Sensors and Actuators B 192 (2014) 648–657

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Sensors and Actuators B: Chemical

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

Voltammetric monitoring of Cd (II) by nano-TiO2 modified carbon

paste electrode sensitized using 1,2-bis-[o-aminophenyl thio] ethane
as a new ion receptor
Soleyman Ramezani a,∗ , Massoud Ghobadi b , Babak Nemati Bideh c
a
Faculty of Chemistry, Kharazmi (Tarbiat Moallem) University, Tehran, Iran
b
Department of Chemistry, Faculty of Science, Ilam University, Ilam, Iran
c
Faculty of Chemistry, Sharif University of Technology, Tehran, Iran

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

Article history: The objective of the work ahead is presentation of a new carbon paste electrode (CPE) modified by TiO2
Received 27 August 2013 nanoparticles (TiO2 NPs) and 1,2-bis-[o-aminophenyl thio] ethane (APTE) ligand as a selective cation
Received in revised form 6 November 2013 receptor for determination of the Cd (II) ions using differential pulse anodic stripping voltammetry
Accepted 12 November 2013
(DPASV). The electrode shows an excellent tendency to Cd (II) ions in presence of some interfering
Available online 20 November 2013
species. Under the optimum conditions, a linear calibration curve was obtained in the concentration
range of 2.9 nM to 4.6 ␮M with a correlation coefficient of 0.9969 in the anodic potential of 0.54 (V vs.
Keywords:
Ag/AgCl). The metal detection limit was 2.0 nM after 10 min preconcentration (S/N = 3). The sensor shows
Carbon paste electrode
TiO2 NPs
high applicability in solutions with the optimal pH of 9.0 adjusted by 0.1 M phosphate buffer as supporting
Differential pulse voltammetry (DPV) electrolyte and open circuit accumulation optimum time of 10 min. The stability of the modified elec-
Cadmium (II) trode was studied in the period of 2 months week by week. The results showed that for a series of several
determinations of Cd (II) at 25 ␮M relative standard deviations (RSDs) are below 3.4% for modified CPEs.
Eventually, the electrode was successfully used for determination of Cd (II) in tap water, Livergol herbal
medicine and garden soil aqueous samples.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction So, it is worthy to expand an accurate, rapid and sensitive

Undoubtedly, cadmium is one of the environmental countless
hazards, and it’s exposures to environment comes primarily from
fossil fuel combustion, phosphate fertilizers, natural sources, iron
and steel production, cement production and related activities,
nonferrous metals production, and municipal solid waste incinera-
tion [1]. Cadmium is one of six substances banned by the European
Union’s Restriction on Hazardous Substances (RoHS) directive,
which bans certain hazardous substances in electrical and elec-
tronic equipment but allows for certain exemptions and exclusions
from the scope of the law [2]. Bread, root crops, and vegetables also
contribute to the cadmium in modern populations [3]. Long-term
exposure to cadmium in contaminated food and water has resulted
in a few instances of general population toxicity, and researches are
ongoing regarding the estrogen mimicry that may induce breast
cancer [3]. Concisely, for all of the mentioned reasons, the cadmium
(II) like many chemical elements is extremely harmful to human
and other living organism health.
∗ Corresponding author. Tel.: +98 25 38745629.
E-mail address: Soleyman.ramezani@yahoo.com (S. Ramezani).
method to monitor Cd (II) concentration in the environmental sam-
ples. For this purpose, many instrumental methods such as atomic
absorption spectrometry (AAS) [4], inductively coupled plasma
mass spectrometry (ICP-MS) [5], and atomic fluorescence spec-
trometry (AFS) [6] have been used. Although these techniques
have good selectivity and high sensitivity, they are somewhat
time-consuming, expensive and not convenient for the in situ
measurement. On the contrary, the electrochemical techniques for
determination of trace metals have attracted increasing interests
due to their high sensitivity, rapid performance, portability, low
cost and the simple instrumentation. Because of the toxicity of mer-
cury and the feasibility of formation of intermetallic compounds
in amalgams, numerous new electrode materials and methods are
desired to replace it. At present, several mercury-free electrodes,
such as bismuth film electrodes [7], carbon nanotube modified
electrodes [8], nano-porous pseudo carbon paste electrodes (nano-
PPCPEs) [9,10], acetylene black electrode [11], lead film electrode
[12], boron-doped diamond electrode [13], nano-TiO2 /chitosan
combination film [14] and carbon paste electrodes [15] are devel-
oped for sensitive electrochemical determination of diverse metals
ion in various aqueous and non-aqueous media. Among them,
chemically modified carbon paste electrodes (CMCPEs) have seized

0925-4005/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.11.033
 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657 649

Germany) whenever it was necessary. UV–vis absorption spectrum

S S was recorded with a UV–vis spectrometer (Perkin-Elmer model
Lambda 25, USA). All measurements were carried out at the room
temperature.

