Scholarly article on topic ' Photocatalytic Activity of   TiO 2   -   WO 3   Composites '

Photocatalytic Activity of TiO 2 - WO 3 Composites Academic research paper on "Chemical engineering"

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Academic research paper on topic " Photocatalytic Activity of TiO 2 - WO 3 Composites "

Hindawi Publishing Corporation International Journal of Photoenergy Volume 2009, Article ID 297319, 7 pages doi:10.1155/2009/297319

Research Article

Photocatalytic Activity of TiO2-WO3 Composites

Beata Tryba, Michal Piszcz, and Antoni W. Morawski

Department of Chemical Technology and Engineering, Institute of Chemical Technology and Environmental Engineering, West Pomeranian University of Technology, ul. Pulaskiego 10, 70-322 Szczecin, Poland

Correspondence should be addressed to Beata Tryba, beata.tryba@ps.pl

Received 11 March 2009; Revised 17 April 2009; Accepted 22 May 2009

Recommended by Mohamed Sabry Abdel-Mottaleb

TiO2-WO3 photocatalysts were prepared in a vacuum evaporator by impregnation of TiO2 with WO2 dissolved in an H2O2 solution (30%) and followed by calcination at 400 and 600° C. XRD analyses showed that at 400°C monoclinic phase ofWO3 was dominated whereas at 600° C both monoclinic and regular phases of WO3 were present. Modification of TiO2 by WO3 caused increasing in the absorption of light to the visible range. TiO2 and photocatalysts modified with low amount of WO3 (1-5 wt.%) showed high adsorption of Acid Red (AR) on their surface and enhanced photocatalytic activity under UV irradiation. Under visible light irradiation, TiO2-WO3 photocatalysts prepared at 400°C were more active for AR decomposition than those prepared at 600°C suggesting that monoclinic phase of WO3 is more active under visible light than regular WO3. Although TiO2-WO3 photocatalysts appeared to be active under visible light for decomposition of AR, the UV irradiation was more efficient.

Copyright © 2009 Beata Tryba et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

1. Introduction

The photocatalytic process using TiO2 photocatalyst is very promising for application in the water purification, because many organic compounds can be decomposed and mineralized by the proceeding oxidation and reduction processes on TiO2 surface. The most commonly tested compounds for decomposition through the photocatalysis are phenols, chlorophenols, pesticides, herbicides, benzenes, alcohols, dyes, pharmaceutics, humic acids, organic acids, and others

[1-3].

TiO2 is the most commonly used photocatalyst, because it is nontoxic, chemically stable, cheap, and very efficient. However it has some disadvantages, from which one of the most important is a relatively high value of the band gap, around 3.2eV, which limits its using to the UV light. Therefore nowadays a lot of research work is focused on the preparation of visible light active photocatalysts in order to utilize the solar light more efficiently and stop using UV lamps as a driving force of photocatalytic process, because it consumes a lot of energy.

A lot of works have been done in preparation of anion-doped TiO2 photocatalysts, such as nitrogen, carbon, and sulphur-doped TiO2, which showed the photocatalytic

activity under visible light [4-6]. The other solution is coupling of TiO2 with semiconductor, which has sensitivity to the visible light. Such semiconductor can be WO3, which has a band gap of 2.8 eV and can absorb the light in the visible range. However it also shows high speed of recombination process between generated free carriers. It was reported that by coupling of these two semiconductors, TiO2 and WO3, an efficient charge separation can be achieved which results in enhanced photocatalytic activity of TiO2 photocatalyst [79].

Different methods of preparation of TiO2/WO3 pho-tocatalysts were applied, such as sol-gel, ball milling, hydrothermal, sol-precipitation, and impregnation [9-14].

In presented results the preparation of TiO2-WO3 pho-tocatalysts was performed by dissolving ofWO2 in hydrogen peroxide, wet impregantaion on the anatase particles, and calcination at 400 and 600 °C. The impregnation method was selected for preparation to get well dispersion oftangsten oxide particles on the used TiO2 material, which as original exhibits high BET surface area, around 300m2/g. Addition oftangsten oxide before calcination can also retard the phase transformation of anatase to less active rutile. The influence of doping WO3 to TiO2 on its photocatalytic activity under UV and visible light irradiations was tested.

