Top Catal (2011) 54:519526 DOI 10.

1007/s11244-011-9616-y

ORIGINAL PAPER

Effect of Gold Particle Size and Deposition Method on the Photodegradation of 4-Chlorophenol by Au/TiO2
S. Oros-Ruiz J. A. Pedraza-Avella C. Guzman M. Quintana E. Moctezuma G. del Angel R. Gomez E. Perez

Published online: 19 January 2011 Springer Science+Business Media, LLC 2011

Abstract The photoactivity of TiO2 P25 modied by surface-deposition of gold nanoparticles was investigated trough the photocatalytic degradation of aqueous 4-Chlorophenol (4-CP). The Au/TiO2 materials were prepared by three methods: photodeposition, depositionprecipitation (DP) and colloidal deposition. Each preparation yields to different particle size, distribution and properties of gold nanoparticles. However, the photoactivity of these systems depends mainly on the gold particle size. All the materials t well to a pseudo rst order rate model and a relationship between the kinetic rate and the resulting particle sizes was found, which shows the importance of the nanoparticle size

in the photoactivity of the TiO2 modied by gold. The optimal load was found to be 0.5 wt% Au/TiO2 for the material prepared by DP, since this material increased the photoactivity degradation of commercial TiO2 in 80%. Keywords Titanium dioxide Gold nanoparticles Photocatalysis 4-chlorophenol

1 Introduction In photocatalysis, the most common material used for the photodegradation of organic pollutants in aqueous solutions is the titanium dioxide semiconductor, due to its low cost, chemical and physical stability, availability and no toxicity. Recently it has been reported that metallic nanoparticles deposited on the TiO2 support improve the photoactivity of this material. The interaction of metallic nanoparticles with TiO2 induces modications in the electronic state of the solids, leading to important enhancement of the photocatalytic activity [1]. It has been reported that gold nanoparticles supported on the surface of semiconductors present a great catalytic activity for several reactions [2, 3]. They have also been applied for different photocatalytic reactions since they increase the separation of the hole-electron by acting as a sink of electrons, displacing the absorption of light to the visible region and modifying the surface of the catalyst [47]. The use of noble metal nanoparticles have generated a great interest in the recent years for many purposes as for catalysis, optical devices, detection, purication, biosensors and photovoltaic devices [820]. There are several strategies to perform the deposition of nanoparticles on the TiO2, among the most common methods to deposit gold nanoparticles on titania are:

S. Oros-Ruiz (&) Doctorado Institucional en Ingeniera y Ciencia de Materiales, Universidad Autonoma de San Luis Potos, Av. Manuel Nava No. 6, Zona Universitaria, San Luis Potos, SLP, Mexico e-mail: cocoros@dec1.isica.uaslp.mx J. A. Pedraza-Avella Centro de Investigaciones en Catalisis (CICAT), Universidad Industrial de Santander (UIS), Sede Guatiguara, Km. 2 va El Refugio, 681011 Piedecuesta (Santander), Colombia C. Guzman G. del Angel R. Gomez Departamento de Qumica, Area de Catalisis, Grupo ECOCATAL, Universidad Autonoma Metropolitana-Iztapalapa (UAM-I), Av. San Rafael Atlixco No. 186, 09340 Mexico, DF, Mexico M. Quintana E. Perez Instituto de Fsica, Universidad Autonoma de San Luis Potos, Av. Manuel Nava No.6 Zona Universitaria, San Luis Potos, SLP, Mexico E. Moctezuma Facultad de Ciencias Qumicas, Universidad Autonoma de San Luis Potos, Av. Manuel Nava No. 6, Zona Universitaria, San Luis Potos, SLP, Mexico

