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Hao Bin Wu, Huey Hoon Hng, and Xiong Wen (David) Lou*
Nanostructured materials with controlled shapes and structures have drawn considerable attention for both fundamental
research and practical applications.[15] Particularly, onedimensional (1D) nanostructures such as nanowires, nanorods,
and nanotubes are of great importance owing to their unique
physicochemical properties and anisotropic structures.[69] 1D
nanostructures of a wide variety of materials have been successfully synthesized, including carbons (e.g., carbon nanotubes[10]
and nanofibers[11]), metals/metalloids (e.g., Si[12] and Ag[13]), and
metal oxides (e.g., ZnO[14] and MoO3[15]). Except for some materials with a highly anisotropic crystallographic structure, facile
and scalable synthesis of 1D nanostructures has never been a
trivial task. Solution-phase approaches have been extensively
adopted to prepare nanostructured materials with relatively
low cost and good scalability. The formation of 1D nanostructures in solution is typically realized by facilitating the crystal
growth along a particular direction with the assistance of capping agents.[9]
As one of the most important metal oxides and semiconductors, titanium dioxide (TiO2), especially anatase TiO2, has found
its applications in a wide range of fields including solar cells,
photocatalysis, and lithium-ion batteries.[16,17] It has been generally accepted that the geometric shape and surface property
have tremendous effects on the physicochemical properties of
TiO2.[1822] Recently, TiO2 nanowires, nanorods, and nanobelts
with enhanced performance in photocatalysis, dye-sensitized
solar cells, and lithium-ion batteries have been widely reported,
largely due to the particular exposed facets and the unique
anisotropic structure.[21,2328] However, it is well-known that
according to the Wulff construction, under normal conditions,
anatase TiO2 crystals will adopt the octahedral shape with the
majority of the exposed surface being the energetically stable
(101) facets, and direct formation of anatase 1D nanostructures
is not favored. As a result, except some anatase TiO2 nanorods
with small aspect ratios, most anatase TiO2 materials with
1D nanostructures reported so far are synthesized via tedious
multi-step processes. For example, anatase TiO2 nanowires/
rods/belts could be obtained from hydrothermal treatment or
H. B. Wu, Prof. X. W. Lou
School of Chemical and Biomedical Engineering
Nanyang Technological University
70 Nanyang Drive, Singapore 637457, Singapore
E-mail: xwlou@ntu.edu.sg
Webpage: http://www.ntu.edu.sg/home/xwlou
H. B. Wu, Prof. H. H. Hng
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore

DOI: 10.1002/adma.201200564

Adv. Mater. 2012, 24, 25672571

calcination of protonated titanate nanowires/tubes that are typically prepared by alkaline hydrothermal methods and subsequent acid washing.[21,24,27] To the best of our knowledge, direct
synthesis of 1D anatase TiO2 nanowires with high quality and
large quantity has not be achieved before.
In this work, we report the direct synthesis of anatase TiO2
nanowires (TNWs) in gram-scale via a facile one-pot solvothermal approach. A novel organic solvent system containing
N, N-dimethylformamide (DMF) and acetic acid (HAc) with
lithium acetate (LiAc) as an additive has been developed to produce TNWs. After the solvothermal reaction, a large amount
of white mud-like product is obtained because of the high productivity and yield. The TNWs are assembled into hierarchical
architectures or remain in freestanding form depending on
the DMF/HAc volumetric ratio of the solvents in the synthesis.
Typically, the as-synthesized TNWs manifest the curve and flexible feature, with several hundred nanometers in length and
less than 20 nm in diameter. The adsorbed organic species on
surface can be removed by annealing in air at 350 C without
affecting the nanowire structure. Both of the as-synthesized
and annealed TiO2 nanowires manifest excellent photocatalytic
activity for the degradation of Rhodamine B.
The morphology and structure of the TNWs are first characterized by field-emission scanning electron microscopy
(FESEM) and transmission electron microscopy (TEM). All of
the three samples presented in Figure 1 are of high uniformity.
It is found that the assembled structure of the nanowires would
be significantly affected by the volumetric ratio of DMF/HAc
in the mixed solvent. When a DMF/HAc ratio (v/v) of 4/6 is
used, flower-like assemblies with a size of ca. 500 nm are
obtained in the sample (Figure 1A). The TEM image of an individual assembly (Figure 1B) clearly reveals that it consists of
thin nanowires with length of ca. 200 nm and diameter of a
few nanometers. Interestingly, the nanowires are observed to
form small bundles first, and these bundles serve as subunits
to further build the hierarchical structure via attaching one
head to the center. If the solvent is obtained by mixing with
equal volume of DMF and HAc, similar hierarchical assemblies
are also observed (Figure 1C). However, each assembly is composed of much fewer nanowires with slightly increased length
and diameter (Figure 1D). By forming such hierarchical structures, these ultrathin nanowires are probably able to reduce the
surface energy and increase the stability. Further increasing
the DMF/HAc ratio to 6/4 results in formation of freestanding
nanowires with a typical length of several hundred nanometers
and diameter of tens of nanometers.
The crystallographic structure of the TNWs is confirmed by
powder X-ray diffraction (XRD) analysis. The XRD pattern of
the TNWs prepared with a DMF/HAc volumetric ratio of 5/5 is
depicted in Figure 2A. All diffraction peaks are unambiguously

