J. Am. Ceram. Soc.
, 89 [2] 720–723 (2006)
Journal
Synthesis and Characterization of Porous Single-Crystalline Titanium
Dioxide Nanorods
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, Shanghai 200050, China
Porous single-crystalline titanium dioxide (TiO2) nanorods were
prepared though a solution aggregation-based growth process
followed by the calcination treatment. The products were char-
acterized by X-ray diffraction, transmission electron micros-
copy, and nitrogen adsorption–desorption isotherm analysis.
The prepared nanorods were of the single-crystalline nature
and the mesoporosity characteristic. The prepared porous
single-crystalline TiO2 nanorods had high BET-specific area,
70.3 m2/g. The formation mechanism of the porous single-crys-
talline TiO2 nanorods was also investigated. The solution
aggregation-based growth of the nanoparticulates and the fol-
lowing calcination process may result in the formation of the
porous single-crystalline TiO2 nanorods.
I. Introduction
C ONSIDERABLE efforts have been devoted to the design and
synthesis of low-dimensionally nanostructured materials
because of their morphology-dependently distinguished per-
formances manifested in nanoelectronics, optoelectronics, bio-
medicine, and catalysis.1–4 Titanium dioxide (TiO2) is a versatile
material with applications in photocatalysis, solar cells, sensors,
etc. Nanocrystalline or porous TiO2 has promising applications
in dye-sensitized oxide semiconductor solar cells.5 Therefore, the
synthesis of crystalline porous TiO2 has attracted much inter-
est.6 A lot of efforts have been exerted for the crystallization of
the walls of mesoporous TiO2,7,8 and yet the increase of the
thermal stability of the synthesized mesostructures becomes a
big problem.9 Mesoporous spherical aggregates composed of
small nanocrystallites were prepared by Zhou and Antonietti10
in a room temperature ionic liquid. However, nanocrystalline
porous TiO2 belongs to the class of materials with very low drift
mobilities of charge carriers.11
Recently, a TiO2 nanonetwork structure composed of single-
crystal-like anatase nanowires was successfully synthesized, and
a high light-to-electricity conversion yield was achieved by ap-
plying the nanonetwork structure as the TiO2 thin film of dye-
sensitized solar cells because this kind of single-crystal-like
nanonetwork structure results in the high rate of electron trans-
fer through the nanonetwork.12 Therefore, alternate strategies
should be desirable for the synthesis of crystalline porous ma-
terials. The preparation of porous single-crystalline TiO2 should
be of significant interest because the porous single-crystalline
TiO2 has both a high surface area and high carrier transfer rate.
To the best of our knowledge, previous reports about the crys-
talline mesoporous TiO2 materials are polycrystalline. In this
H.-M. Cheng—contributing editor
Manuscript No. 20856. Received August 9, 2005; approved August 31, 2005.
Supported by National Science Foundation of China (50372079) and Shanghai Nano-
technology Promotion Center (0352 nm 093).
*Member, American Ceramic Society.
w
Author to whom correspondence should be addressed. e-mail: liangaoc@online.sh.cn
720
DOI: 10.1111/j.1551-2916.2005.00752.x
r 2005 The American Ceramic Society
Songwang Yang and Lian Gao*,w
paper, we have reported the preparation of porous single-crys-
talline TiO2 nanorods with a high specific BET area, 70.3 m2/g.
The morphological and structural characteristics of the prepared
porous single-crystalline TiO2 nanorods have been investigated
in detail.
II. Experimental Procedure
The typical preparation procedure was as follows: 2.0 g of tri-
block copolymer EO20PO70EO20 (Pluronic P123, BASF, Lud-
wigshafen, Germany) was added to a mixture of 15.0 g of n-
butyl alcohol and 60.0 g of 2M HCl aqueous solution with stir-
ring at 401C overnight. Then, 6.95 g of tetrabutyl titanate was
added to this solution, followed by further stirring for 2 h. The
gained solution was transferred into a Teflon-lined stainless-steel
autoclave and kept at 751C for 5 days under static conditions.
The precipitates were filtered, carefully washed with ethanol re-
peatedly, and dried in a vacuum oven at 601C overnight. At last,
the as-synthesized powders were calcined at 4501C for 2 h to get
the final product.
