Available online at www.sciencedirect.

com

Powder Technology 181 (2008) 83 88

www.elsevier.com/locate/powtec

Synthesis of mesoporous TiO2/-Al2O3 composite granules with different sol

composition and calcination temperature
Junseo Choi a , Jinsoo Kim a,, Kye Sang Yoo b,, Tai Gyu Lee c
a

College of Environment and Applied Chemistry, Kyung Hee University, 1 Seochen-dong, Giheung-gu, Yongin, Gyeonggi-do 449-701, South Korea
b
Clean Energy Research Center, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791, South Korea
c
Department of Chemical Engineering, Yonsei University, 134 Sinchon-dong, Seodaemun-gu, Seoul 120-749, South Korea
Received 20 September 2006; received in revised form 19 June 2007; accepted 26 June 2007
Available online 30 June 2007

Abstract
Mesoporous TiO2/-Al2O3 composite granules were prepared by combining solgel method and oil-drop method. After calcination at 450 C,
the composite granules showed anatase and -Al2O3 phases with the specific surface area of 240310 m2/g. The phase composition and pore
structure of the granules can be controlled by calcination temperature and the mixing ratio of boehmite sol and titania sol. The product granules
can be used as a photocatalyst or adsorbent in moving or fluidized bed reactors.
2007 Elsevier B.V. All rights reserved.
Keywords: Alumina; Titania; Granulation; Solgel; Pore structure; Nanostructure

1. Introduction
The support materials, like ceramic oxide powder, with high
surface area and thermal stability have been the interest for
various applications in many chemical processes. There are
some drawbacks to synthesize a single-phase oxide material
with desirable properties. One of promising approaches has
focused on the supports consisting of composite that integrate
the favorable aspects of the constituents. For example, titanium
dioxide (TiO2, titania) has received significant attention because
of its numerous applications in photocatalysis and catalyst
support [1]. However a relatively low surface area and poor
structural stability at high temperatures are major disadvantages. Alumina (Al2O3) has been usually applied to several
fields as a support material due to its high surface area and
abrasion resistance, even though Al2O3-supported catalyst has
relatively low activity [2,3].
For these reasons, TiO2Al2O3 composite oxide has been
prepared to overcome the shortcomings [46]. The composite
was used in the dehydrosulfurization catalyst [7,8] and

Corresponding authors.
E-mail addresses: jkim21@khu.ac.kr (J. Kim), kyoo@kist.re.kr (K.S. Yoo).
0032-5910/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2007.06.022

photocatalyst [9]. To obtain a well-controlled composite, it is

very important to choose a suitable preparation route. Conventionally, TiO2Al2O3 composite powders are formed from a
mixture of Al2O3 and TiO2 powders ball-milled for the
subsequent shaping and sintering [10]. This method has hardly
produced mixed powders homogeneously.
Furthermore, industrial applications in many separation and
reaction processes require the use of the composite in the
granular form. However, the granules prepared by conventional
methods, i.e. tumble growth, tabletting and extrusion, suffer
from some drawbacks such as poor mechanical strength and low
attrition resistance [11]. In our previous work [12], spherical
alumina granules were prepared by the solgel granulation
process with various calcinations temperature. It was found that
the structural properties of the granules were affected by the
calcinations temperature. However, to our best knowledge, no
significant work has been reported on the synthesis of TiO2
Al2O3 composite granules with high surface area, controlled
porosity and tailor-designed pore size distribution. In this study,
mesoporous TiO2Al2O3 composite granules were prepared by
combining solgel method and oil-drop method. Effects of the
TiO2/Al2O3 ratios and calcinations temperature on the various
physical properties of the composite granules are reported with
sophisticated characterizations.

