J Sol-Gel Sci Technol (2012) 62:304312 DOI 10.

1007/s10971-012-2725-7

ORIGINAL PAPER

Photocatalytic and antibacterial activities of Ag-doped ZnO thin lms prepared by a solgel dip-coating method
K. Thongsuriwong P. Amornpitoksuk S. Suwanboon

Received: 12 November 2011 / Accepted: 22 February 2012 / Published online: 14 March 2012 Springer Science+Business Media, LLC 2012

Abstract Silver-doped ZnO thin lms with various loadings of Ag in the range of 010 mol% were prepared by the solgel dip-coating method. All prepared lms show X-ray powder diffraction patterns that matched with ZnO rtzite structure. The grain size decreased as the Ag in its wu loading increased. The prepared lms, under UV blacklight illumination, produced a photocatalytic degradation of methylene blue, rhodamine B and reactive orange solutions. Furthermore, they inhibited the growth of Escherichia coli bacteria under UV blacklight irradiation and to a lesser extent in dark conditions. The photocatalytic and antibacterial activities of the prepared lms increased with Ag loading, presumably because Ag enhanced the efciency of generation of superoxide anion radicals (O2-) and hydroxyl radicals (OH). Keywords Ag-doped ZnO thin lm Inorganic antibacterial agent Photocatalytic degradation

1 Introduction In recent years, research on ZnO has shown it to have many attractive and useful applications such as: in semiconductors [1], piezoelectric devices [2], transparent electrodes [3], solar cells [4], sensors [5], as a photocatalyst [6] and an antibacterial agent [7], because of its excellent electrical, optical and chemical properties. Investigations of applications of its photocatalytic activity have probably been the one area that has achieved the most interesting results [8, 9]. Photocatalytic activity occurs when the ZnO absorbs photons with an energy equal to or greater than its band gap energy and generates such reactive species as H2O2, superoxide anion radicals (O2-) and hydroxyl radicals (OH) [10]. These photogenerated reactive species are very strong oxidizing agents that can degrade organic and dye molecules. Moreover, they can also react and destroy the outer membrane of bacteria and inhibit their growth [11]. Thus, it can be used as an inorganic antibacterial agent. Comparing the properties of organic antibacterial agents with inorganic antibacterial agents, the inorganic ones are safer and more stable. Furthermore, ZnO is one of the inorganic metal oxides that shows antibacterial activity without UV irradiation. Such properties have enabled many applications such as in waste water treatment [12], photocatalytic lms on windows of buildings [13], and lms with antibacterial activity [14]. Nowadays, a material that exhibits self-cleaning behavior with antibacterial activity is of increasing interest, as humans become more concerned with healthcare. Coating a thin lm of ZnO onto a materials surface is one of the ways to provide this self-cleaning property. From many coating technologies, the dip-coating method has many advantages and can be applied to a wide rage of materials. Moreover, it is a fast technique, needs simple equipment and can be used on material that has a complicated shape.

K. Thongsuriwong P. Amornpitoksuk (&) Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand e-mail: ampongsa@yahoo.com K. Thongsuriwong e-mail: cutekanny@hotmail.com S. Suwanboon Department of Materials Science and Technology, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand e-mail: ssuwanboon@yahoo.com

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Silver is a promoter that has been used previously to improve the photocatalytic efciency of ZnO particles [15]. Metallic silver present on the surface of ZnO generates a new energy level that can receive the photogenerated electrons from the conduction band of ZnO, and so limits the recombination of the opposite charges [16]. As mentioned above, Ag on the ZnO surface can improve the photocatalytic properties then the greater generation of reactive species will also increase the bacterial killing rate. Moreover, silver and silver salts themselves have been used for decades as antimicrobial agents in curative and preventive healthcare. Thus, Ag itself should enhance the antibacterial activity of ZnO particles without UV irradiation [17]. Although there have been numerous previously published reports on the photocatalytic activity of Ag/ZnO particles, there has been little detail provided on how these Ag/ZnO thin lms were applied to the support materials surface. In this work, Ag-doped ZnO thin lms coated onto glass were prepared by a solgel dip-coating method. The inuence of morphology was studied at varying dopant concentrations. The photocatalytic and antibacterial activities in this research were activated by illuminating with blacklight uorescent tubes, an inexpensive irradiation source compared to other UV light sources. The photocatalytic activities of all prepared lms were investigated through the degradation of methylene blue, rhodamin B and reactive orange all in aqueous solutions. Their antibacterial activity was determined by testing their ability to inhibit the growth of Escherichia coli (E. coli) bacteria. E. coli is the Gram-negative bacteria that is usually found in the intestines of humans and animals without causing any problems but some types of E. coli are a leading cause of illness or death. For antibacterial activity testing, it is one of the recommended bacteria that is widely used as a control Gram-negative bacterium for various laboratory experiments. In general, the Gram-negative bacteria are harder to kill than Gram-positive bacteria because the cell wall of Gram-negative bacteria is different from the Grampositive bacteria by having an outer lipopolysaccherice membrane that covers the peptidoglycan layer. It also helps the bacteria to survive when they come into contact with external substance that can harm them [18].