The phases of the products were characterized by powder X-
ray diffraction (XRD; Model D/Max 2550 V, Rigaku Co., To-
kyo, Japan) with CuKa (l 5 0.15418 nm). The morphologies of
the products were observed by transmission electron microscopy
(TEM/HRTEM; Model JEM-2010, JEOL, Tokyo, Japan). Ni-
trogen adsorption and desorption isotherms were measured at
77 K on a Micromeritics Tristar 3000 system (Norcross, GA).
The specific surface area and the pore size distribution were
calculated using the BET and Barrett–Joyner–Halenda (BJH)
method, respectively.
III. Results and Discussion
Figure 1 shows the XRD patterns of the as-synthesized and the
calcined powders, respectively. It can be seen that both of the
powders are exclusively indexed as rutile phase of TiO2 (S. G.:
P42/mnm; a0 5 b0 5 4.593 Å, c0 5 2.959 Å; JCPDS No. 21-1276)
110
101
211
Intensity (a.u.)
111
(b) 220
210 002 301
200 310
(a)
10 20 30 40 50 60 70
2
(degree)
Fig. 1. X-ray diffraction patterns of (a) the as-synthesized titanium
dioxide (TiO2) powders; and (b) the porous single-crystalline TiO2
nanorods.
February 2006 Communications of the American Ceramic Society 721

Fig. 2. (a) Transmission electron microscopy (TEM) image of the porous single-crystalline titanium dioxide (TiO2) nanorods; (b) HRTEM image of
one end of a typical nanorod, and the insert is the corresponding Fourier transform pattern; (c) TEM image of the as-synthesized TiO2 nanorods before
the calcination treatment; and (d) HRTEM image of a typical part of the as-synthesized nanorods; the white badge highlights an edge dislocation, and
there are a large amount of such edge dislocations in the image.

with high crystallinity. The relative sharpening of the peaks of

dV/dD (cm3 g−1 nm−1)

the calcined powders reveals the growth of the crystallites during 80 0.020
Volume adsorbed (cm3 g−1) STP

the calcination treatment according to the Scherrer formula. 0.015

Transmission electron microscopy observations reveal the 70
0.010
morphological and structural features of the products. Figure
60
2(a) shows the gained TiO2 nanoparticles have irregularly rod- 0.005
like morphology. The edges and surfaces of the nanorods are
50 0.000
not straightly smooth so that the diameter and length of the 0 5 10 15 20
nanorods are difficult to determine exactly. But the average as- 40 Pore diameter (nm)
pect ratio of the nanorods is estimated to be B5 through the
value of the mean diameter and the maximum length of a single 30
nanorod. Both ends of the nanorod are often unsymmetric,
which implies that the whole nanorod may come from the ag- 20
gregation of several thinner nanorods. It can be clearly seen that
there exist a large amount of pores in the nanorods with the 10
diameter ranging from 2 to 20 nm. Figure 2(b) shows the
HRTEM image and the corresponding fast Fourier transform 0.0 0.2 0.4 0.6 0.8 1.0
(FFT) pattern of one end of the TiO2 nanorod. The HRTEM Relative pressure (P/P0)
image shows that the lattice fringes run coherently across the
pores and the corresponding FFT pattern of the HRTEM image Fig. 3. Nitrogen adsorption–desorption isotherms and the correspond-
ing pore size distribution (inset) of the prepared porous single-crystalline
exhibits sharp spots, which demonstrate the single-crystalline
titanium dioxide nanorods.
nature of the whole nanorods. It should be noted that the amor-
phous layer on the surface of the crystalline TiO2 in Fig. 2(b) is a Figure 2(c) shows the TEM image of the as-synthesized pow-
contamination caused by the long time exposure in the strong ders before calcination treatment in the presence of n-butyl
electron beam during the HRTEM determination. alcohol. It can be seen that there exist apparent aggregations
722 Communications of the American Ceramic Society
(a)
Intensity (a.u.)
