TiO2 nanocrystals fabricated with hydrothermal method

FU Sanling, LIU Shuhua*

College of Science, Agricultural University of Hebei, Baoding 071001

ABSTRACT
Pure rutile TiO2 nanorods are fabricated using TiCl3 as the predecessor at 180°C for 24h. TiO2 nanomaterials turn into
pure anatase when KF serves as mineralizer and the concentration of KF solution is higher than a proper concentration. It
is indicated that the fluorin-ion has a great effect on the phase transition of TiO2 crysta1. The length and diameter of
nanocrystal granules also change when changing the concentration of KF solution. The anatase TiO2 nanocrystals are
synthesized at 150°C for 24h with TiCl3 and titanate sodium nanotubes as the predecessors at the filling factor of 68%.
Keywords: Nanocrystals, TiO2, Hydrothermal method, Mineralizer, Doping

1. INTRODUCTION
TiO2 is a kind of important inorganic functional material and can be applied in many fields such as light emission, gas
sensors, solar cells, and so on[1,2]. Recent years, it attracts worldwide interest to study TiO2 nanocrystal solar cells for its
low costs, longevity and relative higher light-electricity conversion efficiency. TiO2 nanocrystal has three structures in
nature, which are rutile, anatase, and brookite. The Density of rutile TiO2 nanocrystal is the largest in the three states and
the anatase is the smallest. Brookite structure is not applied widely because of its instability. Anatase TiO2 nanocrystal
has higher light-electricity conversion efficiency. Rutile structure has more stable structure, higher cover capability, and
relative higher ultraviolet radiation absorption capability. According, synthesizing pure rutile and anatas TiO2
nanocrystal has promising application value in the future. Many methods can be used to fabricate TiO2 nanocrystals such
as sol and gel method, homogeneous deposition method, tiny emulsification method, hydrothermal method and so on,
among which hydrothermal method is one of the most popular methods for its advantages of friendly environment,
higher purity, uniform size, easy industrialized produce, etc [3-4]. Hydrothermal method is to make a high temperature and
high pressure environment by heating the special-made autoclave. It provides a special physics-chemistries condition
which is difficult to realize in atmosphere pressure.

2. EQUIPMENTS AND METHODS

The low-temperature reaction is realized in the polytetrafluoroethylene-lined stainless steal autoclave with a cubage of
25ml. The high-temperature reaction is realized in the auto-locking single-pore minitype metal-lined autoclave with a
cubage of 8.2ml. The heating adopt the SG2-7.5-10 crucible stove with a temperature controller. The obtained samples
are analyzed with X-ray energy dispersive spectrometer (EDS), X-ray diffraction (XRD), and transmission electron
microscope (TEM).

3. RESULTS AND DISCUSSION

3.1 Synthesize pure rutile TiO2 nanocrystals
3.1.1 Experiments
To Synthesize the pure rutile TiO2: Making two groups of 5ml pure TiCl3 solution, one of which add pure deionized
water only, and the other add NaCl of 10mol/L serves as mineralizer. After mixing homogeneously by stirring, the two
groups of solution are poured into two autoclaves (filling factor is 68%), the autoclaves are sealed and heated to 180°C.
Keep the temperature for 24h and then cool down to the room temperature naturally. Take out the samples from the
autoclaves and rinse them with deionized water repeatedly till pH=7, then dry them with infrared lamp.
3.1.2 Results and discussion
Figure 1 shows the transmission electron microscope image obtained using TiCl3 as the predecessor. Figure 2 shows the
corresponding X-ray diffraction pattern of the sample in figure 1. The peak positions of the XRD patterns are consistent

*
Supported by the non-living and rising scientific research project of Hebei Agricultural University, key project: No.FSZ200631.
Corresponding author: Liu Shuhua

4th International Symposium on Advanced Optical Manufacturing and Testing Technologies: Design, Manufacturing,
and Testing of Micro- and Nano-Optical Devices and Systems, edited by Sen Han, Masaomi Kameyama, Xiangang Luo
Proc. of SPIE Vol. 7284, 72840B · © 2009 SPIE · CCC code: 0277-786X/09/$18 · doi: 10.1117/12.832069

Proc. of SPIE Vol. 7284 72840B-1

 A 10000

8000

intensity(a.u.)
6000

4000

2000

0
20 30 40 50 60 70 80
2θ(degree)

Figure 1: Transmission electron microscope image of Figure 2: X-ray diffraction pattern of the
the sample obtained using TiCl3+ 10mol/L NaCl sample in figure 1

with the standard diffraction pattern of rutile TiO2, so both of the samples are pure rutiles. And from the transmission
electron microscope image it can be seen that they are both nanorods. When only TiCl3 serves as mineralizer, the
diameter of the nanorod is ca. 40-100nm. When the mineralizer NaCl is added, the length of the nanorod is about
100-500nm and the diameter becomes 50-80nm.
3.2 Synthesize pure anatase TiO2 nanocrystals
3.2.1 Experiments
To synthesize the pure anatase TiO2 : KF are added into TiCl3 solution with different concentration. Put them into
autoclaves after mixing homogeneously. The filling factor is 68%. The autoclaves are sealed and heated to 180°C for 24h.
Take out the samples from the autoclaves and rinse them with deionized water till pH=7, then dry them.
3.2.2 Results and discussion
Figure 3 shows the transmission electron microscope image of the sample obtained using TiCl3 as the predecessor and
adding KF with concentration of 0.7 mol/L severs as mineralizer. Figure 4 shows the corresponding X-ray diffraction
pattern of the sample in figure 3. From figure 4 we can see clearly that the obtained sample is pure anatase TiO2.

bOpm
15000

12000
intensity(a.u.)

