COMMUNICATION

DOI: 10.1002/adma.200601822

Enhanced Photocatalytic Performance of Brookite TiO2 Macroporous Particles Prepared by Spray Drying with Colloidal Templating**
By Ferry Iskandar, Asep Bayu Dani Nandiyanto, Ki Myoung Yun, Christopher Joseph Hogan, Jr., Kikuo Okuyama,* and Pratim Biswas
The removal of hazardous organic compounds from water has become an issue of serious concern.[13] Efficient wastewater treatment is essential in the face of increasing population, industrial activity, and decreasing energy resources. Currently used methods for the removal of organic compounds from wastewater include biological, physical, and chemical treatment. However, traditional wastewater treatment methods have several disadvantages.[3,4] Photooxidation is an attractive alternative method for wastewater treatment because it utilizes solar energy (free and inexhaustible), does not produce secondary product waste since the organic waste is decomposed to harmless chemicals during process,[3] and can eliminate toxic, bioresistant, and inorganic compounds from wastewater.[4] The photocatalyst TiO2 is a wide-bandgap semiconductor that can be used to readily degrade organic compounds,[2,5,6] and is found in three different crystalline phases: anatase, rutile, and brookite. Most titania photocatalyst studies have utilized the anatase crystalline phase, which can be synthesized in large quantities by aerosol flame reactors using vapor-phase titaniumorganic or titaniumchloride precursors.[7,8] Recently, however, it has been demonstrated that brookite is more electrochemically active than anatase.[9,10] Both titania particles[3,5,11,12] and films[6,1316] have been used in photocatalyis. Studies of the photocatalytic activity of titania particles have shown that photocatalytic activity is largely size dependent, and the optimum particle size is in the nanoparticle size range.[12] However, such nanoparticles are somewhat impractical for industrial applications because downstream nanoparticle removal processes are typically expensive.[11] Implementation of titania films in large-scale industrial processes is also difficult. Methods for circumventing the problems associated with titania photocatalysts have been suggested by several research groups.[5,1517] The preparation of macroporous and mesoporous films[1520] and particles[21,22] has been proposed as a method to increase the effective surface area of titania photocatalysts, which would allow for increased light absorption and improve photocatalytic performance. Macroporous and mesoporous structures would presumably have a photocatalytic activity similar to nanoparticles but would not require the high maintenance costs associated with nanoparticles. However, there are some unresolved issues with the preparation and photocatalytic activity of porous photocatalysts. Heat treatment and UV irradiation of porous materials usually induces collapse of the porous structure,[16] and surfactant from the synthesis process is not always removed completely,[15] which deters photocatalytic performance. The purpose of this study was to develop a method for the preparation of macroporous titania particles and demonstrate that they have improved photocatalytic performance over nonporous titania particles. In light of recent studies,[9] brookite titania particles were used, although the general conclusions found here would also apply to macroporous particles made of anatase or any other photocatalytic material. In our initial reports, we prepared macroporous silica particles with sub-micrometer diameters using a spraydrying method,[2327] and the resulting particle size and morphology were investigated experimentally and theoretically.[23,24] Here, macroporous brookite titania particles with sub-micrometer diameters were prepared by spray drying a suspension of brookite nanoparticles and polystyrene latex (PSL) particles, which were used for colloidal templating (Fig. 1). Spherical, monodisperse PSL particles can be easily prepared from styrene monomers, which are relatively inexpensive;[28] thus, the spraydrying method is a cost-effective method to produce porous particles. For simplification, commercial PSL particles were used in this study. Porous titania particles prepared by using the spraydrying method are expected to have enhanced photocatalytic performance over nonporous titania microparticles. In addition, unlike nanoparticles, porous titania particles would be easy to separate and collect after use in wastewater treatment processes. Therefore, the use of porous

