Jorge M. Meichtry Hurng J. Lin Luciana de la Fuente Ivana K. Levy Eduardo A.

Gautier
Unidad de Actividad Qumica, Centro Atmico Constituyentes, Comisin Nacional de Energa Atmica, Av. Gral. Paz 1499, 1650 San Martn, Prov. de Buenos Aires, Argentina

Low-Cost TiO2 Photocatalytic Technology for Water Potabilization in Plastic Bottles For Isolated Regions. Photocatalyst Fixation
Experiments to evaluate the photocatalytic activity of supported TiO2 to potabilize water in common plastic PET bottles under solar irradiation were performed. Commercial titanium dioxide (Degussa P-25) was applied to different cheap materialsglass rings, glass rods and porcelain beadsby dip coating, or directly to the plastic wall of the bottles. The adherence and stability of TiO2 on the supports and the photocatalytic activity in bottles under solar irradiation was evaluated using model compounds as 4-chlorophenol and 2,4-dichlorophenoxyacetic acid. Rings were found to be the best glass supports, but PET bottles were superior for this specic application, as no fragile llings are used, and the materials can be easily fabricated on site. DOI: 10.1115/1.2391317 Keywords: solar photocatalysis, SODIS, titanium dioxide xation

Miguel A. Blesa Marta I. Litter

e-mail: litter@cnea.gov.ar Unidad de Actividad Qumica, Centro Atmico Constituyentes, Comisin Nacional de Energa Atmica, Av. Gral. Paz 1499, 1650 San Martn, Prov. de Buenos Aires, Argentina and Escuela de Posgrado, Universidad Nacional de General San Martn, Av. 25 de Mayo e Irigoyen, San Martn, Prov. de Buenos Aires, Argentina

Introduction
Low-cost technologies are needed to bring solutions to the serious problem of a safe water provision to extended groups of an isolated population in developing countries without access to a municipal water network. This situation is especially critical in tropical regions of Africa, Asia, and Latin America. These sunny regions are characterized by high solar radiance, in some cases more than an average of 3000 sun hours per year. As traditional methodologies for water treatment are often too expensive to be applied in these places, it is imperative to develop simple, efcient and low-cost technologies for the in situ elimination of the chemical and biological pollution. The technologies should be friendly, accepted by the population and easy to handle or to be applied. Solar irradiation in plastic PET bottles SODIS is a costless technology based on the solar exposure for some hours of commercial beverage bottles containing nondrinkable water 1. The technology was initiated by Acra et al. 2 and developed by Wegelin et al., who conrmed its efciency for the removal of indicators of bacteriological pollution 1. The combination of UV-A 315 400 nm and infrared radiation, which raises the temperature of water to 50 C 55 C, destroys bacteria and viruses including Vibrio cholerae. The disposable plastic bottles are readily available, and can be used also for storage and as a drinking vessel, thus avoiding the risk of recontamination. Some articles on the scientic grounds of SODIS appeared recently
Contributed by the Solar Energy Division of ASME for publication in the JOURSOLAR ENERGY ENGINEERING. Manuscript received July 5, 2005; nal manuscript received September 28, 2005. Review conducted by Sixto Malato.

NAL OF

311. Diverse factors as weather, type and aging of bottles, initial water quality, etc. have been thoroughly analyzed 12. Although SODIS is effective to abate microbial pollution of very different origin and type, it is not able to provide residual protection against bacterial growth after irradiation has ceased. It is also unable to eliminate most chemical contamination. TiO2 heterogeneous photocatalysis HP belongs to the group of Advanced Oxidation Processes or Technologies AOPs, AOTs for water and air remediation, methods that seek the quantitative transformation of organic matter to carbon dioxide, water, and other simple compounds, affording complete mineralization 13. The technology uses TiO2 particlesan UV absorbing semiconductorand generates highly oxidizing species like hydroxyl radicals HO, which destroy chemical pollutants and promote the removal of pathogens. The technology presents various advantages: solar light may be used, it can destroy totally the organic pollutants, and the photocatalyst TiO2 is a cheap, reusable, and nontoxic material. It is possible to abate organic and toxic inorganic pollution CrVI, HgII, As, etc. 14,15 and it is effective for disinfection, destroying bacteria and viruses with promising results 16,17. Therefore, it seems advantageous to make efforts to combine SODIS with HP as a means of developing a simple and inexpensive procedure to simultaneously reduce microbial, organic matter, and metal contamination in poor regions. Recently, TiO2 has been successfully tested within SODIS reactors to enhance and accelerate the inactivation rate of bacterial pathogens 1822 in a process named solar photocatalytic disinfection SPC-DIS. In most of these works, TiO2 was used as a powdered suspension, and an additional operation is needed to eliminate the semicon-

