Accepted Manuscript

Construction of core-shell structured nickel@platinum

nanoparticles on graphene sheets for electrochemical
determination of nitrite in drinking water samples

R.M. Abdel Hameed, Shymaa S. Medany

PII: S0026-265X(18)30906-8
DOI: https://doi.org/10.1016/j.microc.2018.10.045
Reference: MICROC 3428
To appear in: Microchemical Journal
Received date: 24 July 2018
Revised date: 8 October 2018
Accepted date: 22 October 2018

Please cite this article as: R.M. Abdel Hameed, Shymaa S. Medany , Construction of core-
shell structured nickel@platinum nanoparticles on graphene sheets for electrochemical
determination of nitrite in drinking water samples. Microc (2018), https://doi.org/10.1016/
j.microc.2018.10.045

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 ACCEPTED MANUSCRIPT

Construction of core-shell structured nickel@platinum nanoparticles on graphene

sheets for electrochemical determination of nitrite in drinking water samples

R.M. Abdel Hameed*, Shymaa S. Medany

Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt

Abstract

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Core-shell structured Ni@Pt nanoparticles were fabricated on graphene [Ni@Pt/Gr] using ethylene
glycol during the reduction step. X-ray diffraction (XRD), transmission electron microscopy (TEM) and

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electrochemical studies were applied to characterize this synthesized nanocomposite. Ni@Pt/Gr
electrode demonstrated an enhanced electrocatalytic activity towards nitrite determination in relation to

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that at Pt/Gr. The catalytic rate constant value at Ni@Pt/Gr electrode was 1.92 times higher than that at
Pt/Gr. Linear calibration curves were measured at Pt/Gr and Ni@Pt/Gr electrodes in nitrite
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concentration range of 10 M15 mM. The corresponding sensitivity values of Pt/Gr and Ni@Pt/Gr
electrodes were 33.04 and 85.18 A mM1 cm2. The prepared nanocomposite could successfully
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estimate nitrite concentration in drinking water samples.

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Keywords

Electro-oxidation; nitrite; nickel; platinum; core-shell structure.

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Corresponding author:
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E-mail: randa311eg@yahoo.com (R.M. Abdel Hameed).

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1. Introduction

As a result of the carcinogenic effect of nitrite, it is essential to accurately determine its concentration in
food samples. Nitrite is highly poisonous. When it is present in food, it could react with amines and
amides in human stomach to form nitrosamines. Nitrite could also combine with blood pigments to form
meta-hemoglobin causing oxygen deficiency in living tissues. The concentration of nitrite in natural
water could be considered as an estimate for the extent of pollution [13]. Nitrite is applied to inhibit the

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corrosion of carbon steel pipelines in tap water [4]. Based on the World Health Organization reports, the

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allowed concentration of nitrite ions in pickled food and drinking water should not exceed 0.2 mg kg1
and 3 mg L1, respectively. The deadly dose of nitrite absorption in the stomach is between 8.7 and 28.3

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µmole L1 [5].

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Electrochemically, there are two possible routes for determining nitrite either by anodic oxidation or
cathodic reduction. The oxidation method is preferable over the reduction as a result of the interference
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effects of oxygen and nitrates during the cathodic reduction process [6, 7]. Nitrite ions could be oxidized
through the following mechanism:
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NO2 ↔ NO2 + e (1)

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2NO2 + H2O → NO3 + NO2 + 2H+ (2)

Total reaction: NO2 + H2O  NO3 + 2H+ + 2e (3)

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Many research groups have directed to estimate nitrite ions concentration by developing new
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electrocatalyst materials on different electrode surfaces in order to fabricate an amperometric nitrite

sensor with high sensitivity and good selectivity. Zhang et al. [8] have fabricated gold nanowires
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modified electrodes. They showed a rapid response (˂5s) for nitrite oxidation with a linear range of 1
µM0.97 mM at a detection limit of 0.2 µM (S/N=3). The synergistic effect of gold and platinum
nanoparticles in AuPt alloy was responsible for its good electrocatalytic activity towards nitrite
oxidation [9]. Chen et al. [10] have measured high sensitivity values of 16.94 and 4.34 µA mM1 in the
two linear ranges of 1 M24 mM and 24 mM132 mM, respectively for nitrite detection at free-
standing Pt nanowire networks.

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Graphene as sp2 hybrid atoms in a two dimensional lattice network offered many unique properties
including increased specific surface area, strong mechanical strength, high conductivity and improved
electrochemical activity [11]. Good results for nitrite detection in river and lake water samples were
shown at graphene/polypyrrole/chitosan nanocomposite [12]. Jiang et al. [13] have fabricated a new
biosensor based on the immobilization of hemoglobin on graphene-gold nanoparticles. It was examined
for determining nitrite in pickled radish. Good results were achieved in accordance with those reported
by spectrophotometry technique using the National Food Safety Standard. Li et al. [14] have

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investigated worm-like AuPd nanoparticles formed on reduced graphene oxide for nitrite detection.
Good reproducibility, long-term stability and low detection limit of 0.02 M (S/N = 3) were measured.

