Desalination 286 (2012) 41–48

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Desalination
journal homepage: www.elsevier.com/locate/desal

Effective photocatalytic decolorization of methyl orange utilizing TiO2/ZnO/chitosan

nanocomposite films under simulated solar irradiation
Huayue Zhu a, b, Ru Jiang a,⁎, Yongqian Fu a, Yujiang Guan a, Jun Yao a, Ling Xiao b, Guangming Zeng c
a
School of Life Science, Taizhou University, Taizhou 317000, PR China
b
Key Laboratory for Biomass-Resource Chemistry and Environmental Biotechnology of Hubei Province, College of Resource and Environmental Science, Wuhan University,
Wuhan 430072, PR China
c
Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, PR China

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

Article history: Titanium dioxide/zinc oxide/chitosan nanocomposite thin films (TiO2/ZnO/chitosan NTFs) were prepared by
Received 29 April 2011 entrapping zinc ions and nanosized TiO2 in chitosan thin films under mild conditions. The structure, thermal
Received in revised form 24 October 2011 property, and surface morphology of TiO2/ZnO/chitosan NTFs were characterized by X-ray diffraction (XRD),
Accepted 26 October 2011
thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and high-resolution transmission
Available online 21 November 2011
electron microscopy (HRTEM). The photocatalytic activity of TiO2/ZnO/chitosan NTFs was evaluated by
Keywords:
photocatalytic decolorization of methyl orange in aqueous solution as a model pollutant under simulated
Photocatalysis solar irradiation. The HRTEM results revealed that well-dispersed and uniform TiO2/ZnO nanocomposite
Decolorization with diameters of 5–15 nm were embedded in chitosan films. The TiO2/ZnO/chitosan NTFs exhibited high
Methyl orange photocatalytic activity under simulated solar irradiation. After 4 h of irradiation by simulated solar light,
TiO2/ZnO/chitosan over 97% of methyl orange solution (15 mg L− 1) was decolorized with 0.5 g L − 1 of the photocatalyst. The
Simulated solar light TiO2/ZnO/chitosan NTFs could be reused, which meant that the adsorption-photocatalytic decolorization pro-
cess could be operated at a relatively low cost. Since this process does not require the addition of hydrogen
peroxide and uses solar light, it can be developed as an economically feasible and environmentally friendly
method to decolorize or treat dye wastewater using sunlight.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction (anatase) [4,5]. It can be activated by ultraviolet (UV) light of wave-

Dyes from textile industry are significant pollutants. About half of
the global production of synthetic textile dyes (7,000,000 tons per
year) are azo compounds, which have chromophore (–N=N–) in
their molecular structures [1]. About 15% of the total amount of
dyes produced are lost during dyeing process and released as efflu-
ents. These colored compounds in textile effluents are usually readily
detected in the effluent, and has to be removed before discharging
into water bodies since these dyeing effluents have toxic effects on
the ecosystem, especially on microorganisms, and their long degrada-
tion time in the environment is a cause for concern. However, most of
the azo dyes are generally resistant to biological decolorization.
Recently, heterogeneous photocatalysis using semiconductors such
as titanium dioxide has attracted much attention because of its ability
to decolorize dye-containing wastewater [2,3]. This process can
mineralize organic dyes completely into H2O, CO2 and other nontoxic
inorganic compounds without bringing secondary pollution. Titanium
dioxide (TiO2) is a semiconductor with a wide band gap of 3.2 eV
⁎ Corresponding author at: No. 605, Orient Avenue, Linhai City, Zhejiang Province,
P R China (317000). Tel.: + 86 158 6763 6396; fax: + 86 0576 8513 7066.
E-mail address: jiangru0576@163.com (R. Jiang).
lengths below 385 nm, which greatly limits the use of sunlight as an
energy source for the photoreactions since only about 3%–4% of the
solar spectrum falls within the UV range [5,6]. In addition, high
recombination rate of electron/hole pairs reduces the quantum yield
of a single TiO2 semiconductor [7]. Recently, zinc oxide (ZnO) nano-
crystal has been proposed as a suitable alternative to titanium dioxide
[8–10]. Meanwhile, some researchers have proven that titanium
dioxide–zinc oxide coupled semiconductor systems with various
band gap widths can enhance charge separation rate and visible-
light photocatalytic activity compared with a single component
catalyst [10–14]. The nanosized interfaces and microstructural
properties may play a vital role in the improved photocatalytic
activity of composite photocatalysts [15]. However, nanosized
materials have a trend to aggregate in aqueous solution during
preparation and utilization through direct inter-particle interac-
tions such as van der Waals forces. In addition, the difficulty in
separating and recovering nanosized composite powders from
the treated solution seriously limits their practical applications.
Chitosan [β-(1→4)-2-amino-2-deoxy-D-glucose] is a natural
cationic biopolymer produced by N-deacetylation of chitin, the next
most abundant natural polysaccharide after cellulose. Chitosan mole-
cules contain a large number of reactive hydroxyl (–OH) and amino

