J Sol-Gel Sci Technol (2011) 58:201208 DOI 10.

1007/s10971-010-2378-3

ORIGINAL PAPER

The inuence of titanium dioxide phase composition on dyes photocatalysis

Luminita Andronic Diana Andrasi Alexandru Enesca Maria Visa Anca Duta

Received: 29 September 2010 / Accepted: 2 December 2010 / Published online: 14 December 2010 Springer Science+Business Media, LLC 2010

Abstract A comparative study of TiO2 powders prepared by solgel methods is presented. Titanium tetraisopropoxide was used as the precursor for the solgel processes. The effects of the annealing treatment on phase, crystallite size, porosity and photodegradation of dyes (methyl orange and methylene blue) were studied. The phase structure, microstructure and surface properties of the lms were characterized by using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The X-ray diffraction was used for crystal phase identication, for the accurate estimation of the anataserutile ratio and for the crystallite size evaluation of each polymorph in the samples. It was found that the only TiO2 anatase phase of the synthesized TiO2 develops below 500 C, between 600 and 800 C the anatase coexist with rutile and above 800 C only the rutile phase was found in the samples. Attention has been paid not only to crystal structures, but also to the porosity, the particle size and the photocatalytic properties. However, the annealing temperature was found to have signicant inuence on the photocatalytic properties. Different TiO2 doctor blade thin lms were obtained mixing the sol gel powder (100% anatase) and TiO2 Aldrich with TiO2 Degussa P25. The surfactant (Triton X100 or sodium dodecyl sulfate) affects the packing density of the particles during deposition and the photocatalytic degradation efciency of the dyes. The photocatalytic degradation kinetics of methyl orange and methylene blue using TiO2 thin lm were investigated. Keywords Titanium oxide Solgel deposition Photocatalysis Dyes
L. Andronic (&) D. Andrasi A. Enesca M. Visa A. Duta The Centre: Product Design for Sustainable Development, Transilvania University of Brasov, Eroilor 29, 500036 Brasov, Romania e-mail: andronic-luminita@unitbv.ro

1 Introduction Heterogeneous photocatalysis is a relatively novel method used for removing organic pollutants (particularly, dyes) from wastewaters resulted in the textile nishing industry [1, 2]. Many photocatalysts have been reported to degrade organic pollutants such as semiconductors: WO3, SnO2, CdS, ZnO, Nb2O5, TiO2 [38], metal and nonmetal doped semiconductors [914], coupled semiconductors: TiO2/ CdS, TiO2/SnO2, TiO2/ZnO, TiO2/WO3 [1517]. Titanium dioxide (TiO2) is frequently used for environmental purication because of its many desirable properties: non-toxicity, photochemical stability, and low cost [18, 19]. It is usually used in two forms: particles suspended in aqueous solution and thin lms immobilized on substrates. In most of the experiments concerning the TiO2 photocatalysis, the photocatalyst was used in the powder form and the recovery of powder was difcult to execute. Thus, immobilization of the TiO2 semiconductor particles is necessary for industrial applications. The methods used for the synthesis of titanium dioxide powder include alkali precipitation, thermal decomposition, hydrothermal synthesis, solgel [2022] and other routes. Among all these procedures, preparation of TiO2 by a solgel route remains one of the most attractive due to the less energetic conditions and the possibility of preparing powders or thin lms with controlled properties. Preparing thin lms from solgel powder can be done by dipping or by doctor blade techniques. The doctor blade technique requires no expensive apparatus, is exible in terms of substrate geometry, and can be used to obtain, in optimized conditions, highly omogeneous surface surfaces in terms of morphology. Titanium oxide crystallizes in three polymorphic forms: anatase (tetragonal), rutile (tetragonal) and brookite