ductor from the treated water: as TiO2 particles are extremely small micrometric aggregates of nanoparticles, ltration through a very thin pore diameter membrane lter would be needed. These lters are very expensive or not available in the poor localities of application. Therefore, the catalyst should be used conveniently supported: the effective xation of TiO2 is a crucial aspect in the development of the technology. Nevertheless, real and sustainable xation is very dependent on the support and on the nal application of the xed catalyst. For example, we reported TiO2 xation on very cheap porcelain beads, obtaining a stable material with good photocatalytic activity; it presented rather superior adherence and very low detachment when submitted to a turbulent regime, useful then for ow or recirculation photoreactors 23. However, the use in bottles requires the xation of TiO2 in small pieces, with stability against abrasion and shocks, and easy handling by the people. Fixation on the same plastic wall of the bottle might also be a solution. In Refs. 21,22, TiO2 was xed to supports by different techniques, but no comments on the stability of these xations appear. References 24,25 describe TiO2 coatings on projector acetate transparencies, which were introduced in PET bottles for testing bacteria inactivation and isopropanol oxidation under simulated solar light. The use of the supported photocatalyst was found to be more effective than SODIS. Similar tests, indicating the validity of the SODIS technology to abate microbial pollution in waters of different origin of Argentina, arrived at the conclusion that the presence of the photocatalyst was essential for a complete disinfection, with no regrowth, independently of the bacterial concentration. One of the important improvements of combining SODIS and HP is associated to better residual effects after irradiation has ceased 26,27. In this paper, we explore the possible ways to support the catalyst, while maintaining the basic tenet of extreme simplicity and very low cost. Results of the xation of powdered TiO2 to different cheap materials and the evaluation of the solar photocatalytic activity in bottles for degradation of model chemical pollutants, 4-chlorophenol 4-CP and 2,4-dichlorophenoxyacetic acid 2,4D, are presented. 4-CP is a chemical model compound representative of industrial contamination, while 2,4-D is a commonly used herbicide in the Northwestern region of Argentina NOA region, especially in the Province of Tucumn, where disinfection tests in bottles are in progress. The focus of this work is to demonstrate the availability and efciency of the materials as inexpensive photocatalysts in very low-cost photoreactors bottles to potabilize water in isolated populations.

other chemicals were of analytical reagent grade. Deionized water resistivity= 18.0 M cm, obtained from a Millipore Milli Q apparatus, was used for the preparation of solutions and washings. For spectrophotometric measurements, a Hewlett-Packard diode array UV-visible spectrophotometer, model HP 8453 A, was used. A Konik-500-A HPLC chromatograph, with a LINEAR UVVIS-204 detector was used for liquid chromatographic measurements. NPOC nonpurgeable organic carbon measurements were carried out using a Shimadzu 5000-A TOC analyzer. XRD patterns were obtained at room temperature with a Philips PW-3710 diffractometer using CuK radiation. Ultrasonications were performed with a Cleanson 25 KHz ultrasonicator, model CS-1109. It was determined that the ultrasound frequency did not deteriorate porcelain, glass, or PET, as detected by the constancy of weight before and after the most prolonged sonication of each material in this work. Articial and solar UV radiation was measured at 365 nm with a Spectroline DM-365 XA radiometer. For solar UV radiation, average values were taken from periodical measurements each hour.

Impregnation Procedure
Porcelain Beads. Beads were impregnated with TiO2 according to the previously published procedure 23. Briey, spheres were introduced in a 0.1 M HNO3 solution for 2 h, washed 4 times with water and dried at 100 C. Then, they were immersed in a 1 M KOH solution for 48 h, washed 4 times with water, and dried again at 100 C. A 10% w/v TiO2 suspension, previously adjusted at pH 2.5 with HClO4, was ultrasonicated for 30 min, and the spheres immersed in the suspension for 15 min. The excess of suspension was drained and the material dried at 100 C and calcined at 450 C for 2 h at a 3.3 C min1 heating rate. Finally, the spheres were rinsed for 15 30 min with a vigorous water jet to eliminate loose particles, and dried at 100 C. The impregnation procedure was repeated 2, 4, and 6 times. Before the photocatalytic experiments, beads were washed according to the following procedure. The number of llings to be used in each experiment was introduced into a sm bottle together with 250 mL of water. Each set of beads was arranged in a longitudinal tulle bag, tied at the top with a nylon thread, to reduce shocks between them and with the walls. The bottle was manually shaken for 30 s moderate shaking, and the 365 nm transmittance of the washings was measured. This procedure was repeated until constant transmittance in the washings. In the case of the beads impregnated with 6 TiO2 layers, 7 washings were needed to arrive to a limit value of 80% transmittance. These materials will be called beads. Glass Supports Microslides Preliminary tests to evaluate the best procedure for TiO2 xation on glass llings were carried out on microscope slides plain and frosted. For frosting, carborundum powder was rubbed directly on the glass surface on only one face the other remaining unfrosted. Several impregnation methods were tested in different conditions. Only 75% of the microslide surface i.e., 14.85 cm2 per face was impregnated with TiO2 in all cases. Calculations with noncoated slides have been made to discount the amount of TiO2 xed to the nonfrosted surface. The following ve procedures were found to be the best. 1 The plate was immersed in KOH pH 13.5 for 24 h, washed with water and dried at 130 C for 24 h. Then, a 2% w/v TiO2 aqueous suspension at pH 2.5 HClO4 was applied by dip coating at 3 mm/ s. The material was dried at room temperature for 10 min and then at 130 C for 24 h. The procedure was repeated four times. Finally, the microslide was calcined at 550 C for 2 h at a 3.3 C min1 heating rate.

