You are on page 1of 7

Applied Surface Science 257 (2011) 8850–8856

Contents lists available at ScienceDirect

Applied Surface Science
journal homepage:

The potential use of nanosilver-decorated titanium dioxide nanofibers for toxin
decomposition with antimicrobial and self-cleaning properties
Chutima Srisitthiratkul, Voraluck Pongsorrarith, Narupol Intasanta ∗
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), 130 Thailand Science Park, Phahonyothin Road, Klong Luang,
Pathumthani 12120, Thailand

a r t i c l e

i n f o

Article history:
Received 29 December 2010
Received in revised form 18 April 2011
Accepted 18 April 2011
Available online 12 June 2011
Titanium dioxide
Japan Industrial Standard (JIS)
Nitrogen oxide
Volatile organic compound (VOC)
Staphylococcus aureus
Escherichia coli
Self cleaning

a b s t r a c t
While chemical and biological attacks pose risk to human health, clean air is of scientific, environmental
and physiological concerns. In the present contribution, the potential use of nanosilver-decorated titanium dioxide (TiO2 ) nanofibers for toxin decomposition with antimicrobial activity and self-cleaning
properties was investigated. Titanium dioxide nanofibers were prepared through sol–gel reaction
followed by an electrospinning process. Following the Japan Industrial Standard (JIS) protocol, decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) by the TiO2 nanofibers suggested
that these materials were capable of air treatment. To further enhance their anti-microbial activity, silver
nanoparticles were decorated onto the TiO2 nanofibers’ surfaces via photoreduction of silver ion in the
presence of the nanofibers suspension. Furthermore, tests of photocatalytic activity of the samples were
performed by photodegrading methylene blue in water. The nanofibrous membranes prepared from these
nanofibers showed superhydrophilicity under UV. Finally, the possibility of using these hybrid nanofibers
in environmental and hygienic nanofiltration was proposed, where the self-cleaning characteristics was
expected to be valuable in maintenance processes.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Clean air is of scientific, environmental and health concerns
[1,2]. Both chemical [3,4] and biological [5] contaminants pose risks
to both industrial settings and household. Nitrogen oxide (NOx)
[4] and volatile organic compounds (VOCs) [3] are among common noxious byproducts from transportation and manufacturing.
In addition, bacteria and virus have been the pinpoint of physiological apprehension in recent times [5]. In general, antimicrobial
proteins in the pulmonary systems constitute to our physiological defense mechanism [6]. However, recent reports on effects
of airborne chemical and biological pollutions on human health
[4,5] implied that more effective protection systems are still highly
sought after.
Degradation of chemical pollutions [7–9] and biological disinfection [10,11] has been proven possible with photocatalysis.
Photocatalysts harvest light as an energy source to excite elec-

∗ Corresponding author. Tel.: +66 2564 7100x6580; fax: +66 2564 6981.
E-mail address: (N. Intasanta).
URL: (N. Intasanta).
0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.

trons from valence to conduction bands [12,13]. The generated
electrons and holes make possible reductive and oxidative reactions of organic pollutant into carbon dioxide and water. Titanium
dioxide (TiO2 ), a metal-oxide semiconductor, has been studied and
widely used as a photocatalytic material owing to its relatively high
photocatalytic activity, chemical stability, non-hazardous nature,
superhydrophilic property and antibacterial activity [13,14]. The
TiO2 photocatalyst which is driven by the clean energy of sunlight
is expected to be applied in many potential applications such as
self-cleaning [15–18], degradation of organic pollutants [19–22],
photoelectrode and electrochromic device [23–26].
Due to their high surface area and unique properties, the use of
nanomaterials has gained tremendous attention in both industrial
and academic arena. In photocatalysis, exploitation of nanomaterials involves some limitation which depends strongly on their
dimension. Spherical-shaped nanomaterials inherit practical problems relating to self-agglomeration [27,28] which lead to low active
surface area and, thus, low efficiency. In contrast, one-dimensional
materials such as nanofibers show much less agglomeration.
As such, electrospinning is a facile and cost-effective route to
generate fibers with diameters at nanometer length scale [29–32].
As a typical approach, metal alkoxides are used as precursors for