2. Preparation of WOa-TiO2 Photocatalysts

As a source of TiO2, a raw material of white TiO2 was used, which was supported by the Police S.A. Company in Poland. This TiO2 has BET surface area of 300m2/g and contains poorly crystalized anatase phase and some nuclei of rutile. WO3 -TiO2 composites were prepared by mixing of TiO2 with WO2 dissolved in an H2O2 solution (30%) in a vacuum evaporator at 70 °C for 1 hour. Then the solution was heated up to 100 ° C to evaporate the water. The obtained powder was dried in a dryer overnight and then was subjected to calcination at 400 and 600 °C. The amount of WO3 in the prepared WO3-TiO2 samples ranged from 1 to 90 wt.%.

3. Analytical Methods

The phase composition of TiO2 and WO3-TiO2 composites was measured by XRD in X'Pert PRO diffractometer of Philips Company, with CuKa lamp (35kW, 30mA). The obtained XRD patterns were compared with (JCPDSs Joint Committee on Powder Diffraction Standards) cards. The morphology of the photocatalysts surface and content of WO3 in WO3-TiO2 composites were evaluated by SEM measurements with EDS analysis. The particle size was measured in Zetasizer Nano ZS of Malvern Company by (DLS Dynamic Light Scattering) method. For measurements photocatalyst samples were suspended in ultra pure water solution with dispersant and were treated with ultrasonic vibrations.

UV-Vis spectra of TiO2 and WO3-TiO2 powders were taken in UV-Vis spectrometer Jasco V-540. These spectra were transformed to Kubelka-Munk equation for indirect semiconductor, and the band gap was calculated.

Hydroxyl radicals were detected by using fluorescence techinque. Coumarine can easily react with hydroxyl radicals to form highly fluorescence compound, 7-hydroxycoumarine, which is determined in the Fluorescence Spectrometer Hitachi F-2500. For these measurements the photocatalyst samples were irradiated under UV in the coumarine solution (10~3M), and then the solution after separation from a photocatalyst was taken to analysis. The fluorescence measurements were performed at the excitation wavelength of 332 nm and the emission of 335-600 nm with maximum peak at 460 nm. The detailed procedure has been described elsewhere [15].

For photocatalytic test, azo dye, Acid Red (AR) was decomposed, 30 mg/L AR in 500 mL solution and catalyst loading 0.2 g/L under UV irradiation with UV intensity 154W/m2 and Vis 100 W/m2. Experiments of AR decomposition were also performed under fluorescence light irradiation with intensity of Vis = 715 W/m2, for that photocatalytic test lower concentration of AR solution was used, 10 mg/L. Fading of AR solution was monitored by UV-Vis spectroscopy.

4. Photocatalytic Activity Test

The photoactivities of prepared samples were tested for decomposition of azo dye Acid Red under irradiation of two different sources: UV and fluorescence lamps. UV was

Wavelength (nm) (a)

Wavelength (nm)

Wavelength (nm)

- TiO2 - TiO2-WO3-10%

- TiO2-WO3-1% - TiO2-WO3-90%

- TiO2-WO3-5%

Figure 1: Diffuse reflectance spectra of TiO2 and WO3-TiO2 photocatalysts, (a) as received, (b) calcined at 400 ° C, and (c) calcined at 600 °C.

emited from UV six lamps of Philips Company with power of 20 W each. These lamps emit the radiation at UV range of 154W/m2 and at the visible region of about 100W/m2 in the range of 312-553 nm with a maximum at around 350 nm. The fluorescence lamps used as a source of visible light (4 X 18 W) emit light in the visible region with intensity of 715 W/m2 and insignificant amount of UV with intensity of 0.22 W/m2.

