Journal of Ceramic Processing Research. Vol. 11, No. 6, pp.

736~741 (2010) J O U R N A L O F

Ceramic
Processing Research

Reaction morphology and the effect of pH on the preparation of TiO2 nanoparti-

cles by a sol-gel method
Chang Sung Lima, Jeong Ho Ryub,*, Do-Hwan Kimc, Sung-Yong Choc and Won-Chun Oha
a
Department of Advanced Materials Science & Engineering, Hanseo University, Seosan 356-706, Korea
b
R&D Institute, Samsung LED Co., LTD., 314, Maetan3-dong, Yeongtong-gu, Suwon 443-743, Korea
c
Department of Environmental Engineering, 77 Yongbong-ro, Buk-gu, Gwangju 500-757, Korea

Titanium dioxide nanoparticles were prepared by hydrolysis of titanium tetra-isopropoxide. Aqueous solutions with various
pH and the resultant reaction morphology on the preparation of TiO2 nanoparticles were investigated. The influence of pH
on the reaction morphology of using a titanium tetra-isopropoxide was evaluated depending on the amounts of the catalysts
such as HCl and NH4OH. The morphology and phase transformation of TiO2 particles prepared by the hydrolysis of titanium
tetra-isopropoxide were strongly influenced by the presence of the catalysts. In the case of using NH4OH, the morphology of
the TiO2 particles exhibited a powder form. In the case of using HCl, it showed a bulk or granular form. The phase
transformations of amorphous Ti(OH)4 to anatase TiO2 and the anatase to rutile were significantly influenced by the type and
the amount of the catalysts.

Key words : TiO2 nanoparticle, hydrolysis, TTIP, pH, reaction morphology.

Introduction The anatase phase is thermodynamically metastable and

easily transforms into the stable rutile phase, however, when
Nanosized TiO2 has attracted increasing attention in the TiO2 is calcined at high temperature. Moreover, anatase
scientific community for its wide applications in photo- TiO2 with a higher crystallinity means fewer defects for the
catalysts, solar cells, gas sensors and optoelectronic devices recombination of photogenerated electrons and holes [12].
[1, 2]. The applications of TiO2 arise primarily from its Rutile TiO2 has been shown to be negligibly photoactive for
physicochemical properties, such as crystalline structure, the photo-oxidation of many organic pollutants in aqueous
particle size, specific surface area, porosity and thermal media, but its resistance to disaggregation is higher than
stability. Controllable synthesis of nanosized TiO2 particles that of anatase TiO2 [11, 12].
with these propereties, especially crystalline structure, repre- The increase of the lifetime of the photo-produced pairs,
sents some of the key subjects in its applications. In recent due to hole and electron transfer between the two coupled
years, semiconductor photocatalysis has attracted a great semiconductors, is invoked in many cases as the key factor
deal of research attention due to its potential application for the improvement of the photoactivity. Nevertheless, it
to solve environmental problems [3-5]. Among the various should be considered that photoactivity also strongly depends
semiconductors employed, TiO2 is versatile material and on bulk and surface physicochemical properties of the
good photocatalyst for the degradation of environmental photocatalysts, such as the type of phases, the surface
contaminants due to its high photocatalytic avtivity, absence hydroxylation, the porosity, the surface area, the adsorption
of toxicity, relatively low cost, and excellent chemical capacity, the distribution of the supported photoactive com-
stability under various conditions [6-8]. The excellent photo- ponent, and the surface acid-base properties [13-15]. The
catalytic property of TiO2 is due to its wide band gap and physical, chemical, and photochemical properties of TiO2
the long lifetime of photogenerated holes and electrons. With nanoparticles are dependent on the manufacturing method.
an appropriate light source, a TiO2 photocatalyst generates To enhance the application of TiO2, several processes have
electron/hole pairs to initiate a series of chemical reactions been developed over the last decade and can be classified
that eventually mineralize the pollutants [9, 10]. as liquid process sol-gel [16-21], solvothermal [22, 23],
TiO2 usually exists in the form of anatase, rutile and hydrothermal [24-26], solid state processing routes (me-
brookite. In a photocatalytic study, anatase TiO2 is generally chanochemical alloying/milling) [27-30], thermal hydrolysis
considered to be more active than rutile crystalline [11]. [31, 32] and other routes such as laser evaporation [33],
and ultrasonic synthesis [34]. However, TiO2 particles
*Corresponding author:
prepared by these processes are relatively large with inhomo-
Tel : +82-31-2103089 geneous morphologies. From the above methods, the sol-gel
Fax: +82-31-3007900(#3466) method is normally used for the preparation of nanosized
E-mail: jimihen.ryu@samsung.com TiO2 particles. The sol-gel process has notable advantages
736
Reaction morphology and the effect of pH on the preparation of TiO2 nanoparticles by a sol-gel method 737