/ Applied Surface Science 257 (2011) 8850–8856 the syntheses of several semiconductor nanofiber such as titanium dioxide [13. Preparation of nanofibrous layers for gas-phase photocatalytic and contact angle measurement Nanofibrous layers were prepared for gas-phase photocatalytic and contact angle measurements.41].2. TiO2 nanofibers were prepared through sol–gel reaction and electrospinning process [29–32].40. Germany). 0.0 and 6.02◦ /min. The precursor gel for electrospinning titanium dioxides nanofibers was prepared using titanium (IV) isopropoxide. P25 (Degussa. 3. Variation of solution properties and spinning parameters leads to a wide range of one-dimensional nanostructures ranging from single to multi-component nanofibers [33]. In the present contribution. Photocatalytic activities The photocatalytic activities of the samples were performed against degradation of methylene blue. The resulting dark dispersion was filtered. 97%. Electron microscopy The nanofibers’ morphologies were characterized by scanning electron microscope (SEM. P25 layer was prepared with the same method. hydrochloric acid. hydrochloric acid (HCl. 3.5. the precursor gel was loaded into a 3 ml polypropylene syringe barrel. USA). To further enhance their anti-microbial activity. using scan rate of 0. 2. Decomposition of model toxin The decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) followed Japan Industrial Standard (JIS) protocol [34. Japan. Chemicals Titanium (IV) isopropoxide (TiP. material and energy applications [ g of TiP into a mixture of 2 g of ethanol and 0.0 mg. respectively. Characterization and instrumentation 3. The measurements were carried out with JOEL.6 mg of silver nitrate was added and the solution was magnetically stirred for 10 min. The as-spun nanofibers were calcined at 500 ◦ C for 4 h under air in order to remove organic contents and form crystalline titanium dioxide. 2 kW instrument at room temperature with CuK␣ as the irradiation source.8%. 3. Before the photoreaction. The patterns were recorded over the angular range of 15–80◦ (2Â). In so doing. washed and dried before further characterization. In a separate beaker. 0. 8851 Immediately afterward. X-ray diffraction The crystal structures presented in the titanium dioxide nanofibers were determined by powder X-ray diffraction or XRD method. The experiment was conducted at AIST. Methylene blue has been used widely as a standard model contaminant for photocatalysis [42]. this technique has been exploited for medical. equipped with a 21-guage. USA).1. In a typical protocol. The following protocol is given as an example.1. 3. 3. Then. using 300 W high-pressure Hg lamp UV source.3. The spatial distribution of silver element and nanosilver was determined from SEM under elemental mapping mode. Finally. a TiO2 sol was prepared by adding 3. JDX-3530. 200 mg of titanium dioxide nanofibers were dispersed in 2 ml of deionized water and sonicated for 5 min.2. During the process. Malaysia). flat tip needle connected to a high-voltage supply (Spellman. Aldrich) were used as received. 10 mg of the prepared nanofibers was dispersed in 20 ml of 5 ppm methylene blue solution for 10 min using ultrasonicator (Crest. Srisitthiratkul et al. polyvinylpyrrolidone and pluronic. The nanofibrous membranes prepared from these nanofibers showed superhydrophilicity under UV. stainless steel.14]. Furthermore. where the self-cleaning characteristics was expected to be valuable in maintenance processes. Fluka).39]. Preparation of titanium dioxide nanofibers Titanium nanofibers were prepared by an electrospinning process [29–32. Then UV irradiation at 365 nm was applied onto the solution under magnetic stirring for another 1 h. The suspension was kept in the dark and continuously magnetically stirred for 30 min to equilibrate the . 2. 100 mg of active materials was sonicated in 2 ml deionized water. Firstly. JEOL JEM-2010). 60 mg of calcined titanium dioxide nanofibers were dispersed in 60 ml deionized water and sonicated for 10 min. The average size of nanosilver decorating on the fibers was calculated from FWHM using Program MDI Jade 6. this solution was mixed with the PVP–pluronic solution followed by magnetic stirring at room temperature for 15 min. The concentration of active materials was 2 mg/cm2 . Preparation of nanosilver-decorated titanium dioxide nanofibers Deposition of nanosilver onto the surfaces of titanium dioxide nanofibers was performed by a facile and cost-effective photochemical reaction [35]. the resulting dispersion was spread over a 5 cm × 10 cm glass slide before drying at 70 ◦ C for 1 h. 2. ethanol. Mw ∼ 360. silver nanoparticles were decorated onto the nanofibers’ surfaces by photoreduction [35–38]. The resulting precursor gel was heated at 50 ◦ C for 24 h. tests of photocatalytic activity of the samples were performed by photodegrading methylene blue in water.3 ml/h by a syringe pump (Vernon Hills. The resulting slurry was coated on a 5 cm × 10 cm glass substrate. the solution was fed at a constant rate of 0.2. Then. Aldrich) and silver nitrate (AgNO3 . Carlo Erba). Photoluminescence Photoluminescence was measured at room temperature with Perkin Elmer LS-55 Fluorescence Spectrometer using a high energy pulsed xenon source for excitation. In the synthetic procedure. Japan) and transmission electron microscope (TEM. In a typical protocol. An electrical potential of 10 kV was then applied between the tip of the needle and the grounded aluminum foil target which were 15 cm apart. pluronic (Mw ∼ 5800. Carlo Erba). 2. As a reference. As a consequence. aqueous-base photoreduction of silver ion in the presence of nanofiber suspension resulted in nanosilverdecorated TiO2 nanofibers. Experimental 2. the possibility of using these hybrid nanofibers in environmental and hygienic nanofiltration was proposed.% – of silver were deposited onto titanium dioxide nanofibers by varying silver nitrate content from 1.3. polyvinylpyrrolidone (PVP. The potential use of these nanofibers as air nanofilters was shown in the decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) under Japan Industrial Standard (JIS) protocol [34]. 5 and 10 wt.25 ml of HCl. 37%.5 g of PVP were firstly dissolved in 7 g of ethanol under magnetic stirring.14].4. Aldrich). In the electrospinning set up. S3400N. ethanol (C2 H5 OH. 3.000.C. Different amounts – 2.5 g of pluronic and 0. 99.

