Thin Solid Films 519 (2011) 35963602

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Electrosynthesis and analysis of the electrochemical properties of a composite material: Polyaniline + titanium oxide
Souhila Abaci a, Belkacem Nessark a,, Rabah Boukherroub b, Kamal Lmimouni b
a b

Laboratoire d'Electrochimie, Dpartement de Gnie des Procds, Facult de Technologie, Universit Ferhat-Abbas 19000 Stif, Algeria Universit des Sciences et Technologies de Lille, IEMN-UMR CNRS 8520, BP 60069 avenue Poincar, 59652 Villeneuve d'Ascq Cedex, France

a r t i c l e

i n f o

a b s t r a c t
The analysis of the electrochemical and spectroscopic properties of a composite material obtained starting from the polyaniline and TiO2 in H2SO4 medium, using cyclic voltamperometry, shows three redox couples characteristic of the different oxidation and reduction states of produced polymer. The electroactivity of the composite in acid medium was better than that obtained in basic medium. The impedance spectroscopy study shows that the resistance of the lm increases with the aniline concentration, but is not signicantly affected by the amount of TiO2 incorporated in polymer. The increase of pH decreases the resistance of the lms and consequently increases its conductivity. 2011 Elsevier B.V. All rights reserved.

Article history: Received 16 January 2010 Received in revised form 18 January 2011 Accepted 21 January 2011 Available online 31 January 2011 Keywords: Conducting organic polymer Polyaniline Titanium oxide Composite Cyclic voltamperometry Electrochemical impedance spectroscopy

1. Introduction Polyaniline, existing under different oxidation states, can be synthesized either by chemical or electrochemical oxidation of aniline. Like other conducting organic polymers, the polyaniline (PAn) was largely studied because of its metal behavior, good chemical and thermal stabilities, redox reversibility and its high electric conductivity when it is doped in acid medium [1,2]. In addition, polyaniline aroused a great interest due to its large eld of applications like batteries [3], protection of metals against corrosion [4], electrocatalysis [5,6], biosensors (analysis of ADN, proteins, and antipollution) [7,8], electrochromism (at-faced screens and diodes) and use in electronic components [912]. However, PAn shows nearly no electroactivity in media with pH N4. Thus, the redox potential of species to be oxidized and reduced by PAn should be within the potential range in which PAn itself is electroactive. This restricts its application in bioelectrochemistry, which requires an environment neutral pH [7]. The synthesis of polyaniline is known for a long time. It is in 1862 that Lethby [13] obtained it for the rst time, by an electrochemical synthesis. He describes this product as a dark green precipitate, deposited on the electrode. In 1986 Mac Diarmid (Nobel Prize of Chemistry 2000) described the PAn like an organic conducting polymer [14]. Polyaniline as an intrinsic conducting polymer shows a

Corresponding author at: Laboratoire d'Electrochimie et Matriaux, Dpartement de Gnie des Procds, Facult de Technologie, Universit Ferhat-Abbas 19000 Stif, Algeria. Tel./fax: +213 36 92 51 33. E-mail address: b.nessark@yahoo.fr (B. Nessark). 0040-6090/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2011.01.277

marked redox behavior. In its reduced state, it is considered as an insulator whereas when it is partially oxidized, it is a conductor ( = 10 S cm 1). The form of conducting polymer can be synthesized by electrochemical oxidation of the entirely protoned form of the PAn [16,17]. The conducting polymer can be synthesized from a base form of emeraldine acidied with varying pH or by electrochemical oxidation of the entirely protonic form of PAn which is leucoemeraldine. Various factors such as the oxidation degree of polymer, the protonation and its percentage inuence the conductivity of PAn. The latter is also affected by the degree of moisture content, morphology and texture of the polymer, the method of the deposit, the temperature and the degree of crystallinity [15]. The polyaniline can indeed be prepared in various states of oxidation. The reversibility controls its electronic structure and its electrical properties [18]. As for other conducting polymers [1921], the doping of the polyaniline can be carried out according to oxydoreduction reactions which are accompanied by a modication of the number of electrons of the system. The stability of the polyaniline depends on its oxidation state, the doping agent, the physical state of the sample and its environment (inert or oxidizing atmosphere). Organic conducting polymers are materials which have applications in the current industrial techniques, but start to bore at this beginning of the millennium. In 1977 Heeger and Mac Diarmid [14,22] worked on the doping of polycetylene with iodine, giving a polymer having metallic properties, and thus leading to an increase in conductivity of about ten. The same group [23] also tested the PAn

