PBS solution containing 0.2 mM nitrite at a scan rate of 50 mV s−1 . The
dotted black curve corresponds to the CV recorded with a bare gold electrode in the absence of nitrite (a). CVs recorded with the NPG modified gold electrode at different
scan rates (5–200 mV s−1 ) (b) and a plot of the influence of scan rate on peak current (c). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

leading to a surface having densely branched morphology [43].
At more negative Ed values, the rate of electron-transfer increases
and the low energy nucleation sites, which were dormant at less
negative potentials, become active. The nucleation process is thus
predominantly progressive, i.e., new nucleation sites are formed
continuously in time. These conditions favor a diffusion limited
aggregation (DLA) growth [44], from which a dense surface is
developed. The coexistence of porous islands on the dense sur-
face is a consequence of hydrogen bubbles evolution, a process that
becomes more vigorous at more negative Ed values.
Changes in the surface with increasing td at a fixed Ed can be bet-
ter correlated with the change in diffusion layer pattern around the
substrate surface. In the beginning of the electrodeposition process,
the substrate surface remains flat and the transport of gold ions
takes place through a planar diffusion layer. With increasing time,
gold atoms are deposited on the surface making it rougher with
many protrusions that will develop localized spherical diffusion
layers. As a consequence, subsequent transport of gold ions from
bulk solution will take place through a matrix of three-dimensional
spherical diffusion layers [45]. Enhanced rates of mass transport
are observed for such nonplanar diffusion to the growing protru-
sions and, if spherical diffusive transport continues for longer times,
dendrites are finally developed.
The growth mechanism has profound effects on the electrocat-
alytic properties of a NPG film towards nitrite oxidation. The initial
peak current decrease by changing Ed from −1 V to −2 V, as shown
in Figs. 1b and 2a, can thus be justified by a decrease in porosity
and surface area because of the collapse of the standing branches
and formation of dense layers. Such decrease in surface area and
porosity is however compensated by the development of porous
islands, whose amount and height increase with more negative Ed
values, leading to an increase in peak current from −2 V to −4 V.
The increase in td leads to the development of more porous surfaces
above a dense layer, and defects continue to grow on the surface
because of enhanced mass transport. These changes in turn increase
the number of electrocatalytic sites, explaining the increased sen-
sitivity for longer td . As a matter of fact, the exponential increase in
peak current for td = 600 s is attributed to the formation of three-
dimensional dendritic structures. Multiple branching as well as
nanopores present within each branch provide a lot of new surface,
edges, kinks and other forms of dislocations, thus exposing more
electrocatalytic sites for the electron-transfer reaction. It should be
pointed out, however, that thicker films retard the electron transfer
process and induce a huge capacitive current.
Based on these considerations, the NPG platform designed by
applying −4 V for 100 s was found to be the ideal one for sensor
applications, since it has an optimum ratio of porous phase and
dense phase. If the porous phase provides electrocatalytic sites for
nitrite oxidation, the thin dense phase ensures low capacitance,
which is an important requirement to achieve higher sensitivity.
3.3. Electrochemical determination of nitrite
3.3.1. General electrochemical characterization
A comparison of the electrochemical oxidation of nitrite at the
optimized NPG modified electrode and a bare gold electrode is
shown in Fig. 6a. The two-fold peak current enhancement and
the 100 mV shift towards less positive potentials demonstrate
the advantages of the proposed platform for nitrite sensing. The
absence of a reduction peak in the reverse scan confirms the oxida-
tion of nitrite is an irreversible process [46,47] that leads to nitrate
through a 2-electron transfer process.
The influence of scan rate on nitrite CVs was examined in the
range from 5 to 200 mV s−1 in 0.1 M PBS and the results are pre-
sented in Fig. 6b. The linear increase in peak current (ip ) with the
square root of scan rate, as shown in Fig. 6c, is an evidence that
the electrochemical process is mass-transport controlled. To fur-
ther assess the presence of any adsorption process, log (ip ) was
244 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247
Fig. 7. Amperometric responses corresponding to consecutive additions of standard solutions of nitrite to a stirred 0.1 M PBS solution using the NPG modified electrode
biased at 0.77 V (a). Calibration plot in the range 1 ␮M to 110 ␮M nitrite (b). Expanded amperometric plot from Fig. a in the range 1 ␮M to 10 ␮M nitrite (c).
plotted as a function of log (scan rate), as shown in Fig. S4. In princi-
ple, slope values of 0.5 or 1 indicate the process to be pure diffusion
or pure adsorption controlled, respectively [48,49]. In our case, the
slope of the linear regression in Fig. S4 was found to be 0.497, con-
firming a purely diffusion controlled process. A slow and gradual
shift of the peak potential can be also noted with increasing scan
rate, and this also corroborates the electrooxidation process to be
chemically irreversible [50].
