RSC Advances

View Article Online

PAPER View Journal | View Issue
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.

Ag/TiO2 and Ag/SiO2 composite spheres: synthesis,

characterization and antibacterial properties3
Cite this: RSC Advances, 2013, 3,
9739
Qiushuang Zhang,a Junwei Ye,*a Peng Tian,a Xinyi Lu,a Yuan Lin,a Qi Zhao*b
and Guiling Ning*a

Received 2nd February 2013,
Accepted 22nd April 2013
DOI: 10.1039/c3ra40596f
www.rsc.org/advances
Ag/TiO2 and Ag/SiO2 composite spheres with coreshell structures were synthesized via an ion-exchange
method. Thin layers of TiO2 or SiO2 are deposited onto CaMg(CO3)2 templates using tetrabutyl titanate or
tetraethoxysilane, respectively, and the CaMg(CO3)2 cores are subsequently replaced by Ag2CO3 based on
the solubility product constant gap, followed by calcination of the intermediates, resulting in Ag/TiO2 and
Ag/SiO2 composite particles. The samples were characterized by X-ray powder diffraction (XRD), scanning
electron microscopy (SEM), thermogravimetry analysis (TGA), Fourier transform infrared spectroscopy (FT-
IR) and energy dispersive X-ray spectroscopy (EDX). The amount of Ag nanoparticles in the composites can
be adjusted using the relative concentration of the AgNO3 solution. Both the Ag/TiO2 and Ag/SiO2
composites exhibit excellent antibacterial activities using E. coli and S. aureus as test bacterial spawn.

Introduction polymers, metal oxides and carbon materials according to

Metal nanoparticles have received considerable attention due
to their remarkable properties and promising applications in
catalysis, optoelectronic devices, chemical and biological
sensors and drug delivery.14 Among these metal nanoparti-
cles, silver nanoparticles (Ag NPs) are well known for their
excellent inhibitory and bactericidal effects on both Gram-
negative and Gram-positive bacteria. Ag NPs have been used in
antibacterial devices, such as catheters, surgical devices, and
wound dressings.5 However, the toxicity and higher cost of
naked Ag NPs constitute severe drawbacks for practical
biomedical applications.6 Kim and co-workers showed that
free Ag NPs may accumulate in different organs and result in
neurotoxicity by generating free radicals through induced
oxidative stress.7 Besides, the stability of free Ag NPs has a
negative influence on their antibacterial activity. They may
aggregate or be destroyed under oxygen enriched condi-
tions.8,9 So there is great interest in incorporating Ag NPs
into various matrices to extend their utility as biomedical
materials.
To date, many attempts have been made to fabricate
composites containing Ag NPs and other components. The
main matrices can be clarified into three kinds: organic
a
State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian
University of Technology, 2 Linggong Road, Dalian 116012, P. R. China.
E-mail: junweiye@dlut.edu.cn; ninggl@dlut.edu.cn; Fax: +86-411-84986065
b
Department of Mechanical Engineering, University of Dundee, DD1 4HN, UK.
E-mail: Q.Zhao@dundee.ac.uk
3 Electronic supplementary information (ESI) available: Figures showing
extensive structural characterisation by SEM, XRD, EDX and IR. See DOI:
10.1039/c3ra40596f
their components. In recent years, the reported organic
polymer matrixes have included chitosan,10 PEPP,11 methyl
methacrylate,12 (acrylamide-co-itaconic acid)-grafted cotton
fabric etc.13 But Agorganic polymer composites are generally
sensitive to external stimuli such as heat, light and pH,
resulting in reduced stability of the materials.14,15 Thus design
and synthesis of Ag NPsinorganic composites is an important
topic in the field of biochemistry and materials science. For
example, Cui and co-workers9 have developed a AgFe3O4
composite which exhibits potent antibacterial properties and
can be separated easily by an applied magnetic field. In
addition, composites such as AgZnO,14,16 AgSiO2,1719 Ag
TiO2,20,21 AgAg2S,22 AgTiO2KIT-6,23 AgAgBrTiO224 etc.
have been developed recently using various approaches, for
example, solgel processing,2527 hydrothermal methods,28,29
anodic oxidation with electrodeposition,30 and photoreduction
methods.31,32 Nevertheless, the above methods still have some
drawbacks such as the occurrence of phase transfer in
aqueous solution, high cost and high energy consumption.33
So it is still a great challenge to find a more facile method for
synthesizing Ag NPs on multipurpose support materials or Ag
NPinorganic composites with excellent antibacterial bioactive
functionalities.
In this contribution, we present a general method to
synthesize Ag/TiO2 and Ag/SiO2 composite coreshell spheres
by using CaMg(CO3)2 as a template (Scheme 1). The
antibacterial activities of the Ag/TiO2 and Ag/SiO2 composites
were investigated by inhibition zone testing, in which the
bactericidal experiment was carried out with the Gram-
negative bacteria Escherichia coli and the Gram-positive
bacteria Staphylococcus aureus. The mechanism of action of