were used without further purication. The glass substrates were cleaned in a mixed solution of hydrochloric acid (HCl) and nitric acid (HNO3) with a ratio of 1:2 for 10 min, and rinsed with distilled water and ethanol several times. Before use, they were nally dried at room temperature. Ag-doped ZnO thin lms were deposited on glass slide substrates by a solgel dip-coating method. The required amounts of CH3COOAg were added into 0.1 M Zn(CH3COO)22H2O dissolved in 10 mL of iso-propanol to obtained mole ratios of Ag? : Zn2? = 110 mol%. Thirty microlitres of MEA, acting as a stabilizer, was added into the above solution in order to keep the mole ratio of Zn2? to MEA = 1. The homogenous solution was then stirred at 70 C for 1 h to accelerate the hydrolysis reaction and to obtain a transparent sol which was used as the coating sol, after being cooled to room temperature, and aged for 24 h. Ag-doped ZnO thin lms were deposited on soda lime glass substrates (10 mm 9 15 mm 9 1.5 mm) by a dip-coating method with a withdrawal speed of 1 cm/min. After coating each layer, the lms were dried at 80 C in an oven for 10 min to evaporate the solvent. The dip coating and the drying were repeated ten times. The as-coated lms were calcined subsequently at 400 C for 1 h to remove any undesired species and nally the coated glass slides were cooled to room temperature in the furnace before being investigated for their properties. 2.2 Characterization The structural identications of ZnO and Ag-doped ZnO thin lms were carried out using an X-ray diffractometer (XRD, XPert MPD, Philips) with Cu Ka radiation at a wavelength (k) of 0.15406 nm. The elemental analysis for all prepared lms was performed on the X-ray uorescence (XRF) spectrometer (PW 2400, Philips). The morphology and thickness of the ZnO thin lms at different Ag contents were determined by a scanning electron microscope (SEM, Quanta400, FEI). The roughness and surface topography of undoped and Ag-doped ZnO thin lms at different loadings of Ag were examined using an atomic force microscope (AMF, SPI 4000, SEIKO instrument) operated in the tapping mode. The oxidation state of Ag on the surface of ZnO thin lms was measured by X-ray photoelectron spectroscopy (XPS) technique. The surface analysis chamber is equipped with an aluminium Ka source using a 500 mm Rowland circle silicon single crystal monochromator giving monochromatic radiation at 1486.6 eV. All spectra were charge referenced to C 1s at 285.0 eV. 2.3 Photocatalytic studies

2 Experimental 2.1 Preparation of Ag-doped ZnO thin lms Zinc acetate dihydrate (Zn(CH3COO)22H2O, Fluka), monoethanolamine (MEA, H2N(CH2CH2OH), Fluka), isopropanol (CH3C2H5OH, Merck) and silver (I) acetate (CH3COOAg, Sigma-Aldrich) were analytical grade and

The photocatalytic activity was investigated through the degradation or decolorization of methylene blue (MB), rhodamin B (Rh-B) and reactive orange (RO) all in

