Chemical Engineering Science 66 (2011) 721728

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Chemical Engineering Science

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Effect of coarsening of sonochemical synthesized anatase on BET surface characteristics

Leonardo Gonzalez-Reyes a,b, Isaias Hernandez-Perez b,d, F.C. Robles Hernandez c,n
a

Instituto de Ciencia y Tecnologa del Distrito Federal, ICyTDF. Republica de Chile 6, Centro 06010, Mexico D.F., Mexico Universidad Autonoma Metropolitana-A, Departamento de Ciencias Basicas, Av. Sn. Pablo no. 180, Mexico 02200 D.F., Mexico c University of Houston, College of Technology, Mechanical Engineering Technology, 304 Technology Building, Houston, TX, 77204-4020, USA d Universidad Autonoma Metropolitana-L, Division de Ciencias Basicas e Ingeniera, Lerma de Villada 52006 Edo. Mex. Mexico
b

a r t i c l e in f o
Article history: Received 3 May 2010 Received in revised form 16 November 2010 Accepted 17 November 2010 Available online 26 November 2010 Keywords: Anatase Coarsening Coalescence Raman Infrared XRD

abstract
In the present paper TiO2 (anatase) nanoparticles were synthesized by ultrasonic means proving the potential of this method. The synthesized anatase is heat treated at a temperature of 500 1C in open air atmosphere to coarse it. The heat treatment times went from 1 to 72 h, the temperature/time conditions were selected to prevent phase transformation and to solely coarsen anatase from 6.2 to 28.3 nm. The synthesized and heat treated anatase were characterized using Electron Microscopy (Transmission and Scanning), X-ray diffraction (XRD), BrunauerEmmettTeller (BET) method, UVvis, Raman and Infrared spectroscopy. In the present paper are proposed two algorithms that are capable of determining the BET surface characteristics or the grain size based on the XRD or BET results, respectively. Published by Elsevier Ltd.

1. Introduction There are three allotropes of titanium dioxide (TiO2) in nature that are mentioned in following along with their respective crystalline structures. Rutile has a P42/mnm symmetry with a tetragonal crystalline structure; anatase is I41/amd and has a body centred tetragonal crystalline structure and brookite is P/cab with an orthorhombic structure. Rutile can be obtained from heat treated anatase under different conditions (Henrich and Cox, 1994; Gouma and Mills, 2001). Anatase is widely used for photo-catalysis, solar energy conversion, protective surface coating, ceramics, pigments, biological, catalysis, as a reductor, for photo-corrosion applications, etc. (Hoffmann et al., 1995; Cai et al., 1992; Diebold, 2003; Gan et al., 1998; Fujishima et al., 2000; Braun, 1997; Al-Salim et al., 2000; Ito et al., 1999). The transformation between anatase and rutile has been extensively studied suggesting that this transformation is highly dependent on the conditions of the synthesis (e.g. temperature, purity of the components, texture, grain size, specic surface area, pore dimensions, etc; Kumar et al., 1992; Reidy et al., 2006; Burns et al., 2004; Shannon, 1964; Gamboa and Pasquevich, 1992). Many efforts have been directed to control the TiO2

Corresponding author. Fax: + 1 505 213 7106. E-mail addresses: quarkkz@yahoo.com.mx (L. Gonzalez-Reyes), ihp@correo.azc.uam.mx (I. Hernandez-Perez), fcrobles@uh.edu (F.C. Robles Hernandez). 0009-2509/$ - see front matter Published by Elsevier Ltd. doi:10.1016/j.ces.2010.11.030

