Colloids and Surfaces A: Physicochem. Eng.

Aspects 443 (2014) 501–507

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Efficient degradation of organic dyes by titanium

dioxide–silicotungstic acid nanocomposite films: Influence
of inorganic salts and surfactants
Ping Niu a,b , Jingcheng Hao a,∗
a
Key Laboratory of Colloid and Interface Chemistry & Key Laboratory of Special Aggregated Materials, Shandong University, Ministry of Education, Jinan
250100, PR China
b
Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, Dezhou University, Dezhou 253023, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Photocatalytic degradation of Photocatalytic nanocomposite films (TiO2 /SiW12 )n hybrids can be fabricated via an electrostatic layer-
(TiO2 /SiW12 )n films was fabricated by-layer (LbL) self-assembly method and a marked inhibition of anionic sodium dodecylsulfate (SDS) on
by LbL method. the degradation of methyl orange through the hybrids films was found.
• The photocatalytic degradation was
significantly suppressed with inor-
ganic salts.
• Nonionic C12 E23 and anionic SDS
have different degradation effect on
methyl orange.
• The nanocomposite films could have
substantial applications in textile
industries.

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

Article history: Photocatalytic nanocomposite films (TiO2 /SiW12 )n (TiO2 = titanium dioxide, SiW12 = H4 SiW12 O40 ) were
Received 11 June 2013 fabricated via an electrostatic layer-by-layer (LbL) self-assembly method, which is a rapid and simple
Received in revised form experimental fabrication process. UV–vis absorption spectra, atomic force microscopy (AFM), and X-ray
30 November 2013
photoelectron spectroscopy (XPS) were performed to characterize the LbL assembly process, surface mor-
Accepted 7 December 2013
Available online 17 December 2013
phology, and elemental composition of (TiO2 /SiW12 )n multilayer films. The influence of bilayers number
of (TiO2 /SiW12 )n composite films on the efficient removal of methyl orange (MO) was studied. In order
to determine the feasibility of the film catalysts for dye pollutants degradation, we chose three types
Keywords:
Layer-by-layer of colorful dyes including azoic, fluorescent, and sulfonic. Photodegradation rate of MO is significantly
TiO2 /SiW12 -nanocomposite films suppressed by inorganic salts including sodium chloride and sodium sulphate due to the aggregation or
Photodegradation association of ionic dye in water. The presence of nonionic polyoxyethylene dodecyl ether (C12 E23 ) accel-
Organic dyes erates the MO degradation. However, a marked inhibition of anionic sodium dodecylsulfate (SDS) on MO
Additives degradation is found at different SDS concentrations. It is expected that the fabricated photocatalytic
nanocomposite films could have substantial applications in textile industries or wastewater purification.

© 2013 Published by Elsevier B.V.

1. Introduction

Large quantities of highly colored dye effluents are produced

from textile industries. Their release causes seriously damage
∗ Corresponding author. Tel.: +86 531 8366074; fax: +86 531 88564750. to aquatic environments due to high toxicity, slow biodegrada-
E-mail address: jhao@sdu.edu.cn (J. Hao). tion and potential carcinogenicity [1]. Physical and traditional

