JOURNAL OF COLLOID AND INTERFACE SCIENCE

ARTICLE NO.

193, 140143 (1997)

CS975037

LETTER TO THE EDITOR

Synthesis of Uniform Spindle-Type Titania Particles by the GelSol Method 1

Uniform spindle-type titania (TiO2 ) particles were prepared by

a novel gelsol method. A mixed solution of titanium(IV) isopropoxide and triethanolamine at molar ratio 1:2 prepared in a drybox
was mixed with doubly distilled water to make the final concentration of titanium(IV) 0.50 mol dm03 . The mixture was further
mixed with an equal volume of 2.0 mol dm03 ammonia solution,
and the resulting solution was aged for 24 h at 1007C. By this
aging a highly viscous gel was formed, but there was no sign of
nucleation of titania at this stage. The gel was then aged at 1407C
for 3 days to nucleate and grow the titania particles. The gel
network formed in the first aging played a decisive role in the
second aging to produce the uniform particles of titania, as a
reservoir of the metal ions to lower the supersaturation for preventing extensive nucleation and as an anticoagulant fixing the
growing particles in the matrix. The product was identified by
XRD as anatase particles elongated in the direction of the c-axis.
The aspect ratio, as well as the size of the resulting particles, was
reduced as the concentration of ammonia was decreased. q 1997
Academic Press

Key Words: synthesis; gelsol method; titania; anatase; uniform

particles; spindle-type particles.

INTRODUCTION

Thus, precipitation of pure crystalline titania particles in large quantities

with controlled shape and size is of considerable practical interest. In particular, well-defined anatase-type particles may be useful as photocatalysts.
On the other hand, a novel general method for the preparation of monodisperse particles has recently been invented and developed for the synthesis
of uniform hematite ( a-Fe2O3 ) particles (510). The novel method, named
the gelsol method, for preparation of monodisperse particles in large
quantities is based on the idea of using a highly condensed precursory metal
hydroxide gel as a protective matrix against the coagulation of the growing
particles as well as a reservoir of the metal ions, and it has successfully
been applied to the synthesis of monodisperse CdS (1114), ZnS (13),
and basic aluminum sulfate (15) particles.
This paper pertains to the synthesis of pure and uniform spindle-like
anatase-type particles different in size and aspect ratio in alkaline media as
an application of the gelsol method.

EXPERIMENTAL

Preparation of Uniform Spindle-Type Titania Particles

The established standard conditions for the preparation of uniform spindle-like anatase-type titania particles were as follows. First, a stock solution
of Ti 4/ was prepared by mixing titanium(IV) isopropoxide (TIPO) with
triethanolamine (TEOA) under nitrogen atmosphere at a molar ratio of
TIPO:TEOA 1:2 to form a stable complex of Ti 4/ for preventing the
excessively rapid hydrolysis of Ti 4/ . Doubly distilled water was then added
to make the solution 0.50 mol dm03 in Ti 4/ . Then, 10 cm3 of the stock
solution was mixed with the same volume of 2.0 mol dm03 ammonia solu-

Titania (TiO2 ) particles are widely used as photocatalysts, ceramic materials, fillers, coatings, pigments, cosmetics, etc. For these purposes, it is
strongly desired that the titania particles be uniform and completely controlled in size, shape, and crystal structure. With respect to the preparation
of uniform titania, Matijevic et al. (1) prepared uniform spherical particles
of titania by the forced hydrolysis of Ti 4/ ions in acidic solutions of TiCl4
with sulfate ions. The products were crystalline particles of rutile at lowered
sulfate contents, while, as the sulfate content increased, the proportion of
anatase increased in their mixture. On the other hand, Barringer and Bowen
(2) prepared monodisperse spherical titania by hydrolysis of titanium alkoxides in their dilute alcohol solutions. This method is based on the so-called
solgel process (3), and its advantage is that spherical uniform particles
can be obtained at relatively low temperatures without impurities such as
inorganic anions. However, the products are mostly hydrated amorphous
particles, and titania prepared by this method is also no exception. In addition, uniform titania particles cannot be obtained at a high temperature
necessary for the crystallization or in alkaline solutions in the solgel
systems due to the excessively rapid hydrolysis of titanium alkoxides (4).

Presented in part at the 49th Symposium on Colloid and Interface Chemistry, Hachioji, Japan, September 1921, 1996.

140

0021-9797/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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FIG. 1. Scanning electron micrographs of the TiO2 particles prepared

under the standard conditions (a) and by skipping the first aging for gelation
under otherwise the standard conditions (b).

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141

FIG. 2. Effect of the ammonia concentration on the shape and size of the TiO2 particles. Ammonia concentrations in a suspension were (a) 0, (b)
0.50, (c) 1.0 (standard condition), and (d) 2.0 mol dm03 , where the initial pH values were (a) 9.5, (b) 10.8, (c) 11.3, and (d) 11.6 at room temperature.
The other conditions were the same as the standard.

tion. The resulting solution of pH 11.3 was placed into a screw-capped

Pyrex tube and aged for 24 h at 1007C for gelation. Finally, the gel was
transferred to a Teflon-lined autoclave and aged at 1407C for 3 days to
nucleate and grow the titania particles.
For the study of the reaction conditions, some conditions were altered.

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Characterization of the Particles

After being washed three times with doubly distilled water by centrifugation, the particles were observed using a Hitachi H-600 transmission electron
microscope and a Hitachi S-4100L scanning electron microscope.

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LETTER TO THE EDITOR

FIG. 3. Powder XRD (a) and OPMLXRD (b) patterns of the spindletype TiO2 particles prepared under the standard conditions.