nanostructure; however, several problems still remain unsolved. For instance, annealing signicantly affects microstructure, crystalline structure, phase(s) and the grain size of anatase that might inuence its catalytic and photo-catalytic efciency (Inagaki et al., 2001; Maira et al., 2000; Chan et al., 1999). Unfortunately, these parameters cannot be controlled independently making this a challenging topic. Sonochemical treatment has been reported as a successful methodology to produce nanostructured materials (Kenneth et al., 1999; lez-Reyes et al., 2008; Suslick et al., 1999). The present work Gonza proposes a method assisted by ultrasonic means to synthesize nanostructured anatase. The nanostructured anatase is heat treated at a temperature of 500 1C for different times to investigate the effects of control coarsening and preventing phase transformation to rutile or any other phase(s). The main goal of this work is to investigate the effect of the grain size of anatase on BET particle characteristics as well as other effects (e.g. band gap) and how these changes can be predicted using different characterization methods. In a parallel research lez-Reyes et al., 2010) demonstrated that the band gap of (Gonza anatase is affected by the grain size. This effect is directly related to the quantum characteristics that evolve in grain smaller than 21 nm; such grains have a relatively large number of broken bonds and these effects are minimized as the anatase grains coarsen. Based on the above arguments the coarsening studies of anatase are of great importance and are the main motivation of the present publication. In the present work the anatase powders were characterized by means of: X-ray

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diffraction (XRD), BrunauerEmmettTeller (BET) method, Electron (Transmission and Scanning) Microscopy, UVvis, Infrared and Raman Spectroscopy, the results are provided and discussed in the present paper.

2. Experimental 2.1. Synthesis and materials A mixture of 150 ml of titanium (IV) tetraisopropoxide ([(CH3)2CHO]4Ti) of commercial grade (97 wt% pure), acetone (30 mL) and methanol (30 mL) are subjected to sonochemical treatment. Methanol and acetone are used as pressure-transmitting media. The mix of alcohol, acetone and [(CH3)2CHO]4Ti is added into the ultrasonic bath and the mix is ultrasonically treated at 38 kHz for 50 min. The resultant colloid is dried out on a magnetic mixer-heater set at 150 1C until the powders have a dry appearance. No treatment above 150 1C is conducted to preserve the crystalline structure and the grain size of the synthesized anatase. 2.2. Heat treatment The synthesized anatase was heat treated at 500 1C in a conventional electric resistance furnace in open air atmosphere for times varying from 1 to 72 h. The heat treatment as a main objective closely control the coarsening of anatase, but it does prevent any phase transformation to rutile or any other phase. Anatase obtained from sonochemical synthesis is identied in the present paper as original anatase or original sample. Samples of anatase heat treated at 500 1C are identied for their respective heat treatment time (xh; where x denotes heat treatment time in hours). 2.3. Characterization methods The X-ray diffraction (XRD) was conducted on a Bruker D8 Discover apparatus that operates under y2y conditions. The samples were scanned from 20 to 80, 2y degrees using a Cu Ka radiation with a characteristic wavelength (l) of 0.15405 nm. Lattice parameters (a and c) were determined using the (1 0 1) and (2 0 0) reections, respectively. Scherrer method was used to determine the grain size (Cullity and Stock, 2001) based on the (1 0 1) reection, Scherrer equation follows: D Kl b1=2 Cos y 1

KulbekaMunk method (Zanjanchi et al., 2006). Infrared spectroscopy was carried out on a NicoletMagna 750 FTIR apparatus in the region from 4000 to 400 cm 1 with a scanning of 1 cm 1. The KBr disk method was used to prepare the anatase samples, no mulling was required due to the size of the anatase powders; the ratio KBr:TiO2 was 30:1. The particle characteristics were determined using BET method on a Micrometrics ASAP 2000 nitrogen adsorption apparatus. Prior to the BET analysis, the samples were degassed and aged at 100 1C for 24 h. The adsorption analysis was conducted using nitrogen with relative pressures (P/Po) between 0.5 and 1.0. P indicates the equilibrium pressure among the gas and the solid and Po is the pressure of the gas required for the saturation at the temperature of the experiment.