After the preparation of nanofibrous layers. Contact angle measurements Contact angle measurements were performed using Tensiometer with water as a probe liquid (Dataphysics Instruments. 2a and b. Lambda 650. Srisitthiratkul et al. This entailed low production cost in practical uses and future industrial production. JIS has been adopted widely in academia and industries [34. 4. Unlike spherical-shaped TiO2 nanomaterials. coli. Maneerat et al. the nanofibers did not show any agglomeration among the primary particles (Fig. a common noxious solvent extensively used in industries.6. The detailed mechanism of photocatalytic decomposition of VOC and NOx were described elsewhere [46–48]. Fig. their efficiencies. respectively. / Applied Surface Science 257 (2011) 8850–8856 adsorption–desorption processes [42]. thus. three small dishes containing similar sample were placed in close proximity. To further enhance their anti-microbial activity. Six measurements were made on different areas and the average values were reported. ATCC 6538) and Escherichia coli (E. Physical characteristics of photocatalyst nanofibers. the fibers were fully dispersed in the layer. After every given interval of UV irradiation. From Fig. 1. The concentration of methylene blue was measured with UV-Vis spectrophotometer (Perkin Elmer. condensation and elimination of all the organic components. the resulting suspension was illuminated with UV under magnetic stirring. JIS R 17011:2010 or ISO 22197-1:2007 exploited NOx to represent harmful Fig. This characteristic was quite the opposite from most of spherical-shaped nanomaterials which tended to agglomerate. where Staphylococcus aureus (S. which included grinding the catalyst. the layer was not only fibrous but also highly porous.50]. Japanese Industrial Standards (JIS). aureus.40. The potential use of these nanofibers as air nanofilters was shown in the decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) under Japan Industrial Standard (JIS) protocol. Lack of inhibitory zones implied that there were no antibacterial activities. USA) at 663 nm. While these results implied that the TiO2 nanofibers could be effective in air pollution abatement. Antibacterial activities Antibacterial activities of samples were examined by agar diffusion method [43–45]. respectively. gaseous byproducts from industrial productions and transportation. aqueous-base photoreduction of silver ion in the presence of the nanofiber suspension resulted in . Formation of inhibitory zones entailed antibacterial activities. As shown in Fig. 1b). However. photocatalytic reactions have been reported to be strongly dependent on film thicknesses and amount of active material [48]. centrifuged and filtered to remove the photocatalyst. These nanofibers appeared smooth with diameters of about 200–300 nm which were quantitatively evaluated using their high-magnification SEM images.7. calcination was applied. Another dish containing antibacterial agent was placed towards the upper area. the nanofibers became broken with their average length decreased to about 5 ␮m. 1a shows an SEM micrograph of the resulting TiO2 nanofibers. their ability to reduce microbial infection might push their potential application further. Subsequently. the maximum absorption of methylene blue. ATCC 25922) were utilized as Gram positive and Gram negative bacterial strains.8852 C. A water droplet was placed onto the surface of a nanofibrous membrane. Self-agglomeration of photocatalytic nanomaterials might lead to a decrease in accessible active surface and. 3. was used as a model toxin for VOC decomposition measurement. As evident. It is noted. titanium nanofibrous membrane showed 21% and 30% removal for NOx and toluene. Static contact angles were then measured. Briefly. Results and discussion Electrospinning was chosen to fabricate TiO2 nanofibers from titanium alkoxide precursor containing PVP as a polymer additive. a 1 ml aliquot of the sample was collected. respectively. 1b. 3. Comparison with literature data has been difficult due to variation in testing sample preparation and model gases used [49. On each testing plate. In particular. The standardization progression has been synchronized by Japanese Industrial Standards Committee. From JIS R 1701-3:2008. reported that ST-01-coated polyester nonwovens showed 49% removal of toluene under JIS protocol [49]. The physical characteristics of the TiO2 fibers after calcination at 500 ◦ C were unveiled by SEM. TC/TPC 150). Zones of inhibition were averaged from the three small dishes on the same testing plate. stipulated the standards employed for procedures in Japanese industries. To complete the hydrolysis. Toluene. Similarly. the photocatalysis of toluene and NOx mainly resulted in carbon dioxide and HNO3 . This facile approach gave rise to organic–inorganic nanofibers with diameter at nanometer length scale. The distance between the UV source and the reaction containers was fixed at 10 cm. however.41]. the TiO2 nanofibers were decorated with silver nanoparticles via photoreduction. that the fibrous and porous structure of our sample should lead to large surface area for adsorption and decomposition of the model toxin. In so doing. (a) SEM micrograph of electrospun TiO2 nanofibers. An antimicrobial agent was utilized as a positive control. (b) SEM image of TiO2 nanofiber coated substrate.