0927-7757/$ – see front matter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.colsurfa.2013.12.005
502 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507
biological treatments have been proven insufficiently to removal
textile dyes with strong color [2]. The photocatalytic technology
assisted by titanium oxide (TiO2 ) has received enormous attentions
in recent years [3]. This technique has the advantage of strong oxi-
dation ability, low energy consumption, and simple operation and
has become an effective method for water purification.
Among the catalysts developed, anatase TiO2 has been exten-
sively studied [4]. However, the application of TiO2 nanoparticles
is limited owe to the fast recombination of photogenerated
carriers and inability to be recovered. The addition of polyoxo-
metalates (POMs) to TiO2 is an effective approach to increase
the electron–hole separation efficiency in TiO2 /POMs composites
[3,5,6]. In addition, the functional materials assembled into mul-
tilayer films can endow the films with specific properties [7,8].
Taking advantage of immobilization of catalysts on glass slides via
layer-by-layer method, the problem of catalyst recovery is solved
[9,10]. In the past decade, the photocatalytic degradation of dye
pollutants by TiO2 or POMs-containing films via LbL method has
been widely studied [9,11–14]. However, less attention was paid
on the photodegradation of dyes using TiO2 /POMs composite films
by this method.
It is well known that wastewaters discharged from the tex-
tile industries contain considerable amounts of inorganic salts
and surfactants. The presence of inorganic salts and surfactants
has complicated influence on the photocatalytic treatment pro-
cesses of dye effluents. Dong et al. [15] found that photocatalytic
decoloration of three azo dyes was significantly hindered by
inorganic salts. The inhibition effect caused by inorganic anions
was also reported on the degradation of dye Reactive Brilliant
Red X-3B at pH 2.7 [16] or Methylene Blue (MB) at neutral
and basic pH [17]. However, opposite results were discovered in
the Reactive Black 5 (RB5) degradation process, which attributed
to the enhancement in the amount of dye adsorbed on TiO2
[1].
Surfactants are one of the most widely used auxiliary agents
in textile and dyeing industries. After used, they are discharged
together with dyes. Zhao et al. [18] reported that anionic surfactant
sodium dodecylbenzenesulfonate (DBS) greatly enhanced adsorp-
tion on TiO2 particles and thus accelerated the photodegradation of
Rhodamine B (RhB). However, an inhibitory effect of three different
surfactants on the swep photodegradation was detected [19]. Other
researchers found that the presence of nonionic surfactant Tri-
ton X-100 could either enhance the photocatalytic degradation of
phenanthrene [20] or retard the photodegradation of carbaryl [21].
Either favorable or adverse effect of surfactants on the degrada-
tion of Reactive Black 5 by zero-valent iron (ZVI) particles modified
with surfactants was observed, which was decided by the types
of surfactants [2]. To our knowledge, however, no reports have
focused on the influence of salts and surfactants on photocatalytic
performance of the POM-containing nanocomposite films until
now.
In a recent study, we prepared TiO2 /PW12 nanocomposite thin
films using LbL method and investigated their photocatalytic activ-
ity for the MO decomposition [10]. Composite films with 10 bilayers
exhibited high photocatalytic activity at pH 2.0, which owed to
the synergistic effect of TiO2 and PW12 . The MO photodegrada-
tion reaction was dominated by active holes (h+ ). In this report,
we successfully prepared TiO2 /SiW12 nanocomposite films via LbL
self-assembly method and found that the films exhibited highly
photocatalytic activity toward methyl orange (MO) at acidic media.