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aqueous solutions. The Ag-doped ZnO thin lms on the glass with different Ag contents were placed into a beaker containing 3 mL of 1 9 10-5 M dye solutions and they were then irradiated with 3 parallel blacklight uorescent tubes (15 W, Sylvania). The blacklight uorescent tubes used emit UVA efciently in the range of 315400 nm with peaks at 352 and 368 nm. After irradiating for 4 h, the concentration of the residual MB, Rh-B and RO was determined by a UVVis spectrophotometer (lambda 25, Perkin Elmer). 2.4 Antibacterial studies Escherichia coli ATCC 25922 was streaked onto nutrient agar (NA) and incubated at 35 C for 1824 h. Three to ve single colonies of bacteria were picked into nutrient broth (NB) and incubated at 35 C for 18 h while shaking at 150 rpm. After incubation, sterile distilled water was used to adjust to the required cell density. 3 mL of E. coli containing 4.72 9 105 colony forming units (CFU)/mL were pipetted into the beaker containing the Ag-doped ZnO thin lm. After irradiating for 10, 20 and 30 min, 1 mL of reacted solution was pipetted onto the petrilmTM E. coli coliform count plate (3MTM). Plates were incubated at 35 C for 24 h. Only blue colonies with entrapped gas were conrmed as E. coli and counted.

Fig. 1 X-ray diffraction patterns of Ag-doped ZnO thin lms with (a) 0, (b) 1, (c) 5 and (d) 10 mol% of Ag loading

3 Results and discussion 3.1 Structure, topography and oxidation state The XRD patterns of the Ag-doped ZnO thin lms at various loadings of Ag of between 0 and 10 mol% after calcination at 400 C for 1 h are presented in Fig. 1. From this gure, the XRD patterns show the characteristic dif rtzite structure (JCPDS card fraction peak of ZnO in a wu no. 36-1451) without any secondary phase. The existence of Ag in the ZnO thin lms was conrmed by the XRF technique as shown in Fig. 2. Therefore, not being able to detect a Ag phase in the XRD patterns possibly comes from an undetectable Ag that the Ag as a secondary phase might be lower than the detection limit of this technique or could segregate as a non-crystalline phase at the grain boundary [19, 20] or a solid solution that Ag? ions might substitute at the Zn2? position in the ZnO structure. From Fig. 2, the atomic ratios of Ag to Zn in the Ag-doped ZnO thin lms at different Ag loadings (1, 3, 5, 7 and 10 mol%) were calculated to be 0.4, 1.0, 1.6, 2.1 and 3.3 mol%, respectively. The Ag content in the ZnO thin lm is lower than its composition in the solution. This might come from the partial formation of silver clusters in the sol and these metallic species could precipitate or are less well adsorbed

onto the glass substrate during the dip-coating process. Another consideration is that Ag? ions can be easily reduced to metallic silver. Hada et al. [21] reported that the Ag? ions in an aqueous alcoholic solution can be reduced to Ag under UV irradiation. However, in an alcoholic media, alcohol can also act as a weak reducing agent that can reduce Ag? ions to Ag species at high temperature without irradiation [22]. Concerning the rate of reaction, the hydrolysis rate of Ag? is faster than for Zn2? as the formation constant of the hydroxo complexes of Ag? and Zn2? ions resulting from hydrolysis are about 10-24 and 10-41, respectively. The partial condensation might have occurred when the precursor sol was heated and aged. In general, a greater rate of condensation is usually obtained for cations with a smaller charge and larger size [23]. Therefore, the higher rate of hydrolysis and condensation will destabilize the hydrolyzed complexes of Ag? in the sol and facilitate the formation of a small amount of polymeric of the hydrolyzed complexes or cluster of Ag or silver oxide such as Ag2O or AgO. Concerning the Shanon-Prewit crystal radius, the radius of Ag? (114 pm) is higher than for the Zn2? (74 pm). The XRD peak will therefore shift to a smaller angle if Zn2? is substituted by Ag?. Returning to Fig. 1, a slight shift of the peak (0002) to a lower angle was only found in a sample at 1 mol% Ag. It can be implied that Zn2? might be substituted by Ag?. Because of the large difference in the radius between Ag? and Zn2?, it might be possible for some Ag? to substitute for Zn2? and some Ag? could form an Ag cluster. Unfortunately, the substitution of Zn2? by Ag? in this sample (1 mol% of Ag) cannot be conrmed by the XPS technique because no signal of Ag 3d was detected

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Fig. 3 X-ray photoelectron spectra of Ag 3d for Ag-doped thin lms with (a) 3, (b) 5 and (c) 10 mol% of Ag loading