respectively. The results implied that photoreduction of silver ions and formation of silver nanoparticles occurred on the surface of the fibers.4◦ and 64. it could be seen that the silver particles were homogeneously distributed all over the coated layer. 63. 3d). The XRD pattern of TiO2 nanofibers (Graph 4a) exhibited characteristic reflections at 2Â of 25. Physical characteristics of nanosilver-decorated TiO2 nanofibers.C. TEM image showed more clearly that these nanosized silver particles attached onto the surface of the nanofibers. Fig. it could be said that silver nanoparticles appeared only on the nanofibers’ surfaces. Furthermore. After the photoreduction of silver ions. Since independent silver nanoparticles were not observed. these characteristic reflections remained with some additional reflections present (Graph 4b). (d) Elemental mapping of silver by SEM.6◦ and 75. 48. 4.0◦ . 3b. It could be seen that the nanosized silver particles were randomly distributed along the nanofibers’ surfaces. 2.2◦ . 55. These reflections at 38. 3c revealed the spherical shape of these silver particles.5◦ . (b) A similar membrane showed 30% removal of toluene.7◦ Fig.3◦ . nanosilver-decorated TiO2 nanofibers. 44. . (1 0 5). (0 0 4). By elemental mapping of silver under SEM (Fig. Srisitthiratkul et al. As shown in Fig. (b) TEM image of nanosilver-decorated TiO2 nanofibers. (2 1 1) and (2 0 4) planes of the anatase phase. The white spots corresponded to clusters of silver element. This was consistent with Fig. 3a reveals SEM images of the resulting hybrid nanofibers. / Applied Surface Science 257 (2011) 8850–8856 8853 Fig.0◦ corresponding to (1 0 1). Decomposition of NOx and toluene under JIS protocol. 3a. (c) High magnification TEM image of the fibers. The presence of silver on the TiO2 could be further corroborated. (2 0 0). a high magnification TEM image in Fig. The crystal structures presented in the TiO2 and nanosilverdecorated TiO2 nanofibers were determined by powder X-ray diffraction or XRD method as shown in Fig. (a) SEM micrograph of nanosilver-decorated TiO2 nanofibers.2◦ . 3. 38. (a) TiO2 nanofibrous membrane showed 21% efficiency for the decomposition of nitrogen oxide (NOx).