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Because of the unique properties of noble metal nanoparticles, they were widely used as electrocatalysts
for electrochemical sensing reactions. Platinum nanoparticles, for example, have received a great

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attention among all other noble metals [1518]. Cyclic voltammetry and chronoamperometry indicated
that Pt/graphene electrocatalyst, formed by one-pot hydrothermal method, displayed a linear correlation
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between nitrite oxidation current density and its concentration. High sensitivity of 496.4 μA mM 1 and
low detection limit of 0.1 μM were shown [18]. To overcome the high cost of Pt electrocatalysts, efforts
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were directed to examine the incorporation of cheap metals with decreasing platinum amount during
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their manufacture. Nickel, as a cheap metal, was extensively investigated in many electrochemical
reactions. PtNi nanocomposites were employed in oxygen reduction [19, 20], methanol [21, 22] and
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ethanol oxidation reactions [23, 24] and as a counter electrode material in dye-sensitized solar cells [25].
Rosado et al. [19] have concluded that Pt:Ni atomic ratio in PtNi/MWCNTs electrocatalysts
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appreciably affected their electrocatalytic activity for oxygen reduction reaction. The one containing
Pt:Ni atomic ratio of 1:1.4 exhibited the highest electrochemical performance. Moreover, Suh et al. [20]
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have examined the effect of altering the carbon support of PtNi nanoparticles on their electrocatalytic
behavior. Nanoparticles supported on graphene displayed higher electrocatalytic activity towards
oxygen reduction reaction when compared to those loaded on Vulcan XC-72 carbon black or MWCNTs.
The bifunctional effect and PtNi electronic interaction could account for the improved performance of
Ni@Pt/reduced graphene oxide nanodisks towards methanol and CO electrooxidation [22]. Binary
transition metals of nickel and cobalt were chemically reduced using sodium borohydride on Pt/C and
examined for ethanol and acetaldehyde oxidation reactions [24]. The initial stages of oxidation reaction
were activated by nickel, whereas cobalt could promote the final steps illustrating the co-catalytic effect

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in improving the electrocatalytic activity of fabricated nanocomposite. Ghasemi et al. [25] have
measured an efficiency value of 6.14% and open circuit voltage of 749 mV during the operation of the
dye-sensitized solar cell using PtNi/reduced graphene oxide as the counter electrode.

In the present work, Ni@Pt/Gr nanocomposite was prepared in a core-shell structured protocol using
ethylene glycol as a reducing agent. This could enable the formation of highly dispersed platinum
nanoparticles on the surface of graphene supported nickel core. An increased electrochemical active

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surface area would be predicted giving the chance for an enhanced electrochemical performance of our

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fabricated Ni@Pt/Gr nanocomposite during the investigated nitrite oxidation reaction in phosphate

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buffer solution. Small sized Pt nanoparticles were shown in TEM image of Ni@Pt/Gr nanocomposite
within a short particle size distribution histogram when compared to that at Pt/Gr. This could shed the
light on the role played by these sequential steps during the preparation method in improving the

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physical properties of our prepared Ni@Pt/Gr nanocomposite. A detailed electrochemical study was
carried out including the effect of varying solution pH and the scan rate on the electrochemical behavior
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of Ni@Pt/Gr electrode. Some electrokinetic parameters were estimated during nitrite oxidation reaction
such as Tafel slope, the exchange current density, the catalytic rate constant and the diffusion coefficient
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values of nitrite molecules at the electrode surface. The charge transfer properties of Ni@Pt/Gr electrode
were also examined using electrochemical impedance spectroscopy measurements. The calculated
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sensitivity and detection limit values at Ni@Pt/Gr electrode demonstrated an extraordinary performance
in relation to those at other reported modified electrodes. The combined specific electronic
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characteristics of graphene and unique core-shell structured nanoparticles of nickel-platinum

nanocomposite, in addition to its increased catalytic activity and chemical stability, offered a synergistic
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performance during this nanocomposite evaluation for nitrite assaying in real samples.
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2. Experimental section

2.1. Chemicals

The used chemicals in this work were brought from Sigma-Aldrich. They were applied without the need
to purify them. Double distilled water was used to wash electrodes and prepare solutions.

2.2. Preparation of Ni@Pt/Gr powder

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Hummer’s method was followed to synthesize graphene oxide using natural graphite powder [26]. This
obtained graphene oxide powder could be then reduced to form graphene. In brief, graphite powder was
treated with 5% HCl solution in the first stage. A cold concentrated H2SO4 solution was then added,
followed by inserting drops of KMnO4 under stirring for 2 h inside an ice bath. 30% H2O2 solution was
added together with double distilled water drop by drop to the above mixture increasing its temperature
value up to 38ºC. This formed graphene oxide powder could be collected through filtration, washing
with 10% HCl solution and double distilled water and drying in an air oven at a temperature value of

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50ºC for 12 h. Sodium borohydride was then employed as a reducing agent for graphene oxide into

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graphene using the adopted method by Murat et al. [27]. Here, a certain weight of graphene oxide was

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sonicated in double distilled water for 2 h. pH value of this mixture was raised to 910 by adding drops
of saturated Na2CO3 solution. NaBH4 solution was introduced drop by drop to the above mixture with

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constant stirring at an elevated temperature of 50  5ºC for 24 h. The obtained graphene powder was
then separated by filtration, washing and drying at 40ºC under vacuum.
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Core-shell Ni@Pt/Gr powder was synthesized through two-step method as illustrated in Fig. (1). To
form Ni/Gr as the core part of this powder, 0.1 g sodium citrate and 38 mg NiCl2.6H2O were dissolved
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in 10 mL double distilled water. An appropriate weight of graphene was suspended in this solution. To
reduce nickel ions, 15 mL ethylene glycol was added with adjusting this solution pH at 10 by
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introducing 5 wt.% KOH solution in ethylene glycol with stirring for 30 min. Afterward, this mixture
was sonicated for 30 min and subjected to microwave irradiation into an oven (Caira CA-MW 1025,
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touch pad digital control, 50 MHz, 1400 W) in one continuous mode for 50 s. Ni/Gr powder was filtered
and washed for 6 times with double distilled water. It was further dried into an air oven at 80ºC for 6 h.
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The obtained powder was introduced to a mixture of ethylene glycol, citric acid and hexachloroplatinic
acid to fabricate the shell layer. Drops of 5 wt.% KOH solution in ethylene glycol was then added to
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elevate the mixture pH value to 8 with constant stirring. It was sonicated for 30 min and heated into a
microwave oven for complete metal ions reduction. Filtration, washing and drying steps were operated
to finally obtain Ni@Pt/Gr powder. The added metal weight percentage value was kept as 30 wt.%.
Pt/Gr powder was also prepared using the same above steps for comparing its electrochemical
performance with that of Ni@Pt/Gr.