84

J. Choi et al. / Powder Technology 181 (2008) 8388

2. Experimental
2.1. Preparation procedures
Spherical TiO2/-Al2O3 composite granules of 12 mm in
diameter were prepared by the solgel granulation process
reported by elsewhere [1214]. Boehmite and titania sols were
prepared separately by the methods reported earlier. Initially,
2 M stable boehmite sols were synthesized from hydrolysis and
condensation of aluminum isopropoxide, ALISOP (Aldrich,
Mw = 204.25, 98% purity), using the modified Yoldas process
[13]. This method, which avoids the evaporation step, was used
as a direct preparation of high-concentration boehmite sol. The
precursor ALISOP is first hydrolyzed in 500 ml distilled water
at 8085 C, and after stirring for 1 h, the resulting slurry (with
AlOOH precipitates) was peptized with 1 M HNO3, at an HNO3
to AlOOH molar ratio of 0.07. The sol was refluxed overnight
for more than 12 h at 95 C. The remnant alcohol was
evaporated by refluxing the sol exposed to air for 2 h at 95 C.
0.5 M titania sols were synthesized by hydrolysis and
condensation of titanium tetraisopropoxide, TTIP (Aldrich,
Mw = 284.26, 97% purity). TTIP was dissolved in isopropanol
at room temperature and in a water-free atmosphere. Then, this
solution was added slowly into the distilled water with stirring
at high speed for 1.5 h, thus white precipitates formed. The
precipitates obtained was separated and washed repeatedly with
distilled water until the precipitates became free of alcohol.
These precipitates were converted into a stable sol by dispersing
in 1000 ml of water, followed by peptization with an addition of
1M HNO3 solution. Then, the solution was refluxed at 80 C for
12 h [15].
For granulation process, both boehmite and titania sols were
mixed together at a predetermined concentration, followed by
stirring for 1.5 h. Before sol mixing, both boehmite and titania
sols were ultrasonically dispersed by a homogenizer. After adding
a small amount of 1 M HNO3, the sol mixture was aged at 70 C
for 12 h until the mixture reached the gelation point. This
partially gelled sol was transferred into droppers for the
generation of sol droplets of about 5 mm in size. The droplets
fell through a liquid bath consisting of a paraffin oil layer (mineral
oil, from Yakuri Pure Chemicals Co. Ltd.) and a 10 wt.%
ammonia solution layer [13]. The paraffin oil layer facilitated the
droplets into spherical wet-gel granules by surface tension. The
structures of the wet-gel particles were strengthened after aging in
the ammonia solution for 1 h. The granules were then collected
with a sieve and washed several times with alcohol and distilled
water. After these wet granules were dried at 40 C for 48 h, the
granules were treated at various temperatures from 450 to 750 C
for 3 h at a heating rate of 1 C min 1. The product granules were
labeled as PA, TA0.25, TA0.50 and TA0.75, respectively, for
TiO2 / (TiO2 + Al2O3) = 0, 0.25, 0.50 and 0.75.
2.2. Characterization techniques
The shape and size of the TiO2/Al2O3 composite granules
were observed using an optical microscope (Microscope
System STVMS 305R, Sometech). An X-ray diffractometer

Fig. 1. Optical photographs of the TiO2/-Al2O3 granules: (a) TA0.25,

(b) TA0.50, and (c) TA0.75.

(M18XHF-SRA, Mac Science) was used for the identification

of crystallinity with Ni filtered CuK ( = 1.54056 ) radiation
over the range of 2 from 20 to 80, with a scanning speed of 1
min 1. The crystallite sizes (Dhkl) were calculated using the
Scherrer relationship [16]:
Dhkl Kk=Bhkl cosh

J. Choi et al. / Powder Technology 181 (2008) 8388

85

where IA and IR are the X-ray integrated intensities of the (101)

reflection of anatase and the (110) reflection of rutile.
The specific surface area (SSA), pore size distribution (PSD)
and pore volume of the Al2O3 and TiO2/Al2O3 granules were
obtained by N2 adsorption/desorption at 77 K using a
Micromeritics ASAP2020 equipment. All granules were
degassed at 150 C for 1 h prior to measurement. The specific
surface area was determined by the multipoint Brunauer
EmmettTeller (BET) method using the adsorption data in the
relative pressure (P / P0) range of 0.050.25. The pore size
distribution data were calculated by the ASAP 2020 software

Fig. 2. SEM images of the TiO2/-Al2O3 granules after calcinations at 750 C:

(a) TA0.25, (b) TA0.50, and (c) TA0.75.

where is the wavelength and Bhkl is the full width at half

maximum, with K = 0.98. The weight fraction of rutile in the
granules was calculated using the equation given below [17]:
X

1
1 0:8IA =IR

Fig. 3. XRD patterns of the TiO2/-Al2O3 granules after calcination for 3 h at

various temperatures: (a) 450 C, (b) 600 C, and (c) 750 C.

86

J. Choi et al. / Powder Technology 181 (2008) 8388

phase showing typical peaks at about 2 = 37, 47 and 67.