52]. In a subsequently investigation. respectively. / Applied Surface Science 257 (2011) 8850–8856 Table 1 Formation of inhibitory zones. .0 In agreement with the above result. which released from the surface. For all nanofibrous samples and P25 as a reference. While deposition of nanosilver influenced the photocatalytic performances. In contrast. respectively. (c) and (d) represented P25. (e) and (f) represented silver-decorated TiO2 nanofibers. 6. Agar diffusion tests. To further understand the roles of nanosilver-decorated TiO2 nanofibers as photocatalysts. C0 and C were the initial concentration of MB and that after a given period of UV light irradiation. From the table.0 0. smaller silver particles tended to show more potent antibacterial activity. 4.8 1. represented (1 1 1). it could be said that the silver nanoparticles had been successfully deposited on the TiO2 nanofibers.5 1. (2 0 0) and (2 2 0) planes of the face-centered phase of silver metal [35. Zone of Inhibition (mm) Staphylococcus aureus ATCC 6538 Escherichia coli ATCC 25922 0. the antibacterial activity of nanosilver was usually explained in terms of the interaction between the cell membranes and silver ions.0 0. the concentration of MB decreased with time.5 1. the antimicrobial activity of titanium nanofibers was tested after nanosilver deposition using agar diffusion test as shown in Fig. Srisitthiratkul et al. (a) and (b) represented TiO2 nanofibers. 2% and 10% nanosilver-decorated TiO2 nanofibers resulted in the highest and lowest photocatalytic performances. The antimicrobial activity of the nanofibers can be summarized in Table 1. The influence of nanosilver on both Gram positive and Gram negative bacteria suggested that inclusion of nanosilver enhanced the antimicrobial activity of the nanofibers. but also influence the photocatalytic performance of TiO2 . Top and bottom rows represented Gram positive and Gram negative bacteria.5 0.8 0. As illustrated. TiO2 nanofibers showed no inhibitory zone.0 0. implying that the materials comprised no antimicrobial property without UV. Finally. nanosized silver particles have been shown to be potent antibacterial agents [51. Materials TiO2 Nanofibers P25 1% Ag–TiO2 Nanofibers 2% Ag–TiO2 Nanofibers 5% Ag–TiO2 Nanofibers 10% Ag–TiO2 Nanofibers Fig. Since particles’ surface area increased with the decrease in diameter. 5. From these results.43]. the average size of nanosilver decorating on the fibers was calculated from FWHM to be 32 nm. the photodegradation of methylene blue (MB) was carried out as shown in Fig. their nanosilver-decorated counterparts showed clear inhibitory zones which expanded with the increase of nanosilver extent. the 2% nanosilver inclusion left the activity Fig. (a) XRD pattern of TiO2 nanofibers. Even though the nanoparticles could directly interact and damage cell membranes. In contrast. Silver nanoparticles might not only affect the antibacterial characteristics.36. respectively. 5. Their antibacterial property correlated strongly with their sizes. Structural characterizations by XRD.0 0. The reduction of activity in the latter might come from high surface coverage of nanosilver on the TiO2 nanofibers. (b) XRD of TiO2 nanofibers after the photoreduction of silver ions.0 1.5 0.8854 C.

nanosilver helped improve the performance of the nanofibers. Shown in Fig. After 1 h of UV irradiation. Photodegradation of methylene blue (MB). PL intensity decreased with the increase of nanosilver deposition. . both layers showed superhydrophilicity with static contact angles around and less than 10. the contact angles of both layers decreased substantially. (Inset) Water droplets on P25. It was strongly believed that this result would be useful in maintenance of the membrane when used in nanofiltration applications. As illustrated in Fig. Furthermore. Those of P25 were given as a reference. 8. 7. it is possible to apply these hybrid nanofibers in environmental and hygienic nanofiltration. improved the photocatalytic performance of TiO2 [38.C. the electron–hole recombination rate of each sample was indirectly monitored from their photoluminescence (PL). While the antibacterial and photocatalytic activities were crucial for nanofiltration applications. To strengthen this assumption. significantly enhanced. the more electron–hole recombination rate. Hence. Finally. Â s . after 4 h of UV irradiation. Static contact angles. 8. The samples showed enhanced antimicrobial activity after nanosilver inclusion.0◦ . Nanostructured silver had been known to act as an electron trapping site which reduced the electron–hole recombination rates and. The latter result implied that nanosilver imparted hydrophilicity onto the TiO2 nanofibers. nanosilver might play a role in reducing electron hole recombination rate. it was observed that water droplets spread rapidly on the surface of the membranes. thus.8◦ . As illustrated. Static contact angles. the nanofibrous membranes prepared from these nanofibers showed superhydrophilicity under UV. in high surface coverage. but also influenced the photocatalytic performance of TiO2 . It was assumed herein that nanosilver also behaved as such and the recombination rate in the 2% nanosilver sample was reduced. respectively. decompositions of nitrogen oxide (NOx) and volatile organic compound (VOC) showed 21% and 30% efficiency. 7. TiO2 nanofibers were prepared via an electrospinning process. respectively. it could be summarized that. At 0 h. interfacial phenomena on the nanofiber coated layers were unveiled by contact angle measurements to examine their wetting characteristics. From the MB degradation and PL measurement. the TiO2 and nanosilver-decorated TiO2 nanofibrous layers showed contact angles of 38. only imparted the antibacterial characteristics. From the above rationale. middle and bottom series. Photodegradation of methylene blue revealed that addition of 2% nanosilver significantly enhanced the photocatalytic performances of TiO2 nanofibers. Srisitthiratkul et al. Following Japan Industrial Standard (JIS) protocol. Additionally. The results were consistent with the assumption that nanosilver acted as electron trapping sites where the interface between nanosilver and TiO2 formed heterojunctions [53].53]. C0 and C were the initial concentrations of MB and that after a given period of UV light irradiation. / Applied Surface Science 257 (2011) 8850–8856 Fig. in low density. it could be said that silver nanoparticles not Fig. silver might downgrade the efficiency of the photocatalyst. 6. TiO2 nanofibrous and nanosilver-decorated TiO2 nanofibrous layers were shown on the top. Photoluminescence (PL) intensity as a function of nanosilver extent. respectively. 8855 Fig. as the self-cleaning characteristic was expected to be valuable in maintenance processes. as a function of UV irradiation time. Â s . 5. respectively. the interfacial properties might play a significant role during maintenance processes. the static contact angles of both TiO2 and nanosilver-decorated TiO2 nanofibrous layers decreased as a function of UV irradiation time. Increasing the amount of nanosilver on TiO2 nanofibers’ surface subsequently increased heterojunctions between these two entities [55].7◦ and 27. the more photoluminescence. The correlation between the electron–hole recombination rate and photoluminescence in a photocatalytic sample could be found elsewhere [54]. the electron–hole recombination on the titanium dioxide nanofibers’ surfaces was reduced. Conclusions The potential use of nanosilver-decorated TiO2 nanofibers for toxin decomposition with antimicrobial activity and self-cleaning properties was investigated. In such condition. However. were recorded after a given interval of UV irradiation. or without any UV irradiation. giving rise to a weaker PL signal in the more heavily nanosilver-decorated samples. From these results. In short. From the photoluminescence measurements.

