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ARTICLE

Journal of

Department of Polymer Science and Engineering, State Key Laboratory of Silicon

Materials, Zhejiang University, Hangzhou 310027, P. R. China.
E-mail: sunjz@zju.edu.cn; mwang@zju.edu.cn

Materials
Chemistry

Jian Cao, Jing-Zhi Sun,* Han-Ying Li, Jian Hong and Mang Wang*

www.rsc.org/materials

A facile room-temperature chemical reduction method to

TiO2@CdS core/sheath heterostructure nanowires

Published on 23 February 2004. Downloaded by Sungkyunkwan University on 10/12/2013 02:52:13.

Received 27th October 2003, Accepted 16th January 2004

First published as an Advance Article on the web 23rd February 2004

We have prepared functional TiO2@CdS core/sheath heterostructure nanowires using a simple chemical
reduction method at room temperature. The core/sheath nanowires were characterized by scanning electron
microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV-visible
spectroscopic techniques. It was found that the thickness of the CdS sheath could be controlled by the
concentration of the precursors. The continuous and polycrystalline CdS outer layer could be formed on the
TiO2 nanowires when the concentration of the S precursor was higher than 0.2 mmol. A possible multi-site
growth mechanism of the formation of the composite nanowires was proposed.

DOI: 10.1039/b313541a

1 Introduction
Recently, templating against existing nanostructures has become
an important approach to generate one-dimensional (1D) nanostructures such as nanotubes, nanowires and nanorods.14 As a
representative example, carbon nanotubes (CNTs) are widely
exploited as a template to fabricate metal, metal carbides and
many other nanowires.59 Another template, i.e. metal
nanowires, has also been used to form coaxial nanocable or
nanotubes by selective removal of the metal cores.1014 Xia and
co-workers obtained Ag@SiO2 nanocables by coating silver
nanowires with silica derived from a solgel precursor and
prepared the SiO2 nanotubes by etching the Ag in an ammonia
solution.12 Zhu et al. have prepared Zn/ZnS nanocables by a
thermal chemical process in a simple way, where the
evaporation of the Zn core led to the formation of the ZnS
nanotubes.13 The method of templating against existing
nanostructures provides a generic and powerful approach to
greatly expand the diversity of materials that can be processed
as uniform 1D nanostructures. Furthermore it opens new
opportunities to create composite nanowires with defined
properties and surface characteristics. Quite recently, Yang and
co-workers demonstrated that functional films such as TiO2 or
Co0.05Ti0.95O2 could be grown epitaxially on SnO2 to yield
functional composite nanotapes, which showed ferromagnetic
properties at room temperature.15 Lieber and co-workers
synthesized semiconductor core-shell and core-multishell
nanowire heterostructures via epitaxial growth by modulating
the composition of reactant gases in sequential steps.16 These
investigations clearly show the possibility of incorporating
multi-functions into an individual nanowire, which will find
new applications in various areas.
TiO2/CdS composites have been extensively investigated for
their applications in solar energy cells, catalysis, water purification and electrochromic devices.1719 It has been well established that in the composites, CdS and TiO2 serve for light
collection and photoinduced charge transfer, respectively.20,21
Owing to the expanded contact area and excellent capacity of
charge transport in 1D nanostructures, the TiO2@CdS composite nanowires can be expected to present eminent prospects
for both fundamental study and applications. However, the
reported investigations only focus on the composite films or
nanocrystals. In this research, we report our synthesis of

TiO2@CdS core/sheath heterostructure nanowires using a

simple wet chemical method at room temperature. The
morphologies, crystal structure and element composition of
the obtained core/sheath nanowires have been characterized; a
possible mechanism is proposed for the formation of these
composite nanowires. Our results of the tightly controlled
composition and crystallinity of the TiO2@CdS core/sheath
nanowires suggest that this technique can be expected to be
extended to obtain other functional composite nanowires.

