2514 Chem. Mater.

2002, 14, 2514-2518

Inhibition of the Anatase-Rutile Phase Transformation

with Addition of CeO2 to CuO-TiO2 System: Raman
Spectroscopy, X-ray Diffraction, and Textural Studies
Maria Suzana P. Francisco* and Valmor R. Mastelaro
Departamento de Fı́sica e Ciência dos Materiais, Instituto de Fı́sica de São Carlos,
Universidade de São Paulo, P.O. Box 369, 13560-970, São Carlos SP, Brazil
Received October 29, 2001. Revised Manuscript Received March 5, 2002

The effect of the addition of CeO2 on the structural and textural properties of TiO2 and
TiO2-CuO samples calcined at different temperatures was analyzed. The structural and
textural transformation when the temperature of calcination was varied was followed by
X-ray diffraction, Raman spectroscopy, and N2 adsorption techniques. The addition of CeO2
to the TiO2 and TiO2-CuO samples decreases the anatase-rutile phase transformation when
compared with the case of pure TiO2. This decrease observed for the phase transformation
prevents the substantial surface loss and pore growth associated with this process.

Introduction rutile phase has the highest refractive index and ultra-
violet absortivity among the titania phases; thus, it is
Titania (TiO2) has been widely studied due its inter- employed in pigments, paints, ultraviolet absorbents.14
esting properties such as high dielectric constant, According to the temperature, the anatase-rutile
humidity, and oxygen sensitivities and photoelectric and transformation is related to some extent with the degree
catalytic conversion properties.1,2 of packing of the particles, since the transformation
Copper supported on TiO2 presents interesting prop- begins with the nucleation of rutile on anatase and the
erties in the field of heterogeneous catalysis and has rutile nuclei grow throughout the anatase particle until
been widely used in the industry for selective oxidation completion.14 High surface area titania is commonly
of o-xylene to phthalic anhydride,3,4 steam reforming formed by the metastable anatase phase which, upon
and methanol dehydrogenation,5,6 CO oxidation,7,8 NOx heating at temperatures above 800 K, transforms into
decomposition,7 and complete mineralization of a variety the more stable rutile form with extensive surface area
of volatile organic compounds (VOCs).9 loss.14,15 Since anatase is a metastable TiO2 polymorph,
Titania crystallizes in three natural phases: brookite it tends to transform into the rutile phase, decreasing
(orthorhombic), anatase (tetragonal), and rutile (tet- the surface area, inducing a loss of catalytic activity.16
ragonal). The brookite and anatase crystalline phases, The anatase-rutile transformation was found to be
which are stable at low temperature, transform into a major cause of deactivation in vanadio-titania oxida-
rutile when the sample is calcined at higher tempera- tion catalysts.17 Anatase shows a better performance in