3. Results Fig. 1(a) shows a SEM micrograph of original anatase particles (as synthesized) and can be observed that the size of the particles go from nanometric to micrometric and have aky appearance. The large surface area exposed by the original anatase particles is clearly shown in Fig. 1(a). Although, the anatase particles are agglomerated they still have a large ratio surface area/particle size that can represent advantages for catalysis and other applications. Fig. 1(a) and (b) shows SEM micrographs anatase particles heat treated at 500 1C for 72 h. In the SEM micrograph it can be observed that the morphology of the anatase particles lose its aky appearance on the agglomerated particles. This is attributed to the coarsening of anatase growing that is in preferential directions resulting in anisotropic, thus polymorphic, growth (Fig. 1b). The anatase particles observed in Fig. 1 are in fact composed of agglomerations of nanometric crystals forming the observed akes (Fig. 2). The nanostructured nature of the above described anatase (original) is clearly observed in the TEM dark elds (Fig. 2(a)). An anatase particle heat treated for 72 h at 500 1C is presented in Fig. 2(b) showing that the grain size increases with heat treatment time. Fig. 2(c) compares the TEM-Selected Area Electron Diffraction Patters (SAEDP) for original anatase and anatase heat treated for 72 h. The comparison of the SAEDP demonstrates that after 72 h of heat treatment at 500 1C anatase do not present phase transformations. The better dened rings in the heat treated anatase (Fig. 2(c)) are the result of coarsening; although, the nanometric nature of the anatase is preserved. Fig. 3 shows the XRD difractograms for the original and heat treated samples from 1 to 72 h. The anatase heat treated for 72 h at 500 1C does not show evidences of phase transformation, which is a major objective in this research work. From Fig. 3 it is observed there is an the increase in intensity of the reections of anatase peaks and the reduction in width as the heat treatment time increases. This is translated in coarsening that results in higher crystal quality (Cullity and Stock, 2001), hence more dened XRD reections. This conrms the TEM-SAEDP results presented in Fig. 2(c). Fig. 4 shows the analysis of lattice volume for anatase as determined from XRD and is compared with their respective band gap as a function of heat treatment time. It can be observed that as the grain size coarsens the lattice volume of anatase is unstable for heat treatment times of less than 8 h corresponding to grain sizes smaller than 17 nm and the changes in band gap are also observed at similar times. The 17 nm is somehow in agreement with the recently published work by (Gonzalez-Reyes et al., 2010) where they report a critical value of 21 nm. The average lattice volume, as determined by XRD, for the original and heat treated anatase is 135.53 nm3 with a standard deviation of 7 0.28 nm (0.21% difference). Such change in lattice volume can be considered negligible

where D is the average diameter of the calculated particles, K is the shape factor of the average grain size (the expected shape factor is 0.9), l is the wavelength characteristic in A (in this particular case l 1.5405 A), b1/2 is the width of the X-ray peak at half its high, based on the XRD tables the (1 0 1) reection for anatase is identied at y E12.651. Transmission Electron Microscopy (TEM) was carried out on a JEOL-2000FXII operated at 200 kV. Using TEM, phases, crystalline structure and grain size were determined. Scanning Electron Microscopy (SEM) was conducted on a Phillips XL-30 operated at 20 kV to determine the morphological changes of anatase for different heat treatment times. Raman spectroscopy was conducted on a Thermo Nicolet apparatus model Almega, equipped with a laser with a wavelength of 532 nm using medium intensity, a 1 cm 1 shift and a resolution of 0.5 cm 1. UVvis was conducted on a Varian Cary I apparatus using the diffuse reectance method for powders in wavelengths between 190900 nm. The band gap was determined with the

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5 m

100 m

Fig. 1. SEM micrographs of original anatase (a) as obtained from the sonochemical synthesis and (b) heat treated for 72 h at 500 1C.

200 m

100 m

Reference

Heat treated for 72 hours

(110) (101) (200) (111) (210) (211) (002) (310) (112)

Fig. 2. TEM micrographs of the (a) as-synthesized anatase, (b) heat treated anatase for 72 h at 500 1C and (c) comparison of the Selected Area Electron Diffraction Patterns (SAEDP) of anatase in the as synthesized and heat treated (72 h at 5001C) conditions. Note: the SAEDP shows no phase transformations even after 72 h of heat treatment.

that is consistent with the volume conservation (Callister, 2007). Perhaps these changes seem insignicant the instability of the volume can be related to residual stresses that evolve as a result of the relative large number of broken bonds along the surface of the anatase grains resulting in a quantum effects.