Experiments on the study of the influence of pH on the
voltammetric behavior of nitrite at the modified electrode were
also performed (Fig. S6). The optimum sensor performance was
observed at pH values close to 7, hence further experiments were
carried out in PBS solutions (pH 7.4) taking into account the pH of
real samples, especially in biological systems.
3.3.2. Amperometric detection
A typical amperometric plot of consecutive additions of nitrite
to a strongly stirred 0.1 M PBS solution at 0.77 V is shown in Fig. 7.
The experiment was designed in such a way that the nitrite concen-
tration in the electrochemical cell changed from 1 ␮M to 1000 ␮M
by adding standardized nitrite solutions of different concentra-
tions. After each nitrite addition, a steep increase in anodic current
and a fast attainment of a steady state condition were observed.
Response time, which is defined in the present case as the time
after which current reached 90% of its final steady-state value
after addition of nitrite, was determined to be less than 4 s. The
change in current with each addition was plotted against the con-
centration of added nitrite in the 1–110 ␮M range, and a linear
relationship between current and nitrite concentration was found
(I(␮A) = 0.243 +0.2 Cnitrite (␮M), correlation coefficient = 0.9997), as
shown in Fig. 7b. The slope of this linear calibration plot relates
to the sensitivity of the sensor, which was found to be 0.02 ␮A
␮M−1 cm−2 taking into account the effective surface area of NPG
electrode ∼10 cm2 . The linearity in sensor response was further
examined in a wide concentration range, from 110 to 2000 ␮M, and
a linear correlation was again achieved, as shown in Fig. S5 (sen-
sitivity of 0.012 ␮A ␮M−1 cm−2 ). The loss of sensitivity at higher
nitrite concentrations can be rationalized as follows: At low analyte
concentrations, a relatively high number of surface active electro-
chemical sites per analyte is available. On the other hand, at very
high analyte concentration, surface sites get saturated and there is
a competition among analyte molecules to occupy favorable active
sites. Hence, sensitivity is higher at low concentrations as compared
to very high concentrations.
Fig. 7c clearly demonstrates the fabricated sensor is highly sen-
sitive to low concentrations of the analyte, as significant current
changes were noticed upon addition of nitrite to give concentra-
tions in the range of 1 ␮M. Such high sensitivity associated with
a very low background signal are responsible for the significantly
low limit of detection (LOD), which was estimated as 10 nM taking
into account a signal to noise ratio of 3. This LOD value is much
lower than the permitted levels of nitrite defined by different envi-
ronmental protection agencies (WHO and USFDA, as explained in
the introduction section).
3.3.3. Selectivity, reproducibility and stability
The selectivity of the NPG modified electrode towards the
amperometric detection of nitrite was investigated for compounds
that usually coexist with nitrite in samples where its detection
is recommended. Hence, PO4 3− , CO3 2− , NO3 − , Cl− , SO4 2− , ClO4 − ,
SO3 2− , ascorbic acid, glucose, ethanol, K+ , Na+ and Ca2+ were added
to a supporting electrolyte solution containing 0.1 mM nitrite. In
this study, the concentration of such possible interfering species
was 50-fold higher than that of nitrite. Fig. 8a depicts current mon-
itoring at 0.77 V during addition of nitrite and the investigated
compounds to a stirred 0.1 M PBS solution and from the results
one can conclude the influence of PO4 3− , CO3 2− , NO3 − , Cl− , SO4 2− ,
ClO4 − , glucose, ethanol, K+ , Na+ and Ca2+ on the sensor response is
negligible. Nevertheless, ascorbic acid (AA) and sulfite are clearly
oxidized at the selected working potential and their exclusion from
examined samples will be a necessary requirement for a precise
amperometric quantification of nitrite. To overcome the sulfite and
 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247 245

Fig. 8. Amperometric measurements performed with the NPG modified electrode biased at 0.77 V during sequential addition of different compounds tested as interferants
(final concentration = 5 mM) and nitrite (final concentration = 0.1 mM) to a stirred 0.1 M PBS solution (a). Amperometric responses for 0.1 mM nitrite recorded with 5 different
NPG modified electrodes prepared by using the same electrodeposition protocol (b). Shelf-life investigation of the NPG modified electrode response as a function of the
storage time (c).*MSG: Monosodium glutamate.