9000

6000

e 3000

0
20 30 40 50 60 70 80
2θ(degree)

Figure 3: Transmission electron microscope image of Figure 4: X-ray diffraction patterns of the
the samples obtained when KF with concentration of obtained crystal corresponding to the
0.7 mol/L serve as mineralizer. sample in figure 3.

In the experiments, KF with different concentration (0.05mol/L，0.2mol/L，0.7mol/L，1mol/L) are added into TiCl3
solution to find the influence of KF. It is found that when the concentration of KF is low（0.05mol/L）, the length of the
crystal is ca. 130-150nm, the diameter is 30-50nm which becomes a little shorter compared with pure TiCl3 as the
predecessor. When increasing the concentration of KF, the crystal displays a square morphology. The results shows that
the TiO2 nanomaterials turn into pure anatase when the KF serves as mineralizer and the concentration of KF solution is

Proc. of SPIE Vol. 7284 72840B-2

higher than 0.2mol/L. And the length of the crystal decreases from ca.
100nm to 50nm. Figure 5 shows the length of the obtained

Length of the nanocrystals/nm

nanocrystals versus the concentration of KF. It can be seen that the 140

length of the TiO2 nanocrystals decreased as the concentration of KF

120
increased. Furthermore, the crystal has better square morphology and
nicer dispersive property as the concentration of KF is increased.
100

It can be seen from the experiment results above that the fluorin-ion
80
has a great effect on the phase transition of anatase TiO2 crysta1, and
the diameter of the nanocrystal grain changes when changing the 60
concentration of KF solution. In the experiment, the strong acid
condition is changed when KF is added. By calculating the 0.0 0.2 0.4 0.6 0.8 1.0

hydrolysis ratio, it is concluded that the phase transformation of the Concentration of KF

crystal is owing to the single-polymer structure formed in the Figure 5: Length of the obtained nanocrystals
hydrolyze course. Rutile formed in strong acid circumstance. versus the concentration of KF.
Titanium-ion mainly exist in the form of [TiO(OH2)5] 2+. The
single-polymer forms straight-chain multi-polymer by losing two water numerators, and produces the crystal nucleus of
rutile consequently. Under weak acid or strong alkaline condition, Titanium-ion mainly exist in the form of [Ti（OH）
2+
2·(OH2)4] . The straight-chain multi-polymer forms when the two water numerators have been lost. The granules in
TiO2 sol gradually form unabridged three dimensional structure networks. One Titanium-ion can co-ordinate with 6 O2- to
form TiO62-. The TiO62- octahedron units can form long-range order Ti-O crystal structure in two different modes, which
are share-fringe and share-acme. Anatase has share-fringe structure, while rutile has both share-acme structure and
share-fringe structure. In the terms of dynamics, it is more difficult to form share-acme structure. Accordingly, in the
normal temperature and acid condition, TiO62- octahedron tend to share-fringe and form the anatase TiO2 crystal[5,6]. The
microcosmic mechanism needs further study.
3.3 Effect on crystal morphology by changing predecessors
3.3.1 Experiments
To synthesize titanate sodium nanotubes: take 2g TiO2 , mix with
10mol/L NaOH proportionally, after stirring homogeneously, put
them into polytetrafluoroethylene–lined autoclaves (the filling
factor is 68%), seal the autoclaves and heat them to 150°C for 24h
and then cool down to the room temperature naturally. Take out the
samples from the autoclaves and rinse them with deionized water
till pH=7, then dry them with infrared lamp and the titanate sodium
nanotubes is obtained. Figure 6 shows its morphology picture. The
crystal has lone-thin tube-like morphology with the diameter of
8-10nm, and the length of 500nm. Figure 6: Transmission electron microscope
images of the titanate sodium nanotubes
To synthesize titanic acid: take titanate sodium nanotubes
proportionally dip in 10% HCl for hours. Then rinse them with
deionized water till pH=7 and dry them.
To synthesize titanic acid nanotubes: take the titanic acid samples obtained above proportionally and sinter them at
400°C for 2h.
To synthesize anatase TiO2 nanorods: Put 5ml TiCl3 and 1.0mol/L KF into autoclaves with the filling factor of 68%. Heat
it to 150°C for 24h. And then make them cool and dry.
3.3.2 Results and discussion
Figure 7 shows a transmission electron microscope image of the obtained TiO2. It is nanorod. From the X-ray diffraction
pattern it can conclude that all the obtained samples are pure anatase nanocrystals. Figure 8 shows the diameter variation

Proc. of SPIE Vol. 7284 72840B-3

 100

Diameter of the nanocrystals/nm

h
80
(B)

60
(A)
40

20 (C) (D)
1.