Experimental
Materials and Equipment. The following supports for TiO2 were used: commercial porcelain beads Del Morro S.A., Argentina, 6 mm diameter, 1.13 cm2 surface, Pyrex glass rings Raschig type, 5 mm outside diameter, 1 mm thick, 10 mm long, 2.51 cm2 total surface, internal and external, Pyrex glass rods 5 mm diameter, 176 mm long, 27.60 cm2 lateral surface, and Pyrex glass microslides Superior, Germany, 76 26 mm, 1 mm thick, 19.8 cm2 per face were used. PET soft drink and mineral water bottles of different local brands with the highest UV transmittance were selected, on the basis of spectrophotometric measurements. Two of them resulted the most convenient as they transmitted more than 90% of the light at 200 nm. Finally, soft drink Coca-Cola bottles were chosen because of the potential higher availability in the places where the technology might be used. Small sm, 650 mL total capacity and large lg, 1560 mL total capacity PET bottles were tested. Commercial TiO2 Degussa P-25 Germany was used as provided. 2,4-D Herbifen, Atanor S.A., dimethylammonium salt of the 2,4-dichlorophenoxyacetic acid, 48.5% w/v as acid was used. Titanium tetraisopropoxide 98%, Merck, 4-CP Fluka, and all

2 The same procedure as in 1, but HNO3 was used instead of HClO4 to adjust the pH to 2.5. 3 The microslide was washed for 30 min with water under ultrasound, and dried at 130 C for 24 h. Then, a 2% w/v TiO2 suspension in isopropanol was applied by dip coating at 3 mm/ s. The drying procedure was the same as in 1. The coating was repeated four times. The slide was nally calcined at 550 C for 2 h at a 3.3 C min1 heating rate. 4 The microslide was washed for 30 min with water under ultrasound, and dried at 130 C for 24 h. Then, the support was dip coated at 1 mm/ s with a solution of titanium tetraisopropoxide in isopropanol at a molar 1:3 ratio. The equivalent TiO2 concentration provided by the Ti precursor was 15% w/v. The material was dried at 130 C for 24 h, followed by calcination at 550 C for 6 h at a 3.3 C min1 heating rate. A transparent, compact lm was obtained over the glass surface. 5 The same procedure as in 4, followed, after calcination, by dip coating 3 mm/ s of a 2% w/v TiO2 aqueous suspension at pH 2.5 HClO4. Drying was at room temperature for 10 min and at 130 C for 24 h. The impregnation and drying procedure were repeated four times. Finally, the microslide was calcined at 550 C for 2 h at a 3.3 C min1 heating rate. As the material prepared according to procedure 1 showed the best adherence and photocatalytic activity see later, this procedure was applied for the impregnation of glass rods and rings both frosted, with some slight modications as follows: Glass Rods. Rods were introduced in a sanding machine to frost the surface, washed with water under ultrasound for 1 h, left 48 h in KOH pH 13.5, rinsed abundantly with water and dried 2 h at 130 C. Then, each rod was dip coated at 3 mm s1, 85% of the surface, i.e., 23.56 cm2 with a 2% w/v aqueous TiO2 suspension, pH 2.5 HClO4, previously ultrasonicated for 30 min. After coating, rods were dried 24 h at 130 C. The impregnation procedure was repeated four times. Finally, supports were calcined at 450 C for 2 h at a 3.3 C min1heating rate. Before the photocatalytic experiments, llings were washed as in the case of beads; only 2 washings were needed to attain a constant 365 nm transmittance 99% in the washings. These materials will be called rods. Glass Rings. The TiO2 impregnation procedure was the same as in the case of rods. Internal surface frosting was not necessary, as abrasion by contact, causing TiO2 detachment, would not take place. For dip coating, 11 rings were threaded in a cotton string. Before the photocatalytic experiments, the llings were washed as the previous materials; in this case, 8 washings were needed to attain a constant 365 nm transmittance 100%. These materials will be called ringsk. One lot rings was prepared skipping the KOH immersion step. PET Bottles. Sm and lg bottles were washed with water under ultrasound for 1 h, and dried 48 h at room temperature. Ten mL of a 2% w/v TiO2 suspension, pH 2.5 HClO4, previously ultrasonicated for 30 min, were introduced in the bottle, which was then shaken and rolled long enough to obtain a homogeneous lm over the entire wall. The remaining suspension was drained and the bottle left inverted, taking care that no drops or irregularities were formed on the surface. The bottle was dried at room temperature for 24 h. The impregnation was repeated twice, resulting nally a thin, semitransparent, and homogeneous TiO2 lm. To eliminate loose particles, the bottle was half lled with water and vigorously manually shaken for 0.5 min. This procedure was repeated twice; no TiO2 detachment was noticed. Before the photocatalytic experiments, the bottle was washed as in previous cases; only 2 washings were needed to attain a constant 365 nm transmittance 100%. These materials will be called 2% bot. As an alternative, a 10% w/v TiO2 suspension was used, but

only 1 layer was applied; the resulting TiO2 lm was not as regular as the one obtained by the previous procedure, but the detachment behavior was the same. These materials will be called 10% bot. A 100% of transmittance in the washings was obtained after washing as in the case of 2% bot.