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(orthorhombic). The phase composition has a crucial impact on the photocatalytic activity. It is well known that anatase phase is found suitable for photocatalytic oxidation of organic pollutants in water and air [1]. This effect has often been attributed to the larger surface area of anatase compared to rutile, the higher afnity of anatase for organic compounds, and slightly larger band gap (3.2 vs. 3.0 eV for rutile). The aim of this work was to optimize the polymorphs composition of TiO2 (anatase: rutil) efcient for dyes degradation. The powders used were TiO2 prepare by sol gel and other two commercial powders: Aldrich (99.9% anatase) and Degussa P25 (80% anatase, 20% rutile). The effects of the annealing temperature on the crystal structure, morphology, porosity, and photocatalytic efciency towards degradation of methyl orange and methylene blue are studied. Further, the effects of mixing two powders with different polymorph composition (solgel, Aldrich, respectively Degussa P25) on the photocatalytic properties of the TiO2 lms is investigated.

TiO2 Degussa P25 (with BET surface area 55 15 m2/g; average primary particle size around 30 nm, purity above 97% and a 80:20 anatase: rutile ratio), TiO2 Aldrich (99.9% anatase, specic surface area 48 m2 g-1 and a mean particle size of 1 lm), ethanol, acetylacetonate (C5H8O2, 99.9%, Alfa Aesar), Triton X100 (TX) (non-ionic surfactant, Scharlau Chemie), sodium dodecyl sulfate (SDS) (anionic surfactant, Scharlau Chemie).

2.2.2 Doctor blade deposition For the doctor blade deposition of nanoporous TiO2 lms, an aqueous colloid paste is formed by mixing TiO2 powder (solgel or Aldrich with Degussa P25) with 3.6 mL of ethanol, 0.4 mL acetylacetone and 0.4 mL surfactant 10 g/L (Triton X100 or SDS). The paste was diluted by very slow addition of 2 mL of ethanol. Finally, the paste is smeared on glass substrate (1.5 9 2.5 cm2) cleaned using ethanol, distilled water, acetone in successive sonication processes. After drying in air at 60 C for about 2 min, the lms were annealed in an oven at temperatures 500 C, for 3 h. The solgel powder was mixed with Degussa P25 in a weight ratio 1:1, the surfactant used was Triton X100 (sample SG-P25(TX)) or sodium dodecyl sulfate (sample SG-P25(SDS)). After drying in air at 60 C for about 2 min, the lms were annealed in an oven at 400 C, for 3 h. The Aldrich powder was mixed with Degussa P25 in a weight ratio 1:1, the surfactant used was Triton X100 (sample AldrichP25(TX)). 2.3 The catalyst characterization The crystalline phase transformation temperature and enthalpy were measured for the predominant amorphous powder dried at 100 C using a differential scanning calorimeter (PerkinElmer, DSC-2). The DSC and analysis of the sample were performed from ambient temperature up to 500 C with a heating rate of 5 C/min. During the measurements, pure nitrogen (N2) was used as a purging gas at a ow rate of 20 cm3/min. The phase structure, microstructure and surface properties of the lms were characterized by using X-ray diffraction (XRD-Brucker D8 Discover diffractometer with CuKa radiation) and Atomic Force Microscopy (AFM-NT-MDT model NTGRA PRIMA EC). The images were taken in semi-contact mode with GOLDEN silicon cantilever (NCSG10, force constant 0.15 N/m, tip radius 10 nm). Scanning was conducted on three different places (a certain area of 5 9 5 lm for each section) chosen randomly at a scanning rate of 1 Hz.

2 Experimental 2.1 Synthesis of TiO2 powder by solgel technique The TiO2 sol was synthesized by acid catalyzed solgel formation method using 60 mL of 1 M HNO3 and 15 mL of titanium tetra-isopropoxide following the hydrolysis reaction. Titanium tetra-isopropoxide was added gradually to the aqueous solution of HNO3 solution under continuous stirring for 3 h to produce a transparent sol. Subsequently, the pH of the colloid solution was adjusted to 3 with the addition of 1 M NaOH resulting in a turbid colloid. The pH adjustment was necessary to prevent the destruction of the structure of adsorbent in the acidic media. The mixed suspension was agitated by magnetically stirrer for another 2 h at room temperature, followed by ltration (Millipore 0.45 lm) and washings with de-ionized water until the pH of the supernatant was about 6. The resulting TiO2 powder was dried in a furnace for 1 h at 100 C and nally the powder was annealed at temperatures from 100 to 900 C for 3 h. 2.2 Thin lms preparation 2.2.1 Materials The materials used for catalyst preparation were: TiO2 solgel powders annealed at 100900 C for 3h; for thin lms preparation, based on the optimized results, the powder annealed at 500 C was used,