NH2 H2N
2.2. Reagent and materials
Fig. 1. Chemical structure of the APTE.
Analytical reagent grade chemicals and double distilled (DD)
water were used to prepare all aqueous solutions at 25 ◦ C. Car-
special position and popularity among the electrochemists because
bon graphite powder and paraffin oil were purchased from the
of their unique properties such as low cost, Availability of starter
Fluka (USA). The titanium chloride (TiCl4 , 99.90%) and H2 SO4 (98%)
materials, low background current, non-toxicity, simple usability,
were obtained from the Merck (Germany). The cadmium nitrate,
high conductivity, renewability, high atmospheric stability, and
and nitrate salts of other metals (all from Merck) were of the
most importantly unparalleled adaptability with various chemical
highest purity available and used without any further purification
modifiers.
to prepare all of the metallic ions stock solutions. Synthesis and
Nowadays, metal and metal oxides NPs are extensively used
purification of the APTE was performed in the Polymer and Macro-
to modify the electrochemical sensors and biosensors in various
molecules Research Lab. of the Chemistry Department of Kharazmi
chemical and physical methods. The properties of these materials
University (Tehran, Iran) according to the reference [19] and used
are quite different from those of their bulk counterparts, due to
without any manipulation. Buffer solutions were prepared from
their extremely small size, special structure and large surface-to-
HNO3 , H2 SO4 , NaOH, H3 PO4 and its salts for pH range of 3.00–12.00
bulk ratio [16]. Among them, TiO2 NPs is the promising material as
adjusted by pH/mV meter in order to diminish any errors. All other
semiconductor having high photochemical stability and low cost.
chemicals used, were of the analytical reagent grade (from Merck,
Well-dispersed Titania NPs with very fine sizes are promising in
Aldrich or Fluka). All glassware used in the experiments were
many applications such as pigments, adsorbents and catalytic sup-
washed with freshly prepared aqua regia and rinsed thoroughly
ports. Hence, there is a considerable interest in using TiO2 NPs as
in tap water first and then DD water before using.
a modifier since they have high surface area, optical transparency,
good biocompatibility and relatively good conductivity [17]. As a
result, in continuation of modification, the TiO2 NPs was prepared 2.3. Preparation
and used in a physical method to amplify some essential charac-
teristics of the introduced electrode. 2.3.1. Preparation of the TiO2 NPs
Another option for improvement of CMCPEs sensitivity is appli- Nano-crystalline anatase form of the titanium NPs were
cation of the novel functionalized organic materials which are prepared according to a special technique that is presented in
known as ion receptor agents. It is evident that, the outstanding role reference [20]. Accordingly, TiCl4 and H2 SO4 were used as the
of the ion receptor compounds is in the preconcentration stage of main starting materials. Fig. 2 shows the UV–vis diffuse reflectance
the SADPV. These compounds could have a selective formation of spectra of the Titania samples calcinated at 400 and 600 ◦ C. This
the reversible organometallic complex with the target ions. This absorbance rate decreases and shifts to slightly higher wave-
phenomenon is not too surprising due to the presence of some lengths as temperature of the powder increases. It clearly shows
electron-donor functional groups which have high affinity to the that Titania has strong electronic absorption in the UV region.
alkali, alkaline earth and transition metal ions. Hereto, this strategy UV–vis technique was successfully used to confirm the formation
truly improves the preconcentration of the target ion on the elec- of the TiO2 NPs. Consequently, by using this particular method
trode surface that impact extremely the modified sensor sensitivity the highly pure and uniform anatase crystals are obtained. After
and selectivity [18]. calcination at 400 and 600 ◦ C, most of the particles in the samples
In the study ahead, the synthetic compound of APTE (Fig. 1) have diameters in the range of 10–50 nm. The presence of a certain
was used as an appropriate mediator to improve selectivity and amount of H2 SO4 well expands the anatase phase and inhibits
sensitivity of the prepared CPE for stripping determination of
the cadmium (II) in the aqueous media. The preliminary studies
were performed to evaluate the sensitivity of the APTE partic-
ular compound toward certain ions by cyclic voltammetry (CV).
The obtained results showed that the APTE have the most affinity
toward Cd (II) ion among other heavy metal ions. Nevertheless, it
shows partial tendency to Hg (II) and Cu (II) ions and can be ignored
due to its low quantity. Eventually, the Cd (II) ion concentration was
successfully detected in some real samples using standard addition
method through the SADPV three electrode systems.

2. Materials and methods

2.1. Apparatus

All voltammetric measurements were made by a conventional

three-electrode system using a Potentiostat (Palm Sens, EN 50081-
2) and the proposed sensor (CMCPE) as a working electrode in
conjunction with an Ag/AgCl reference and a Pt wire counter
electrodes (Azar electrode, Iran). A Metrohm-827 pH/mV meter
(Switzerland) was used for all pH measurements. Some solutions
were homogenized by ultrasonic homogenizer (Bandelin UW 3200, Fig. 2. UV–vis spectra of the TiO2 NPs calcinated at 400 and 600 ◦ C.
650 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657

Fig. 3. XRD spectrum of anatase TiO2 nanoparticles.