This journal is The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 97399744 | 9739

Paper
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.
Scheme 1 Schematic diagram of the synthesis of the Ag/TiO2 or Ag/SiO2
composites. (ad) The synthesis of the CaMg(CO3)2 template; (e) CaMg(CO3)2/
TiO2?xH2O or CaMg(CO3)2/SiO2?xH2O; (f) Ag2CO3/TiO2?xH2O or Ag2CO3/
SiO2?xH2O; (g) Ag/TiO2 or Ag/SiO2 composite.
the bacteriostat was discussed. The results indicate that the
Ag/TiO2 and Ag/SiO2 composites show better antibacterial
activity compared with free Ag NPs and could be candidates for
practical application as antibacterial materials.
Experimental section
Preparation of the CaMg(CO3)2 spheres
In a typical experiment, 50 mL MgCl2 solution (1 mol L21) and
50 mL Ca(NO3)2 solution (1 mol L21) were mixed homo-
geneously in a beaker. Then Na2CO3 solution (1 mol L21) was
added with continuous stirring for 10 min to form a white
suspension in the solution, which was then transferred into an
oven at 60 uC for 24 h. The obtained product was isolated by
centrifugation, washed with deionized water and then dried.
Preparation of the coreshell structured CaMg(CO3)2/
TiO2?xH2O and CaMg(CO3)2/SiO2?xH2O intermediates
The detailed synthesis procedure is described as follows:
firstly, the CaMg(CO3)2 template (0.5 g) was dispersed in 50 mL
absolute ethyl alcohol, followed by addition of tetrabutyl
titanate (TBT). To obtain the monocoated intermediate, a
mixture of distilled water and ethyl alcohol was slowly dropped
into the above mixture with vigorous stirring for 4 h at room
temperature. The intermediate sample CaMg(CO3)2/TiO2?xH2O
was washed with deionized water and ethyl alcohol sequen-
tially and then dried. The synthesis of CaMg(CO3)2/SiO2?xH2O
was similar to the above description for CaMg(CO3)2/
TiO2?xH2O except that TBT was replaced by tetraethoxysilane
(TEOS).
Preparation of the Ag/TiO2 and Ag/SiO2 composites
The CaMg(CO3)2/TiO2?xH2O or CaMg(CO3)2/SiO2?xH2O inter-
mediate was dispersed into ethyl alcohol via ultrasonication.
Then an appropriate amount of AgNO3 solution was added
into the above turbid liquid and stirred for several hours. The
obtained products were centrifuged with distilled water and
ethyl alcohol three times each and dried for 4 h at 60 uC. To
obtain the Ag/TiO2 and Ag/SiO2 composites, the above
9740 | RSC Adv., 2013, 3, 97399744
View Article Online
RSC Advances
products were calcined at a set temperature under a N2
atmosphere.
Antibacterial testing
The antimicrobial activities of the Ag/TiO2 and Ag/SiO2
composite spheres were analyzed by inhibition zone testing
and the bactericidal experiment was carried out with the
Gram-negative bacteria Escherichia coli and the Gram-positive
bacteria Staphylococcus aureus. The experiment using the Ag/
TiO2 composite spheres is described in detail as an example:
the first procedure was cultivating the bacteria solution with
100 mL nutrition media composed of peptone (10 g L21), NaCl
(10 g L21) and yeast powder (5 g L21). Then the bacteria
containing solution was diluted 102 times to enable the
separate bacterial colonies to be distinctly visible. The
concentration of the Ag/TiO2 mixing solution was adjusted to
be 500 mg L21. In the inhibition zone test, 50 mL E. coli or S.
aureus suspension was uniformly spread over several Luria
Bertani (LB) agar plates. The Ag/TiO2 solution (5 mL) was added
onto the center of the agar plates. At last, the Petri dishes were
incubated at 40 uC overnight. The clear zones in the center of
the disks were measured with the help of a scale that
represented the antibacterial properties of the different
composites.
Characterization
The morphology and sizes of the as-prepared samples were
observed with a JEOL-6360LV scanning electron microscope
(SEM) operated at 20 kV and with a NOVA NANOSEM 450 field
emission scanning electron microscope (FE-SEM) operated at
15 kV. Energy Dispersive X-Ray (EDX) analysis was also
performed on the JEOL-6360LV instrument during SEM. The
X-ray diffraction (XRD) patterns were obtained using a D/max-
2400 diffractometer using a Cu-Ka radiation source (l =
1.5406 ) with a 2h scan configuration in the range 580u. The
thermogravimetry analysis was carried out on a TGA/SDTA851u
(METTLER TOLEDO) instrument at a heating rate of 10 K
min21 under a N2 atmosphere. The Fourier Transform
Infrared Spectroscopy (FT-IR) was carried out using a JASCO
FT/IR 4100 instrument.
Results and discussion
Synthesis and characterization of the composites
For the sake of simplicity, the Ag/TiO2 composite spheres were
introduced to explain the synthesis process. The SEM images
and XRD patterns of the Ag/SiO2 composite spheres are shown
in the supporting information (Fig. S1 and S2, ESI3). As part of
our continuing studies on magnesium chemistry, CaMg(CO3)2
was selected as the template to prepare functional materials
with coreshell structures based on the significant difference
in the solubilities of CaMg(CO3)2 and other insoluble metal
salts.34,35 The basic synthetic process for the Ag/TiO2 compo-
site spheres via an ion-exchange reaction is illustrated in
This journal is The Royal Society of Chemistry 2013