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as active electrodes in rechargeable batteries. The use of conducting organic polymers such as polyaniline, polypyrrole and polythiophene made it possible to obtain composites having high conductivity, and good electrochemical, mechanical and optical properties. The doping of the polyaniline in electrochemical terminology is equivalent to the electrochemical oxidation or reduction. Thus, inorganic/organic composites have been investigated extensively in recent years due to a wide range of potential use of these materials [2426]. One important class of such hybrid materials is that in which the organic fraction is composed of conducting polymers, such as polyaniline or polypyrrole. It is hopeful to obtain composite materials with synergetic or complementary behaviors between polymer and inorganic matrices. For this reason, a large number of studies have been devoted to the preparation of polyaniline-TiO2 nano-composite materials and their morphological characterization, such as size and shape of the oxide particles, degree of dispersion, kind of interaction, and interface between organic and inorganic compounds, etc. [27 29]. Schnitzler et al. [30] have prepared the polyaniline-TiO2 composite materials and characterized them. Their works proved that TiO2 could improve the thermal stability of polyaniline. Our study concerns the synthesis, and electrochemical and spectroscopic characterization of a PAn + TiO2 composite material obtained from the polyaniline, and titanium oxide semiconductor. The purpose of this work is the use of this composite material in certain applications like: energy storage, electrode material, photovoltaic cells and electrocatalysis. Thus, the analysis of the reactional mechanism, transport charge and diffusion, occurring inside this composite material, and the doping effect on the electrochemical properties were studied by cyclic voltamperometry and impedance spectroscopy measurements, in order to have information on its electrochemical properties. 2. Experimental details In this study, distilled water is used as solvent. The medium is made acid adding one of these acids H2SO4, HCl, or HClO4. The supporting electrolyte used is lithium perchlorate (LiClO4) (Fluka product), which is a pure salt for analysis. This electrolyte is chosen because of its solubility in organic and aqueous solution, and of its electrochemical stability on a large domain of potential. The reagents (Aldrich product) are: titanium (IV) oxide (TiO2) rutile 99.9, powder, as doping semiconductor, and aniline with 99.99% purity as monomer. Cyclic voltamperometry was carried out in a glass cell with double walls closed by a cover, containing the solution, in which three electrodes are immerged: the working electrode is a platinum disk (= 2 mm), the reference electrode is a saturated calomel electrode with KCl (SCE) and the auxiliary electrode is a platinum wire. The material composite was obtained by cycling, from the colloid: H2O/ (LiClO4 0.1 M + H2SO4 0.5 M + An 0.1 M + TiO2 0.1 M), at v = 10 mV/s, between 0.2 and 0.9 V/SCE. The electrolysis was carried out under stirring, in order to keep the TiO2 particles in suspension and let the particles to be continuously in contact with the electrode surface where the composite lm is being deposited. Electrochemical impedance spectroscopy (EIS) measurements were performed using an alternative current voltage of 10 mV, at open circuit potential (Eocp), in the frequency range 10 3105 Hz. The cell and the electrodes used are identical to those used in cyclic voltamperometry. The study was related to lms of polyaniline doped or not by TiO2. In this case, the working electrode is a platinum disk ( = 2 mm) modied by this lm, obtained electrochemically by cycling on a potential domain ranging between 0.2 and 0.9 V/SCE. The analysis of the lm was carried out in a system solvent/supporting electrolyte, in absence of the monomer. The recording of the curves I = f(E) or Im(Z) = f(Re(Z)) is ensured by a standard potentiostat Voltalab PG 301, piloted by a microcomputer equipped with a voltamaster 4 software for the data processing. The surface morphol-