the anatase/rutile transformation even at 600 ◦ C that give high
conductivity to the TiO2 NPs due to its uniform crystalline form. In
presence of the excess amount of the sulfuric acid, Raman spectra
and electron diffraction confirmed that the nanoparticles are com-
posed of anatase TiO2 . NPs, no other Titania phases, such as Rutile
or Brookite, were detected. (More details are in reference [20]).
In addition, for more confirmations, the X-ray diffraction (XRD)
analysis of the TiO2 NPs was well obtained (Fig. 3). It can be claimed
that, The XRD analysis agrees fully with the previously reported
XRD analysis of the TiO2 nanostructure. The X-ray patterns of
the nanoparticles obtained by the above mentioned method
shows anatase crystalline nature of the NPs relying on the reasons
interpreted in the relevant previously reported references [21].
Eventually, SEM was used in order to investigate the morphology
of the TiO2 NPs. As can be seen clearly in Fig. 4, the morphology of
the particles is close to sphere. The most of the nanocrystals in the
sample exhibit diameters in the range of 10–50 nm.
2.3.2. Preparation of unmodified and modified CPE
Bare CPEs were prepared by mixing 66 mg of graphite pow-
der (heated at 700 ◦ C for 15 min) with 34 mg of paraffin oil with
a mortar and pestle. The modified CPE was prepared by the same
method except that the graphite powder was mixed with a desired
amount of chemical modifiers of APTE ligand and TiO2 NPs. Then,
the mixture was dissolved in appropriate amount of acetone as a
more volatile and inert solvent, and the resulting solution was well
homogenized by ultrasonic homogenizer for 5 min, and then, the
solution was left at room temperature to evaporate thoroughly the
excess solvent. Both unmodified and modified pastes were packed
into a polyethylene tube (2.5 mm diameter), the tip of which had
been cut off. Electrical contact to the paste was established via
inserting a copper wire thorough flank. A fresh electrode surface
of paste was cut out with a glass rod and the exposed-end polished
on a slick paper until the surface showed shiny appearance.
2.4. Analytical procedure
Voltammetric determination process consists of preconcentra-
tion (accumulation), deposition (cathodic electrolysis), stripping
(detection), and regeneration steps (if necessary). During precon-
centration step, the CMCPE was immersed in a 50 mL cell containing
30 mL of metal ion solution at open circuit conditions for a specified
period of time (i.e., normally 10 min, but varied from 1 to 30 min
in the preconcentration time study). During preconcentration, the
50 mL cell containing 30 mL of Cd (II) ion and 0.1 M phosphate buffer
(pH = 9.0) as a supporting electrolyte was stirred at over 350 rpm

Fig. 4. SEM images of TiO2 nanoparticles calcinated at 600 ◦ C.