tures.10 However, brookite and anatase can be stabilized photocatalysis than rutile.18 It has been found that a
at high temperatures if dopants are present during 70/30 anatase/rutile mix makes the best photocatalyst
synthesis, inhibiting their transformation into rutile.11-13 for the oxidation of organics in wastewater. The anatase
It has been demonstrated that some properties of TiO2 phase is found to have a better performance as a support
are very sensitive to its structure. Since the anatase of V2O5/TiO2 for selective partial oxidation reactions,
phase is chemically and optically active, it is suitable relative to the pure rutile phase.19
for catalysts and supports.14,15 On the other hand, the The stabilization of TiO2 in the anatase phase can
usually be achieved by changing its bulk or surface
* To whom correspondence should be addressed. E-mail: suzana@ composition, and as mentioned before, it is usual to add
[Link].
(1) Bersani, D.; Lottici, P. P.; Ding, X. Z. Appl. Phys. Lett. 1998, other atoms to titania in order to improve TiO2 proper-
72, 73. ties such as structural stability. It has been reported
(2) Wijnhiven, J. E. G. J.; Vos, W. L. Science 1998, 281, 802. that CeO2 has the property of stabilizing the active
(3) Busca, G.; Ramis, G.; Gallando-Amores, J. M.; Escribano, V. S.;
Piaggio, P. J. Chem. Soc., Faraday Trans. 1994, 90, 3181. phase in a fine dispersed state and improving the
(4) Wainwright, M. S.; Foster, N. R. Catat. Ver. 1979, 19, 211. resistance to thermal loss of the supported catalyst
(5) Breen, J. P.; Ross, J. R. H. Catal. Today 1999, 51, 521.
(6) Takezawa, N.; Iwasa, N. Catal. Today 1997, 36, 45.
surface area and the catalytic activity.21-23
(7) Larsson, P.-O.; Andersson, A. Appl. Catal. B 2000, 24, 175.
(8) Dong, G.; Wang, J.; Gao, Y.; Chen, S. Catal. Lett. 1999, 58, 37. (14) Xia, B.; Huang, H.; Xie, Y. Mater. Sci. Eng. B 1999, 57, 150.
(9) Kumar, P. M.; Badrinarayanan, S.; Sastry, M. Thin Solid Films (15) Foger, K.; Anderson, J. R. Appl. Catal. 1986, 23, 139.
2000, 358, 122. (16) Gallando-Amores, J. M.; Escribano, V. S.; Busca, G.; Lorezelli,
(10) Bokhimi, X.; Novaro, O.; Gonzalez, R. D.; López, T.; Chimal, V. J. Mater. Chem. 1994, 4, 965.
O.; Asomoza, A.; Gómez, R. J. Solid State Chem. 1999, 144, 349. (17) Saleh, R. Y.; Wachs, I. E.; Chan, S. S.; Chersich J. Catal. 1986,
(11) Sánchez, E.; López, T.; Gómez, R.; Bokhimi, X.; Morales, A.; 98, 102.
Novaro, O. J. Solid State Chem. 1996, 122, 309. (18) Augustynski, J. Electrochim. Acta 1993, 38, 43.
(12) Zaspalis, V. T.; Van Praag, W.; Keizer, K.; Ross, J. R. H.; (19) Deo, G.; Turek, A. M.; Wachs, I. E.; Machej, T.; Haber, J.; Das,
Burggraaf, A. J. J. Mater. Sci. 1995, 27, 1023. N.; Eckert, H.; Hirt, A. M. Appl. Catal., A 1992, 91, 27.
(13) Shannon, R. D.; Pask, J. A. J. Am. Ceram. Soc. 1965, 48, 391. (20) Berry, R. J.; Mueller, M. R. Microchem. J. 1994, 50, 28.

