3160 Langmuir 1998, 14, 3160-3163

Formation of Titanium Oxide Nanotube

Tomoko Kasuga,*,† Masayoshi Hiramatsu,† Akihiko Hoson,† Toru Sekino,‡ and
Koichi Niihara‡
Electrotechnology Applications R & D Center, Chubu Electric Power Co. Inc.,
Oodaka, Midori-ku, Nagoya 459, Japan, and The Institute of Scientific and
Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567, Japan
Received December 16, 1997. In Final Form: April 8, 1998

Nanotubes composed of various materials such as carbon, boron nitride, and oxides have been studied
recently. In this report, the discovery of a new route for the synthesis of a nanotube made of titanium
oxide is presented. Needle-shaped TiO2 crystals (anatase phase) with a diameter of ≈8 nm and a length
of ≈100 nm were obtained when sol-gel-derived fine TiO2-based powders were treated chemically (e.g.,
for 20 h at 110 °C) with a 5-10 M NaOH aqueous solution. It was found by observation using a transmission
electron microscope that the needle-shaped products have a tube structure. The TiO2 nanotubes have a
large specific surface area of ≈400 m2‚g-1. TiO2 nanotubes obtained in the present work are anticipated
to have great potential for use in the preparation of catalysts, adsorbants, and deodorants with high
activities, because their specific surface area is greatly increased. If metallic-, inorganic-, or organic-based
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materials can be inserted into the TiO2 nanotubes, novel characteristics such as electric, electromagnetic,
or chemical properties may be induced in the TiO2 materials.
Publication Date (Web): May 23, 1998 | doi: 10.1021/la9713816

Introduction much attention is being paid to TiO2 crystals (anatase

Carbon nanotubes, which were found by Iijima et al.,
have great potential as materials with novel properties
that are not found in conventional graphite or carbon
fullerene.1-3 Much research has been conducted on
developing nanotubes with novel properties by controlling
the nanostructure. Recently, pure boron nitride (BN)
nanotubes with the inner diameter 1-3 nm and the length
e200 nm were produced in a carbon-free plasma discharge
between a BN-packed tungsten rod and a cooled electrode.4
Nanotubes made of oxides such as SiO2, Al2O3, V2O5, and
MoO3, with diameters of about several tens of nanometers
have been prepared by templating carbon nanotubes and
subsequently removing the template.5 In the templating
method, carbon nanotubes are indispensable for producing
oxide nanotubes. Needle-shaped TiO2 having the diameter
0.1 ( 0.05 µm and the aspect ratio 40-100 has also been
reported.6 They are expected to be applied as reinforcing
materials or fillers for plastics and ceramics. Recently,
TiO2 nanotubes with diameters of 70-100 nm were
reported to be produced using a replication method.7 Since,
in this method, the dimension of the tubes is controlled
by the pore size of the mold prepared using porous
materials such as alumina, it is not easy to obtain
nanotubes with smaller diameters. We prepared TiO2
nanotubes with the diameter ≈8 nm using a simple method
different from templating or replication.
TiO2 shows a shielding effect against ultraviolet rays.8
TiO2 has been used in various applications such as in
paint, paper, cloth fibers and cosmetics. Since recently,
† Chubu Electric Power Co. Inc.
‡ Osaka University.
(1) Iijima, S. Nature 1991, 354, 56.
(2) Iijima, S; Ichihashi, T. Nature 1993, 363, 603.
(3) Hamada, N., Sawada, S; Oshiyama, A. Phys. Rev. Lett. 1992, 68,
1579.
(4) Chopra, N. G.; Luyken, R. J.; Cherry, K.; Crespi, V. H.; Cohen,
M. L.; Louie, S. G; Zettl, A. Science 1995, 269, 966.
(5) Satishkumar, B. C.; Govindaraj, A.; Voli, E. M.; Basumallic, L.;
Rao, C. N. R. J. Mater. Res. 1997, 12, 604.
(6) Nakamura, H.; Matsui, Y.; J. Am. Chem. Soc. 1995, 117, 2651.
(7) Hoyer, P. Langmuir 1996, 12, 141.
(8) For example: Hird, M. J. J. Coatings Technol.1976, 48, 75.
phase) having photocatalytic activities,9 because they have
great potential for such applications as environmental
purification, decomposition of carbonic acid gas, and
generation of hydrogen gas.10,11 Much effort has been
directed at obtaining high-performance TiO2 powders with
a large surface area. In general, TiO2 powders are
prepared by vapor deposition12 or by precipitation in
solution.13 For preparing very fine TiO2 powders, the sol-
gel method14 using a metal alkoxide is well-known. These
fabrication methods yield TiO2 particles smaller than
several hundreds of nanometers in size. It has been
reported15,16 that TiO2-based powders doped with a small
amount of SiO2 prepared by the sol-gel method with
subsequent heat treatment have large specific surface
areas. After the powders were treated with a strong
aqueous solution of caustic soda, they showed very high
photocatalytic activity in the decomposition of acetic
acid.15,16 In the present work, TiO2 nanotubes with the
diameter ≈8 nm were found to be obtained by controlling
the chemical treatment conditions.
TiO2-SiO2 powders were prepared using a sol-gel
method by the following procedure, as described in our
earlier work.15,16 Commercial reagents such as Ti-
(Oi-C3H7)4 (>99%, Kishida Regents Chemicals) and Si-
(OEt)4 (>99%, Kishida Regents Chemicals) were mixed
with EtOH (>99.5%, Kanto Chemicals), HCl (35-37%,
(9) Fujishima, A.; Honda, K. Nature 1972, 238, 37.
(10) Yamashita, H.; Ichihashi, Y.; Anpo, M. Hyoumen-Kagaku 1995,
16, 194.
(11) Perlizzetti, E; Minero, C. Electrochim. Acta 1993, 38, 47.
(12) For example: Manocha, R. Trans. Ind. Inst. Met. 1953, 7, 95.
Patel, C. C; Jere, G. V. Trans. Am. Inst. Min., Metall. Pet. Eng. 1960,
218, 219.
(13) For example: Prasad, S; Tripathi, J. B. P. J. Ind. Appl. Chem.
1958, 21, 162. Feng, A. A; Hanna, T. R. TAPPI Proc. Plas. Laminates
Symp. 1994, 71.
(14) For example: Prassas, M; Hench, L. L. Ultrastructure Processing
of Ceramics, Glasses and Composites; John Wiley and Sons: New York,
1984; p 101. Livage, J. Mater. Res. Soc. Symp. 1986, 73, 717.
(15) Kasuga, T.; Hiramatsu, M.; Hirano, M.; Hoson, A.; Oyamada,
K. J. Mater. Res. 1997, 12, 607.
(16) Kasuga, T.; Hiramatsu, M.; Hoson, A.; Oyamada, K. Proceedings
of the 2nd International Meeting of the Pacific Rim Ceramic Society,
Cairns, 1996, in press.

