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Facile preparation of anatase/SiO2 spherical nanocomposites and their

application in self-cleaning textiles{
Kaihong Qi,a Xianqiong Chen,a Yuyang Liu,a John H. Xin,*a C. L. Makb and Walid A. Daouda
Received 26th February 2007, Accepted 24th May 2007
First published as an Advance Article on the web 12th June 2007
DOI: 10.1039/b702887c

Anatase TiO2/SiO2 nanocomposites were prepared by a sol–gel process at a low temperature. The
structural properties of these as-prepared nanocomposites were characterized with scanning
electron microscopy (SEM) and X-ray diffraction (XRD), showing that TiO2 nanoparticles were
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deposited on the surface of SiO2 spheres. The spherical TiO2/SiO2 nanocomposites were coated
onto cotton fabrics by a simple dip-pad–dry-cure process. The treated cotton fabrics
demonstrated higher photocatalytic activity in comparison to pure TiO2 treated cotton fabrics in a
typical photocatalytic test using a model compound of Neolan Blue 2G dye. Our results
demonstrate that this composite material is a step towards better self-cleaning performance of
textile materials.

1. Introduction composite microspheres by calcining at 400 uC and 600 uC.

However, these studies were focused on the preparation of
Titanium dioxide nanocrystallites have become promising TiO2 coatings on monodispersed SiO2 spheres, the photo-
photocatalytic materials owing to their ability to catalyze the catalytic activities of TiO2/SiO2 composite microspheres were
complete degradation of many organic contaminants and not reported. In addition, the temperatures used during the
environmental toxins. Anatase TiO2 has the highest photoactivity calcining processes were too high for any organic substrates.
among different crystal phases of TiO2.1 Sol–gel processes offer Zhang et al.11 reported that a poly(divinylbenzene) core/
an attractive means of producing anatase TiO2-based thin films anatase TiO2 shell hybrid microsphere powder prepared at a
at a low temperature which can extend the application of anatase low temperature showed high photocatalytic activities.
TiO2 to substrates with low thermal resistance. Recently, some work was carried out on the photocatalysis
Much work has been conducted on the optimization of the of TiO2/SiO2 nanocomposite thin films on substrates with low
catalytic properties of TiO2 films at low temperatures by using thermal resistance. It has been reported that TiO2 coatings on
modified TiO2 thin films. Parkin and Palgrave2 published a PET monoliths showed high photocatalytic activities and the
systematic review of photocatalytic TiO2 self-cleaning coatings adherence of TiO2 to the polymer surface was promoted.12
for the destruction of organic dirt. Recently, we investigated Matsuda et al.13,14 prepared the anatase TiO2/SiO2 nanocom-
the low temperature fabrication of anatase TiO2 thin films on posite films on organic polymer substrates using a sol–gel
cotton and demonstrated that anatase TiO2 thin films possess process followed by a boiling treatment. However, the films
good self-cleaning properties.3 To further improve the photo- were easily leached out from the substrates. Zhou et al.15
catalytic activity of TiO2 films, the combination of photoactive reported the preparation of a TiO2/SiO2 mixed film on
TiO2 material with other oxides can be a good strategy. In modified PET substrates at 100 uC, and the photocatalytic
most cases, mixed or supported TiO2 films showed higher activity of the TiO2/SiO2 mixed film was enhanced. The
photocatalytic activity than pure TiO2. Among them, TiO2/ enhancement of photocatalytic activity of the mixed TiO2/SiO2
SiO2 films have been widely used in industrial applications and treated cotton textiles was also reported.16 In that study, the
are the most extensively studied. Anderson and Bard4,5 TiO2/SiO2 films on the cotton were obtained by immersing the
reported that a mixed oxide powder of TiO2 and SiO2 was a cotton in a mixture of TiO2 colloid and commercial SiO2
more efficient photocatalyst for photocatalytic decomposition solution, subsequently followed by thermal treatment at 100 uC
than pure TiO2 powder. Several other studies6–9 reported the for 1 h. However, the long treatment time is not feasible in the
preparation of titania coating on monodisperse silica spheres. industrial textile application. In addition, no comparison
Yu et al.10 also prepared monodispersed anatase TiO2/SiO2 between the mixture of TiO2/SiO2 and TiO2 was reported.
In the present study, we extended our previous work3 in an
a
Nanotechnology Center, Institute of Textiles & Clothing, The Hong attempt to further improve the photocatalytic activity of the
Kong Polytechnic University, Hung Hom, Hong Kong. anatase TiO2 films. Anatase TiO2/SiO2 nanocomposites were
E-mail: tcxinjh@inet.polyu.edu.hk; Fax: +852 2773 1432;
Tel: +852 2766 6474
prepared in an aqueous solution using a sol–gel process at a
b
Department of Applied Physics, The Hong Kong Polytechnic low temperature. TiO2/SiO2 spherical nanocomposites were
University, Hung Hom, Hong Kong applied to cotton fabrics from a colloidal sol by a simple dip-
{ Electronic supplementary information (ESI) available: pad–dry-cure process with a much shorter time duration
Photocatalytic activities and amine titration method for determination
of the surface acidity of pure TiO2 powder and TiO2/SiO2 nanocom- compared with the process reported before.16 TiO2/SiO2 nano-
posite powder. See DOI: 10.1039/b702887c composite treated cotton fabrics showed higher photocatalytic

