J. Chem. Chem. Eng.

7 (2013) 1121-1126

DAVID

PUBLISHING

Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines

Maksim Zagorny*, lexander Zhygotsky, Tatyana Lobunets, Anatoliy Pozniy and Andrey Ragulya
Department of Physical Chemistry and Technology of Nanostructure Ceramic and Composites, Ivan Nikitovich Frantsevich Institute for Problems of Materials Science of NAS of Ukraine, Kiev 03680, Ukraine Received: October 09, 2013 / Accepted: October 26, 2013 / Published: December 25, 2013. Abstract: Photocatalytic activity of doped polyaniline nanopowders with different molar ratio of An/O (aniline/oxidizer) has been studied in the process of photocatalytic decolorization of aqueous solutions of methylene blu. By means of scanning electron microscopy and low-temperature N2 adsorption method, it was found that doped PANI (polyaniline) nanopowders have the particles size of 30-50 nm with the specific surface area of 20-35 m2g-1. It was found that PANI photocatalytic activity essentially depends on molar ratio of An/O and adsorption interactions between the dye molecules and catalytic active centers on PANI surface and these interactions are greatly affected by pH of the solution 9.2. An optimum of the synergetic effect is found for an initial molar ratio of aniline to oxidizer equal to 0.8. Key words: Photocatalyst, doped polyaniline, conducting polymer, mesoporous structure.

1. Introduction
Conducting polymers have received ever-increasing attention, especially in last two decades. Among them, PANI (polyaniline) is unique due to its ease of synthesis, environmental and chemical stability, and simple doping/dedoping chemistry. Most important is its forbidden band gap of 2.8 eV, which is suitable for the sensitization of TiO2 [1]. The general formula of PANI is the same structure in all cases and consists of a succession of reduced benzenoid nuclei and oxidized quinoid nuclei, but the method of oxidation affects the performance of the polymer and the reproducibility of the synthesis [2]. The properties of PANI depend on pH, reaction temperature, nature of the used acid, the mode of doping and the structure of the monomer (presence of substituents). An important aspect of PANI synthesis is the nature of the acid-dopant. The role of the acid
Corresponding author: Maksim Zagorny, Ph.D., research fields: conducting nanocomposites PANI, TiO2, polyaniline E-mail: and ferroelectric films BaTiO3. maksimmaksim@bigmir.net.
*

dissociation constant, pKa, is known; in PANI, the protonation equilibrium involves the quinoid nucleus having two imine nitrogens with pKa1 = 1.05 and pKa2 = 2.556, therefore any acid is suitable as a dopant if its pKa value lies in this range [3]. Any acid having a pKa around the value of the anilinium ion (pKa = 4.60) would be suitable as the solvent and prevents over oxidation [3]. Thus, the properties of PANI are affected by the type of the employed dopant ion. The type of dopant anion affects the stability, electrical conductivity, polymerization kinetics and yield of the polymer. The synthesis and characterization of PANI doped with different anions are critical since many properties of the final polymer are greatly influenced by the nature of the dopant ion [3-4, 9-11]. Previous researchers have shown that doped PANI has excellently electrical and optical properties in dependence of type dopant. It should be noted that for the majority of the published studies the synthesis and surface structure of PANI using acid-dopants [5, 6, 9]. The authors think that study photocatalytic activity of doped PANI is very important with usage short

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Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines

time UV (ultra violet) irradiation at pH 9.2 because of forbidden band gap of doped PANI. The combination doped PANI and TiO2 nanopowders [7] in situ process can bring a good capacitive material. So we tried to show effect photosentisizer of nanopowders doped PANI using MB dye as model during UV irradiation. In the present study, a series of polyaniline nanopowders with different molar ratio of An/O were prepared by chemical oxidative polymerization of aniline. In addition, their surface structure, conductivity and photocatalytic degradation of methylene blue were investigated. When initial molar ratio of aniline to ammonium peroxydisulfate equal to 0.8, the photocatalytic efficiency of composite was enhanced under UV light irradiation at pH 9.2.