In order to further check the photocatalytic efficiency of com-
posite films, other six colorful dyes were used as probes. The
influence of inorganic salts and surfactants on photodegradation
of MO in TiO2 /SiW12 system was also investigated under the same
conditions.
2. Experimental
2.1. Materials
Titanium dioxide (TiO2 ) colloid was prepared according to liter-
ature [22]. X-ray diffraction revealed that colloidal TiO2 nanoparti-
cles were anatase with mean particle size 4 nm. H4 SiW12 O40 ·xH2 O
(SiW12 ) was purchased from Sinopharm Chemical reagent Co. Ltd.,
China. MO and Reactive Brilliant Red X-3B were obtained from Jin-
ing Chemical Engineering Research Institute. Acid Orange (AO7),
Ponceau G (PG), Rhodamine B (Rh B), Fushion Acid (FA), and Netu-
tal Red (NR) were from Aladdin Chemistry Co. Ltd. The chemical
structures, formula, and mole weights of organic dyes used in our
study were listed in Table 1. Poly(sodium 4-styrenesulfonate) (PSS,
Mw ∼70,000), poly(allylamine hydrochloride) (PAH, Mw ∼70,000),
and polyoxyethylene dodecyl ether (C12 E23 ) were purchased from
Sigma–Aldrich Inc., USA. Dodecyltrimethylammonium bromide
(DTAB) and sodium dodecylsulfate (SDS) were obtained from J&K
Scientific Ltd. Perchloric acid was obtained from Shanghai Jinlu
Chemical Co. Ltd., China. Sodium chloride and sodium sulfate were
provided by Tianjin Chemical Reagent Company, China. All chemi-
cals were used without further treatment.
2.2. Assembly of multilayer films
The solid substrates containing quartz slides, silicon wafers and
microscopic glass slides were firstly ultrasonicated in a sequence of
acetone, H2 O, ethanol and H2 O at 50 ◦ C for 20 min. Further purifi-
cation was conducted by immersing in piranha solution at 80 ◦ C
for 1 h and H2 O–H2 O2 –NH4 OH (5/1/1, v/v/v) solution at 70 ◦ C for
30 min to gain a hydrophilic surface before LbL deposition. Rinsing
by abundant deionized water was necessary at each purification
step. The clean substrates were firstly immersed in PAH and PSS
aqueous solution (2.0 g L−1 with 0.5 mol/L NaCl, pH 2.5) for 20 min
to gain a surface with uniform charge. After rinsed with water
(adjusted to pH 2.5 by perchloric acid solution) and dried by N2 , the
substrates with two precursor layers was then alternately dipped
in positive charged TiO2 colloid solution (16.0 g L−1 , pH 2.0) and
negative charged SiW12 solution (3.0 mmol L−1 ) for 15 min, respec-
tively. Substrates were rinsed and dried after each deposition cycle.
(TiO2 /SiW12 )n multilayer films with desired bilayers number could
be formed by repeating the procedure as described above.
2.3. Characterization of thin films
UV–vis absorption spectra were recorded using HITACHIU-4100
spectrophotometer. Atomic force microscopy (AFM) measure-
ments operated in tapping mode were carried out using Digital
Instruments Nanoscope IIIa in air. XPS spectra were obtained on a
PHI-5702 multifunctional X-ray photoelectron spectroscopy, using
Al K␣ radiation (photon energy 1476.6 eV) as the excitation source.
2.4. Photocatalytic experiments and analyses
Photocatalytic experiments of dyes were carried out on XPA-
system photoreactor (Xujiang Electromechanical Plant, Nanjing of
China). The energy source was a 300 W medium-pressure mercury
lamp (output mainly at 365 nm), which was cooled by circulat-
ing water through a double walled quartz glass tube. The light
was positioned horizontally and located 18 cm above the dye solu-
tion. The reaction of photodegradation of dyes proceeded in culture
dish open to air at ambient temperature. In a typical experiment,
six pieces of glass slides (12.7 mm × 38.1 mm/piece) coated with
(TiO2 /SiW12 )n films were placed in 20 mL fresh dye (10 mg L−1 )
aqueous solution with pH 2.0. The absorbance of dye solution
 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507 503

