Thin Solid Films 540 (2013) 3640

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Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Enhancing the visible-light-induced photocatalytic activity of the

self-cleaning TiO2-coated cotton by loading Ag/AgCl nanoparticles
Deyong Wu , Lianzhi Wang, Xinjian Song , Yuanbin Tan
School of Chemical and Environmental Engineering, Hubei University for Nationalities, Enshi, Hubei, 445000, China

a r t i c l e

i n f o

Article history:
Received 23 June 2012
Received in revised form 29 May 2013
Accepted 29 May 2013
Available online 11 June 2013
Keywords:
TiO2
Cotton
Self-cleaning
Visible light
Plasmonic photocatalysis

a b s t r a c t
TiO2-coated cotton possesses excellent self-cleaning properties but requires ultraviolet irradiation for effective
photocatalysis. It is highly desirable to develop self-cleaning cotton fabrics that can use visible light in high efciency
under sunlight irradiation. In this work, Ag/AgCl-TiO2-cotton was prepared by coating TiO2 lms at low temperature
and then loading Ag/AgCl nanoparticles via an impregnating precipitation photoreduction method. It was characterized by meanings of scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and
UV-visible diffuse reectance spectrophotometer. In comparison with TiO2-cotton, Ag/AgCl-TiO2-cotton exhibits a
highly visible-light-induced photocatalytic activity for degradation of methyl orange in water. The mechanism for
the degradation of methyl orange over the Ag/AgCl-TiO2-cotton was discussed. Under visible light irradiation, Ag
NPs are photoexcited due to surface plasmon resonance, and then the photoexcited electrons from Ag NPs inject
into the TiO2 conduction band and the holes transfer to the surface of the AgCl particles. The produced radical
groups, such as O2, H2O2, OH and Cl0, can cause the photocatalytic degradation of organic pollutants.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Recently, many scientists have been working on TiO2-functionalized
textiles which can be photoactivated under sun irradiation, inducing
self-cleaning [15], UV-blocking [6,7], photo-oxidative [8] and bactericidal properties [1,2]. Several techniques have been applied for xing
nano-TiO2 on textile surface, and for increasing functionality and reactivity of TiO2-functionalized textiles, the structure of the textile surface was
modied by pretreatment of RF-plasma, MW-plasma and vacuum-UV
irradiation [4,911] and introducing a variable density of negative groups
[6] and utilizing different approaches [8,1214]. The mechanism of
self-cleaning cotton is that TiO2 absorb energy equal to or more than its
energy gap to generate electronhole pairs and then form superoxide
anion and hydroxyl radical [15,16].
However, due to its large band gap (3.2 eV for anatase), UV light
( b 400 nm) is necessary to generate the electronhole pairs, thus
restricting its absorption of solar energy (about 4% of the total energy).
For the sake of efcient utilization of the visible light (about 45% of
the total energy), TiO2 modied with noble metals like Au and Ag
has received more and more attention [1721] because noble metal
nanoparticles (Au, Ag) exhibit unique optical properties due to the
surface plasmonic resonance (SPR). SPR can dramatically amplify
the absorption of visible light and is therefore utilized to develop efcient
visible-light-driven plasmonic photocatalysts [2224]. Moreover, AgCl,
AgBr and AgI, known as widely applied photosensitive materials, have
Corresponding author. Tel./fax: +86 718 8437531.
E-mail addresses: wdy001815@126.com (D. Wu), whxjsong@163.com (X. Song).
0040-6090/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.05.113