3504 | J. Mater. Chem., 2007, 17, 3504–3508 This journal is ß The Royal Society of Chemistry 2007
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activity compared to those treated with only TiO2, which diffractometer) operating at 40 kV and 40 mA. Interaction
enhances the self-cleaning performance of textiles. between TiO2 and SiO2 was analyzed by FT-IR (Perkin Elmer
System 2000 FT-IR).
2. Experimental
2.4 Assessment of dye decomposition activity
2.1 Preparation of TiO2/SiO2 nanocomposites
The detailed procedure for the assessment of dye decomposi-
Preparation of TiO2 sols. TiO2 sols with different concentra- tion activity was discussed in our previous work.3 In this
tions were prepared as follows. In a typical procedure, 5 ml research, pure TiO2 and the TiO2/SiO2 nanocomposite used to
titanium tetraisopropoxide (Aldrich, 97%) was added dropwise treat the woven white cotton fabrics were investigated. The UV
into 100 ml acidic water containing 1 ml nitric acid (Aldrich, intensity (365 nm, Philips TLD 18 W/08) on the top of the
70%) and 10 ml acetic acid (Aldrich, 99.9%) under vigorous beakers was 0.7–0.8 mW cm22.
stirring. The mixture was heated to 60 uC and kept at that
temperature while being stirred for 16 h (pH = 1–2).
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3. Results and discussion

