Materials Chemistry and Physics 129 (2011) 501–505

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Materials Chemistry and Physics

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

Preparation of Ag-doped TiO2 nanoparticles by a miniemulsion

method and their photoactivity in visible light illuminations
Youji Li ∗ , Mingyuan Ma, Wei Chen, Leiyong Li, Mengxiong Zen
College of Chemistry and Chemical Engineering, Jishou University, Jishou 46000, Hunan, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Visible-light-driven photocatalysts based on silver-doped TiO2 (Ag–TiO2 ) nanoparticles were successfully
Received 26 June 2009 synthesized by a miniemulsion method and characterized by X-ray diffraction (XRD), scanning elec-
Received in revised form 9 March 2011 tron microscope (SEM), X-ray photoelectron spectroscopy (XPS), BET surface area analysis and UV–vis
Accepted 22 April 2011
diffuse reflectance spectroscopy (DRS). Degradation of methylene blue (MB) was applied to evaluate
photocatalytic activity of samples. The results show that Ag doping showed a controlling effect on the
Keywords:
transformation of titania from anatase to rutile. A red shift occurred in the absorption edge of titania with
Nanostructures
the certain Ag-doped amount. Moreover, the addition of Ag resulted in a higher Brunauer–Emmett–Teller
Chemical synthesis
Electron microscopy
(BET) surface area as well as a larger average pore size of TiO2 nanoparticles. The specific surface area
Oxidation increased with the Ag-doped amount to reach a maximum (86.3 m2 g−1 ) at Ag/Ti molar ratio of 0.8%
and then decreased with further increase of the Ag-doped amount. The Ag–TiO2 nanoparticles could
effectively photodegrade MB under visible light irradiation and the obtained maximum reaction con-
stant (kapp = 0.007 min−1 ) was three times higher than that of pure TiO2 (kapp = 0.002 min−1 ) when the
Ag-doped amount was 0.8%. The commendable visible photoactivities of Ag–TiO2 photocatalysts are pre-
dominantly attributable to simultaneous effects of Ag deposits by the acting as electron traps, enhancing
the MB adsorption on the Ag–TiO2 surface, occurring red shift of the absorption edge and decreasing band
gap.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Ag+ ions makes a dramatic improvement in the performance of TiO2

Recently, TiO2 has been widely studied for its wide application
in photocatalysis [1], solar cells [2], hydrogen production [3] and
catalyst support [4,5]. However, its wide band gap (anatase: 3.2 eV;
rutile: 3.0 eV), the extensive exploitation of TiO2 created an expec-
tation to use merely 3–4% UV light of the whole radiant solar energy.
Extensive efforts have been made in the development of TiO2 pho-
tocatalysts that can efficiently utilize solar or indoor light to extend
the activating spectrum from UV to visible light [6–10]. These stud-
ies include doping metal ions into the TiO2 lattice [11,12], dye
photosensitization on the TiO2 surface [1,13–16], and deposition of
noble metals [17–21]. In particular, noble metal-modified semicon-
ductor nanoparticles become of current importance for maximizing
the efficiency of photocatalytic reactions. In recent years, there
have been some reports on the preparation of Ag+ -doped TiO2 films
and nanoparticles that degrade some textile dyes (methyl orange,
crystal violet, and methyl red) in aqueous medium [22–24]. Fur-
thermore, silver halides, such as AgBr/SiO2 and AgCl catalysts, have
also been used in photocatalysis [25,26]. It appears that doping with
∗ Corresponding author. Tel.: +86 13762157748.
E-mail address: bcclyj@163.com (Y. Li).
photocatalysts, however, the aforementioned silver based photo-
catalysts function only under UV light. There are only few articles
reported about the photoactivity of Ag–TiO2 in visible light illumi-
nations. Additionally, researchers discovered that materials in the
nano-size domain exhibit a unique surface chemical reactivity for
the destructive absorption of acid gas and chemical warfare agents
[27,28]. Moreover, this unique surface reactivity of nanomaterials
was attributed to the high surface areas and the presence of defects,
edges, and corners, which are available of improving photoactiv-
ity of TiO2 in visible light illuminations. There are different routes
that can be used to synthesize titanium dioxide. These include
flame synthesis [29], chemical vapor deposition [30], precipitation
[31] and the alkoxide sol–gel method [32]. The miniemulsifica-
tion technique, having a controlled reaction rate, is a promising
method to synthesize nanomaterials with high surface area [33].
Therefore, it is rationally more desirable to synthesize visible-light-
driven photocatalysts based on silver-doped TiO2 nanoparticles by
a miniemulsion method.
In this paper, silver-doped titania nanoparticles were prepared
by a miniemulsion method with the hydrolysis of Ti(OBun)4 in the
presence of silver nitrate. The photoreactivity of the synthesized
materials was evaluated by degradation of methylene blue, cho-
sen as a standard model molecule, was performed under visible