 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657
using a magnetic stirring bar. After the pre-concentration step, the
solution is allowed to achieve quiescence for 30 s. Then, a negative
cathodic potential (0.1 V vs. Ag/AgCl) was applied to the electrode in
the phosphate buffer solution for 50 s. The potential is then scanned
in the positive direction (i.e., from 0.1 to 1.0 V) with the scan rate of
100 mV s−1 , when the potential is sufficiently positive (0.54 V); an
anodic current is generated due to the oxidation of metals. The oxi-
dation peaks grows and then dies down. Eventually, the data were
recorded for more analysis.
2.5. Voltammetric behavior of Cd (II)
As was already hinted, the most probable mechanism of the Cd
(II) electrochemical behavior on the APTE-TiO2 NPs-CPE surface is
nearly as follow. At first, in order to accumulate the cadmium ion
at the CPE surface via formation of the APTE-Cd (II) complex, the
prepared electrode was immersed in to the unknown cadmium
solution in open circuit conditions for appropriate period of time
(optimal time is 10 min). In the next step, the Cd (II) accumulated
was reduced at 0.1 V and the product was then oxidized in the strip-
ping stage in the applied potential swept from 0.1 to 1.0 V. The steps
can be briefly described as follows:
(Cd2+ )(solution) + (APTE)(CPE)  (Cd2+ -APTE)(CPE) + 2H+
(accumulationstage, opencircuit, 10 min, pH = 9.0)
(Cd2+ -APTE)(CPE) + 2e− → (Cd0 + APTE)(CPE)
(depositionstage,E applied = 0.1 V, 50 s)
Cd0 (CPE)  Cd2+ (solution) + 2e−
(strippingstage,E applied = 0.1–1.0 V,E p = 0.54 V)
3. Results
3.1. Step by step voltammetric characterization of the CPE
modification
Cyclic voltammetry technique was used to follow up each of
the modifying additives effect on the electrochemical response
of the proposed electrode. The perceptible cyclic voltammograms
recorded in 0.1 M of phosphate buffer solution with pH 9.0 as sup-
porting electrolyte in the absence and presence of 25 ␮M of Cd (II)
ion at unmodified (bare) CPE, APTE modified CPE and TiO2 NPs-APTE
modified CPE at the scan rate of 100 mV s−1 and accumulation opti-
mal time of 10 min are shown in Fig. 5. As the figure suggests, the
bare CPE show no response in absence of Cd (II) ion due to no sig-
nificant peak current (curve a). The trifle current that can be seen
in this manner, is definitely belongs to the back ground current of
the CPE. Also, the curve b was recorded by the same electrode (bare
CPE) in the presence of 25 ␮M of the Cd (II) solution. In this manner,
it is clearly evident that the observed slight current is due to sponta-
neous physical adsorption of cadmium ions on the CPE surface after
10 min open circuit preconcentration. By adding a certain amount
of the APTE ion receptor to the carbon paste composition (APTE-
CPE), there is a significant increase in the peak current from 1.18 to
8.13 ␮A pertain to the unmodified and APTE modified CPE respec-
tively, which suggested that presence of the APTE in the carbon
paste composition improves markedly the sensitivity of the CMCPE
(curve c). This phenomenon certainly arises from high affinity of
the APTE ligand to form APTE-Cd (II) complex and subsequently
to accumulate the Cd (II) ion on the CPE surface in the preconcen-
tration stage. In Comparison with the bare-CPE and APTE-CPE, the
highest peak current of Cd (II) is obtained at the TiO2 NPs-APTE-CPE
651
Fig. 5. Cyclic voltammograms of the (a, b) Bare-CPE, (c) APTE-CPE, (d) APTE-
TiO2 NPs-CPE in 0.1 M of phosphate buffer solution with pH 9.0 at scan rate of
100 mV s−1 . Electrodes were exposed in 30 mL of blank (a), and 25 ␮M of Cd (II)
solution (b–d).
(I)
(curve d), demonstrating the strong preconcentration of Cd (II) at
the TiO2 NPs-APTE-CPE surface. It is worth noting that, the improve-
(II) ment in the sensitivity of the CMCPE can certainly be attributed
to the multi-functional characteristics underlined in theTiO2 NPs-
APTE combination: the high chelating ability of N and S atoms of
APTE to Cd (II), the strong anodic ability of APTE for Cd (II), and
(III)
promotion of the surface area to volume ratio of the carbon paste.
On the basis of the above-mentioned factors, the adsorption effi-
ciency of Cd (II) on the TiO2 NPs-APTE-CPE surface is much higher
than that at the bare CPE and the APTE modified CPE. Therefore,
the stripping peak current of Cd (II) at the ultimate modified CPE
increase significantly that is the main objective of this research.
Therefore, all subsequent experiments in this study, is performed
successfully by the TiO2 NPs-APTE-CPE.
3.2. Carbon paste components optimization process
So far, a known fact about CPE that has been proven is the
high impressionability of its efficiency by the type and amount of
the carbon paste ingredients. Thus, the influence of presence and
amount of ion receptor (APTE), TiO2 NPs and amount of binding
agent (paraffin oil), on the voltammetric response (peak current)
of the electrodes over Cd2+ ion concentration were evaluated care-
fully and the results were summarized in Table 1. As can be seen, in
the absence of APTE, the electrode has low response (low peak cur-
rent) toward cadmium (II) ion (No.1). Also, by increasing amount
of the APTE (%wt.) in the carbon paste composition, the calibra-
tion curve slope increases, manifesting the impressive effect of the
ion receptor (APTE) in the accumulation quantity and consequently
its effect on the peak current (No. 2, 3 and 4). Super abound scale
of the ionophor amount in the carbon paste composition (Nos.
5), albeit, resulted in a little decrease in electrode response as a
result of decrease of GP/ligand weight percentage ratio, and in con-
sequence decreases of paste homogeneities and of course in the
conductivity of the carbon paste [22]. In a separate assay, influence
of the TiO2 NPs on the electrochemical response of the modified
electrode was evaluated. The results revealed that, peak current in
presence of the TiO2 NPs grows obviously (No. 6–9). It is probably
due to enhancement of the surface/volume ratio of carbon paste
bulk by Nano-scale dimension of the titanium dioxide crystals, as
652 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657

Table 1
The paste compositions and the electrode characteristics of cadmium (II) sensor.

No. GP (mg) APTE (mg) TiO2 Nps (mg) PO (mg) Ip,a (␮A)a LR (M) LOD (M)

1 66 – – 34 1.18(±0.3) – –
2 65 2 – 33 4.11(±0.2) – –
3 64 3 – 33 6.50(±0.2) – –
4 63 5 – 32 8.13(±0.4) 1.5 × 10−3 to 2.3 × 10−6 2.0 × 10−6
5 62 6 – 31 5.11(±0.1) 1.8 × 10−3 to 2.6 × 10−5 2.3 × 10−5
6 63 4 2 31 13.20(±0.3) 2.4 × 10−3 to 2.7 × 10−6 2.0 × 10−6
7 62 4 3 31 14.70(±0.1) 3.4 × 10−3 to 1.8 × 10−7 1.0 × 10−7
8 61 4 4 31 15.80(±0.3) 2.2 × 10−3 to 2.2 × 10−8 2.0 × 10−8
9 61 5 4 30 16.58(±0.3) 2.2 × 10−3 to 2.2 × 10−9 2.0 ×10−9
10 60 5 5 30 14.50(±2.0) 2.2 × 10−2 to 2.5 × 10−7 2.3 × 10−7
11 60 4 6 30 14.20(±2.0) 2.2 × 10−1 to 2.3 × 10−5 2.0 × 10−5
a
Values in parentheses are SDs based on three replicate analyses of Cd (II) 25 ␮M solution.