2.3. Physical and electrochemical characterization of Ni@Pt/Gr nanocomposite

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Ni@Pt/Gr powder could be characterized using XRD and TEM to investigate the crystal structure and
depict the surface morphology, respectively. The (2θ) and (d) values of different diffraction planes of
prepared powder could be accurately determined using Rigaku-D/MAX-PC2500 X-ray diffractometer. It
was working through Ni filtered CuKα as the radiation source with a wavelength value of 0.154056 nm.
The voltage and current values of its tube were 40 kV and 40 mA, respectively. JEOL-JEM 2010
transmission electron microscope was also conducted to describe the surface picture. It was adjusted at
an accelerating voltage of 160 kV. The diameter values of formed nanoparticles were estimated using

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Gatan program. EDX chart of our prepared Ni@Pt/Gr nanocomposite was studied using SEM model

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Quanta 250 FEG (field emission gun) attached with EDX unit with an accelerating voltage of 30 kV.

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The atomic ratio of Pt:Ni could be determined and the elemental mapping pictures of carbon, platinum
and nickel were depicted.

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The electrochemical investigation of electrode activity was run at IM6d.AMOS system (Zahner Elektrik
GmbH & Co., Kronach, Germany). Different electrochemical techniques were employed including
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cyclic voltammetry, linear sweep voltammetry, chronoamperometry and electrochemical impedance
spectroscopy. A three-electrodes cell was constructed. It was formed from Ag/AgCl/KCl (sat.) as the
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reference electrode, Pt wire as the counter electrode, while the working electrode was carbon surface
modified with the formed Ni@Pt/Gr powder. The stated potential values in this work were referred
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versus the used reference electrode. The parameters of electrochemical impedance spectroscopy
measurements were a frequency range of 1×1040.1 Hz and ac voltage amplitude of 10 mV at a constant
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dc potential value. A complex non-linear least squares (CNLS) circuit fitting software was operating to
estimate the corresponding electric circuit parameters through a fitting process for the obtained data
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using a suitable electric circuit model. All electrochemical studies were carried out at room temperature
of 30ºC ± 0.2.
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Before modifying the carbon surface with Ni@Pt/Gr powder, it was polished with soft emery papers,
followed by cleaning its surface through rinsing with double distilled water and acetone. The electrode
ink was prepared by suspending a suitable weight of Ni@Pt/Gr powder in a mixture of isopropyl alcohol
and double distilled water with adding a drop of Nafion solution (5 wt.% in ethanol). This mixture was
sonicated for 30 min before withdrawing 50 L of this ink with fixing at the carbon electrode surface. It
was left to dry overnight before use.

3. Results and discussion

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Figs. (2a, 2b) depicted TEM images of Pt/Gr and Ni@Pt/Gr nanocomposites, respectively. Pt
nanoparticles were clearly observed at graphene support in both images; however, some degree of
agglomeration was noticed in Pt/Gr [see Fig. (2a)]. The diameter of about 200 nanoparticles was
measured and the corresponding particle size distribution histograms were shown in Figs. (2a, 2b).
Although both nanocomposites had the same value of most predominated Pt particle size [2.0 nm],
highly frequent Pt particles in Ni@Pt/Gr had diameter values ≤ 2.0 nm. Pt/Gr, on the other hand, had Pt

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particles with larger diameters up to 2.6 nm. Elsherif et al. [28] have prepared PtNi/Gr nanocomposites

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via polyol process in one-step with comparable Pt particle size of 13 nm. On the other hand, larger Pt
particle size values were measured at PtNi/Vulcan XC-72 carbon black through electroless plating

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[48 nm] [29], PtxNi1x with variable compositions using organic solution approach [5 nm] [30],
colloidal nanocrystal clusters of PtNi by one-pot solvothermal method [78 nm] [31], PtNi