2000 -, 1800 -1600 -& 1400 -- 1200 -« 1000 -g 800 -§ 600 -400 200 0

A: Anatase R: Rutile

40 50 20 (deg)

1600 1400 1200 1000 800 600 400 200 0

A: Anatase R: Rutile

40 50 20 (deg)

1600 -I

1400 ■ 1200 1000 ^ 800 600 -400 -200 0

A: Anatase R: Rutile

40 50 20 (deg)

1200 1000

10 15 20 25

A: Anatase R: Rutile

30 35 40 20 (deg)

45 50 55 60

л Monoclinic WO3 С Regular WO3

Figure 2: XRD patterns of (a) TiO2, (b) TiO2-WO3-3%, (c) Ti02-W03-10%, and (d) Ti02-W03-90% photocatalysts: (1) as received, (2) 400 °C-treated, (3) 600 °C-treated.

Each time, for the photocatalytic test, the beaker with 500 mL of a dye solution of concentrations around 0.03 g/L under UV, and 0.01 g/L under visible light and 0.1 g of photocatalyst was used. The solutions were first magnetically stirred in a dark for 30 minutes in order to estimate the adsorption of dye on the photocatalyst surface and then were irradiated under UV or visible lights from the top of the beaker. The concentration of a dye solution was analyzed in UV-Vis spectrophotometer,

5. Results and Discussion

UV-Vis spectra of measured TiO2 and WO3 -TiO2 photocatalysts are shown in Figures 1(a)- 1(c).

In general modification of TiO2 by WO3 caused increasing the absorption of light to the visible range; however heat treatment caused almost complete reduction of absorption in the range of 400-700 nm, and only a few percentage of light absorption in the range of 500-700 nm could be noticed for modified samples; the exception is WO3 -TiO2 with doped amount of 5 and 90 wt.%, which exhibited higher absorption of visible light even after heat treatment.

XRD measurements of TiO2 and WO3 -TiO2 photocatalysts were performed. Phase WO3 was difficult to observe in the prepared samples with doping WO2 less than 50%. In Figure 2 XRD patterns of TiO2 and TiO2 with different amounts of doped WO3 photocatalysts as received and calcined at different temperatures are presented.

Original TiO2 consists of poorly crystalized antase phase with insignificant amount of rutile. Heating of anatase-TiO2 caused narrowing of the diffraction peaks of anatase phase due to the growing of its crystals. The additional reflexes from anatase phase such as 103, 112, 116, 220, 215, and 301 were clearly observed for-well crystalized antase. In case of TiO2-WO3-90% photocatalyst monoclinic phase of WO3 appeared at 4000C whereas at 600 °C additionally regular WO3 phase was present.

Doping WO3 to TiO2 caused inhibition of growing anatase crystals during heat treatment, and narrowing of the anatase reflex (101) was insignificant, mostly for the samples with doped WO3 amount up to 3%. Above 3% of doped WO3 the anatase reflexes 103 and 112 were not observed, and some reflexes as 105 and 211 were not distinguished due to the presence of broad peaks, even after heated at 600 0C.

J 90 13 80 J 70 1 60 50 8 40

S3 20 о 10 S 0

10 20 30 40 50 60

UV irradiation time (min)

90 100

X102 250

10 20 30 40 50 60 70 UV irradiation time (min)

90 100

Figure 3: OH radicals formation on the photocatalyst surface by the fluorescence measurements of 7-hydroxycoumarine for (a) TiO2and (b) TiO2-WO3-3%; (1) as received, (2) 400°C-treated, and (3) 600 °C-treated.

The exception is TiO2 with doped amount of WO3 10%, in which narrowing of anatase 101 reflex was significant, and reflexes 105 and 211 were clearly identified. In this sample probably distribution of WO3 particles on TiO2 was not homogoneous.

Photoactivity of TiO2 and prepared photocatalysts in direction of OH radicals formation was tested by the fluorescence technique. In Figure 3 there are presented results from OH radicals measurements on TiO2 and TiO2-WO3 photocatalysts during UV irradiation.