S0743-7463(97)01381-4 CCC: $15.00 © 1998 American Chemical Society

Published on Web 05/23/1998
 Letters
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Figure 1. SEM photographs of (a) 80TiO2‚20SiO2 (in mol %) powders prepared by heating at 600 °C and (b) the powders obtained
by treating the powders in part a chemically with 10 M NaOH aqueous solution for 20 h at 110 °C. Numerous needle-shaped products
of ≈100 nm in length are seen.
Publication Date (Web): May 23, 1998 | doi: 10.1021/la9713816
Figure 2. TEM photograph of 80TiO2‚20SiO2 (in mol %)
powders treated with 10 M NaOH aqueous solution for 20 h at
110 °C.
Kishida Regents Chemicals) and H2O so as to obtain
nominal compositions of 80TiO2‚20SiO2 in mole percent;
23.5 mL of Ti(Oi-C3H7)4 and 4.5 mL of Si(OEt)4 were added
to 23 mL of ethanol, respectively, and subsequently, the
resulting solution was stirred for 15 min at room tem-
perature. A mixed solution of 23 mL of ethanol and 18
g of 4.4 M HCl aqueous solution was added slowly to the
mixed solution of Ti(Oi-C3H7)4, Si(OEt)4, and EtOH. The
mixture was held for hydrolysis and gelled in an incubator
at 40 °C at a humidity of 70% for 5 days. The obtained
Langmuir, Vol. 14, No. 12, 1998 3161
Figure 3. Selected-area electron diffraction (SAED) pattern
from Figure 2.
gel was heated to 600 °C and held for 2 h, resulting in the
precipitation of fine TiO2 crystals (anatase phase). No
SiO2-containing crystalline phase was precipitated. Amor-
phous SiO2-related phases are also present. The crystal-
line size was estimated to be 6 nm using XRD patterns
and Sherrer’s equation. The crystallized product was
pulverized into powders of <45 µm. Five milligrams of
the powders was put into a Teflon vessel with 20 mL of
NaOH aqueous solution with the concentration 2.5, 5, 10,
or 20 M. The vessel was then placed in a stainless steel
vessel, which was closed tightly, and held for 20 h at 20,
60, or 110 °C. The treated powders were washed well
with 0.1 N HCl aqueous solution and distilled water and
were subsequently separated from the washing solution
by centrifugation. This operation was repeated until the
washing water showed pH < 7. The residual amount of
the element Si in the powders after the chemical treatment
was estimated to be ≈0.7 mol % by inductively coupled
plasma atomic emission spectroscopic (ICP-AES; SEIKO
SPS-1500VR) analysis. It was found that the amorphous
SiO2 phase in the powders is removed effectively by this
treatment. The residual amount of Na+ ions in the
powders after the treatment was estimated to be ≈0.15
 3162 Langmuir, Vol. 14, No. 12, 1998 Letters
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Figure 4. TEM photographs of needle-shaped products on the sample holder tilted at angles of -20°, 0°, and +20°.
Publication Date (Web): May 23, 1998 | doi: 10.1021/la9713816

