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Res Chem Intermed
DOI 10.1007/s11164-012-0954-6
M. M. Radhi (&)
Department of Radiological Techniques, College of Health and Medical Technology, Baghdad, Iraq
e-mail: mmradhi@yahoo.com
E. A. Jaffar Al-Mulla
Department of Chemistry, College of Science, University of Kufa, P.O. Box 21,
An-Najaf 54001, Iraq
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Introduction
Working electrodes act as a source or sink of electrons for exchange with molecules
in the interfacial region, and must also be electronic conductors and electrochem-
ically inert. Commonly used working solid electrode materials for cyclic
voltammetry include platinum, gold, and glassy carbon. Other materials (e.g.,
semi-conductors, for example, ITO, indium-tin oxide, conductive polymers or
grafted polymers) are also used for more specific applications. Polystyrene is a
polymer made from the monomer styrene. At room temperature, polystyrene is
normally a solid thermoplastic, colorless and harder plastic, and it has low thermal
conductivity 0.08 W/(mk), while electrical conductivity (r) is 1016 S m-1. A
common thermoplastic is a copolymer of acrylonitrile and styrene, toughened with
polybutadiene. Conductive polymers are good candidates for preparation of
conducting grafted copolymers [16]. The thermal degradation of a grafted
copolymer in which acrylonitrile is grafted on to polystyrene has been studied by
thermogravimetric analysis [7, 8]. Polystyrenepolyacrylonitrile copolymers have
been prepared by the direct radio-induced grafting method [9]. Grafted copolymers
were prepared by copolymerization of acrylonitrile with poly (sodium styrene
sulfonate) macromonomers. Macromonomers were prepared by stable free radical
polymerization, and then the ionic conductivity of the new copolymer was studied
by electrochemical reduction [10, 11]: electrochemical synthesis of electrically
conducting polymers chemically grafted to conducting surfaces (e.g., glassy carbon,
stainless steel, nickel, gold). This is based on new functional acrylate monomers,
i.e., 3-(2-acryloyloxyethyl) thiophene and N-(2-acryloyloxyethyl) pyrrole. Cyclic
voltammetry was used to confirm that the two-component film is conducting and
electrochemically active (reversible doping and dedoping) [12]. The cathodic
electropolymerization of acrylonitrile (AN), ethylacrylate (EA), and methylmeth-
acrylate (MMA) has been monitored for the first time by coupled electrochemical
quartz crystal microbalance (QCM) and cyclic voltammetry analyses [13]. A new
conducting copolymer, polyacrylonitrile-graft-polyaniline (PAN-g-PANi), has been
prepared by chemical and electrochemical methods from a precursor polymer.
Electrical conductivity of the copolymer was studied using the four-probe method,
which gave a conductivity of 4.5 9 10-3 S cm-1 with 51.4 % PANi [14].
In this work, a grafted polymer electrode (GPE) was fabricated from 15 % grafted
polystyrene with acrylonitrile using gamma irradiation. This new working electrode was
successfully used in cyclic voltammetry with large advantages in comparison with other
working electrodes like GCE, Pt-E, and Au-E. GPE was characterized electrochemically
in aqueous electrolyte in which it proved successful with good results.
Experimental
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Electrochemical characterization of the redox
Reagents
All reagents were analytical reagents or electrochemical grade purity. All solutions
were prepared using distilled water. Unless otherwise specified, the supporting
electrolyte was used 0.1 M KCl in aqueous media at room temperature.
The grafted polymer electrode (GPE) has been fabricated from grafted polymer. The
percentage of grafted polymer and the diameter of electrode were 15 % and 3 mm,
respectively. A hole was bored (1 mm) to allow 1 cm length of platinum wire to
come out from the other side of the electrode. A copper wire was then joined with
the platinum wire. After that, all parts of the fabricated electrode was covered with a
glass tube and then fixed with epoxy resin.
