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Applied Catalysis B: Environmental 58 (2005) 193202

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Photoactivity of anataserutile TiO2 nanocrystalline mixtures obtained


by heat treatment of homogeneously precipitated anatase
Snejana Bakardjievaa,*, Jan Subrta, Vaclav Stengla, Maria Jesus Dianezb,
Maria Jesus Sayaguesb
a
Institute of Inorganic Chemistry ASCR, 25068 Rez near Prague, Czech Republic
b
Institute of Materials Sciences, C.S.I.C., Seville University, c-Americo Vespucio s/a,
Isla de La Cartuja 41092 Seville, Spain
Received 17 September 2003; received in revised form 17 March 2004; accepted 20 June 2004
Available online 15 January 2005

Abstract

Nanosized titanium dioxide photocatalysts with varying amount of anatase and rutile phases have been synthesized. Homogeneous
precipitation of aqueous solutions containing TiOSO4 with urea was used to prepare porous spherical clusters of anatase TiO2. Photoactive
titania powders with variable amount of anatase and rutile phases were prepared by heating of pure anatase in the temperatutre range 800
1150 8C. The structure evolution during heating of the starting anatase powders was studied by XRD analysis in overall temperature range of
phase transformation. The morphology and microstucture characteristics were also obtained by HRTEM, BET and BJH. The spherical particle
morphology of TiO2 mixtures determined by SEM was stable in air up to 900 8C. The photocatalytic activity of the sample titania TIT85/825
heated to 825 8C in air, contained 77.4% anatase and 22.6% rutile was higher than that nanocrystalline anatase powder. Titania sample TIT85/
825 reveals the highest catalytic activity during the photocatalyzed degradation of 4-chlorophenol in aqueous suspension.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Microstructure; Anatase; Rutile; Nanocrystals; Photoactivity; Photodegradation; Kinetics

1. Introduction and rutile phases, particle size distribution, specific surface


area and mean pore size [4,5].
Homogeneous photocatalysis using semiconducting The most commonly studied TiO2 photocatalyst Degussa
oxide catalysts has recently emerged as an efficient method P25 standard material is a three-phase mixture of the
for purifying water and air. The photocatalytic oxidation of amorphous, anatase and rutile forms of TiO2 arranged in a
organic compounds in aqueous solution containing a complex microstructure, anatase constitutes the greatest
suspension of titanium dioxide is still thoroughly studied volume fraction of approximately 80% of this mixture [6].
method for the removal of impurities [1]. Attention was Porter et al. [7] reported the microstucture characteristics
focused on the adsorption phenomena occurring on TiO2 of original and calcinated Degussa P-25 TiO2 powder
aqueous solution interfaces. The literature contains only a and correlated the photoactivity of the catalysts with the
few references on the effect of the size of suspended surface area, porosity, crystal composition, and variation of
photocatalyst particles on photocatalytic reactions [2]. crystallite size and crystallinity. Recently, Chan et al. [8]
Various models have been used to show that the photo- studied effects of calcination on the microstructures and
activity of TiO2 depends on quite number of parameters photocatalytic properties of nanosized titanium dioxide
including the crystal structure [3], the ratio between anatase powders prepared by vapour hydrolysis. Authors suggested,
that the role of both anatase and rutile crystallinity needs to
* Corresponding author. Tel.: +420 2 6617 3534; fax: +420 2 2094 0157. be investigated and correlated with photoactivity. For the fist
E-mail address: snejana@iic.cas.cz (S. Bakardjieva). time Basca and Kiwi [4] reported the most efficient titania

0926-3373/$ see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2004.06.019
194 S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202