123

520

Top Catal (2011) 54:519526

photodeposition (PD), depositionprecipitation (DP) and colloidal deposition (CD). PD is a method that uses UV light to excite TiO2 and thus generate electrons that promote the reduction of Au on the titania surface. This method does not use stabilizing agents and the metallic particles are formed and deposited on the surface of the TiO2 in aqueous solution. It requires several washes to eliminate chloride ions and calcination is not necessary [21]. The DP method is commonly used for producing commercial Au catalysts, in this method the surface of the support acts as a nucleating agent, and the metal is strongly attached to the support. This permits the gradual and homogeneous addition of hydroxide ions throughout the whole solution by the reduction of the metallic precursor with urea. The DP method requires washing and calcination [22]. Finally, the CD method requires a metal precursor soluble in organic solvents, the gold nanoparticles are then stabilized by long alkyl thiols and the TiO2 is added to the solution of these capped nanoparticles. The metallic nanoparticles are deposited by weak interactions with the TiO2 support. The method also requires calcination to remove the organic capping ligands from the surface [23]. By using these three methods, in the present work we expect to obtain different gold particle sizes, high metallic dispersion on the substrate, and different particle shapes. Our main interest is to evaluate the effect of the nanoparticle deposition method on the photocatalytic behavior of TiO2. The 4-CP is a model molecule of halogenated aromatics; they are used as solvents or reagents in industrial processes, therefore they are common contaminants in industrial waste waters [24]. 4-CP is a toxic and recalcitrant compound that can not be mineralized by traditional waste water treatment processes, and might be totally mineralized by advanced oxidation processes as photocatalysis. Furthermore 4-CP has been used as a standard for evaluating various experimental parameters in photocatalytic processes [2527].

well known that the photocatalytic process involves the generation of a free electron and a positive hole on the surface of the semiconductor, they induce reactions of reduction and oxidation that proceed at the same time. In order to start the photoreduction of the metallic source, it is required to provide a reactant to be oxidized; in this case we used methanol (Caledon 99.8%) in a concentration 1 M in a nal volume of 400 mL [28]. The quartz reactor was then placed in dark conditions, and deoxygenated for 30 min with N2 ow (100 mL/min) in continuous stirring. The gold deposition was carried out under constant stirring with UVVis radiation provided by four lamps 15 W with a primary emission at 365 nm. The solution was ltered after 1 h of irradiation, and the collected material was washed 4 times with 100 mL of Milli-Q water. The samples were stored at room temperature in dark conditions in a desiccator. 2.2 DepositionPrecipitation (DP) This preparation was made in the absence of light. The deposition of gold was performed with urea (J.T. Baker 99%) following the methodology reported elsewhere [29]. TiO2 (4 g) were dispersed in 100 mL of aqueous HAuCl4 (Aldrich 30 wt%) solutions with concentrations corresponding to Au loads of 0.25, 0.5, 1.0, and 1.5 wt% of the support. Urea was added in a concentration 100 times higher than that of the HAuCl4 concentration. The suspension was heated at 80 C and stirred for 8 h. The urea decomposition led to a gradual rise in the pH of the solution from 2 to 8. After gold deposition, the solids were ltered and washed 4 times with 100 mL of Milli-Q water in order to remove chloride ions which are known to cause particle sintering. The samples were dried at 80 C for 12 h and calcined in air ow (100 mL/min) at 300 C for 4 h [29]. The samples were stored at room temperature in dark conditions in a desiccator. 2.3 Colloidal Deposition (CD)

2 Experimental Methods TiO2 Degussa P25 was used as semiconductor in all the reported experiments. It showed a BET specic surface area of 56 m2/g, an average particle size of 25 nm, a purity of 97% and an anatase/rutile ratio of 80/20. 2.1 Photodeposition (PD) A suspension containing 1 g of TiO2 in 100 mL of Milli-Q distilled water was prepared in a cylindrical quartz reactor with ultrasonic agitation for 30 min. HAuCl4 (Aldrich 30 wt%) was added to the suspension to reach the desired gold loads on the TiO2 (0.25, 0.5, 1.0 and 1.5 wt%). It is For this method a metallic source was rstly prepared as follows: The corresponding to 1 g of HAuCl4 (Aldrich 30 wt%) was dissolved in 50 mL of ethanol (Caledon 95%) and degassed with N2 for 30 min. Then, a solution of 1.364 g of phosphine (Aldrich 99%) in 50 mL of ethanol, previously deoxygenated with N2 was added. The reaction mixture immediately became colorless and a white precipitate appeared. The mixture was stirred for 2 min and the product was removed by ltration, washed with diethyl ether (Fisher 99%) and dried in vacuum. This solid was dissolved in 10 mL of dichloromethane (Merck 99%), and 60 mL of pentane (Aldrich 99%) were added at 4 C resulting in the formation of white needles of