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.10.036
42 H. Zhu et al. / Desalination 286 (2012) 41–48
(–NH2) groups and exhibit unique adsorption and chelating proper-
ties for all kinds of heavy metal ions [16–18]. These characteristics
make chitosan a suitable and excellent bio-matrix for synthesis of
nanosized particles or quantum dots of various inorganic photocata-
lysts such as cadmium sulfide [19,20], zinc sulfide [21], zinc oxide
[22] and cuprous oxide [23]. In addition, immobilized nanosized
photocatalysts on the chitosan bio-matrix can effectively prevent
nanoparticles from agglomeration during growth and can overcome
the difficulty in separation and recovery of nanosized powder mate-
rials [24].
In this study, titanium dioxide/zinc oxide/chitosan nanocomposite
thin films (TiO2/ZnO/chitosan NTFs) were prepared under mild
conditions and characterized by XRD, TGA, SEM, and HRTEM. Methyl
orange (MO) was selected as a model hazardous azo dye to evaluate
the feasibility of the adsorption-photocatalytic decolorization by
TiO2/ZnO/chitosan NTFs under simulated solar irradiation. Effects of
key operational factors including initial dye concentration, photocata-
lyst dosage, and initial pH of solution on the photocatalytic decolori-
zation of MO were studied. TiO2/ZnO/chitosan NTFs was expected to
result in complementation of advantages of each component, and
hence provide an economically feasible and environmentally friendly
method in the treatment of azo dye effluents.
2. Materials and methods
2.1. Materials
Chitosan used as matrix for photocatalyst synthesis was pur-
chased from Yuhuan Ocean Biochemical Co., Ltd. (Taizhou, China).
The degree of deacetylation was 92% and its average molecular
weight (Mw) was 2.1 × 10 5. Anatase titanium dioxide (10–25 nm
size, 210 ± 10 m 2 g − 1 specific surface areas) was purchased from
Xiamen Micaren Technology Co., Ltd. (Xiamen, China). Methyl orange
was obtained from Yongjia Fine Chemical Factory (Wenzhou, China)
and has a pKa of 3.47 in water at 25 °C. Zinc acetate was used as the
precursor of nanosized ZnO. Glutaraldehyde (v/v, 25%) was of analyt-
ical grade from Shanghai Chemical Reagent Co., Ltd (Shanghai,
China). All other chemicals were of analytical grade and were pur-
chased from Shanghai Chemical Reagent Co., Ltd. (Shanghai, China).
The pH of reaction mixture was adjusted with 0.1 mol L − 1 sodium
hydroxide or hydrochloric acid to reach required pH values.
2.2. Preparation of TiO2/ZnO/chitosan NTFs
TiO2/ZnO/chitosan NTFs were prepared by a solution casting
technology, the procedure of which is described as follows. First, 2%
(w/v) of chitosan solution was prepared by dissolving 2 g of chitosan
in 100 mL of 2% (v/v) aqueous acetic acid under ultrasonic stirring for
1.5 h at room temperature. Subsequently, 0.2 g of nanosized titanium
dioxide and 1.17 g of zinc acetate were added into the chitosan-acetic
acid solution. The reaction mixture was stirred for 1 h. To obtain even
thin films, 25 mL of the viscous mixture was cast on a rectangular
glass plate (10 × 20 cm 2) and dried at room temperature. Glass plates
with dried thin films were immersed into 0.2 mol L − 1 sodium
hydroxide coagulant solution for wet phase separation. After coagula-
tion, the solidified films were kept in a constant-temperature water
bath at 60 ± 0.2 °C for 3.5 h and were subsequently immersed in
100 mL of 0.5% (v/v) glutaraldehyde solution for 30 min to complete
crosslinking reaction. The resulting nanocomposite thin films (TiO2/
ZnO/chitosan NTFs) were sequentially washed with absolute ethanol