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2.4 Photocatalytic experiments The photocatalytic activity of the thin lms was evaluated using two testing dyes: methyl orange (C14H14N3NaO3S, MO, Merck, reagent grade) and methylene blue (C16H18N3S, MB, Fluka AG, Buchs SG, reagent grade). In 25 mL dye solution (initial concentration 0.0125 mM), the powder (0.1 g) or lm (sample of 1.5 9 2.5 cm2) was added and then irradiated with three F18 W/T8 black light tubes (Philips) (UVA light, typically 340400 nm, with kmax (emission) = 365 nm), for different periods of time. The variation of the dyes concentration was analyzed using UVVis spectrophotometer Perkin-Elmer Lambda 25 at the maximum absorption wavelength registered at 464 nm for MO, respectively 664 nm for MB using the calibration curve (Fig. 1). For comparison a blank sample, which contained only MO or MB and no photocatalyst, was subjected to UV irradiation in the photocatalytic reactor. In the absence of the photocatalyst, the dyes solution (with and without H2O2), was found to be stable under irradiation with UV light. We could conclude that UV light does not directly degrade the dye but activates the TiO2 (Fig. 1).

Fig. 2 Differential scanning calorimetric curves of TiO2 solgel powder

3 Results and discussions 3.1 Structural and morphological characterization of the photocatalyst Properties of TiO2 depend on the chemical composition, the crystalline structure, the phase composition, the crystallization degree and the microstructure. The differential scanning calorimeter (DSC) results of the sample (dried in a furnace for 1 h at 100 C) are shown in Fig. 2. The exothermal peak in the range 240310 C (Fig. 2a) can be attributed to the decomposition and burning of organic by-product. These organics residues may signicantly affect the crystallization behavior and, therefore, it is important their removal from the sample. It was found that the sample treatment at 300 C in oxygen atmosphere for 3 h reaches this goal and that the sample still retains its predominant amorphous character. The exothermal peak in the range 450480 C (Fig. 2b) is attributed to the complete phase transition of amorphous TiO2 to anatase, which the XRD results also indicate. Titanium oxide obtained by the solgel method is usually amorphous, and thermal treatments are necessary to obtain the nal materials with the desired structural characteristics. The thermodynamic stability of the nanostructured phases can be tuned by controlling the crystallite size and the energy of the exposed surfaces. Anatase is usually more stable when the crystals are smaller than 30 nm while rutile is the most favored phase at larger crystal size. The annealing treatment contributes to crystal growth, transforming anatase in rutile, at temperatures bellow the regular polymorph transition (750 C). Therefore, it is necessary to investigate how the phase transition is inuenced with increasing annealing temperature.

Fig. 1 The absorbance measurements of the dyes solution (methyl orange and methylene blue), respectively, of the F18 W/T8 blacklight tubes

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Fig. 3 The XRD patterns of the TiO2 solgel powder annealing in different temperature: a 100600 C and b 600900 C

In Fig. 3 there are presents the XRD patterns obtained for the samples annealed at temperatures between 300 and 900 C for 3 h. The samples annealed above 500 C showed pronounced peaks indicating that the material was fully crystalline. This is consistent with the DSC data, which showed that the decomposition and crystallization reactions are completed at temperatures above 470 C. The XRD pattern of the sample annealed at 300-500 C shows only the anatase phase. Between 600 and 700 C, the rutile phase appears and coexists with the anatase phase. The single rutile phase formation was observed in TiO2 sample annealed above 800 C. The weight ratios of anatase and rutile in the sol gel samples were calculated using the following equation [23]: A% 1 IA 100 1 1:265I
R