such as high purity, good uniformity of the microstructure, The crystalline phases and average crystallite sizes after
low temperature synthesis, easily controlled reaction con- heat-treatment were identified by powder X-ray diffraction
ditions, and hence has been widely adopted for preparing (XRD, CuKα, 40 kV, 30 mA, Rigaku, Japan) with a scan
nanostructured TiO2 particles. rate of 3 oC/min. The particle size and microstructural
There are several parameters for controlling the sol-gel morphology of the nanocrystalline powders were observed
process to prepare TiO2 particles with significant properties. by scanning electron microscopy (SEM, JSM-35CF, JEOL).
It has been demonstrated that the precursor’s concentration
of precursor titanium alkoxide greatly affects the crys- Results and Discussion
tallization behavior and the characteristics of the final
particle [35-37]. The size, stability, and morphology of the The preparation of the TiO2 colloids in the nanometre
sol produced from alkoxide is strongly affected by the range can be effectively conducted through the hydrolysis
hydrolysis and pH. The pH of the prepared solution has and condensation of titanium alkoxides in aqueous media.
a great influence on the final size of TiO2 nanoparticles In the presence of water, alkoxides are hydrolysed and
[38-42]. The reaction morphology and the effect of the pH subsequently polymerized to from a three-dimensional oxide
on the formation of TiO2 particles is of great interest, network. These reactions can be schematically represented
because nanosized particles are formed under these con- as follows:
ditions. Therefore, a controlled pH and reaction morphology
are required for the optimization of the preparation con- Ti(OR)4 + 4H2O → Ti(OH)4 + 4ROH (hydrolysis) (1)
ditions of TiO2.
In this study, TiO2 nanopartices were prepared by the Ti(OH)4 → TiO2·xH2O + (2-x)H2O (condensation) (2)
sol-gel route using titanium tetra-isopropoxide. The reaction
morphology was investigated depending on the amounts where R is ethyl, i-propyl, n-butyl, etc. [43]. It is well known
of HCl and NH4OH, and the effect of the pH on the that the tetravalent cations are too acidic so that the nucleation
preparation of TiO2 nanoparticles was studied. Subsequently, of the stable hydroxide Ti(OH)4 cannot occur. Water
the phase transformations of amorphous Ti(OH)4 to anatase molecules formed according to reaction (2) always bear
TiO2 and anatase to rutile was investigated in detail. a positive partial charge. Therefore, oxolation and olation
can proceed simultaneously during nucleation and growth
Experimental leading to an amorphous oxide TiO2·nH2O where the
number n of water molecules depends on the experimental
Titanium tetra-isopropoxide (TTIP, Ti(OCH(CH3)2)4) and conditions. Depending on the experimental procedure, the
isopropyl alcohol (IPA, C3H8O) were mixed in the molar precipitation of TiO2 leads to rutile or anatase phases
ratio of 1 : 10 and stirred for 1 hour. Another solution was [44, 45]. The stage of deoxilation prior to olation can be
prepared from a mixture of H2O and IPA with a molar controlled by adjusting the pH and initial water concen-
ratio of 10 : 1. This solution was then titrated into the TTIP- tration. This control leads to precipitation of anatase nono-
IPA solution and stirred for 2 h until a uniform colloidal particles of TiO2 in the experimental procedure.
TiO2 sol was produced. A TiO2 sol is chemically very Table 1 shows the effect of catalysts of NH4OH/HCl,
unstable in the neutral pH range and therefore it easily the molar ratio of catalyst/TTIP, and pH on the morphology
agglomerates when it transforms into the gel state. However, and crystalline structure of the TiO2. When the catalyst
this instability can be controlled by adding an acid. is NH4OH or there is none in the solution with the pH
Solutions with various pH were used as the hydrolysis level from 10.07 to 5.04, powder forms with amorphous
catalyst. The desired pH value of the solution was adjusted
by adding HCl and NH4OH. The gel preparation process
started when both solutions were mixed together under Table 1. Effect of catalysts of NH4OH/HCl, the molar ratio of
vigorous stirring. After the peptization process, the volume catalyst/TTIP, and pH on the morphology and crystalline structure
of the solution decreased and a suspension was produced. of the TiO2
Depending on the preparation conditions, the resultant molar ratio crystal
samples catalyst pH morphology
suspension was white-blue or opaque with a high viscosity. catalyst/TTIP structure
The viscous solution was dried at 100 oC in an oven for N 1.00 NH4OH 1.0 10.07 powder amorphous
24 h. After being washed with ethanol and dried at 100 oC N 0.50 NH4OH 0.5 9.45 powder amorphous
in an oven for 10 h, a yellow-white powder was obtained.
Finally, the prepared powder was heat-treated at tem- N 0.25 NH4OH 0.25 7.77 powder amorphous
peratures ranging from 200 to 600 oC for 3 h. N 0.00 no catalyst 0.0 5.04 powder amorphous
Several techniques were employed for characterization H 0.05 HCl 0.05 3.96 agglomerate amorphous
of the powders. The crystallization process of the precursor
H 0.10 HCl 0.1 2.95 granule amorphous
was evaluated by thermogravimetry-differential thermal
analysis (TG-DTA, SETRAM, France), using a sample H 0.25 HCl 0.25 2.12 bulk anatase
weight of about 24 mg and a heating rate of 10 oC/min. H 0.50 HCl 0.5 1.90 bulk anatase
738 Chang Sung Lim, Jeong Ho Ryu, Do-Hwan Kim, Sung-Yong Cho and Won-Chun Oh