K. Photobiol. Technol. The enhancement of photodegradation efficiency using Pt–TiO2 catalyst. Mao. Pfefferle.G. Sano of AIST. 62 (2008) 4470–4472. [40] N. Kotzias. Y. K. C. 196 (2009) 241–245.T. Y. Sharma.V. Ghaemi. Lett. [54] D. C. G. Kumar. J. Du. A review of photocatalysts prepared by sol–gel method for VOCs removal. C. Johnston. [18] W.D. Relationship between photocatalytic activity. 43 (2009) 2229–2246. [10] C. Zhang. J. Sci. Holgate. Wang. Teo. Photodegradation of methylene blue in water. Clean air and the Adirondacks: science.L. Photocatalytic activities enhanced for decompositions of organic compounds over metal-photodepositing titanium dioxide. Tseng. Adv. Grywna. Matsuzawa. 43 (2008) 368–377. Negishi. Photobiol. Nanosci. Felix. H. Appl.J. [2] M. Rev.M. Personal exposure to nitrogen dioxide (NO2 ) and the severity of virusinduced asthma in children. Cryst. Crit. Japan for JIS testing and helpful discussions. J. 34 (2008) 381–392. C. Hirakawa. J. X. Atmos. Sedlarik. 7 (2006) 29. Li. Smith. Suslu. Park. Infect. Small 5 (2009) 2349–2370.J. R. S. [9] T. S. 121–122 (1997) 417–420. Hayata. [15] K. Majima. Antibacterial efficacy and cytotoxicity studies of copper (II) and titanium (IV) substituted hydroxyapatite nanoparticles. Yong. Catal. B 83 (2008) 39–45. Photoelectrocatalytic properties of nitrogen doped TiO2 /Ti photoelectrode prepared by plasma based ion implantation under visible light. D. Saha. Arabatzis. Takeuchi. Growth 311 (2009) 508–511. Sci. 198 (2005) 340–344. J. Z. 38 (2008) 197–226. Xu. Mesa. Kraft. Antimicrobial proteins and polypeptides in pulmonary innate defence. J. Hoek. [22] B.H. Today 9 (2006) 40–50. A 107 (1997) 245–248.K. Negishi. [23] L. W. K. F. Hayata. Int. 191 (2005) 155–160.J.S. Chen. Hazard. Wang. Chauhan. Takeuchi.K. Colloid Interface Sci. ASABE 51 (2008) 163–168. Tian. Quasi solid state dye-sensitized solar cells with modified TiO2 photoelectrodes and triphenylamine-based dye. Yngard. [27] N. Veronovski. Wang. Dillert. Pazouki. Photocatalytic applications of micro.O. Chemosphere 48 (2002) 1103–1111. Photochem. Gupta. Photocatalytic oxidation of nitrogen monoxide using TiO2 thin films under continuous UV light illumination. N. T. An efficient bicomponent TiO2 /SnO2 nanofiber photocatalyst fabricated by electrospinning with a side-by-side dual spinneret method. Sano. Nano Lett. Kim. Sci.W.S. [19] S. T. Chovelon. Sci. The surface structure of titanium dioxide thin film photocatalyst. A 205 (2009) 28–33. T. Preparation of Fe3+-doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation. Songara. C 30 (2010) 1137–1144.8856 C. 195 (2007) 675–679. Q. Mater. [53] Z. Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles. T.Z.E. coli. Lee. [38] M. Photochem.D.B. Bao. Shen. J. H.G. A.J. M. Leva. Superhydrophilic Fe doped titanium dioxide thin films prepared by a spray pyrolysis deposition. E. Guo. Surf. McElvaney. Nakamura. K. Environ. Degrad. and applications. S. T. C. Greene. Sleiman. Tryba.E. S. Mo.L. Chem. 97 (2004) 203–211. C. Hazard. J. Hirano. Lancet 361 (2003) 1939–1944. J.C. Y. Thin Solid Films 502 (2006) 112–120.M. T. J. P. [12] T. 33 (2007) 694–705. Valasek. Kato. M. [46] M.T. Jin. Fujishima. [20] M. R. Nahar. Sharma. J.O. Ma. Taggart. Sci. Bartzis. Y. Tschirch. Ohko. 11 (2008) 107–113. P. Polym.J. Surf. K. Photocatalytic oxidation of toluene at indoor air levels (ppbv): towards a better assessment of conversion. H. Titanium