and double distilled water for three times, respectively. At last, the
TiO2/ZnO/chitosan NTFs were dried in an oven at 105 °C.
ZnO/chitosan nanocomposite thin films (ZnO/chitosan NTFs) and
TiO2/chitosan nanocomposite thin films (TiO2/chitosan NTFs) were
prepared using the same procedure, but without the addition of tita-
nium dioxide or zinc acetate, respectively.
2.3. Characterization of materials
X-ray diffraction (XRD) patterns of the samples were obtained in
a scanning range of 20–75° on a D8 Advance X-ray diffractometer
(Bruker, Germany) with Cu Kα radiation (λ = 0.15406 nm). Thermo-
gravimetric analysis (TGA) was performed on a Setaram Setsys 16
thermogravimetric analyzer (France) to investigate the thermal
stability of the samples. Each sample was heated from 25 to 800 °C
at a scanning rate of 2 °C min − 1 under a dynamic nitrogen atmo-
sphere. Surface morphology of samples was observed by scanning
electron microscopy (SEM) on a Holland Quanta 200 SEM after the
samples were sputtered with a layer of gold to prevent the charging
effect. High-resolution transmission electron microscopy (HRTEM)
photographs were obtained on a JEOL 2010 machine (Tokyo, Japan)
at an accelerating voltage of 200 kV.
2.4. Water sorption on TiO2/ZnO/chitosan NTFs
Water sorption experiments of TiO2/ZnO/chitosan NTFs were esti-
mated at room temperature. The dry TiO2/ZnO/chitosan NTFs were
weighted and immersed into double distilled water. At time intervals,
the wet TiO2/ZnO/chitosan NTFs were removed from water, had the
water from surface wiped off, weighted and returned to water. The
swelling index was calculated according to Eq. (1).
swelling index ð% Þ ¼ ½ðmw −md Þ  100=md ð1Þ
where md and mw are the mass of dry and wet films (g), respectively.
2.5. Liquid-phase adsorption of MO by TiO2/ZnO/chitosan NTFs
Since the photo-oxidation reaction usually takes place on the
photocatalysts surface, the adsorption of pollutant on photocatalysts
are important for the photocatalytic process. 0.05 g of TiO2/ZnO/
chitosan NTFs was added to 100 mL of MO solution (15 mg L − 1 of
initial concentration). The adsorption system was continuously stir-
red in dark. The supernate was withdrawn periodically and analyzed
using a Cary 50 Model ultraviolet–visible (UV–vis) spectrophotome-
ter (Varian, USA) at a maximum absorption wavelength (λmax) of
464.9 nm. The amount of MO adsorbed on the TiO2/ZnO/chitosan
NTFs (qt) and the decolorization percentage of MO (η %) were calcu-
lated according to Eqs. (2) and (3), respectively.
qt ¼ ½ðC 0 −C t Þ  100=ð1000  mÞ ð2Þ
η% ¼ ½ðC 0 −C t Þ  100=C 0 ð3Þ
where qt is adsorption capacity (mg g − 1); C0 and Ct are initial and
instantaneous concentrations of MO (mg L − 1), respectively; m is
the mass of photocatalyst (g).
2.6. Photocatalytic decolorization of MO under simulated solar
irradiation
The photocatalytic activity of the TiO2/ZnO/chitosan NTFs was
evaluated by photocatalytic decolorization of MO in aqueous solution
under simulated solar irradiation. A 300 W xenon lamp (PLS-SXE300,
Beijing Trusttech Co. Ltd., China) was used as a light source. The
wavelength of simulated solar irradiation was in the range from
300 nm to 1100 nm. According to a technical report on PLS-SXE300,
UV output (b390 nm) was about 5.2% of irradiation energy while
Vis output (390 nm–770 nm) was about 39.2%. The MO solution
(100 mL) was introduced into the photoreactor, and the pH of dye
solution was adjusted to 5.6. Photocatalytic experiments were carried
out using a certain amount of photocatalysts under simulated
solar irradiation. To ensure effective mixing of the photocatalyst and