0254-0584/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2011.04.055
502 Y. Li et al. / Materials Chemistry and Physics 129 (2011) 501–505

light irradiation. The samples were characterized using DRS, XRD,

nitrogen adsorption–desorption and SEM measurements.

2. Experimental

2.1. Preparation of Ag–TiO2 nanoparticles

The tetrabutyltitanate, cyclohexanol, hexadecyl trimethyl ammonium bromide,

triethylamine and acetone were used as titanium source, impregnant, surfactant,
precipitator, and lotion, respectively. Oil–water components system was con-
firmed in the experiments of preparing Ag–TiO2 nanoparticles by a miniemulsion
method. The particularly synthesizing process was followed: tetrabutyltitanate
(10 ml) was used to produce titanium dioxide particles by hydrolysis and miniemul-
sion dispersed in cyclohexanol (50 ml) was added to a premixed solution among,
cyclohexanol (50 ml), a certain weight of hexadecyl trimethyl ammonium bro-
mide, distilled water and silver nitrate at room temperature. This solution had been
aged for 12 h to obtain silver-doped TiO2 particles with using triethylamine as pre-
cipitator. These particles were recovered and washed three times with acetone.
Centrifugation was used to recover the particles. The particles were then allowed to
dry in an oven at 80 ◦ C for 2 h, followed by calcinations at different temperature for
2 h. Four kinds of Ag–TiO2 were prepared by varying the molar ratio of silver relative
to titania after vigorous stirring for several hours. The samples were denominated
X% Ag–TiO2 (X% denoted the molar ratio of silver to titanium).
2.2. Catalyst characterization
The crystalline phase was identified by X-ray diffraction (Bruker, Germany)
using Cu-K␣ as radiation and were analyzed from 20◦ to 80◦ (2). Nitrogen
adsorption–desorption isotherms were recorded at 77 K (Micromeritics ASAP 2020)
and the specific surface areas were determined by the Brunauer–Emmett–Teller
(BET) method. The diffuse reflectance UV–Vis spectra of the samples were deter-
mined by a Cray-300 UV/VIS spectrophotometer at room temperature. BaSO4 was
used as the standard in all measurements. The morphology of the prepared samples
were observed by SEM (JSM-5600LV, Japan). Samples were prepared by ultrasonic
dispersion of the powder in alcohol prior to testing at the room temperature. The
average particle size of TiO2 was measured by photon correlation spectroscopy (PCS)
with an argon ion laser (Lexel Laser Inc. Model 95-2) operated at 514.4 nm and
200 mW. The chemical states of silver and titanium were studied by XPS measure-
ments, using a VG Scientific ESCALAB Mark spectrometer (England), where the X-ray
photoelectron spectra were reference to the C1s peak (Eb = 285.0 eV).
2.3. Photoactivity measurements
Methylene blue (MB) was chosen as a model organic compound to evaluate the
photoactivity of the prepared Ag–TiO2 nanoparticles. Fig. 1 shows a scheme of the
experimental apparatus. The main component of the system was the reactor, on
which there was a 1000 W high-pressure mercury lamp to provide the irradiance
source with internal stirring by a magnetic stirrer. There is a filter to assure visible
light in photocatalytic experiments at a distance of 20 cm from the top. The initial
concentration of methylene blue in stirred aqueous solution was fixed at 2 mg l−1
with a catalyst loading of 5 g l−1 . To determine the change of methylene blue concen-