ogy of the lms was investigated by scanning electron microscopy (ZEISS ultra 55). The operating voltage used is 1 kV. The apparatus is coupled with energy dispersive X-ray spectroscopy. The EDX operating parameters are HV:10 kV and Puls:12.84 kcps, where cps is the current gross count rate. 3. Results and discussion 3.1. Electropolymerization of aniline in H2SO4 medium Fig. 1 shows a successive cyclic voltamperograms corresponding to aniline 10 1 M dissolved in H2O/(LiClO4 0.1 M + H2SO4 0.5 M) solution, recorded in a potential range between 0.2 and 0.9 V/SCE, with scan rate v = 10 mV/s. The voltamperograms (Fig.1a) show during the positive scan potential three anodic peaks at Epa1 = 0.226, Epa2 = 0.472 and Epa3 = 0.682 V/SCE respectively. During cathodic scan three peaks at Epc1 = 0.088, Epc2 = 0.406 and Epc3 = 0.586 V/SCE are observed respectively. These peaks correspond to different oxidation and reduction states of polyaniline. The difference between anodic and cathodic peak Ep (with Ep = EPa EPc) of the three redox couples are Ep1 = 0.138, Ep2 = 0.066 and Ep3 = 0.096 V/SCE, respectively. The second redox couple is the most reversible. This is justied by the value of Ep which is very close to 60 mV [31], variation which is generally obtained for reversible systems. In addition, the ratio of the Ipa2 anodic and cathodic peak currents is about 1. Ipc2

(a)
I(A/cm2)
-0.2

140

70

0 0.0 -70

0.2

0.4

0.6

0.8

E(V/SCE)

-140

(b)
I(mA/cm2)
8

0 0.0 -4

0.4

0.8

E(V/SCE)

Fig. 1. Cyclic voltammograms corresponding to a solution of aniline (An) 10 1 M dissolved in H2O/(LiClO4 0.1 M + H2SO4 0.5 M), obtained with v = 10 mV/s, between 0.2 and 0.9 V/SCE, a) First cycle, and b) cycling.

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During the successive cyclic voltamperograms (Fig.1b), the potential of oxidation of the rst redox couple shifts slightly to more positive values and that of the third couple moves towards more negative values. However, the potential of the second redox couple remains unchanged during cycling. The displacement of the potential peaks is accompanied by an increase in the current intensity of the oxidation and reduction peaks of the three redox systems. This is done at the same time as the accumulation of a deposit of polyaniline on the electrode surface. The current intensity and the potential of the different peaks are stabilized after several cycles, attesting by this fact that a thermodynamic and kinetic stability of lm is obtained on the electrode. The increase of the two electrochemical parameters (current and potential) is weak only in the case of the second redox couple. However, it is noted that we observe the same peaks of oxidation and reduction in the three cases of acid (HCl, HClO4, and H2SO4), but the peaks are very well denite only with the sulfuric acid. 3.2. Cyclic voltamperometry of polyaniline on Pt electrode (PAn/Pt) Fig. 2 shows the cyclic voltamperograms corresponding to polyaniline deposit, analyzed in H2O/(LiClO4 0.1 M + H2SO4 0.5 M) free solution, recorded with v = 10 mV/s, between 0.2 and 0.9 V/ SCE. Polyaniline is obtained by successive scanning of potential (cycling) starting from a solution of aniline 10 1 M. As the cycling continues, a steady-state voltamperogram is reached after several scans. On washing the modied electrode and transferring it into a free electrolyte, the cyclic voltamperogram revealed the same peaks