Fig. 5(a) shows the Raman spectrum of original anatase as obtained by sonochemical synthesis. In Fig. 5(a) are observed Raman bands at 143, 397, 515 and 637 cm 1, the original sample has all the Raman scattering bands observed in anatase previously reported (Toshiaki et al., 1978; Balachandran and Eror, 1982).

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A (101)

500C A (200) A (202) A (103) A (004) A (112) A (204) A (116) A (220) A (215) A (206) A (105) A (211)

72h

Intensity (arb. unit)

48h 24h 16h 8h 4h 2h 1h Original

72h 2 theta (degree)

Fig. 3. Shows the XRD diffractograms for the original and the heat treated anatase particles for various heat treatment times at 500 1C in ambient.

Intensity, (a.u.)

20

30

40

50

60

70

80

48h 24h 16h

136

Lattice Volume of Anatasa, (3)

3.19 3.17 135 3.15 3.13 3.11 134 3.09 Lattice Volume 133 0 10 20 30 40 50 60 70 Time, (h) Band Gap 3.07 3.05 Band Gap, (eV)

8h 4h 2h 1h Original 100 200 300 400 500

-1

600

700

800

Raman Shift, (cm )

Fig. 5. Raman spectrum of the (a) original sample synthesized by sonochemical means and (b) Raman spectra of the heat treated anatase at 500 1C for various times.

Fig. 4. Change in the lattice volume and band gap for anatase as a function of the heat treatment time at 500 1C.

No other band were detected or identied. A well-resolved Raman peak is observed at 143 cm 1 showing the highest intensity of all the bands in the anatase phase. The Raman results further conrm that the only phase present is anatase and the intensity of the peaks increases with heat treatment time. Fig. 5(b) shows the Raman spectra of the original and heat treated samples for different times. All bands show that Raman scattering increases as the anatase grain size coarsen that is consistent with the XRD and TEM results (Figs. 2 and 3). From Fig. 5(b) is evident that the intensity of the Raman scattering increases indicating that the number of atoms (Ti and O) forming molecules of anatase also increases. This is consistent with the coalescence and coarsening that is reected in a surface area reduction. In contrast, the width of the band decreases with heat treatment time indicating the number of bonds forming anatase increases with heat treatment time. Fig. 6 shows selected IR spectroscopy results for the original and heat treated anatase for 16 and 72 h at 500 1C. In the IR results the following anatase bands are observed: 813.7, 1614.2, 1585.9, 2366.4 and 2328.2 cm 1. It is important to notice that the intensity and location of these peaks change with heat treatment time that is attributed to the reduction in surface area and the increase in

crystal quality of the anatase powders. The main band observed at 813.7 cm 1 corresponds to TiO vibration and the TiOTi torsion. The identied bands between 1500 and 3500 cm 1 for the original samples correspond to the organic residue of carboxyl groups (CO) and water (Mayo et al., 2004). Similar bands are observed in the heat treated samples for up to 8 h (Figures not presented herein). The C O residue was previously reported and detected by thermo gravimetric analysis (Gonzalez-Reyes et al., 2008). In the present work neither water nor the CO groups have been reported by any other characterization method but infrared spectroscopy; although, this was previously reported by Mayo et al. (2004). This water is probably absorbed by the sample during its handling and exposure to the environment as previously reported in reference Mayo et al. (2004). In Fig. 6 it is observed that the infrared bands of anatase in the original sample are weak, in fact, the band at 3387 cm 1 from water is more intense. This is attributed to two main reasons: (i) the size and number of pores that allow easy adsorption of water and (ii) ne grain size of original anatase. After 16 h of heat treatment the intensity of the OH symmetric and anti-symmetric stretches (3380 cm 1) is signicantly reduced. The intensity of the scissoring band (1624 cm 1) is almost constant for heat treatment times as long as 16 h and at this point is the only water band identied. This is translated in a densication effect of anatase preventing the excessive adsorption of water and limiting the interaction of water to the surface of anatase. Fig. 7(a) shows the coarsening path of the anatase particles as a function of time. Except for the original anatase the coarsening path occurs in a quasi-exponential fashion similarly to the behaviour