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nanoparticles via galvanic displacement process with chemical reduction reaction [52.6 nm] [32] and
PtNi/SiO2 nanofibers [18.7 nm] [33]. XRD pattern of Ni@Pt/Gr nanocomposite was presented in Fig.
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(3a). It was compared with the standard XRD patterns of carbon, platinum, nickel and nickel oxide
species. The graphite structure displayed a sharp peak at around 25.9º [JCPDS card file no. 411487].
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Moreover, Pt(111) crystal plane was observed at 2 value of 39.13º [JCPDS card file no. 652868]. This
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was in a good agreement with the obtained results at related PtNi nanoparticles in previous reports
[2834]. The deposited nickel appeared in two diffraction planes as metallic nickel and nickel oxide
species at 44.00º and 53.60º to describe Ni(111) [JCPDS card file no. 87–0712] and NiO(004) [JCPDS
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card file no. 021216], respectively. HRTEM image of Ni@Pt/Gr nanocomposite was shown in Fig.
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(3b). It reflected two main features; firstly, some particles definitely showed two layers. The inner part
was dark in color and surrounded by lighter outer layer. This dark core could represent nickel, while
platinum appeared as the outer shell. Lattice fringes with spacing values of 2.11 and 2.30 Å were
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secondly shown [see the inset figure] at the core and edges of formed nanoparticle, respectively. They
have coincided with d spacing values of Ni(002) and Pt(111) planes to ensure the formation of nickel
(core)-platinum (shell) structure in Ni@Pt/Gr nanocomposite. The atomic ratio of Pt:Ni in Ni@Pt/Gr
nanocomposite was calculated by EDX analysis technique. The respective EDX chart was represented in
Fig. (4a). Three characteristic peaks of carbon, nickel and platinum appeared to confirm the successful
synthesis process of our Ni@Pt/Gr nanocomposite. By measuring the atomic ratio of Pt:Ni in this
nanocomposite, it was found to be 1:1.05, which was comparable to the proposed nominal ratio. The

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elemental mapping pictures of carbon, platinum and nickel were depicted in Figs. (4b), (4c) and (4d),
respectively. They revealed nearly equal distribution of platinum and nickel on graphene support.

The electrocatalytic activity of Ni@Pt/Gr electrode towards nitrite oxidation reaction was examined by
applying cyclic voltammetry technique in 0.1 M phosphate buffer solution at pH 4 before and after
adding 10 mM nitrite at 10 mV s1 in Fig. (5a). A silent electrochemical behavior was recorded for
Ni@Pt/Gr electrode when nitrite ions were absent in buffer solution. Accordingly, the appearance of a

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new peak after introducing nitrite ions to buffer solution would illustrate the good electrocatalytic

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activity of Ni@Pt/Gr electrode for electrooxidizing nitrite. At this peak potential, nitrite ions could be

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converted to nitrate ones through two-electrons transfer process [35]. Moreover, the components of this
investigated electrode could also affect this activity. This could be explained by comparing the
electrochemical behavior of our synthesized Ni@Pt/Gr electrode with those of Pt/Gr and Ni/Gr in Fig.

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(5b). It was observed that nitrite ions started to be oxidized at Ni@Pt/Gr electrode at less positive
potential value by 23 mV in relation to that at Pt/Gr. This may be attributed to the presence of nickel in
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Ni@Pt/Gr, where a facilitated nitrite oxidation process was predicted from its lowered onset potential
value. On the other hand, nitrite oxidation current density value at the three studied electrodes was
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arranged in an ascending order as Pt/Gr  Ni/Gr  Ni@Pt/Gr. It could be concluded that combining
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platinum and nickel in such especially arranged structure would offer increased active sites for the
oxidation process resulting in enhanced electrocatalytic performance. Li et al. [14] have examined the
electrocatalytic activity of worm-like AuPd/reduced graphene oxide/glassy carbon electrode towards
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nitrite oxidation in phosphate buffer solution. It displayed an oxidation current density value of 70.7 µA
cm2 that was 14.71 times lower than that recorded at our Ni@Pt/Gr electrode. Ye et al. [36] have also
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measured a lowered oxidation current density at carboxylated graphene oxide/lanthanum/glassy carbon

modified electrode by 2 folds. Jayabal and Ramaraj [37] have fabricated core-shell Au@Ag nanorods
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that were embedded in amine functionalized silicate sol–gel matrix in aqueous solution. The presence of
gold as a core and silver as a shell in this formed composite presented a synergetic catalytic effect during
nitrite ions detection. Liu et al. [38] have demonstrated a nitrite oxidation peak at Fe3O4@Pt core-shell
nanocomposite at more negative oxidation potential and enhanced current density values in relation to
that at Pt. They rationalized this improved behavior to the increased electrochemical active surface area
of Pt nanocomposite after incorporating Fe3O4.

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Nitrite oxidation peak current density value at Ni@Pt/Gr electrode was clearly influenced by pH value
of phosphate buffer solution because this catalytic reaction involved a protonation step. Cyclic
voltammograms of this electrode in 10 mM nitrite in buffer solution at pH values ranging from 3 up to 8
at 10 mV s1 were provided in Fig. (5c). The oxidation peak current density value was almost constant at
lower pH values (3 and 4); afterward, it decreased at elevated pH values up to 8. Huang et al. [39] have
explained this observation to the decreased number of protons in buffer solution at higher pH values,
resulting in the decay of oxidation reaction rate. Accordingly, buffer solution at pH 4 was selected as the

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best one for subsequent experiments. The inset in Fig. (5c) clarified this relation between nitrite
oxidation peak current density and solution pH. This situation is in a good agreement with the results

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obtained by Wang et al. [40] and Pham et al. [41] who investigated nitrite determination at platinum
nanoclusters electrochemically deposited on glassy carbon electrode surface after its modification by a