catalyst containing 70% anatase and 30% rutile, which The aim of our research was to obtain nanosized TiO2
showed a higher catalytic activity during the degradation of products with variable anataserutile ratio and appropriate
p-coumaric acid than Degussa P-25. Hydrolysis of tetra- microstrucrure characteristics and morphology, allowing its
isopropyl-orthotitanate followed by densification under application as photocatalysts in aqueous solution. Based on
hydrothermal conditions (15004000 kPa) was used as the work in our laboratory, we succeeded in preparing pure
method of preparation. Yung-Fang Chen et al. reported the anatase TiO2 using hydrolysis of TiOSO4 with urea as the
preparation of TiO2 nanopowders using titanium tetraiso- precipitation agent [14]. Titanium dioxide powders with
propoxide in varied pH aqueous solutions with cationic and varying amount of anatase and rutile phases were obtained
non-ionic surfactants. TiO2 particles precipitated were dried by carefully controlling the treatment temperature of the
at 100 8C in a vacuum system and finally calcined at anatase powder. The relationship between the photocatalytic
temperature range 250900 8C in N2 atmosphere. The activity of suspended anataserutile nanocrystalline TiO2
authors paid attention on the effect of calcinations mixture and its physical properties will be discussed, due to
temperature on the crystallinity of TiO2 powders without obtain a reasonable microstructureactivity correlation. The
relation to photoactivity [9]. Ha et al. prepared titanium attention has been paid not only to crystal structures, but also
dioxide powders by controlled precipitation at room to BET surface area, particle size, porosity and the effect of
temperature from titanium chloride and NH4OH at pH the individual anatase and rutile nanocrystallites on the
10.3. The authors studied the effect of alcohol washing on photoactivity. The commercially available form of TiO2,
the anataserutile transition behaviour of TiO2 precipitates Degussa P-25 was used as standard. Kinetics of disap-
[10]. Photocatalytic oxidation of naphthalene in a mixed pearance of 4-chlorophenol in aqueous suspension was used
solution of acetonitrile and water using various kinds of as a test reaction.
industrial titanium dioxide powders having anatase and
rutile structure were tested as photocatalysts by Ohno et al.
[11]. Studies on TiO2 thin films prepared by solgel method 2. Experimental
and calcinated for 1 h in air from 300 to 1100 8C have been
reported from Kim et al. The effect of calcinations 2.1. Preparation of TiO2 samples
temperature on their optical properties were examined [12].
Current attention has focussed on the preparation of The starting nanocrystalline anatase TiO2 (sample
nanocrystalline semiconductors, in particular TiO2, under denoted as TIT 85) was prepared by hydrolysis of TiOSO4
milder conditions. Recently, Hurum et al. published aqueous solutions using urea as the precipitation agent:
explanation of high photocatalytic activity of anatase rutile TiOSO4 (30 g) was dissolved in 100 mL hot water acidified
mixtures represented by the Degussa P-25 TiO2 [13]. The with 98% H2SO4. The pellucid liquid was diluted into 4 L of
authors concluded that within mixed-phase titania there is a distilled water and mixed with 200 g of urea. The mixture
morphology of nanoclusters containing atypically small was heated to 100 8C under stirring and kept at this
rutile crystallites interwoven with anatase crystallites. The temperature for 6 h until pH 7 was reached and ammonia
transition points between these two phases allow for rapid escaped from the solution. The precipitates formed have
electron transfer from rutile to anatase. Thus, according to been washed by distilled water with decantation, filtered off
the authors, rutile acts as an antenna to extend the and dried at laboratory temperature.
photoactivity into visible wavelengths and the structural In order to see a phase transition temperature the pure
arrangement of the similarly sized TiO2 crystallites creates anatase TiO2 (TIT 85) was heated in wide temperature
catalytic hot spots at the rutileanatase interface. interval from 200 to 1150 8C. Nine new samples denoted as
Table 1
Microstructural characteristic and rate constants of anataserutile mixtures
Sample Calcination Anatase Rutile Anatase by Rutile BET Total pore Rate
temperature crystallite crystallite XRD (%) by XRD surface volume constant,
(8C) size (nm) size (nm) (%) area (m2 g1) (cm3 g1) k (min1)
TIT 85 0 3.5 100 0 279a 0.1991 0.0145
TIT 85/200 200 3.9 100 0 279.3 0.1991 0.0043
TIT 85/400 400 6.2 100 0 137.81 0.1570 0.0037
TIT 85/600 600 20.2 99.6 0.4 67.57 0.0253 0.0045
TIT 85/800 800 52.6 99.5 91.1 8.9 37.28 0.0270 0.016
TIT 85/825 825 59.8 59.8 77.4 22.6 32.22 0.0260 0.0195
TIT 85/850 850 70.7 70.7 47.1 52.9 13.04 0.0200 0.0151
TIT 85/875 875 70.1 108.1 26.7 73.3 11.96 0.0190 0.0065
TIT 85/900 900 69.4 100.3 8.5 91.5 7.16 0.0170 0.0061
TIT 85/1150 1150 111.4 0 100 3.11 0.0150 0.0057
Degussa P25 20.8 30.5 83 17 51.46 0.1700 0.0203
a
Before measurement surface area and porosity, the sample was heated by 30 min at temperature 120 8C.
S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202 195