dioxide nanomaterials: synthesis.A. Proft. A. C 29 (2009) 663–668. M.A. J. Enhanced photocatalytic activity of silver metallized TiO2 particles in the degradation of an azo dye methyl orange: characterization and activity at different pH values. B. and policy choice. J. 95 (2010) 399–404. M. Surf.A. N. Cells 95 (2011) 332–335. Maneerat. Appl. Patra. D. Chemosphere 65 (2006) 1976–1982. K. 303 (2007) 221–233. Zhang. A. J. Durucan. Hasegawa. M. J. M. Y. Liu. Ramakrishna. Fujihara. Zhang. T. Wei. [39] C. S. Vadera. The effect of preparation temperature on the mechanical and antibacterial properties of poly(vinyl alcohol)/silver nitrate films. He. 7 (2007) 1081–1085. Mikroyannidis. Yang. Tekman. Removal of high concentration dimethyl methylphosphonate in the gas phase by repeatedbatch reactions using TiO2 . P. Coat. Phys. N. Emmerich. P. S. K. S. Phys. Sci. V. Y. [16] S. D. Amin. [21] T. F.G. Su. Application of photocatalytic technology for NOx removal. A 209 (2010) 68–73. Miyauchi. Trans. Negishi and Dr. Gamage. Electrospinning of nanomaterials and applications in electronic components and devices. Effect of electrospinning parameters on the nanofiber diameter and length. Matsuzawa. P. Dordick. Characterization of self-cleaning RO membranes coated with TiO2 particles under UV irradiation. [36] L. D. Build. Sonochemical deposition of nanosized Au on titanium oxides with different surface coverage and their photocatalytic activity. Lejeune. 19 (2007) 3808–3814. Dis. Tang. [43] S.J. Suresh.K. Catal. T. S. properties. J. H. Y. Catal.J. Sfiligoj-Smole. J. Silver-modified titanium dioxide thin films for efficient photodegradation of methyl orange. Maneerat. Sci. Sol. [31] S. Lin. P.M. Eng. R.P. Rep. J. Technol. T. Eng. Yang.M. Mellott. Energy Mater. Environ. Lu. Manoth. Linhardt. Bahnemann. Inskip. Synthesis and studies on photochromic properties of vanadium doped TiO2 nanoparticles. Solution processed thin films of nonaggregated TiO2 nanoparticles prepared by mild solvothermal treatment.M. Ma. Matsuzawa. Mater. Chen. Sano. Teo.A.S. M. Devi. Conchon. Appl. Mera. Sano. Chem. Hosseinnia. Falaras. Mater. N. Photocatalytic purification of volatile organic compounds in indoor air: a literature review. Technol. Rogan. [3] S. Hirakawa. Respir. [13] S. Policy 1 (1998) 167–173. Hazard. [26] L. Negishi. Mol. [48] Y.H. 175 (2010) 524–531. P. [30] J. Volatile organic compounds in indoor environment and photocatalytic oxidation: state of the art. D. 59 (2005) 2194–2198. X. Pantano. Howard-Reed. Eng. Appl. [52] V. Lee. Wen. N.P. J. Stab. Immobilization of TiO2 nanoparticles on polymeric substrates by using electrostatic interaction in the aqueous phase. [50] S. A. [24] G. Powder Technol.R. Zhang. Weng. . Sedlarikova. Beachley. Guillard.G. Xin. A review on electrospinning design and nanofibre assemblies. Characterizing gaseous air cleaner performance in the field. Sci. Synthesis of TiO2 –Ag nanocomposite with sol–gel method and investigation of its antibacterial activity against E. Fan. S. 107 (2007) 2891–2959. Ramaseshan. J. Shiraishi. reaction intermediates and mineralization. Lee. D. Bernard. K. Miao. J. modifications. Marambio-Jones. [55] F. J. C. S. Seto. Cocen. 177 (2010) 274–280. N.and nano-TiO2 in environmental engineering. 12 (2010) 1531–1551. Z. P. [11] J. Res. Applications of photocatalytic disinfection. 