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monolayer of choline film and urchin-like palladium nanoparticles on carbon nanotube electrode,
respectively.
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Linear sweep voltammograms of Pt/Gr and Ni@Pt/Gr electrodes in 10 mM nitrite in 0.1 M phosphate
buffer solution at pH 4 were depicted in Figs. (6a) and (6b), respectively at different scan rate values of
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1, 2.5, 5, 10, 20, 30, 40, 50, 75, 100 and 200 mV s1. Increasing the scan rate value was accompanied by
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enhancing nitrite oxidation current density values at studied electrodes in addition to recording the
oxidation peak potential at more positive values. The diffusion nature of oxidation process at Pt/Gr and
Ni@Pt/Gr electrodes could be explored by observing the non-linear dependence of nitrite oxidation peak
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current density values on the scan rate in Fig. (6c). This may lead to a linear relationship between the
oxidation peak current density values and the square root of scan rate for both studied electrodes in Fig.
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(6d). Ni@Pt/Gr electrode generally exhibited higher nitrite oxidation peak current density values when
compared to Pt/Gr at all studied scan rate values. Moreover, a plot of the scan rate-normalized current
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(Iυ1/2) against scan rate in Fig. (6e) showed a typical shape of a catalytic process involving electron
transfer in the rate determining step followed by a chemical step [42]. Tafel plots could be drawn in Fig.
(6f) as a relation between log I and E for the rising part of currentvoltage curves of Pt/Gr and
Ni@Pt/Gr electrodes in 10 mM nitrite in 0.1 M phosphate buffer solution (pH 4) at 1 mV s 1. Pt/Gr and
Ni@Pt/Gr electrodes exhibited Tafel slope values of 117.54 and 85.17 mV decade1, respectively.
Accordingly, nitrite oxidation reaction at Ni@Pt/Gr electrode was easier to be carried out when
compared to Pt/Gr. Agboola and Nyokong [43] have measured higher Tafel slope values at Co(II) [114

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mV decade1] and Fe(II) [123 mV decade1] tetrakis (dodecylmercapto) phthalocyanines on gold

electrode. The exchange current density values were also calculated as 1.95×109 and 1.75×107 A cm2
at Pt/Gr and Ni@Pt/Gr electrodes, respectively. This one hundred folds increase in the exchange current
density value at Pt/Gr electrode after introducing nickel suggests this core-shell structured
nanocomposite as a good active component for nitrite sensing.

Chronoamperometry could be employed to calculate the catalytic rate constant and diffusion coefficient

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values of nitrite ions at the studied electrodes. The related chronoamperograms were operated at a

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potential value of 850 mV in 0.1 M phosphate buffer solution (pH 4) containing nitrite concentration

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range of 115 mM in Figs. (7a) and (7b) at Pt/Gr and Ni@Pt/Gr electrodes, respectively. An increase in
the steady state oxidation current density value was measured with increasing nitrite ions concentration

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at both studied electrodes. Moreover, Ni@Pt/Gr electrode exhibited increased oxidation current density
values when compared to those at Pt/Gr. Based on this study, the following equation could be used to
estimate the catalytic rate constant ‘k’ [44]:
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IC/IL = [0.5 (0.5 erf (0.5)) + exp (/0.5)] (4a)
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Where: IC and IL are the current density values of Ni@Pt/Gr electrode in 0.1 M phosphate buffer
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solution when nitrite ions were present or absent, respectively and erf is the error function.  is the
argument of the error function that equals to kC0t, where: t is elapsed time in s, C0 is nitrite ions
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concentration in mol cm−3 and k is the catalytic rate constant in cm3 mol−1 s−1. erf (0.5) is substituted by
unity when  is greater than 1.5. Accordingly, the above equation could be approximated to the
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following one:

IC/IL = 0.5 0.5 = 0.5 (kC0t)0.5

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(4b)
Fig. (7c) showed IC/IL values as a function of t0.5 at different nitrite concentrations at Ni@Pt/Gr
electrode. Straight line relations were obtained. The catalytic rate constant value of nitrite oxidation
reaction at Ni@Pt/Gr electrode was estimated as 1.70×103 cm3 mol1 s1 when nitrite concentration of
10 mM was considered. The corresponding k value of nitrite oxidation at Pt/Gr was also calculated
under the same conditions as 8.86×102 cm3 mol1 s1. Accordingly, the presence of nickel in Ni@Pt/Gr
electrode significantly accelerated nitrite oxidation reaction rate at its surface.

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Cottrell’s equation describes the linear dependence of the current density value of a certain
electrochemical reaction under diffusion control on the minus square root of time as follows [45]:

I = nFAD1/2C1/2 t1/2 (5)

Using this relation, the transient current density values of nitrite oxidation at Ni@Pt/Gr electrode were
drawn as a function of t1/2 in 0.1 M phosphate buffer solution containing nitrite concentration values
ranging from 1 mM up to 15 mM in Fig. (7d). These obtained straight line plots displayed increased

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slope values with increasing nitrite concentration. Moreover, comparing this relation at Ni@Pt/Gr

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electrode in 10 mM nitrite in buffer solution with that at Pt/Gr in Fig. (7e) demonstrated much increased

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oxidation current density and slope values at Ni@Pt/Gr electrode. To calculate the diffusion coefficient
value of nitrite molecules at Pt/Gr and Ni@Pt/Gr electrodes surface, the slope values of It1/2 relation at