The linear correlation of OH radicals formation from the irradiation time can be noticed. Doping WO3 to TiO2 and higher calcination temperature caused increasing in the amount of OH radicals formation. This tendency was observed for modified samples with doping WO3 up to 3%; for higher amount of doped WO3 the photocatalysts heat treated at 400 °C showed higher amount of OH radicals formation than those as received and calcined at 600 °C. The highest photoactivity toward OH radicals formation was noted for TiO2-WO3-3% heat treated at 600 °C. In Figure 4 OH radicals formation on the photocatalysts under visible light are presented.

OH radicals formation under visible light was much lower than under UV, when we compare Figures 3 and 4, but again TiO2 doped with WO3 showed higher amount of OH radicals formation than TiO2. From Figure 4 it can be seen that TiO2-WO3-10% heat treated at 400 °C was much more photoactive than heat treated at 600 °C and no calncinated one. The same tendency was kept for the other photocatalysts

450 400 350 300 250 200 150 100 50 0

1600 1400 1200 1000 800 600 400 200 0

Vis irradiation time (min)

90 100

Vis irradiation time (min)

Figure 4: OH radicals formation on the photocatalyst surface by the fluorescence measurements of 7-hydroxycoumarine for (a) TiO2, (b) Ti02-W03-I0%; (1) as received, (2) 400 °C -treated, (3) 600 °C-treated.

with doping WO3 from 5%-90%. The highest OH radicals formation under visible light was obtained on the TiO2-WO3 photocatalyst with doping amount of 10% heat treated at 400°C. However this sample did not show significant absorption of light in the visible range; coupling of WO3 and TiO2 could occur at small amount of visible light absorption by WO3 and absorption of UV light by TiO2, even although the energy of UV light was insignificant. TiO2 with 90% of doped WO3 showed much higher absorption of visible light than the other samples with lower content of WO3 but had low activity under visible light. It is concluded that TiO2 activity is much more powerful than WO3 in generation of OH radicals, and WO3 can serve as a support in OH radicals formation by transfer electrons to the conductive band of TiO2 under visible light or can retard the recombination reaction occurring in TiO2.

The influence of doping WO3 to TiO2 on the particles size of photocatalysts was measured. The results from the measurements of particles size of TiO2 and TiO2-WO3 samples are listed in Table 1.

In general particles size of WO3 doped TiO2 photocatalysts were lower than TiO2. Calcination caused growing of crystals, and so some heat-treated samples exhibited higher size of particles than those as received ones.

The structure of photocatalysts and particles size were observed on SEM photos. For comparison SEM of not modified TiO2 and TiO2-WO3-3% calcinated at 600 °C are presented in Figure 5.

Some agglomerates of primary particles of TiO2 can be seen with size over 1 ^m in Figure 5(a) whereas TiO2 doped with WO3 comprises of much smaller particles.

(a) (b)

Figure 5: SEM of (a) TiO2 and (b) TiO2-WO3-3% heat treated at 600 °C.

Table 1: Particles size of photocatalysts measured by DLS method.

Sample Particles size [nm]

Amount of doped WO3 (%) 0 1 3 5 10 30 50 90

As received 365 444 355 365 172 190 174 185

400 °C-treated 369 380 367 373 222 178 199 175

600 °C-treated 402 369 400 415 201 207 205 192

Table 2: Adsorption of AR on the photocatalysts surface.

Adsorption of acid red/% Heat treatment temperature/ °C

400 600

30 10 30 10 30 10 mg/L mg/L mg/L mg/L mg/L mg/L

TiO2 19.8 21.5 14.8 26.9 2.0 14.1

TiO2- -WO3- -1% 28 36.5 16.8 32.5 3.7 14.6

TiO2- -WO3- -3% 15.8 38.4 7.8 16.7 — —

TiO2- -WO3- -5% 14.1 12.6 15.2 20.5 15.9 21.3

TiO2- -WO3- -10% 0 1 2.8 5.8 0 0

TiO2 -WO3- -30% 0 0 0 0 0 0.5

TiO2 -WO3 -50% 0 0 0 0 0 0

TiO2 -WO3 -90% 0 0 0 0 0 0

Both measurements, DLS and SEM, showed that doping WO3 to TiO2 cause, reduction of its particles size, mostly because of reducing tendency of TiO2 particles to form agglomerates. Smaller particle size of TiO2-WO3 composites in comparison to TiO2 prepared by the sol-gel method was also reported by Li et al. [7].