Published on 12 June 2007 on http://pubs.rsc.org | doi:10.1039/B702887C

Preparation of SiO2 nanoparticles. Uniform silica with a 3.1 SEM

particle size of around 500 nm was prepared as follows. A
Fig. 1 shows representative SEM micrographs of the mono-
250 ml one-neck flask was charged with 100 ml nitric acid
dispersed spherical SiO2 nanoparticles, a grainy film of TiO2
aqueous solution (1 6 1024 M), and then the flask with a
and spherical TiO2/SiO2 nanocomposites. It can be seen that
magnetic stirrer was immersed into a heated water-bath. The
the average diameter of the spherical SiO2 particles is about
solution was heated to 60 uC, and then 2.5 ml of the silica
500 nm as shown in Fig. 1(a). A film of TiO2 was formed on
precursor methyl-trimethoxysilane (MTMS, Sigma, 98%) was
the silicon wafer [as shown in Fig. 1(b)] with a very fine grain
introduced to the solution. After stirring for 1 min, 2.5 ml
size around 4–5 nm according to the characterization in our
ammonia was added to the solution. A milky suspension of
silica nanoparticles was obtained (pH = 9–11). The suspension previous study.17 In contrast to the near perfect spherical SiO2
was centrifuged to obtain SiO2 powder. particles, the TiO2 deposited SiO2 particles show a rough
surface and less than perfect spherical shape with the average
TiO2/SiO2 nanocomposites. The as-prepared SiO2 powder diameter increasing to about 600–620 nm as shown in Fig. 1(c).
above was added to TiO2 sol and dispersed in an ultrasonic This is clearly attributed to the coating of a TiO2 layer on the
bath for 15 min. The TiO2/SiO2 mixture was kept for 12 h to spherical SiO2 particles. The formation mechanism of TiO2/
form SiO2 supported TiO2 spherical nanocomposites with a SiO2 nanocomposites is considered to be caused by electro-
core–shell structure (pH = 3–5) (as shown in Scheme 1). static deposition. The isoelectric point of TiO2 nanoparticles
was reported 5.6,18 5.9,19 6.2,20 and that of the SiO2 particles
2.2 Preparation of TiO2/SiO2 nanocomposites on cotton ranged from 1.821 to 2.7.22 As the pH value in this study was
3–5, the TiO2 would have a positive surface charge density and
The as-prepared suspension was used to prepare TiO2/SiO2 the SiO2 particles would have a negative surface charge
nanocomposites on woven white cotton fabrics. The detailed density. Thus, TiO2 could be deposited on the surface of the
process of preparing TiO2/SiO2 nanocomposites was reported SiO2 particles driven by the electrostatic attraction between
in our previous work.3 For comparison, the TiO2 sol was also TiO2 and SiO2.
applied to the cotton fabric substrate by the same process. Fig. 2 shows SEM micrographs of untreated cotton fibres,
TiO2 treated cotton fibres and TiO2/SiO2 nanocomposite
2.3 Surface characterization treated cotton fibres. It can be seen that spherical TiO2/SiO2
The structures and morphologies of SiO2, TiO2, TiO2/SiO2 nanocomposites were deposited on the cotton fibres [as shown
nanocomposites and the treated cotton fibres were investigated in Fig. 2(c)] in contrast to the fibrous texture of the pristine
using field emission scanning electron microscopy (FESEM, cotton fibres [as shown in Fig. 2(a)] and the flat TiO2 layer
JSM-6335F at 3.0 kV, JEOL, Tokyo, Japan). The crystal deposited on the cotton fibres [as shown in Fig. 2(b)].
phase of silica, titania and silica/titania solid powder extracted
from the solution respectively was studied by an X-ray 3.2 XRD
diffraction spectrometer (XRD, Bruker D8 Discover X-ray
Fig. 3 shows the XRD patterns of pure SiO2, TiO2 and
TiO2/SiO2 nanocomposites. No crystal peak was observed
for SiO2 particles [Fig. 3(a)], indicating that the SiO2 particles
are amorphous. Anatase peaks at 25.4u, 38.0u and 48.0u for
solid titania particles [Fig. 3(b)] were observed and no traces
of brookite or rutile were observed, indicating that single-
phase anatase nanocrystallites were formed. Anatase peaks
at 25.4u, 38.0u and 48.0u were also observed in the XRD
spectra of spherical SiO2 particles coated with a TiO2 layer
Scheme 1 The formation mechanism of TiO2/SiO2 nanocomposites [Fig. 3(c)], which was very similar to that of titania solid
with a core–shell structure. particles.

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Fig. 1 SEM images of (a) SiO2 nanopartciles (b)TiO2 film and (c)
spherical TiO2/SiO2 nanocomposites on silicon wafer (A: TiO2 shell, B:
SiO2 core).

3.3 Photocatalytic activities

The photocatalytic activity of TiO2/SiO2 nanocomposite
treated cotton fabrics and TiO2 only treated cotton fabrics
were evaluated by the decomposition of Neolan Blue 2G
under UV irradiation (the intensity of UV light was 0.7–
0.8 mW cm22) as shown in Fig. 4. It can be seen that the dye
concentration in the aqueous solution containing the TiO2/
SiO2 treated cotton fabrics was reduced by more than that in
the aqueous solution containing TiO2 treated cotton fabrics Fig. 2 SEM images of (a) untreated cotton fibres, (b) TiO2 treated
under UV irradiation. This result indicates that the TiO2/SiO2 cotton fibres and (c) TiO2/SiO2 nanocomposite treated cotton fibres.