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725

101 Original % Transmittance 99 2355 96 93 90 87 3500 3000 2500 2000 3387

Crystallite Size (nm)

30 25 20 15 10 5 0 10 20 30 40 time (h) 50 60 70

1646

2334

1522

1500
-1

1432

1000

824

500
0 10 20 30 40 50 60 70 5 Pore Diameter (nm) 800 640 480 320 3.75 3.00 2.25 1.50 300 240 180 120 60 0 0 10 20 30 40 50 60 70 5 time (h) 10 15 20 Grain Size, (nm) 25 10 15 20 25

Wavenumbers (cm ) 101 16 h % Transmittance 99 1702 96 93 90 87 3500 3000 2500 1370.47

465

2000

1500

1000

500

Wavenumbers (cm-1) 2342 2329 72h 1614

101 % Transmittance 99 96 93 90 87

Fig. 7. (a) Coarsening path of anatase, BET characteristics of anatase as a function of (b) heat treatment time and (c) grain size.

813

3500

3000

2500

2000
-1

1500

1000

500

Wave length (cm )

Fig. 6. Selected infrared spectroscopy results for original and heat treated anatase for (b) 16 and (c) 72 h.

proposed by the Lifshitz, Slyozov and Wagner (LSW theory) (Hays et al., 2005; Voorhees, 1992; Voorhees and Glicksman, 1984). The results shown in Fig. 7(a) are in agreement with coarsening mechanisms previously reported (Gonzalez-Reyes et al., 2008; Hays et al., 2005; Voorhees, 1992; Voorhees and Glicksman, 1984). In Fig. 7(b) and (c) the comparison of heat, the effect of treatment time and grain size of anatase vs. BET and XRD results are presented. Table 1 shows the regression equations of the curves given in Fig. 7(b) and (c) based on the two approaches (time and grain size, respectively). These regression equations can be used to predict the surface characteristics of the heat treated anatase as a function of time and grain size. All regression equations have R2 larger than 0.93 except for the regression equation of the surface area as a function of time (R2 0.81). The high R2 values indicate good correlation among the BET results with XRD results and heat treatment time. The rst set of graphs in Fig. 7(b) and (c) show that the pore diameter grows with heat treatment time that is the result of coalescence of anatase particles. The second set of graphs in Fig. 7(b) and (c) depict the reduction in pore volume with heat treatment time as well as grain size. This effect indicates a densication effect that is further conrmed with the infrared results. Further, in order to express the phenomena presented in the three graphs shown in Fig. 7(b) a more complex algorithms are

required (compare the equations given in Table 1). The algorithms given in Table 1 for time ignore the original sample; it means, they ignore the coalescence phenomenon. On the contrary the algorithms for the curves presented in Fig. 7(c) are simpler and are a better t between the BET surface characteristics with grain sizes. The third graph in Fig. 7(c) is potentially the most important because it relates the grain size with surface area. The analysis of Fig. 7 demonstrates that using the XRD results it is possible to determine the surface area of anatase particles that is a key parameter to estimate the potential of anatase for numerous applications (e.g. catalytic, photo-catalytic, etc.). Fig. 8 shows the coarsening evolution of the anatase particles. The aky appearance of the original anatase is again observed in Fig. 8(a). It is important to notice that the original anatase is in the form of micrometric and in some cases sub micrometric powders. However, after 1 h of heat treatment an agglomeration effect is observed and is associated with coalescence during the heat treatment. Fig. 8(b)(i) show denser aggregates of nanostructured anatase. The heat treated anatase from 1 to 16 h (Fig. 8cf) does not show notorious differences. After this time the densication becomes more apparent and at 72 h of heat treatment (Fig. 8(i)) the preferential growth of anatase particles is evident. Such preferential growth is also identied by XRD, Raman and Infrared and is associated to the preferential growth of the planes (1 1 1) and (1 1 2) and the 143 cm 1 Raman band.