Fig. 2 X-ray uorescence spectra of Ag-doped ZnO thin lms with (a) 1, (b) 5 and (c) 10 mol% of Ag loading

since the Ag content might be lower than the detection limit as is usually observed in the literature [24]. However, a slight shift of the peak (0002) to a lower angle was not observed as the amount of Ag loading further increases. When the Ag? concentration in solution became more than 1 mol%, it is possible that the Ag probably forms a cluster more than becoming substituted for the Zn2? position in the ZnO structure. The existence of Ag clusters in ZnO thin lms was conrmed by the XPS technique. Figure 3 shows the Ag 3d XPS spectra of ZnO thin lms at various Ag loadings of between 3 and 10 mol%. The binding energies of Ag 3d5/2 and 3d3/2 were observed at 367.68 and 373.68 eV, respectively, and the splitting of the Ag 3d5/2 and Ag 3d3/2 peaks is 6.0 eV which indicates that the silver is in the form of a metal [25]. The binding energy of Ag 3d5/2 exhibited a negative shift compared to that of the

bulk Ag (368.2 eV [26]) because of the interaction between Ag and ZnO. The Ag/ZnO heterostructure generated a new Fermi energy level and electrons in this level can tunnel into the conduction band of ZnO which is vacant, resulting in a higher valence of Ag [27]. Then the binding energy of Ag 3d5/2 shifts to the lower binding energy comparing with pure metallic silver. The AMF topography images (Fig. 4a) and histograms of the distribution of grain sizes (Fig. 4b) of the ZnO thin lms at different Ag concentrations clearly showed that the grain size was slightly decreased depending on the Ag loading as indicated by a little broadening of the diffraction peak as seen in Fig. 1. Moreover, this can also inuence the surface morphology of a prepared lm. Figure 5 shows the surface morphology and lm thickness of ZnO thin lms at different Ag loadings. In general, the smaller grain sizes will pack together more densely than the larger one then the denseness of the lms increased when the concentration of the dopant increased. The decrease of the grain size that is dependent on the Ag loading might be explained by the Zener pining effect. From the XPS results for samples with 310 mol% of Ag, the Ag in these samples presented as a metallic phase and did not substitute for Zn2? in the rtzite structure. In general, if the Ag does not become wu incorporated into the ZnO structure, it will become segregated at the grain boundary. The segregated Ag clusters at the grain boundary then act as an obstacle that prevents the grain growth and recombination [28]. Furthermore, the root mean square (RMS) roughness values of their thin lms were 2.839 (0 mol% Ag), 3.327 (1 mol% Ag), 3.612 (3 mol% Ag), 4.406 (5 mol% Ag), 4.750 (7 mol% Ag) and 4.989 (10 mol% Ag) nm.

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308 Fig. 4 Atomic force microscope images (a) and grain size distribution (b) of Ag-doped ZnO thin lms at different loadings of Ag

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Fig. 5 Surface and cross-sectional SEM images of Ag-doped ZnO thin lms at different loadings of Ag

Fig. 6 Effect of Ag loading on the efciency of the photocatalytic degradation of methylene blue by Ag-doped ZnO thin lms after 4 h of irradiation (a) and comparison of the photocatalytic degradation of three dyes (methylene blue, MB, rhodamine, Rh-B and reactive orange, RO) in the presence of a 10 mol% Ag-doped ZnO thin lm after 4 h of irradiation (b). The inset shows the linear relationship between the efciency of the MB degradation and the determined Ag contents in the ZnO thin lms by XRF technique

3.2 Photocatalytic activities The photocatalytic activities of the prepared Ag-doped ZnO thin lms at different Ag concentration were rst investigated through the degradation of a methylene blue dye solution. Degradation of the dye can be calculated by the following formula: Degradation% Co Ct =Co 100 Ao At =Ao 100 where Ct and At are the concentration or absorbance at 664, 554 and 493 nm of the methylene blue (MB), rhodamine B (Rh-B) and reactive orange (RO) solutions, respectively, after irradiation for 4 h, and Co and Ao are the concentration or absorbance at 664, 554 and 493 nm of the MB, Rh-B and RO solutions, respectively, before irradiation.