transferring of MO dye in the photoreactor, the reaction solution
was agitated by bubbling air continuously during the reaction. After
irradiating for regular periods of time, residual MO concentration
was analyzed in a Cary 50 UV–vis spectrophotometer at λmax =
464.9 nm. The decolorization percentage of MO was calculated
according to Eq. (3).
Effects of key operational factors (MO) concentration, photocata-
lyst dosage, initial pH of solution, and reuse of photocatalyst on MO
decolorization were investigated. All photocatalytic experiments
were performed at ambient temperature (25 ± 1 °C).
3. Results and discussion
3.1. Characterization of samples
3.1.1. XRD
X-ray diffraction patterns of the samples are shown in Fig. 1.
Diffraction peaks corresponding to anatase titanium dioxide and
cubic zinc oxide were marked with “A” and “C”, respectively, along
with the corresponding diffraction planes. As shown in Fig. 1, the dif-
fractogram of chitosan consisted of two typical crystalline peaks at 2θ
of 11.68° and 20.93°, while raw titanium dioxide exhibited peaks at
2θ of 25.31°, 37.95°, 47.97°, 55.13°, 62.77°, and 68.80°. The XRD
pattern of ZnO/chitosan NTFs showed peaks for zinc oxide cubic
phase, the most intense of which were at 2θ of 31.65°, 34.35°,
36.14°, 47.28°, 56.53°, 62.70°, and 67.79°, which were corresponded
to the (100), (002), (101), (102), (110), (103), and (112) planes,
respectively [14]. All pertinent diffraction peaks for ZnO in the XRD
pattern of TiO2/ZnO/chitosan NTFs were unambiguously indexed to
the cubic phase and matched well with the reported data, indicating
that the ZnO cubic phase was synthesized in the novel TiO2/ZnO/
chitosan NTFs [12]. The XRD pattern of the anatase titanium dioxide
in the TiO2/ZnO/chitosan NTFs was identical to that of raw titanium
dioxide. This indicated that the introduction of nanosized ZnO in the
TiO2/ZnO/chitosan NTFs had no effect on the crystalline phase of the
titanium dioxide. At the same time, the typical crystalline peak of
chitosan at 2θ of 20.93° ratherish shifted to 19.80° and 19.98° for
ZnO/chitosan NTFs and TiO2/ZnO/chitosan NTFs, respectively. The
possible reason was that the intermolecular interaction of chitosan
has been destroyed by combining with Zn 2 + during the preparation
of ZnO/chitosan NTFs and TiO2/ZnO/chitosan NTFs.
3.1.2. TGA
The thermal stability behaviors of pure chitosan film, TiO2/chitosan
NTFs and TiO2/ZnO/chitosan NTFs were investigated by TGA. For pure
A
A of the chitosan films was rather smooth. However, with the introduc-
d C CC A
C
AAC
C in the ZnO/chitosan NTFs [Fig. 3(b)]. The surface of the TiO2/chitosan
A C C A:anatase TiO2
c C:cubic ZnO
Intensity
A
C C
A
b A AA
a sentative HRTEM image shown in Fig. 4 revealed that the particle
10 20 30 40 50
2 theta(degree)
Fig. 1. XRD patterns of (a) chitosan, (b) pure TiO2 powder, (c) ZnO/chitosan NTFs and
(d) TiO2/ZnO/chitosan NTFs.
H. Zhu et al. / Desalination 286 (2012) 41–48 43
100
90
80
Weight percent (%)
70
60
50 c
b
40
a
30
100 200 300 400 500 600 700 800
O
Temperature ( C)
Fig. 2. TG curves for pure chitosan film (a), TiO2/chitosan NTFs (b) and TiO2/ZnO/chit-
osan NTFs (c).
chitosan film [Fig. 2(a)], weight loss took place in two obvious stages.
The first one started at 30 °C and ended at 140 °C with a weight loss
of 5%, which was assigned to the loss of water in chitosan films. The
second stage started at 230 °C and reached a maximum at 380 °C with
a weight loss of 62%, which corresponded to the decomposition of chit-
osan, vaporization and elimination of volatile products [25]. As shown
in Fig. 2(b), the TG curve of the TiO2/chitosan NTFs also exhibits two
distinct weight-loss stages. The first stage, with weight loss of about
3.0%, started at 25 °C and continued up to 180 °C; this was attributed
to the release of surface-bound water. The rapid weight loss of about
52% in the second range (180–430 °C) was due to the degradation of
the polymer [26]. The TG curve of the TiO2/ZnO/chitosan NTFs
[Fig. 2(c)] was similar to that of the TiO2/chitosan NTFs [Fig. 2(b)].
Weight losses during the two stages were 4% and 43%, respectively. In
addition, the residual weight percentage at 788 °C was proportional to
the inorganic content and reflected titanium dioxide or zinc oxide/
titanium dioxide. The residual weight of the TiO2/ZnO/chitosan NTFs
and TiO2/chitosan NTFs was 7.9% and 15.3% more than that of pure chit-
osan film, respectively. This indicated that titanium dioxide was also
entrapped by the polymer while the nanosized ZnO was synthesized
in the nanocomposite films.
3.1.3. SEM and HRTEM
Fig. 3 shows the SEM photographs illustrating the surface mor-
phology of pure chitosan film, ZnO/chitosan NTFs, TiO2/chitosan
NTFs and TiO2/ZnO/chitosan NTFs. As shown in Fig. 3(a), the surface
A
C C tion of ZnO, some well-dispersed and fine granules were embedded
NTFs was rather coarse and had many irregular small granules
[Fig. 3(c)]. The surface morphology of TiO2/ZnO/chitosan NTFs was
similar to that of the TiO2/chitosan NTFs. However, there are much
C C
C more fine granules on the surface of TiO2/ZnO/chitosan NTFs than
that of TiO2/chitosan NTFs [Fig. 3(d)], which might result from the in-
troduction of ZnO. These results suggested that titanium dioxide and
A A
ZnO were embedded in the surface of the TiO2/ZnO/chitosan NTFs,
which were in good agreement with those of the XRD data. A repre-
diameters were in the range of 5–15 nm.
60 70
3.2. Water sorption capacity
Fig. 5 shows the results of water sorption capacities for the cross-
linked chitosan, TiO2/chitosan NTFs and TiO2/ZnO/chitosan NTFs. All
44 H. Zhu et al. / Desalination 286 (2012) 41–48