been exploited as photocatalysts in recently [2527]. Inspired by the

photosensitive properties and the SPR effect of Ag NPs, high efcient
plasmonic photocatalysts Ag/AgX have been developed and aroused
broad interesting [2837]. Huang et al. have prepared several kinds of
plasmonic photocatalysts by a simple ion-exchange process and a
light-induced chemical reduction reaction, such as Ag@AgBr [37], Ag@
AgCl [36], Ag@Ag(Br,I) [35], Ag@Ag(Cl,Br) and Ag@AgCl-AgI [31]. All the
plasmonic photocatalysts show excellent visible light activation. Especially, the preparation and mechanism of Ag/AgCl have been researched by
a lot of researchers [33,36,3840]. In addition, the visible-light-driven
plasmonic photocatalyst Ag/AgCl/TiO2 has been developed by a great
diversity of methods to make the best of sunlight [29,4143].
Based on the above discussions, to realize the immobilization of
TiO2 on the substrates with low thermal resistance and the utilization
of the visible light, Ag/AgCl-TiO2-cotton was prepared by coating TiO2
lms on the surface of cotton at low temperature and then loading
plasmonic photocatalyst Ag/AgCl nanoparticles on the TiO2 lms.
The prepared samples showed high visible light photocatalytic activity for the photocatalytic degradation of methyl orange (MO) and the
mechanism has been discussed.
2. Experimental section
2.1. Materials
Tetrabutyl titanate (Ti(OBu)4), silver nitrate (AgNO3), ammonium
hydroxide (NH3.H2O), hydrogen chloride (HCl), nitric acid (HNO3) and
isopropanol (C3H8O) were purchased from China National Medicines

D. Wu et al. / Thin Solid Films 540 (2013) 3640

Corporation Ltd. All chemicals were analytical grade without further

purication. Deionized water was used throughout this study.
2.2. Preparation of anatase TiO2 hydrosol
A typical synthesis of the TiO2 nanosol can be described as follows.
Tetrabutyl titanate (5 ml) was dissolved in isopropanol (5 ml), and
then the solution was dropwise added into 0.04 M HNO3 solution
(50 ml) under a vigorous stir at room temperature. Subsequently, the
suspension was kept stirring for 12 h to ensure complete hydrolysis
nucleation and growth of titania crystallites. Then the sol was reuxed
at 100 C for 6 h.
2.3. TiO2 coating process
The cotton fabrics, which have been pretreated with the method
described in our earlier study [5], were immersed in the TiO2 hydrosol
for 1 min and then pressed at a pressure of 1.25 kg cm2 for 5 min.
The coated substrates were heated at 60 C 5 min in preheated oven
and then cured at 100 C for 5 min to complete the formation of titanium dioxide. Finally, the fabrics were immersed in 70 C hot water for
3 h to remove unattached TiO2 particles from the fabric surface.
2.4. Ag/AgCl loading process
Firstly, TiO2-cotton fabrics were immersed 0.01 M [Ag(NH3)2]+
solution for 1 h in order to absorb large numbers of Ag+ as much as
possible on the surface. Secondly, the cotton fabrics were immersed
into 0.01 M HCl solution for 1 h so that the absorbed Ag+ on the cotton fabrics can react with Cl to generate AgCl nanoparticles. Thirdly,
the cotton fabrics were washed by a mass of water to remove unattached AgCl particles from the fabric surface. Finally, the prepared
samples were irradiated with a 1000-W xenon lamp for 10 min to reduce partial Ag+ ions in the AgCl particles to Ag0 species by photochemical decomposition of AgCl or TiO2 photocatalytic reduction [29].

3. Results and discussion

The microscope morphologies of the as-prepared TiO2-cotton and
Ag/AgCl-TiO2-cotton were investigated by SEM observation. Fig. 1a
shows a typical SEM image of the TiO2-cotton, which displays a homogeneous TiO2 coating on the surface of cotton with several cracks,
resulting in a smooth surface covered by TiO2 nanoparticles. Fig. 1b is
a low-magnication SEM image of the Ag/AgCl-TiO2-cotton, whose
surface has been covered obviously with a large number of Ag/AgCl
particles. However, the heterocomponents interface of Ag and AgCl
cannot be veried in current analysis.
XRD patterns of cotton, TiO2-cotton and Ag/AgCl-TiO2-cotton are
shown in Fig. 2. Because TiO2 prepared at 100 C has a relatively poor
degree of crystallinity, the diffraction peaks of cotton are so strong
that the diffraction peaks of TiO2 cannot be visibly displayed in the
TiO2-cotton sample. As a matter of fact, the anatase is observed for the
pure TiO2 nanoparticle powders [26]. In comparison with the diffraction
prole of cotton and TiO2-cotton, new strong diffraction peaks in
Ag/AgCl-TiO2-cotton appear at the position about 27.8, 32.3 and
46.4, corresponding to the peaks of (111), (200) and (220) diffraction
peaks of AgCl, and at the position about 38.2, 44.5 and 64.6 77.6, corresponding to the peaks of (111), (200), (220) and (311) diffraction
peaks of Ag. The XRD pattern of the obtained products can be indexed
to the cubic phase of Ag with lattice constant a = 4.074 (JCPDS le:
3-921) coexisting with the cubic phase of AgCl with lattice constant
a = 5.5491 (JCPDS le: 31-1238) (Fig. 3).
The surface components and chemical states of Ag/AgCl-TiO2-cotton
have been investigated by XPS analysis. The position of Ti 2p peaks for
the sample are at the value of 458.4 eV and 464.2 eV (Fig. 4a), which
conrms that the Ti element exists in the form of Ti4+ in the sample.
The Ag 3d spectrum consists of two peaks at about 367.4 and about
373.4 eV (Fig. 4b), which correspond to the binding energies of Ag

