Chemical Physics Letters 380 (2003) 577582

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Nanotubes of lepidocrocite titanates

Renzhi Ma *, Yoshio Bando, Takayoshi Sasaki
Advanced Materials Laboratory, National Institute for Materials Science, Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan
Received 29 July 2003; in nal form 13 September 2003
Published online: 7 October 2003

Abstract
Titanate nanotubes were synthesized in hydrothermal treatment of anatase titania powders and concentrated NaOH
solution and their structure was investigated. It was suggested that the nanotubes might be constructed from lepidocrocite Hx Ti2
x=4 x=4 O4 x  0:7, : vacancy) sheets. The newly proposed lepidocrocite titanate nanotube model was
supported by X-ray diraction, electron diraction, and thermogravimetry studies.
2003 Elsevier B.V. All rights reserved.

1. Introduction
Since the rst report claiming the hydrothermal
synthesis of titania (TiO2 ) nanotubes [1], there
have been intense researches on the growth and
structure of this kind of peculiar nanotubes owing
to their potential photocatalytic applications [29].
Titania, either anatase or rutile, does not exhibit a
lamellar feature, contradicting the observations of
well-resolved layered walls in the nanotubes. It
was later realized that the nanotubes were actually
not TiO2 , but might be of protonic titanate nature.
Peng and coworkers [8] carried out a structural
investigation presenting that the nanotubes could
be constructed from trititanate (H2 Ti3 O7 , monoclinic, a 1:603 nm, b 0:375 nm, c 0:919 nm
and b 101:45). Trititanate is composed of cor-

Corresponding author. Fax: +81298516280.

E-mail address: MA.Renzhi@nims.go.jp (R. Ma).

rugated ribbons of edge-sharing TiO6 octahedra

(Fig. 1A). The ribbons are three octahedral wide,
and these octahedra join corners to form stepped
sheets. The sheets are separated by H ions in an
inter-sheet spacing of d2 0 0  0:786 nm. According
to this model, the nanotubes are scrolls of single
trititanate sheets. However, this trititanate nanotube model may be not unassailable. For example,
in the X-ray diraction (XRD) patterns of the
nanotubes, the strongest reection peak was observed at d 0:926 nm [3,8]. It was assigned to the
0 0 1 reection d 0:901 nm) of trititanate.
However, the 0 0 1 reection of trititanate should
be very faint compared with the 2 0 0 peak d
0:786 nm). But this 2 0 0 reection peak, supposed
to be the strongest, actually does not appear in
the XRD pattern. Taken in consideration of the
discrepancy, the XRD pattern could not be undoubtedly ascribed to H2 Ti3 O7 . The argument
on the validity of the trititanate nanotube model
thus arises.

0009-2614/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2003.09.069

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R. Ma et al. / Chemical Physics Letters 380 (2003) 577582

Fig. 1. Structure models of H2 Ti3 O7 (A) and lepidocrocite Hx Ti2
x=4 x=4 O4 (B). The unit cells were indicated in red lines.

There are often some sheet-like crystallites coproduced with titanate nanotubes in hydrothermal
procedures [2,4,7]. It is well known that another
protonic titanate, Hx Ti2
x=4 x=4 O4 (x  0:7, :
vacancy) could be readily exfoliated into unilamellar nanosheets through a soft chemistry route
[1013]. Unlike the stepped trititanate sheets,
Hx Ti2
x=4 x=4 O4 host layers are lepidocrocite
c-(FeOOH)-type two-dimensional sheets in which
TiO6 octahedra are combined with each other via
edge-sharing (Fig. 1B). It is worth investigating the
possible relation between the lepidocrocite sheets
and nanotubes.
In this Letter, we revisited the hydrothermal
procedure to titanate nanotubes. After thoroughly
checking the XRD and electron diraction (ED)
patterns together with thermal stability of the nanotubes, we oer strong evidences that it is more
reasonable to suggest the nanotubes are constructed from lepidocrocite Hx Ti2
x=4 x=4 O4
sheets, rather than trititanate ones.

2. Experimental
The method employed for the synthesis of nanotubes was essentially the same as described in
references [2,7]. In a typical procedure, commercial
anatase-type titania powders (2 g) were dispersed
in an aqueous solution of NaOH (10 M, 40 ml)
and charged into a Teon-lined autoclave. The

autoclave was heated at 110150 C for 1272 h.

After the hydrothermal treatment, the precipitate
was separated by ltration and washed with diluted HCl and deionized water. Final product was
obtained through centrifugation and air-dried.
XRD patterns were collected on a Rigaku Rint2000 diractometer with a monochromatized Cu
Ka irradiation (k 0:15405 nm). The product was
also observed by scanning electron microscope
(SEM). Transmission electron microscopy (TEM)
characterizations were performed using a highresolution transmission electron microscopy
(HRTEM, JEM-3000F, JEOL) with energy dispersive X-ray spectrometer (EDS) and electron
energy loss spectrometer (EELS). Thermogravimetric and dierential thermal analyses (TG/DTA)
were carried out in air at a heating rate of 10 C/
min on a Rigaku TG 8120 thermal analyzer.