tration in solution during the photocatalytic process, a few milliliters of the solution
was taken from the reaction mixture, subsequently centrifuged, filtered through a
Millipore filter (pore size 0.22 ␮m) to separate the catalysts, and loaded in a UV–vis
spectrometer (JascoV-500, Japan). For accurate evaluation of photocatalytic degra-
dation rate of MB, each experiment was repeated at least twice. The absorption peak
at 660 nm was adopted to make calibration curve as shown in small illustration of
Fig. 2. The methylene blue concentration was calculated by using a calibration curve
according to the absorbance intensity at 660 nm in photocatalytic process.
Fig. 1. Experimental apparatus for photocatalytic reaction.
3. Results and discussion
3.1. Catalyst characterization
Liquid nitrogen absorption-desorption experimental results are
presented in Table 1, the Brunauer–Emmett–Teller (BET) surface
area was strongly dependent on Ag-doped amount. Obviously, the
specific surface areas of the doped TiO2 samples are higher than
that of the undoped TiO2 . When the Ag-doped amount was 0, 0.5,
0.8, 1.0 and 2.0%, the SBET of Ag–TiO2 was 47.7, 72.5, 86.3, 69.5
and 60.2 m2 g−1 , respectively. It can be seen that SBET increased
with the Ag-doped amount to reach a maximum at 0.8% and then
decreased with further increase of the Ag-doped amount. It is
understandable that the higher the Ag-doped amount, the lower
the BET surface area because of sintering of the smaller parti-
cles into the bigger particles. That is why TiO2 catalysts at 2.0% of
Ag-doped amount have the least surface area (60.2 m2 g−1 ). Mean-
while, the Ag-doped amount has a profound effect on the pore
size distribution of samples calcined at 500 ◦ C as shown in Fig. 3.
The narrow pore size distribution of pores is in range of 3–12 nm,
and the average pore size of Ag–TiO2 increased with an increase
in Ag-doped amount. As presented in Table 1, doped samples still
retained intra-particles mesopores, while the intra-particles meso-
pores almost decreased for the undoped samples. Fig. 4 illustrates
the X-ray diffraction (XRD) profiles of silver-doped TiO2 samples
calcined progressively at 400, 500, and 600 ◦ C for 2 h and undoped
TiO2 calcined at 550 ◦ C. It can be seen that there were sharp and
strong peaks of anatase phase at 2 = 25.3◦ in XRD patterns of all
samples. There appeared no peaks for rutile (2 = 27.5◦ ) phases in
all 0.8% Ag–TiO2 samples. It indicated that the phase transforma-
tion from anatase to rutile did not take place when 0.8% Ag–TiO2
powder was calcined at temperatures below 600 ◦ C. It meant that
silver could control the phase transformation from anatase to rutile.
It was well known that the occurrence of the anatase-to-rutile tran-
sition actually depends on several factors (e.g. preparation method,
particle sizes, heating rate, doping level). Similar findings were also
reported by other authors [18,20]. They had found that silver pre-

30
a b
Concentration (mg·L–1)

20

10 Y2 = 0.997
y = 6.1705x

0
500 550 600 650 700 0 2 4 6

Wavelength (nm) Absorption intensity (a.u.)

Fig. 2. UV–vis spectrum of methylene blue (a) and relationship between concentration of MB and its absorption intensity of UV–vis at 660 nm (b).
 Y. Li et al. / Materials Chemistry and Physics 129 (2011) 501–505 503

Table 1
The characteristics of titanium dioxide with Ag doping.