10.1021/cm011520b CCC: $22.00 © 2002 American Chemical Society

Published on Web 05/18/2002
Anatase-Rutile Phase Transformations Chem. Mater., Vol. 14, No. 6, 2002 2515

In this work, our goal is to study the anatase-rutile Table 1. BET Surface Area (S), Pore Size (PS), and the
phase transformation after the addition of CeO2 into Crystallographic Phases Observed by XRD and Raman
Spectroscopy of TiO2, CuO-TiO2, and CuO/CeO2-TiO2
TiO2 and into CuO-TiO2 matrices prepared by the sol- Samples Calcined at 450 and 650 °C
gel process. To accomplish that goal, we employed
T ) 450 °C T ) 650 °C
physical absorption, X-ray diffraction (XRD), and Ra-
man spectroscopy techniques. S/ PS/ S/ PS/
samples m2 g-1 nm phasea m2 g-1 nm phasea

Experimental Section TiO2 79 20.2 a 15 a/r

Ti0.91O1.91Cu0.09 84 35.0 a 10 r, t
Sample Preparation. The sol-gel method was employed Ce0.09Ti0.82O1.91Cu0.09 124 18.4 a, c 61 43.0 a/r, c, t
to prepare titania-based mixed oxides. Commercial (NH4)2Ce- Ce0.27Ti0.64O1.91Cu0.09 105 18.7 a, c 51 58.1 a/r, c, t
(NO3)6 powder (Vetec) was dissolved in an aqueous nitric acid a (a) anatase and (r) rutile TiO phases; (c) cerianite CeO phase;
2 2
solution (1.5 mol/L). Cu(NO3)2‚3H2O powder (Vetec) was then (t) tenorite CuO phase.
added, heated to 80 °C, and kept at this temperature for 30
min. The resulting solution was called A. Another solution,
called B, was prepared with tetraisopropyl orthotitanate
(C12H28O4TiO, Merck), which was dissolved in isopropyl alcohol
(mole ratio ) 1). Solution A was added to solution B and
subjected to a 50 W ultrasonic vibration for 2 min. The mixture
was allowed to rest for 24 h in a saturated atmosphere of
isopropyl alcohol. Finally, the resulting gel was dried at 110
°C for 16 h and then calcined at 450, 650, and 850 °C for 16 h
in air. The prepared powder samples were called TiO2,
Ti0.91O1.91Cu0.09, Ce0.09Ti0.82O1.91Cu0.09, and Ce0.27Ti0.64O1.91Cu0.09,
expressing the amount of each component as atomic fractions.
Sample Characterizations. (a) Physical Absorption
Measurements. N2 adsorption/desorption measurements were
carried out at liquid N2 temperature in a Micromeritics
AccuSorb 2100E instrument. The specific surface area (BET)
and the pore size were measured using the adsorption and
desorption branches, respectively. Prior to measuring, all the
samples were degassed at 250 °C for 16 h and finally outgassed
to 10-4 Pa. Figure 1. XRD patterns of samples calcined at 450 °C: (a)
TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d)
(b) X-ray Diffraction Study. The X-ray powder diffraction
Ce0.27Ti0.64O1.91Cu0.09. (*) fase TiO2 anatase, (+) fase TiO2 rutile,
patterns were obtained using an automatic Rigaku Rotaflex
(9) fase CeO2 cerianite.
model RU 200B diffractometer with Cu KR radiation (40 kV/
40 mA, 1.5405 Å) and a graphite monochromator. The scan-
ning range was 20-60° (2θ) with a step size of 0.02° and a °C present higher surface. After the calcination at 650
step time of 3.0 s. The identification of crystalline phases was °C, an average surface area around 55 m2/g was found,