obtain particles of polymer. 2.3 Characterizations of Doped Polyaniline The morphology of PANI particles were

investigated using scanning electron microscopes Ultra Plus Carl Zeis (Germany) and JSM-7600F JEOL (Japan) at acceleration voltage of 200 kV. ASAP (accelerated surface area and porosimetry) 2000 System was used for N2 adsorption studies at 77 K. BET (Brunauer-Emmet-Teller) and BJH (Barrett-Joyner-Halenda) methods were used to estimate the N2-adsorption isotherms. UV irradiation of the solutions was carried out for 5-60 min with a high pressure Hg lamp of CVD-120 type with UV intensity of 18.9 Wm-2 in a wavelength range of 200-400 nm. Hydrochloric and boric acids were used to adjust pH values of the feed solutions. The initial concentrations of dye and PANI in aqueous solutions were 0.04 gdm-3 and 1 gdm-3, respectively. For conductivity and electrical properties, silver paste was used to attach the gold wires as contacts. Then, I-V (current-voltage) measurements were done using the four-point probe method and resistivity measurements were derived using the Van der Pauw method in an in-line configuration.

2. Experiments
2.1 Reagents and Materials MB (methylen blue), An (aniline), ammonium peroxydisulfate and hydrochloric acid were obtained from Merck Chemical Reagents Company. All these reagents were used without further purification. 2.2 Synthesis of Doped Polyaniline Doped polyaniline were prepared by chemical oxidative polymerization of An (Aniline) were dispersed into 80 mL of 1 mol/L HCl aqueous solutions with ultrasonic vibrations for 15 min to obtain a uniform suspension. Quantitative ammonium peroxydisulfate (APS) aqueous solution in 1 mol/L HCl was added into this mixture dropwise under vigorously stirring in the ice-water bath to the reaction vessel. Then, the mixture was allowed to polymerize under stirring for 2 h. Finally the doped polyaniline was filtered and washed with large amount of deionized water, then with 100 mL of ethanol and 50 mL of ether, after that particles were dried at 60 C till the constant mass was reached. In the experiment, different initial molar ratios of monomer to oxidizer 1/1, 1/1.25, 1/1.4, 1/3 (1, 0.8, 0.71, 0.33) were used to

3. Results and Discussion

3.1 Surface Structure of Doped PANI Nitrogen adsorption isotherms on doped PANI may be referred to IV type of adsorption isotherms according to BET and IUPAC (international union of pure and applied chemistry) classification for solid porous materials. Taking into account the shape and location of a hysteresis loop at the adsorptiondesorption isotherm, the studied PANI powders may be considered as adsorbents with cylindrical and slide-like pores in accordance to De Bur classification (Fig. 1). The volume value of mesoporous (Table 1) was a higher for PANI synthesized with HCl at ratio of An/O 0.8 in comparison with PANI [6].

Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines

1123

1-An/O = 1 2-An/O = 0.8

polymer yield more than 90%. From these data, it is evident that molar ratio An/O greatly influences on the yield of polymer. The acid polymer yield reaches greater than 80% compared to water medium. Analysis TG curves of the samples PANI-s (Fig. 3) shows that the thermal decomposition process is characterized mainly by the three temperature range of 52-190 C, 190-311 C and 311-850 C. Initial weight loss in the first sample of PANI temperature range is carried out by volatile products and partial dedoping polymer. On further heating of the sample PANI, there is a slight loss of weight up to 287-290 C with no thermal effect (Fig. 3a). This is probably due to the change of the phase state of the polymer. When a temperature above of 300 C, especially at 400 C, the process of weight loss increases sharply, due to the process of oxidative degradation of the polymer which extends almost right up to the linear velocity of the complete decomposition of the polymer at 800 C. In the second interval of 190-311 C for the sample, PANI (Fig. 3b) is also a slight loss in weight.

Fig. 1 The isotherm of nitrogen adsorption on polyanilines powders at 77 K with different ratio of An/O (Origin).