TIT 85/200, 85/400, 85/600, 85/800, 85/825, 85/850, 85/ desorption isotherm using the cylindrical pore model
875, 85/890 and 85/1150 were obtained (see Table 1). The (BJH). The samples was outgassed 30 min at temperature
calcination was carried out in a laboratory muffle furnace at 120 8C.
a rate of 10 8C min1. Heating the anatase powder was
continued for 3 h at each temperature. 2.3. Photocatalytic degradation 4-chlorophenol

2.2. Physical characterization of the materials Kinetics of decay of 0.1377 mM solution of 4-chlor-
ophenol (4-CP) in 60 mL of aerated aqueous suspension of
The XRD patterns were obtained using the Siemens mixtures with varying amount of anataserutile photo-
D5005 powder diffractometer operating in the reflection catalysts (1 g L1) were monitored. 4-chlorophenol (99%)
mode with Cu Ka radiation (40 kV, 45 mA) and diffracted was purchased from Fluka and used without further
beam monochromator, using a step scan mode with the step purification. The laboratory irradiation experiments were
of 0.02o 2Q and 2.4 s per step. Diffraction patterns of both performed in a self-constructed photoreactor (see Fig. 1). It
anatase and rutile powders were compared with reference to consists of two coaxial quartz tubes placed in the middle of a
PDF-2 database. The Scherrer equation was applied to steel cylinder with an aluminum foil covering its inner wall.
estimate a crystallite size. Inner quartz tube (diameter 24 mm, length 300 mm) was
Transmission electron micrographs were obtained using a filled with the investigated suspension (70 mL) and
JEOL 2000 FX microscope operating at accelerating voltage magnetically stirred. Cooling water was circulating between
of 200 kV. The samples for electron microscopy were the inner and the outer quartz tube to keep constant
prepared by grinding and subsequent dispersing the powder temperature of 20 8C. The used source of UV irradiation was
in propanol and applying a drop of very dilute suspension on a high-pressure mercury lamp enclosed in a glass filter bulb
carbon-coated grids. The suspensions were dried by slow (HPW, 125 W, Philips) whose emission consists to 93% of
evaporation at ambient temperature. 365 nm radiation. It was placed close to the quartz tubes. By
The SEM micrographs were obtained using Philips XL means of the ferrioxalate actinometry, an average light
30 CP equipped with EDX, SE, BSE and Robinson intensity entering the volume of 5070 mL of the irradiated
detectors. The powder samples were studied in native form solution was determined as I0 = 5.3  105 Einstein
without coating by conductive metal layers. dm3 s1.
BET surface areas of TiO2 powders were determined by The TiO2 mixtures were sonicated for 20 min with a
means of Coulter SA 3100 instrument using nitrogen sonicator (230 W, 30 kHz) before use. The pH of the resulting
adsorption at 196 8C. The pore size distributions (pore suspension was taken as the initial value for neutral conditions
diameter and pore volume) were measured from the N2 and under the experiment was kept at 7.00. pH was measured

Fig. 1. Diagram of photoreactor.