Evaluation of Adherence and Amount of TiO2 Deposited

The amount of titania attached to the different supports and to PET bottles was determined gravimetrically. In the case of beads, the procedure has been described previously 23, mainly consisting in the ultrasonication of some beads in water for 30 min, rinsing with water, and drying for 24 h at 100 C; the TiO2 mass was the difference in weight before and after the detachment. The adherence of this material was evaluated in Ref. 23. In microslides, the amount of xed TiO2 was calculated as the difference in weight after and before impregnation. To evaluate the xation stability and adherence, the plates were immersed in 50 mL water and ultrasonicated for 30 min. The amount of TiO2 remaining at the end of the ultrasound treatment was calculated as the difference in weight of the support after sonication and before impregnation. The amount of TiO2 xed in rings, rods, and bottles was estimated as in the case of beads. Rods 4, ringsk 40, and rings 40 were dried at 130 C for 15 h, while sm bottles of both classes were dried 2 h at 35 C. The mass of each set of coated supports and of each coated bottle was registered. Then, the glass llings were introduced in a sm clean bottle together with 200 mL of water and ultrasonicated for 4 h; the same was made with the 2% sm bottle, while it was necessary to sonicate 8 h the 10% sm bottle to eliminate all TiO2. In each case, the water was ltered through a previously weighed 0.45 m membrane lter, and the supports or bottles were dried as before and weighed again. In addition, each lter was dried in an oven at 60 C for 12 h, and then weighed to have independent measurements. In all cases, both sets of data differed in no more than 15% and average values were taken. Aging of TiO2-Coated PET Bottles. TiO2-coated sm PET bottles were totally lled 650 mL with water and left in the rooftop for a prolonged period 30 days. Five mL samples of the water were withdrawn after 15 and 30 days for NPOC measurements and 2 mL for UV-vis spectrophotometric analysis, previously ltered by 0.45 m lters.

Photocatalytic Tests
Preliminary tests to evaluate the activity of TiO2-coated microslides were done under articial UV irradiation using a Philips HPA 400S 9G lamp, with a cutoff lter 300 nm; the 365 nm light intensity was 45 W / m2. Here 25 mL of a 0.2 mM 4-CP solution, adjusted at pH 3 with diluted HClO4, were poured in a Pyrex Petri dish and irradiated from above under magnetic stirring, taking periodically 1 mL samples to follow 4-CP concentration. The same photocatalytic system was used to determine the best number of TiO2 layers on porcelain beads. Solar tests were performed on sunny days of June 2005, on the rooftop of the laboratory in Buenos Aires 34 38 S, 58 28 W, between 10 a.m. and 4 p.m. The average insolation in the city during June 2005 can be estimated in 2.1 KWh/ m2 monthly mean global energy, in the range 0.3 3 m, from which 4.5%, i.e. around 0.1 KWh/ m2, is UV light 28. The ambient daytime temperature during the test period was 11 14 C. PET bottles were used as solar photoreactors. Tests were performed with 4-CP the same conditions as before and 2,4-D 0.5 mM, pH 6.8. Sm and lg bottles containing coated llings or TiO2 on their wall, were lled with 250 and 600 mL, respectively, of the pollutant solution. The bottles were placed directly on the rooftop oor over aluminum wrapping foil, and

Table 1 Amount of TiO2 xed to the microslides and remaining after ultrasonication Fixed TiO2 g 0.0011 0.0002 0.0011 0.0004 0.0020 0.0011 0.0010 0.0012 0.0024 0.0020 g TiO2 / m2 0.74 0.13 0.74 0.27 1.35 0.74 0.67 0.81 1.62 1.35 TiO2 remaining mass g 0.0011 0.0000 0.0001 0.0001 0.0000 0.0000 0.0010 0.0010 0.0008 0.0010 % remaining TiO2 100 0 7.1 14.3 0 0 100 82.6 33.3 47.5

Table 2 Amount of TiO2 xed to the different supports used in the solar photocatalytic experiments Impregnated area cm2 1.13 2.51 2.51 23.56 525.00 525.00 mg TiO2 / g of support 2.10 1.24 1.01 0.08 0.18 0.21 g TiO2 / m2 8.00 2.57 2.12 0.27 0.09 0.10

Slide 1 1 2 2 3 3 4 4 5 5 frosted nonfrosted frosted nonfrosted frosted nonfrosted frosted nonfrosted frosted nonfrosted

Support Beads six layers Ringska Ringsa Rods Sm 2% bot Sm 10% bot
a

Includes the whole surface, internal and external.