phases were observed. Otherwise, when the catalyst is micrographs of the TiO2 powders dried at 100 oC with HC
HCl in the solution with the pH level from 3.96 to 1.9, an as the catalyst. It showed a granular form for pH 3.96 in
agglomerated granular and bulk form with amorphous Fig 2(a) and a bulk-like form for pH 2.95(b), 2.12(c), 1.92(d).
and anatase phases were observed. Therefore, TiO2 nano- The effect of pH on the TiO2 nanopowder after heat-
particles with various morphologies and crystal structures treatment was evaluated for the crystalline phase and size.
were synthesized by the hydrolysis reaction of titanium Fig. 3 shows XRD patterns of TiO2 powders calcined for
tetra-isopropoxide using the molar ratio of catalyst and 3 h at (a) 200, (b) 300, (c) 400 and (d) 500 oC with NH4OH
TTIP with various pH values in acid and base solutions. as the catalyst; (A) NH4OH/TTIP = 0.5, (B) NH4OH/TTIP =
The morphology and phase transformation of TiO2 powder 0.25. The representative (101) plane diffraction peak at
prepared by hydrolysis of titanium tetra-isopropoxide were 25.3o is used for anatase and (110) peak at 27.5o for rutile.
strongly influenced by the presence of the catalysts HCl This shows that the anatase phase was observed above
and NH4OH. 200 oC, while the rutile phase above 500 oC. In the case of
Fig. 1 shows SEM micrographs of the TiO2 powders (A) NH4OH/TTIP = 0.5 (pH 9.45), the rutile phase was
dried at 100 oC with NH4OH as the base catalyst or none. increased compared to the case of (B) NH4OH/TTIP = 0.25
The TiO2 powder exhibited a homogeneous spherical mor- (pH 7.77) in Fig. 3. The effect of calcination temperature
phology and a particle size distribution with sizes of 100- on the crystallization with HCl as the catalyst was also
200 nm for pH 10.67 in Fig. 1(a) and 9.45 in Fig 1(b). investigated. Fig. 4 shows XRD patterns of TiO2 powders
The particle morphology and particle size distribution calcined for 3 h at (a) dried, (b) 200, (c) 300 and (d) 400
had an inhomogeneous tendency to decrease depending and (e) 500 oC with HCl as the catalyst; (A) HCl/TTIP =
on a relatively lower pH value of 7.77 in Fig. 1(c) and 0.25, (B) HCl/TTIP = 0.5 in Fig. 4. It shows that the anatase
5.04 in Fig 1(d). On the other hand, Fig. 2 shows SEM phase was observed above 100 oC and the rutile phase
was observed above 500 oC in the case of (A) HCl/TTIP =

Fig. 1. SEM micrographs of the TiO2 powders dried at 100 oC

with NH4OH as the catalyst or none; (a) pH 10.67, (b) pH 9.45, (c)
pH 7.77 and (d) pH 5.04.