Samples Surface areas (m2 g−1 ) Mean pore size (nm) Band energy (eV) Kinetic constant (mine−1 )

TiO2 47.4 – 3.16 0.002

0.5% Ag–TiO2 72.5 3 3.08 0.005
0.8% Ag–TiO2 86.3 5 3.00 0.007
1.0% Ag–TiO2 69.5 8 2.98 0.006
2.0% Ag–TiO2 60.2 12 2.92 0.004

als with photon energies. Therefore, it is absolutely imperative to

e e: 2%Ag- TiO 2 include this technique to examine for the photoactivity of synthe-
b c d d: 1%Ag- TiO 2 sized photocatalysts. Fig. 5 demonstrates the DRS spectra profiles
c: 0.8%Ag- TiO 2 of titanium dioxide with various amount of silver calcined at 500 ◦ C
for 2 h. Here, we perceived a noticeable shift of the optical absorp-
b: 0.5%Ag- TiO 2
tion edges of the doped TiO2 systems toward the visible regions of
dV(dR) / (cc/g)

a: TiO 2
a
1 2 4 8 16 32 64
Diameter size(nm)
Fig. 3. The pore size distribution curve of TiO2 calcined at 500 ◦ C for 2 h.
vented the phase transformation as well as had an inhibition effect
on the growth of anatase crystallite. However, the opposite results
about promoting effect of Ag doping on the phase transformation
were appeared in some articles [34,35]. Additionally, no notice-
able peaks of silver oxide and silver metal were observed in the
X-ray diffractograms perhaps due to the microscale of Ag-doped
amount. Diffuse reflectance UV–vis spectroscopy directly provides
some insight into the interactions of the photocatalyst materi-
the solar spectrum. Notably, this redshift toward the longer wave-
lengths originates from the band gap narrowing of titanium dioxide
by silver doping and the band gap energy of the doped samples
was determined from the equation, Eg = 1239.8/, where  is the
wavelength (nm) of the exciting light [36]. The band gap energies
of the samples were listed in Table 1. Because the doped samples
have lower band gap energies than the undoped TiO2 (3.16 eV),
these photocatalysts are, therefore, likely to operate under visi-
ble light illumination. Additionally, it is evidently observed that
the Ag-doped amount can result the profound effect on UV–vis
absorption spectra of the Ag–TiO2 catalysts. The absorption of the
sample in the visible range was of 400–600 nm and increased with
the increase of the Ag-doped amount in TiO2 . In the SEM micro-
graphs shown in Fig. 6, only titanium dioxide particles can be seen
although the doped Ag is coloured for the presence of the silver.
Thus it can be concluded that either the amount of silver parti-
cles is too low, so that the probability to find a silver particle in
SEM is small, or that the size of the silver particles is too small, so
that the resolution of SEM is not sufficient to detect them. The par-
ticle size of the Ag–TiO2 nanoparticles was measured by PCS. The
TiO2 particles prepared without the addition of silver (Fig. 6a) were
aggregated and the average size of the particles was 30 nm. When
Ag-doped amount was 0.8%, the Ag–TiO2 particles were spheri-
cal and the aggregation was reduced (Fig. 6b). The particles were
homogeneously dispersed and the size was about 20–30 nm with
the average of 25 nm. However, the excess silver (2.0%) deterio-
rated the dispersion of the particles and the aggregation appeared

Fig. 5. Diffuse reflectance UV–vis spectra of TiO2 samples, prepared by a miniemul-

Fig. 4. XRD patterns of titania powders calcined at different temperatures. sion method at 500 ◦ C for 2 h.
504 Y. Li et al. / Materials Chemistry and Physics 129 (2011) 501–505

Fig. 6. Scanning electron micrographs of Ag–TiO2 calcined at 500 ◦ C for 2 h. (a) TiO2 . (b) 0.8% Ag–TiO2 . (c) 2% Ag–TiO2 .