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different nitrite concentration values were plotted against nitrite concentration at Pt/Gr and Ni@Pt/Gr
electrodes in Fig. (7f). The average diffusion coefficient value of nitrite molecules at Pt/Gr and
Ni@Pt/Gr electrodes was 2.64×106 and 1.11×105 cm2 s1, respectively.
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The amperometric response of Ni@Pt/Gr electrode was examined by adding gradual concentrations of
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nitrite molecules to 0.1 M phosphate buffer solution (pH 4) at a constant potential value of 850 mV in
Fig. (8a). After adding nitrite, the electrode achieved 95% of its steady state current density value within
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a very short time. The calibration curves of Pt/Gr and Ni@Pt/Gr electrodes were derived from their
amperometric responses in the concentration range of 10 μM15 mM in Fig. (8b). Linear relations were
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obtained with slope values of 33.04 and 85.18 A mM1 cm2 at Pt/Gr and Ni@Pt/Gr electrodes,
respectively. Lower sensitivity values were previously achieved at unsupported Pt nanowire networks
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[16.94 A mM1] [10] and gold nanoparticles supported on sulfonated graphene at glassy carbon
electrode [45.44 A mM1] [46]. The detection limit (LOD) was also calculated as 0.62 and 0.49 M at
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Pt/Gr and Ni@Pt/Gr electrodes, respectively using the relation LOD = 3Sb/m, where: Sb represents the
standard deviation of blank solution and m is the slope of calibration curve [47]. These calculated LOD
values were much lower than those reported at poly(3-methylthiophene) nanorods containing platinum
nanoparticles at glassy carbon electrode [1.5 M] [48], crystalline silver nanoparticles [1.2 M] [49] and
reduced graphene oxide-multiwalled carbon nanotubes-myoglobin platinum nanoparticles [0.93 M]
[50]. The electroanalytical parameters of some related nanocomposites were compared with those of our
work in Table (1) including the oxidation potential, sensitivity and the method of its estimation, linear

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range and detection limit values [18, 41, 5159]. It could be concluded that our Ni@Pt/Gr
nanocomposite displayed lower detection limit than poly(diallyldimethylammonium chloride) coated
Fe3O4 nanoparticles supported on L-cysteine/multi-walled carbon nanotubes [0.846 μM] [55], copper
(II) complexes with Algerian humic acids and triethylenetetramine supported on carbon paste electrode
[1.46 μM] [59] and silver nanoparticles modified carbon paste electrode with ionic liquid [3.00 μM]
[53]. A wider linear range for nitrite molecules determination could be also achieved at our Ni@Pt/Gr

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electrode in relation to earlier reports [18, 41, 5355, 57]. These promising results encourage the

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possibility of wider application of our Ni@Pt/Gr electrode for nitrite sensing. Besides the
electrochemical tools, nitrite ions were also determined using some analytical techniques including ion

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chromatography [60], automated hydrodynamic sequential injection method [61], high performance
liquid chromatography [62], fluorometry [63], spectrophotometry [64] and fluorescence [65]. Somnam

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et al. [61] have developed a method for estimating nitrite ions based on gathering the advantages of
automated hydrodynamic sequential injection method and spectrophotometry. They proposed a linear
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range extending from 0.7 up to 40 µM with a low detection limit value of 0.3 µM. A wider detection
linear range was measured at our prepared Ni@Pt/Gr electrode. Additionally, employing
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electrochemical methods for detecting nitrite ions could offer a safe and economical tool without any
sophisticated steps. This could save much time and effort.
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Adding nitrite ions to phosphate buffer solution appreciably changed the charge transfer features at
Ni@Pt/Gr electrode. This could be illustrated by considering EIS measurements of this studied electrode
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in supporting electrolyte (pH 4) before and after introducing 10 mM nitrite at a potential value of 850
mV in the frequency range from 10 kHz up to 0.1 Hz in Fig. (9a). Generally, high and low frequency
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regions contained two overlapping capacitive semicircles in Nyquist plots of Ni@Pt/Gr electrode. The
presence of nitrite resulted in a decreased charge transfer resistance value [577.45  cm2] in relation to
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that in phosphate buffer solution alone [644.94  cm2]. This Nyquist plot of Ni@Pt/Gr electrode was
compared with that of Pt/Gr in Fig. (9b). Ni@Pt/Gr displayed a decreased Rct value by 1.32 folds than
that recorded at Pt/Gr in 0.1 M phosphate buffer solution containing 10 mM nitrite. Nyquist plots of
Ni@Pt/Gr electrode were also investigated for nitrite oxidation in buffer solution with different pH
values in Fig. (9c). The resistance values for solutions with lower pH (3 and 4) were almost comparable.
However, increased diameters were shown in low frequency regions when solution pH was raised up to
8 to infer a hindered charge transfer step under such conditions. The used equivalent electric circuit for

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fitting the experimental results to the theoretical ones consisted of three components attached in serial
manner [see Fig. (9d)]. Rs could describe the solution resistance value, while two parallel RCPE
connections would represent the resistance and capacitance values of inner and outer electrode layers.
The obtained results by EIS study were in a good agreement with those measured by cyclic
voltammetry.

The selectivity of Ni@Pt/Gr electrode was examined for determining nitrite by adding common ionic

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compounds (K2CO3, NH4F, MgSO4, CuCl2 and NaCl) and biological interfering materials (ascorbic

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acid, dopamine, uric acid and maltose) to 0.1 M phosphate buffer solution (pH 4) in presence of 10 mM

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nitrite. The amperometric response of tested electrode at a potential value of 850 mV was represented in
Fig. (10A). The obtained steady state current density value was almost unaffected by introducing around
30-folds excess of interfering compounds to phosphate buffer solution containing nitrite. Accordingly, a