exposed to sunlight for several hours. During irradiation, the temperature in the bottles never exceeded 40 C. In sm bottles, 165 beads were arranged in a longitudinal tulle bag 200 mm length, 20 mm width; in lg bottles, 396 beads were arranged in an irregular shape 480 mm total length, 20 mm width. Rings and ringsk were threaded in a cotton string, 36 in the sm bottle and 87 in the lg one. Rods were put free inside the bottle, 4 in the sm and 8 in the lg. In all cases, the total amount of TiO2 on the supports in sm and lg bottles was proportional, with the exception of the rods, whose number was merely duplicated in lg bottles. 4-CP concentration was followed spectrophotometrically at 225 nm, taking 1 mL samples diluted to 10 mL. The validity of the measurement methodology has been explained in Ref. 23. 2,4-D concentration was followed by HPLC taking 3 mL samples that were injected to the chromatograph injection loop: 200 L, previous ltration through 0.45 m membrane lters. The measurement was made, modifying slightly the method reported in 29. A THERMO AQUASTAR RP-18 column length: 150 mm, diameter: 4.6 mm was employed. The eluent was CH3CN-H2O 1 + 4, 0.3 M NaOH, pH 2.95 H3PO4, at a 1.2 mL/ min ow; the measurement was taken at 280 nm. In the case of 2,4-D, NPOC measurements were made on 5 mL samples, only before and at the end of irradiation.

Results and Discussion

Deposition Technique and Amount of TiO2 Deposited. To apply TiO2 suspensions to glass surfaces, the dip-coating method was used because the most uniform layers were obtained in comparison with simple immersion, spraying, or brushing. This method has the advantage that the rate of lm growth and therefore its thickness can be controlled 14. It was found that speeds lower than 3 mm/ s gave nonuniform TiO2 lms, while higher speeds gave thicker lms with bad adherence. The application of more than four layers did not increase the amount of xed TiO2. In the case of titanium tetraisopropoxide solutions, dip-coating speeds lower than 1 mm/ s gave also nonuniform lms, and higher speeds formed unstable coatings after calcination, made of very tiny particles that were easily detached from the surface; the same effect was observed with the application of more than one layer of the solution. Based on all these preliminary results, the nal chosen conditions for xation on microslides were procedures 15 described in the experimental section. TiO2 mass on the supports is shown in Table 1. The amount of catalyst remaining on the solid after 30 min ultrasonication is also presented and allows evaluating the adherence and stability of the xation. The results show that most materials prepared with frosted surfaces x more TiO2 than nonfrosted surfaces, with the exception of microslides 4 and 5. Slides 1 and 2 frosted presented similar amounts of xed TiO2. The use of isopropanol instead of water slide 3 increases the quantity xed in frosted as

well as in unfrosted surfaces, indicating that isopropanol would provide a better medium to link glass with TiO2. Procedures 4 and 5, which form an initial TiO2 layer by titanium isopropoxide hydrolysis, yielded, as said, similar results independently of the roughness of the surface. The highest amount of TiO2 was xed by method 5, which combines both techniques, but, as we will see, the nal adherence by this procedure is not good. After 30 min of ultrasonication, the whole mass or an important quantity of TiO2 was lost in various cases, mainly from unfrosted surfaces 1, 2, 3. This did not occur with materials prepared by procedures 1 and 4 on frosted surfaces. Procedure 4 was the only one that did not lead to a considerable loss of TiO2 when prepared over an unfrosted surface. Although procedure 2, which used HNO3 to acidify the TiO2 suspension, xed an equal amount of the catalyst than procedure 1, which used HClO4, this xation was not stable. In case 3, the frosted and nonfrosted surfaces retained similar amounts of catalyst, which were completely lost after ultrasonication, indicating an unstable xation. In the case of materials prepared by procedure 5, the amount of retained TiO2 was similar to that retained by coatings prepared by procedure 4, meaning that the TiO2 xed in the second step is very unstable and detaches easily; the rst TiO2 layer, prepared by titanium isopropoxide hydrolysis, seems to be strongly attached to the glass surface frosted or not. Of course, titanium isopropoxide is a more expensive precursor than Degussa P-25 and, as we will see later, the photocatalytic efciency of this material is not good. After these preliminary results, procedure 1 was chosen for coating TiO2 on rods and rings. It was also used for coating PET, eliminating all heating treatments. In Table 2, the amount of TiO2 xed to the different supports is shown. Surface areas covered by TiO2 were calculated according to the geometrical shape of each support; in the case of PET Coca-Cola bottles, a cylindrical plus a truncated conical surface was taken as an approximation. It can be seen that immersion in KOH favors impregnation, and this effect will be also observed in photocatalytic experiments. Rods and bottles present a lower amount of TiO2. Evaluation of the Performance of Different Fixation Methodologies. Photocatalytic Tests. Photocatalytic tests to evaluate the activity of the different TiO2-coated microslides all frosted were made following 4-CP degradation, before and after treating coated slides by sonication for 30 min these last will be named treated Fig. 1. Treated 2 and 3 were not evaluated because it did not contain TiO2. For comparison, results without TiO2 and with TiO2 suspensions at two concentrations 0.044 g / L, the same TiO2 amount of slides 1 and 2, and 0.44 g / L are shown. Initial rates R0 have been calculated from the plots and are presented in Table 3. Of course, suspended TiO2 reacted much faster because, as known, the activity is very much reduced when the catalyst is immobilized, due mainly to mass transfer limitations and less light availability 23,22. The results show the highest similar R0 for microslides 1, treated 1 and 5, which present also the highest degradation extent after 120 min of irradiation. Treated 5 shows a much lower activity, in accordance with the loss of an important