mol % by atomic absorption spectroscopic (AAS; SHI-

MADZU AA670) analysis. The specific surface area of
the powders was greatly increased to ≈400 m2‚g-1 after
treatment at 110 °C with 10 M NaOH aqueous solution,
although the specific surface area of the as-precipitated
powders was 150 m2‚g-1. Very fine TiO2 particles can be
obtained by this treatment. It has already been re-
ported13,14 that this process leads to TiO2 powders with
high photocatalytic activities.
Figure 1 shows a scanning electron micrograph (SEM;
HITACHI S5000) of powders treated chemically with 10
M NaOH aqueous solution for 20 h at 110 °C. Numerous
needle-shaped products ≈100 nm in length are seen,
although they are not found in the powders before the
chemical treatment. It is very easy to find the products
by SEM observation, since they are formed everywhere.
The products were formed also by the treatment for 20 h
at 60 °C with 10 M NaOH aqueous solution, but they were
not formed at 20 °C. The treatment at 110 °C led to the
formation of needle-shaped products when NaOH aqueous
solution with the concentration 5 or 10 M was used.
However, when a solution with the concentration <5 M
was used, the products were not formed by the treatment
for 20 h. Dilute NaOH aqueous solution has a poor ability
to form the needle-shaped products.
Small amounts of the chemically treated powders were
dispersed in ethanol in an ultrasonic bath, and the
suspension was dropped onto a perforated carbon grid.
After drying, the powders were observed by transmission Figure 5. Selected-area electron diffraction (SAED) pattern
electron microscopy (TEM; HITACHI H8100) at an from a product in Figure 4.
accelerating voltage of 200 kV. Figure 2 shows a TEM
micrograph of the sample treated with 10 M NaOH TEM photos of the needle-shaped product observed by
aqueous solution for 20 h at 110 °C. Needle-shaped tilting the sample holder at angles of -20°, 0°, and +20°
products with the diameter ≈8 nm are observed. Lattice in TEM, respectively. The dimensions of the products
fringes with 1.5 nm width are present on both sides of the are not changed by tilting the angle. That is, these photos
needle-shaped products, at the distance of ≈5 nm. The indicate that the needle-shaped product is tubelike in
constituent elements of the products were determined to shape. Figure 5 shows an SAED pattern from the product
be Ti and O by energy-dispersive X-ray (EDX) analysis. shown Figure 4. The string pattern is observed, since it
All peaks measured by X-ray diffraction (XRD; RIGAKU is a tube-shaped crystal. To discuss the effect of SiO2
RINT100) analysis could be assigned to the TiO2 crystal doping, commercial TiO2 powders (P25, Nippon Aerosil,
(anatase phase). The selected-area electron diffraction Japan; this sample consists of a mixture of crystalline
(SAED) pattern from agglomerated tube products in TEM phases such as rutile and anatase) were also treated with
observation showed (101), (004), (200), and (105) diffrac- 10 M NaOH aqueous solution for 20 h at 110 °C. The
tions of the anatase phase (Figure 3). Figure 4 shows resultant powders were found to include needle-shaped
 Letters
products. This result indicates that SiO2 plays no role in
the formation of TiO2 nanotubes by our chemical treatment
method.
It was confirmed through several reproducibility tests
that the TiO2 nanotubes (anatase phase) with the diameter
≈8 nm and the length ≈100 nm are formed steadily by
treatment with 10 M NaOH aqueous solution for 20 h at
110 °C.
Although the mechanism of the formation of the nano-
tube is not clear and is under investigation, this work pre-
sents the first evidence that oxide nanotubes can be ob-
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Publication Date (Web): May 23, 1998 | doi: 10.1021/la9713816
Langmuir, Vol. 14, No. 12, 1998 3163
tained easily via chemical treatment, without the need
for molds for replication or templates. Novel nanotubes
with various sizes may be obtained by varying the prepa-
ration conditions. This will be investigated in the near
future.
Acknowledgment. The authors are indebted to Ms.
Kyoko Oyamada of Techno Chubu Company for helpful
discussions and assistance with the experiments.
LA9713816