accomplished by comparison with JCPDS files numbers 21- which corresponds to a decrease of 49%. All the samples
1272, 21-1276, 43-1002, and 41-254 for anatase and rutile calcined at 850 °C presented a surface area smaller than
phases and cerium and copper oxides, respectively. 8 m2/g, which is the reliable inferior limit of the
(c) Raman Spectroscopy. The spectra were recorded on equipment.
a triple Jobin-Yvon T64000 Raman instrument equipped with
Concerning the pore size (Table 1), for the samples
a microscope and a CCD detection system. The spectra were
obtained at room temperature using the 5145 Å line of an calcined at 450 °C, we observed that the pore size
argon ion laser (model Spectra Physics 2020) excited with an increases from about 20 nm for the TiO2 sample to about
incident power of 50 mW. 35 nm for the Ti0.91O1.91Cu0.09 sample. However, when
CeO2 was added to the sample, we observed a decrease
Results in the pore size value to about 18 nm. When the samples
were calcined at 650 °C, for the TiO2 and Ti0.91O1.91Cu0.09
Specific Surface Area (SBET)-N2 Adsorption. samples, it was not possible to distinguish peaks in the
Table 1 gives the surface area and pore size of the pore size distribution curves for the range analyzed (10-
several titanium oxides, pure and after the addition of 300 Å). Concerning the other two samples, the pore sizes
copper oxide and cerium oxide, after being calcined at of the two samples containing cerium oxide increase to
two different temperatures, 450 and 650 °C. values around 43 and 58 nm. These results show that
According to the results presented in Table 1, the BET the addition of CeO2 to the TiO2 and Ti0.91O1.91Cu0.09
area of the samples was strongly dependent on the samples stabilizes their textural structure, hindering
thermal treatment temperature and on cerium oxide agglomeration and thus preventing pore growth. The
addition. When the TiO2 and Ti0.91O1.91Cu0.09 samples dependence of the pore size on the temperature of
were calcined at 650 °C, the surface area was measured calcination is corroborated by the decrease of the BET
as being equal to 15 and 10 m2/g, respectively, which area.
corresponds to a decrease of 81% and 88%, when com- X-ray Diffraction Analysis. Table 1 reports the
pared to the samples calcined at 450 °C. Ce0.09Ti0.82O1.91- crystallographic phases observed by XRD analysis.
Cu0.09 and Ce0.27Ti0.64O1.91Cu0.09 samples treated at 450 The XRD results for CuO/TiO2 and CuO-CeO2/TiO2
calcined at 450 °C (Figure 1) revealed the presence of
(21) Larsson, P.-O.; Andersson, A. J. Catal. 1998, 179, 72. TiO2-anatase and CeO2-cerianite.24 The amount of
(22) Trovarelli, A.; Zamar, F.; Lorca, J.; Leitenburg, C.; Kiss, J. T. these phases depends on the TiO2/CeO2 composition and
J. Catal. 1997, 169, 490.
(23) Francisco, M. S. P.; Mastelaro, V. R.; Florentino, A. O.; Bazin, does not depend on the copper oxide content. A signifi-
D. Top. Catal., in press. cant change in the XRD patterns of anatase phase (TiO2
2516 Chem. Mater., Vol. 14, No. 6, 2002 Francisco and Mastelaro