(101 peak at 2h = 25.4) and the strongest rutile (110 peak at 2h = 27.5) reections, respectively. The average crystallite sizes of each phase were calculated from the Scherrer equation [24], at the full-width at half-maximum (FWHM) of the peak presenting the highest intensity and taking into account the instrument broadening; the crystallite increases with increasing the annealing temperature (Table 1). It should be noted that the average crystal size correspond to anatase (101) in the SG-500 powder was 15 nm, corresponding to the highest photodegradation efciency. The thin lms surface morphology has a pronounced effect on the photocatalytic activity. For a high photocatalytic activity, the thin lm should have a porous structures that can be can be controlled by adding surfactants (Triton X100 or SDS). Quantitative measurements of the surface roughness, using AFM (Figs. 4 and 5) suggest that larger crystallites are likely to aggregate in more open structures (SG-500, SG-900) and the polymorph composition has a much lower inuence. This is also conrmed by the lms developed using the highly regular Degussa powder, where the lowest roughness is obtained, with a narrow voids distribution, that can be slightly inuenced by the surfactant type. By analyzing the AFM images, the distribution curves of the voids, Fig. 5, allows to estimate the most likely inter-particle voids size (calculated at the half width of the peak): 160 20 nm (SG-P25(TX)), 230 14 nm (SG-P25(SDS)), 260 13 nm (SG-300), 350 10 nm (SG-500), 400 11 nm (SG-900), 720 10 nm (AldrichP25(TX)) samples. As expected, the higher voids were found for Aldrich-P25(TX) sample due to the average primary particle size, of 1 lm, comparing to the Degussa P25 powder (30 nm). In all the cases, the voids are large, being able to accommodate any dye molecule with sizes lower than 10 nm. 3.2 Photodegradation activity of the TiO2 powders and lms The optimum contact time was found for methyl orange degradation at 30 min, using TiO2 Degussa P25 powder; the experimental conditions were set at: 4 g/L TiO2 powder, MO initial concentration 0.0125 mM. The photocatalytic activity of the samples annealed between 300 and 900 C was observed by the degradation of a 0.0125 mM methyl orange solution under UV light, measuring the absorption spectra for each, after 30 min (Table 1). As the results prove, the annealing temperature has a signicantly affect on the methyl orange degradation, due to a complex of factors: phase composition, particle size,

where: A% is the weight fraction of the anatase phase, IA and IR represents the intensities of the strongest anatase

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J Sol-Gel Sci Technol (2011) 58:201208 Table 1 The anatase and rutile percentage and crystallite sizes of rutile and anatase correlated with MO photodegradation Sample Annealing temperature [C] 300 400 500 600 700 800 900 Crystallite size [nm] Anatase 8 8 15 32 34 Rutile 45 50 50 34 Crystalline phases [%] Anatase 100 100 100 40 35 Rutile 60 65 100 100 35 40 41 37 23 9 4

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MO degradationa

SG-300 SG-400 SG-500 SG-600 SG-700 SG-800 SG-900

a

Experimental conditions: MO initial concentration 0.0125 mM, TiO2 powder 4 g/L, irradiation time: 30 min

Fig. 4 The AFM image of TiO2

Fig. 5 The interparticle voids distribution

pore size, and roughness. As the annealing temperature increase up to 700 C the photocatalytic degradation of MO decreases as result of a different polymorph composition (increasing the rutile content), a decrease in the crystallite size and a larger voids distribution. A slightly higher MO photodegradation efciency was found for the sample annealed at 500 C and this powder was further used for thin lm preparation. Thin-lm coating of photocatalyst may solve the problems of leaching and separation. Hence, this technique may be a viable one for the treatment of large volumes of textile wastewater of low dyes concentration. Firstly, tests for the photocatalytic activity of the different TiO2 lms: P25, SG-P25(TX), SG-P25(SDS), Aldrich-P25(TX) were done.