20 nm
Fig. 4. (a) Transmission electron microscopy image and (b) X-ray diffraction pattern of the product gained in the absence of n-butyl alcohol followed
by the calcination treatment.
among the primary particulates. HRTEM images show that
there exist considerable defects in the as-synthesized nanorods
(Fig. 2(d)). The white badge in Fig. 2(d) highlights an edge dis-
location in the as-synthesized nanorod. It should be noted that
there are a large amount of such edge dislocations in the as-
synthesized nanorods. The presence of surface defects is an im-
portant characteristic of the aggregation-based growth process,
and aggregation-based growth is favored to adsorb molecules or
ions at particle surfaces.13 Therefore, in the presence of n-butyl
alcohol in the starting solution, aggregation-based growth dom-
inates the formation process of the nanorods so that there also
exist considerable aggregations between the primary nanorods
(Fig. 2(c)). When the particles are heated at 4501C, the particle
perfection increases. However, the loss of the adsorbed mole-
cules results in the formation of pores in the nanorods. As a
result, porous single-crystalline nanorods are finally formed
through a solution aggregation-based growth process followed
by the calcination treatment.
A large amount of pores in the single-crystalline nanorods
make them have high specific surface area. The BET-specific
area of the porous single-crystalline nanorods is 70.3 m2/g. Fig-
ure 3 shows the nitrogen adsorption–desorption isotherm of the
product. The sharp decline in the desorption profile at 0.4oP/P0
o0.45 indicates the mesoporosity of the product. The average
pore diameter, calculated according to the BJH equation from
the desorption branch, is 4.0 nm (the inset to Fig. 3). However,
this kind of materials is different from the mesoporous materials
with the crystalline walls. In the crystalline mesoporous materi-
als the crystalline walls are composed of small nanocrystallites
and they are polycrystalline, while the present porous single-
crystalline nanorods are single crystalline and pores are inserted
in the single-crystalline body.
To explore the formation mechanism of the porous single
crystalline nanorods, the experiment in the absence of n-butyl
alcohol was also carried out when other experimental conditions
and procedures were kept the same. Nanorods with smooth
surface are gained and there are no apparent pores in the nano-
rods (Fig. 4(a)). The HRTEM image and the corresponding
FFT pattern (not shown here) demonstrate the nanorods are
single-crystalline. The crystal structure of the nanorods are also
phase-pure rutile as shown in the XRD pattern (Fig. 4(b)).
However, their BET-specific area, 35.6 m2/g is much lower than
that of the synthesized porous single-crystalline nanorods. At
least two important conclusions can be drawn from this com-
parison experiment. One is that the presence of n-butyl alcohol
plays a key role in the formation of the present porous struc-
tures. The other is that the formation of rodlike morphology is
independent of the addition of n-butyl alcohol. In fact, the for-
mation mechanism of the nonporous TiO2 nanorods in this kind
Vol. 89, No. 2
(b)
110
101
211
111
220 301
002
200 210 310
10 20 30 40 50 60 70
2
(degree)
of surfactant-assisted low-temperature solution system has dem-
onstrated that surfactant P123 is responsible for the formation
of the rodlike morphology.14
It seems that the addition of n-butyl alcohol renders the ag-
gregation-based growth more pronounced. First, titanium hy-
droxide (Ti(OH)4) has low solubility in the alcohol/water
mixture media15 so that mass transfer process required by
Ostwald-ripening mechanism is arrested. Second, the increase
of the concentration of alcohol in the solution results in the de-
crease of the dielectric constant of the solvent,16 which could
reduce the stability of the system and cause the reaggregation of
the nanorods. That is to say, with the increase of concentration
of primary nanorods, the collision frequency among them in-
creases. As a result, the aggregations among nanorods increase
in order to decrease the total energy of the system through the
elimination of the solid–liquid or solid–gas interface.17
IV. Conclusions
Porous single-crystalline TiO2 nanorods have been prepared
though a solution aggregation-based growth process followed
by the calcination treatment. The HRTEM and the correspond-
ing FFT images demonstrate the single-crystalline nature of the
nanorods, and the pore size distribution demonstrates the me-
soporosity characteristic of the nanorods. The porous single-
crystalline TiO2 nanorods have high BET-specific area, 70.3 m2/
g. This kind of structurally novel TiO2 material promises its po-
tential and significant applications in photocatalysts, catalysts,
and semiconductor solar cells.
References
1
M. S. Gudiksen, L. J. Lauhon, J. Wang, D. Smith, and C. M. Lieber, ‘‘Growth
of Nanowire Superlattice Structures for Nanoscale Photonics and Electronics,’’
Nature, 415, 617–20 (2002).