196 S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202

using an Alpha 500 pH meter equipped with a glass pH 3. Results and discussion
electrode. Probes of irradiated suspensions (1 mL) were taken
at appropriate irradiation times. The solid photocatalyst 3.1. X-ray diffraction
(necessarily together with the adsorbed portions of the
dissolved molecular species) was removed before HPLC, The crystal structure of TiO2 depends on the temperature
employing filtration by a Millipore syringe adapter (diameter of heat treatment. Polycrystalline anatase-type TiO2 could
13 mm) with filter 408 (porosity 0.45 mm). be obtained by heating up to 600 8C, in which temperature
The HPLC experiments were run on a Merck device with only 0.4% rutile-type TiO2 was registered (see Table 1).
L-6200 Intelligent Pump, L-3000 Photo Diode Array Our attention was focused on the inspection of the
Detector and D-2500 Chromato-Integrator. Mobile phase temperature interval from 800 to 1150 8C, where the
methanol/water (2:3, v/v) and a Merck column LiChro- anatase intensive transforms to the stable rutile form. The
CART 125-4 filled with LiChrosphere 100 RP-18 (5 mm) characteristic parts of XRD patterns of anatase TiO2
were used, injection loop was 20 mL, flow rate 1 mL min1 (sample TIT 85) and the solid post-products of its thermal
and detection wavelength 280 nm were applied. treatment at 800, 825, 850, 875, 900 and 1150 8C are shown
The kinetic analysis was understood in terms of in Fig. 2. Powder X-ray diffraction (XRD) was used for
modified (for solidliquid reactions) LangmuirHinshe- crystal phase identification and the estimation of the
wood kinetic treatment [1518]. This mechanism results in anataserutile ratio and the crystallite size of each phase
pseudo-first-order kinetics at the photostationary state present. The anatase (1 0 1) peak at 2Q = 25.48 and the
[16]. The order reaction constant for photodegradation of rutile (1 1 0) peak at 2Q = 27.58 were analyzed using the
4-chlorophenol in water suspension for several half-lives formula [19]:
was calculated.  
IA 1
x 1 0:8
2.3.1. Irradiation experiment IR
Seventy milligrams of the investigated photocatalyst where x is the weight fraction of rutile in the powders, and IA
sample were quantitatively transferred, using 63 mL of and IR are the X-ray intensities of the anatase and rutile
distilled water, into the inner tube of the photoreactor and peaks, respectively (see Table 1).
kept in dark for about one hour. Then, 7 mL of 0.001 M XRD pattern of sample TIT 85 is shown on Fig. 2. XRD
stock solution of 4-chlorophenol (4-CP) were added that of the initial sample (trace a) indicated that the sample was
completed the total volume up to 70 mL. It was performed in polycrystalline anatase TiO2. This is the raw, uncalcined
a dark room. The prepared suspension was then magneti- precipitate (sample TIT 85) recovered at the end of 6 h of
cally stirred for about one hour in dark to achieve the precipitation from mother liquor containing TiOSO4 and
adsorption equilibrium. After then, 1 mL was taken as a urea. The positions of all diffraction peaks and distribution
blank probe before irradiation and, after filtration of the of intensites correspond to ICDD PDF card 21-1272 [20].
catalyst, injected for the HPLC analysis. After that, the inner The XRD pattern of the powder heated at 800 8C reveals
tube was put into the photoreactor and irradiation started. At the anatase (1 0 1) and emerging peak of rutile (1 1 0),
appropriate irradiation times, 1 mL probes of the irradiated indicating that the sample TIT 85/800 (trace b) is a mixture
suspension were taken and analyzed by HPLC in the same of anatase and rutile. Calcination at 825 8C (trace c) for 3 h
way as the blank probe. To complete a set of HPLC resulted in change in the intensity of both peaks (sample
measurements for one particular photocatalyst sample, TIT85/825).
0.0001 M 4-CP solution in water was analyzed under the The intensity of the rutile peak significantly increased
same conditions. From this reading we can estimate the while that of anatase peak decreased. Sample TIT85/825
amount of 4-CP initially adsorbed on TiO2 particles, which contains 77.4% of anatase and 22.6% of rutile and the
was removed together with the powder in the filtration mixture looks like the standard product Degussa P-25. At
process. After finishing the HPLC set for the particular 850 8C, the sample contains 52.9% of rutile (sample TIT85/
photocatalyst sample, the integrated areas or heights of the 875, trace d). On increasing the temperature up to 900 8C,
peaks were plotted as a function of the irradiation time. In the amount of anatase decreases and powders produced at
some cases, additional manual corrections of the auto- 875 8C (sample TIT 85/875, trace e) and 900 8C (sample TIT
matically integrated areas were performed. A Microcal 85/900, trace f) are predominantly rutile (see Table 1). For
software Origin was used for this purpose. In the sample TIT 85/1150, calcinated at 1150 8C for 3 h (trace g),
corresponding kinetic plot, the automatically integrated the anatase peak disappeared and rutile as a major phase is
areas are shown as separated experimental points, the observed (ICDD PDF card 21-1276) [20]. The rutile exhibits
manually corrected values are represented as a time profile. sharp XRD lines (Fig. 2, trace g) without signs of
Kinetic curves of the first order, which were fitted to all broadening. The difference in the crystal structure in our
experimental points, are also plotted. For comparison, the titania powders with different anatase/rutile ratio is due to a
corresponding kinetic curve of the standard photocatalyst thermal treatment at varying temperature of the anatase
TiO2 P25 (Degussa) is included. precipitate and spontaneous transformation from anatase to
S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202 197