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the packing density (crystallite aggregation) during deposition, conrmed by the results in Fig. 5. The surfactant at the solidwater interface could benecially affect the contaminant interaction with the catalyst surface by enhancing the surface afnity, or adversely by blocking the reactive sites. The enhancement of the degradation efciency of dyes on SG-P25(TX) might be due to increased hydrophobic interactions between dye and TX100 molecules. Catalyst SG-P25(SDS) exhibited less MO degradation than MB due to electrostatic repulsion between SDS and MO molecules. Another reason could be the amount of sodium cations resulted in the lm when adding SDS, with negative effect on the n-type TiO2 conduction. By adding an electron acceptor (H2O2 30%4 mL/L dye solution) in the photocatalytic systems a 2030% enhancement in the photocatalytic efciency of the TiO2 thin lms was registered, the MB degradation being more sensitive (Fig. 6). 3.3 Photodegradation kinetics The kinetic investigations in heterogeneous photocatalysis are developed for analyzing the reaction mechanism at molecular level and for optimizing the process conditions. The LangmuirHinshelwood (LH) kinetic is the mostly used kinetic expression to explain the kinetics of the heterogeneous catalytic processes [2528]. The Langmuir Hinshelwood expression is given by equation: ln c ln c0 kt 2

Fig. 6 Photodegradation efciency of dyes (a methyl orange, b methylene blue) vs. TiO2 photocatalyst after 6 h of UV irradiation

The photocatalytic activity of the TiO2 lms was evaluated for the dyes (methyl orange-MO and methylene blueMB) degradation efciency at the initial concentration 0.0125 mM (Fig. 6). Experiments were done at the oxygen saturation concentration for the system under stirring (dye/UV/O2) and by adding an initial amount of hydrogen peroxide (4 ml/L) in the systems described as dye/UV/H2O2. The methyl orange dye is more difcult to degrade probably due to the less adsorption/interaction of these molecules on the TiO2 surface. The stronger adsorption/ interaction between methylene blue (fully at molecule) and TiO2 surface leads to a higher photodegradation efciency. The highest MO photodegradation efciency of the mixed lm SG-P25(TX) lm can be mainly related to the fact that the solgel (15 nm) and the Degussa P25 (30 nm) grains are of similar size and the average value of the inter-particle voids are low (150 75 nm) comparing to the other lms. This cumulative conditions support the spatial charge separation and hindered electronhole recombination. The dyes removal efciency was inuenced by the surfactant added during preparation. The surfactant affects

where c0 is the initial concentration of dyes aqueous solution, mM; c is the concentration of dyes, mM, measured at the time t, minute; k is the apparent photodegradation rate constant, min-1. For the dyes photodegradation, kinetics calculations were done, Fig. 7 (catalyst: SG-P25(TX)) respectively Fig. 8 (catalyst: SG-P25(TX)). The rate constants in the dyes photodegradation reaction on P25 and SG-P25(TX) are presented in Table 2. The high values of the regression coefcient (R2) for the linear t conrm that the dyes photodegradation follows the LangmuirHinshelwood kinetic. These constant values are of same order of magnitude with those reported in literature for organic pollutants photocatalysis [29]. As shown in Fig. 7, the dyes degradation rate on SGP25(TX) (Table 2), k1 = 0.00109 min-1 for MO, respectively, k2 = 0.001586 min-1 for MB, was higher than the dyes degradation rate on P25 photocatalyst (Table 2), k3 = 0.00084 min-1 for MO, respectively, k4 = 0.001386 min-1 for MB, indicating that the SG-P25(TX) photocatalyst could be recommendable for upscale applications, having not only good efciency but also convenient reaction rate.