Figure 6a shows the effect of Ag loading on the photocatalytic degradation by modied ZnO thin lms. It is clearly seen that the efciency of the photocatalytic degradation of MB dye solution increases with increased Ag loading on the ZnO thin lms. When the initial Ag concentration in solution was more than 10 mol%, precipitating particles appeared in the coating sol so they were not further studied. The photocatalytic degradation of MB showed a linear increase with the Ag contents determined by XRF as shown in Fig. 6a inset. The Ag-doped ZnO thin lm with the most efcient photocatalytic degradation of MB (10 mol% Ag) was further investigated using the other dyes as rhodamine B and reactive orange (Fig. 6b). This showed that all three dye solutions were effectively degraded by the photocatalytic activity of the Ag-doped ZnO thin lms. The dye solutions themselves, without any

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J Sol-Gel Sci Technol (2012) 62:304312 Table 1 Viable colonies of Escherichia coli bacteria after irradiation under UV blacklight uorescent tubes and in the dark for Ag-doped ZnO thin lms prepared with different loadings of Ag Irradiation 7.72 9 105

catalytic thin lm, were irradiated under blacklight uorescent tubes and the Ag-doped ZnO thin lms were also placed into the dye solutions in dark conditions in order to investigate the effect of self-photodegradation of the dye and the loss of dye by adsorption onto the catalyst thin lms, respectively. Although these effects did slightly reduce the absorbance of the dye solutions, they were negligible compared to the photocatalytic effect of the Ag-doped ZnO thin lms (Fig. 6b). Thus, the decrease of the absorbance of the dye solution after illuminating for 4 h was mainly due to the photocatalytic effect of the Ag-doped ZnO rather than to either self-photodegradation of the dye or adsorption of the dye onto the catalyst thin lm. In general, when the electrons in the valence band of ZnO absorb photons with an energy equal to or higher than the energy band gap of ZnO, they transfer to the conduction band and in their place leave a hole in the valence band. The photogenerated electrons react with O2 or oxygen species on the surface to generate the superoxide anion radicals (O2-) while the photogenerated holes react with water molecules to give the hydroxyl radials (OH). Both these reactive radicals work together to decompose organic compounds [29]. However, these electronhole pairs can recombine and thus decrease the photocatalytic efciency. In the Ag/ZnO system, the rate of electronhole pair recombination is reduced because the incorporated Ag within the ZnO lm generates a new Fermi energy level that is lower than the lowest energy level of the conduction band of the ZnO [30]. Then, the photogenerated electrons on the conduction band of ZnO can transfer to this energy level yet can still react with O2 or oxygen species on the surface to produce the superoxide anion radicals (O2-) hence the advantage of the Ag doping. 3.3 Antibacterial activity The antibacterial activity of the prepared Ag-doped ZnO thin lms was tested through the inhibition of E. coli under UV blacklight irradiation and also in dark conditions (Table 1). To ensure that the antibacterial activity did not derive from the effect of the UV blacklight itself, the suspension of bacteria was irradiated under three parallel blacklight uorescent tubes in the absence of the catalyst. After 1 h of irradiation, viable counts were made and there was no signicant change in the viable counts over the control at zero time (the data is not shown). We can therefore conclude that the UV blacklight itself did not kill the E. coli and this is in agreement with other publications [31, 32]. However, all the prepared ZnO and Ag-doped ZnO thin lms did show antibacterial activity as indicated by the decrease of viable counts after irradiation. The antibacterial mechanism of metal oxides has been reported to occur in 2 ways. One way assumes that the

0
5

0 2.10 9 104 0 1.90 9 104 0 2.10 9 104 0 1.50 9 104 0 2.02 9 104 1.14 9 104 2.54 9 105 20

10 mol% Ag

7.72 9 105

1.10 9 10 0 1.01 9 10 0 1.12 9 10 7.80 9 10 5.27 9 10 1.05 9 10 8.01 9 10 5.24 9 10 10 1.10 9 10

Dark

Irradiation

7.72 9 105

7 mol% Ag

7.72 9 105

Dark

Irradiation

7.72 9 105

5 mol% Ag

7.72 9 105

Dark

7.72 9 105

Irradiation

3 mol% Ag

7.72 9 105

Dark

7.72 9 105

Irradiation

1 mol% Ag

7.72 9 105

Viable colonies (CFU/mL)