Ag+ Ag 0 a b
Ti3+ Ti4+

Intensity (arb.units)
Intensity (arb.units)

Ag3d5/2 Ag3d3/2

Ti2p3/2

Ti2p1/2

360 365 370 375 380 456 460 464 468

Binding energy (eV) Binding energy (eV)

Fig. 7. High-resolution XPS spectra of the 0.8% Ag–TiO2 nanoparticles: Ag 3d (a) and Ti 2p (b).

again (Fig. 6c). The size of the TiO2 particles was about 30–40 nm
with the average of 35 nm. X-ray photoelectron spectroscopy (XPS)
experiments were performed to elucidate both the chemical state
of the silver particles and the titania structure. As shown in Fig. 7a,
in terms of the chemical bonding states of Ag2 O (Ag+ , 367.8 eV) and
Ag (Ag0 , 368.2 eV) in the Ag 3d XPS peaks, respectively [37,38], the
presence of both Ag0 and Ag+ species was determined by measuring
the XPS of the best Ag–TiO2 catalyst. In general, advisable amount
of Ag doping is available of enhancing the catalytic property of the
material because the presence of both Ag0 and Ag+ species facilitate
the charge separation (electron–hole) and suppress the recombina-
tion of the photoexcited charge carriers. Additionally, Fig. 7b shows
the narrow scans for Ti 2p peaks located at 464.8 eV (Ti 2p1/2) and
458.8 eV (Ti 2p3/2) of the Ag–TiO2 photocatalysts which represent
the existence of two peaks at 457.5 eV and 458.9 eV matching the
trivalent and tetravalent states of Ti, respectively. Acted as active
trates the profound effect of Ag-doped amount on the methylene
blue degradation on Ag–TiO2 in visible light illuminations. After
450 min photodegradation reaction excitated by visible light irradi-
ation, 82–100% methylene blue were decomposed on the Ag–TiO2
samples, while only 24% methylene blue were degraded on the
pure TiO2 prepared without the addition of Ag. The degradation of
methylene blue on pure TiO2 catalyst under visible light irradiation
was attributed to the photosensitization process [40]. Anatase tita-
nia could not be directly excitated by visible light due to its 3.2 eV
band gap, but the photobleaching reaction still occurred under
TiO2 /dye/visiblelight system due to dye molecule acting as photo-
100
Residue rate of methylene blue (%)

center, vacancy sites (Ti3+ sites) can trap the photogenerated elec- 80
trons in the conduction band and prevent the recombination of
electron–hole pairs under UV. So these Ti3+ sites play important TiO2
roles in the photooxidation of organic compound on the TiO2 pho- 2%Ag- TiO2
60
tocatalysts [39]. 0.5%Ag- TiO2
1%Ag- TiO2
0.8%Ag- TiO2
3.2. Photocatalytic activity 40