From EDS analysis the measured amount of Ti was 93wt.%, W - 6wt.%, and S - 1wt.%. Sulphur came from the production process of TiO2.

Photocatalytic activity of prepared samples was tested for Acid Red decomposition under UV and visible light irradiations. Preliminary adsorption of this dye on the photocatalysts surface was performed. The results from the adsorption measurements are presented in Table 2. The

initial concentrations of AR used in case of UV and Vis radiations were 30 and 10 mg/L, respectively.

Noncalcined samples of TiO2 and TiO2 doped with low amount of WO3 up to 5% showed quantitatively adsorption of AR on their surface, which generaly was decreasing with heat treatment temperature; only TiO2-WO3 photocatalyst with doping amount of 5% showed opposite tendency, that is increased adsorption of AR after heat treatment.

After adsorption, these photocatalysts were submitted to UV and Vis radiations. The results from the measurements are presented in Figures 6 and 7.

Photocatalysts which exhibited high adsorption of AR on their surface showed no linear correlation of ln (C0/C) from time of irradiation during AR decomposition. The high acceleration of AR decomposition with time of irradiation on these photocatalysts could be caused by occurring sensitized photocatalysis. Therefore doping WO3 to TiO2, which caused their increased absorption of light to the visible range and high adsorption of AR, appeared to be beneficial for decomposition of AR, as it can be seen especially in case of noncalcined samples used under UV irradiation and TiO2-WO3-5% heat treated at 600 °C used under visible light. Although both TiO2 and TiO2-WO3 photocatalysts were active under visible light irradiation, UV light was more powerful in AR degradation.

Under visible light irradiation WO3-TiO2 photocatalysts prepared at 400 °C were more active for AR decomposition than those prepared at 600 °C and noncalcined one.

6. Conclusions

Doping WO3 to TiO2 caused increasing its absorption of light to the visible range; however it was observed mostly for noncalcined samples. Although OH radicals formation on prepared TiO2-WO3 photocatalysts was higher than on TiO2 it was not a key factor affecting the rate of AR decomposition. Both high adsorption of AR on the photocatalyst surface and their ability to absorption of visible light were responsible for the photocatalytic properties of photocatalysts, and therefore the TiO2-WO3 photocatalysts with low amount of WO3 (1-5wt.%) were more active than the others. Doping WO3 to

Time (h)

Time (h)

Time (h)

♦ TiO2 * 10%

■ 1% • 30%

д 3% + 50%

о 5% о 90%

Figure 6: AR decomposition under UV irradiation on TiO2 and TiO2-WO3 photocatalysts, (a) as received, (b) 400 °C-treated, and (c) 600 °C-treated.

TiO2 caused also reduction of its particles size, which could improve ability of TiO2 for dispersion in water and increase the accessible surface for adsorbates. Under visible light irradiation WO3-TiO2 photocatalysts prepared at 400 °C were more active for AR decomposition than those prepared at 600 °C suggesting that monoclinic phase of WO3 is more active under visible light than regular WO3. Although the photocatalysts were active under both UV and visible light

Time (h)

Time (h)

Time (h)

♦ TiO2 A 10%

■ 1% • 30%

A 3% <> 90%

о 5% + 50%

Figure 7: AR decomposition under Vis irradiation on TiO2 and TiO2-WO3 photocatalysts, (a) as received, (b) 400 °C-treated, and (c) 600 °C-treated.

irradiations, UV light was more powerful for decomposition of AR than visible light, but the latter had important meaning during occurring sensitized photocatalysis.

Acknowledgment

This work was supported by the research project from the Ministry of Science and Higher Education no.COST/299/2006 for 2007-2010.

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