This -Al2O3 phase was maintained even after calcination at
750 C for 3 h without further phase transformation. After
calcinations at 450 C and 600 C, all TiO2/Al2O3 composite
granules showed both anatase phase and -Al2O3 phase. In
contrast, the TiO2 of the TA0.50 and TA0.75 granules started to
show rutile phase, while that of TA0.25 granules maintained
anatase phase. However, aluminum titanate (Al2TiO5) was not
found in this experiment, even for the TA0.75 granules. This is

Fig. 4. Anatase crystallite sizes of TiO2/-Al2O3 granules as a function of

calcinations temperature.

from the N2 desorption isotherms. The BarrettJoyner

Halender (BJH) method with cylindrical pore size calculated
from the Kelvin equation was used in the data processing. The
crush strength of the individual granules, taken as the maximum
load applied to break the granule, was measured by a universal
testing instrument (Instron 4465). The porosity was calculated
based on the pore volume and density of the materials.
3. Results and discussion
The granulation process conditions, such as the amount of
acid, aging temperature and aging time, are critical to determine
the properties of the product granules. In this work, the amount
of 1M HNO3 was fixed at the volume ratio of acid/sol = 0.25 and
the sol mixture was aged at 70 C for 1.02.0 h. Under these
conditions, the granulation process was easy to control, and the
wet-gel granules were fairly strong enough to maintain good
integrity after the washing step. The TiO2 concentration
strongly affected the shape and mechanical properties of the
product composite granules. Fig. 1 shows the optical photographs of the TiO2/Al2O3 composite granules. The TA0.25 and
TA0.50 granules are spherical with a diameter of ca. 2 mm. In
contrast, the TA0.75 granules have a little bit poor sphericity
due to the large shrinkage during drying process. Fig. 2 shows
the SEM image of composite granules samples with different
TiO2 concentration. The surface of TA0.25 is relatively smooth
than the other samples. With increasing TiO2 concentration, the
crystallites easily aggregated leading to formation of rough
surface on the composite granule. The result is in a good
agreement with the fact that the granule with higher TiO2
concentration possesses poor sphericity.
The phase structure of the composite granules was
investigated after calcination at various temperatures from
450 C to 750 C. Calcination above 450 C not only
consolidated the granules, but also facilitated the phase
transformation of both alumina and titania. Fig. 3 shows the
XRD patterns of the TiO2/Al2O3 composite granules as well as
the pure alumina granules. After calcination above 450 C, the
pure alumina granules transformed from boehmite to -Al2O3

Fig. 5. Isotherms and pore size distributions (inset) of TiO2/-Al2O3 granules

after calcination at various temperatures: (a) 450 C, (b) 600 C, and (c) 750 C.

J. Choi et al. / Powder Technology 181 (2008) 8388

Fig. 6. Specific surface areas of TiO2/-Al2O3 granules as a function of

calcinations temperature.

in good agreement with Xiong et al. [4], who found aluminum

titanate phase after calcinations above 900 C.
Fig. 4 shows the anatase crystallite size of the composite
granules as a function of calcination temperature. The anatase
crystallite size of the TA0.25 granules increases rather slowly
from 4.3 nm to 8.5 nm with increasing calcination temperature
from 450 C to 750 C. On the other hand, the TA0.50 and
TA0.75 granules show a rather rapid increase of crystallite sizes
at 750 C. This can be explained by the appearance of rutile
phase for the TA0.50 and TA0.75 granules. In general, the rutile
phase starts to show up after the anatase crystallites attain a
critical particle size. The rutile fractions of the TA0.50 and
TA0.75 granules, calculated from the intensities of the (101)
reflection plane of anatase phase and (110) reflection plane of
rutile phase, are 4.0% and 7.9%, respectively.
Fig. 5 shows the isotherms and pore size distributions
(inserted) of the TiO2/Al2O3 composite granules after calcination at various temperatures. According to BDDT classification
[18], all isotherms are of type IV with a hysteresis loop,
indicating the presence of mesopores. Also, the shape of
hysteresis loop is a combination of type H2 and H3, which
indicates the presence of both narrow slit-shaped pores and inkbottle pores. The pore size distributions of the granules are
calculated from the desorption branch of the isotherms. After
calcination at 450 C, the isotherms of the composite granules
have hysteresis loops in the similar relative pressure from 0.55
to 0.8, showing almost identical pore size distributions in the
range of 3 to 6 nm with the same average pore size of 4.4 nm.
With increasing calcination temperature as shown in Fig. 5(b)