[*] Prof. K. Okuyama, Dr. F. Iskandar, A. B. D. Nandiyanto, K. M. Yun Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University 1-4-1 Kagamiyama, Higashi Hiroshima 739-8527 (Japan) E-mail: okuyama@hiroshima-u.ac.jp C. J. Hogan, Jr., Prof. P. Biswas Aerosol and Air Quality Research Laboratory, Department of Energy, Environmental & Chemical Engineering, Washington University 1 Brookings Dr., Campus Box 1180, Saint Louis, MO 63132 (USA) [**] F.I. acknowledges support from a Japan Society for Promotion of Science (JSPS) Postdoctoral Fellowship, A.B.D.N. acknowledges support from a Japanese Ministry of Education, Science, Sports, and Culture scholarship, and C.J.H., Jr. acknowledges support from an NSF Graduate Research Fellowship. The authors thank Masatomo Tohi and Takashi Ozaki for assistantship in this research. Supporting Information is available online from Wiley InterScience or from the author.

1408

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2007, 19, 14081412

COMMUNICATION

Figure 1. Macroporous particle formation by spraydrying and colloidal templating.

particles in wastewater treatment processes would be more cost effective than the use of either microparticles or nanoparticles. To optimize the photocatalytic performance of porous particles, the change in particle diameter and pore diameter with precursor concentration (i.e. titania and PSL in the spray solution) and PSL diameter were investigated. The photocatalytic performance of prepared particles was evaluated by measuring the photodegradation of rhodamine B catalyzed by prepared particles under UV illumination. The X-ray diffraction (XRD) patterns of brookite nanoparticles and spray-dried macroporous particles are shown in Figure 2, along with the reference pattern for brookite titania, Joint Committee on Powder Diffraction Standards, number 291361. High temperatures and long heating times can lead to the conversion of brookite to the more thermodynamically stable but less photocatalytically active rutile phase.[29,30] Significant heating could also cause nanoparticle coalescence, making the rutile phase even more thermodynamically stable.[31] The patterns clearly show that both the nanoparticles and spray-dried particles were brookite, and the crystal sizes of the nanoparticles and spray-dried particles were 8.42 and 9.36 nm respectively, which implies that the spray-drying process does not substantially alter the crystalline size or phase of the titania particles. Figure 3 shows scanning electron microscopy (SEM) images of titania particles produced with various nanoparticle to PSL

Figure 2. XRD patterns of porous brookite particles, brookite nanoparticles, and a brookite reference.

particle mass ratios and PSL particle sizes. Spray-dried particles without PSL were nonporous and spherical (Fig. 3a). The addition of PSL particles to the precursor solution allowed for the production of porous particles (Fig. 3ac), with the number of pores increasing with increasing PSL concentration. Further increases in the PSL particle concentration resulted in the formation of aspherical particles and fragmented particles (Fig. 3d). Particles with highly organized macropores were obtained when the brookite nanoparticle to PSL particle mass ratio in the precursor suspension was 1:2. With this mass ratio, macropores appeared in a hexagonal packing arrangement. Deviations from the 1:2 mass ratio resulted in nonhexagonal pore structures. Figure 3c, e, and f shows macroporous particles produced with nanoparticle to PSL particle mass ratios of 1:2 with PSL particle sizes of 300, 200, and 410 nm, respectively. As expected, the pore sizes increased with PSL particle size, demonstrating that the pore size can be easily controlled by changing the diameter of the PSL particles used in the precursor suspension. With 100 nm PSL particles in the precursor suspension, highly ordered macropores could not be formed because the void space between contacting 100 nm spheres was not large enough to contain multiple titania nanoparticles. For three contacting spheres (PSL particles) of diameter D with a hexagonal packing arrangement, the maximum diameter, d, of a smaller sphere (nanoparticle)p that can fit within the void space between spheres is d = (2/3 31)D or d/D = 0.155. For titania nanoparticles with diameters ranging from 10 to 20 nm, the PSL particles must be at least 65 to 130 nm in diameter for a single nanoparticle to fit within the void space; thus, only one nanoparticle could fit between 100 nm PSL spheres. During the PSL evaporation process, single nanoparticle structures would likely collapse and not have highly ordered macropores. Figure 4 shows SEM images of spray-dried particles with brookite to PSL mass ratios of 1:2 with various initial precursor concentrations. As expected, the size of the spray-dried particles increased with increasing precursor concentration. The mean diameters of porous particles with initial precursor concentrations of 0.125, 0.625, and 1.825 % were 432, 539, and 648 nm, respectively. Light-absorption spectra of rhodamine B solutions photocatalytically degraded by titania particles were measured using a UV-vis spectrometer. Absorbance at all wavelengths decreased over time due to the degradation of rhodamine B. Rhodamine B concentrations during experiments were determined based on Beers Law and the absorbance of 555 nm wavelength light by rhodamine B. Normalized rhodamine B concentrations (with respect to the initial concentration) over time during photocatalysis experiments are shown in Figure 5. Photodegradation was measured for 100 min, which was an ample amount of time to observe differences in the photocatalytic performances of porous particles prepared using PSL particles of different sizes. Photodegradation of a solution of 10 higher concentration of rhodamine B over a 25 h period is shown in the Supporting Information.