RSC Advances
Scheme 1. The chemical equations summarising the whole
reaction are given as follows:
Ca2+ + Mg2+ + 2CO322 A CaMg(CO3)2
CaMg(CO3)2 + 4Ag+ A 2Ag2CO3 + Mg2+ + Ca2+
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.
N2
2Ag2 CO3 4Agz2CO2 zO2
The CaMg(CO3)2 spheres were prepared via a homogeneous
precipitation reaction (I). The spherical size of the CaMg(CO3)2
templates could be tuned by altering the concentration of the
raw solution, the ratio of Ca2+ to Mg2+ and the temperature
used in the crystal aging step. The optimum conditions for the
preparation of the CaMg(CO3)2 templates was stirring at 400 r
min21 for 10 min and aging for 24 h at 60 uC with a raw
material concentration of 1 mol L21. As the proposed ion-
exchange reaction (II) proceeded, a gradual color change from
white to creamy yellow, earthy brown and then to black was
observed in the mixed solution of AgNO3 and CaMg(CO3)2. The
procedure (III) was carried out to obtain pure Ag/TiO2
composite spheres. From eqn (I)(III), the original solution
containing Ca2+ and Mg2+ is retrieved which indicates this
method is more appropriate for industrialized production.
As demonstrated in the Scanning Electron Microscope
(SEM) images (Fig. 1), the Ag/TiO2 composite retains the
spherical structure of CaMg(CO3)2. The XRD analyses were
studied to further explain the synthesis mechanism. Fig. 2
indicates the structural evolution of the products from
CaMg(CO3)2 to CaMg(CO3)2/TiO2?xH2O, Ag2CO3/TiO2?xH2O
and finally to the Ag/TiO2 composite. The diffraction peaks
in Fig. 2d correspond to the (111), (200), (220) and (311) crystal
planes of Ag NPs. As shown in the amplified image (the inset
of Fig. 2d), there is only an amorphous peak, except for the
characteristic crystalline state corresponding to the main peak
of anatase TiO2, observed at 500 uC. To identify whether the
TiO2 shell was present, pure TiO2 hollow spheres after
Fig. 1 SEM images of (a) the CaMg(CO3)2 template, (b) the coated CaMg(CO3)2/
TiO2?xH2O precursor, (c) Ag2CO3/TiO2?xH2O and (d) the Ag/TiO2 composite.
This journal is The Royal Society of Chemistry 2013
View Article Online
Paper
(I)
(II)
(III)
Fig. 2 XRD patterns of samples: (a) the CaMg(CO3)2 template, (b) CaMg(CO3)2/
TiO2?xH2O, (c) Ag2CO3/TiO2?xH2O and (d) the Ag/TiO2 composite.
calcination at 500 uC were characterized by XRD (Fig. S3,
ESI3), which corresponded well with the typical anatase peaks.
Meanwhile the energy dispersive X-ray spectrum (EDX) was
used to investigate the elemental composition and further
confirmed that the sphere mainly consists of Ag, Ti and O (Fig.
S4, ESI3).
The thermal behaviour of the intermediate Ag2CO3/
TiO2?xH2O sample was studied by thermogravimetric analysis
(TGA) under a nitrogen atmosphere (Fig. S5, ESI3). The clear
peak before 200 uC may correspond to the loss of adsorbed
water and combined water. The small sharp weight loss at
around 257 uC is probably the result of decomposition of the
thermally-labile species Ag2O, which decomposed into Ag and
O2 above 227 uC.36 The FT-IR spectra of the different samples
are shown in Fig. S6 in the ESI.3 The spectrum of the
CaMg(CO3)2 spheres displays bands at 14501420, 890870,
10001100 and 720700 cm21 (Fig. S6a, ESI3), corresponding
to the asymmetric stretching and vibrations of the CO322
group, which are in agreement with the literature.37 Compared
with Fig. S6a, ESI,3 the band corresponding to the OH
vibration at 3478 cm21 in Fig. S6b, ESI,3 is present due to the
coating of Ti(OH)4 on the CaMg(CO3)2 spheres. When Ca2+ and
Mg2+ were replaced by Ag+, the stretching vibration of AgO
appears at 1713 cm21. After calcination at 400 uC for 2 h, the
bands corresponding to AgO and OH disappear but the band
corresponding to TiOTi increases as shown in Fig. S6d, ESI.3
Fig. 3 shows typical SEM images of the Ag/TiO2 composite
spheres. As can be seen from the SEM images, the product
consists of coreshell spheres with Ag NPs encapsulated. The
diameter of the composite spheres is about 6 mm (Fig. 3a) and
the shell thickness is 45 nm. A large-scale view (Fig. 3b)
indicates that the as-synthesized spheres have typical hollow
structures and nearly monodisperse encapsulated Ag NPs
(Fig. 3d). Fig. 3c reveals that the shell is composed of close-
packed Ag NPs, with an average diameter of 63 nm (light), and
TiO2 particles (dark). The inset images in Fig. 3b and d
indicate that TiO2 exists in the shell only with a percentage by
weight of 0.78 (Ti) to 67.20 (Ag), while there is no Ti inside the
composite spheres.
RSC Adv., 2013, 3, 97399744 | 9741