1 2 3 4
Figure 7: Transmission electron microscope samples
images of the TiO2 nanocrystals obtained with Figure 8: Diameter of the crystal obtained
titanate sodium+ HCl(10%) +TiCl3+KF with different predecessors

of crystal with different predecessors. (A) is synthesized at 150°C for 24h with 5ml TiCl3 and 1.0mol/L KF as the
predecessors at the filling factor of 68%. The diameter of the obtained samples is ca. 40-60nm. (B) is obtained by adding
proper titanate sodium nanotubes. It has a relative uniform morphology. (C) is obtained by adding proper titanate
nanotubes and the diameter is about 10-30nm. (D) is obtained when added proper titanate sodium nanotubes sintered at
400°C. The obtained crystals have regular rod morphology. The diameter is from 10nm to 20 nm. But the length is about
50nm, and the aspect ratio (i.e., length divided by diameter) is ca.5:1.
Figure 9 shows the growth of the different crystal surface. From it we can see that in general the relative growth status of
the crystal surfaces does not change when the predecessor changed. The (1 0 1) crystal surface is the most preference one
and the (2 0 0) crystal surface is the second. In the stronger acid environment, the (1 0 1) crystal surface became
predominate, and the crystal shows nanorod morphology consequently.

1000 (A)
(B)
(C)
800 (D)
Intensity(a.u.)

101 004 200 105 211 310

600

400

200

0
20 30 40 50 60 70
2θ(degree)

Figure 9: Growth of the different crystal surface.

With predecessors: (A)TiCl3+KF;(B)titanate sodium + TiCl3+KF;(C) titanate sodium +
HCl(10%)+TiCl3+KF; (D) titanate sodium+ HCl(10%)+ sintered at 400°C +TiCl3+KF
When there is no titanate sodium nanotube in the predecessors, the obtained sample is square morphology. When adding
titanate sodium nanotube in the predecessors, the crystal structure is destroyed in the hydrothermal acid circumstance,
which provides the solute environment for growing crystals and make the crystals growth better. If adding itanate
nanotubes, anatase will form when the tube-walls of the nanotubes contract or break. A mount of new crystal-nucleus
accelerate the crystallize process and the crystal granules become even smaller consequently. titanate sodium nanotubes
turn into stable TiO2 nanotubes after sintering. Because the tube-like structure has low stability, the nanotubes break and
form the crystal-nucleus for the crystal to growth again. The nanorods form consequently.
3.4 Effect of adulterating microelement
By adulterating microelement, the structure of bandgap can be changed and it has effect on the process of electron
transmission and combination. Consequently, it can change the electric and optical characteristics of the materials. In the
experiment, rutile Sn-doped TiO2 nanocrystals are synthesized with TiCl4 and SnCl4·5H2O as the precursors.

Proc. of SPIE Vol. 7284 72840B-4

When there is no Sn4+ in the precursors, the crystals is 20nm in diameter, and 30-120nm in length. When the TiCl4 and
SnCl4·5H2O serve as precursors with ratio of Ti4+/Sn4+ 4:1, most of the Synthesized crystals are square morphology, with
diameter of 30nm. When the ratio of Ti4+/Sn4+ changed to 1:1, the obtained samples display various kinds of morphology.
Some of them are tiny square crystals with the size less than 20nm. The bigger ones is about 100-120nm in length and
30-50nm in diameter. And the aspect ratio is 3:1. The results indicate that combination of Ti4+ and Sn4+ has relative
evident effect on the crystals morphology.
The component of the obtained samples has been analyzed by X-ray energy dispersive spectroscopy (EDS). Figure 10 is
one of the results. The result shows that the highest atomic percent concentration of the doped-Sn is only 2.81% , which
is very low. The experiments results indicate that it is hard for other metal ions to dope into the rutile TiO2.

700-
Ti

0
Lt

n
t
S

Sn Ti
Sn
0 A
J.000 ksV 20.480

Figure 10: EDS spectra of the product by treating TiCl4 and SnCl4·5H2O with ratio of Ti4+/Sn4+ 4:1

4. CONCLUSION
In this work, pure rutile TiO2 nanorods are fabricated using TiCl3 as the predecessor at 180°C for 24h. The anatase TiO2
nanocrystals are synthesized at 150°C for 24h with TiCl3 and titanate sodium nanotubes as the predecessors at the filling
factor of 68%. TiO2 nanomaterials turn into pure anatase when KF serves as mineralizer and the concentration of KF
solution is higher than 0.2mol/L. It is indicated that the fluorin-ion has a great effect on phase transition of anatase TiO2
crysta1, and the diameter of the nanocrystal grain changes when changing the concentration of KF solution.

REFERENCES
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3. S. Pavasupree, et al. Preparation and characterization of high surface area nanosheet titania with mesoporous
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4. H. Yu, et al. Synthesis and optical properties of rutile TiO2 microspheres composed of radially aligned nanorods,
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