Table 1
The characteristics of seven organic dyes.

Dye max (nm) Chemical structure Formula Mw (g mol)

H
NaO3S N N N(CH 3 )2
Methyl orange (MO)a C14 H14 N3 O3 SNa 327.34
507
Cl

N N

OH HN N Cl

N N

NaO 3S SO3Na
Reactive Brilliant Red X-3B C19 H10 Cl2 N6 O7 S2 Na2 615.39
538
OH

N N SO 3Na

Acid Orange 7 (AO7) C16 H11 N2 NaO4 S 350.32

484
CH 3 OH SO 3Na

H3 C N N

Ponceau G (PG) SO 3Na C18 H14 N2 Na2 O7 S2 480.43

508
N CH 3
HCl
Netutal Red (NR) (H3C)2N N NH 2 C15 H17 ClN4 288.78
528
CH 3

NH2
SO 3Na
H 2N
NH2
SO 3
Fushion Acid (FA) C20 H17 N3 Na2 O9 S3 585.54
544

(C2H5) 2N O N(C 2H5) 2 Cl

COOH

Rhodamine B (RhB) C28 H31 N2 O3 Cl 479.01

553
a
Quinoid structure of methyl orange when pH value is lower than 3.1.

was measured by Shimadzu 2450 UV–vis spectrophotometer. The characteristic band at 263 nm is assigned to charge transfer from
removal efficiency could be estimated according to the following oxygen to tungsten atom of H4 SiW12 O40 [23]. A plot of absorbance
formula: at 263 nm versus bilayers number of (TiO2 /SiW12 )n is shown in
A0 − A inset of Fig. 1. It is indicated that the absorption peak intensity
removal efficiency (%) = × 100%
A0
0.21
where A0 represents original absorbance of dye solution at their 0.20
maximum absorption wavelength, A is residual absorbance of dye 0.18 0.16
Absorbance

after photodegradation. 0.12

0.15
10
Absorbance

0.08
3. Results and discussion 0.12 8
0.04
6 2 4 6 8 10
Number of Bilayers
0.09 4
3.1. Characterization of composite films
2
0.06
The LbL assembly process of TiO2 –SiW12 multilayer films was
monitored by UV–vis spectroscopy. Fig. 1 shows the evolution of 0.03

UV–vis spectra of the (TiO2 /SiW12 )n composite films (with n = 2, 0.00

4, 6, 8, and 10) assembled on (PAH/PSS)1 precursor film-coated 250 300 350 400 450 500 550 600
quartz slides. The precursor film shows no absorption peaks in the Wavelength / nm
wavelength range of 230–600 nm. One can see that the absorbance
Fig. 1. UV–vis spectra of the (TiO2 /SiW12 )n composite films assembled on quartz
of composite films increases steadily with the number of bilay- slides. Inset is the relationship between absorbance at 263 nm and number of
ers, which confirms irreversible adsorption of TiO2 and SiW12 . The bilayers.
504 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507
Fig. 2. AFM images of (a) (PAH/PSS)1 precursor film and (b) (TiO2 /SiW12 )4 composite film assembled on silicon slides.
of this band is increased almost linearly with increasing of bilay-
ers number, suggesting that the amount of catalysts deposited is
identical at each deposition cycle. The near-linearity of the curve
also proves that the LbL assembly of the multilayer films is regular
and the deposition process of TiO2 and SiW12 in composite films is
reproducible.
To obtain the detailed information about the surface morphol-
ogy and homogeneity of multilayer films, AFM investigation was
performed. Fig. 2 presents AFM images of the (PAH/PSS)1 precursor
film and (TiO2 /SiW12 )4 nanocomposite film. It can be clearly seen
from Fig. 2a that the (PAH/PSS)1 precursor film is smooth and uni-
form. Its root-mean-square (rms) roughness is 1.639 nm calculated
from an area of 2.0 ␮m × 2.0 ␮m. As shown in Fig. 2b, the surface of
(TiO2 /SiW12 )4 film presents typical spherical or granular patterns
with size ranged from 70 to 90 nm, which is similar to other TiO2 -
deposited films constructed by LbL method [24,25]. The formation
of these patterns may arise from the aggregation of TiO2 colloidal
nanoparticles and SiW12 polyanions. The rms roughness increases
to 7.108 nm for (TiO2 /SiW12 )4 after alternative deposition of TiO2
and SiW12 . The three-dimensional AFM image of (TiO2 /SiW12 )4 film
(seen in Fig. 2b) reveals a fine-grain structure indicating the uniform
distribution of agglomerates in the film.
XPS measurements were carried out to investigate the atomic
composition and chemical state of elements in LbL film. The results
are given in Fig. 3. It is clearly seen that the multilayer films contain
Ti and W elements. The Ti 2p3/2 and Ti 2p1/2 peaks are presented at
ca. 459.1 and 464.9 eV, respectively. The two peaks of Ti 2p can be
ascribed to Ti4+ of anatase TiO2 nanoparticles in multilayer films
[26]. Fig. 3b shows the XPS spectra of W 4f. The binding energy
(BE) of W 4f7/2 is found at 35.8 eV, and the peak position of W 4f5/2
locates at 37.8 eV [27]. The W 4f peaks corresponding to the high-
est oxidant state of W confirm the presence of Keggin type POM
molecules. The XPS analyses clearly reveal the existence of the TiO2
nanoparticles and SiW12 polyanions in the composite films, which
are in agreement with the results of UV–vis spectra.
3.2. Photocatalytic performance of composite films
To study the effect of bilayers number of (TiO2 /SiW12 )n films on
dye degradation, controlling experiments were performed. Methyl
orange (MO), azoic dye, is chosen as a probe because of its wide
use in industries of textiles, foodstuffs, papers and leathers. Fig. 4
shows the effect of bilayers number on dye photodegradation. In
the dark, MO degradation is hardly observed in the presence of
catalysts (not shown here). In addition, only 12.91% degradation is
observed after UV light irradiation for 60 min without any catalysts.
It can be seen from Fig. 4 that photocatalytic efficiency of compos-
ite films increases with increasing number of bilayers. The removal
efficiency can reach 60.48%, 77.30%, 83.10%, 95.53%, 95.95%, and
97.44% with 2, 4, 6, 8, 10, and 15 bilayers, respectively. It is obviously
seen from above data that when the number of bilayers is larger
than 8, the degradation of MO increases slowly. Therefore, the opti-
mum bilayers number of (TiO2 /SiW12 )n film as a catalyst is 8. The
rapid degradation of MO is the result of synergistic effect of TiO2
and H4 SiW12 O40 [3,5,6,10]. Another reason for MO with higher
removal efficiency at acidic condition is that its quinoid form is
more readily photodecomposed [10,28]. It is worthwhile to note
that the removal efficiency of MO is not linearly increased with
increasing of number of bilayers as shown in Fig. 4b. Similar result
was also reported by Priya et al. [9] Above results could account for
the fact that the contribution to pollutant degradation is different
for TiO2 and SiW12 in inner and outer layers. What is more, the sur-
face structure and porosity of LbL films also have influences on dye
degradation in addition to the film thickness [9].
To well evaluate the photocatalytic activity of composite
films, we chose other six colorful dyes including azoic (PG, AO7,
 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507 505