Fig. 3. SEM images for pure chitosan film (a), ZnO/chitosan NTFs (b), TiO2 /chitosan NTFs (c) and TiO2/ZnO/chitosan NTFs (d).

films exhibited water sorption values fewer than 60%. Obviously, the
water sorption capacities of crosslinked chitosan, TiO2/chitosan NTFs
and TiO2/ZnO/chitosan NTFs were lower when compared with
uncrosslinked chitosan reported by Santos [27]. It is known that the
hydrophilicity of chitosan is due to the presence of amino and hy-
droxyl groups in its molecular chains. However, crosslinking method
can reduce remarkably water sorption capacities onto chitosan-based
composite materials. On the other hand, the water sorption capacity
onto crosslinked chitosan, TiO2/chitosan NTFs and TiO2/ZnO/chitosan
NTFs was found to be 29.3%, 38.4% and 45.6%, respectively. The in-
crease in water sorption capacity could result from the change of
film surface, which were in good agreement with those of the SEM
images.

60

50
Water sorption (%)

40

30

20 a
b
c
10

0 1 2 3 4 5
Time (hr)

Fig. 5. Water sorption of crosslinked chitosan (a), TiO2/chitosan NTFs (b) and TiO2/
Fig. 4. TEM image for TiO2/ZnO/chitosan NTFs. ZnO/chitosan NTFs (c).
 H. Zhu et al. / Desalination 286 (2012) 41–48 45