87

and (c), the hysteresis loop shifted to the right indicating the
increase of pore size.
Fig. 6 shows the surface areas of the composite granules as a
function of calcination temperature. The surface area of the
composite granules was strongly affected by the calcination
temperature. For all granules, the surface area decreases with
increasing calcination temperature, which is the typical
phenomenon related with sintering and phase transformation.
Up to 600 C the pore structure change is mostly attributed to
sintering, since the granules maintained -Al2O3 and anatase
phases without any phase transformation as shown in Fig. 3. For
sintering of the crystalline materials at medium temperatures, it
can be explained by the surface diffusion mechanism and the
surface area reduction can be correlated to the sintering time, t,
and temperature, T, by [19]:
DS=S kgtexpE=RT =T 1=3:5

where S is the surface area, is the specific surface area, E is

the activation energy for surface diffusion, and k is a constant.
Chang et al. [20] reported that anatase titania has the greater
sintering rate than -Al2O3 due to its larger specific surface
energy and lower activation energy for the surface diffusion.
Therefore, the higher the titania concentration of the composite
granules, the more the reduction in the surface area of the
granules with calcinations temperature. At the same temperature, the granules with higher titania concentration have smaller
surface areas. The big decrease of the surface area at 750 C, for
the TA0.50 and TA0.75 granules, is attributed to the phase
transformation from anatase to rutile as well as sintering.
The pore structure data and crush strength of the composite
granules are summarized in Table 1. The evolution of pore
structure as a function of calcinations temperature was strongly
affected by the concentration of the composite granules. In all
cases, the average pore size increases with increasing
calcination temperature. For the crystalline ceramic materials,
surface area reduction accompanies the pore size increase due to
the removal of materials from the convex grain to the more
concave necks. This is in good agreement with our results,
shown in Fig. 5. After calcinations at 750 C, the average pore
sizes are 5.9 nm, 6.8 nm, 7.9 nm and 10.1 nm, respectively, for
the PA, TA0.25, TA0.50 and TA0.75 granules. This trend is in a
good agreement with the SEM result shown in Fig. 2.
In contrast, the pore volume of the composite granules
slightly decreased with calcinations temperature. Even after
calcinations at 750 C, the pore volumes are 0.47, 0.49, 0.46,
and 0.36 cm3/g, respectively, for the PA, TA0.25, TA0.50 and

Table 1
Pore structure data and crush strength of TiO2/Al2O3 composite granules as a function of calcination temperature
After calcination at 450 C

Pore size (nm)

Pore volume (cm3/g)
Porosity (%)
Crush strength (N/granule)
a

After calcination at 600 C

After calcination at 750 C

PA

TA0.25

TA0.50

TA0.75

PA

TA0.25

TA0.50

TA0.75

PA

TA0.25

TA0.50

TA0.75

4.2 a
0.52 a
65.8 a
205 14

4.4
0.51
65.7
154 21

4.3
0.47
64.1
69 20

4.4
0.39
60.0
50 18

5.2 a
0.51 a
65.5 a
167 13

5.3
0.49
64.7
139 19

5.4
0.47
64.1
66 21

5.7
0.38
59.4
49 23

5.9 a
0.47 a
63.5 a
137 13

6.8
0.49
64.7
135 22

7.9
0.46
63.6
64 16

10.1
0.36
58.2
35 14

This data have been reported in Ref. [12].

88

J. Choi et al. / Powder Technology 181 (2008) 8388

TA0.75 granules. This result is similar with Yoldas [21] and

Maeda et al. [22], who found that the pore volume of alkoxidederived alumina did not change very much during heat
treatment while the pore size increased and the surface area
decreased. The porosity of the composite granules showed
comparable trend with pore volume of samples as illustrated in
Table 1. After calcinations at various temperatures, the porosity
of the composite granules was maintained almost the same
value. In practical applications, porosity is one of the important
factors that influence the chemical reactivity and physical
interactions of solids with gases and liquids. This suggests that
the present TiO2/-Al2O3 composite granules have potential
applications in separation or reaction processes.
The crush strength of the granules decreased with TiO2
concentration and calcination temperature. Conventionally, the
crush strength of single oxides correlates with the pore volume
or bulk density; i.e., the higher the bulk density, the higher the
strength. However, this relation does not hold for binary oxides.
Buelna et al. [14] found that the crush strength of solgel
derived -alumina granules is about 5 times that of commercial
-alumina granules from UOP and Alcoa. They reported that, in
solgel process, uniform primary particles are connected
together during gelation, followed by structural rearrangement
by capillary force during drying, and then formation of a very
stiff solid network and a large intraparticle space with uniform
nanoscale pores during calcinations step. As a result, the solgel
derived -alumina granules have a tightly packed structure with
highly interconnected pores showing high crush strength as
illustrated in Table 1. For the TA0.25 granules, the alumina
particles are well connected together, having dispersed titania
particles. Therefore, the TA0.25 granules have high crush
strength. In contrast, the TA0.50 and TA0.75 granules have
relatively low crush strength, which is attributed to the less
connected alumina phase with increasing titania concentration.
Still, the crush strength of TA0.50 and TA0.75 granules is better
than the commercial -alumina granules (about 25 N/granule)
[14].
4. Conclusions
Spherical TiO2/Al2O3 composite granules were prepared by
a solgel granulation process. The TiO2 concentration of the
composite granules is a critical factor for the shape and
properties of the product granules. With increasing TiO2
concentration, the product granules slowly deviate from perfect
spheres with weaker mechanical properties. The pore structure