(a)
I(mA/cm2)
12

0 0.0 0.4 0.8

E(V/SCE)
-6

showing that the PAn polymer formed has the same electrochemical behavior than that observed for the monomer. As shown by the cyclic voltamperograms, we note three anodic peaks during the positive potential scan and three cathodic peaks during negative scan (Fig. 2a). However, contrary to what was observed for the monomer, the intensity of the oxidation and reduction peaks of the polymer lm decreases slightly during the cycling, and stabilizes after several cycles. The potential of the oxidation and reduction peaks moves towards more positive values. As shown in Fig. 2b, the cathodic peaks shift to positive potentials and therefore the difference between the anodic and the cathodic peak potentials (Ep) decreases in comparison with that observed during the electropolymerization of the monomer, indicating better reversibility. However, the peak ratio of the rst redox couple is much higher than unity, which indicates that the lm formed undergoes a follow-up reaction on this lm. Moreover, cycling PAn lm between reduced and oxidized states at PAn covered electrode is accompanied by the decrease of peak intensity essentially for the rst and the third two couples assignable to PAn, i.e. those corresponding to leucoemeraldine/emeraldine and emeraldine/pernigraniline transitions. Simultaneously the development of a new redox system (Epa2 = 0.472 V, Epc2 = 0.406 V) may be seen. Note also a positive shift of the rst PAn couple simultaneously with a negative shift of the third couple, leading nally to their merging with the peaks of the second couple. The same shifts were noticed for substituted PAns [5,32], and were attributed to steric and electronic effects provided by bulky organic doping ions. Fig. 3 shows the cyclic voltamperograms obtained for different concentrations of aniline 10 4, 10 3, 10 2, and 10 1 M dissolved in H2O/(LiClO4 0.1 M + H2SO4 0.5 M) solution. The voltamperograms are recorded, in a potential domain ranging between 0.2 and 0.9 V/SCE, with v = 50 mV/s. It is noticed that the shape (intensity, potential, and number of redox couple) of the cyclic voltamperogram varies with the concentration of aniline. Cyclic voltamperogram shows at the weak concentrations only one wave of oxidation and another of reduction which is very slightly marked. However, for strong concentration the CV shows three reversible redox couples. The peaks of the rst couple were most denite and intense. The second couple was most reversible but it is the less intense. The concentration for which the oxidation and reduction peaks are well dened is 10 1 M. For that we choose this concentration in what follows. We note here that we remarked that the open circuit potential decreases with the increasing of the concentration of aniline. These values are: 0.493, 0.385, 0.340 and 0.130 V/SCE, respectively for the concentrations 10 4, 10 3, 10 2 and 10 1 M. The experimental

(b)
I(mA/cm2)
12

I(mA/cm2)

12

(a) [An] = 10-4 M (c) [An] = 10-2 M (b) [An] = 10-3 M (d) [An] = 10-1 M (d) (c) (b) (a)
0.4 0.8

0 0.0

0 0.0 0.4 0.8

E(V/SCE)
-6

E(V/SCE)
-6

-12

Fig. 2. Cyclic voltammograms relating to polyaniline (PAn/Pt), in a H2O/(LiClO4 0.1 M + H2SO4 0.5 M) solution, obtained at v = 10 mV/s and between 0.2 and 0.9 V/SCE. a) First cycle, and b) cycling.

Fig. 3. Cyclic voltammograms obtained for different aniline concentration (indicated on the gure) dissolved in H2O/(LiClO4 0.1 M + H2SO4 0.5 M) solution, recorded with v = 50 mV/s, between 0.2 and 0.9 V/SCE.