Fig. 2. X-ray diffraction patterns of annealed anatase TIT 85. (a) Starting sample; (b) sample heated for 2 h at 800 8C; (c) sample heated for 2 h at 825 8C; (d)
sample heated for 2 h at 850 8C; (e) sample heated for 2 h at 875 8C; (f) sample heated for 2 h at 900 8C; and (g) sample heated for 2 h at 1150 8C.

rutile. This transformation is an irreversible metastable-to- hand, in case of rutile significant increase in crystallite
stable phase transition in temperature range 6501200 8C size was observed.
[5,21]. We obtained the results similar to other studies [8]
The average size of crystallites was calculated from the concerning the effect of crystallite size of both anatase and
peak half-width B, using the Sherrer equation [22], rutile phases on the photoactivity. These models suggest
kl that rutile can grow to a size much larger than anatase due
t to sintering and growth of nanophase titania [24]. In our
B cos Q
cases, as the calcination temperature increases from 800 to
where k is a shape factor of the particle (it is 1 if the 1150 8C, the crystallite size of rutile grow progressively,
spherical shape is assumed), l and Q are the wavelength while the crystallite size of anatase established maximum at
and the incident angle of the X-rays, respectively. The peak 850 8C and after this temperature small decrease was
width was measured at half of the maximum intensity. The registered. This is in accordance with the published data
estimation shows that the mean crystal size of the initial showing that bigger anatase microcrystals transform to
anatase TiO2 individual particles (sample TIT/85) was 4 rutile easier than the smaller ones. This fact results in
5 nm, supposing that the broadening of peak is due to the relative depletion of the mixture by anatase during the
size effect. Phase transformation anatase to rutile and anatserutile phase transformation [25]. Based on the
calcination is usually accompanied with crystal growth results obtained by HRTEM, the starting anatase powder
[23]. The crystallite size of each phase present in the (TIT 85) consists of anatase nanocrystalls with some
anatase/rutile mixtures (samples TIT 85/800, 825, 850, amorphous domains located between them (Fig. 3A and B).
875, 890, 900 and 1150) are presented in Table 1. From This fact seems to be a main reason for smaller growth of
the data obtained we can see that a small increase in the anatase nanocrystallites (see Table 1) during heating at
anatase crystallite size was observed after calcination at lower temperatures. The competition reactions [8] between
overall temperature interval 8001150 8C. On the other the growth of existing anatase nanocrystallites and the
198 S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202

Fig. 3. TEM micrographs of annealed anatase TIT 85.

formation of a number new, small anatase nuclei by The SEM image of the initial TIT 85 anatase sample
crystallization of the amorphous fractions are the main (Fig. 4A) reveals that the titania powder consists of 12 mm
reasons for slighter growth of anatase crystallites size spherical particles. Based on the HRTEM results (see
during heating. Fig. 4A and B), these spherical particles consist of primary
45 nm anatase nanocrystals interlayed by small fraction of
3.2. Particle morphology amorphous material. During the annealing temperature
increase, the size and shape of these spherical particles
As it has been shown earlier [26], the urea precipitation remain unchanged almost up to 1000 8C (See Fig. 4BG).
method leads (at the reaction conditions used) to colloid Structural alterations in the material (growth of anatase
anatase nanoparticles assembled into rather big (12 mm) nanocrystals, anatase to rutile transformation, growth of
porous spherical clusters (see Fig. 4, sample TIT 85). rutile nanocrystals, changes of porosity) take place inside
Recently [21], we reported high photocatalytical activity in of these spherical particles. Significant sintering between
4-chlorophenol decomposition reaction, comparable to P-25 these spherical particles was observed only on the speci-
TiO2 activity. Fig. 4 shows also the SEM micrographs of the mens TIT 85/1000 and more distinctly at the TIT 85/1150
TIT 85 sample annealed for 3 h at constant temperatures in (Fig. 4G), heated for 3 h at 1000 and 1150 8C (Fig. 4H),
range 2001150 8C. respectively.
S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202 199