2
M. Law, D. J. Sirbuly, J. C. Johnson, J. Goldberger, R. J. Saykally, and P. D.
Yang, ‘‘Nanoribbon Waveguides for Subwavelength Photonics Integration,’’ Sci-
ence, 305, 1269–73 (2004).
3
T. A. Taton, C. A. Mirkin, and R. L. Letsinger, ‘‘Scanometric DNA Array
Detection with Nanoparticle Probes,’’ Science, 289, 1757–60 (2000).
4
V. Subramanian, E. E. Wolf, and P. V. Kamat, ‘‘Catalysis with TiO2/Gold
Nanocomposites. Effect of Metal Particle Size on the Fermi Level Equilibration,’’
J. Am. Chem. Soc., 126, 4943–50 (2004).
5
M. Grätzel, ‘‘Photoelectrochemical Cells,’’ Nature, 414, 338–44 (2001).
6
P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka, and G. D. Stucky, ‘‘Gen-
eralized Syntheses of Large-Pore Mesoporous Metal Oxides with Semicrystalline
Frameworks,’’ Nature, 396, 152–5 (1998).
7
J. N. Kondo, T. Yamashita, K. Nakajima, D. Lu, M. Hara, and K. Domen,
‘‘Preparation and Crystallization Characteristics of Mesoporous TiO2 and Mixed
Oxides,’’ J. Mater. Chem., 15, 2035–40 (2005).
8
Y. Yue and Z. Gao, ‘‘Synthesis of Mesoporous TiO2 with a Crystalline Frame-
work,’’ Chem. Commun., 1755–6 (2000).
February 2006 Communications of the American Ceramic Society 723
9 13
D. Grosso, G. J. de A. A. Soler-Illia, E. L. Crepaldi, F. Cagnol, C. Sinturel, A. J. F. Banfield, S. A. Welch, H. Zhang, T. T. Ebert, and R. L. Penn,
Bourgeois, A. Brunet-Bruneau, H. Amenitsch, P. A. Albouy, and C. Sanchez, ‘‘Aggregation-Based Crystal Growth and Microstructure Development in Natural
‘‘Highly Porous TiO2 Anatase Optical Thin Films with Cubic Mesostructure Sta- Iron Oxyhydroxide Biomineralization Products,’’ Science, 289, 751–4 (2000).
14
bilized at 7001C,’’ Chem. Mater., 15, 4562–70 (2003). S. Yang and L. Gao, ‘‘Low-Temperature Synthesis of Crystalline TiO2
10
Y. Zhou and M. Antonietti, ‘‘Synthesis of Very Small TiO2 Nanocrystals in a Nanorods: Mass Production Assisted by Surfactant,’’ Chem. Lett., 34, 964–5
Room-Temperature Ionic Liquid and Their Self-Assembly Toward Mesoporous (2005).
15
Spherical Aggregates,’’ J. Am. Chem. Soc., 125, 14960–1 (2003). H. K. Park, D. K. Kim, and C. H. Kim, ‘‘Effect of Solvent on Titania Particle
11
V. Duzhko, V. Yu. Timoshenko, F. Koch, and Th. Dittrich, ‘‘Photovoltage in Formation and Morphology in Thermal Hydrolysis of TiCl4,’’ J. Am. Ceram. Soc.,
Nanocrystalline Porous TiO2,’’ Phys. Rev. B, 64, 075204 (2001). 80, 743–9 (1997).
12 16
M. Adachi, Y. Murata, J. Takao, J. Jiu, M. Sakamoto, and F. Wang, ‘‘Highly D. Vorkapic and T. Matsoukas, ‘‘Effect of Temperature and Alcohols in
Efficient Dye-Sensitized Solar Cells with a Titania Thin-Film Electrode Com- the Preparation of Titania Nanoparticles from Alkoxides,’’ J. Am. Ceram. Soc.,
posed of a Network Structure of Single-Crystal-Like TiO2 Nanowires Made 81, 2815–20 (1998).
17
by the ‘‘Oriented Attachment’’ Mechanism,’’ J. Am. Chem. Soc., 126, 14943–9 A. P. Alivisatos, ‘‘Naturally Aligned Nanocrystals,’’ Science, 289, 736–7
(2004). (2000). &