123

Top Catal (2011) 54:519526

521

chloro(triphenylphosphine)gold that are stable in air and soluble in organic solvents [30]. The gold nanoparticles in colloidal suspension were prepared by mixing the chloro(triphenylphosphine)gold with 0.125 mL of dodecanethiol (Aldrich 98%) in 50 mL of chloroform (Caledon 98%) forming a clear solution. Tert-butylamine-borane (Aldrich 99%) was then added in a concentration 10 times higher than the metallic source. The color of the mixture gradually darkened and became purple. This synthesis was made at room temperature and was left for 6 h in constant agitation under dark conditions. The deposition of these colloidal metallic particles on TiO2 was made by adding the support to the solvent containing the gold nanoparticles. The resulting slurry was decolorated while the color of the oxide powder was darkened. The solution was stirred for 3 h and the powder was then centrifugated and dried for 12 h at 80 C. The metallic nanoparticles in the as-prepared metal oxide composites were capped by organic thiols, these were removed by calcination, for 4 h in air ow (100 mL/min) at 3008. Stucky et al. reported that after the calcination, the organic capping ligands are decomposed and no sulfur is detected by XPS [31]. The samples were stored at room temperature in dark conditions in a desiccator. 2.4 Characterization The amount of gold deposited was determined by means of a SpectrAA 220-FS atomic absorption spectrometer. The XRD was used to identify the TiO2 phases with a Bruker D-8 Diffractometer using Cu Ka radiation at a step of 0.03 degrees/min of 2h. The specic surface area was determined by N2 adsorption using a Quantachrome sorptometer apparatus. The specic surface areas (BET) were calculated from the nitrogen adsorptiondesorption isotherms. The UVVis spectra of the materials were obtained in a UVVis Diffuse Reectance Spectrophotometer Varian Cary 100. Transmission electron microscopy (TEM) was performed in a JEOL JEM 1230 electron microscope operated at 100 keV. Particle size distributions were determined by counting at least 200 particles. Carbon monoxide temperature programmed desorption (TPD) was carried out to evaluate the dispersion of the metallic particles using a Chembet-3000 apparatus equipped with a TCD detector. The sample was reactivated under H2 ow at 300 C for 1 h. Afterwards the sample was cooled at room temperature and purged with He ow for 15 min, then a gas mixture (5%CO/95%He) was passed through the sample for 1 h. After this time the sample was purged with He ow for 15 min. The sample was heated up to 300 C at a heating rate of 10 C/min under a constant He ow of 10 C/min to induce the desorption of carbon monoxide.

2.5 Evaluation of the Photocatalytic Activity in the 4-Chlorophenol Degradation The evaluation of the photocatalytic activity of the resulting materials was made for the degradation of 4-CP, and it was monitored for a period of 6 h taking the TiO2 P25 as reference. The reactions were carried out in a well mixed heterogeneous batch reactor with a UV-PC mercury lamp of primary emission at 254 nm. The temperature was stabilized at 20 C with a water recirculation bath connected to the outer jacket of the reactor. Air was supplied to the reactor at a constant rate of 100 mL/min using a mass ow controller. In a typical experiment, the reactor was loaded with 200 mg of the photocatalyst in 200 mL of 4-CP solution (40 ppm). To assure the adsorption/desorption equilibrium, the system was stirred in the dark for 1 h before turning the UV light on. The progress of the reaction was followed by measuring the disappearance of the 4-CP as a function of time with a Cary UVVis spectrophotometer.