a Ti 2p3/2 b W 4f5/2
W 4f7/2

Intensity
Intensity Ti 2p1/2

452 456 460 464 468 472 32 34 36 38 40 42 44

Binding Energy / eV Binding Energy / eV

Fig. 3. XPS spectra of the (TiO2 /SiW12 )4 nanocomposite film assembled on silicon slides.

100
10
a b
90
8

Removal / %
-1
cMO / mg•L

6 80
Bilayer
0
4 2
4 70
6
2 8
10 60
15
0
0 15 30 45 60 2 4 6 8 10 12 14 16
Illumination Time / min Number of Bilayers
Fig. 4. The effect of bilayers number of (TiO2 /SiW12 )n composite films on degradation of MO; the corresponding concentration was calculated in the light of standard curve
of MO at pH 2.0.

and X-3B), fluorescent (NR and RB), and sulfonic (FA). Their char- by TiO2 /POM composite films and MO photodegradation mainly
acteristics are listed in Table 1. The degradation processes were attributed to active hole (h+ ) [10]. The difference between two inor-
monitored by the change of absorbance at their maximum absorp- ganic salts may be mostly due to the aggregation or association of
tion wavelength. The results are shown in Fig. 5. For three other ionic dye in water. The aggregation degree of ionic dye in water
azo dyes (PG, AO7, and X-3B), the removal efficiency of AO7 in is greatly affected by concentration and structure of dye [15,30].
the presence of (TiO2 /SiW12 )8 composite catalysts is the highest, High concentration of salts and sulphonic group on one end of dye
which exceeds 91.00% after UV irradiation for 120 min. However, molecule is favorable for aggregation or association. Hence, aggre-
it is much less than that of MO. Therefore, we speculate it is gation is enhanced by the addition of sodium sulphate due to higher
the chemical structure of dye molecule and different substitutes ion concentration than sodium chloride and then subsequently give
of aromatic nuclei of the dyes that have significant influence rise to lose the chance of dye reacted with catalysts.
on the reactivity of dyes, thereby resulting in difference in the Surfactants are widely used as wetting, penetrating, dispersing,
removal efficiency [29]. In the case of other two types of dyes, and leveling agents in dyeing processes. The main role of surfac-
high removal efficiency can also be achieved under the same test tants is to increase the solubility of dyes in water, to improve
conditions as degradation of MO. The results mentioned above indi- the dye-uptake and dye fastness, to reduce the dyeing temper-
cate that TiO2 /SiW12 composite films exhibit high photoactivity ature. Therefore, actual dyes wastewaters contain not only dyes,
on different dyes degradation and thus have potential applica- but also other auxiliaries such as salts and surfactants. A large
tions in wastewater treatment. The detailed reaction conditions
and removal efficiency of dyes are presented in Table 2. Table 2
In textile industries, high concentrations of various inorganic Photocatalytic activity of TiO2 –SiW12 composite catalysts for degradation of organic
salts such as NaCl, Na2 SO4 and KCl were frequently used to improve dyes.
the dyeing rate of dyes [1]. Hence, huge amounts of inorganic salts Dyea,b Time (min) Removal (%)
are discharged with dyes. For this reason, we mainly discuss the
Methyl orange (MO) 60 95.53
effect of two inorganic salts, NaCl and Na2 SO4 , on the photocat- Reactive Brilliant Red X-3B 120 87.94
alytic degradation of methyl orange (MO). The results are shown Acid Orange (AO7) 90 91.44
in Fig. 6. It turns out that the presence of inorganic salts, especially Ponceau G (PG) 60 46.20
Na2 SO4 , shows an obvious inhibition effect on the MO degradation. Netutal Red (NR) 120 79.09
Fushion Acid (FA) 90 61.15
Increasing in the concentration of inorganic salts leads to a decrease
Rhodamine B (Rh B) 90 87.33