4. Discussions of the results In the present work the heat treatment allowed the coarsening of anatase from 6.2 nm (original anatase) to a size of 28.3 nm (heat treated for 72 h). The grain sizes of anatase particles previously

Surface Area Total Pore (m2g-1) Volume, (m3)

1636

963

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Table 1 Summary of the regression equations obtained of the BET and XRD characteristics of heat treated anatase in function of heat treatment time and grain size. Particle characteristic (nm) Pore volume 10 6 (m3 g 1) Surface area (m2 g 1) Pore diameter (nm) Grain Size as a function of the heat treatment time (h) Time (h) Pore volume 3563:6t7:38 R2 0.98 Surface area 1:19t 123:3 R2 0.81 Pore_diam: 0:455t308:47 R2 0.97 Crystallite size 13t0:208 R2 0.97 Grain size of anatase Pore volume 9:3Size 39:4 R2 0.95 Surface area 783:6Size0:85 R2 0.99 Pore_diam: 0:86Size2 38:9Size 501:2 R2 0.98

10 mm

10 m

10 m

10 m

10 m

10 m 10 m

10 m

10 m

Fig. 8. Scanning Electron Micrographs of (a) original and (bi) heat treated anatase for 1, 2, 4, 8, 16, 24, 48, 72 h, respectively.

reported in the literature are between 11.3 and 35 nm that are comparable, in size, to the anatase studied in this research (Ding et al., 1996; Reddy et al., 2003; Gribb and Baneld, 1997; Zhu et al., 2005). Current ndings at University of Houston show that commercial anatase, with reported purity of 4 99%, can have

up to 4% of rutile. Hence, anatase produce by sonochemical means do not show any presence of rutile by any of the characterization methods used in the present research work. In the present work was determined that using the Spurr-Myers was not possible to detect any rutile in the as synthesized or heat treated anatase for up

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to 72 h at 500 1C. This is further conrmed by Raman. IR, on the other hand, shows the presence of water and traces of organic residue in the as synthesized anatase. The water is usually removed during the heat treatment. And the organic residue can be removed by further washing with deionised water. Equations presented in Table 1 can be used for anatase particles with grain sizes of up to 28.3 nm covering most of the spectrum of anatase produced by different methods (Ding et al., 1996; Reddy et al., 2003; Gribb and Baneld, 1997; Zhu et al., 2005; Li et al., 2004; Baneld et al., 1993). Based on the high correlation of the coarsening behaviour presented by anatase as a function of grain size; it is possible to extrapolated these results to larger sizes (35 nm) to cover the entire sizes where pure anatase coexist. However, this practice may not always guarantee the high accuracy reported in the results presented in Table 1. The constants used in the equations presented in Table 1 may vary for anatase produced by other methods. However, once the constants are determined the equations can be used as an alternative to predict BET results based on XRD results, or vice versa, with good accuracy. The coarsening of anatase particles follows an anisotropic growth promoting the formation of polymorphic particles at long heat treatment times. The coarsening of anatase particles is conrmed by the better dened rings observed on the TEM-SAEDP that is observed in the dark elds. This coarsening can certainly be associated to an increase in crystal quality, but unfortunately, reduces the surface area of the anatase particles as seen in the BET results. The coarsening of anatase can be detailed studied by means of XRD and directly correlated to BET surface characteristics. Similar approach is possible using the heat treatment time; however, the heat treatment time approach is limited to heat treated anatase ignoring the coalescense of anatase. The use of grain size as an independent variable to determine BET characteristics of anatase is better than the use of heat treatment time, and most importantly this process considers the phenomena of coalescence. Coalescence is time independent and can be observed in Fig. 7 and further demonstrated in Fig. 8. The algorithm proposed in this work can represent technological advantages that can be translated in time savings, allowing an easy prediction of BET characteristics using XRD results and vice versa. It is expected that with the work recently published by (Gonzalez-Reyes et al., 2010) this work can be used to further determine other characteristics such as band gap and in the near future, catalytic, electro-catalytic and photo-catalytic activities of anatase. In the literature reported different phase transformation temperatures and heat treatment times at which anatase transforms to rutile have been reported. But in general, these temperatures are similar to the temperature used in the present work (500 1C) (Reddy et al., 2003; Gribb and Baneld, 1997; Zhu et al., 2005; Li et al., 2004). In addition to that, some reports indicate that anatase can reach grain sizes of 60 nm or more, but in all of those cases this anatase is reported as mix with rutile (Li et al., 2004). The XRD results indicate that the change in lattice volume occur only in samples heat treated for less than 8 h (Fig. 4). After the 8 h of heat treatment the lattice volume is almost constant and is attributed to a higher crystal quality (less broken bonds at the surface of the anatase grains) that is attributed to coalescence and coarsening of anatase. During coalescence and coarsening of anatase some of the atoms with broken bonds, at the grain boundary, re-combine with the atoms of neighbouring grains forming complete bonds and thus larger crystallographic planes. This phenomenon is observed in the XRD, Raman and TEM results presented herein. The effect of coarsening relaxes or lowers the stress and strain levels in anatase lattices reducing the number of broken TiO bonds in the anatase that results in stable band-gaps. This implies that