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I(A/cm2)

potential value, corresponding to the concentration of 10 1 M was situated between the rst and the second oxidation peak. This suggests that the chemical structure and the thermodynamic properties of the electrochemical double layer change with aniline concentration. 3.3. Synthesis of composite material (PAn + TiO2)/Pt Fig. 4 shows the cyclic voltamperograms of the H2O/(LiClO4 0.1 M + H2SO4 0.5 M) solution, containing An (0.1 M) and TiO2 at different concentrations indicated on the curve obtained at v = 10 mV/s, between 0.2 and 0.9 V/SCE. The recording of cyclic voltamperograms (rst cycles), show three redox couples as those usually observed in the absence of TiO2. However, we observe a shift of the oxidation potential of the rst peak toward more positive values and the third toward more negative values, whereas the oxidation potential of the second redox couple remains practically unchanged. Also, the oxidation and reduction peak current intensities of the rst two peaks increase slightly with the concentration of the semiconductor (TiO2). However, the third oxidation peak remains invariant. We note here that the previous studies [33] have shown that TiO2 incorporation into a PPy matrix during its electrochemical synthesis on mild steel under magnetic stirring leads to the formation of PPy + TiO2 composite lms containing a signicant quantity by weight. These composite lms show a slight improvement in the PPy corrosion protection of mild steel [27]. Further studies of TiO2 incorporation onto Pt during electrochemical synthesis of PAn using stronger electrolyte convection with looping to increase TiO2 concentration into PAn are shown in this work. The Pt coated with the PAn + TiO2 composite lms were then submitted to electrochemical characterizations. The time of formation of the lm on the electrode and the concentration of the titanium oxide incorporated in the matrix of polymer, increase with stirring. The electropolymerization of aniline leads to the formation of thicker and homogenous PAn + TiO2 composite lms on the platinum. Thus, stirring keeps the TiO2 particles in suspension and causes the particles to be continuously in contact with the electrode surface where the composite lm is being deposited. The results conrm that this incorporation is greatly facilitated by mechanical stirring. In accord with what was reported [34], a very small quantity of TiO2 was detected in the composite materials synthesized in the H2O/(LiClO4 + H2SO4) electrolyte without stirring even using pH values weaker than 4, compared to those obtained in the same medium with stirring.

I(A/cm2)

(a) pH = 1 (d) pH = 12 (b) pH = 4.5 (e) pH = 14 (c) pH = 7

pH = 1

28 14

(e)

500

0 0.0 -14 -28 -42

0.4

0.8 E(V/SCE)

250

(d) (c)
0.8

(a)
0 0.0 0.4

(b)

E(V/SCE)
Fig. 5. Cyclic voltammograms relating to a solution of aniline 10 M dissolved in H2O/ (LiClO4 0.1 M + TiO2 10 3 M), obtained for different pH values, with v = 10 mV/s, between 0.2 and 0.9 V/SCE.
1

I(A/cm2)

280

(a) [TiO2] = 0 M (c) [TiO2] = 10-2 M (b) [TiO2] = 10-3 M (d) [TiO2] = 10-1 M (d) (c) (b) (a)
0.0 0.4 0.8

140

Fig. 5 shows the cyclic voltamperograms (rst cycles), of aniline 10 1 M dissolved in H2O/(LiClO4 0.1 M + H2SO4 0.5 M + TiO2 10 3 M) colloidal solution, recorded in a potential range of 0.2 to 0.9 V/SCE, obtained for different pH of the solution, with a scan rate v = 10 mV/s. The variation of pH is obtained by adding NaOH 2.5 10 3 M to the colloid. In a strongly acid medium we observe the oxidation and reduction peaks of the three redox couples. Whereas, the increase of the pH leads to the disappearance of oxidation and reduction peaks usually observed in acid medium and reveals only one irreversible oxidation peak which is approximately at potential of oxidation of the third redox couple. The later is very intense at pH = 14 and it corresponds to emeraldine/pernigraniline transition. The analysis of lms obtained in basic medium in a system solvent/supporting electrolyte shows that these lms are less electroactive. As reported [23], on pH rising above 4, the inner PAn layer becomes deprotonated and thus acts as insulator, making it difcult for electrons to transfer between the electrode support and the outer redox polymer. In contrast, thin lms are almost completely converted into the redox polymer and thus by close contact with the platinum electrode are able to exchange electrons in a wide range of pH. Thus, to investigate the electroactivity of the PAn + TiO2 composite lm, the CVs of this latter have been recorded for different pH-values of solution. The results indicate that (PAn + TiO2)/Pt shows nearly no redox activity in media with pH N5. While it can be seen from Fig. 4 that the modied electrode shows three pairs of redox peaks in pH acid (1 and 4.5) the two sets of peaks at around 0.226/0.088 V and 0.682/0.586 V are attributed to the transformations of leucoemeraldine/emeraldine and emeraldine/pernigraniline, respectively, and the third pair of peaks in the middle (0.472/0.406 V) is attributed to the defects in the linear structure of the polymer. This is in accordance with that reported by Lei Zhang et al. [7] who remarked that the middle pair of peaks almost disappears when solution pH value is more than 5. 3.4. Characterization by electrochemical impedance spectroscopy (EIS) 3.4.1. Effect of the concentration of aniline The impedance spectra of PAn/Pt lms measured at open circuit potential (0.230 V/SCE) is shown as Nyquist diagrams in Fig. 6. The lm was analyzed in aqueous solution containing (H2SO4 0.5 M + LiClO4 0.1 M). The polyaniline lm is obtained starting from a variable concentration (10 4, 10 3, 10 2, and 10 1 M) of the monomer in