ascorbic acid interference in nitrite determinations, Linear Sweep Table 2

Determination of nitrite in real samples by the proposed amperometric methods
Voltammetry (LSV) can be used as such compounds are oxidized
and by spectrophotometry: (n = 3).
at different potentials compared to nitrite. This can be confirmed
by looking at voltammograms recorded with the NPG electrode in Sample Quantity of NO2 − (ppm)
a 0.1 M PBS solution containing nitrite, AA and sulfite at the same Electrochemical method Spectrophotometric method
concentration (0.4 mM). Fig. S7 shows well discriminated current
Sausage 29.0 ± 0.6 30.6 ± 0.4
peaks corresponding to the oxidation of AA, sulfite and nitrite at Hot dog 12.8 ± 0.4 14.1 ± 0.3
0.10 V, 0.33 V and 0.78 V, respectively. The separation between each Lake water 0.69 ± 0.02 NA
peak is sufficient to assess simultaneous analytical determination Tap water 0.41 ± 0.01 NA
of these three compounds.
The reproducibility of the sensor response was assessed by
calculating the relative standard deviations (RSD) of nitrite mea- samples containing unknown concentrations of nitrite. Accord-
surements performed with 5 different NPG modified electrodes ingly, nitrite determinations were performed in sausage, hot dog,
fabricated using the same electrodeposition parameters. Fig. 8b lake water and tap water by using the standard addition method
shows a bar plot of amperometric responses towards 0.1 mM nitrite and the results are given in Table 2. To estimate the accuracy of our
measured for each NPG modified electrode in 0.1 M PBS and the proposed method, the quantification of nitrite was also performed
RSD was found to be <4%, confirming that very reproducible plat- by the Griess assay, details of which are shown in Fig. S8. A close
forms can be fabricated by careful control of the electrodeposition agreement in measured values of nitrite in meat samples can be
process. noticed at a 95% confidence level, reinforcing the reliability of our
The storage stability of the proposed sensor was investigated proposed method.
by recording the response towards 0.1 mM nitrite after one week The sensing characteristics of the fabricated sensor were com-
intervals of a total period of two months. Between measurements, pared with those of other reported electrochemical nitrite sensors.
the sensor was stored in atmospheric air environment. Fig. 8c The values are better, or at least comparable, in terms of dynamic
shows the storage time effect on the sensor response where a concentration range, working potential and limit of detection, as
decrease of about 30% was noticed after 4 weeks, followed by a shown in Table S1.
slower decline in the next 4 weeks. The decrease in sensor response
over time can be explained by the slow oxidation of NPG surfaces,
4. Conclusions
hence the resulting gold oxide layer may inhibit the electron trans-
fer at the electrode interface [51].
The porous gold nanostructures electrodeposited on a solid gold
substrate are strongly dependent on electrodeposition parameters,
3.3.4. Real sample analysis especially the applied potential and time of deposition, influenc-
To explore the usefulness of the NPG modified electrode in prac- ing the electrocatalytic activity towards nitrite oxidation. Based
tical applications, its sensing performance was validated with real on results of surface characterization experiments, it was estab-
246 A. Kumar et al. / Sensors and Actuators B 263 (2018) 237–247
lished that the film gets denser with more negative potential,
while a more porous morphology was achieved, including nan-
odendrite formation, as the deposition time increased. Changes in
the gold surface were correlated with different growth models and
nucleation processes. Based on electrochemical and surface char-
acterization studies, an NPG platform prepared at −4 V for 100 s
was found to be the most suitable for electrochemical nitrite sens-
ing applications because of a potential shift towards less positive
potentials with enhanced sensitivity. The sensor was employed for
amperometric detection of nitrite and sensitivity and limit of detec-
tion values were found to be 0.2 ␮A ␮M−1 and 10 nM, respectively,
better than most of the nitrite sensors reported so far in the liter-
ature. The modified electrode exhibited good reproducibility and
shelf-life stability in experiments carried out for a prolonged time
(two months). Finally, the applicability of the proposed NPG mod-
ified electrode was successfully confirmed by measuring nitrite in
real samples including processed meat and lake and tap water,
whose results were validated by the spectrophotometric Griess
method.
To further understand the growth mechanism of NPG, elec-
trodeposition on a single crystal gold substrate has been envisaged.