3.3. Comparisons among different processes of MO decolorization initial solution

TiO2/ZnO/chitosan NTFs in dark
For comparison, four sets of decolorization experiments were TiO2/chitosan NTFs under light irradiation
carried out under different experimental conditions and the results TiO2/ZnO/chitosan NTFs under light irradiation
are shown in Fig. 6. After stirring the dispersion containing 0.05 g of CH3 O
464.9
TiO2/ZnO/chitosan NTFs and 15 mg L − 1 aqueous MO solution in 1.0 N N N S O Na
CH3 O
dark for 4 h, about 30.8% decolorization was attained. After 4 h of
simulated solar irradiation, the decolorization percentage of MO 464.8
solution (15 mg L − 1) reached 71.8% and 58.2% by TiO2/chitosan
NTFs and ZnO/chitosan NTFs, respectively. However, 97.8% of MO
(15 mg L − 1) was decolorized in the presence of 0.05 g of TiO2/ZnO/ 0.5
chitosan NTFs under simulated solar irradiation for 4 h, which was 445.1
67.0% and 26.0% higher than adsorption in dark and photocatalysis
in the presence of TiO2/chitosan NTFs, respectively. With the intro-
duction of zinc oxide in the nanocomposite films, the decolorization 0.0
percent of MO evidently increased. These results implied that the 200 300 400 500 600
TiO2/ZnO/chitosan NTFs exhibited higher photocatalytic decolorization Wavelength (nm)
activity under simulated solar irradiation. Compared with parylene–
TiO2 flexible thin films and AgBr/TiO2[28,29], the TiO2/ZnO/chitosan Fig. 7. UV–vis spectra of MO solution under different experimental conditions (Inset:
the chemical structure of MO) (MO concentration: 15 mg L− 1; TiO2/ZnO/chitosan
NTFs also showed comparable photocatalytic ability towards MO dye. NTFs dosage: 0.5 g L− 1).
The UV–vis spectra of the original MO solution and decolorized
dye solutions under three different experimental conditions after
4 h are illustrated in Fig. 7. The absorption spectrum of the original attack [Fig. 8 (inset)]. In addition, the absorption peak shifted from
MO solution was characterized by one main band in the visible 464.9 to 438.9 nm after 180 min of irradiation. Similar phenomena
region (maximum absorption at 464.9 nm) and another band in have also been observed during the photo-decolorization of other
the UV region (235.96 nm). During the dark adsorption process in dyes in previous studies [30]. As shown in Fig. 8, two distinct stages
the presence of TiO2/ZnO/chitosan NTFs, the absorbance values at were observed in the hypsochromic shifts of the λmax in our experi-
464.9 nm decreased from 1.06 to 0.74 and no displacement of the ment. Before 150 min of irradiation, a slight hypsochromic shift of
peak was observed. With irradiation time of 4 h in the presence of the λmax was observed; this indicated that the decolorization of the
TiO2/chitosan NTFs, the absorbance at 464.9 nm dropped from 1.06 dye solution was mainly attributed to the adsorption of the TiO2/
to 0.28 and the λmax shifted from 464.9 to 445.1 nm. However, the ZnO/chitosan NTFs. After 150 min of reaction, the hypsochromic
absorbance peak at the visible region disappeared entirely after shift was distinct because of the dye sensitization of the catalyst,
4 h of irradiation in the presence of the TiO2/ZnO/chitosan NTFs. which resulted from the adsorption of MO on the nanocomposite
This indicates that MO was almost completely decolorized and the films. Thus, the decolorization of MO by photocatalytic decolorization
azo bond of MO was destroyed by the adsorption-photocatalytic under simulated solar irradiation was accelerated thereafter.
process using the TiO2/ZnO/chitosan NTFs under simulated solar Adsorption of methyl orange resulted in dye sensitization of TiO2/
irradiation. ZnO/chitosan NTFs. Previous research has revealed that dye sensitiza-
To clarify further the nature of the adsorption-photocatalytic tion can cause a red-shift absorption threshold of titanium dioxide
synergistic process, the variations of the UV–vis spectra of the MO toward the visible light region [5]. In addition, the introduction of
solution with irradiation time were recorded [Fig. 8 (inset)]. With zinc oxide in nanocomposite photocatalysts and dye-sensitized titani-
irradiation in the presence of TiO2/ZnO/chitosan NTFs, the λmax um dioxide has a beneficial role in improving the charge separation
(464.9 nm) peak in the visible region of UV–vis spectrum weakened and extending the response to visible light.
rapidly and finally disappeared completely. These changes suggested
that the chromophores of MO were the most active sites for oxidative

a bc
100 TiO2/ZnO/chitosan NTFs in dark 460
d
ZnO/chitosan NTFs under light
TiO2/chitosan NTFs under light e
Maximal wavelength(nm)
decolorization percentage (%)