E(V/SCE)
-140

Fig. 4. Cyclic voltammograms relating to a solution of An 10 1 M dissolved in H2O/ (LiClO4 0.1 M + H2SO4 0.5 M), obtained for different contents of TiO2 shown in the gure, recorded at v = 10 mV/s, between 0.2 and 0.9 V/SCE, on a Pt electrode ( = 2 mm).

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0.04

0.03

-Im(Z)[k.cm2]

(a) (b) (c)

0.02

(a) [An] = 10-4 M (b) [An] = 10-3 M (c) [An] = 10-2 M (d) [An] = 10-1 M

(d)

(PAn + TiO2/Pt), increases with aniline concentration. The lm becomes less conductive and more capacitive for high concentrations. According to what is shown in further studies [3740], these features are typical for a polymer lm-coated metal in the asymmetric metal/ lm/electrolyte conguration. This result implies that the lm obtained from the weak concentration of aniline increases the electronic conductivity of the PAn/Pt and it can guarantee faster electron exchange on the electrolyte/electrode interface. 3.4.2. Effect of the pH of the solution EIS has been employed to investigate the impedance changes of the electrode surface in the modied process. Fig. 7 represents the Nyquist diagrams corresponding to a modied platinum electrode by a (PAn+ TiO2) composite material lm obtained for different pH values of the solution. The variation of pH is obtained by dosage of the H2O/ (LiClO4 0.1 M + H2SO4 0.5 M + TiO2 10 3 M + An 0.1 M), by a soda solution (NaOH 2.5.10 3 M). This lm is analyzed in an aqueous solution containing (H2SO4 0.5 M + LiClO4 0.1 M), without monomer and dopant. The curves were recorded on a frequency ranging between 105 Hz and 0.5 Hz, at the open circuit potential (Eocp = 0.230 V/SCE) at an alternative current voltage of 10 mV. We note here that we have remarked that the Eocp decreases with the increase of the pH of the solution. The open circuit potential (Eocp) values obtained for pH= 1, 4.5, 7, 12 and 14, for example, are 0.563, 0.408, 0.393, 0.390 and 0.380 V/SCE, respectively. This variation which is more signicant for acid pH values is stabilized for basic pHs.