well as diminishing the Ohmic resistance of the carbon graphite
paste in consequence of the TiO2 NPs high electrical conductivity
[23]. As the data in Table 1 suggest, at the end of the optimiza-
tion process of the carbon paste ingredients weight percentage
ratio, the APTE-TiO2 NPs-CPE with the highest performance (high
peak current) and APTE/TiO2 NPs/GP/PO optimal percentage ratio
of 5/4/61/30 was found and used as a working electrode in voltam-
metric quantitative assessment of Cd (II) ion aqueous solution
and supplementary experiments (No. 9). In continuation of inor-
dinately increasing weight percentage ratio of the both modifiers,
the observed electrode response comes down significantly (No. 10
and 11). This phenomenon absolutely depends on the impressive
decrease in the carbon paste uniformity.
3.3. Electrolyte and pH-dependence of peak current
Since, the APTE-Cd (II) complex formation depends likely on the
environment pH value (preconcentration step), it can be one of the
effective variable parameters, which strongly influenced the peak
current and shape of the stripping voltammograms. Therefore, at
first, the pH-dependance of the Cd (II)-APTE complex stripping
peak current was investigated in the pH range of 3.0–12 using
cyclic voltammetry in 0.1 M phosphate buffered solution with fixed
ionic strength and the results were shown in Fig. 6. As can be seen
overtly from the figure, by enhanced growing up of the pH from 3.0
to 9.0, the peak current Continuously promote due to increasing
the complex formation of Cd (II) with APTE at the electrode surface
with increasing pH and the completion of complex formation
at higher pHs of supporting electrolyte. But, in the higher than
pH 9.0, immediately, the peak current value begins drastically to
degrease. Unmistakably, This could be due to the formation of
metal hydroxide complexes of Cd(OH)2 that is indubitably insol-
uble, by providing of the Ksp required OH− value of the Cd(OH)2
precipitation in the high concentration of OH− (Ksp = 7.2 × 10−15 ,
pH = 9.0). In the one hand, these hydroxide complexes by pre-
cipitating either on the inner wall of the electrolytic cell or on
the electrode surface in contact with the solution, performs as
inhibitor and occupant of the active sites of CMCPE. In the other
hand, by forming relatively insoluble hydroxide precipitation, the
identifiable ions are kept away from access of the sensitive sites
of the electrode. Thereby, it causes a significant decrease in the
quantity of solution phase electrode-detectable metal ions that
may reach to the electrode surface, thereupon, causes a significant
decrease in the analytical parameter of peak current. Therefore,
the pH 9.0 was selected as an optimum condition in order to obtain
maximum sensitivity in quantitative analytical measurements.
Furthermore, the effects of some common electrolytes, such as
KCl, HCl, HNO3 , Britton–Robinson, citrate, acetate, and phosphate
buffer solutions, as supporting media on the peak currents of Cd (II)
were carefully compared. It was found that Cd (II) had the best elec-
trochemical responses (high peak current and free from interfering
peaks) in phosphate buffer solution. Therefore, phosphate buffer
(pH 9.0) was chosen as supporting electrolyte for voltammetric
determination of the Cd (II) in the supplementary experiments.
3.4. Effect of preconcentration and deposition time