Figure 2. XRD patterns of samples calcined at 650 °C: (a) Figure 3. XRD patterns of samples calcined at 850 °C: (a)
TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d) Ce0.27- TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d) Ce0.27-
Ti0.64O1.91Cu0.09. (*) fase TiO2 anatase, (+) fase TiO2 rutile, (9) Ti0.64O1.91Cu0.09. (+) fase TiO2 rutile, (9) fase CeO2 cerianite.
fase CeO2 cerianite.

sample, Figure 1a) took place after the addition of ceria.

In this situation, diffraction peaks of anatase-TiO2
became broadened, and the diffraction peaks of ceria
can be clearly observed (Ce0.09Ti0.82O1.91Cu0.09 sample,
Figure 1c). For the Ce0.27Ti0.64O1.91Cu0.09 sample (Figure
1d), only the main peak of the TiO2 anatase phase, ca.
25.4° (2θ), was barely observable. Furthermore, no solid
solution was identified since no significant peak shift
of the above-mentioned diffraction peaks was observed.
Figure 2 shows the diffractograms of the samples
calcined at 650 °C. The diffractogram of the TiO2 ref-
erence compound (Figure 2a) presents two crystalline
phases: anatase and rutile. When copper oxide was
added to TiO2 (Figure 2b), only the rutile phase was
identified and the CuO phase was barely observed. After
Figure 4. FT-Raman spectra of samples calcined at 450 °C:
the addition of cerium oxide (Figure 2c), the diffraction
(a) TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d)
peaks of the TiO2 rutile phase became smaller and the Ce0.27Ti0.64O1.91Cu0.09.
peaks related to the anatase and the CuO phases
practically disappear. As indicated in Figure 2d, in the
Ce0.27Ti0.64O1.91Cu0.09 sample, the X-ray diffraction pat-
tern showed the presence of TiO2 anatase and CeO2
cerianite phases and few peaks related to the CuO
phase.
The XRD patterns of the samples calcined at 850 °C
are shown in Figure 3. In all samples, we observed the
presence of the TiO2 rutile phase. In the samples that
also contain cerium and copper oxides, we observed the
presence of CeO2 cerianite and CuO phases. In no
sample calcined at this temperature did we observe the
presence of the TiO2 anatase phase.
Raman Spectroscopy Data. Raman spectroscopy
was also employed to study the structure of the samples.
Table 1 summarizes the crystallographic phases ob-
served by Raman spectroscopy, which are in agreement
with the XRD results. Figure 5. FT-Raman spectra of samples calcined at 650 °C:
Raman spectroscopy of samples calcined at 450 °C (a) TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d)
Ce0.27Ti0.64O1.91Cu0.09.
(Figure 4) revealed the presence of only two crystalline
phases, TiO2 anatase and CeO2 cerianite, indicating a
pure TiO2 sample (Figure 5a) reveals six strong Raman
good dispersion of copper species.26
bands. Three bands at 232, 446, and 609 cm-1 are in
The Raman spectra of the samples calcined at 650
agreement with data observed in the spectra of a rutile
°C are shown in Figure 5. The Raman spectrum of a
phase;4,25 the other three bands, at 395, 515, and 636
cm-1, are observed in the spectra of anatase phase.
(24) Francisco, M. S. P.; Nascente, P. A. P.; Mastelaro, V. R.;
Florentino, A. O. J. Vac. Sci. Technol. A 2001, 19, 1150.
(25) Wu, M.; Zhang, W.; Du, Z.; Huang, Y. Mod. Phys. Lett. B 1999, (26) Francisco, M. S. P.; Nascente, V. R.; Florentino, A. O. J. Phys.
13, 167. Chem. B 2001, 105, 10515.
Anatase-Rutile Phase Transformations Chem. Mater., Vol. 14, No. 6, 2002 2517