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Fig. 1 Cyclic voltammetry of different electrodes a GP/Pt electrode, b Pt wire electrode, and c GCE in
1 mM K3Fe(CN)6 with 0.1 M KCl as supporting electrolyte versus Ag/AgCl and 100 mV s-1
chemical and physical effects were assessed in order to determine the optimum
conditions under which maximum current response at the GPE can be obtained.
Figure 2 shows the two redox peaks of Fe(CN)3- 6 when the working electrode
GPE is used as the working electrode in 0.1 M KCl as the supporting electrolyte.
The first redox process of Fe(III)/Fe(II) produced ?0.1 and ?0.3 V for reduction
and oxidation peaks, respectively, while the second redox process of Fe(II)/Fe(0) at
-0.3 V can be assigned for the reduction and -0.05 V for oxidation.
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Electrochemical characterization of the redox
Fig. 2 Cyclic voltammetry of GPE in different concentrations of 1 mM K3Fe(CN)6 and 0.1 M KCl two
redox peaks of Fe versus Ag/AgCl and 100 mV s-1
Fig. 3 Cyclic voltammogram of (a) GCE, (b) GPE in 0.1 M KCl. SR = 100 mV s-1 versus Ag/AgCl
The different type of supporting electrolyte exerts slight influence on the redox peak
potential of Fe(III) as expected, especially in non-complexing solutions (Table 1).
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In general, redox peaks of Fe(III) appear to have a similar pattern of peak formation
in various supporting electrolytes. However, the redox current peak of the Fe(II)/
Fe(III) couple shows that the greatest enhancement effect is obtained when
potassium perchlorate is used as electrolyte. In general, the degree of redox current
enhancement in varying electrolyte varies in the following order:
Oxidation peak: KClO4 [ K2SO4 [ K2HPO4 [ KCl [ KNO3
Reduction peak: KClO4 [ KNO3 [ K2SO4 [ K2HPO4 [ KCl
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Electrochemical characterization of the redox
The effect of varying scan rates on the cyclic voltammograms using GPE as
working electrode in 0.1 M KCl supporting electrolyte was studied with 1 mM
K3Fe(CN)6 over a scan rate range of 51,000 mV s-1. Oxidation and reduction
currents of the Fe(III)/Fe(II) couple was observed to increase with scan rate due to
heterogeneous kinetics and IR effect as shown in Fig. 5.
Based on a plot of log(Ipa) versus log (scan rate) for the oxidation current of the
first cycle, a straight line was obtained in Fig. 6 fulfilling the equation
y = 0.4388 9 ?1.7912 with R2 = 0.9988. A slope of 0.44 is quite comparable
with the theoretical slope of 0.5 for the diffusion controlled process.
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Fig. 5 Cyclic voltammetry of GPE in 0.1 M KCl and 1 mM K3Fe(CN)6 at different scan rates (5,10, 50,
100, 250 and 500 mV s-1) versus Ag/AgCl and 100 mV s-1
3.1
3 y = 0.4388x + 1.7912
2.9 2
R = 0.9988
2.8
LogIpa
2.7
2.6
2.5
2.4
2.3
2.2
2.1
0.69 1.19 1.69 2.19 2.69 3.19
logV
Fig. 6 Plot log Ipa (anodic current) versus log SR (scan rate) of GPE in 0.1 M KCl and 1 mM
K3Fe(CN)6 versus Ag/AgCl
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2.75
y = -0.2098x + 3.2967
2
2.7 R = 0.9937
2.65
LogIpa
2.6
2.55
2.5
2.6 2.8 3 3.2 3.4 3.6
1/TX0.001
Fig. 7 Plot of log(Ipa) versus 1/T910-3 of 1 mM K3Fe(CN)6 in 0.1 M KCl at different temperatures
(1090 C) using GPE versus Ag/AgCl and 100 mV s-1
3.5
3.2
Log(Ipc)
3.1
3
2.9
2.8
2.7
2.6 2.65 2.7 2.75 2.8 2.85
1/TX0.001
Fig. 8 Plot of log(Ipc) versus 1/T910-3 of 1 mM K3Fe(CN)6 in 0.1 M KCl at different temperatures
(1090 C) using GPE versus Ag/AgCl and 100 mV s-1
390
y = 41.802x - 69.113
340 2