3 Results and Discussion The specic surface areas of the solids were obtained in order to evaluate the modication of the surface due to the deposition of the metal. The nitrogen adsorption/desorption isotherms for the materials with the maximum load of gold for the three preparations were obtained. The specic surface area obtained for bare TiO2 was 56 m2/g. Degussa P-25 consists of agglomerates of crystallites, and possess a low porosity, the surface area is largely external to the agglomerates and the pore volume measured is mainly located between the agglomerates (interagglomerate pores) [32]. The specic surface areas were 56, 46 and 55 m2/g for the PD, DP and CD materials respectively, at 1.5 wt% of Au/TiO2. The BET areas were practically of the same order in all the samples, which show that no signicant modication of the textural properties of the TiO2 support were produced due to the deposition of the metal nanoparticles on its surface. XRD spectra for the bare TiO2 and for the materials at 1.5 wt% Au were recorded. The presence of anatase and rutile phases can be observed in the materials after gold deposition. This indicates that no structural effect on the substrate was made by the different treatments performed during the gold deposition. The presence of gold is not detected in the diffractograms since the gold load is very low. However, the content of gold on the materials was determined by atomic absorption obtaining a good agreement with the nominal amount of gold on the substrate (0.25, 0.50, 1.00 and 1.50%). The materials prepared by PD reported 0.30, 0.60, 1.30 and 2.00 wt%, for the materials

123

522

Top Catal (2011) 54:519526

3.6 3.4 3.2

prepared by DP, 0.27, 0.54, 1.20 and 1.40 wt%, and nally the materials prepared by CD reported 0.20, 0.55, 1.3 and 1.6 wt%. The optical properties of TiO2 are usually modied by the presence of gold nanoparticles on the surface. The UVVis absorption spectra for the bare support and the synthesized gold supported materials are presented in Fig. 1. A signicant enhancement of the absorption due to plasmon surface resonance (PSR) at 550 nm is observed due to the interaction of the metallic particles with the incident light, when this oscillates in the electron conduction band of the metal, [33]. The band gap appears shifted to the visible region on the Au/TiO2 samples. The forbidden energy levels (Eg) were determined for the TiO2 P25 and for the materials prepared with different gold contents by diffusive reectance spectroscopy. The obtained values are shown in Fig. 2 where the Eg for the bare TiO2 is only plotted as a reference with a dashed line. As expected, the band gap is displaced to lower values for the Au/TiO2 semiconductors. The Eg values of the modied materials are close to each other and it is difcult to establish a general behavior. However, the Eg decreased for every case where the deposition of gold was made, and at intermediate Au contents (1.0 and 1.5 wt% of Au/TiO2), the materials prepared by DP showed the lowest Eg value while the materials prepared by PD presented the highest value. Kamat et al. [34] have reported that when the semiconductor and metal nanoparticles are in contact the photogenerated electrons are distributed from TiO2 to the Au particles, and the transfer continues until the two systems attain equilibrium. The electron accumulation increases the

Eg (eV)

3.0 2.8 2.6 2.4 2.2 2.0 0.25 0.50 0.75 1.00 1.25 1.50
TiO2 PD D-P CD

% Au
Fig. 2 Variation of the Eg as a function of Au load. Dashed line represents Eg for bare TiO2

PD D-P CD TiO2

200

300

400

500

600

700

800

Wavelenght (nm)
Fig. 1 UV-Vis diffusive reectance of solids for bare TiO2 and TiO2 modied with gold nanoparticles by: PD, DP and CD. The arrow point up the increase in gold load 0.25, 0.5, 1.0, and 1.5 wt% of Au/TiO2