Discussion
TiO2 and Ti0.91O1.91Cu0.09 Samples. According to
Ramis et al.,29 the anatase phase transforms into the
rutile phase at 700 °C, and such a transformation will
be complete at 800 °C. The sol-gel method when
processed in highly acid conditions induces hydrolysis
of titanium alkoxide at a faster rate than is the
condensation, producing samples with many hydroxy-
ls.30 The presence of these hydroxyl groups produces
defects in the framework, which are titanium and
oxygen vacancies.30 These defects are responsible for
promoting the anatase-rutile transformation in a lower
temperature, explaining the presence of the rutile phase
in pure TiO2 calcined at 650 °C (Figures 2-5a), together
with the anatase phase.
The XRD and Raman patterns of the Ti0.91O1.91Cu0.09
Figure 6. FT-Raman spectra of samples calcined at 850 °C: sample calcined at 650 °C (Figures 2-5b) showed that
(a) TiO2, (b) Ti0.91O1.91Cu0.09, (c) Ce0.09Ti0.82O1.91Cu0.09, and (d) copper oxide probably catalyzes the mass transport to
Ce0.27Ti0.64O1.91Cu0.09.
the nucleation region of rutile phase (with higher mass
These modes correspond to the fundamental modes for density), promoting rutile nuclei growth, thus favoring
these phases.2,4,25 The peak at 232 cm-1 is assigned to the phase transition. The mass movement can be
a disordered-induced scattering mode of rutile.4 After thought as the removal of the defects in excess formed
the addition of CuO to TiO2 (Ti0.91O1.91Cu0.09 sample, during the sol-gel process from the nucleation region.
Figure 5b), the Raman lines related to the anatase Likely, CuO is responsible for a higher number of
phase disappear, and only two broad bands at 446 and defects inside the anatase phase, in such a way that
609 cm-1 which correspond to the rutile phase were formation and growth of a higher number of rutile nuclei
identified. When cerium oxide is added to the Ti0.91O1.91- into TiO2 anatase take place faster.
Cu0.09 sample (Ce0.09Ti0.82O1.91Cu0.09 sample, Figure 5c), Some works have been reported on the modification
the two Raman bands ascribed to the rutile phase are of the anatase-rutile phase transformation when copper
still observed in the spectrum, however, accompanied oxide is used as a dopant; it was concluded that the
by the appearance of the three Raman lines at 395, 515, mechanism responsible for such a modification is an
and 636 cm-1 ascribed as being anatase phase. The excess of oxygen vacancies that accelerates the transi-
typical strong line of cerium oxide at 460 cm-1 is barely tion and the crystallite growth.16,31,32
recognizable as a shoulder on the rutile bands, and it Nair et al.31 studied the microstructure and phase
is due to the Raman-active mode characteristic of transformation behavior of doped nanostructured tita-
fluorite-structured materials.21,27 In the spectrum of the nia. According to this work, CuO and NiO enhanced the
sample with the highest amount of cerium oxide (Ce0.27- anatase transformation and the sintering. On the other
Ti0.64O1.91Cu0.09 sample, Figure 5d) the band of ceria at hand, La2O5 retarded both transformation and densi-
460 cm-1 was easily identified while no rutile band was fication. Dopants with an oxidation state above 4+ will
observed. However, in addition to the anatase funda- reduce the oxygen vacancy concentration in the titania
mentals at 395, 515, and 636 cm-1,3,25 this spectrum lattice as an interstitial impurity. Dopants with an
showed a great number of smaller bands which do not oxidation state of 3+ or lower are placed in the titania
correspond to the Raman modes in single-crystal and lattice points, creating a charge-compensating anion
polycrystalline anatase. The 244 cm-1 mode was fre- vacancy.
quently observed in nanophase TiO2 whereas the modes The anatase-rutile transformation involves an over-
at 322 and 363 cm-1 have been associated with defects all contraction of the oxygen structure and a cooperative
in the TiO2 nanocrystalline phase.25 movement of ions.9 It is not easy to obtain a conclusion
Figure 6 presents the Raman spectra of the samples about a link between anatase-rutile transformation and
calcined at 850 °C. At this temperature, only the bands crystallite growth, but it is very well-known that the
of the TiO2 rutile phase were identified, except for the phase transformation and sintering behaviors are inter-
band at 445 cm-1 in the spectrum of the Ce0.27Ti0.64O1.91- related.
Cu0.09 sample, in which we can observe a shoulder re- Our the BET surface area, XRD and Raman spec-
lated to the presence of the CeO2 crystalline phase. The troscopy results for TiO2 and Ti0.91O1.91Cu0.09 samples
Raman line at 459 cm-1 of CeO2 was easily distin- are in good agreement with the statements discussed
guished, even for the spectrum of the sample with the above. The addition of CuO to TiO2 was responsible for
least amount of CeO2 (Ce0.09Ti0.82O1.91Cu0.09 sample,
Figure 6c). (28) Reimann, K.; Syassen, K. Solid State Commun. 1990, 76,
All the samples containing copper oxide and calcined 137.
at 650 and 850 °C presented a band near 293 cm-1, (29) Ramis, G.; Busca, G.; Cristiani, C.; Liette, L.; Forzatti, P.;
Bregani, F. Langmuir 1992, 8, 1744.
which has been reported by other authors as due to the (30) López, T.; Gómez, R.; Pecci, G.; Reyes, P.; Bokhimi; Novaro,
CuO crystalline phase.27,28 O. Mater. Lett. 1999, 40, 59.
(31) Nair, J.; Nair, P.; Mizukami, F.; Oosawa, Y.; Okubo, T. Mater.
Res. Bull. 1999, 34, 1275.
(27) Shyu, J. Z.; Weber, W. H.; Gandhi, H. S. J. Phys. Chem. 1988, (32) Yuan, S.; Mériaudeau, P.; Perrichon, V. Appl. Catal., B 1994,
92, 17. 3, 319.
2518 Chem. Mater., Vol. 14, No. 6, 2002 Francisco and Mastelaro