Fig. 1 4-CP photocatalytic degradation under articial light irradiation on TiO2-coated microslides. 4-CP = 0.2 mM, pH 3, I0365 = 45 W / m2.

amount of TiO2. Interestingly, slide 2, containing the same TiO2 amount than slide 1, is less active, taking into account that the only experimental difference between them is the use of HNO3 instead of HClO4 to adjust pH in the TiO2 suspension used for impregnation. This might be related with the observation by TRMC of a decreased recombination of electron and holes when TiO2 supported on trans-decalin was irradiated in the presence of NaClO4 30. Slide 3 is less efcient than slide 1, although containing more TiO2; as it was prepared with isopropanol instead of water, some rests of organic matter might have remained even after calcination, competing with 4-CP. The activity of plate 4, containing TiO2 prepared from titanium isopropoxide hydrolysis, was lower than those containing P-25, a result frequently observed in photocatalytic works. In agreement, DRX patterns showed that the anatase/rutile ratio of P-25 ca. 80:20 was maintained in the coating of slide 1, while TiO2 on slide 4 was pure anatase. Normalized initial rates, taking into account the mass of TiO2 on each slide, are presented also in Table 3. Of course, this is a very rough comparison because not all TiO2 participates in the photocatalytic reaction, as the deep-lying particles are badly exposed to the light and far away from the pollutant solution; however, this calculation allows making a different comparison of the results. The best sample is microslide 1, because it holds the lowest amount of TiO2 and produces the highest rate. In addition, it shows a similar efciency before and after the ultrasound treatment, which means that the xation procedure would be suitable for supports subjected to extreme mechanical stress and shocking. Note that the normalized rate for suspended TiO2 at the highest concentration is lower than the rate using a TiO2 suspension ten times more diluted.

Porcelain Beads. Evaluation of the Activity According to the Number of Applied Layers. The evaluation was made also with 4-CP in the same conditions and setup as in the case of the microslides. Beads coated two, four, and six times were tested. Results are shown in Fig. 2. As shown, the best results were those obtained with beads impregnated six times. Consequently, this material was the one used in the nal solar tests in bottles. Aging of TiO2-Coated PET Bottles. NPOC and 254 nm absorbances were measured in samples taken from TiO2-coated PET bottles 2% bot and 10% bot completely lled with water and left for 30 days on the rooftop. In all cases, the measured amount of organic carbon was under the limit of determination of the equipment or very close to it 0.5 1.5 mg/ L, while absorbances ranged 0.0060.010. Therefore, it is concluded that TiO2 does not deteriorate the plastic and that no strange substances are introduced to the water, a condition already established for SODIS 8. Besides, it is not expected that water be stored in the bottles for a long time before consumption.

Solar Photocatalytic Tests in Bottles

The bottles were used as the photoreactors, using ringsk, rings, beads, rods, and TiO2-coated bottles. The rational design of the modied bottle as a solar photoreactor is not easy. The disinfection or decontamination process must take place in the interface catalyst/substrate, practically in the same moment the photon is absorbed by the catalyst. Any delay in

Table 3 Initial rate, normalized initial rate and extent of degradation at 120 min for 4-CP degradation over TiO2-coated microslides g TiO2 / L 0.044 0.440 0.044 0.044 0.044 0.080 0.040 0.040 0.096 0.032 % degradation 100 100 66.1 63.0 31.4 39.5 17.4 17.4 69.0 14.0 R0 107 M min1 22.6 29.4 12.8 10.6 6.8 7.2 3.8 2.8 13.0 2.4 R0Norm 104 M min1 g1 20.5 2.7 11.6 9.6 6.2 3.6 3.8 2.8 5.4 3.0

Material TiO2 suspension TiO2 suspension Slide 1 Slide 1 treated Slide 2 Slide 3 Slide 4 Slide 4 treated Slide 5 Slide 5 treated

Fig. 2 Inuence of the number of layers on the 4-CP photocatalytic degradation on beads. 4-CP = 0.2 mM, pH 3, I0365 = 45 W / m2.

Table 4 Active TiO2 surface per bottle, concentration of irradiated TiO2, rst order rate constant and percentage of 4-CP degradation after 18 h of solar irradiation in bottles Active surface cm2 g TiO2 irradiated/L Sm bottles Beads Ringsk Rings Rods 2% bot 10% bot 83.90 81.32 81.32 58.90 194.25 194.25 0.268 0.084 0.069 0.006 0.007 0.008 Lg bottles Fig. 3 4-CP photocatalytic degradation under solar irradiation on different supports in sm bottles. 4-CP = 0.2 mM, pH 3. Average UV light intensity at 365 nm: 5.9 W / m2. Beads Rings Rods 2% bot 10% bot 201.37 196.53 106.02 357.79 357.79 0.268 0.070 0.005 0.005 0.006 21 15 7 9 8 55 at 360 min 83 48 63 59 40 19 17 9 10 13 88 at 360 min 88 82 60 66 77 k 104 min1 % degradation