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Fig. 7 The kinetics of dyes photodegradation (a methyl orange, b methylene blue) on the P25 and SG-P25(TX) lms

Fig. 8 The kinetics of dyes photodegradation (a methyl orange, b methylene blue) on the SG-P25(SDS) lm

Under the experimental conditions, the dyes photodegradation on SG-P25(SDS) lms follows a two step reaction mechanism as presented in Table 3 and Fig. 8: in the rst 240 min (I step) the slower reaction rates can be the result of a slower active species generation (HO) simultaneous with side-reactions not leading to photo-degradation. The faster step II (after 240 min) can be the result of decreasing these side-reactions (passivating the corners and edges on the TiO2 surface) and/or an increased amount of HO (co)generated by the photo-degradation intermediates. (Fig. 8). The selection of the optimum concentration may be possible based on the rate constant in the photodegradation reaction (k). These values, along with the regression coefcients (R2) of the linear ttings for dyes phodegradation are shown in Table 3. The data show that with or without H2O2 the constant rates are in the same order of magnitude thus, the amount of HO is responsible for the efciency increase and not a change in mechanism. The results also show that MB removal is faster due to the higher interaction between the dyes molecules and the catalyst. With one exception, their removal leads in the rst 240 min to slower reaction rates, probably as result of adsorption or by-products resulted in photocatalysis that degrade (much) slower. The exception, systems of MO

Table 2 The kinetics parameters for dyes photodegradation on P25 and SG-P25(TX) Catalyst/electron acceptor MO k [min ] R P25 O2 H2O2 SG-P25(TX) O2 H2O2 0.00084 0.00159 0.00109 0.002042 0.992 0.001386 0.9706 0.9997 0.9793 0.9855 0.9997 0.003049 0.9967 0.001586 0.9931 0.003707
-1 2

MB k [min-1] R2

without oxidant addition, has the highest rate in the rst step (0240 min), recommending this as an optimum contact time for large scale applications. For practical applications, the catalyst must conserve the activity over a long period of utilization. The photocatalytic lms were used for 3 times (18 h) in the same conditions and the dyes photodegradation efciency was comparable. For the lm with the best performance (SGP25(TX)) the efciency data after 6 h (rst cycle), 12 h (second cycle), respectively, 18 h (third cycle) are presented in Fig. 9.

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208 Table 3 The kinetics parameters for dyes photodegradation on SGP25(SDS) TiO2-SG-SDS Time [min] MO k [min ] R UV/O2 I II UV/H2O2 I II 0240 240360 0240 240360 6.66E-04 2.74E-04 7.84E-04 3.09E-03 0.9974 1.14E-03 0.9984 2.35E-03 0.9963 2.36E-03 0.9898 3.21E-03 0.9912 1.0000 0.9996 0.9903
-1 2

J Sol-Gel Sci Technol (2011) 58:201208 Acknowledgments This paper is supported by the Sectoral Operational Programme Human Resources Development (SOP HRD), nanced from the European Social Fund and by the Romanian Government under the contract number POSDRU ID59323.

MB k [min-1] R2

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Fig. 9 The photocatalytic activity of SG-P25(TX) lm after three cycles

4 Conclusions Nanocrystalline TiO2 catalysts with different contents of anatase and rutile phases were obtained by sol gel method. The solgel synthesis route resulted in TiO2 with good structural properties such as homogeneity, controlled pore size distribution, and high porosity as well as enhanced catalytic properties. Anatase phase was found to be the unique phase in the samples annealed below 500 C. Phase transformation of anatase into rutile was only observed in the sample synthesized by the solgel method when annealing at/above 600 C. As the calcinations temperature increases, crystallite size also increased and the photocatalytic efciency decreased as expected. The use of surfactant provide a higher pack density, increasing the available surface area. Our results suggest that a tailored mixture of anatase and rutile could be a good perspective for improving the dyes degradation efciency, if the mixture is adapted to the dyes composition. The kinetic characteristics of the photocatalytic degradation of dyes by a TiO2 thin lm catalyst were experimentally investigated. The kinetic characteristics were ascertained to follow the LangmuirHinshelwood kinetic mechanism.

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