80 TiO2/ZnO/chitosan NTFs under light

440 a
1.0 a:0 min
b

60 420 b:20 min

c:60 min
c
0.5
d:100 min
40 400 d
e:150 min
e
f f:240 min
380 f
20 0.0
400 500 600
Wavelength(nm)

360
0 0 50 100 150 200 250
0 60 120 180 240
Time(min)
Time (min)
Fig. 8. Maximum absorption wavelength shifts of MO solution as function of irradiation
Fig. 6. Decolorization of 15 mg L− 1 MO as a function of reaction time under different time in the presence of TiO2/ZnO/chitosan NTFs (Inset: partly enlarged UV–vis spectra
experimental conditions. evolution) (MO concentration: 15 mg L− 1; TiO2/ZnO/chitosan NTFs dosage: 0.5 g L− 1).
46
3.4. Effects of operational parameters on MO decolorization
3.4.1. Effect of initial MO concentration
Studying the dependence of decolorization efficiency on the initial
dye concentration is important from an application point of view [31].
Fig. 9(a) shows the effect of the initial MO concentration on the
photocatalytic decolorization in the presence of 0.5 g L − 1 TiO2/ZnO/
chitosan NTFs at natural pH. The decolorization percentage decreased
markedly with the increase in the initial dye concentration, especially
when the initial dye concentration varied from 15 to 20 mg L − 1. An
explanation for this change was that as the initial concentration of
methyl orange increased, the path length of the photons entering
the solution decreased. The reversal occurred at lower concentration,
and thereby increased the number of photons absorbed by the cata-
lyst [32]. The same effect was observed by Wang et al. during the
photocatalytic decolorization of commercial dyes using zinc oxide
power as photocatalyst [33].
According to previous studies, the influence of initial dye concentra-
tion on photocatalytic decolorization is described by the Langmuir–
Hinshelwood kinetic model [34], which is commonly expressed as
−dC=dt ¼ kKC=ð1 þ KC Þ
where k is the reaction rate constant (mg L − 1 min− 1); K is the ad-
sorption coefficient of the reactant (L mg− 1); and C is the reactant
concentration (mg L − 1).
When C is very small, KC is negligible with respect to unity and
photocatalysis can be simplified to an apparent pseudo-first-order
kinetics [35]:
−dC=dt ¼ kKC
i:e: lnðC 0 =C i Þ ¼ kKC ¼ kapp: t
where kapp is the apparent pseudo-first-order rate constant (min − 1).
The linear fit between ln(C0/Ci) and irradiation time t under different
initial MO concentrations can be used to describe the pseudo-first-order
kinetics. Results are shown in Fig. 9(b). All correlation coefficients were
higher than 0.991, indicating that the proposed kinetic model was
in good agreement with our experimental data. The order of rate
constants was 0.02569 min− 1 (2 mg L− 1)>0.01767 min− 1 (5 mg L− 1)
>0.01155 min− 1 (15 mg L− 1)>0.00703 min− 1 (20 mg L− 1). There-
fore, the initial dye concentration had a fundamental effect on the decol-
orization rate, i.e., the rate constant decreased with the increase in initial
dye concentration.
a 100
decolorization percentage (%)
80
60
40
20
0 0.0
0 60 120
Time(min)
Fig. 9. Effect of initial MO concentration on decolorization percentage (a) and the kinetics (b). (TiO2/ZnOchitosan NTF dosage: 0.5 g L− 1; natural pH).
H. Zhu et al. / Desalination 286 (2012) 41–48
3.4.2. Effect of photocatalyst amount
The photocatalyst amount was another important parameter of
dye decolorization under simulated solar irradiation. Amounts of
TiO2/ZnO/chitosan NTFs ranging from 0.05 to 1.0 g L − 1 in
15 mg L − 1 MO solutions were employed in this study. An increase
in the decolorization percentage of MO was observed with the
increase in catalyst amount from 0.05 g L − 1 to 0.5 g L − 1. However,
further increase of the photocatalyst amount above 0.5 g L − 1 was
less effective in the photo-decolorization of MO. The reaction rate
constants were calculated from the linear fits of each logarithmic
decolorization curve, the results of which are illustrated in Fig. 10.
As the catalyst dosage increased from 0.05 to 0.5 g L − 1, the decolori-
zation rate constant increased and reached the maximum of
0.0135 min − 1 when the catalyst dosage was 0.5 g L − 1. The increase
in the photocatalyst amount increased the number of active sites on
the photocatalyst [9]. Consequently, the number of dye molecules
and photons absorbed increased. However, at photocatalyst dosages
above 0.5 g L − 1, the rate constants decreased due to the blocking of
light penetration by the excessive amount of photocatalysts [36].
From a practical viewpoint, the optimum dosage of TiO2/ZnO/
chitosan NTFs (0.5 g L − 1) for 15 mg L − 1 of MO solution was moderate
ð4Þ since the optimum dosage (0.5 g L − 1) was much lower than that of
AgBr/TiO2 (2.5 g L− 1) reported by Zang [27].
3.4.3. Effect of initial pH of the solution
Wastewaters from textile industries usually have a wide range of
pH values. Usually, pH plays an important role in the characteristics
of dye wastewaters and is one of the most important parameters
that influence the photo-oxidation processes [37]. The effect of the
initial solution pH on the photocatalytic decolorization is presented
ð5Þ in Fig. 11. The MO decolorization percentages were 99.8%, 50.7%,
and 28.2% at pH 2.0, 6.0, and 12, respectively, after 60 min of simulat-
ð6Þ ed solar irradiation. The effect of pH on the dye photocatalytic decol-
orization is difficult to explain since it had multiple roles. First, it was
related to the surface-charge properties of the photocatalysts, and
could be explained based on the point of zero charge (pzc). At pH
values lower than pHpzc, the surface became positively charged, and
the opposite phenomenon occurred at pH values higher than pHpzc.
The highest degree of photocatalytic decolorization of MO was
observed at pH 2.0 and was attributed to the electrostatic attraction
between the positively charged catalyst surface and MO anions,
which led to the increase of degree of adsorption and photo-
decolorization. The amino groups of chitosan in the TiO2/ZnO/
chitosan NTFs were more easily protonated at low pH. Both titanium
dioxide and zinc oxide are positively charged in acidic media, with pHpzc
b 2.0
-1 -1
2 mg L kapp=0.02569 (min ) R=0.991
-1 -1
5 mg L kapp=0.01767 (min ) R=0.999
-1 -1
15 mg L kapp=0.01155 (min ) R=0.999
1.5 -1 -1
20 mg L kapp=0.00703 (min ) R=0.994
ln(C0 /Ct)
-1
1.0
2 mg L
-1
5 mg L
-1
15 mg L
-1
20 mg L 0.5
180 240 300 0 20 40 60 80 100 120
Time(min)
 H. Zhu et al. / Desalination 286 (2012) 41–48 47