Adv. Mater. 2007, 19, 14081412

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advmat.de

1409

COMMUNICATION
Figure 3. SEM images of titania porous particles with precursor solutions consisting of brookite nanoparticles only (a), 1:1 brookite nanoparticles to PSL particles, 300 nm PSL particles (b), 1:2 brookite to PSL, 300 nm PSL particles (c), 1:3 brookite to PSL, 300 nm PSL particles (d), 1:2 brookite to PSL, 200 nm PSL particles (e), and 1:2 brookite to PSL, 400 nm particles (f).

Figure 5. Degradation of rhodamine B over time by dense particles, porous particles, and nanoparticles. Empirically determined rate constants for each particle type are indicated.

Figure 4. SEM images of titania porous particles with an initial precursor concentration of 0.125 % (a), 0.625 % (b), and 1.875 % (c).

Typically, the LangmuirHinshelwood kinetic model is used to describe solidsolute photochemical reactions.[11,17,32] At low solute concentrations, as were used here, this model collapses to a first-order kinetic model; thus, a first-order rate constant was empirically determined for these data. Rate constants for each type of particle used in photocatalysis experiments are shown in Figure 5. The rate of photocatalysis was fastest for nanoparticles (k = 0.0442 min1) and slowest for dense spray-dried particles (k = 0.0123 min1). Macroporous particles had intermediate photocatalysis rates, and, in general, particles with small pores (200 and 100 nm) had faster photocatalysis rates than larger pore (300 and 410 nm) parti-

cles. The rate of photocatalysis for smaller pore diameter particles approached the rate of photocatalysis for nanoparticles, that is, macroporous particles have similar photocatalytic properties to nanoparticles but are more economical to use in industrial applications.[5] The crystallite size and phase of nonporous and porous titania and titania nanoparticles were the same, which implies that the fundamental reason behind the difference in photocatalytic performance between particles is purely morphological. It is proposed here that the photocatalytic performance of solid sub-micrometer titania particles is limited by excessive light attenuation on the outer surface of the particle, preventing the titania on the inside of the particle from absorbing photons. Furthermore, an increased available surface area would allow for enhanced loading of organic contaminants

1410

www.advmat.de

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2007, 19, 14081412

COMMUNICATION

onto the surface of the titania particles. Therefore, nanoparticles and macroporous particles, which have higher surface area to volume ratios than solid sub-micrometer particles, are more photocatalytically active, that is, titania photocatalysts with higher surface areas have better photocatalytic performance. BrunauerEmmettTeller (BET) analysis is often used to measure surface area in particulate samples.[33] However, BET measurements on spray-dried particles with nanoparticle precursors are misleading; the surface area of the individual nanoparticles is measured and little difference between solid and porous particles is detectable. As an alternative to BET measurement, a simple geometric model is used here to describe the increased surface area of macroporous particles as compared to solid particles. A physical representation of this model is shown in Figure 6. Assuming that the PSL particles were hexagonally packed within a drying droplet, an explicit equation for the maximum surface area of

Table 1 shows the calculated Am/Amdense values (ratio of calculated porous particle surface area to the surface area of a solid spray-dried particle) for particles with an outer diameter