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Direct Synthesis of Anatase TiO2 Nanowires with Enhanced

Photocatalytic Activity

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are attributed to (004) and (101) planes of the

anatase phase, respectively. The zone axis is
determined to be along the [101] direction on
the basis of the indexed fast Fourier transform (FFT) pattern.[24] The lattice fringes that
correspond to (101) planes are parallel to the
longitudinal axis of the nanowire. Based on
the above observation and the crystal structure of anatase TiO2, the growth direction
(the longitudinal axis) of the nanowires is
determined to be the [101] direction. Such
a hierarchical structure with 1D building
blocks results in a moderate BrunauerEmmett-Teller (BET) specific surface area of
67.2 m2 g1 (the Nitrogen adsorption/desorption isotherm is given in Figure S2, see Supporting Information).
The solvothermal method developed in
this work is highly efficient in producing
TNWs in large-scale. For example, about 2 g
of TNWs (Figure S3, see Supporting Information) can be synthesized in merely 40 mL
of solvent with almost 100% yield (the yield
based on as-synthesized materials here is
higher than 100% due to the adsorbed organic
species as discussed shortly). It should be
pointed out that synthesis of nanowires in
solution-phase with such a high precursor
concentration is quite unusual. Time series
analysis has been performed to elucidate the
formation process of TNWs. Instead of direct
growth of nanowires from titanium(IV)
butoxide precursor, a gel-like intermediate is
first formed after solvothermal reaction for
about 1 h. Poorly-defined nanowires start to
appear when the reaction is prolonged to 2 h,
and evolve to well-defined nanowires after
about 4 h (Figure S4, see supporting inforFigure 1. FESEM and TEM images of TiO2 NWs (TNWs) prepared in organic solvents with
mation). Similar TNWs are also obtained
different volumetric ratios of DMF/HAc: (A, B) 4/6, (C, D) 5/5, and (E, F) 6/4.
using titanium(IV) isopropoxide as the precursor, suggesting the versatility of this
system (Figure S5). Interestingly, it is found that only polyassigned to anatase TiO2 (tetragonal, I41/amd, JCPDS card no.
hedral nanocrystals are produced without the addition of LiAc as
21-1272) except for the very small peak at around 31o as indithe additive (Figure S6). On the other hand, replacing LiAc with
cated by an asterisk that might come from the trace impurity of
lithium chloride (LiCl) also gives rise to hierarchically assembrookite. However, TNWs prepared with the DMF/HAc ratios
bled nanowires, while other acetate salts such as sodium aceof 4/6 and 6/4 show obvious co-existence of rutile and brookite
tate (NaAc) fail to promote the formation of TNWs (Figure S7).
impurities, respectively (Figure S1, see supporting informaTherefore, it could be concluded that Li+ ions are crucial for the
tion). Thus, the anatase TNWs with the highest purity (sample
formation of 1D nanostructure in the present system, although
shown in Figure 1C and D, with the DMF/HAc volumetric
the exact mechanism is still unclear at this moment. On the
ratio of 5/5) are selected for further characterization. Figure 2B
basis of above observations, a possible formation mechanism of
clearly reveals the curved 1D structure with good flexibility, and
the TNWs can be proposed. Firstly, the gelation of Ti precursor
the diameter of TNWs is generally in the range of 5 to 20 nm.
forms a gel-like intermediate, which is unstable under the solAnother observation is that some TNWs appear easily attached
vothermal condition. The intermediate gradually dissolves and
to adjacent ones to form a bundle. The high resolution TEM
re-crystallizes into stable anatase TiO2. With the assistance of
(HRTEM) image of a typical nanowire is depicted in Figure 2C,
the solvent molecules and Li+ ions, anatase TiO2 nanocrysin which the continuous lattice fringes are clearly observed.
tals preferentially grow along the [101] direction and finally
Therefore, each individual nanowire is likely single-crystalline.
form the nanowires. At the same time, the composition of the
Two sets of lattice fringes with inter-plane spacings of 0.24 and
solvent has significant effects on the hierarchical architecture.
0.35 nm indicated in the magnified HRTEM image (Figure 2D)