Dark

7.72 9 105

Irradiation

7.72 9 105

Time (min)

Dark

ZnO

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1.22 9 10

1.32 9 10

1.72 9 10

1.68 9 10

1.78 9 10

1.68 9 10

1.70 9 10

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photogenerated H2O2 penetrates into the cell and kills the bacteria before being degraded by peroxidase [33] while the other assumes that the photogenerated reactive species reacts with organic substances on the surface and this leads to the death of the bacteria [34]. Although H2O2, as an intermediate specie, is generated by recombination ? between HO that have been produced in the 2 and H photocatalytic reaction, it is not a very stable compound and is easily destroyed by heat, UV light and peroxidase enzymes. In our experiment, it is possible that the antibacterial activity of all samples arises from the other reactive species such as OH and O2- that were generated when the ZnO or Ag-doped ZnO absorbs the suitable energy photon as described in Sect. 3.2. Furthermore, it was observed that the antibacterial activity of Ag-doped ZnO thin lms increased with the Ag loading. In that case, the enhancing effect of Ag on the antibacterial activity of the ZnO thin lms might be due to its higher efciency for generating the reactive species. This was conrmed by the increasing photocatalytic efciency with the Ag loading as seen in Fig. 6a. After exposure to blacklight for 10 min, no viable colonies of E. coli were detected when the Ag content was greater than or equal to 5 mol% as shown in Table 1. ZnO and Ag-doped ZnO thin lms show antibacterial activities not only under blacklight but also in dark conditions (Table 1). For the ZnO thin lm, this activity presumably arises from the nding by Hirota et al. [35] who used ESR and chemical PL to conrm the generation of O2- that originated from the surface of ZnO in the dark and this might kill the bacteria. For the Ag-doped ZnO thin lm, an increase of Ag content did not signicantly improve their antibacterial activity in the dark condition, however its activity was still higher than for the pure ZnO thin lm as shown in Table 1. Compared with the pure ZnO thin lm, the enhancing effect of Ag on this activity is still a matter for debate. Yu et al. [36] reported that the antibacterial activity of Ag-TiO2 came from the effect of the leaching of Ag? ions. In order to study the release of Ag? ions from the Ag-doped ZnO thin lms at different Ag loading, they were immersed in distilled water for 30 min under UV irradiation or in the dark condition. All these solutions produced no detectable Ag? ions using ICP-MS (inductively coupled plasma mass spectrometry) so there is no release of Ag? ions from the surface of Ag-doped ZnO thin lms or probably any released Ag? ions might be at a lower concentration than the detection limit. If no Ag? ions are released from the surface, the enhancing of the antibacterial activity with increased Ag loading in the dark condition might come from the contact between E. coli and Ag on the surface of ZnO thin lms.

4 Conclusion The Ag-doped ZnO thin lms were successfully prepared by the solgel dip-coating method. From the AFM images, the grain size of the Ag-doped ZnO decreased with increased Ag concentration. These prepared thin lms did degrade methylene blue, rhodamin B and reactive orange solutions under blacklight irradiation. Furthermore, they showed antibacterial activity against E. coli under both UV blacklight irradiation and to a lesser extent in the dark. Under UV blacklight illumination, the efciency of killing the bacteria increased with the Ag loading on the ZnO thin lm because of the enhancing effect of Ag on the photocatalytic activity. A more efcient generation of reactive species increased the bacterial killing rate.
Acknowledgments Financial support from the Center for Innovation in Chemistry (PERCH-CIC), Commission on Higher Education, Ministry of Education is gratefully acknowledged. We would like to thank Dr. Brian Hodgson for assistance with the English.