Fermi level of Au to more negative potentials, and the resultant Fermi level gets closer to the conduction band of the semiconductor, which improves the charge distribution of the system. Kamat also observed that small Au particles induce larger shifts in the Fermi level than the large particles do. This might indicate that the particles obtained by DP are smaller than the particles obtained by the other methods. The size of the nanoparticles evidently an important parameter in this discussion, but it is also important in order to elucidate the effect of the different methods used here on the photocatalytic activity. Figure 3 shows the micrographs of the materials at contents of 1.5 wt% of Au/TiO2 for each deposition method. This concentration corresponds to the highest value of gold deposition, where a higher contrast for the different deposition methods can be seen. The images denote the presence of nanosized metallic particles. The average diameters and standard deviations were calculated after counting at least 200 of these particles. The micrographs (Fig. 3) show some important differences between the particles synthesized by the three depositions methods: the particles deposited by the PD and CD presented large particle size and they are not as well distributed on the support, whereas the particles deposited by the DP method (Fig. 3a, c) presented smaller sizes and narrow size particles, well dened and well distributed on the substrate (Fig. 3b). The average particle size and the corresponding standard deviations are plotted as functions of the gold load in Fig. 4. The DP method produced particles with smaller sizes and standard deviations with respect to the other methods since this deposition method is less sensible to the variations in the metal load. Otherwise, the particles prepared by CD presented particle size values from 6.8 to 9.3 nm, while the particles prepared by PD had larger

123

Absorbance (a.u.)

Top Catal (2011) 54:519526

523

Fig. 3 TEM images of materials at 1.5 wt% Au/TiO2 prepared by PD (3A), DP (3B), and CD (3C)

particle sizes from 7.5 to 12.1 nm and larger standard deviations. Another important parameter in the Au deposition is the dispersion of the metallic particles on the surface of the TiO2. All the materials analyzed by carbon monoxide TPD studies indicated that CO is desorbed as a single peak at temperatures below 100 C. The results of carbon monoxide desorption also indicated that bare TiO2 adsorbs a

considerable amount of the probe molecule. The amount adsorbed on the support was subtracted from the amount of CO chemisorbed on the Au/TiO2 materials under identical conditions. It has been reported that there is a good agreement between the mean particle size estimated by TPD and the mean particle size obtained by TEM, for gold contents of 2% [35], however, in our case, only those materials with gold contents of 1.5% presented a good

123

524

Top Catal (2011) 54:519526

14 12

3.5 3.0 2.5

TiO2 0.25% Au/TiO 2 0.50% Au/TiO 2 1.00% Au/TiO 2 1.50% Au/TiO 2

Particle Size (nm)

10 8 6 4 2 0 0.25 0.50 0.75 1.00 1.25 1.50 PD D-P CD

- ln (C/C0)

2.0 1.5 1.0 0.5 0.0 0 50 100 150 200 250 300 350 400

% Au
Fig. 4 Particle size as a function of the Au deposited on the TiO2

time (min)

5.0 4.5

TiO 2 0.25% Au/TiO 2 0.50% Au/TiO 2 1.00% Au/TiO 2 1.50% Au/TiO 2

Table 1 Comparative results of the Au/TiO2 photocatalysts, gold particle size, constant rate, % of 4-CP degraded at half life time

4.0 3.5

-ln(C/C0)

Au/TiO2 TEM Catalysts (wt%) Dav (nm) TiO2 PD PD PD PD DP DP DP DP CD CD CD CD 0.25 0.50 1.00 1.50 0.25 0.50 1.00 1.50 0.25 0.50 1.00 1.50 7.5 0.9

Constant rate % 4-CP degraded 1/K0 (min) t = 120 min 169 66 52 82 20 36 39 55 96 91 51 74 46 59 36

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 50 100 150

12.2 2.0 556 10.3 1.4 244 9.2 1.0 257 7.6 1.0 161 6.1 0.4 6.5 0.4 6.8 0.9 39 39 79

200

250

300

350

400

7.6 0.5 196 9.3 1.4 159 7.7 0.8 156 9.3 1.0 294

time (min)

5.0 4.5 4.0 3.5

TiO 2 0.25% Au/TiO 2 0.50% Au/TiO 2 1.00% Au/TiO 2 1.50% Au/TiO 2

-ln (C/C0)