0.01

0.03 Re(Z)[k.cm2]

0.06

Fig. 6. Nyquist diagrams relating to lms of PAn/Pt in a solution exempt of monomer H2O/ (LiClO4 0.1 M + H2SO4 0.5 M), recorded on a frequency range 105 Hz and 5.10 2 Hz, at the abandonment potential, at a disturbance of 10 mV. The lm is obtained starting from the solutions containing various aniline concentrations 10 4, 10 3, 10 2, and 10 1 M.

solution. The Nyquist diagrams were plotted on a frequency band ranging between 105 Hz and 0.5 Hz, with an alternative current voltage of 10 mV. As can be seen, EIS spectra have a single semi-circle in the high frequency region and a straight line in the low-frequency region, which are characteristic respectively of a process of charge transfer and another of diffusion. The diameter of half-circle increases with the augmentation of the concentration of aniline suggesting by this fact an augmentation in resistance and thus a decrease in the conductivity of lm. All the half circles start from the same resistance. This means that the resistance of the electrolyte remains unchanged. The straight lines of diffusion are all parallel with the same slopes. It comes out from this that the diffusion process of the electroactive species is independent of the aniline concentration. We note here that, we have in all times analyzed the lm in the same experimental conditions to avoid any change that comes from the modication of lm thickness. So, the lms were analyzed by impedance spectroscopy when the cyclic voltammogram becomes reproducible indicating no change in the potential and current peaks. This indicates that the lm thickness remains constant. This thickness is approximated to a value of few microns. For example, measurements of lm thickness of the polyaniline obtained under experimental conditions more or less similar than those we used; show that the thickness is of the order of several microns [35]. The optimized thickness of the lm calculated by a weight difference method, employing a sensitive microbalance was 0.9 m [36]. However, we note here that the presence of TiO2 in the polymer lm, affects slightly the electrochemical behavior of PAn. The composite lms (PAn + TiO2)/Pt, obtained from different concentrations of the TiO2 for xed concentration of aniline, analyzed in aqueous solution containing (H2SO4 0.5 M + LiClO4 0.1 M), give an arc of circle characteristic of the charge transfer process at high frequencies, followed by a straight line at low frequencies, corresponding to a diffusion process. The Nyquist diagrams obtained are the same and this, whatever is the content of TiO2. This suggests that the phenomenon which governs the kinetic process is not affected by the presence of the titanium oxide. This is probably due to the non electroactivity of TiO2 and its non-solubility in the medium. However the increase of the current intensities observed in cyclic voltamperometry for different peaks can be due to the capacitive effect resulting to specic surface which becomes more important and more porous. It is deduced from the semicircle diameters that the resistance of charge transfer polarization (Rp) of the composite material

1.8

-Im(Z)[k.cm2]

(a) pH = 1 (b) pH = 4.5

1.2

(a)

0.6

(b)

0.0 0.0

0.8

1.6

2.4

Re(Z)[k.cm2]

0.3

-Im(Z)[k.cm2]

(c) pH = 7 (d) pH = 12 (e) pH = 14 (e) (d) (c)

0.2

0.1

0.0

0.4

0.8

Re(Z)[k.cm2]
Fig. 7. Nyquist diagrams relative to lms of (PAn + TiO2)/Pt, obtained for various values of pH of the solution and analyzed in a solution in the absence of the monomer and TiO2.

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As shown, The Nyquist diagrams show a semicircle at high frequencies and a straight line at low frequencies for pH = 1, 12, and 14. The semicircle part corresponds to the electron transfer limited process and the linear part to the diffusion process. Whereas, for values of pH close to 4.5 and 7, we observe, a change of the diagram form. In this case, we notice the appearance of two successive arcs of circles at high frequencies, suggesting the presence of two processes of charge transfer, followed by a straight line to the low frequencies characteristic of diffusion process. In acidic medium, the semicircle is very capacitive. However, in the basic pH, the half-circle radius decreases with the increase of the pH and the slope of the diffusion straight line remains practically similar in all observed cases. As shown by impedance diagrams, the polarization resistance of the (PAn + TiO2)/Pt composite, changes with the modifying pH and aniline concentrations. These changes of the resistance of polarization (Rp) indicate that the structure, the adherence to the electrode surface and the physical properties of composite material PAn + TiO2 are very dependent to the concentration of aniline and the pH value of the colloidal solution. 3.5. Morphology and elemental composition The morphology and elemental composition of formed PAn and PAn + TiO2 lms were examined by SEM analysis. From the image of the PAn lm in Fig. 8a, it is clearly observed that the electrodeposited polymer layer on Pt substrate is homogeneous and compact. The PAn + TiO2 composite SEM micrograph (Fig. 8b) suggests that the inorganic semiconductor particles with a grain size of 0.5 m approximately, were incorporated in organic conducting polymer, which consequently modies the morphology of the lm signicantly. The inorganic semiconductor particles TiO2 are relatively piled up with PAn. Also, the micrographs conrm the underlying distribution