Looking for more analytical parameters effective on DPASV

Fig. 6. Variation in solution pH in the wide range of 3.0–12 and its effect on the
voltammetric response of the APTE-TiO2 NPs-CPE to Cd (II) ion (applied scan rate
was 100 mV s−1 in presence of phosphate buffer as supporting electrolyte).
peak current of Cd (II) ion at the surface of proposed CMCPE,
the effect of preconcentration and deposition time were evalu-
ated and the results were shown in Fig. 7a. It was found that the
surface concentration of the cadmium (II) species increase with
increasing preconcentration time until the saturation surface con-
centration is reached. As can be seen in Fig. 7a, the peak current
(␮A) versus preconcentration time (min) increased linearly until
the surface became saturated, where the peak current is almost
independent of preconcentration time. It was found that 600 s is
an appropriate period of time for a successful and complete pre-
concentration. Moreover, the deposition time effect on the anodic
stripping peak current (Ip,a ) was studied in the range of 10–100 s.
It was found that, Increasing the time required for deposition of
cadmium ions adsorbed on the electrode interface immersed in
the phosphate buffered solution in pH of 9.0 containing 25 ␮M of
Cd (II) ion causes to increase discernibly the observed peak cur-
rent in constant applied potential of 0.1 V vs. Ag/AgCl (Fig. 7b). As
it can be seen clearly in Fig. 7b, after elapsing 50 s the observed
peak current is independent from the deposition time represent-
ing a restricted amount of the adsorbed Cd (II) ion on the CPE
surface.
 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657
Fig. 7. Effect of varying (a) accumulation time and (b) deposition time on the DPASV
peak current of 2.5 × 10−5 mol L−1 Cadmium ion in presence of phosphate buffer
0.1 M; scan rate 100 mV s−1 , pH 9.0.
3.5. Effect of scan rate
In order to investigate the anodic peak current (Ip,a ) proportion
with potential scan rate, the applied potential was swept from 10
to 100 mV s−1 in 25 ␮M of Cd (II) phosphate buffered solution with
adjusted pH around 9.0 (Fig. 8a). The resulting data were evalu-
ated as an Ip,a (␮A) versus v and (v)1/2 (mV s−1 ) variation curve
(Fig. 8b and c). As can be seen overtly, peak current for anodic oxi-
dation of Cd (II) (Ip,a ) at the surface of modified electrode shows
a linear variation with potential sweep rate (v) in the range of
10–100 mV s−1 manifesting an adsorption-like behavior of corre-
sponding mechanism. Statistical data for this regression analysis
(Ip,a = b + a) shows a slope of 0.1244 and R2 = 0.9991. The results
illustrate that the electrocatalytic oxidation of Cd (0) at the sur-
face of APTE-TiO2 NPs modified electrode may be proceed via the
creating of an adsorbed adduct of Cd (II) ion to form a reversible
Cd (II)-APTE complex by N and S electron donor atoms of APTE
cation receptor that well coordinate with Cd (II) ion center (see Sec-
tion 2.5). In support of this claim, the low correlation coefficients
(R2 = 0.97) of the Ip vs. (v)1/2 plot subscribes that the electrode
surface processes do not have a diffusion-controlled behavior. Fur-
thermore, by enhancing the scan rate, the peak potential (Ep ) shifted
to more positive values, approving the kinetic limitation in the
interfacial dynamic process that occur at the CPE/solution inter-
face (Fig. 8 d). For evaluation of the kinetic parameters, there
653
is a useful device that called Tafel plot. In general, there is an
anodic branch with slope, (1 − ␣)F/2.3RT and a cathodic branch
with slope −␣F/23RT. For the Cd (II)/Cd(0) system in phosphate
buffered solution, There is a linear relation between Ep,a and log v
in the range of 10–100 mV s−1 (Fig. 8e). The linear regression equa-
tion is [Ep,a = 0.0105 log v (±0.0052) + 1.0551(±0.005), R2 = 0.9143].
The Tafel slope (b) should be linear with a slope of 0.0105 using
[Ep,a = (b/2) log v + Constant] equation. Therefore, it was found that,
the Tafel slope is 0.021 V by applying n = 2 in the 0.1 M phosphate
buffered solution at the ATPE-TiO2 NPs modified electrode/solution
interface. Hereby, the mass transfer coefficient (˛), was found
˛ = 0.24 in according to above noted anodic branch slope. Accord-
ingly, both anodic and cathodic processes contribute significantly
to the currents measured in the over potential () range where mass
transfer effects are not important [24,25].
4. Discussion
4.1. Distinguishing figure of merits of the electrode
4.1.1. Linear range and limit of detection
Emphatically, two of the most important and most widely appli-
cable figure of merits of the ion selective electrodes (ISEs), are
linear range (LR) and limit of detection (LOD). Hence, these two
distinguishing analytical characteristics of the modified electrode
are needed to be evaluated after preparing the modified electrode
using DPASV. Hereby, the Cd (II) ion stripping Ip,a (␮A) versus E (V vs.
Ag/AgCl) curves at various concentrations in the 0.1 M phosphate
buffer at pH 9.0 was shown in Fig. 9. Notably, The DPV parame-
ters were 50 mV pulse amplitude, pulse width 50 ms, and a scan
rate 100 mV s−1 . Also, the Ip,a (␮A) versus – [Cd (II)] (␮mol L−1 ) plot
(Fig. 9) suggests a wide dynamic LR of 2.9 nM to 4.6 ␮M with a
LOD of 2.0 nM (S/N = 3) and correlation coefficient of R2 = 0.9969.
An electrochemical sensor with such unparalleled high sensitivity
can be achieved only in presence of some good modifier additives
that possess high performance modifying effect.
4.1.2. Lifetime and reproducibility
Unmistakably, stability and reproducibility of the chemical sen-
sors, intensively depends more than anything on the chemical
nature of the electrode components especially on the modifier
additives. It is noteworthy, in this particular case, the CPE ingre-
dients including APTE and TiO2 NPs have adequate chemical and
atmospheric stability for construction a proper chemical sensor.
The operational reproducibility of the modified electrodes was sur-
veyed by monitoring the DPV in 25 ␮M Cd2+ solution via 5 diverse
APTE-TiO2 NPs modified sensors built in the same conditions as
possible. The obtained results (Cd (II) stripping peak currents) of
the 5 electrodes had the lowest possible relative standard devia-
tion (RSD = 4.0%) representing high reproducibility of the proposed
sensor.
Also, the lifetime of the APTE-TiO2 NPs modified electrode was
studied within two months by periodically (week by week) recali-
brating the sensor applicable in electrochemical stripping analysis
of 25 ␮M of cadmium (II) standard solution. No significant change
in the electrode performance (LOD) was observed after two months
storage (8 replicate experiments, RSD = 5.0%). Certainly, the secret
of long lifetime for the modified electrode lies in the high atmo-
spheric and chemical stability of the CPE ingredients. It should be
noted that, for long time storage, the electrode must be kept in DD
water and in cool dark place. To reuse the electrode after a long
period of not-using time, a fresh surface of the APTE-TiO2 NPs mod-
ified electrode could be produced by scraping out the old surface
by a smooth graph or weighing paper. Of course, to achieve an ade-
quate stable and repeatable response, the electrode surface should
654 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657

Fig. 8. (a) Cyclic voltammograms of the APTE-TiO2 NP-MCPE in phosphate buffer solution (pH 9.0) containing 25 ␮M of Cd (II) at various a to f scan rates of 10, 20, 40, 60, 80,
100 mV s−1 respectively, and variation of the (b) Ip,a vs. v, (c) Ip,a vs. (v)1/2 , (d) Ep,a vs. v and (e) Ep,a vs. log v (all experimental conditions are exactly same as Fig. 3).