Moreover, a detailed investigation on NPG crystallites size and crys-
tallographic orientation is under development aiming to assess the
implication on the size of the surface pores and the electrocatalytic
activity.
Acknowledgments
This work was financially supported by research grants from
the São Paulo Research Foundation (FAPESP) (2016/07461-1,
2015/20776-9 and 2014/15215-5). Josué M. Gonçalves thanks CNPq
for his doctoral fellowships. We also thank Prof. Antonio C. Seabra
(Laboratório de Sistemas Integrados, POLI-USP) for the profilome-
try measurements. All authors deeply appreciate Central Analytical
facilities of the Institute of Chemistry, USP and Dr. Mario R. Gongora
Rubio, Roberta M. Cardoso and Luciana Wasnievski S.L. Ramos (IPT-
Instituto de Pesquisas Tecnológicas, USP) for carrying out SEM char-
acterizations.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.snb.2018.02.125.
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Biographies
Abhishek Kumar is currently working as a postdoctoral
researcher at São Paulo University, Brazil in Electro-
chemical sensors research group headed by Prof. Mauro
Bertotti. He received his PhD in 2016 at Blaise Pas-
cal University (Clermont-Ferrand, France) under the
supervision of Dr. Christelle Varenne and Dr. Jerome
Brunet. His PhD research was focused on understanding
structure-properties correlation in organic macromolec-
ular materials and their applications in gas sensors
development. He obtained his Master in Nanoscience
and Nanotechnology from the Université Joseph Fourier
(Grenoble, France) and undergraduate bachelor in chem-
istry at Delhi University. His current research interest
encompasses electrocatalytic nanomaterials development intended for sensing and
catalysis application.
Josué Martins Gonçalves is a PhD candidate in chemistry
at the University of São Paulo (USP) at Brazil studying
under Prof. Koiti Araki supervision. He received his BS
in chemistry from the University Vale do Acaraú (UVA)
in 2014 where he conducted research in electroanalyt-
ical chemistry under the supervision of Prof. Murilo S.
S. Julião. His current research interests include applica-
tions of nanomaterials based on metal nanoparticles and
graphene for use in sensor, electroctalysis and energy stor-
age devices.
247
Anandhakumar Sukeri received his PhD from Bharathi-
dasan University, Tamilnadu, India during 2015 and
currently he is a Postdoctoral Research Fellow (FAPESP)
in Electrochemical Sensors and Electroanalytical Methods
Laboratory at the Department of Fundamental Chemistry,
Institute of Chemistry, University of Sao Paulo, SP, Brazil
since 2015. His research interest includes electrochemi-
cal sensor, porous nanomaterials, fabrication of micro and
nanoelectrodes, SECM and electroanalytical chemistry.
Koiti Araki is a full professor at Institute of Chemistry,
University of Sao Paulo, Brazil, since 2006, and principal
researcher of Supramolecular Chemistry and Nanotech-
nology Lab and coordinator of SisNANO-USP. He got the
PhD degree in chemistry from USP in 1994 under the
supervision of Prof. Henrique E Toma. As fellow of the
BID/USP human resources training program, stayed for six
months (1990/1991) at Caltech/USA under the supervi-
sion of Prof. Fred C. Anson. Was a post-doctoral fellow of
the chemistry department of MIT/USA for sixteen months
(1995/1996) under supervision of Prof. Mark S. Wrighton,
and of Institute for Molecular Science, National Institutes
of Natural Science, Okazaki, Japan, under supervision of
Prof. Takuji Ogawa in 2003/2004. His attention is focused on supramolecular coor-
dination chemistry, electrocatalysis, spectroelectrochemistry, and nanotechnology,
particularly the research on and large-scale production of hybrid nanomaterials and
nanocomposites aiming application in electrochemical sensors, water treatment,
and theragnostics.
Mauro Bertotti received a B.Sc. from the Institute of
Chemistry of the University of São Paulo in 1983 and
became a postgraduate student at the same institution,
where he received his M.Sc. (1986) and Ph.D. (1991)
under the supervision of Dr. Roberto Tokoro. For a year
(1995/96), he was a postdoctoral fellow in the group of
Professor Derek Pletcher at the University of Southamp-
ton, UK. At the University of São Paulo he has remained
throughout his career, where he was appointed Full Pro-
fessor in 2008. Since March 2014 he has been the Head of
the Department of Chemistry. His research interests are
Electrochemical Sensors, Microelectrodes and Scanning
Electrochemical Microscopy.