Prior to photocatalytic reactions, the suspension was mag-

netically stirred in the dark for 60 min to establish an 20
adsorption–desorption equilibrium at room temperature. Photoac-
tivities for methylene blue in the dark in the presence of the
photocatalysts and under visible light irradiation in the absence 0
of the photocatalysts were also evaluated. It was found that there 0 100 200 300 400 500
was no degradation for the methylene blue in the dark and in the
Time (mine)
presence of the photocatalyst. Also no degradation was observed
for methylene blue when the solution was placed under visible light Fig. 8. Decomposition of methylene blue in aqueous solution by TiO2 process in
radiation without the addition of photocatalyst powder. Fig. 8 illus- visible light illuminations with various Ag incorporated content.
 Y. Li et al. / Materials Chemistry and Physics 129 (2011) 501–505
sensitizer. The electron from the excited dye molecule was injected
into the conduction band (CB) of the TiO2 , and the cation radical
formed at the dye surface quickly undergoes degradation reaction
to oxidise methylene blue into products. Additionally, it greatly
affected the Ag–TiO2 photoactivity that the addition concentration
of silver was varied from 0.5 to 2.0%. The optimal photoactivity of
the catalyst was achieved for 0.8% of Ag+ ion. This means that 0.8%
Ag+ ion concentration effectively suppresses the recombination of
the photogenerated charge-carriers on the surface of the catalyst.
Unfortunately, an increase in Ag+ ion concentration from 0.8 to 2.0%
has a deleterious effect on the photoactivity of the catalysts. Con-
ceivably, this happens because of the creation of recombination
centers of charge-carriers at a higher loading of dopant concentra-
tion [11]. Meanwhile, 0.8% Ag+ ion concentration can result in high
surface area of catalyst so that a large number of reactant molecules
are absorbed and undergo subsequent oxidation reactions. The
decomposition behavior of methylene blue in aqueous solution by
doped TiO2 process was adequately described by pseudo first-order
reaction kinetics and the calculated rate constants are depicted
in Table 1. The photodecomposition rate constant of methylene
blue by doped TiO2 process enhanced from 0.002 to 0.007 min−1
with an increase in the silver incorporated content up to a certain
level (optimum silver incorporated content) and then decreased.
The rate of organic oxidation is dependent on the concentration
of organic molecules and oxidising agents in the suspension [2,4].
The excess incorporated content of silver-laden particles may cover
active sites on the TiO2 surface, and thereby reducing photodegra-
dation efficiency.
4. Conclusions
Ag–TiO2 nanoparticles were prepared by a miniemulsion
method using Ti(OBun)4 and Ag(NO3 ) as starting materials. Ag dop-
ing could control the transformation of titania from anatase to
rutile. With increasing of the Ag-doped amount, the absorption
edge of Ag–TiO2 shifted to longer wavelength, and the band gap
energy of Ag–TiO2 decreased. With a suitable amount (0.5–2.0%),
the Ag dopant increases the specific surface area of TiO2 pow-
der. In photodegradation MB solution, the photocatalytic activity of
Ag–TiO2 increased with the increase of Ag-doped molar ratio from
0 to 0.8%, but declined with the further increase to 2.0%. The optimal
molar ratio for photocatalytic activity of Ag–TiO2 was found as 0.8%
with the high BET surface area of 86.3 m2 g−1 , of which rate con-
stant (kapp = 0.007 min−1 ) was three times higher than that of pure
TiO2 (kapp = 0.002 min−1 ). The commendable visible photoactivi-
