Please cite this article in press as: A. Safavi, et al., Electrocatalytic oxidation of thiourea on graphene nanosheets–Ag nanoparticles hybrid
ionic liquid electrode, Sens. Actuators B: Chem. (2014), http://dx.doi.org/10.1016/j.snb.2014.10.057
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Electrocatalytic oxidation of thiourea on graphene nanosheets–Ag
nanoparticles hybrid ionic liquid electrode
Afsaneh Safavi
∗
, Raheleh Ahmadi, Farzaneh Aghakhani Mahyari, Maryam Tohidi
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
a r t i c l e i n f o
Article history:
Received 2 August 2014
Received in revised form 1 October 2014
Accepted 14 October 2014
Available online xxx
Keywords:
Graphene nanosheets
Silver nanoparticles
Ionic liquid electrode
Thiourea
Amperometric method
a b s t r a c t
A simple, selective and sensitive graphene nanosheets–Ag nanoparticles hybrid ionic liquid electrode
(GNSs-AgNPs/ILE) was used for the electrochemical determination of thiourea (TU). Cyclic voltammo-
gram of TU showed two well defined oxidation signals at the potentials of -0.2 and 0.1 V vs. Ag/AgCl.
Amperometric method was used for quantification of TU in the range of 1.0–3000 M. The theoretical
detection limit was obtained as 0.7 M. The sensor was successfully applied for TU determination in
orange juice and waste water.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
Thiourea (TU) is known to be a serious environmental organic
pollutant, with harmful effects on mammalian species and nitri-
fying bacteria [1,2]. It is a carcinogenic [3] and allergenic [4]
substance. Furthermore, TU causes the disturbance of carbohydrate
metabolism [5], induce hypothyroidism [6] and inhibits nitrifi-
cation in soil and water [7]. However, it has a widespread use
in various fields of science and technology such as electroplat-
ing industry [8], rubber industry [9], photography [2], analytical
chemistry [10], agriculture [11] and for induction of early ripen-
ing in several fruits [12]. Thus, a convenient, selective, sensitive,
rapid and cost-effective method is demanded for the analysis of
this hazardous material in waste water and environment.
Several analytical methods have been reported for determina-
tion of TU such as titrimetry [13], piezoelectric method [14], high
performance liquid chromatography (HPLC) [15], Fourier transform
infrared (FT-IR) spectrometry [16], chemiluminescence [10], flow
injection methods [11], UV–vis spectrophotometry [17,18] and
electrochemical methods [1,8,19–24]. Compared with other meth-
ods, electrochemical techniques have some advantages including
simplicity, rapidity, high selectivity and sensitivity.
The unique electronic, catalytic and optical properties of metal
nanoparticles make them attractive for potential applications in
∗
Corresponding author. Tel.: +98 711 6137150; fax: +98 711 2286008.
E-mail address: safavi@chem.susc.ac.ir (A. Safavi).
the electrochemical and optical sensors [25,26]. Recently, sev-
eral metal nanoparticles modified electrochemical sensors have
been reported for the determination of different important ana-
lytes [26–30]. In the case of electrochemical sensors, the important
functions provided by metal nanoparticles include the catalysis of
electrochemical reactions and the enhancement of electron trans-
fer [25].
Graphene nanosheets (GNSs), a new member of carbon mate-
rials has become a hot topic of interest in different fields of
chemistry owing to its unique nanostructure and its extraor-
dinary electronic, mechanical and catalytic properties [31]. In
recent years, GNSs has attracted tremendous attention as a new
support of metal nanoparticles mainly due to its chemical stabil-
ity, high electrical conductivity and the high surface to volume
ratio [32–35]. Metal nanoparticles-embedded GNS hybrids display
special features in sensors, catalysis and electrical applications
[32–35]. Recently, a facile and rapid one-step procedure has been
reported in our research group for the preparation of graphene
nanosheets–Ag nanoparticles hybrid (GNSs-AgNPs) [35]. GNSs-
AgNPs/ILE was prepared using GNSs-AgNPs as the conductive phase
and octylpyridinium hexafluorophosphate (OPFP) as a binder [35].
OPFP was introduced for the first time in our research group as a
very suitable binder for preparation of carbon ionic liquid electrode
(CILE) [36,37]. It shows an excellent performance compared to con-
ventional organic binders due to high conductivity, high thermal
stability, wide electrochemical window, non-volatility and non-
inflammability [36,37]. CILE exhibits highly desirable features such
as simple preparation, renewable surface, low background current,
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