Table 1. Surface-area ratios calculated using a geometric model and photocatalysis rate constants determined empirically for brookite titania particles.
Type of titania particle nanoparticle 100 nm pores 200 nm pores 300 nm pores 410 nm pores dense particle h i Am= dense Am 4.65 2.29 2.25 2.15 1.00 h k=kdense 3.59 2.30 2.46 1.65 1.07 1.00 i

Figure 6. An SEM image of a titania particle with 300 nm pores (a), a three-dimensional representation of a hexagonally packed porous particle (b), and parameters used in porous particle surface area calculation (c).

porous particles was developed which takes into account the total volume occupied by PSL particles, the PSL particle and titania diameter, and the number of PSL particles in each spray-dried droplet. The derivation of this equation is shown in the Supporting Information. In applying this equation to surface-area calculation for macroporous particles and demonstrating that their calculated surface area correlates with their photocatalytic activity it is assumed that 1) photon absorption by titania only occurs on the particle surface,[34] 2) significant necking due to sintering of titania nanoparticles does not occur (supported by XRD data), 3) the appearance diameter of surface pores is approximately 80 % of the diameter of the PSL particles (confirmed from SEM measurements), and 4) all the surface area of the porous particles is exposed and is photocatalytically active.

of 620 nm (typical diameter of spray-dried particles) as well as the photodegradation rate constants for each type of particle normalized by the photodegradation rate of dense particles. Particles with 100 nm pores have substantially enhanced surface area because during the spray-drying process 100 nm PSL will form two layers within the drying droplet (see Supporting Information). The normalized surface area and normalized rate constants are in qualitative agreement with each other, which implies that the increased photocatalytic activity of macroporous particles as compared to dense particles was due to their increased surface area. For particles with 100 nm pores, the rate constant was actually lower than the rate constant of particles with 200 nm pores despite the fact that a porous particle with hexagonally arranged 100 nm pores has a higher surface area than a porous particle with 200 nm pores. However, the particles made from spray drying a precursor suspension with 100 nm PSL particles did not have hexagonally organized pores. Therefore, particles with 100 nm pores had substantially less surface area than would be predicted by the model used here. To be effective in industrial applications, photocatalysts must be reusable. No change in the macroporous particle morphology before and after photocatalysis experiments was apparent from SEM images. The XRD patterns for spray-dried particles indicated that partial sintering occurred, as the crystal size increased slightly owing to spray drying. Partial sintering would presumably bond together neighboring nanoparticles such that macroporous particles retain their structure during dispersion in aqueous systems and when irradiated by UV light. In addition, the photocatalytic performance of particles must not change over time. The photodegradation rate of rhodamine B for macroporous particles for particles collected and used repeatedly is shown in the Supporting Information. Almost no decrease in the photodegration rate was observed for particles reused up to three times. In summary, macroporous brookite titania particles were prepared by using a spray-drying process with a precursor solution of brookite nanoparticles and PSL particles. Macroporous particles are more photocatalytically active than dense

Adv. Mater. 2007, 19, 14081412

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.advmat.de

1411

COMMUNICATION

particles as a result of their increased surface area, which allows more titania molecules to absorb photons. Macroporous particles retain their structure in the liquid phase and unlike nanoparticles they can be easily collected and reused. Therefore, the macroporous particles prepared in this study would be useful in many industrial applications, such as degradation of organic waste, pathogen inactivation, and fuel-cell technology. The spray-drying technique with PSL particle templating used in this study is a simple technique that can be used to prepare many types of particles with good control over the porous particle size and pore size.

experiments, particles were collected and examined by using SEM to determine if the particle morphology had changed. Received: August 9, 2006 Revised: November 14, 2006 Published online: April 24, 2007