Fig. 3. XRD patterns of TiO2 powders calcined for 3 h at (a) 200,

Fig. 2. SEM micrographs of the TiO2 powders dried at 100 oC with (b) 300, (c) 400 and (d) 500 oC with NH4OH as the catalyst; (A)
HC as the catalyst; (a) pH 3.96, (b) pH 2.95, (c) pH 2.12 and (d) pH 1.92. NH4OH/TTIP = 0.5, (B) NH4OH/TTIP = 0.25.
Reaction morphology and the effect of pH on the preparation of TiO2 nanoparticles by a sol-gel method 739

Table 2. Formation of various phases for the TiO2 powders as a

function of pH and calcination temperature
sample pH dried 200 300 400 500
N 1.00 10.07 Am Am A A A+R
N 0.50 9.45 Am Am A A A+R
N 0.25 7.77 Am Am A A A+R
N 0.00 5.04 Am Am A A A+R
H 0.05 3.96 Am Am A A A
H 0.10 2.95 Am Am A A A
H 0.25 2.12 A A A A+R A+R
H 0.50 1.90 A A A+R A+R A+R
*Am : amorphous, A : anatase, R : rutile

Fig. 4. XRD patterns of TiO2 powders calcined for 3 h at (a)

dried, (b) 200, (c) 300 and (d) 400 and (e) 500 oC with HCl as the Fig. 5. Calculated rutile weight fractions of the TiO2 powders as a
catalyst; (A) HCl/TTIP = 0.25, (B) HCl/TTIP = 0.5. function of pH.

0.25(pH 2.12), while the rutile phase was increased above X = 1/(1 + 0.8 IA/IR) (3)
400 oC in the case of (B) HCl/TTIP = 0.5(pH 1.92) in Fig. 4.
Table 2 shows the formation of various phases for the where,
TiO2 powders as a function of pH and the calcination X ; weight fraction of rutile in the powders
temperature (Am : amorphous, A : anatase, R : rutile). When IA ; X-ray integrated intensity of the strongest peaks
the temperature was raised, the anatase phase transformed of anatase (2θ = 25.3o, (101) plane)
to the rutile phase, which could be attributed to the thermally- IR ; X-ray integrated intensity of the strongest peaks
promoted crystallite growth. In particular, the phase trans- of rutile (2θ = 27.5o, (110) plane)
formation of amorphous Ti(OH)4 to anatase TiO2 and anatase
to rutile were significantly activated by the HCl catalyst. The anatase to rutile transformation is shown as a function
On the other hand, the phase transformation and the of the temperature and pH level in Fig. 5. It is noted
crystallization of the particles were not activated by the that the temperature of the rutile ratio is shifted to a low
NH4OH catalyst. This reveals that nucleation and growth temperature of 300-400 oC in strong acid. This is attributed
of the rutile phase have been initiated at temperatures to the high surface energy of the particles in strong acid.
somewhere from 400-600 oC. It may be assumed that the Therefore, the rutile ratio increases rapidly depending on
growth of rutile crystallization was affected by the pH the lower pH level as well as at higher temperatures, while
value of acid. increases slowly at the higher pH level. It is assumed that
Fig. 5 shows the average calculated weight fractions of the anatase phase has been eliminated following large rutile
anatase as a function of the calcination temperature. The particles with poor agglomeration, and aggregation takes
existing phase in the powder after heat-treatment was place during the particle growth process at higher tem-
identified by XRD. The weight fraction of rutile in the peratures.
powders was estimated in the following equation [46]. The average crystallite size of the heat-treated powders
740 Chang Sung Lim, Jeong Ho Ryu, Do-Hwan Kim, Sung-Yong Cho and Won-Chun Oh

titanium tetra-isopropoxide were strongly influenced by the

presence of catalysts. In the case of NH4OH, the morphology
of the TiO2 powder exhibited a powder form. In the case
of HCl, it showed a bulk or granular form. The phase trans-
formations of amorphous Ti(OH)4 to anatase TiO2 and
anatase to rutile were significantly activated by the HCl
catalyst. On the other hand, the phase transformation and
the crystallization of the particles were not activated by
the NH4OH catalyst.

Acknowledgement
This research was supported by Basic Science Research
Program through the National Research Foundation of
Korea(NRF) funded by the Ministry of Education, Science
and Technology (2010-0023911).
Fig. 6. Average grain size of anatase as a function of calcination
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