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Previously, we have reported the synthesis

of asymmetric anatase TiO2 nanocrystals in
a similar organic solvent system without the
lithium salt additive and with much lower
concentrations of Ti precursor.[29] The differences in product structures between these
two works indicate that both the presence of
metal ions and precursor concentration significantly affect the morphology and structure
of the product, which provides vast opportunities to tailor the unique nanostructures.
As revealed by the thermogravimetric
analysis (TGA), the as-synthesized TNWs
show a total weight loss of about 5% below
350 C (Figure S8, see supporting information). The weight loss is largely attributed to
the loss of surface adsorbed organic species,
which could be the solvent molecules and
their derivatives. To obtain TNWs with clean
surface, the as-synthesized sample is further
annealed in air at 350 C for 2 h, denoted
as TNW-A. As depicted in Figure 3A, the
XRD pattern of the material remains almost
unchanged after the thermal treatment.
FESEM and TEM images in Figure 3B and C
confirm that the morphology is well retained
after the removal of surface adsorbed species,
except that the nanowires become slightly
shorter. More importantly, the continuous
lattice fringes that correspond to (101) planes
of anatase TiO2 are clearly observed in the

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Figure 2. (A) XRD pattern, (B) TEM and (C) HRTEM images of TNWs
prepared with a DMF/HAc volumetric ratio of 5/5. (D) Magnified HRTEM
image taken from the dotted square in (C) and corresponding FFT pattern
(inset). The asterisk in (A) indicates the possible impurity of brookite.

HRTEM image (Figure 3D). In agreement with that of the asprepared TNWs (Figure 2C), the lattice fringes of (101) planes
in the annealed TNWs are also parallel to the growth direction,
suggesting the perfect retention of the structure. The TNW-A
sample shows a similar BET surface area of 72.2 m2 g1, which
again demonstrates the intact structure after annealing (the
Nitrogen adsorption/desorption isotherm is given in Figure S9,
see Supporting Information).
Recent studies have suggested that 1D TiO2 nanostructures
might possess advantages such as facile charge transport along
the longitudinal dimension and low electron-hole recombination rate.[21] Thus 1D TiO2 nanomaterials could manifest
superior performance in many important applications such
as dye-sensitized solar cells and photocatalysis. Here we demonstrate the potential application of these TiO2 nanowires as
an excellent photocatalyst for the degradation of Rhodamine B
(RhB). Figure 4 shows the photocatalytic activity of as-prepared
TNWs, annealed TNWs (TNW-A), and commercial Degussa
P25 nanoparticles for comparison. The as-prepared TNWs
exhibit high degradation efficiency that is similar to P25,
whereas the TNW-A sample demonstrates even higher degradation efficiency for RhB (Figure 4A). Under the UV irradiation in a short period of 10 minutes, the TNW-A sample is able
to degrade over 50% of the original organic dye as depicted in
Figure 4B (the data is simply obtained from the degradation
curves in Figure 4A), while values for the TNWs sample and

Figure 3. (A) XRD pattern, (B) FESEM, (C) TEM and (D) HRTEM images of TNWs after
annealing (TNW-A).