Paper
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.
Fig. 3 Field emission scanning electron microscopic (FESEM) images of the Ag/
TiO2 composite spheres (ad). The insets in (b) and (d) are EDX spectra.
The effect of synthesis factors on the structure of the
composites
In order to investigate the ion-exchange reaction, some
influencing factors were considered. The reactant concentra-
tion is an important factor in the preparation of composite
materials, especially for those with hybrid structures. In the
process of these experiments, the effect of changing the Ag+
concentration on the structure, morphology and properties
was investigated. Fig. S7, ESI,3 shows the XRD patterns of the
samples obtained with different Ag+ concentrations. There is
no variation in the peak positions of the Ag NPs, but the
intensity decreases with increasing Ag+ concentration. The
reason may be that the crystallite dimensions are larger at
lower concentrations. This phenomenon can also be observed
in the SEM images in Fig. S8 in the ESI.3 There is also a large
amount of inhomogeneous Ag NPs outside the TiO2 shell (Fig.
S8a, ESI3). This result confirms that the reaction rate may slow
down when the reactant concentration decreases.
In order to further investigate the effect of reaction time on
the products, the reaction was controlled from 2 h to 8 h. Fig. 4
and Fig. S9, ESI,3 show the SEM images and EDX spectra of
products obtained at different reaction times. There was a
large amount of CaMg(CO3)2 left in the sample obtained after
2 h, which corresponds well with the EDX spectrum (Fig. 4b).
Fig. 4c exhibits that the sample obtained at 4 h possesses a
good spherical morphology. There are no impurities in the
composite when the reaction time was extended to 8 h (Fig.
S9b, ESI3) but many irregular Ag NPs aggregated on the shell of
the spheres (Fig. 4d). It can be seen that there are a few Ca2+
ions still remaining while the Mg2+ ions were completely
removed. These results are consistent with the different Ksp of
MgCO3 (1.0 6 1026) and CaCO3 (0.87 6 1028), and the rate of
ion exchange of Ag+ with Mg2+ ions is quicker than that with
Ca2+ ions. Additionally, the amount of Ag+ ions can be
controlled by the reaction time. The SEM images show that
the morphology of the products will be damaged if the
reaction time is too long.
9742 | RSC Adv., 2013, 3, 97399744
View Article Online
RSC Advances
Fig. 4 SEM (a, c and d) and EDX (b) images of the Ag/TiO2 composite spheres
obtained with different reaction times: (a) and (b) 2 h, (c) 4 h, (d) 8 h.
The calcination temperature is also an important factor in
the preparation of the materials. In the XRD patterns of the
samples obtained at different reaction temperatures (Fig. S10,
ESI3), all of the peaks are in good agreement with the Ag NPs/
TiO2 composite. A sample with good crystallization and an
integrated spherical morphology can be obtained after
calcination at 400 uC. However, there is much fragmentation
in the composite when the temperature is increased to 600 uC
(Fig. S11, ESI3).
Antibacterial properties
To evaluate the antibacterial activity of the Ag/TiO2 and Ag/
SiO2 composite spheres, inhibition zone experiments were
carried out with the Gram-negative bacteria Escherichia coli
and the Gram-positive bacteria Staphylococcus aureus (Fig. 5
and 6). The relationship between antibacterial properties and
concentration was investigated using the Ag/TiO2 composite
spheres. As shown in Fig. S12 in the ESI,3 whether Gram-
negative or Gram-positive bacteria are used, the Ag/TiO2
composite spheres show better antimicrobial activity to some
extent. From the images and data, the diameter of the
inhibition zone decreases from 11 mm to 9 mm when the
concentration of Ag/TiO2 composite spheres decreases from
1000 ppm to 250 ppm. It is believed that the silver NPs can
bind with the thiol groups in proteins,3840 interact with the
bacterial membranes,41 and this subsequently results in DNA
becoming more condensed. However, the specific reason for
the antibacterial properties is that the silver NPs are released
into an aqueous solution, forming Ag+ ions. Then the Ag+ ions
strongly bind to electron donating groups in biological
molecules containing sulfur, oxygen or nitrogen.33 All these
phenomena lead to damage or even the death of the
microorganisms.32 Therefore as the sample concentration
rises, the Ag ion concentration increases and the antibacterial
properties are also improved.
In order to determine whether the TiO2 or SiO2 matrices
and/or supports improve the bactericidal activity of Ag NPs,
control experiments were carried out. Free Ag NPs of several
dozen nanometers in size, TiO2 and SiO2 hollow microspheres
This journal is The Royal Society of Chemistry 2013