ties of Ag–TiO2 photocatalysts are predominantly attributable to
505
simultaneous effects of Ag deposits by the acting as electron traps,
enhancing the MB adsorption on the Ag–TiO2 surface, occurring red
shift of the absorption edge resulting from a decrease in band gap.
References
[1] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. A: Chem. C: Pho-
tochem. Rev. 1 (2000) 1.
[2] B. O’Regan, M. Gratzel, Nature 353 (1991) 737, 10.
[3] A. Fujishima, K. Honda, Nature 238 (1972) 37.
[4] S. Koutsopoulos, S.B. Rasmussen, K.M. Eriksen, R. Fehrmann, Appl. Catal. A: Gen.
306 (2006) 142.
[5] J.T. Miller, A.J. Kropf, Y. Zha, J.R. Regalbuto, L. Delannoy, C. Louis, E. Bus, J.A. van
Bokhoven, J. Catal. 240 (2) (2006) 222.
[6] R. Asahi, T. Morikawa, T. Ohwaki, Science 293 (2001) 269.
[7] S.U.M. Khan, M. Al-Shahry, W.B. Ingler Jr., Science 297 (2002) 2243.
[8] M. Anpo, M. Takeuchi, J. Catal. 216 (2003) 505.
[9] T. Ihara, M. Miyoshi, Y. Iriyama, O. Matsumoto, S. Sugihara, Appl. Catal. B:
Environ. 42 (2003) 403.
[10] Y.B. Xie, C.W. Yuan, Appl. Catal. B 46 (2003) 251.
[11] S.D. Mo, L.B. Lin, J. Phys. Chem. Solids 55 (1994) 1309.
[12] W. Choi, A. Termin, M.R. Hoffmann, J. Phys. Chem. 98 (1994) 13669.
[13] K. Vinodgopal, D.E. Wynkoop, P.V. Kamat, Environ. Sci. Technol. 30 (1996) 1660.
[14] J. Zhao, T. Wu, K.Wu.K. Oikawa, H. Hidaka, N. Serpone, Environ. Sci. Technol. 32
(1998) 2394.
[15] T. Wu, G. Liu, J. Zhao, H. Hidaka, N. Serpone, J. Phys. Chem. B 102 (1998) 5845.
[16] G. Liu, T. Wu, T. Lin, J. Zhao, Environ. Sci. Technol. 33 (1999) 1379.
[17] A. Sclafani, J.-M. Herrmann, J. Photochem. Photobiol. A 113 (1998) 181.
[18] B.H. Dambar, J.K. Amal, Kenneth, J. Colloid Interface Sci. 311 (2007) 514.
[19] V. Subramanian, E. Wolf, P. Kamat, J. Phys. Chem. B 105 (2001) 11439.
[20] J.Y. Park, J.J. Yun, C.H. Hwang, I.H. Lee, Mater. Lett. 64 (24) (2010) 2692.
[21] V. Vamathevan, R. Amal, D. Beydoun, G. Low, S. McEvoy, J. Photochem. Photo-
biol. A 148 (2002) 233.
[22] P. Falaras, I.M. Arabatzis, T. Stergiopoulos, M.C. Bernard, Int. J. Photoenergy 5
(2003) 123.
[23] K. Gupta, A. Pal, C. Sahoo, Dyes Pigments 69 (2006) 224.
[24] Y. Liu, C.Y. Liu, Q.H. Rong, Z. Zhang, Appl. Surf. Sci. 220 (2003) 7.
[25] N. Kakuta, N. Goto, H. Ohkita, T. Mizushima, J. Phys. Chem. B 103 (9) (1999)
5917.
[26] A. Currao, V.R. Reddy, M.K. van Veen, R.E.I. Schropp, G. Calzferri, Photochem.
Photobiol. Sci. 3 (2004) 1017.
[27] C.L. Carnes, K.J. Klabunde, Chem. Mater. 14 (4) (2002) 1807.
[28] G.M. Medine, V. Zaikovskii, K.J. Klabunde, J. Mater. Chem. 14 (2004) 757.
[29] S.E. Pratsinis, J. Aerosol Sci. 27 (1996) 153.
[30] Z. Ding, X. Hu, P.L. Yue, G.Q. Lu, P.F. Greenfield, Catal. Today 68 (2001) 178.
[31] H.D. Nam, B.H. Lee, S. Kim, C. Jung, J. Lee, S. Park, J. Appl. Phys. 37 (1998) 4606.
[32] K.Y. Jung, S.B. Park, J. Photochem. Photobiol.: A Chem. 127 (1999) 119.
[33] K.C. Song, J.H. Kim, Powder Technol. 107 (2000) 270.
[34] H.E. Chao, Y.U. Yun, H.U. Xingfang, A. Larbot, J. Eur. Ceram. Soc. 23 (9) (2003)
1457.
[35] X.B. Li, L.L. Wang, X.H. Lu, J. Hazard. Mater. 177 (1–3) (2010) 639.
[36] A.R. Gandhe, J.B. Fernandes, Bull. Catal. Soc. India 4 (2005) 131.
[37] X.Y. Gao, S.Y. Wang, J. Li, Y.X. Zheng, R.J. Zhang, P. Zhou, Y.M. Yang, L.Y. Chen,
Thin Solid. Films 455/456 (2004) 438.
[38] F.X. Bocka, T.M. Christensenb, S.B. Riversc, L.D. Doucettea, R.J. Lad, Thin Solid
Films 468 (2004) 57.
[39] H. Liu, H.T. Ma, X.Z. Li, W.Z. Li, M. Wu, X.H. Bao, Chemosphere 50 (2003) 39.
[40] M.S.S. Hyung, R.C. Jae, J.H. Hoe, M.K. Sang, C.B. Young, J. Photochem. Photobiol.
A: Chem. 163 (2004) 37, 12.