be perfectly smooth and free of any scratches that much depends
on the skill of the examiner.
4.2. Interference study
As the name implies, selectivity is one of the most critical and
important characteristics of the ISEs which often can be excellence
agent of an electrode to the other with the same analytical aim.
Thereby, performance of the proposed electrode for determination
of the cadmium in presence of some interfering ions was carefully
evaluated. For this purpose, the influence of other metal ions, which
can compete for complexation at binding sites on the APTE com-
pound embedded throughout of the carbon paste, were tested using
the same procedure as that optimized for cadmium quantitative
determination and the results were summarized in Table 2. This
table surveys the results obtained by studying the selected inter-
ference ions at concentrations of 100 times as large as that of Cd
(II). The interaction of some possibly more interfering species such
as; Pb (II), Ag (I), Hg (II), Cu (II), Zn (II), Ni (II), Co (II), NO3 − , F− ,
SCN− ions and some biological species with the ASDPV peak current
was investigated by adding increasing amounts of these interfering
species to a solution containing 25 ␮M of Cd (II). The data presented
in this table clearly shows that, the peak current intensity of Cd
(II) was not dramatically affected by lower concentrations of these
cations. Nonetheless, at high concentrations, 100-fold excess over
Cd (II) in the analyte solution, the interfering ions reduced the elec-
trode response by competing with cadmium (II) ions for the binding
sites. These results are in agreement with our previous research,
which includes amplification of the response of ion selective elec-
trode to a given target ion by presence of a selective ion receptor
 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657 655

interfere partially with Cd (II). This phenomenon is quite consistent

with the HSAB rule of Pearson.
After this, another factor affects the selectivity of the electrode
is various electroreduction potentials of the APTE-Ion complexes.
Certainly, in the potential range of the 0–1 V vs. Ag/AgCl only the
APTE-Cd (II) complex can be reduced. Therefore, spontaneously,
other interfering species cannot interfere with Cd (II) ion.
As Table 2 suggests discernibly, The Hg (II) interfere more than
other ions shown in the table. Peak current of Cd (II) decreased
relatively in the presence of Hg (II) because it can be reducing at
the surface of the electrode and form a mercury film. The interfer-
ence can be eliminated using appropriate masking agent. The effect
of other interfering metal ions arises from partial interaction with
APTE that are in competition with Cd (II) ion.

4.3. Comparative study

In Table 3, some of the proposed electrode figures of merits were

Fig. 9. DPAS voltammograms of APTE-TiO2 NPs-MCPE in the various Cd (II) con-
centrations in the range of 2.9 nM to 4.6 ␮M (Conditions: 0.1 M phosphate buffer
solution as a supporting electrolyte, pH adjusted at 9.0, DPV parameters were 50 mV
pulse amplitude, pulse width 50 ms, and a scan rate of 100 mV s−1 ).
Table 2
Changes of the cadmium (II) (25 ␮M) peak current, affected by some interference
ions with concentration of 2.5 × 10−3 M.
Interference ion Peak current changes (%)
compared with number of previously reported Cd (II) voltammetric
sensors. As can be seen, the proposed electrode in some respects
is better than other Cd (II) sensors. As shown in the table, there
are a few reports [12,14] that have lower LOD than this study. But,
one of the greatest prominences of the TiO2 NPs-APTE-CPE to other
electrodes shown in Table 3 is the wide linear range that certainly
goes back to the type of the modifiers. Apart from this, the presented
sensor has better performance in selectivity rather than some of the
previously reported electrodes [29,31,32].

Hg2+ −7.0 4.4. Analytical performance

Cu2+ −5.0
Ag+ −4.5 At the end, it was necessary to evaluate the electrode perfor-
Pb2+ −6.0 mance for quantitative determination of the cadmium ion in real
Zn2+ −3.8
Ni2+ −4.0
environments. To do so, the proposed electrode was utilized as
Co2+ −3.3 a sensitive and selective working electrode for determination of
SCN− −4.5 Cd (II) in different environmental (tap water, herbal medicine and
NO3 − −1.5 garden soil) samples. Since differential pulse voltammetry (DPV)
F− −2.2
has a much higher current sensitivity and a better resolution than
Cysteine −3.1
Fructose −2.4 cyclic voltammetry, it was used to estimate concentration of Cd (II)
Urea −3.2 using the standard addition method (SAM) and the results were
Glucose −4.8 shown in Table 4. The pharmaceutical and soil samples were care-
fully prepared according to the literature [34] and [35] respectively,
and the water samples were used directly and there were no need
(an organic compound) [26,27]. It is noteworthy that, in general for any pretreatments. All experiments conditions used are exactly
the response and selectivity mechanism of the some ion selective same as above mentioned optimal conditions. As it is obvious, the
CMCPEs that use some synthetic organic compounds as ion recep- determination of cadmium in each sample has been performed
tor additives, obey somewhat from the hard-soft acid base (HSAB) satisfactorily accurate and the obtained results were completely
rule of Pearson. It is therefore expected that, the active sites on the adaptable with the results of FAAS method (data are not reported).
APTE compound containing sulfur and nitrogen soft atoms are more This is demonstrating the fact that, the proposed Cd (II)-CMCPE can
willing to some soft ions such as Cd (II). Nevertheless, according to act very well as a working electrode in voltammetric determination
Table 2 some species such as Hg (II), Cu (II), Ag (I) and Pb (II) ions of Cd (II) ion without any fault or defect (Table 4).