3. Results and discussion

By optimizing the applied temperature and time
of the hydrothermal treatment, high purity nanotubes could be produced. Fig. 2a shows the SEM
observation on the product after treating anatase
powders in 10 M NaOH at 150 C for 48 h and
subsequent water washing. High purity nanotubes
were entangled together. Fig. 2b depicts a typical
TEM image demonstrating uniform nanotubes with
inner diameters 5 nm and outer diameter 10 nm.

R. Ma et al. / Chemical Physics Letters 380 (2003) 577582

579

Fig. 2. Nanotubes synthesized in hydrothermal procedures. (a) Typical SEM image. (b) Typical TEM shows the high purity uniform
nanotubes. (c) HRTEM demonstrates that the nanotubes are usually three to ve layers. Note the dierent wall thickness on either
side. (d) Sheet-like crystallites co-produced with nanotubes.

The HRTEM observations reveal that nanotubes

are usually three to ve layers in wall thickness
(Fig. 2c). The layer numbers on either side are
usually not equal, indicating they are likely to be
scrolls. In the product, some sheet-like crystallites
were also observed (Fig. 2d). Both the EDS and
EELS clearly identify that the nanotubes and sheets
are composed of Ti and O. There is almost no Na
(detection limit 2 wt%) recorded in the nanotubes.
Taking into consideration of H, they should therefore be attributed to protonic titanate, consistent
with the previous studies [2,8].
Fig. 3 depicts the typical XRD patterns collected from samples before and after the washing
procedure. They are basically the same implying

Fig. 3. XRD patterns from samples before and after washing.

Both are indexed to be lepidocrocite titanates.

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R. Ma et al. / Chemical Physics Letters 380 (2003) 577582

the identical structure origin. The peak at

2h 9:5 corresponding to a d-spacing of 0.93 nm
is observed to be the strongest in both patterns. As
mentioned above, the patterns could not be ascribed to Na2 Ti3 O7 or H2 Ti3 O7 . On the other
hand, all the peaks can be readily indexed to a
lepidocrocite-type titanate phase (e.g., orthorhombic Hx Ti2
x=4 x=4 O4  H2 O, a 0:3783 nm,
b 1:8735 nm and c 0:2978 nm) [1013]. The
broad peaks at 2h 9:5, 24.5, 28, 48 and 62
correspond well with 0 2 0, 1 1 0, 1 3 0, 2 0 0 and
0 0 2 reections of the lepidocrocite titanates. It is
well known that acid leaching and water washing
is essential for the formation of titanate nanotubes
[2,4]. We suspect that lepidocrocite-type sodium
titanate sheets were initially formed in the hydrothermal stage. The subsequent acid leaching and
water washing is believed to exchange Na with

H into Hx Ti2
x=4 x=4 O4 and simultaneously roll

them into nanotubes.
A typical ED pattern taken from a single
nanotube is shown in Fig. 4A. It is characteristic of
a tubular structure exhibiting a series of {0 k 0}
basal spots and streaked {h 0 l} reections [14].
The inter-layer distance measured from the ED
pattern is 0.8 nm, smaller than the d0 2 0 (0.93 nm)
in XRD. In Pengs work, they have also measured
an inter-layer distance of 0.78 nm in tube walls
from HRTEM images and ED patterns. They assigned it to d2 0 0 of trititanate. It is well known that
titanates may be dehydrated during microscopic
observations due to the high vacuum environment,
leading to some shrinkage in the inter-layer spacing. Thus the inter-layer distances measured from
ED pattern and HRTEM image might not be accurate and most likely to be decreased with the loss

Fig. 4. (A) Typical ED pattern from nanotubes. It is characteristic of tubular structure. The inter-layer distance in the walls was
measured to be 0.8 nm due to inter-layer shrinkage in microscopes. The other spots exhibit a face-centered rectangular reciprocal unit
cell a 0:38 nm, c 0:30 nm). (B) Typical ED pattern from sheet-like crystallites. The face-centered rectangular reciprocal unit cells
are also apparent. (C,D) The comparison of single sheet structure models of Hx Ti2
x=4 x=4 O4 and H2 Ti3 O7 . Only Hx Ti2
x=4 x=4 O4
projected along the sheet normal (a 0:3783 nm, c 0:2978 nm) agrees with the ED characterizations.