RSC Advances
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.
Fig. 5 Optical images (I) and diameter (II) of the zones of inhibition formed by
using E. coli (1) and S. aureus (2) as the test bacterial spawn for (a) TiO2, (b) Ag
NPs, and (c) the Ag/TiO2 composite.
were synthesized using CaMg(CO3)2 as the template (Fig. S13,
ESI3). The control experiment antibacterial results are shown
in Fig. 5 and 6. As can be seen from the data, the Ag/TiO2 and
Ag/SiO2 composite spheres showed better antibacterial activ-
ities than the Ag nanoparticles and SiO2 or TiO2 microspheres.
According to the reported results,15,42 Ag NPs can bind to
bacterial cell wall membranes (with slightly negative charges),
so that electron transport between the Ag NPs and the bacteria
disrupt their wall membranes. It was also proposed that Ag
NPs can interact with the thiol groups in proteins, resulting in
the generation of reactive oxygen species. Moreover, interac-
tion between the Ag NPs and the DNA structure of bacteria
may prevent DNA multiplication. For silver-containing bacter-
icidal materials, both strong antibacterial activities and low
silver release are the key characteristics. High silver release
lead to a decrease in the lifetime and efficiency of the
antibacterial activity of the samples. So in this paper, the
reason that the obtained Ag/SiO2 and TiO2 sphere composites
possessed better antibacterial properties than the pure Ag NPs
was attributed to the direct interaction of the Ag NPs on the
shell of the composites with the bacteria, and further damage
to the bacteria was caused by the Ag NPs released from inside
the composites.
This journal is The Royal Society of Chemistry 2013
View Article Online
Paper
Fig. 6 Optical images (I) and diameter (II) of the zones of inhibition formed by
using E. coli (1) and S. aureus (2) as the test bacterial spawn for (a) SiO2, (b) Ag
NPs, (c) the Ag/SiO2 composite.
Conclusions
In this paper, a facile synthesis route for Ag/TiO2 and Ag/SiO2
composite spheres is presented based on the Ksp difference
between Ag2CO3 and CaMg(CO3)2. The obtained Ag/TiO2 and
Ag/SiO2 composite spheres possess coreshell structures with
Ag NPs encapsulated. The assembly process can be controlled
by the reactant concentration, reaction time and calcination
temperature. The as-prepared Ag/TiO2 and Ag/SiO2 composite
spheres exhibited excellent antibacterial activities with E. coli
and S. aureus as test bacteria. The results indicated that both
Ag/TiO2 and Ag/SiO2 composites have better antibacterial
activity compared with free Ag NPs and could be candidates for
practical applications as antibacterial materials.
Acknowledgements
This work was supported by National Natural Science
Foundation of China (21076041 and 21276046), and the
ministry of education science and technology research project,
and High-Tech R&D projects in Magnesium Industry of
Liaoning Province in China. We thank Dr Wenjie Yuan for
discussion about antibacterial experiments.
RSC Adv., 2013, 3, 97399744 | 9743