R = 0.9484
290
Current, uA
240
190
140
90
40
2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 10.5
Concentration, mM
Fig. 9 Plot Ipc (cathodic current) versus different concentration K3Fe(CN)6 (110 mM) in 0.1 M KCl at
scan rate 100 mV s-1 using GPE versus Ag/AgCl
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Fig. 10 Chronoamperograms or Cottrell plot obtained for 1 mM K3Fe(CN)6 and 0.1 M KCl as
supporting electrolyte using GPE versus Ag/AgCl. Potential was scanned in a negative direction from
-1,800 to ?1,800 mV with 250 ms pulse width
Fig. 11 Choronocoulomogram or Anson plot of charge, versus t1/2 obtained for the redox of 1 mM
K3Fe(CN)6 and 0.1 M KCl as supporting electrolyte using GPE versus Ag/AgCl
on the diffusion process to a planar electrode. The diffusion coefficient (D) of 0.1 M
KCl using GPE as a working electrode is 3.2 9 10-7 cm2 s-1. It was found that the
GPE has a total charge transferred of 12.8 lC m-2 in Fe(CN)3- 6 ion as in Fig. 11.
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Fig. 12 Cyclic voltammetry of GPE in 0.1 M KCl and 1 mM K3Fe(CN)6 at different pH (1, 2, 3, and 4)
versus Ag/AgCl and 100 mV s-1
Figures 12 and 13 are cyclic voltammograms for studying the effect of different pH
of 1 mM K3Fe(CN)6 in 0.1 M KCl solution using HCl or NaOH solution on the
working GPE. It was found that the redox current of Fe(CN)3- 6 increases at a
solution of highly acidic pH, and 50 mV potential shifted to higher potential. For the
pH 11 electrolyte solution, redox peaks were shifted to the original potential with a
decrease of the redox current.
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Fig. 13 Scanning electron micrographs of mV s-1grafted polymer as electrode a before and b after
electroanalysis with potassium ferricyanide in aqueous solution of 0.1 M KCl
Scanning electron microscopy of the grafted polymer GP was studied using a JEOL
attached with Oxford Inca Energy 300 EDXFEL scanning electron microscope
operated at 2030 kV. The scanning electron photographs were recorded at a
magnification of 100k9 depending on the nature of the sample. Samples were
dehydrated for 45 min before being coated with gold particles using the Baltec
SC030 Sputter Coater. SEM was used to examine the morphology of the grafted
polymer (GP) before (Fig. 13a) and after (Fig. 13b) electrolysis in K3Fe(CN)6 by
cyclic voltammetry. Before electroanalysis, the GP surface appears compact and
nonporous, while the uniformity of the GP surface is marred by a wavelike
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Conclusion
A GPE has an extended potential working region as compared to GCE. The stability
of GPE as a working electrode was evaluated by using a K3Fe(CN)6 solution. Redox
peaks of Fe(CN)3- 4-
6 /Fe(CN)6 obtained at GPE appears as a high current compared
with GCE. Although the oxidative and reductive region is limited with the high
range of ?2.0 to -2.0 V, the use of potential cycling helps to significantly widen
the redox working potential range. Electrocatalytic activity of GPE is therefore
evident in this study.
A new grafted polymer electrode (GPE) was studied by the redox process of
K3Fe(CN)6 during cyclic voltammetry, and the redox peaks potential shifted
slightly to a less negative value by about 100 mV for the oxidative peak and 50 mV
for the reductive peak with current enhancement of about threefivefold. The
sensitivity under conditions of cyclic voltammetry is significantly dependent on the
concentration, pH, temperature, electrolyte, and scan rate.
References
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