Table 3
Comparing the performance of the proposed electrode with some cadmium (II) electrodes reported previously.

Modified electrode Method LR (mol L−1 ) LOD (mol L−1 ) Interfering ion Ref.
−9 −6
Lead film electrode SWV 2.0 × 10 to 1.0 × 10 6.0 × 10−10 No [12]
SbNPs BDEa LSV 4.5 × 10−7 to 4.5 × 10−6 3.4 × 10−7 No [13]
Nano-TiO2 /chitosan composite film DPV 1.0 × 10−9 to 1.0 × 10−6 2.0 × 10−10 No [14]
Zirconium phosphated amorphous silica DPV 2.7 × 10−8 to 1.2 × 10−5 2.6 × 10−8 No [28]
Antimony film CPE ASV 4.5 × 10−8 to 4.5 × 10−7 7.1 × 10−9 NR [29]
Kaolin modified Platinum electrode SWV 9.0 × 10−8 to 8.3 × 10−6 5.4 × 10−9 No [30]
N-p-chlorophenyl-cinnamohydro-xamic acid modified CPE DPV 4.0 × 10−8 to 1.6 × 10−7 9.8 × 10−9 Cu2+ , Pb2+ [31]
Zeolite-modified electrode CV 5.0 × 10−8 to 1.0 × 10−6 8.9 × 10−9 Fe3+ [32]
Thiol-functionalized mesoporous film and ILs-GCE LSV 2.9 × 10−8 to 8.7 × 10−4 1.0 × 10−9 No [33]
TiO2 NPs-APTE-CPE DPV 2.2 × 10−9 to 2.0 × 10−3 2.0 × 10−9 No This work
a
Antimony nanoparticle modified boron-doped diamond electrode. NR, not reported.
656 S. Ramezani et al. / Sensors and Actuators B 192 (2014) 648–657
Table 4
Quantitative determination of cadmium (II) in some real samples.
Sample Cd2+ (mg L−1 )a
Added (SAM)
Tap water 0 Nd c
10.0
Livergol herbal medicines 0 Nd
10.0
Garden soil 0 Nd
10.0
a
Values in parentheses are SDs based on three replicate analyses.
b
Optimal conditions: supporting electrolyte; phosphate buffer in adjusted pH of 9.0, scan rate; 100 mV s−1 , pulse amplitude; 50 mV, pulse width; 50 ms, preconcentration
and deposition time; 10 min and 50 s respectively.
c
Not detected.
5. Conclusions
According to the obtained experimental results, it is clearly evi-
dent that the APTE synthetic compound and the TiO2 NPs have well
obviated the urgent need to a suitable CPE modifier. These sub-
stances based on its unparalleled characteristics make impressive
change in the electrochemical response of the modified electrode.
The presented APTE-TiO2 NPs-CPE displayed well-defined, sharp
and highly reproducible stripping peaks for low concentrations of
Cd (II) with a minimum background current. The best results were
obtained using the combination of APTE/TiO2 NPs/GP/PO in the
optimal weight percentage ratio of 5/4/61/30 (mg). Such electrode,
illustrated a good LOD of 2.0 nM over a wide linear concentration
range of 2.9 nM to 4.6 ␮M. Meanwhile, the CMCPE presents a good
selectivity over Cd2+ ion contaminated by some of the inorganic
and biological interfering species. Thereupon, a novel Cd (II) CPE
was successfully designed and manufactured with some prominent
characteristics compared with previously reported electrochemical
Cd (II) sensors.
Acknowledgement
Our research group is very grateful to General Chemistry (I)
Laboratory staff and the headman of Kharazmi (Tarbiat Moallem)
University faculty of chemistry for their sincere cooperation in the
accomplishment of this research.
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Biographies
Soleyman Ramezani currently is a research assistant of Dr. Ahmad Ali Pourbabaei
in the Department of biotechnology, university collage of agriculture and natural
657
resources, University of Tehran, Karaj, Iran. He received a BS degree in 2009 from
Arak University, Arak, Iran and MS degree in 2012 from Kharazmi (Tarbiat Moallem)
University, Tehran, Iran. His current research interests involve chemically modified
sensors and biosensors.
Massoud Ghobadi currently is doing Ph.D. studies on synthesis and characteriza-
tion of phosphine ligands in Ilam University, Ilam, Iran. He received a pure chemistry
BS degree in 2009 from Arak University, Arak, Iran, and inorganic chemistry MS
degree in 2012 from Ilam University, Ilam, Iran.
Babak Nemati Bideh currently is Ph.D. student of Zanjan University, Zanjan, Iran.
He received a pure chemistry BS degree in 2009 from Arak University, Arak,
Iran, and inorganic chemistry MS degree in 2012 from Sharif University of tech-
nology, Tehran, Iran. His current research interests involve dye sensitized solar
cells.