[1] O. Carp, C. L. Huisman, A. Reller, Prog. Solid State Chem. 2004, 32, 33. [2] Y. Ma, J. N. Yao, J. Photochem. Photobiol. A 1998, 116, 167. [3] M. Stylidi, D. I. Kondarides, X. E. Verykios, Appl. Catal. B 2003, 40, 271. [4] D. Chen, A. K. Ray, Chem. Eng. Sci. 2001, 56, 1561. [5] D. Beydoun, R. Amal, G. K. C. Low, S. McEvoy, J. Phys. Chem. B 2000, 104, 4387. [6] S. H. Si, K. L. Huang, X. G. Wang, M. Z. Huang, H. F. Chen, Thin Solid Films 2002, 422, 205. [7] G. X. Yang, H. R. Zhuang, P. Biswas, Nanostruct. Mater. 1996, 7, 675. [8] M. K. Akhtar, X. O. Yun, S. E. Pratsinis, AiChE J. 1991, 37, 1561. [9] M. Koelsch, S. Cassaignon, J. F. Guillemoles, J. R. Jolivet, Thin Solid Films 2002, 403, 312. [10] T. Shibata, H. Irie, M. Ohmori, A. Nakajima, T. Watanabe, K. Hashimoto, Phys. Chem. Chem. Phys. 2004, 6, 1359. [11] H. S. Son, S. J. Lee, I. H. Cho, K. D. Zoh, Chemosphere 2004, 57, 309. [12] C. B. Almquist, P. Biswas, J. Catal. 2002, 212, 145. [13] W. J. Zhang, Y. Q. He, Q. Qi, Mater. Chem. Phys. 2005, 93, 508. [14] Y. Tian, T. Tatsuma, J. Am. Chem. Soc. 2005, 127, 7632. [15] T. Alapi, P. Sipos, I. Ilisz, G. Wittmann, Z. Ambrus, I. Kiricsi, K. Mogyorosi, A. Dombi, Appl. Catal. 2006, 303, 1. [16] H. Shibata, T. Ogura, T. Mukai, T. Ohkubo, H. Sakai, M. Abe, J. Am. Chem. Soc. 2005, 127, 16 396. [17] D. W. Chen, A. K. Ray, Appl. Catal. B 1999, 23, 143. [18] D. S. Zhang, T. Yoshida, H. Minoura, Adv. Mater. 2003, 15, 814. [19] H. S. Yun, K. Miyazawa, H. S. Zhou, I. Honma, M. Kuwabara, Adv. Mater. 2001, 13, 1377. [20] N. G. Park, K. M. Kim, M. G. Kang, K. S. Ryu, S. H. Chang, Y. J. Shin, Adv. Mater. 2005, 17, 2349. [21] Y. Q. Wang, X. H. Tang, L. X. Yin, W. P. Huang, Y. R. Hacohen, A. Gedanken, Adv. Mater. 2000, 12, 1183. [22] S. M. Klein, V. N. Manoharan, D. J. Pine, F. F. Lange, Langmuir 2005, 21, 6669. [23] F. Iskandar, A. Mikrajuddin, K. Okuyama, Nano Lett. 2002, 2, 389. [24] F. Iskandar, A. Mikrajuddin, K. Okuyama, Nano Lett. 2001, 1, 231. [25] F. Iskandar, A. Mikrajuddin, K. Okuyama, in Encyclopedia of Nanoscience and Nanotechnology, Vol. 8 (Ed.: H. S. Nalwa), American Scientific Publishers, California, 2004, 259. [26] K. Okuyama, A. Mikrajuddin, I. W. Lenggoro, F. Iskandar, Adv. Powder Technol. 2006, 17, 587. [27] L. Gradon, S. Janeczko, M. Abdullah, F. Iskandar, K. Okuyama, AiChE J. 2004, 50, 2583. [28] J. W. Goodwin, J. Hearn, C. C. Ho, R. H. Ottewil, Colloid Polym. Sci. 1974, 252, 484. [29] T. Ohno, K. Sarukawa, M. Matsumura, J. Phys. Chem. B 2001, 105, 2417. [30] H. Z. Zhang, J. F. Banfield, J. Phys. Chem. B 2000, 104, 3481. [31] V. N. Koparde, P. T. Cummings, J. Phys. Chem. B 2005, 109, 24 280. [32] Y. Liu, X. Chen, J. Li, C. Burda, Chemosphere 2005, 61, 11. [33] H. K. Kammler, S. E. Pratsinis, J. Mater. Res. 2003, 18, 2670. [34] J. Karger, D. Freude, Chem. Eng. Technol. 2002, 25, 769. [35] F. Iskandar, I. W. Lenggoro, T. O. Kim, N. Nakao, M. Shimada, K. Okuyama, Chem. Eng. Jpn 2001, 34, 1285. [36] T. R. Sosnowski, L. Gradon, F. Iskandar, K. Okuyama, in Optimization of Aerosol Drug Delivery, (Eds.: L. Gradn, J. Marijnissen), Kluwer Academic Publishers, Dordrecht, 2003, 205.