10 (2010) 5507–5519. Commercial and laboratory prepared titanium dioxide thin films for self-cleaning glasses: photocatalytic performance and chemical durability. Simmons. R. X. M. B. [14] X. Environ. Madaeni. Mater. Andreozzi. Photocatalytic degradation of gaseous sulfur compounds by silver-deposited titanium dioxide.J. 151 (2008) 623–627. Mechanistic insight into the TiO2 photocatalytic reactions: design of new photocatalysts. Surf. Guan. Mater. Tsukuba. T. [34] N. Electrochim. Tade. Ibusuki. P. C. Lamson. Spectrum of viruses and atypical bacteria in intercontinental air travelers with symptoms of acute respiratory infection. Xu. Lin. [25] S. Cooper. Ma. Guglielmi. Chim. 204 (2010) 1445–1451. Schreiber. R. Appl. Nanotechnology 17 (2006) R89–R106.C.K. [49] C. Ho. Ferronato. Chem. [5] L. [4] A. Catal. [41] N. [33] V. Li. A 89 (2007) 81–84. Environ. References [1] C. Transparent micrometer-thick TiO2 films on SiO2 -coated glass prepared by related dip-coating/calcination: characteristics and photocatalytic activities for removing acetaldehyde or toluene in air. T.G. M. Mater. G. Moules. O’Neill. Zhang. S. Surf. Maggos. Lee. B 57 (2005) 109–115. [51] C. Environ. Neophytides. S. X. Nanotechnol. Enhanced photocatalytic activity of magnetic TiO2 photocatalyst by silver deposition. Linaker. C. Immobilization of TiO2 and Fe–C–TiO2 photocatalysts on the cotton material for application in a flow photocatalytic reactor for decomposition of phenol in water. C. J. Photobiol. Int. M.S. K. S.G. Chem. Photochromic and photocatalytic behaviors on immobilized TiO2 particulate films. 145 (2009) 83–96. N. H. M. Lu. Nanopart. Y. A review of the antibacterial effects of silver nanomaterials and potential implications for human health and the environment. G. M. U. Luna. Acta 55 (2010) 2368–2372. Rev. Labou.P. [7] T. Fujitsuka. Srisitthiratkul et al.S. [37] S. Lett. B. Takechi. Coat. S. B 42 (2003) 187–201. Z. 256 (2010) 3116–3121.J. Photoenergy 2010 (2010) 1–11. M. [28] Y. R. Saini. [35] I. politics. Zhao. Tryk. Takeuchi. Takeuchi. Appl. Hazard. Mater.E. Tachikawa. G. Iwata. B 86 (2009) 159–165. [47] A. Ooi. Stergiopoulos. C. Bui. V. a standard method to determine the activity of photocatalytic coatings. [17] N. Panning.K. Chen. Ang. Mater. M. J. [42] J. P. W. C. [29] X. P. hydrophilicity and selfcleaning effect of TiO2 /SiO2 films. Silver nanoparticles: green synthesis and their antimicrobial activities. Sol. Galya. J. Han. Leckie. Drosten. Sci. Tong. [32] W.M. [8] J. TiO2 photocatalysis and related surface phenomena. Pichat. Surf. S. Technol. Membr. Ramakrishna. X. Goer. Y. C. Electrospun nanofibers: solving global issues. Negishi. C 111 (2007) 5259–5275. J. Mater.G. S. Titania nanofibers prepared by electrospinning. Intermed. B. 155 (2008) 572–579. T. Seo. Stable TiO2 dispersions for nanocoating preparation. Chem. / Applied Surface Science 257 (2011) 8850–8856 Acknowledgement Authors would like to thank Dr. [44] Y. One-dimensional composite nanomaterials: synthesis by electrospinning and their applications. L. Photochem. [45] V. Gowd. S. Geraghty.A. Han. Liu.E.S. Nabinger. Gas-phase photocatalytic oxidation of ethylene with TiO2 -coated packaging film for horticultural products. T. Appl. G. 11 (2010) 2336–2361. Li. Reddy. P. Zhao. Mater. [6] M. J. Matsuzawa. S. Coat. Chu. Res. Y. Int. Biedermann. Microbiological disinfection of water and air by photocatalysis. Negishi. 63 (2008) 515–582. Lina. Res.W. Y. H. Kagaya. Sun. J. Kwon.