Material

the time required for the electron/hole pair to reach the surface results in a substantial decrease of the efciency. Similarly, any ltering effect by intervening material results also in dark, useless regions in the unshaken bottle. An important variable is thus the direction of impingement of solar radiation on the catalyst covering the inner surface of the bottle. In the case of bottles with completely impregnated walls, the lm thickness must be low enough to permit the radiation to reach the catalyst from above. With llings as impregnated rings, rods, or beads, the way to pack them in the bottle affects the efciency in unpredictable ways. For these reasons, in this paper the efciency was tested experimentally, without any attempt to model the photoreactor. The bottles were put on the oor and the collection of the most possible amount of solar irradiation was facilitated by the use of aluminum foil. Considerations about the oxygen availability into the bottle and about the treated volume and bottle size have been also made. The activity for degradation was measured in partially lled bottles of two different sizes lg, 1560 mL and sm, 650 mL, to evaluate the effect of the optical pathlength into the bottle. All experiments were performed simultaneously to assure the same photon ux and ambient conditions, together with control experiments illuminated, no TiO2. Bottles were periodically opened and shaken to renew the amount of oxygen inside the solution, and samples were taken at regular times for analysis. A rst set of photocatalytic tests was performed with 4-CP. Further experiments with 2,4-D were made only with the two most efcient materials ringsk and 10% bot. The use of similar amounts of TiO2 on each support, although attempted, was not possible because of the many variables ruling

Fig. 4 4-CP photocatalytic degradation under solar irradiation on different supports in lg bottles. 4-CP = 0.2 mM, pH 3. Average UV light intensity at 365 nm: 5.9 W / m2.

this parameter, mainly the impregnation procedure. To compare the efciency of the different materials, the amount of TiO2 reached by solar light and in contact with the pollutant solution in each bottle named active surface was calculated. The following considerations and assumptions were made, taking into account the disposition of glass pieces into the bottles and the volume of water into the TiO2 coated bottles: For rings and ringsk, 10% of the total surface was in contact with the bottom of the bottle, totally in the darkness. Thus, the active surface is 90% of the total. Ten percent of beads were covered by the rest and not irradiated. Only 50% of the remaining surface was illuminated, meaning that only 45% of the total surface is active. If 4 rods were used, the internal two were 50% irradiated and the external two, 75%. In the case of 8 rods, 6 were inner and 2 external. The active surface is around 56% of the total. In both 2% bot and 10% bot, it was calculated that 47% of the surface was covered by the solution the same for sm and lg and 10% was in contact with the bottom; this leads to only 37% of active surface. In Figs. 3 and 4, the results of 4-CP solar degradation tests in sm and lg bottles, respectively, are presented. In all cases, plots could be approximated to a very good rst order decay, from which rate constants were calculated and presented in Table 4, together with the extent of 4-CP degradation after 18 h under sunlight. Small induction periods could be seen in some degradation proles, but they were not taken into account in the analysis. Rate constants and degradation extent in large and small bottles were comparable, only somewhat lower in large bottles. As water volumes were proportional, the results indicate that the amount of oxygen and light inside the bottles was enough for the oxidation and that the size is not a crucial parameter, at least working in bottles of the tested sizes. The best rates and conversions were obtained using beads. However, after around 6 h of solar irradiation and handling of the bottles, a large amount of TiO2visually seenwas detached from these llings, owing to the abrasion and shocks between the small pieces. It was not possible, in this case, to accurately measure 4-CP concentration because of the turbidity caused by TiO2 coming in suspension, corrupting the UV measurements. Moreover, if the evaluation had been done after ltration, the results would have been affected by an error in excess because the more efcient TiO2 in suspension would have contributed to the activity. This effect was not observed with the other llings, very much stable. It seems that the cylindrical shape of rods and rings, having less exposed area for shocks and scratches between pieces, is better than a spherical

Table 5 Behavior of completely and partially lled sm TiO2-coated bottles in the solar degradation of 4-CP Material 2% bot, 650 mL 10% bot, 650 mL 2% bot, 250 mL 10% bot, 250 mL
a b

Table 6 Active surface per bottle, concentration of irradiated TiO2, rst order rate constant and percentage of 2,4-D degradation after 12 h of solar irradiation in bottles Active surface cm2 81.32 194.25 g TiO2 irradiated/L 0.084 0.008 k 104 min1 15 12 % degradation 58 65 % NPOC decrease 27 29

% degradation 83 72a 98b 100b

a

Solar irradiation time 56 56 12 12 h h h h Material Ringsk 10% bot

average UV light intensity at 365 nm: 1.7 W / m2. average UV light intensity at 365 nm: 2.0 W / m2.