Paper
References
1 H. Sakai, D. Kanda, H. Shibata, T. Ohkubo and M. Abe, J.
Am. Chem. Soc., 2006, 128, 49444945.
2 T. Hirakawa and P. V. Kamat, J. Am. Chem. Soc., 2005, 127,
39283934.
Published on 23 April 2013. Downloaded by UNIVERSIT DEGLI STUDI DI TORINO on 20/07/2013 14:15:44.
3 H. Y. Chuang and D. H. Chen, Nanotechnology, 2009, 20,
105704.
4 W. B. Liang, T. L. Church and A. T. Harris, Green Chem.,
2012, 14, 968975.
5 J. H. Cui, C. F. Hu, Y. H. Yang, Y. J. Wu, L. F. Yang, Y.
L. Wang, Y. L. Liu and Z. Y. Jiang, J. Mater. Chem., 2012, 22,
81218126.
6 A. Alonso, N. Vigues, X. M. Berbel, J. Macana s, M. Mun oz, 27 X. L. Cheng, Y. M. Xu, S. Gao, H. Zhao and L. H. Huo, Sens.
J. Mas and D. N. Muraviev, Chem. Commun., 2011, 47,
1046410466.
7 Y. S. Kim, J. S. Kim, H. S. Cho, D. S. Rha, J. M. Kim, J.
D. Park, B. S. Choi, R. Lim, H. K. Chang, Y. H. Chung, I.
H. Kwon, J. Jeong, B. S. Han and I. J. Yu, Inhalation Toxicol.,
2008, 20, 575583.
8 R. Foldbjerg, P. Olesen, M. Hougaard, D. A. Dang, H.
J. Hoffmann and H. Autrup, Toxicol. Lett., 2009, 190,
156162.
9 J. Liu, Z. W. Zhao, H. Feng and F. Y. Cui, J. Mater. Chem.,
2012, 22, 1389113894.
10 X. L. Cao, C. Cheng, Y. L. Ma and C. S. Zhao, J. Mater. Sci.:
Mater. Med., 2010, 21, 28612868.
11 S. H. Jeong, Y. H. Hwang and S. C. Yi, J. Mater. Sci., 2005,
40, 54135418.
12 H. Kong and J. Jang, Langmuir, 2008, 24, 20512056.
13 P. Gupta, M. Bajpai and S. K. Bajpai, J. Cotton Sci., 2008, 12,
280286.
14 H. Koga, T. Kitaoka and H. Wariishi, J. Mater. Chem., 2009,
19, 21352140.
15 O. Akhavan, M. Abdolahad, Y. Abdi and S. Mohajerzadeh, J.
Mater. Chem., 2011, 21, 387393.
16 S. Ghosh, V. S. Goudar, K. G. Padmalekha, S. V. Bhat, S.
S. Indic and H. N. Vasan, RSC Adv., 2012, 2, 930940.
17 A. Sanchez-Iglesias, I. Pastoriza-Santos and L. M. Liz-
Marzan, Nano Lett., 2011, 11, 30163021.
18 M. Lessard-Viger, M. Rioux, L. Rainville and D. Boudreau,
Nano Lett., 2009, 9, 30663071.
19 X. G. Meng, K. Fujita, S. Murai, T. Matoba and K. Tanaka,
Nano Lett., 2011, 11, 13741378.
20 H. Sakai, T. Kanda, H. Shibata, T. Ohkubo and M. Abe, J.
Am. Chem. Soc., 2006, 128, 49444945.
9744 | RSC Adv., 2013, 3, 97399744
View Article Online
RSC Advances