2.5. Characterization of catalysts

X-ray powder diffraction (XRD) patterns of samples were recorded on
a powder X-ray diffractometer (D/max-2200/PC, Rigaku Corporation,
Japan) with Cu K radiation, operating at 40 kV and 30 mA, where
= 0.15418 nm for the Cu K line. XPS experiments were carried out
on an RBD upgraded PHI-5000C ESCA system (Perkin Elmer, USA), and
the shift of the binding energy due to relative surface charging was
corrected using the C 1 s level at 284.6 eV as an internal standard. The
structure and the morphology of the coatings were investigated by the
eld emission scanning electron microscopy (FESEM, FEI SIRION 200,
FEI, USA). UVvis diffuse reectance spectra (DRS) of the samples were
recorded on a UVvis spectrophotometer (TU-1901) with an integrating
sphere attachment. The analyzed range was 230800 nm, and BaSO4 was
used as a reectance standard.
2.6. Photocatalytic activity measurements
Methyl orange (MO) was selected as model chemicals to evaluate
the activity of the samples in our homemade equipment. A 1000-W
Xe lamp was used as the light source of the homemade photoreactor,
surrounded with a water circulation facility at the outer wall through
a quartz jacket. The short wavelength components ( b 400 nm) of
the light were cut off using a glass optical lter. The distance between
the lamp and the center of the beaker was 100 cm. Before irradiation,
50 ml MO solution (5 mg/L) with 4 cm 4 cm Ag/AgCl-TiO2-cotton
fabrics was stirred in the dark for 30 min to achieve adsorption equilibrium. The MO solution was taken out at regular time intervals, and the
MO concentration was monitored at 464 nm using a UVvis spectrophotometer (UNICO 7200).

37

Fig. 1. SEM images of (a) TiO2-cotton and (b) Ag/AgCl-TiO2-cotton.

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D. Wu et al. / Thin Solid Films 540 (2013) 3640

Fig. 2. The XRD patterns of cotton, TiO2-cotton and Ag/AgCl-TiO2-cotton.

3d5/2 and Ag 3d3/2, respectively, with a doublet separation of 6 eV

[44]. For Cl 2p, two peaks are observed at binding energies of about
197.9 and 199.6 eV (Fig. 4c), corresponding to the binding energies of
Cl 2p3/2 and Cl 2p1/2, respectively, with a doublet separation of
1.7 eV [33]. The XPS results of Ag/AgCl-TiO2-cotton show that the calculated surface content of Ti, Ag and Cl is 16.57 mol%, 3.28 mol% and
2.85 mol%, respectively. The Ag/Cl atomic ratio is approximately 1.15,
which suggests that the as-obtained sample contains a small amount
of Ag metal species.
The UVvis diffuse reectance spectra of the samples are shown in
Fig. 5. Pristine cotton has no ability to absorb UV and visible light.
TiO2-cotton exhibits strong absorption in the UV region, which is attributed to the presence of TiO2 on the surface of cotton, which has
a strong capability of UV light absorption [26,45]. In comparison to
TiO2-cotton, Ag/AgCl-TiO2-cotton has strong absorption both in the
ultraviolet and visible-light regions. The absorption in the ultraviolet
region can be ascribed to the characteristic absorption of the AgCl and
TiO2 semiconductors, and the strong absorption in the visible-light
region can be attributed to the surface plasmon resonance of silver
nanoparticles [29,36,39]. The strong absorption makes the sample
use the sunlight more efciently.
The photocatalytic activity of Ag/AgCl-TiO2-cotton was measured by
decomposing methyl orange (MO) under visible irradiation. MO is a typical recalcitrant organic dye with negligible photolysis and sensitization
effect in the range of visible light. Fig. 6 shows the photodegradation of
MO dye as a function of irradiation time over different samples. Under
visible light irradiation, the degradation of MO over the pristine cotton
is negligible and the photodegradation of MO over TiO2-cotton is very
weak. However, the photocatalytic activity of Ag/AgCl-TiO2-cotton was
greatly enhanced, and almost all of MO has been removed after 60 min