accelerating the TiO2 phase transformation and its The decrease of crystallite sizes23 and the inhibition
crystal growth. of titania phase transformation with the addition of
CuO-CeO2/TiO2 Samples. As we discussed before, cerium oxide are consistent with the increase of surface
it is known that the anatase-rutile transformation is area and the inhibition of the sintering of supports with
related to many factors, such as impurities present in added cerium oxide. All these results indicate the
anatase, preparation conditions, precursors, dopants, addition of CeO2 to the matrix modifies the mechanism
morphology of the particles, and others. Lin et al.33 of formation of the titania phases.
studied the influence of adding dopants in the anatase- The proposed model for CuO/CeO2-TiO2, previously
rutile transition temperature. In their work, XRD reported,23,24 corroborate our present data and the
results of mixtures of TiO2 with rare earth oxides (0.5 literature. The model proposed for cerium oxide-modi-
wt %) revealed that the presence of these oxides can fied TiO2 support was well supported by the XPS
inhibit the phase transformation during the thermal results, which showed a second Ti atom species in a
treatment, even with mixtures calcined at moderately distorted structure after the addition of cerium oxide.24
high temperatures (e650 °C for TiO2/La2O3, e700 °C Moreover, EXAFS measurements at the Ce LIII-edge
for TiO2/Y2O3 or CeO2). The inhibition of the transition also revealed that, in sample catalysts containing 9%
was ascribed to the stabilization of the anatase phase of cerium oxide, the cerium atoms presented a well-
by the surrounding rare earth oxides through the distorted local structure, which could also indicate an
formation of Ti-O-rare earth element bonds. At the interaction between Ce, Ti, and Cu atoms.23
interface, titanium atoms substituted the rare earth Yang et al.35-37 studied the effects of different TiO2
elements in the lattice of the rare earth oxides to form modifiers in the anatase-rutile transformation. For
tetragonal Ti sites. The interaction between the differ- ZrO2-containing samples (a system with Zr/Ti molar
ent tetrahedral Ti atoms (in La2O3 and Y2O3) or between rate of 0.10), the DTA curve (differential thermal
the tetrahedral Ti and octahedral Ti (in CeO2) inhibits analysis) indicated an exothermic peak assigned to the
the phase transformation. anatase-rutile transition at 1100 °C.35 The same peak
A similar explanation was offered for the inhibition were observed at 973 °C in the DTA curve of the TiO2
of the phase transformation for a TiO2/SiO2 mixture added with Al2O5 (Al/Ti molar rate of 0.10).36,37 In both
(ratio 30/70).34 The stabilization of the anatase phase systems, the authors suggested that the formation of a
takes place by the surrounding SiO2 phase through the metastable anatase solid solution containing alumina
TiOSi interface. At the interface, TiO2 atoms are substi- and a solid solution of ZrO2 in anatase at low temper-
tuted into the tetrahedral SiO2 lattice forming a tetra- ature are responsible for the higher anatase-rutile
hedral Ti site. The interaction between the tetrahedral transition temperature. Comparing these results with
Ti species and the octahedral Ti sites in the anatase is our data for the Ce0.09Ti0.82O1.91Cu0.09 sample, it seems
thought to prevent the transformation to rutile. The that the effect of the ceria loading in the CeO2/TiO2
SiO2 lattice locks the Ti-O species at the interface with matrix is moderated. Nevertheless, these authors ana-
the TiO2 domains preventing the nucleation that is lyzed the Al2O5/TiO2 and ZrO2/TiO2 samples after a
necessary for anatase transformation to rutile. thermal treatment for 1 h, while our analyses were
The XRD and Raman results of the Ce0.09Ti0.82O1.91- performed in samples thermally treated for 16 h.
Cu0.09 and Ce0.27Ti0.82O1.91Cu0.09 samples calcined at 650
°C (Figures 2-5c,d) showed that the likely formation Conclusions
of Ce-O-Ti interaction took place, inhibiting the
transition of the TiO2 phase. The Ce-O-Ti interaction The phase transformation and the sintering behavior
blocks the Ti-O species at the interface with TiO2 of titania have been studied with the objective to better
domains stabilizing them, hiding the agglomeration of understand the effect of the addition of CeO2 and CuO
TiO2 and thus preventing their growth. Moreover, the dopants. It has been found that the CuO dopant ac-
cerium oxide-modified TiO2 support, in combination celerates the anatase-rutile transition and also assists
with the presence of CuO, promoted greater methanol the sintering process. Copper-doped samples also sin-
conversion than the catalyst using a pure TiO2 support tered to near-zero porosity at 650 °C. The addition of
(Ti0.91O1.91Cu0.09 sample), indicating a synergistic effect CeO2 to the CuO/TiO2 system increased specific surface
between CuO and the CeO2-TiO2 mixed support.23,24 area of the mixed oxide and prevented the sintering of
Our results are in general agreement with data from samples calcined at higher temperature. At the same
the literature. The catalytic combustion of diesel soot time this prevented pore size growth and the titania
particles on copper catalysts supported on TiO2 was phase transformation.
enhanced by the presence of potassium.32 The effect was
attributed to the formation of mixed K-Ti oxides which Acknowledgment. The research work was partially
inhibit the sintering of the TiO2 support and thus performed at the Grupo de Propriedades O Ä pticas (GPO)
increased the surface area of the catalysts. Titania of the IFGW-UNICAMP, Brazil. The authors acknowl-
modified with 3 and 12 µmol Ce/m2 surface area of the edge Prof. Carol H. Collins (IQ-UNICAMP) for manu-
titania (173 m2/g) was used as support for copper script revision. This work was supported by the Bra-
oxides.21 CeO2 added to the CuO/TiO2 system stabilized zilian research funding institutions FAPESP and CNPq.
the surface area of the TiO2 support in the presence of CM011520B
copper oxide.
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