of the granules can be controlled by varying the TiO2

concentration and the calcination temperatures. The TA0.25
granules after calcination at 450 C have the largest SSA of
306 m2/g with the smallest anatase crystallite size of 4.2 nm,
while TA0.75 granules after calcination at 750 C have the
smallest SSA of 105 m2/g with the largest anatase crystallite
size of 17.0 nm.
Acknowledgement
This work was supported by Grant no. R01-2006-00010007-0 from the Basic Research Program of the Korea Science
and Engineering Foundation.
References
[1] A. Fujishima, K. Hashimoto, T. Watanabe, TiO2 photocatalysis, Fundamentals
and Applications, Bkc Inc., Tokyo, 1999.
[2] E. Medvedovski, J. Am. Ceram. Soc. Bull. 81 (2002) 27.
[3] M.F. Zawrah, J. Schneider, K.-H. Zum Gahr, Mater. Sci. Eng., A Struct.
Mater.: Prop. Microstruct. Process. 332 (2002) 167.
[4] G. Xiong, X. Wang, L. Lu, X. Yang, Y. Xu, J. Solid State Chem. 141 (1998) 70.
[5] S. Sivakumar, C.P. Sibu, P. Mukundan, P.K. Pillai, K.G.K. Warrier, Mater.
Lett. 58 (2004) 2664.
[6] S. Liu, W. Tao, J. Li, Z. Yang, F. Liu, Powder Technol. 155 (2005) 187.
[7] B.N. Das, J. Mater. Sci. Lett. 11 (1992) 843.
[8] R. Linacero, M.L. Rojas-Cervantes, J.D.E.D. Lopez-Gonzalez, J. Mater.
Sci. 35 (2000) 3279.
[9] L. Lei, H.P. Chu, X. Hu, P.L. Yue, Ind. Eng. Chem. Res. 38 (1999) 3381.
[10] M. Takahashi, M. Fukuda, M. Fukuda, H. Fukuda, T. Yoko, J. Am. Ceram. Soc.
85 (2002) 3025.
[11] C.E. Capes, A.E. Fouda (Eds.), Handbook of Powder Science and
Technology, Van Nostrand Reinhold, New York, 1984, pp. 269293.
[12] J. Choi, B. Kim, J. Kim, J. Chem. Eng. Jpn. 39 (9) (2006) 1000.
[13] G. Buelna, Y.S. Lin, Microporous Mesoporous Mater. 30 (1999) 359.
[14] G. Buelna, Y.S. Lin, L.X. Liu, J.D. Litster, Ind. Eng. Chem. Res. 42 (2003)
442.
[15] J. Kim, O. Wklhelm, E. Pratsinis, J. Am. Ceram. Soc. 84 (12) (2001) 2802.
[16] B.D. Cullity, Elements of X-ray Diffraction, 2nd ed., Addison-Wesley,
Reading, MA, 1978, pp. 86106.
[17] R.A. Spurr, H. Myers, Anal. Chem. 29 (1957) 760.
[18] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J.
Rouquerol, T. Siemieniewska, Pure Appl. Chem. 57 (1985) 603.
[19] R.M. German, Simulation of diffusion controlled sphere-sphere sintering,
in: M.M. Ristic (Ed.), Sintering-New Development, Elsevier, Amsterdam,
1977, pp. 1825.
[20] C.H. Chang, R. Gopalan, Y.S. Lin, J. Membr. Sci. 91 (1994) 27.
[21] B.E. Yoldas, Am. Ceram. Soc. Bull. 54 (1975) 286.
[22] K. Maeda, F. Mizukami, M. Watanabe, N. Arai, M. Toba, J. Mater. Sci.
Lett. 9 (1990) 522.