Fig. 4. SEM micrographs of annealed anatase TIT 85. (A) Starting sample; (B) sample heated for 3 h at 200 8C; (C) sample heated for 3 h at 400 8C; (D) sample
heated for 3 h at 600 8C; (E) sample heated for 3 h at 800 8C; (F) sample heated for 3 h at 900 8C; (G) sample heated for 3 h at 1000 8C; and (H) sample heated
for 3 h at 1150 8C.
200 S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202

Fig. 5. Porosity of annealed anatase TIT 85. (A) Starting sample; (B) sample heated for 3 h at 825 8C; (C) sample heated for 3 h at 850 8C; (D) sample heated for
3 h at 875 8C; (E) sample heated for 3 h at 900 8C; and (F) sample heated for 3 h at 1150 8C.

3.3. The BET surface area, pore size and pore volume micropores are present inside the spherical clusters of
anatase nanocrystals (Table 2).
The BET surface area of the initial anatase titania TIT 85 The thermal treatment of these particles leads to changes
has been determined to 279 m2 g1 (see Table 1). Pore size of BET surface area, pore volume and pore size distribution.
distribution measurement showed that this total surface area During the thermal treatment over 800 8C rutile content
is attributed mainly to micropores with mean pore radius increases and introduces pores of larger radii (compared to
under 3 nm (see pore size distribution on Fig. 5A). As starting anatase precipitate). The pore radius distribution
reveals the HRTEM micrograph (Fig. 3A and B), the becomes expanded as observed for the mixtures with 22.6%
S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202 201