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solvent containing N, N-dimethylformamide (DMF; Alfa Aesar, 99%) and
acetic acid (HAc; Merck, 100%). After addition of 2 mL of titanium(IV)
butoxide (TB; Fluka, 97%), the solution was transferred into a Teflonlined stainless steel autoclave, and heated in an oven at 200 C for
20 h. Finally, the product was collected and washed thoroughly with
ethanol for several times, and finally dried in a vacuum oven at 60 C
overnight. Mixed solvents with different ratios of DMF/HAc (v/v) were
used for the synthesis: 4/6, 5/5, and 6/4. To investigate the effects
of agents, experiments were also performed without LiAc, replacing
LiAc with lithium chloride (LiCl) and sodium acetate (NaAc), or using
titanium(IV) isopropoxide (TIP; Sigma-Aldrich, 97%) as the Ti precursor.
The as-synthesized TiO2 nanowires (denoted as TNWs) were further
annealed in air at 350 C for 2 h to obtain the annealed TiO2 nanowires
(denoted as TNW-A).
Materials Characterization: The morphologies and structures of the
products were characterized with field-emission scanning electron
microscopy (FESEM; JEOL, JSM-6700F, 5 kV) and transmission
electron microscopy (TEM; JEOL, JEM-2010/JEM-2100F, 200 kV).
The crystallographic information was collected by powder X-ray
diffraction (Bruker D8 Advance diffractometer and Shimadzu XRD6000 diffractometer with Cu K radiation = 1.5406 ). The nitrogen
adsorption-desorption isotherm was measured using a Micromeritics
ASAP 2020 sorptometer. Thermogravimetric analysis (TGA) was
performed with Mettler Toledo TGA/SDTA851e at a heating rate of 10 C
min1 from room temperature to 700 C under air flow.
Photocatalytic degradation of Rhodamine B: To evaluate the
photocatalytic activity of the nanowires, 10 mg of TiO2 sample (e.g.,
TNW, TNW-A, or commercialized Degussa P25) was dispersed in 10 mL
of a 50 M Rhodamine B (RhB) aqueous solution. The mixture was first
stirred in dark for 30 min to reach the adsorption/desorption equilibrium
between the TiO2 catalyst and RhB. After that, the mixture was under UV
radiation (wavelength peak at 365 nm) with continuous stirring. A small
amount of solution was taken out every 10 min for UV-visible spectrum
measurement after removal of the solid catalyst by centrifugation.
The concentration of RhB was determined from the absorbance at the
wavelength of 553 nm using a UV-visible spectrophotometer.
Figure 4. (A) Photocatalytic degradation of RhB and (B) degradation ratio
after 10 min irradiation over TNW, TNW-A, and P25.

P25 are only about 38%. The annealing process might reduce
the defects in the nanowires and remove the surface adsorbed
species that could hinder the photocatalytic degradation of
organic dye. Therefore the enhanced performance of the
annealed TNWs might arise from the less defective structure
and clean surface brought by the annealing process, as well as
the unique 1D nanostructure which promotes the charge separation in the nanocrystals.[21]
In summary, we have developed a facile one-pot solvothermal
method to synthesize anatase TiO2 nanowires (TNWs) with high
productivity and yield. The curved nanowires can be controllably grown into freestanding nanowires or hierarchical assemblies. The TNWs are typically several hundred nanometers in
length and less than 20 nm in diameter, with the longitudinal
axis along the [101] direction. After removing the adsorbed
organic species by annealing, the TNWs perfectly retain the 1D
nanostructure and manifest excellent photocatalytic activity for
degradation of Rhodamine B.

Experimental Section
Materials Synthesis: In a typical synthesis, 0.2 g of lithium acetate
dihydrate (LiAc2H2O; Sigma-Aldrich) was dissolved in 10 mL of organic

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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Received: February 9, 2012
Published online: April 10, 2012

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