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0

agreement between dispersion obtained by TPD and mean particle size obtained by TEM, probably this technique is not sensitive enough to determine the dispersion of metal nanoparticles of our catalysts with gold contents below 1.5 wt%. Therefore, the average particle sizes of the gold nanoparticles, for all the catalysts were determined by TEM. In Table 1 are presented the parameters obtained for the prepared materials: average particle size, constant rate, and % of 4-CP degraded at half life time. The activities of these materials are presented in Fig. 5: PD (5A); DP (5B), and CD (5C). In the case of PD the material with the highest activity was the one prepared with 0.25% Au/TiO2, which improving the degradation rate of the TiO2 P25 in 60%, for higher depositions (0.5, 1.0 and 1.5% Au/TiO2) in this method a detrimental effect on the TiO2 activity is

50

100

150

200

250

300

350

400

time (min)
Fig. 5 Plot of -ln(C/C0) as a function of time for materials prepared by a PD; b DP and c CD

observed. On the other hand, DP method shows that for 0.25, 0.5 and 1.0% of Au/TiO2, the effect of commercial TiO2 is improved even by 80% (for the loads of 0.5 and

123

Top Catal (2011) 54:519526

525

600

600

TiO2
500 400 300 200

1/K0 (min)

1/K0 (min)

PD D-P CD

500 400 300 200 100

100

0
0 0.25 0.50 0.75 1.00 1.25 1.50

10

11

12

13

14

15

% Au
Fig. 6 Inverse of rate of degradation (1/K0) as a function of the Au load on the TiO2

Particle size (nm)

Fig. 7 Inverse of rate of degradation (1/K0) of 4-CP as a function of gold particle size. The continuous line is to guide the eye

1.0% Au/TiO2). These materials were the most effective in the photodegradation of 4-CP of the three evaluated deposition methods. The photoactivity of the materials prepared by CD improved signicantly at 0.25% Au/TiO2 (53%), and slightly modied with 0.5 and 1.0%. The load of 1.5% Au/TiO2 was detrimental as in the other methods used, which indicates that this amount is not effective for photocatalytic purposes. The straight lines in Fig. 6 indicate the tting of the photocatalytic degradation of 4-CP that show that it follows approximate rst-order kinetics, even after the Au nanoparticles deposition. This result can be understood in terms of modied (for solidliquid reactions) Langmuir Hinshelwood kinetics. The degradation was considered to take place on the semiconductor surface and not on the gold surface [36]. Gold nanoparticles deposition was very low in all the cases, thus the mechanism of reaction is not modied, however, the constant rate is effectively modied as one can infer from the slope of the tted line. The UV light degradation of the 4-CP as a function of the gold load on the TiO2 is plotted in Fig. 6. It is shown the activity of TiO2 P25 as a reference, the materials prepared by PD improved the activity of TiO2 only for the one with 0.25 wt% of Au, those with higher loads produced larger particle sizes and this conduced to a detrimental effect. For the materials synthesized by CD, the activity was improved for those with 0.25, 0.50 and 1.0 wt% Au. The photoactivity of materials prepared by DP, presented a better growing control of the particles, and resulted in the smaller particles at different loads of gold, which made them the most active materials for the degradation of the 4-CP presenting a maximum in the activity for the material at 0.5 wt of Au. It is very interesting to remark that Fig. 6

shows the same behavior that the dependence of the nanoparticles size as function of the Au loaded (see Fig. 4). This means that the activity of the materials depends on the particle size of the metal. In order to conrm the role of the gold nanoparticles size, the graph of the inverse of the rate of degradation (1/K0) as a function of the particle size is shown in Fig. 7. It can be observed that the average size of the particle has a strong effect on the degradation rate of the 4-CP. This last holds despite the chemical modication of the TiO2 produced by the different deposition methods. It is clear that the main parameter that rules the photodegradation by TiO2 modied with gold nanoparticles is the particle size.