Experimental
TiO2 Porous Particle Preparation and Characterization: Precursor suspensions were prepared by mixing suspensions of brookite titania nanoparticles (Showa Denko K.K., Tokyo, Japan, diameter size 10 20 nm), and PSL particles (Japan Synthetic Rubber, Tokyo, Japan, with 100, 200, 300, and 410 nm diameters) in aqueous solution with the precursor (nanoparticles and PSL particles) concentration ranging from 0.125 to 2.5 % by mass. Four different mass ratios of brookite nanoparticles to PSL particles were used: 1.0, 0.67, 0.5, and 0.33. Precursor suspensions were sonicated for several minutes to ensure that both nanoparticles and PSL particles were well-dispersed in the suspension. The spraydrying system used was similar to that used in previous studies [2325]. Briefly, the system consisted of an ultrasonic nebulizer (model NE-U12 operated at a frequency of 1.7 MHz, Omron, Kyoto, Japan) for droplet generation, a two-zone laminar flow tubular furnace (a ceramic tube with a 13 mm inner diameter and 1 m length) for droplet drying and PSL evaporation, and an electrostatic precipitator or filter for particle collection. The nebulizer produced droplets with diameters in the 111 lm range with a mean diameter of 4.5 lm [35,36]. Nebulized droplets were carried into the furnace by a flow of 1 L min1 N2 carrier gas. The first zone and second zone of the furnace were set to temperatures of 200 and 500 C respectively. Solvent evaporation occurred within the first zone of the furnace, leaving composites consisting of brookite nanoparticles and PSL particles. PSL particle evaporation occurred within the second zone and gave rise to macroporous particles made of brookite primary nanoparticles. Macroporous particles were collected using either a filter or electrostatic precipitator. Nonporous, dense titania particles were also produced by the same method but without PSL particles incorporated into the precursor suspension. Spray-dried particles were characterized by using SEM (Hitachi S-5000 operating at 20 kV) for size, morphology, and pore-structure determination. The crystallinity of the particles was determined by using XRD (Rigaku Denki RINT 2000, with Cu Ka radiation, with an angular domain between 20 and 80 (2h)). Photocatalytic Characterization: The degradation of rhodamine B (Wako Pure Chemicals Industries, Osaka, Japan) by spray-dried particles was measured to determine the particles photocatalytic capabilities. Aqueous rhodamine B and brookite particles were mixed in a batch reactor and illuminated by two parallel UV light sources with a wavelength of 352 nm (Toshiba FL20S BLB, 20kW). To keep the concentration of dissolved oxygen in the solution constant during experiments, 5 L min1 of air was bubbled into the reactor. Rhodamine B degradation by solid brookite particles, brookite nanoparticles (which were not spray-dried), and macroporous brookite particles prepared using PSL particles 100, 200, 300, and 410 nm in diameter, was measured. In each experiment, the batch reactor contained 3.4 104 g mL1 of titania particles and 1.34 104 g mL1 of rhodamine B. The titania-rhodamine B suspension was allowed to equilibrate for 30 min without any illumination prior to each experiment. Rhodamine B concentrations were measured using a spectrophotometer (Shimadzu UV-VIS-Spectrophotometer, UV-3150). After degradation

1412

www.advmat.de

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2007, 19, 14081412