Fig. 3. XRD patterns of (a) Ag (JCPDS No. 3-921), (b) AgCl (JCPDS No. 31-1238) and
(c) Ag/AgCl-TiO2-cotton.

Fig. 4. XPS spectra of Ti 2p, Ag 3d and Cl 2p of Ag/AgCl-TiO2-cotton.

irradiation. It is well known that photocatalytic oxidation of organic

pollutants follows rst-order kinetics. The apparent rate constant has
been chosen as the basic kinetic parameter for different photocatalysts,

Fig. 5. UVvis diffuse reectance spectra of the samples.

D. Wu et al. / Thin Solid Films 540 (2013) 3640

39

which was tted by the equation ln(C/C0) = kt, where k is the

apparent rate constant, C is the solution-phase concentration of
organic pollutant (in this case, MO) and C0 is the initial concentration
of MO. The rate constant for the photodegradation of the dye over
Ag/AgCl-TiO2-cotton (0.0391 min 1) is about 23 times higher
than that over TiO2-cotton (0.0017 min1). The excellent visiblelight-induced photocatalytic activity of Ag/AgCl-TiO2-cotton is likely related to the surface plasmon resonance effect from the Ag nanoparticles.
The photocatalytic activity of the Ag/AgCl-TiO2-cotton can be understood
by the following suggested mechanism (as shown in Fig. 7). Under visible
light irradiation, photogenerated electronhole pairs are formed in Ag
NPs due to surface plasmon resonance. The photoexcited electrons at
the silver NPs are injected into the TiO2 conduction band, and the active
species (O2, OOH, H2O2, OH) will be formed [46]. Meanwhile, the
holes transfer to the surface of the AgCl particles and cause the oxidation
of Cl ions to Cl0 atoms, which are reactive radical species and can oxidize
organic pollutant [47,48]. The major reaction steps in this plasmonic
photocatalytic mechanism under visible light irradiation are described
by Eqs. (1)(8) as follows [29,41]:

Ag
NPs hAg
NPs

Ag
NPs TiO2 Ag
NPs TiO2 e

Fig. 7. Schematic diagram for the charge separation in the visible light irradiated
Ag/AgCl-TiO2-cotton system.

4. Conclusions

TiO2 e O2 TiO2 O2

O2 H OOH

OOH TiO2 e H H2 O2 TiO2

H2 O2 TiO2 eOH OH TiO2

Ag
NPs Cl Ag
NPs Cl

Organic pollutant
0

Cl or OH or O2 or H2 O2 Degraded or mineralized products

Ag/AgCl-TiO2-cotton with visible-light-driven self-cleaning properties

has been prepared by depositing AgCl NPs on the surface of TiO2-cotton
and then reducing partial Ag+ ions in the surface region of the AgCl
particles to Ag0 species under xenon lamp irradiation. The prepared
Ag/AgCl-TiO2-cotton displays good visible-light absorption and
high visible-light-induced photocatalytic activity, which should be
attributed to the surface plasmon resonance absorption of silver
NPs under visible light irradiation and the charge separation at the silver
NPs, which includes electrons transferring from the plasmon-excited silver to TiO2 to form the active species (O2, OOH, H2O2, OH) and the
holes transfer to the surface of the AgCl particles to form Cl0 atoms.
Thus, Ag/AgCl-TiO2-cotton can be used as efcient visible-light-induced
self-cleaning materials and is promising to be employed for wastewater
treatment and air purication.
Acknowledgments
This project was supported by the State Ethnic Affairs Commission (12HBZ001), the Foundation of Hubei Educational Committee
(Q20122908), the National Natural Science Foundation of China
(21267009) and the Natural Science Foundation of Hubei Province
of China (2012FFB01104).
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Fig. 6. Photocatalytic activities of cotton, TiO2-cotton and Ag/AgCl-TiO2-cotton.

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