Morphological and Structural Characterization of

a Titanium Dioxide System

L. J. Alemany,* M. A. Bañares,† E. Pardo,* F. Martín-Jiménez,*
and J. M. Blasco*
*Departamento de Ingeniería Química, Universidad de Málaga, Campus de Teatinos s/n, E-29071,
Málaga, Spain; and †Instituto de Catálisis y Petroleoquímica, C.S.I.C. Campus Universitario de
Cantoblanco, E-28049, Madrid, Spain

TiO2 was prepared by the homogeneous hydrolysis precipitation method from titanium tet-
raisopropoxide. The decrease of surface area observed with the thermal treatment can be
related to the growth of crystallites, and there is good correlation between the surface area
and the mean crystallite dimension. The coexistence of the three different crystalline TiO2
phases is clearly evidenced by the XRD and FT-Raman measurements. © Elsevier Science
Inc., 2000. All rights reserved.

INTRODUCTION size distribution, porosity, band gap, and

Titanium dioxide can exist in three distinct
crystallographic forms: anatase, brookite,
and rutile. Brookite is a naturally occurring
phase, and is extremely difficult to synthe-
size. Anatase and rutile also occur natu-
rally, but can be synthesized in the labora-
tory without difficulty; these forms have
been employed in many studies of catalysis.
Titania is primarily used in pigments as
an opacifier [1], as a catalytic support [2],
and as a semiconductor [3]. Heterogeneous
photocatalysis by semiconductor powders
is a relatively recent method proposed for
the decontamination treatment of waste-
water effluents [4–6]. There is no general
agreement on which quantities should be
used for a correct comparison of the perfor-
mance of different photocatalytic systems.
The bulk and the surface physico-chemical
properties and the reactivity strongly de-
pend on the method used for the prepara-
tion of the systems. Although a direct cor-
relation between surface properties and
activity is not always possible, it has been
shown that the activity of TiO2 is influ-
enced by the crystal structure, surface area,
271
MATERIALS CHARACTERIZATION 44:271–275 (2000)
© Elsevier Science Inc., 2000. All rights reserved.
655 Avenue of the Americas, New York, NY 10010
surface hydroxyl density [7–10]. Knowl-
edge of the microstructure is of great im-
portance in understanding what processes
limit the efficiency of titania powders. In
this paper we present a morphological and
structural characterization of titanium di-
oxide catalysts.
EXPERIMENTAL
The TiO2 material was prepared by the ho-
mogeneous hydrolysis precipitation method,
and titanium tetraisopropoxide was used
as a precursor for the preparation. In this
method, titanium tetraisopropoxide is sus-
pended in alcohol, to which an appropriate
amount of water is added, while the sus-
pension is ultrasonically dispersed to en-
sure good homogeneity during hydrolysis.
Precipitation of hydrated TiO2 occurs in a
few minutes at room temperature. The
powder is then washed, and the precipitate
is dried in air at 353K overnight. The solid
powders have been calcined at different
temperatures. The samples are denoted by
the temperature of treatment in Kelvin, fol-
1044-5803/00/$–see front matter
PII S1044-5803(99)00066-2
272 L. J. Alemany et al.

Table 1 Morphological and Structural 1800 Series instrument. (DTA) Differential

Properties Thermic Analysis and Thermo-Gravimetric
Anatase
Analysis (TGA) were performed on a Ther-
Thermal Specific surface crystal moflex thermobalance, in air, with a heating
treatment area (m2/g) size (A) Composition (%) rate of 10K/min. Powder diffraction pat-
terns were recorded with a Siemens D-501
353 K 225 56 66.8A ⫹ 33.2B vertical instrument, using nickel CuK␣ ra-
573 K 164 69 66.8A ⫹ 33.2B diation. The microstructure of the samples
723 K 132 83 66.5A ⫹ 33.5B has been studied in terms of crystallite di-
823 K 50 164 58.4A ⫹ 39.3B mensions. The crystallite diameter was cal-
⫹ 2.3R culated from the peak width of the diffrac-
nnA: wt.% of anatase; mmB: wt.% brookite; and ppR: wt.% of tograms by the Scherrer equation. UV-VIS
rutile. spectra of samples, dispersed in water,
were recorded on a Shimadzu UV-2100
spectrophotometer. These conditions should
lowed by TiO2; that is, 333-TiO2, is the sam- be similar to those used in photocatalytic
ple after treatment at 333K. studies for the removal of phenol in water.
The specific surface areas were calculated Raman spectra were obtained using a
by the (B.E.T.) Brunauer, Elmer, and Teller Brucker FT-Raman instrument using the
method from the nitrogen adsorption iso- 1064nm exciting line. Power measured at
therms at 77K measured in a Carlo Erba the sample was 20–40mW.

FIG. 1. DTA and TGA profiles of the precursor.