3506 | J. Mater. Chem., 2007, 17, 3504–3508 This journal is ß The Royal Society of Chemistry 2007
 View Article Online

than that in the aqueous solution containing pure TiO2 powder

under UV irradiation where the amount of TiO2 remained
constant (see ESI-1 in the ESI{), which further confirmed that
TiO2/SiO2 nanocomposites possess higher photocatalytic
activities than pure TiO2. The assessment of photocatalytic
activities of treated cotton fabrics and powders was repeated
five times and the results were close with an error margin of
¡1%. The average results were used in this study.
The dye decomposition in the aqueous solution containing
pure TiO2 treated cotton fabrics and TiO2/SiO2 nanocompo-
site treated cotton fabrics under UV irradiation followed a
pseudo-first-order kinetic model, as shown in Fig. 5. The
pseudo-first-order reaction kinetic model was shown as
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equation (1):
Published on 12 June 2007 on http://pubs.rsc.org | doi:10.1039/B702887C

2lnC/C0 = kt, (1)

where C0 is the initial concentration of the dye before UV

radiation and after the fabric–dye absorption comes to
Fig. 3 XRD patterns of powder extracted from colloids (a) SiO2 and
equilibrium, C is the concentration at time t, k is the pseudo-
(b) TiO2 and (c) TiO2/SiO2 nanocomposites (A: anatase).
first-order rate constant. Fig. 5 shows the 2lnC/C0 of Neolan
Blue 2G versus irradiation time. It is clear that decreasing the
dye concentration obeys a linear pattern. The correlation
coefficient R of the linear fitting for TiO2 is 0.99073, the
correlation coefficient R for TiO2/SiO2 nanocomposites is
0.99206. Rates of dye decomposition (photocatalytic reaction
rate) for pure TiO2 and TiO2/SiO2 nanocomposites are
calculated as 0.079 ¡ 0.006 h21 and 0.111 ¡ 0.008 h21
respectively. This indicates that TiO2/SiO2 nanocomposites
possess higher photocatalytic activities than pure TiO2.
The enhanced photocatalytic activity of the TiO2/SiO2
treated cotton fabrics might be attributed to the unique
physicochemical properties of TiO2/SiO2 nanocomposites
which result from the strong interaction of TiO2 and SiO2
particles at molecular level, such as the increased specific
surface area of TiO2/SiO2 nanocomposites10,15,23–26 and the
enhanced surface acidity of the nanocomposites.24,27–29 The

Fig. 4 Variations in the concentration of Neolan Blue 2G in an

aqueous solution as a function of UV irradiation time for different
substrates: untreated cotton fabrics (&), TiO2 treated cotton fabrics
(m) and TiO2/SiO2 treated cotton fabrics (.).

treated cotton fabrics possess higher photocatalytic activities

than TiO2 only treated cotton fabrics. Under the same UV
irradiation, the dye concentration in the aqueous solution
containing untreated cotton fabrics kept almost the same level,
which indicates that cotton fabrics possess no photocatalytic
activity and the dye itself would not be decomposed by UV
radiation. Furthermore, no photodegradation of the cotton
substrate by the titania coating on the spherical SiO2 particles
was observed during the experiment considering the substan-
tial UV absorption of the titania at the top surface.3 Compared
to the previous study,3 the rate of the dye decomposition
reported here is relatively low. This is because of the lower
amount of TiO2 deposited on the fabric surface. The Fig. 5 The pseudo-first-order degradation rate constants of Neolan
dye concentration in the aqueous solution containing the Blue 2G for TiO2 treated cotton fabrics (&) and TiO2/SiO2
TiO2/SiO2 nanocomposite powder was also decreased by more nanocomposite treated cotton fabrics ($).

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therefore have better self-cleaning activity than TiO2 treated

fabrics. The anatase TiO2/SiO2 nanocomposite treated cotton
fabrics have high potential in commercial applications for self-
cleaning cotton textiles.

Acknowledgements
The authors gratefully acknowledge the Research Grants
Council of the Hong Kong SAR Government (Project No.
PolyU 5289/03E). We would like to thank HKPolyU Materials
Research Center for the use of their facilities.

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Published on 12 June 2007 on http://pubs.rsc.org | doi:10.1039/B702887C

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3508 | J. Mater. Chem., 2007, 17, 3504–3508 This journal is ß The Royal Society of Chemistry 2007