The SEM results of PANI powders (Fig. 2) show that the polymer particles with size 50 nm 70 nm, tend to aggregate to form a slit-like structures, and the tendency to aggregate more pronounced. Thus, adsorption powders PANI structural studies indicate that the test powder PANI can be regarded as highly developed adsorbents slit porous structure. Particularly for PANI synthesized with a ratio of An/O 0.8 at an average pore diameter of 14 nm and
Table 1 Sample N 1 2 3 4 Surface-volume characteristics of PANI nanopowders. An/O 1 0.8 0.71 0.33 SBET (m2g-1) 29.0 35.3 29.1 25.8

Vmeso (cm3g-1) 0.083 0.699 0.099 0.144

D (nm) 12.2 14.2 13.4 8.1

Yild (%) 80.0 93.2 70.0 68.0

(a) Fig. 2

(b)

SEM images of PANI powders at different ratio of An/O: ()An/O = 0.8; (b)An/O = 0.33.

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Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines

100 90 80 70 60

a b

P (%)

50 40 30 20 10 0 0 100 200 300 400 500 600 700 800 900 1000

Fig. 4

I-V characteristics of doped PANI (An/O = 0.8).

T ( C)

Fig. 3 Dependence of weight loss (% P) polyanilines on temperature: aPan (An/O = 1), bPan (An/O = 0.8).

On the TG curve for this, temperature range is visible plateau. This may indicate physical and chemical phenomena are not accompanied by breaking of chemical bonds (reorganization of double bonds). In the third range of 311-832 C causes destruction of the structure of the sample, wherein the process proceeds at a slow rate. On the TG curve in the temperature range of 311-350 C is characterized by a bend. In the latter the temperature oxidation, rearrangement and rupture of the main bonds is accompanied by considerable heat-exothermic effect. Thus, from the analysis of the results obtained revealed that the synthesis conditions and the composition of the original PANI components substantially determined thermo-oxidative degradation of the polymer (heat stability). The molar ratio of An/O 0.8 is optimum for thermal stability of polymer. 3.2 Electric Properties of Doped PANI Conductors generally show ohmic behavior wherein the voltage across the material varies linearly with the current and the I-V plot has a constant slope, which is the resistance of a material. This means that the current linearly increases with the applied electric field. So, very high correlation coefficient R (Fig. 4) is similar to doped PANI the range of 0.9686-0.9997 [10]. Molar ratio of An/O influences on conjugation of benzene and quinoid rings fragments of PANI

Fig. 5 The active component of the complex impedance of doped PANI.

macromolecules. It is very important for PANI-s conductivity. When frequency of electric field increases the value of resistivity Ra decreases (Fig. 5). It may be due to the fact when the frequency increases the activation energy decreases and the electrons move in the areas of PANI macromolecules interfaces and overcome significant potential barrier in the transition from one region to another. 3.3 Photocatalytic Activities of Doped PANI UV irradiation of PANI slurries containing MB is accompanied by decolorization, the speed of the process reaches a maximum during the first 5-10 min (Fig. 6). The maximum degree of decolorization observed for the suspension containing particles PANI doped with HCl acid (An/O = 0.8). This is probably due to the fact that under UV irradiation at of 200 400 nm excitation is a PANI molecule, which results in thrown at the electrons closer to the conduction

Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines

1- An/O=0.8 2-An/O=0.71 3-An/O=0.33 1
80

1125
1-An/O = 0.8 2-An/O = 0.33

100

(1-C/C 0)*100%

60

40

20

0 0 10 20 30 40 50 60

(min) tt (min) Fig. 6 The kinetics of decolorization of MB slution with various PANI nanopowders under UV-irradiation.

band, and further to the formation of the traps (NO OH) of the polymer with varying depth occurrence relative to the conduction band. When conductivity increases, the PANI trap concentration increases. Because of the process proceeds in an oxidizing medium at pH 9.2, the contact surface of these traps dye contributes to its oxidative degradation. MB dye adsorption on the surface of the PANI is the primary instrument of photocatalytic oxidation process since it takes place in an oxidizing environmentan aqueous solution, oxygen, ozone generated by the passage of UV radiation through the air. As shown by adsorption experiments to determine the MB in PANI surface (Fig. 7), this process as well as UV-decolorization MB is characterized mainly the same kinetics. In the case of doped sample, it is significantly higher adsorption MB and reaches a maximum speed in the first 5-20 min, and the absolute decolorization effect considerably less than UV dye decolorization solution. As shown by studies of the adsorption MB solutions at various concentrations (0.02-0.08 gdm-3) for PANI particles for 1 h, the interaction of molecules with the particle surface PANI significantly slowed by MB solution concentration of 0.04 gdm-3 (Table 2). The calculated values of area occupied by a molecule