band gap has a relation with the ratio among surface and bulk atoms and when this ratio is relatively large quantum changes occur. As the number of broken bonds reduces the band gap becomes more stable. Similar effects were reported previously in the literature for Co-doped SnO2 (Hays et al., 2005). Due to the potential to change the band gap of anatase it is of interest to explore different dopants for a wide variety of applications (Janisch and Spalding, 2006; Tang et al., 1993). Modifying the anatases band gap through doping and grain size can result in technological advances increasing its the semi-conductor, catalytic and other properties. The infrared results show that the intensity of the anatase band (813.7 cm1) increases with heat treatment time. Such band has been previously associated with a texturing effect and preferential growth of thin lms along the (1 1 2) plane promoting grain growth along the {1 0 1} planes (Ocama et al., 2006). The coarsening mechanism is responsible for increasing the number of atoms (Ti and O) forming anatase that results in an enlargement of the planes that are capable to obey Braggs law. This is observed by the increase in the XRD intensity and the reduction in the width of the reections. Similar effects are observed in Raman and TEM due to the increase in the number of atoms forming anatase molecules and grains, respectively. The infrared bands observed at approximately 3350, 2100 and 1650 cm1 correspond to water that is absorbed during sample handling. The analysis of water using the infrared results is of great importance in this work because the intensity of the water bands decrease with heat treatment time (Fig. 8). The reduction in the water content results in higher density and can be observed in the SEM micrographs shown in Fig. 8. This effect has also inuence in other BET surface characteristics, such as pore volume and surface area as observed in Fig. 7(b) and (c).

5. Conclusions The characterization methods used herein are complementary and allow a throughout analysis of anatase synthesized by sonochemistry. Demonstrating that anatase produced by sonochemistry is nanostructured with untraceable amounts of rutile or any other substance as indicated by XRD and Raman. Heat treatments at 500 1C allow the coarsening of anatase from 6.2 to 28 nm and hinder phase transformations. A correlation among bang-gap and lattice volume is proposed; however, it is likely that the actual mechanism affecting the band gap is the result of residual stresses that evolve by broken bonds (TiO) at anatases grain surface. There is a good agreement among BET surface characteristics results and XRD that permits proposing a new algorithm to predict BET results based on XRD and vice versa.

Acknowledgements LGR and IHP would like to thank CONACyT-Mexico, SEPI-IPN, and the Instituto de Ciencia y Tecnologa del Distrito Federal, Mexico (ICyTDF) Grant no. BI09-491 (LGR, IHP) for nancial support. FCRH wishes to express his appreciation to the University of Houston and the Government of Texas, for their support through the Start Up, HEAFS and small grant programs. References
Al-Salim, N.I., et al., 2000. Characterisation and activity of solgel-prepared TiO2 photocatalysts modied with Ca, Sr or Ba ion additives. J. Mater. Chem. 10, 23582363. Balachandran, U., Eror, N.G., 1982. Raman spectra of titanium dioxide. J. Sol. State Chem. 42, 276282.

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