of TiO2 in the PAn lm by the presence of the big particles dispersed in the polymer matrix, which consequently contributes to the formation of the pores with an increase in the specic surface of the composite material electrodeposited on the electrode. The incorporation of titanium oxide in the polymer is conrmed by the EDX analysis, which shows the presence of the intense rays of titanium located at 4.50 and 0.40 keV (Fig. 9). Also, the EDX spectrum of the electrochemically prepared composite material lm shows a signal of carbon (C) at 0.25 keV and nitrogen (N) at 0.4 keV characteristic of the PAn polymer. The signals of chlorine (Cl) at 2.62 and 2.82 keV and oxygen (O) at 0.53 keV indicate that the PAn lm is doped by the perchlorate (ClO) ions. This anion results from LiClO4, which was used 4 as supporting electrolyte. The presence of the important peak of sulfur (S) located at 2.34 keV shows that the lm is also doped with SO 4 anions resulting from sulfuric acid medium. Because the platinum is used as working electrode we observe also a peak at 2.07 keV of the platinum. The other elements (Mn, Fe, Na, V, In,..) are characteristic of the presence of traces of impurities in the titanium oxide. Thus, the content of TiO2 in the composite lm is conrmed by SEM and EDX analyses. Therefore, we consider that the TiO2 particles can be incorporated in the polymer during the electropolymerization of aniline, which led to the pigmentation of the polymer lm, and the obtaining of the composite material PAn + TiO2 on the electrode. Thus, interesting electrochemical properties are obtained, allowing the use of this composite as electrode material in the eld of electrochemistry, electronic and electrocatalysis applications. 4. Conclusion We carried out a study on the synthesis and the analysis of the electrochemical properties of a composite material obtained from polyaniline, and titanium oxide, in order to have electrochemical information and to use it as composite material in applications like energy storage and electrocatalysis. Thus, the effect of the pH and the aniline concentration on the electrochemical properties of PAn + TiO2 composite material was studied by cyclic voltamperometry and impedance spectroscopy measurements. The cyclic voltamperometry study shows three redox couples. The oxidation and reduction peak currents increase during cycling, attesting to the formation of polymer lm. The analysis using impedance spectroscopy shows that the resistance of the polymer increases with the aniline concentration. The Nyquist diagrams show a charge transfer process at high frequencies followed by another of diffusion at low frequency values. The increase of pH decreases the lm resistance, and consequently increases its conductivity, whereas the resistance of the electrolyte R is slightly affected by the variation of pH. The electroactivity of composite materials obtained in acid solution was better than those synthesized in basic medium. So, a much more difference is marked in the properties and the structure of the lm during the variation of pH. The PAn + TiO2 composite lm has been synthesized on Pt via electrochemical oxidation of aniline in the presence of TiO2. Cyclic voltamperometry, electrochemical impedance

Fig. 8. SEM images of (a) PAn/Pt, and (b) (PAn + TiO2)/Pt composite lms.

Fig. 9. EDX patterns of: a) PAn/Pt, and b) (PAn + TiO2)/Pt.

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spectroscopy and SEM techniques have been used to characterize the composite material. The PAn exhibits better electrochemical behavior in acidic media, which makes it suitable for use as composite materials in electrochemical and catalysis applications. The resulting composite-modied electrodes have been exploited to achieve electrochemical and electrical applications as electro catalysts and energy conversion as electrodes for photovoltaic cell. The strategy presented here may be of general interest since it provides a route to build a composite material for the modication of electrode surfaces and related applications. References
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