A (mmol/g) t (min) Fig. 7 The kinetics of adsorption of MB dye on various PANI nanopowders. Table 2 The MB molecule area in the powder PANI (An/O = 0.8) adsorption layer. The MB molecule area MB concentration in B adsorption in the adsorption layer -1 -2 solution (mmolL ) (mgm ) (nm2) 0.053 0.56 1.09 0.106 1.03 0.60 0.159 1.46 0.42 0.212 1.64 0.36

MB adsorption equilibrium values show that MB solution at 0.04 gdm-3 in maximum speed adsorption and molecules MB photocatalytic process in a vertical orientation. At higher concentrations of dye molecules form aggregates MB. It is known that in the monolayer molecule MB in vertical and horizontal positions, respectively, covers an area of 0.64 nm2 and 1.20 nm2 [8].

4. Conclusions
PANI nanopowders with different molar ratio of An/O were prepared by chemical oxidative polymerization of aniline. In addition, their surface structure, conductivity and photocatalytic degradation of methylene blue were investigated. It was shown that MB molecules interact with the PANI surface with formation sufficiently strong bonds. Given the rather well-developed mesoporous structure of PANI powder, these links can be a point character. It also confirms the vertical orientation of the

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Mesoporous Structure and Photocatalytic Activity of Doped Polyanilines Stejslal, J.; Gilbert, G. Preparation of a Conducting Polymer. Pure Appl. Chem. 2002, 74, 857-867. [5] Stejslal, J.; Sapurina, I.; Trchova, M. Polyaniline Nanostructures and the Role of Aniline Oligomers in Their Formation. Prog. in Polym. Sci. 2010, 35, 1420-1481. [6] Nandi, M.; Gangopadhyay, R.; Bhaumik, A. Mesoporous Polyaniline Having High Conductivity at Room Temperature. Micropor. Mesopor. Mater. 2008, 109, 239-247. [7] Zhygotsky, A.; Rynda, E.; Kochkodan, V.; Zagorny, M.; Lobunets, T.; Kuzmenko, L.; et al. Effect of Dispersity and Porous Structure of TiO2 Nanopowders on Photocatalytic Destruction of Azodyes in Aqueous Solutions. J. Chem. Chem. Eng. 2013, 7, 949-957. [8] Dtayls, U. Adsorption from Solutions on Solid Material Surface, Moscow, 1986. [9] Vivekanandan, J.; Ponnusamy, V.; Mahudeswaran, A.; Vijayanand S. Synthesis, Characterization and Conductivity Study of Polyaniline Prepared by Chemical Oxidative and Electrochemical Methods. Arch. Appl. Sci. Res. 2011, 3, 147-153. [10] Catedral, M. D.; Tapia, A.; Sarmago, R.; Tamayo, J.; Rosario, J. Effect of Dopant Ions on the Electrical Conductivity and Microstructure of Polyaniline (Emeraldine Salt). Sci. Diliman. 2004, 16, 41-46. [11] Hammos, S. H. Effect of Acidic Dopants Properties on the Electrical Conductivity of Poly Aniline. Tikrit Journal of Pure Science 2012, 17(2), 6-10. [4]

molecules in the adsorbed layer of MB. In dependence of ratio An/O, polymers exhibits a greater or lesser degree of photocatalytic activity. This can be explained by the fact that the PANI has a greater length of conjugated double bonds compared to the MB system. It can be easily move to an excited singlet state, and the reverse transition to the ground state energy transfers in contact with him molecule dye MB. The results suggest that the sensitizing effect of PANI nanopowder (An/O = 0.8) under UV light and degradation of methylene blue solution due to the presence of electron traps in the molecular structure of the photocatalyst.

References
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