4 Conclusions From the results obtained in this work, it is clear that the particle size exerts an effect of on the activity of the materials in the photoactivity, beyond the deposition method, the most important and ruling parameter is the metal particle size. The materials prepared by DP were the most active in the photodegradation of 4-CP since the particle growth is controlled and prevents the agglomeration of gold, by distributing the metal along the surface and controlling the size. The gold load on TiO2 also plays an important role in the activity; the materials prepared by DP shows that 0.5 wt% of gold is the optimum to improve the photodegradation up to 80%. All the materials with loads of 1.5% of Au/TiO2 presented a detrimental effect on the TiO2 photoactivity, so this load of metal is not efcient for photocatalytical purposes. The Au/TiO2 photocatalysts should posses gold particles with diameters below 8.6 nm

123

526

Top Catal (2011) 54:519526 16. Allmond CE, Oleshko VP, Howe JM, Fitz-Gerald JM (2006) Appl Phys A 82:675678 17. Tran H, Scott J, Chiang K, Amal R (2006) J Photochem Photobiol A: Chem 183:4152 18. Wang H, Wu Y, Xu BQ (2005) Appl Catal B: Environ 59:143150 19. Orlov A, Jefferson D, Macleod N, Lambert RM (2004) Catal Lett 92:4147 20. Rodrguez-Gonzalez V, Zanella R, del Angel G, Gomez R (2008) J Mol Catal A: Chem 281:9398 21. Chan SC, Barteau MA (2005) Langmuir 21:55885595 22. Zanella R, Giorgio S, Henry CR, Louis C (2002) J Phys Chem B 106:76347642 23. Zheng N, Fan J, Stucky G (2006) J Am Chem Soc 128:6550 6551 24. Cheng S, Tsai S, Lee Y (1995) Catal Today 26:8796 25. Mills A, Wang J (1998) J Photochem Photobiol A: Chem 118:5363 26. Li X, Cubbage JW, Tetzlaff TA, Jenks W (1999) J Org Chem 64:85098524 27. Guillard C, Disdier J, Herrmann JM, Lehaut C, Chopin T, Malato S, Blanco J (1999) Catal Today 54:217228 28. Bamwenda GR, Tsubota S, Nakamura T, Haruta M (1995) J Photochem Photobiol A: Chem 89:177189 29. Zanella R, Louis C (2005) Catal Today 107108:768777 30. Braunstein P, Lehner H, Matt D (1990) Inorg Synth 27:218221 31. Zheng N, Stucky G (2006) J Am Chem Soc 128:1427814280 32. Porter J, Li Y, Chan C (1999) J Mater Sci 34:15231531 33. Kamat PV (2007) J Phys Chem C 111:28342860 34. Kamat P (2002) J Phys Chem B 106:77297744 35. Guzman C, Del Angel G, Gomez R, Galindo F, Zanella R, Torres G, Angeles-Chavez C, Fierro JLG (2009) J Nano Res 5:1323 36. Pelizzetti E, Minero C (1993) Langmuir 9:29953001

in order to improve the photoactivity of the commonly used TiO2.

Acknowledgments This project was partially supported by PROMEP and CONACyT (Mexico) through grant No. 49482. S. Oros-Ruiz thanks to CONACyT for the fellowship 213621 Granted.

References
1. Pileni MP (2005) Nanocrystals forming mesoscopic structures. Wiley, Weinheim, Germany 2. Haruta M (2003) The chemical record 3:7587 3. Haruta M (2004) Gold Bull 37:2736 4. Salata OV (2004) J Nanobiotech 2:16 5. Alivisatos P (2004) Nat Biotech 22:4752 6. Jakob M, Levanon H (2003) Nano Lett 3:353358 7. Thompson D (2003) Appl Catal A: General 243:201205 8. Sobana N, Muruganadham M, Swaminathan M (2006) J Mol Catal A: Chem 258:124132 9. Li XZ, Li FB (2001) Environ Sci Technol 35:23812387 10. Tian Y, Tatsuma T (2005) J Am Chem Soc 127:76327637 11. Haruta M (1997) Catal Today 36:153166 12. Dawson A, Kamat PV (2001) J Phys Chem B 105:960966 13. Narayanan R, El-Sayed M (2005) J Phys Chem B 109:12663 12676 14. Wood A, Giersig M, Mulvaney P (2001) J Phys Chem B 105:88108815 15. Sivalingam G, Nagaveni K, Hedge MS, Madras G (2003) Appl Catal B: Environ 45:2338

123