X-ray diffractometry (XRD) was conducted using a Rigaku RAD-B

system with a CuKa beam. For the identification of the products the conventional powder method was applied, while for the determination of the crystallographic direction of the long axis of the spindle-type particles, OPML
(oriented particulate monolayer) XRD (9) was carried out. In the latter,
a few drops of 3 wt% gelatin solution containing 1 wt% of sample powder
were evenly spread over a glass plate and dried at room temperature to
array the elongated particles parallel to the glass plate prior to the XRD.

Figure 2 shows the effect of ammonia on the shape and size of the
obtained titania particles. Namely, the aspect ratio and each volume of the
particles increased with increasing concentration of ammonia, up to 1.0
mol dm03 . When ammonia was not added, the gel was not formed in the first
aging at 1007C, and we finally obtained only small and rather polydispersed
particles of a low aspect ratio after the second aging at 1407C for 3 days,
as shown in Fig. 2a. Even when ammonia was replaced by other bases,
such as sodium hydroxide, to adjust the initial pH to the same level as the
standard system (pH 11.3), the results were the same; i.e., no gelation and
nonuniform product of a similar shape and size. In the case of [NH3 ]
0.50 mol dm03 (Fig. 2b), the solution became viscous, but a rigid gel was
not formed in the first aging. On the other hand, an ammonia concentration
too high lowered the growth rate of the elongated particles in the second
aging, as shown in Fig. 2d in which a considerable amount of gel is found
to remain. In an extreme case of 4 mol dm03 NH3 , the gel formed by the
first aging was not transformed into titania at all by second aging. The
retardation of the phase transformation in the high concentration range of
ammonia above 1 mol dm03 was also observed even when the initial pH
was adjusted to 11.3 with nitric acid. This means that the reaction is retarded
by an excessive increase of free ammonia, even if the concentration of free
Ti 4/ ions is equal to the level of the standard conditions.
The spindle-like particles prepared under the standard conditions were
assigned to the anatase form of titania from the powder XRD profile in
Fig. 3a in complete agreement with the JCPDS data (16). Also, the OPML
XRD pattern (Fig. 3b) demonstrates that the long axis of the spindle-like
particles coincides with the c-axis of the anatase-type crystal.
Ammonia is known for its opposite bifunctional character as an accelerator as well as an inhibitor of particle growth. For instance, in AgBr particle
systems, the rate constant of the surface reaction for the growth in the
direction of 100 of the fcc crystals is lowered by adsorption of ammonia
although the overall growth rate is rather increased due to the increase in
the apparent solubility of AgBr by complexation of Ag / ions with ammonia
(17). The acceleration of the particle growth of the titania particles with
increasing concentration of ammonia up to 1.0 mol dm03 seems to be due
to the increase in the concentration of ammonia complexes of Ti 4/ . On the
other hand, the anisotropic growth of the anatase microcrystals may be
explained in terms of the limited growth rate in the direction normal to the
c-axis due to the strong adsorption of NH3 to the faces parallel to the c-axis.
The pronounced retardation in the total growth of titania by the presence of
the extremely high concentration of ammonia suggests that this inhibiting
factor becomes predominant. More detailed study of the growth mechanism
will be reported elsewhere.

REFERENCES

RESULTS AND DISCUSSION

Figure 1a shows a scanning electron micrograph (SEM) of the spindlelike particles of titania prepared under the standard conditions. In the first
aging process at 1007C, the initially transparent solution turned into a highly
viscous translucent gel. In the second aging at 1407C, the gel was totally
transformed into the final product after 3 days. When the mixed solution
was aged at 1407C for 3 days without the first step for gelation at 1007C, only
bulky aggregates of titania were formed, as shown in Fig. 1b. Obviously, the
gel network preformed at a relatively low temperature, such as 1007C, is
essential for the formation of the uniform TiO2 crystals without coagulation
at the higher temperature (1407C). At the same time, the hydroxide gel
acted as a reservoir of Ti 4/ ions to reduce the excessive supersaturation
leading to extensive nucleation during their growth. Incidentally, the gel
structure was complete within 8 h at 1007C, and additional aging thereafter
till 24 h had no effect on the size or shape of the final product. This may
suggest that the possibility of nucleation of titania in the first step, if any,
is negligibly small.

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1. Matijevic, E., Budnik, M., and Meites, L., J. Colloid Interface Sci. 61,
302 (1977).
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(1982).
3. Brinker, C. J., and Scherer, G. W., SolGel Science. Academic
Press, Boston, 1990.
4. Ikemoto, T., Uematsu, K., Mizutani, N., and Kato, M., Yogyo-KyokaiShi 93, 261 (1985).
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(1992).
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167 (1993).
8. Sugimoto, T., Khan, M. M., Muramatsu, A., and Itoh, H., Colloids
Surf. A 79, 233 (1993).

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9. Sugimoto, T., Muramatsu, A., Sakata, K., and Shindo, D., J. Colloid
Interface Sci. 158, 420 (1993).
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Sci. 176, 442 (1995).
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Sci. 180, 305 (1996).
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Sci. 182, 444 (1996).
15. Sugimoto, T., Itoh, H., and Miyake, H., J. Colloid Interface Sci. 188,
101 (1997).
16. Joint Committee on Powder Diffraction Standards, Diffraction Data

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File No. 21-1272. JCPDS International Center for Diffraction Data,

Swarthmore, PA, 1971.
17. Sugimoto, T., J. Colloid Interface Sci. 93, 461 (1983).
Tadao Sugimoto 2
Kazumi Okada
Hiroyuki Itoh
Institute for Advanced Materials Processing
Tohoku University
Katahira 2-1-1, Aobaku
Sendai 980-77, Japan
Received March 7, 1997; accepted June 19, 1997
2

To whom correspondence should be addressed.

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