Characterization of a Titanium Dioxide System 273

RESULTS AND DISCUSSION

Table 1 shows the thermal treatment condi-

tions, specific surface area, mean crystal
size, and the structural composition of the
TiO2 samples. As can be seen, the specific
surface area tends to decrease with increas-
ing the temperature of the calcine treatment.
The DTA plot (Fig. 1) shows an endother-
mic peak centered at 363K, a weak extended
exothermic peak (ca. 573K) typical of a
weak ignition and/or dehydroxilation pro-
cesses, and also a weak, but well-defined
exothermic peak centered at 933K, without
weight loss, which indicates that a phase
transformation has occurred. The total
weight loss is attributed to water, but with
a possible remanent small amount of unre-
acted alcoxy groups that could oxidize at
higher temperatures, thus accounting for
the 11.7%(w/w) weight-loss records.
The weight loss is related to the removal
of hydration water and OH surface groups FIG. 2. X-ray diffraction patterns of different samples:
of titania. Morishige [11] reported that TiO2 (a) 333-TiO2; (b) 573-TiO2; (c) 723-TiO2; and (d) 823-
TiO2.
as the anatase phase undergoes the re-
moval of most surface OH groups in a tem-
perature range extending up to 673K. The FT-Raman spectra of the TiO2 systems
DTA curve shows as exothermic peak cen- are presented in Fig. 3. All samples that
tered at 933K, which is attributed to ana- have undergone calcination mainly display
tase–rutile transition [12]. four modes, with an additional very weak
TiO2 is monotropic [13], and the tempera- shoulder at 195 cm⫺1. Oshaka et al. [15]
ture at which anatase transforms to rutile have assigned the peaks of anatase at 638,
depends on the precursor used and concen- 516, 397, and 144, cm⫺1 as due to modes of
tration of impurities, as well as on the parti- Eg symmetry, while that near 144 cm⫺1
cle size [14]. The anatase/rutile ratio begins arise from the overlapping of two modes,
to decrease as a result of treatment at 723K of B1g and A1g symmetry, respectively.
(Table 1). The anatase lines do not broaden Thus, in agreement with the X-ray diffrac-
concurrently, or as a result of temperature tion (XRD) data, all Raman peaks can be as-
treatment above 723K. sociated with the anatase phase. However,
The XRD features of the samples are dis- for the sample treated at the lowest temper-
played in the Fig. 2. All samples show ature, both the XRD pattern and the Raman
peaks characteristic of the anatase phase. spectrum (peaks at 366, 321, and 246 cm⫺1)
Additional diffraction peaks that can be as- indicate the presence of a small amount of
sociated with TiO2 (brookite) and, to a the brookite phase. Nonetheless, judging
lesser extent to TiO2 (rutile), are observed by the much stronger intensity of the
when these samples are calcined at high brookite Raman bands [16] and the better-
temperatures. Line-broadening analyses resolved XRD peaks, the content of brook-
for all materials reveal that the crystal size ite in our material must be greater than
of the titania phase (A, R, and B) increases those previously reported.
as the temperature of the calcine treatment Bands characteristic of the rutile phase
increases. are observed at 587 and 455 cm⫺1 [16, 17]
274 L. J. Alemany et al.

FIG. 3. FT-Raman spectra of samples, under ambient conditions: (a) 573-TiO2; (b) 723-TiO2; and (c) 823-TiO2.

when the calcination temperature is raised

to 723K. These small crystals are observed
in the Raman spectrum due to the higher
sensitivity of this technique than XRD to
small crystalline aggregates. The intensity
of all the Raman bands increase with ther-
mal treatment.
Figure 4 exhibits the UV-VIS spectra of
TiO2 materials in aqueous solution. Light
absorption is probably due to the appear-
ance of TiO2 microstructures. The absorp-
tion spectra are blue-shifted with decreas-
ing the TiO2 calcination temperature, and
they are dominated by edge relative to a
O2⫺:Ti⫹4 charge transfer of TiO2 anatase.
Absorption spectra are very close to those
of pure bulk titania (anatase). No reduced
titania sites are suggested, because no sig-
nificant absorption is recorded in the visi-
ble region, characteristic of d–d transitions.
The significant shift in the profiles to lower
energies observed on the samples must be
associated with the growth of titania parti-
cles [18, 19], as supported by XRD and FT-
Raman measurements.
Thermal procedures were found to con- FIG. 4. UV-VIS spectra of samples: (a) 333-TiO2; (b)
vert the precursor into the anatase and 573-TiO2; (c) 723-TiO2; and (d) 823-TiO2.
Characterization of a Titanium Dioxide System
rutile forms of the titania. The properties
could then be determined for a range of
well-controlled structures. Its known that
titanium dioxide exists in two tetragonal
structures—anatase and rutile—in addition
to the orthorhombic brookite. Rutile is the
thermodynamically stable form at all tem-
peratures investigated so far, but anatase
and brookite retain their structures until
heated to a fairly high temperature, where
they transform irreversibly to rutile.
CONCLUSIONS
The use of an alcoxide precursor allows the
production, at relatively low temperatures,
of metal oxide particles with a crystalline
structure. The decrease of surface area ob-
served for all samples with the temperature
treatment can be related to the growth of
crystallites. The coexistence of the different
crystalline TiO2 phases on the highest tem-
perature material is clearly evidenced by
the XRD and FT-Raman measurements.
Dirección General de Investigación Científica y
Técnica (DGICYT, Spain) financially supports the
present studies through Research Project PB93-
1009. We are also indebted to Junta Andalucía
(Spain), for funding for our research group 6060.
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Received April 1998; accepted April 1999.