2 Experimental
TiO2 nanowires were synthesized by the hydrothermal method
as described by Kasuga et al.22 10 mg purified TiO2 nanowires
were ultrasonically dispersed in 50 ml dried tetrahydrofuran
(THF), which contained ca. 0.10.4 mmol S powder (99.999%)
and a stoichiometric amount of anhydrous CdCl2. Then excess
KBH4 was gradually added with vigorous stirring at room
temperature. The S was reduced to S22 by the KBH4 and
the suspension gradually turned light yellow. After the mixture
had been stirred for 12 h, a yellow precipitate was formed,
which was filtered and washed thoroughly with dried THF,
deionized water and absolute ethanol several times to remove
the impurities.
The purified samples were characterized using scanning
electron microscopy (SEM; JSM-5510LV), transmission electron microscopy (TEM; JEM-200CX), high-resolution TEM
[HRTEM; Philips CM 200 coupled with an energy dispersive
X-ray (EDX) analyzer], X-ray diffraction (XRD; Rigaku
D/max diffractometer with Cu Ka radiation). UV-visible
absorption spectra of the samples were recorded on a Varian
Cary bio100 spectrometer.

3 Results and discussion

The SEM images of the as-prepared TiO2 nanowires before (A)
and after (B, C) coating with CdS are shown in Fig. 1. It is
shown that the TiO2@CdS composite nanowires have a fine
flossflower surface compared with the TiO2 nanowires. The
contrast is more obvious when the CdS concentration is
increased (Fig. 1C). The thicker and rougher surfaces of the
composite nanowires indicate that CdS has been successfully
deposited on the surfaces of the TiO2 nanowires along their

This journal is The Royal Society of Chemistry 2004

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Fig. 1 SEM images of the TiO2 nanowires before and after being
coated with CdS: (A) the as-prepared TiO2 nanowires; (B) TiO2@CdS
core/sheath nanowires with an S concentration of 0.2 mmol;
(C) TiO2@CdS core/sheath nanowires with an S concentration of
0.4 mmol.

entire length. This is further confirmed by the TEM measurements shown in Fig. 2. The morphology of a pile of as-prepared
TiO2 nanowires is illustrated in Fig. 2A. The TEM image
shows that the TiO2 nanowires present a smooth surface
without contamination, and uniform distribution in an average
diameter of about 80 nm. A distinct morphology of the
as-prepared TiO2 nanowires is demonstrated by an image of a
single nanowire as shown in Fig. 2B. The morphologies of the
TiO2 nanowires changed remarkably when they were coated
with CdS polycrystallines. Fig. 2C and D show the TEM
images of the TiO2@CdS composite nanowires. It demonstrates a sharp contrast between the outer and inner layer in the
axis direction; this distinction suggests that there is a different
phase composition in the radial direction of the wires. These
observations indicate a coaxial structure, thus we assigned the
obtained nanostructures to TiO2@CdS core-shell heterostructure nanowires. The high-resolution TEM image shown in
Fig. 2D clearly reveals the two-layer dark/light contrast core/
sheath structure, in which the thickness of the outer sheath and
the inner layer is ca. 15 and ca. 60 nm, respectively. As
expected, the energy dispersive X-ray (EDX) analysis of the
TiO2@CdS composite nanowire that was shown in Fig. 2D
indicates that the chemical composition of the core/sheath
nanowires is O, Ti, S, Cd (Fig. 3); these data clearly confirm
that the products are TiO2@CdS composite nanowires and that
the CdS coating layer is without any contamination.
X-Ray diffraction (XRD) patterns of as-prepared TiO2 nanowires, and TiO2@CdS core/sheath nanowires are displayed in
Fig. 4. The as-prepared TiO2 nanowires shown in Fig. 4(a) can
be indexed to an anatase phase (JCPDS No. 21-1272). The
well-defined peaks on curve (b) indicate a high crystallinity in
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J. Mater. Chem., 2004, 14, 12031206

Fig. 2 TEM images of TiO2 nanowires and TiO2@CdS core/sheath

nanowires with an S concentration of 0.2 mmol: (A) and (B) as-synthesized
TiO2 nanowires; (C) TiO2@CdS core/sheath nanowires; (D) highresolution TEM of a single TiO2@CdS core/sheath nanowire.