R. Ma et al. / Chemical Physics Letters 380 (2003) 577582

of hydrated water. We therefore consider it is

reasonable to index the 0.8 nm distance to d0 2 0
of Hx Ti2
x=4 x=4 O4 . The other spots in the ED
pattern clearly exhibit a face-centered rectangular
reciprocal cell. It agrees well with the two-dimensional diraction of Hx Ti2
x=4 x=4 O4 sheets
a 0:38 nm, c 0:30 nm) projected along the
sheet normal, i.e., [0 1 0] zone axis [12].
The ED pattern from a sheet-like crystallite is
shown in Fig. 4B. There are two sets of diraction
spots in the pattern, indicating that the sheet-like
crystallite is composed of turbostatic stacking of
two sets of nanosheets. The streaked diraction
spots imply that there is some rotation with respect
to each other in the stacked sheets. Each set of the
spots also clearly demonstrates a face-centered
rectangular reciprocal unit cell as indicated in
Fig. 4B.
The feature of a face-centered rectangular reciprocal cell, both from nanotubes and sheets, is
the same with the diraction feature of body-centered Hx Ti2
x=4 x=4 O4 projected along its sheet
normal and cannot be attributed to trititanate. The
schematic models of a single sheet of both
Hx Ti2
x=4 x=4 O4 and H2 Ti3 O7 are compared in
Fig. 4C,D, respectively. The H2 Ti3 O7 single sheet
has a rectangular unit cell of b 0:375 nm,
c 0:919 nm. Even a possible modulation eect is
considered in the H2 Ti3 O7 single sheets [15], i.e., a
1/3 repetition of c axis creating a pseudo subunit of
b 0:375 nm, c 0:306 nm, it still does not satisfy
with the face-centered feature. Furthermore, the
pseudo structural subunits should lead to a triple
multiplicity of reections along c -axis in ED
patterns projected along the sheet normal. However, the actually observed ED patterns (Fig. 4A,B)
do not exhibit such a triple multiplicity. It is apparent that only the Hx Ti2
x=4 x=4 O4 on the projection along the sheet normal a 0:3783 nm,
c 0:2978 nm) is consistent with the face-centered
rectangular reciprocal unit cell characterized in
ED patterns. It is noteworthy that such complete
and detailed ED patterns capable of identifying
the unit cell of the nanotubes and sheets were
failed to provide in previous studies [7,8].
We further measured the thermogravimetry behavior of the nanotubes in air. Fig. 5a depicts a
typical TG curve. The nanotubes show a weight loss

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Fig. 5. Thermogravimetry behavior of nanotubes. (a) TG curve

exhibits a 13% weight loss after heated to 1000 C in air. (b)
XRD comparison demonstrates a direct crystallization into
anatase above 500 C. (lower) Starting nanotubes. (upper)
Anatase.

13% after heated to 1000 C. The 13% weight

loss is too large for the dehydration of H2 Ti3 O7 , in
which approximate 7% is expected [16]. The TG
prole also shows a quick dehydration rate, losing
10% weight at 140 C. This may be another evidence to identify the lepidocrocite structure of the
nanotubes. Lepidocrocite-type layered titanate
tends to lose weight more quickly than H2 Ti3 O7
[16,17]. The latter has hydroxylated protons, which
needs higher temperature to dehydrate. When the
heating temperature reached 500 C, the nanotubes
were transformed to anatase. Fig. 5b shows the
comparison of XRD patterns from the starting nanotubes and that heated to 500 C. It clearly identies a transformation into the anatase phase. This
transformation is in contrast to the dehydration
behavior of trititanate. For trititanate, owing to
their steeped sheets, they are supposed to yield a

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R. Ma et al. / Chemical Physics Letters 380 (2003) 577582

novel polymorph of titanium oxide, TiO2 (B), at

500 C before transforming into anatase at higher
temperature [16]. However, lepidocrocite-like Hx
Ti2
x=4 x=4 O4 is directly crystallized into anatase
without forming this intermediate phase of TiO2 (B)
[17]. Taking into account of this dierence in dehydration behavior, it is also convincing to suggest
the nanotubes in Hx Ti2
x=4 x=4 O4 structures, rather than trititanate ones.
It is rather surprising that the lepidocrocite
sheets and nanotubes are formed in a Na-rich
environment where Na2 Ti3 O7 is generally supposed to be stabilized. One possible explanation is
that the hydrothermal procedure is quite dierent
from the conventional solid calcinations methods
previously employed to produce alkali metal titanates of stoichiometric compositions [16]. The
true reason why sodium can stabilize a lepidocrocite phase is intriguing and an open question remaining to be investigated. In addition, related
researches
have
demonstrated
that
the
Hx Ti2
x=4 x=4 O4 single sheets exhibit some signicant optical properties, e.g., a very sharp optical absorption peak appreciably blue-shifted
relative to the band gap of bulk titania [11]. It is
thus of genuine interest to probe the optical and
photocatalytic properties of the lepidocrocite titanate nanotubes.

4. Conclusions
In summary, we investigated the structure of
titanate nanotubes synthesized in hydrothermal
treatment of anatase titania powders and concentrated NaOH solution. Based on XRD, ED and
TG results, we conclude that the titanate nanotubes consist of lepidocrocite Hx Ti2
x=4 x=4 O4 , rather than H2 Ti3 O7 as previously demonstrated.
This may clarify some misunderstanding of the

titanate nanotubes in hydrothermal procedures

and predict some peculiar properties for future
applications.

Acknowledgements
This work has been supported by CREST of
JST (Japan Science and Technology).

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