in removal efficiency of dyes. In the literature, the inhibition effect
a
The concentration of dye solution was 10 mg L−1 , the bilayers number of
of inorganic ions on photocatalytic activity was often explained by
TiO2 /SiW12 was 8, and pH value of solution was 2.0.
the scavenging of • OH radicals by anionic ions [17]. However, no b
pH value of NR solution was adjusted by H2 SO4 (3 mol/L), others were adjusted
hydroxyl radicals (• OH) were produced in dye degradation process by HClO4 (3 mol/L).
506 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507

100 of surfactant after being irradiated for 60 min. Compared with

(TiO2 /SiW12 )8 /MO binary system, only 88.00% of dye is removed
80 under the same test time. No spectral changes are observed
when nonionic surfactant C12 E23 is added, indicating that electro-
Removal / %

60 static interaction is nearly non-existent between neutral surfactant

40
20
0
0 15 30 45 60 75
Illumination Time / min
Fig. 5. Removal efficiency of different dyes as a function of irradiation time.
number of published articles on the treatment of textile efflu-
ents focused on principal interest in dyes removal, and often
neglected the influence of surfactants. In our study, in order to
make sure the effect of surfactants in the MO degradation process,
photocatalytic runs were performed in the presence of three differ-
ent surfactants, sodium dodecylsulfate (SDS, cmc = 8.6 mmol L−1 ),
polyoxyethylene dodecyl ether (C12 E23 , cmc = 0.043 mmol L−1 ) and
dodecyltrimethylammonium bromide (DTAB, cmc = 16 mmol L−1 ).
The concentration of surfactants investigated ranges from below to
above their critical micelle concentration (cmc). It can be observed
from Fig. 7a that the nonionic surfactant C12 E23 shows the excel-
lent acceleration effect on the photocatalytic degradation of MO. It
is interesting to note that whatever the concentration of C12 E23 is,
MO removal efficiency do not produce any increase. After 45 min
irradiation, the MO degradation in the presence of C12 E23 exceeds
over 95.00%, which is almost close to the result in the absence
molecules and the amphoteric molecules of MO. The formation of
X-3B
NR a weak complex between SiW12 polyanion and nonionic surfactant
FA C12 E23 is responsible for the enhancement of MO removal effi-
Rh B
ciency. As is well known, W atom of SiW12 polyanions has empty
PG
AO7 d orbitals, and oxygen in the EO groups of C12 E23 has extra lone
90 105 120 pairs of electrons. Hence, SiW12 in outermost layer of multilayer
films can accept lone pairs of electrons in EO groups to form a weak
complex. Similar phenomena were also observed between Fe3+ and
nonionic surfactant with polyoxyethylene groups [21,31]. The for-
mation of complex reduces the electrostatic repulsion between
negatively charged catalysts and MO (with net negative charge
confirmed by zeta potential measurement.), increases MO concen-
tration near catalysts surface via van der Waals attraction between
surfactant and MO molecules [21]. However, the further increase
of C12 E23 concentration hardly leads to any enhancement in dye
removal efficiency because of its saturation adsorption capacity on
(TiO2 /SW12 )8 composite films.
As shown in Fig. 7b, when photocatalytic degradation of MO
is performed in the presence of anionic surfactant SDS, a markedly
suppressing effect is observed. The higher the concentration of SDS,
the lower the removal efficiency of MO. When SDS concentration
reaches 34.4 mmol L−1 , the removal efficiency of dye declines from
95.5% to 67.2% after irradiated for 60 min. In premicellar or micellar
regions formed by anionic surfactant SDS, ionic pairs formed due
to the weak interaction between dye and SDS first adhere to the
micelles surfaces, and then incorporate into the micelles, in which