Fig. 3 EDX spectrum corresponding to a single TiO2@CdS core/

sheath nanowire (in Fig. 2D) showing its chemical composition.

the CdS coating layer and the corresponding indices confirmed

a hexagonal CdS phase (JCPDS No. 75-1545). Our results
suggest that a tight, controllable composition and crystal

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Fig. 4 XRD patterns of (a) the as-prepared TiO2 nanowires, and

(b) the TiO2@CdS core/sheath nanowires.

structure can be achieved in the products, which is particularly

important in the fabrication of electronic nanodevices.
UV-visible absorption spectra of the TiO2 nanowires and
composite nanostructures are depicted in Fig. 5(a) and (b),
respectively. The characteristic absorption band for CdS shown
in Fig. 5(b) further indicates that the CdS layer has been coated
onto the TiO2 nanowires, and the obtained structures are TiO2/
CdS core-shell nanowires.
The thickness of the CdS sheath can be readily controlled by
changing the concentration of the S precursor and the
corresponding stoichiometric amount of anhydrous CdCl2.
Fig. 6 depicts a set of TEM images of the TiO2@CdS core/
sheath nanowires with different S precursor concentrations. It
is evident that the CdS layer evolves from nanocrystals
(Fig. 6A) to a complete sheath layer with a thickness of ca.
15 nm (Fig. 6B) and further to a thicker layer (Fig. 6C) where
the boundary of the core/sheath cannot be distinguished. That
is to say, we can achieve a continuous and polycrystalline CdS
outer layer formed on the TiO2 nanowires when the concertration of the S precursor was higher than 0.2 mmol. The
thickness control is of critical importance for optoelectronic
applications, because the electronic structure, and hence the
optical absorption and carrier transportation, of a semiconductor is greatly influenced by its thickness.

Fig. 6 TEM images of the TiO2@CdS core/sheath nanowires with

different S concentrations: (A) 0.1 mmol S precursor; (B) 0.2 mmol S
precursor; (C) 0.4 mmol S precursor.

We have observed the continuously formed CdS sheath on

the TiO2 nanowires. It is supposed that a multi-point growth
may take place and this would allow the growth of polycrystalline CdS at appropriate sites joining along the template. The
superiority of the multi-point growth mechanism over the
single point lies in the fact that a complete sheath can be
created with the help of the template.23 A schematic diagram of
the multi-site growth mechanism is depicted in Fig. 7. After the
addition of KBH4 to the mixture, S atoms were reduced to S22,
which may attach to oxygen vacancies on the surface of the
TiO2 nanowires. Subsequently, Cd21 ions react in-situ with S22
anions to form CdS nuclei. The nuclei scattered on the template
evoked the multi-point growth of CdS clusters, which in turn
grow into nanocrystals and are prevented from forming large
grains. Consequently, TiO2@CdS core/sheath heterostructure
nanowires are synthesized as observed directly in the TEM
images.

4 Conclusion

Fig. 5 UV-visible absorption spectra of (a) the as-prepared TiO2

nanowires, and (b) the TiO2@CdS core/sheath nanowires with an S
concentration of 0.2 mmol.

In this work we demonstrated that functional TiO2@CdS core/

sheath heterostructure nanowires could be prepared by a wet
chemical approach at room temperature. By adjusting the
concentration of the S, both continuous and discontinuous
CdS coating layers can be achieved. A possible multi-site
growth mechanism of the core/sheath nanowire formation has
been proposed, although further works have to be carried out
to precisely understand the underlying mechanism. The ability
to construct composite nanowires with functional interior and
exterior layers is an important aspect and that will open
new opportunities concerning their areas for application. This
method is a more facile route towards preparation of 1D
nanowires on a large scale. It provides flexibility to synthesize
various functional composite 1D nanowires.
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Fig. 7 Schematic illumination of the multi-site growth mechanism.

Acknowledgements
This research is supported by the National Natural Science
Foundation of China (Grant No. 90101008) and the National
Key Project on Basic Research (Grant No. 2002CB613400).
The authors would like to thank Dr Y. Rong and Dr J. Xu for
help with the SEM and TEM measurements.

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