shape. Ringsk yielded very good results; the activity of rings not treated with KOH was somewhat lower, indicating the importance of this step for the immobilization, as the deposit of the catalyst is facilitated by electrostatic attraction 23. The activity of rods was low, and this material appears to be not very good as a photocatalyst, probably due to the low amount of coated TiO2. Both 2% bot and 10% bot bottles are in between. Comparing the different llings rods, beads, and rings, rings have the largest active/total area ratio 90% and also the largest active area/volume of llings ratio. However, if active surfaces and TiO2 concentration are considered, bottles and rods are much more active than rings, as they hold less TiO2. In particular, bottles have a larger active surface than that of rings or ringsk, suggesting that in these supports some TiO2 is not profited and useless. From both coated bottles, 10% bot is slightly better, with the additional advantage of only one impregnation layer. In previous experiments in small 2% bot and 10% bot performed in March 2005, the oxygen availability had been tested Table 5. Completely lled bottles 650 mL were left on the rooftop for 7 days, exposed in total to 56 h of solar radiation. Although care was taken to open lled bottles each day for oxygenation, it took a very long time to reach a high degradation extent, while these values were rapidly attained in partially lled bottles 250 mL, indicating that the availability of dissolved oxygen is crucial for the photocatalytic degradation. Note that the higher sunlight intensity available in March leads to a faster 4-CP degradation cf. Tables 4 and 5. Results of 2,4-D photocatalytic degradation with the best llings ringsk and 10% bot in sm bottles are presented in Fig. 5. A pH decrease from 6.8 to 4.5 was measured in the ringsk system after 10 h of irradiation. The curves can be tted to a very good rst order, in agreement with the results of Herrmann et al. in a different photocatalytic setup 31. A slight decrease 20% in the control irradiated, no TiO2 was observed at

the beginning; as 2,4-D presents a band in the UV, centered around 290 nm, the degradation can be attributed to direct homogeneous photolysis under sunlight. However, the decrease ceased at longer times. Both supports yielded similar results, although slightly better with ringsk. In Table 6, rate constants, 2,4-D degradation extent and NPOC decrease are presented. In the chromatograms, an increasing unknown peak was noticed since the rst times of irradiation, belonging probably to 2,4dichlorophenol, a known intermediate of 2,4-D degradation 31; however, its detection was not attempted. NPOC results validated this assumption, as the decrease was slower than that of 2,4-D. It was found again that although in absolute terms constant rates and conversion are similar for both materials, coated bottles are much more efcient because of a better prot of TiO2 in a larger area. It is remarkable the good degradation obtained for both pollutants after only a few irradiation hours under the low solar irradiance in the winter of Buenos Aires.

Conclusions
To obtain stable lms of TiO2 on supports for use in bottles to potabilize water, various materials and deposition techniques were tested. TiO2-coated porcelain beads, proved in a previous work to be very stable in turbulent recirculation regimes, were not found to be stable to abrasion and shocks, as needed for application in bottles. In contrast, TiO2-coated glass rings, rods, or TiO2 directly xed to the wall of PET bottles, were better materials for this specic use. The preparation of the best materials only needs an aqueous suspension of the low-cost Degussa P-25, without the use of other more expensive precursors. Although the suspensions were acidied with the costly and unsafe HClO4, only a low amount of the acid was used. All the materials were stable for this particular application, cheap and easy to fabricate. In addition, they presented a good ability to degrade model compounds, even under the low sunlight radiance of winter days in Buenos Aires. With respect to glass materials, rings were the best llings, presenting resistance to shocks and scratches due to their convenient geometrical shape, and good active/total area and active area/ volume of llings ratios. TiO2-impregnated PET bottles were superior to glass materials because they exhibited similar activity, but with the advantage of a lower TiO2 content, a more extended TiO2 area exposed to light, and an easier preparation: only one layer of a TiO2 suspension and no calcination or other thermal treatment are needed. The TiO2 lm is very stable, and no fragile llings are used. The adherence is optimal and no deterioration of PET by TiO2 was observed after a prolonged time under weather conditions. Although a half impregnated bottle would collect more solar light, the formation of a homogeneous TiO2 layer on the entire surface of the bottle may result easier for people; besides, this upper TiO2 layer not in contact with water might eliminate very rapidly bad odors or toxic compounds in the gas phase. The main advantage of the material is that it can be easily handled and directly prepared by conveniently trained people in isolated settlements. Of course, tests with real waters must be done to evaluate probable interferences and inhibitions of the photocatalytic process.

Fig. 5 2,4-D photocatalytic degradation under solar light irradiation on different supports in small bottles. 2 , 4-D = 0.5 mM, pH 6.8. Average UV light intensity at 365 nm: 5.3 W / m2.

Efforts to optimize the plastic material, i.e., to nd the right TiO2 concentration in the impregnating suspension, the effect of painting completely the surface with the catalyst or only the half or in stripes, etc. are underway, together with disinfection experiments and tests with real waters. On the other hand, ringsk or even rings could be used as TiO2-coated supports in other technological applications in which photoreactors must be packaged with small glass llings. Tests are in progress.

Acknowledgment
Work was performed as part of Comisin Nacional de Energa Atmica P5-PID-36-4 Program, American States Organization AE/141/2001 Project and Agencia Nacional de Promocin Cientica y Tecnologa, PICT98-13-03672. We thank A.G. Leyva Unidad de Actividad Fsica, CNEA for help with XRD spectra and P. Babay for help with HPLC measurements. M.I.L. and M.A.B. are members of CONICET. J.M.M. thanks CONICET for a doctoral fellowship. We thank Atanor S.A. for providing the 2,4-D sample.

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