Table 2 rutile is single phase (sample TIT 85/1150), surface area


Specific surface area and total pore volume of anataserutile mixtures collapses and macroposity distribution are observed (see
Sample Calcination BET surface Total pore Fig. 5F). Phase transformation anatase to rutile is completed
temperature area volume
at this temperature (see Table 1).
(8C) (m2 g1) (cm3 g1)
TIT 85 0 279.00 0.1991
3.4. Photocatalytic activity of anatase, rutile and
TIT 85/800 800 37.28 0.0270
TIT 85/825 825 32.22 0.0260 anataserutile nanocrystalline mixtures in
TIT 85/850 850 13.04 0.0200 photodegradation of 4-chlorophenol
TIT 85/875 875 11.96 0.0190
TIT 85/900 900 7.160 0.0170 The course of 4-chlorophenol photocatalyzed decom-
TIT 85/1150 1150 3.11 0.0150
position using TIT 85 TiO2 samples annealed at various
Degussa P25 51.46 0.1700
temperatures is given on Fig. 6. The photocatalytic activity
of the studied samples was expressed by pseudo-first-order
(sample TIT 85/825), 52.9% (sample TIT 85/850) and rate constant, the results are given in Table 1. Degussa P-25
73.3% rutile (sample TIT 85/875). The value of BET surface was used as the reference material. We have found that the
area of sample TIT 85/825 is only 32.22 m2 g1 but pore sample TIT 85/825 exhibited the best photocatalytic
radius distribution is still in microporous dimension range efficiency on the degradation of 4-CP of the all tested
(see Fig. 5B). There is increase in crystallite size of each TiO2 samples. It is evident that the photoactivity of this
phase presented in the mixture compared to the starting sample, as well as of the initial anatase-type TiO2 (TIT 85) is
uncalcined anatase sample TIT85 and new pores could be comparable to the standard photocatalyst Degussa P-25.
formed between anatase and rutile particles. Pore volume of After annealing at temperatures below 800 8C the activity
the sample TIT 85/825 is 0.026 m3 g1 (see Table 1). Such a decreased significantly. Even the sample annealed at 200 8C
low porosity means that the surface area is largely external to for 2 h exhibited almost four times lower activity in
the agglomerates and pore volume measured is mainly comparison with the fresh prepared precipitate (however, the
located between agglomerates (interagglomerate pores) [8]. value of surface area and porosity given in the Table 1 was
The pore radius distribution was very wide after treated to measured for sample heated for 120 8C, whereas the activity
higher temperature (850875 8C). The mesopores are as well as the anatse crystallite size was measured without
prevailing in the TIT 85/850 anataserutile mixtures (see this thermal pre-treatment). However, at further increase the
Fig. 5C). Upon subsequent rise of the annealing temperature annealing temperature the mixtures of anatase and rutile
the micro and mesopores and total BET surface area reduced (TIT 85/850) calcined at 850 8C exhibit again very high
drastically as result of calcination and agglomeration activity in photodegradation of 4-CP. It is generally believed
because anataserutile transformation is associated with that mineralization of a number of organic pollutants can be
crystallization and leads to change of microstrucrure achieved at ambient temperature and pressure, using the
characteristics. In powder produced at 875 and 900 8C pure anatase TiO2 activated by UV irradiation [27]. On the
(see Fig. 5D and E), where rutile is the major phase (sample other hand our results suggest that a mixture of anatase and
TIT 85/900 containing 91.5% rutile) and powder where rutile could be good perspective for improving the
photoactivity for some organic pollutants. It is worth
mentioning that the mixture (TIT 85/850) calcined at 850 8C
also exhibits a high activity of photodegradation of 4-CP,
despite of its considerable rutile content (52.9%). A high
photoactivity of TiO2 powder, synthesized at 900 8C and
43% rutile content has been presented also by Chan et al. [8].
No reports are available on the effect of the size of
suspended photocatalyst particles on photocatalytic reac-
tion. In our experiment we observed an interesting result
the size of anatase and rutile crystallites obtained at 825 and
850 8C are almost equal: 59.8 and 70.7 nm, respectively (see
Table 1). These results assumed that not only the rutile
content, but the effect of particle size of both anatase and
rutile particles in TiO2 mixture photocatalysts on photo-
degradition reactions can be taken into account. Probable,
well crystallized small TiO2 particles with different crystal
structures and an average grain size of less than 100 nm have
Fig. 6. Photocatalytically decomposition of 4-CP on annealed anatase (TIT generated considerable interest because of the improve-
85), mixture anataserutile (TIT85/825, TIT85/850), pure rutile (TIT85/ ments in a variety of properties that are expected to result
1150) and Degussa P25. from grain-size reduction to the nanometer scale.
202 S. Bakardjieva et al. / Applied Catalysis B: Environmental 58 (2005) 193202

The behaviour of photocatalytic reactions of samples TIT Acknowledgments


85, TIT 85/825 and TIT 85/850 are discussed in terms of
modified forms of LangmuirHinshelwood kinetic treat- This work was supported by the grant no. 203/01/0983
ment, which has been used successfully as a model to provided by the Grant Agency of the Czech Republic and by
describe solidliquid reactions [1518]. The obtained the Ministry of Education of the Czech Republic, project no.
reaction rate constants are listed in Table 1. In each case, LN00A028. The authors gratefully acknowledge to Dr. J.
the reaction approximately followed the first order kinetics. Jirkovsky from Physical Institute ASCR for the loan of the
With further increase of the annealing temperature above photochemical reactor and help in interpretation of kinetics
850 8C, the photocatalytic activity of the products again data, to Dr. P. Bezdicka for PXRD measurements and to Mrs.
decreased. The pure rutile sample (TIT 85/1150) prepared at I. Augustova for technical assistance.
1150 8C showed rather poor photocatalytic reactivity (see
Fig. 6). Hence, heating at temperature 1150 8C resulting in
full conversion from anatase to rutile and change of all References
microstructure characteristics leads to samples with very
poor photocatalytic activity. Once the anataserutile [1] R.I. Bickley, T. Gonzalezcarreno, J.S. Lees, L. Palmisano, R.J.D.
transformation is complete, the rutile grain size is no longer Tilley, J. Solid State Chem. 92 (1991) 178.
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