21 I. Medina-Ramirez, Z. P. Luo, S. Bashir, R. Mernaugh and J.
L. Liu, Dalton Trans., 2011, 40, 10471054.
22 M. L. Pang, J. Y. Hu and H. C. Zeng, J. Am. Chem. Soc., 2010,
132, 1077110785.
23 F. L. Zhang, Y. H. Zheng, Y. N. Cao, C. Q. Chen, Y. Y. Zhan,
X. Y. Lin, Q. Zheng, K. M. Wei and J. F. Zhu, J. Mater.
Chem., 2009, 19, 27712777.
24 M. R. Elahifard, S. Rahimnejad, S. Haghighi and M.
R. Gholami, J. Am. Chem. Soc., 2007, 129, 95529553.
25 C. Hu, T. W. Peng, X. X. Hu, Y. L. Nie, X. F. Zhou, J. H. Qu
and H. He, J. Am. Chem. Soc., 2010, 132, 857862.
26 Y. Q. Qu, R. Cheng, Q. Su and X. F. Duan, J. Am. Chem. Soc.,
2011, 133, 1673016733.
Actuators, B, 2011, 155, 716721.
28 B. Cheng, Y. Le and J. Yu, J. Hazard. Mater., 2010, 177,
971977.
29 Y. Lai, Y. Chen, H. Zhuang and C. Lin, Mater. Lett., 2008,
62, 36883690.
30 J. X. Li, L. X. Yang, S. L. Luo, B. B. Chen, J. Li, H. L. Lin, Q.
Y. Cai and S. Z. Yao, Anal. Chem., 2010, 82, 73577361.
31 D. Guin, S. V. Manorama, J. N. L. Latha and S. Singh, J.
Phys. Chem. C, 2007, 111, 1339313397.
32 R. Vinu and G. Madras, Appl. Catal., A, 2009, 366, 130140.
33 N. Ren, R. Li, L. M. Chen, G. C. Wang, D. Liu, Y. J. Wang,
L. Zheng, W. Tang, X. Q. Yu, H. D. Jiang, H. Liu and N.
Q. Wu, J. Mater. Chem., 2012, 22, 1915119160.
34 P. Tian, J. W. Ye, N. Xu, W. T. Gong, Q. S. Zhang, Y. Lin and
G. L. Ning, Chem. Commun., 2011, 47, 1200812010.
35 P. Tian, J. W. Ye, G. L. Ning, W. T. Gong, N. Xu, Q. S. Zhang
and Y. Lin, RSC Adv., 2012, 2, 1021710221.
36 A. V. Rupa, D. Manikandan, D. Divakar and T. Sivakumar, J.
Hazard. Mater., 2007, 147, 906913.
37 S. Gunasekaran, G. Anbalagan and S. Pandi, J. Raman
Spectrosc., 2006, 37, 892899.
38 O. Akhavan and E. Ghaderi, Surf. Coat. Technol., 2010, 204,
36763683.
39 T. Liu, H. Q. Tang, X. M. Cai, J. Zhao, D. J. Li, R. Li and X.
L. Sun, Phys. Res., Sect. B, 2007, 264, 282286.
40 W. Yuan, G. Jiang, J. Che, X. Qi, R. Xu, M. W. Chang,
Y. Chen, S. Y. Lim, J. Dai and M. B. Chan-Park, J. Phys.
Chem. C, 2008, 112, 1875418759.
41 L. P. Lukhele, B. B. Mamba, M. N. Momba and R. W.
M. Krause, J. Appl. Sci., 2010, 10, 6570.
42 H. Zhang and G. Chen, Environ. Sci. Technol., 2009, 43,
29052910.
This journal is The Royal Society of Chemistry 2013