References
1. Farag AAM, Farooq WA, Yakuphanoglu F (2011) Microelec Eng 88:28942899 2. Water W, Fang TH, Ji LW, Lee CC (2009) Mater Sci Eng B 158:7578 3. Lee D, Bae WK, Park I, Yoon DY, Lee S, Lee C (2011) Solar Energy Mater Solar Cells 95:365368 4. Lim DC, Shim WH, Kim KD, Seo HO, Lim JH, Jeong Y, Kim YD, Lee KH (2011) Solar Energy Mater Solar Cells 95:30363040 5. Hongsith N, Wongrat E, Kerdcharoen T, Choopun S (2010) Sens Actuators B: Chem 144:6772 6. Yi Z, Xu X, Duan X, Zhuw W, Zhou Z, Fan X (2011) Rare Met 30:183187 7. Sharma D, Rajput J, Kaith BS, Kaur M, Sharma S (2010) Thin Solid Films 519:12241229 8. Zhao J, Yang X (2003) Building Environ 38:645654 9. Ahmed S, Rasul MG, Martens WN, Brown R, Hashib MA (2010) Desalination 261:318 10. Gaya UI, Abdullah AH (2008) J Photochem Photobiol C: Photochem Rev 9:112 11. Zhu Q, Zhang Y, Zhou F, Lv F, Ye Z, Fan F, Chu PK (2011) Chem Eng J 171:6168 12. Xiong J, Das SN, Shin B, Kar JP, Choi JH, Myoung JM (2010) J Colloid Inter Sci 350:344347 13. Ma XY, Zhang WD (2009) Polym Degrad Stab 94:11031109 14. Tian C, Zhang Q, Jiang B, Tian G, Fu H (2011) J Alloys Compd 509:69356941 15. Zheng Y, Chen C, Zhan Y, Lin X, Zheng Q, Wei K, Zhu J (2008) J Phys Chem C 112:1077310777 16. Padmavathy N, Vijayaraghavan R (2008) Sci Technol Adv Mater 9:035004 17. Chudasama B, Vala AK, Andhariya N, Mehta RV, Upadhyay RV (2010) J Nanopart Res 12:16771685 18. Amornpitoksuk P, Suwanboon S, Sangkanu S, Sukhoom A, Wudtipan J, Srijan K, Kaewtaro S (2011) Powder Technol 212:432438

123

312 19. Xie W, Li Y, Sun W, Huang J, Xie H, Zhao X (2010) J Photochem Photobiol A: Chem 216:149155 20. Kuo ST, Tuan WH, Shieh J, Wang SF (2007) J Eur Cer Soc 27:45214527 21. Hada H, Yonezawa Y, Yoshida A, Kurakake A (1976) J Phys Chem 80:27282731 22. Chou KS, Lu YC, Lee HH (2005) Mater Chem Phys 94:429433 23. Brinker CJ, Scherer GW (1990) Sol-gel science: the physics and chemistry of sol-gel processing. Academic press, USA 24. Kim K, Debnath PC, Lee DH, Kim S, Lee SY (2011) Nanoscale Res Lett 6:5528 25. Wu M, Yang B, Lv Y, Fu Z, Xu J, Guo T, Zhao Y (2010) Appl Sur Sci 256:71257130 26. Waterhouse GIN, Bowmaker GA, Metson JB (2001) Appl Sur Sci 183:191204 27. Habibi MH, Sheibani R (2010) J Sol-Gel Sci Technol 54:195202 28. Wang J, Meng L, Qi Y, Li M, Shi G, Liu M (2009) J Crys Groeth 311:23052308

J Sol-Gel Sci Technol (2012) 62:304312 29. Rajeshwar K, Osugi ME, Chanmanee W, Chenthamarakshan CR, Zanoni MVB, Kajitvichyanukul P, Krishnan-Ayer R (2008) J Photochem Photobiol C: Photochem Rev 9:171192 30. Zheng Y, Zheng L, Zhan Y, Lin X, Zheng Q, Wei K (2007) Inor Chem 46:69806986 31. Sirimahachai U, Phongpaichit S, Wongnawa S (2009) Songklanakarin J Sci Technol 31:517525 32. Akhavan O (2009) J Colloid Inter Sci 336:117124 33. Hu C, Lan Y, Qu J, Hu X, Wang A (2006) J Phys Chem B 110:40664072 34. Blake DM, Maness PC, Huang Z, Wolfrum EJ, Huang J (1999) Sep Purif Methods 28:150 35. Hirota K, Sugimoto M, Kato M, Tsukagoshi K, Tanigawa T, Sugimoto H (2010) Cer Int 36:497506 36. Yu B, Leung KM, Guo Q, Lau WM, Yang J (2011) Nanotechnology 22:1156033

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