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highly selective Ni@Pt/Gr electrode for nitrite detection could be easily developed.
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The reproducibility and repeatability of fabricated Ni@Pt/Gr electrode during nitrite estimation were
studied. For 6 successive measurements in 10 mM nitrite in 0.1 M phosphate buffer solution (pH 4) at a
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potential value of 850 mV, the relative standard deviation of determined steady state current density
value was 3.3%. On the other hand, 6 electrodes were separately prepared and examined for nitrite
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detection. They displayed a relative standard deviation value of 3.4% for the measured amperometric
response in nitrite containing phosphate buffer solution. Therefore, highly reproducible Ni@Pt/Gr
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electrode could be successfully prepared. The stability of Ni@Pt/Gr electrode was investigated by its
storage in a desiccator for 3 weeks. Its current response was measured every day towards 10 mM nitrite
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in 0.1 M phosphate buffer solution (pH 4). No appreciable change was observed in the electrode
response within the first week [see Fig. (10B)]. After 2 weeks, the electrode lost only 4% of its activity.
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At the end of the stability test, the electrode retained 90.23% of its initial current density response to
ensure its good stability under the chosen storage conditions. Serrà et al. [66] have prepared core-shell
structured CoNi@Pt nanomaterial and examined its stability during methanol oxidation reaction. The
good coverage of CoNi with platinum shell could efficiently maintain the measured methanol oxidation
current density during the corrosion test. This good stability was attributed to the unique core-shell
structure that could protect the electrocatalyst components from significant leaching and could also
provide an increased number of active sites for continued oxidation reaction. Lin et al. [67] have
investigated the durability of the membrane electrode assembly containing Co@Pt (1:3)/C (reduced) as

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the cathode material during oxygen reduction reaction in the single cell for 130 h life time. They
concluded that the core-shell structure is favored to attain enhanced stability and durability.

Ni@Pt/Gr nanocomposite was investigated for estimating nitrite concentration in different samples of
tap and river water. The standard addition method was employed and the obtained results were listed in
Table (2). Recovery values in the range of 92.1101% were recorded. These good results elect the
developed nanocomposite for feasible determination of nitrite in real samples.

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4. Conclusion

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We have developed a simple route for synthesizing core-shell structured Ni@Pt/Gr nanocomposite
through ethylene glycol as a reducing agent. It exhibited enhanced electrochemical performance for
nitrite estimation in phosphate buffer solution. The specific nanocatalyst structure and improved

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electronic properties of graphene sheets could account for the wide linear range of nitrite detection at
Ni@Pt/Gr nanocomposite. Increased sensitivity, lower detection limit, good reproducibility and long-
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term stability could characterize nitrite determination at Ni@Pt/Gr. Good recovery results were recorded
during nitrite concentration measurement in water samples recommending its possible application as an
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active component in nitrite sensor.

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Fig. (1): A scheme for the fabrication process of Ni@Pt/Gr nanocomposite using core-shell structured
protocol and nitrite oxidation mechanism at its surface.
Fig. (2): TEM images of (a) Pt/Gr and (b) Ni@Pt/Gr nanocomposites. Their relative particle size
distribution histograms were shown in (a, b).
Fig. (3): (a) XRD pattern of Ni@Pt/Gr nanocomposite. The standard XRD patterns of C, Pt, Ni and NiO
were also shown. (b) HRTEM image of Ni@Pt/Gr.

Fig. (4): (a) EDX chart of Ni@Pt/Gr nanocomposite and the elemental mapping pictures of (b) carbon,

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(c) platinum and (d) nickel.

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Fig. (5): (a) Cyclic voltammograms of Ni@Pt/Gr electrode in 0.1 M phosphate buffer solution (pH 4)
before and after adding 10 mM NaNO2 at 10 mV s1. (b) Comparison between the cyclic

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voltammograms of Pt/Gr and Ni@Pt/Gr electrodes in 10 mM NaNO2 in buffer solution at 10
mV s1. (c) Cyclic voltammograms of Ni@Pt/Gr electrode in 10 mM NaNO2 in 0.1 M

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phosphate buffer solution with different pH values at 10 mV s1. The inset figure is a relation
between the nitrite oxidation peak current density value and pH of buffer solution.
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Fig. (6): Linear sweep voltammograms of nitrite oxidation at (a) Pt/Gr and (b) Ni@Pt/Gr electrodes in
10 mM nitrite in 0.1 M phosphate buffer solution (pH 4) at different scan rate values of 1, 2.5,
5, 10, 20, 30, 40, 50, 75, 100 and 200 mV s1. Variation of nitrite oxidation peak current density
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value with (c) the scan rate and (d) the square root of scan rate at Pt/Gr and Ni@Pt/Gr
electrodes. (e) The scan rate-normalized current values as a function of the scan rate at both
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electrodes. (f) Tafel plots of nitrite oxidation at Pt/Gr and Ni@Pt/Gr electrodes in 10 mM nitrite
in 0.1 M phosphate buffer solution (pH 4) as derived from the rising part of currentvoltage
curves at 1 mV s1.
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Fig. (7): Chronoamperograms of (a) Pt/Gr and (b) Ni@Pt/Gr electrodes in 0.1 M phosphate buffer
solution (pH 4) containing different nitrite concentration values from 1 up to 15 mM. The
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chronoamperogram in red color corresponds to the electrode performance in buffer solution free
from nitrite ions. (c) Variation of IC/IL value with t1/2 at Ni@Pt/Gr electrode in buffer solution
containing nitrite concentration values of 1, 5, 10 and 15 mM. (d) Variation of nitrite oxidation
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current density at Ni@Pt/Gr electrode, as derived from the data in (b), with t1/2 in buffer
solution containing different nitrite concentration values in the range of 115 mM. (e) Variation
of nitrite oxidation current density with t1/2 at Pt/Gr and Ni@Pt/Gr electrodes in buffer solution
containing 10 mM nitrite. (f) Slope values of linear relations of I versus t1/2 in (d) as a function
of nitrite concentration at Pt/Gr and Ni@Pt/Gr electrodes.