100 100
a b
80 80
Removal / %

Removal / %

60 60

40 Na2SO4 / mmol/L−1 40 NaCl / mmol/L-1

0 0
20 20 20
20
60 60
100 100
0 0
0 15 30 45 60 0 15 30 45 60
Illumination time / min Illumination time / min
Fig. 6. Removal efficiency of MO at different concentration of inorganic salts: (a) Na2 SO4 and (b)NaCl.

100 100
a b
80 80
Removal / %
Removal / %

60 60

C12E23 / mmol/L
40 40 SDS / mmol/L
0
0
0.022
4.3
20 0.043
20 8.6
0.43
17.2
1.29
34.4
0 0
0 15 30 45 60 0 15 30 45 60
Illumination Time /min Illumination Time / min
Fig. 7. Effect of surfactants concentration on photodegradation of MO: (a) C12 E23 and (b) SDS.
 P. Niu, J. Hao / Colloids and Surfaces A: Physicochem. Eng. Aspects 443 (2014) 501–507
MO may become inert to react with TiO2 /SiW12 composite films
[32,33]. In addition, the decrease in the photodecomposition rate
of MO may be due to the micellar cage effect and ‘inner filter’ effect
of photoproducts, which result in a significant reduction in the
fraction of incident light absorbed by catalysts [34]. At higher SDS
concentration, the movement of MO incorporated into the micelles
is hindered by excess surfactant micelles, which could account for
the decrease of MO removal efficiency [20].
When adding the cationic surfactant DTAB to MO solution at
pH 2.0, white precipitate forms immediately. It is evidence for the
formation of complexation between cationic surfactant and dye.
Strong interaction of negatively charged sulfonate groups on the
dye with positively charged head groups of DTAB molecules ulti-
mately lead to the formation of precipitation [32]. Consequently,
the degradation of MO in the presence of cationic surfactant DTAB
was not studied in this section.
4. Conclusions
(TiO2 /SiW12 )n nanocomposite films have been prepared by LbL
self-assembly method. The photocatalytic degradation of dye MO is
relatively fast in the presence of TiO2 /SiW12 films, which attributes
to the synergistic effect between TiO2 and SiW12 . The removal
efficiency increases steadily with an increase of bilayers num-
ber and the optimal bilayers number of (TiO2 /SiW12 )n catalyst
is 8. In addition, nanocomposite films show excellent photocat-
alytic performance for the degradation of other six colorful dyes.
The addition of inorganic salts greatly suppresses photocatalytic
activity of (TiO2 /SiW12 )8 due to the aggregation or association
of ionic dye in water. Unlike inorganic salts, nonionic surfactant
C12 E23 plays a positive role in pollutants removal. The formation
of a weak complex and van der Waals attraction increase MO
concentration near catalysts surface, and consequently accelerate
the MO degradation. Contrary to C12 E23 , the presence of anionic
surfactant SDS displays markedly suppressing effect on the photo-
catalytic reaction. This work will provide valuable information for
the researchers who engage in treatment of textile effluents.
Acknowledgements
This work was financially supported by the NSFC (Nos.
21033005 and 21273134), the National Basic Research Program of
China (973 Program, No. 2009CB930103).
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