Fig. (8): (a) Amperometric response of nitrite oxidation at Ni@Pt/Gr electrode by adding gradual
concentrations of nitrite molecules to 0.1 M phosphate buffer solution (pH 4) at a potential
value of 850 mV. Variation of nitrite oxidation current density values at Pt/Gr and Ni@Pt/Gr

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electrodes with nitrite concentration was shown in (b). The inset figure is a magnification for
this calibration curve in nitrite concentration range of 10 μM1 mM.

Fig. (9): Nyquist plots of (a) Ni@Pt/Gr electrode in 0.1 M phosphate buffer solution (pH 4) before and
after adding 10 mM NaNO2 (b) Pt/Gr and Ni@Pt/Gr electrodes in 10 mM NaNO2 in buffer
solution (c) Ni@Pt/Gr electrode in 10 mM NaNO2 in buffer solution with different pH values.
These plots were studied at a potential value of 850 mV in the frequency range of 1×104 – 0.1
Hz. The employed electric circuit for fitting the experimental data to the theoretical ones was
illustrated in section (d).

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Fig. (10): (A) Amperometric response of Ni@Pt/Gr electrode in 0.1 M phosphate buffer solution (pH 4)
at a potential value of 850 mV with successive addition of (a) 10 mM nitrite, (b) 50 mM

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ascorbic acid, (c) 35 mM uric acid, (d) 50 mM dopamine, (e) 50 mM maltose, (f) 0.33 M NH4F,
(g) 0.33 M K2CO3, (h) 0.25 M MgSO4, (i) 0.25 M CuCl2 and (j) 0.25 M NaCl. (B) Cyclic
voltammograms of Ni@Pt/Gr electrode in 0.1 M phosphate buffer solution (pH 4) in presence

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of 10 mM nitrite at 10 mV s1 during its storage for 3 weeks.
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Table (1): Electroanalytical parameters of some related electrodes for nitrite determination in comparison with those of our work.

Potential / Detection
Electrode Method Linear range Sensitivity References
mV (Ag/AgCl) limit
Acid functionalized multi-walled carbon nanotubes
differential pulse
modified with electrochemically deposited 5-amino-1,3,4- 890 10  1000 nM  0.20 nM [51]
voltammetry
thiadiazole-2-thiol
Titanium dioxide nanoparticles/ionic liquid composite linear sweep
P T 0.0829

Silver nanoparticles modified carbon paste electrode with

780

890
voltammetry
Square wave
R I
0.50 – 1500 μM

0.05  1 mM
μA mM−1

0.20 μM

3.00 μM
[52]

[53]
ionic liquid
Cobalt hexacyanoferrate supported on graphene
830
voltammetry

S
differential pulse C 1 – 100 μM 0.846 μA μM1 0.27 μM [54]
nanocomposite
Poly(diallyldimethylammonium chloride) coated Fe3O4
voltammetry

N
cyclic
U 7.49 μM  3.33
nanoparticles supported on L-cysteine/multi-walled carbon
nanotubes
860

M A
voltammetry mM
31.71 μA mM1 0.846 μM [55]

Pt/reduced graphene oxide/glassy carbon electrode 0.25 – 90 μM 496.40 μA mM−1 0.10 μM

D
796 amperometry [18]
Gold nanoparticles assembled on polyethylenimine
E 25 nM  6.6 μM

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covalently linked to graphene oxide on glassy carbon 411
650 amperometry 16 nM [56]
electrode 6.6 μM  1.0 mM μA mM1 cm2

paste electrode
C E
Gold nanoparticles/multi-walled carbon nanotubes/carbon
950
square wave
voltammetry
0.05 – 250 μM
2.5815
μA μM1 cm2
0.01 μM [57]

CoNi/electrochemically
nanosheets
reduced
A C
graphene oxide
715 amperometry
0.1 – 30.0 μM
30.0 – 330.0 μM
0.3428 μA μM1 0.05 μM [58]

Copper (II) complexes with Algerian humic acids and

triethylenetetramine supported on carbon paste electrode 1100 41.06 μA mM1 1.46 μM
cyclic 0  13.8 mM [59]
Copper (II) complexes with Algerian humic acids and voltammetry
960 27.63 μA mM1 2.17 μM
ethylenediamine supported on carbon paste electrode
800 2  238 μM 417 0.25 μM [41]
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differential pulse μA mM−1cm−2
Urchin-like Pd/single-walled carbon nanotubes voltammetry
283  1230 μM 192
μA mM−1cm−2

10 μM  15 mM 85.18
Ni@Pt/Gr 850 amperometry 0.49 μM This work
μA mM−1cm−2

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Table (2a): Measurement of nitrite concentration in various samples of tap water.

Added Found Recovery RSD

Sample
/ M / M % (n = 3)

1 100 101 101.00 0.38

2 300 286 95.33 0.49

P T
3 500 465 93.00 0.67
R I
4 1000 921 92.10
S C
2.53

N U
Added Found
A
Table (2b): Measurement of nitrite concentration in various samples of river water.

M Recovery RSD
Sample

E D
/ M / M % (n = 3)

P T 1 100 96.8 96.8 1.61

C E 2

3
300

500
289.5

472.3
96.5

94.46
0.25

1.03

A C 4 1000 1000.3 100.03 4.43

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Highlights

 Ni@Pt nanoparticles were chemically reduced on graphene in core-shell structure.

 Ni@Pt/Gr displayed an increased electrocatalytic activity for nitrite detection.
 Wider linear range and lower detection limit were measured at Ni@Pt/Gr in relation to Pt/Gr.
 Nitrite concentration was successfully estimated in water samples.

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Figure 1
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