0.015
100 TiO2/ZnO/chitosan NTFs
TiO2/chitosan NTFs

decolorization percentage (%)

ZnO/chitosan NTFs
0.012 80
Rate constant(min-1)

0.009 60

0.006 40

0.003 20

0.000 0
0.0 0.2 0.4 0.6 0.8 1.0 1 2 3 4 5
-1 Recycle time
photocatalyst dosage(g L )
Fig. 12. Recycle and reuse of photocatalysts for MO decolorization (MO concentration:
Fig. 10. Effect of catalyst amount on decolorization rate constants of MO (MO concen-
15 mg L− 1; photocatalyst dosage: 0.5 g L− 1; natural pH; irradiation time: 4 h).
tration: 15 mg L− 1; natural pH).

of about 6–7 and 9, respectively [10,32]. Since MO, with its sulfonic
group that easily ionized at low pH, became a soluble anion, MO anion
adsorption on the surface of the TiO2/ZnO/chitosan NTFs was probably
favored in acidic solutions. A similar effect of pH on MO photo-
decolorization has been observed in a previous reaction system [6]. In
addition, the molecular conformation of MO might have been changed
into the quinonoid derivative, which was unstable and easily destroyed
below pH= 3.2; at this pH, it existed as the azo form, whose azo bonds
were difficult to break above pH 4.4 [38]. Notably, the instantaneous pH
of the solution gradually changed toward neutral during irradiation.
According to the study by Wang [39], the trend of pH toward neutrality
is due to the continuous decomposition of MO and the formation of
simple inorganic ions.
3.5. Evaluation of catalyst stability
To examine the stability of photocatalysts, recycling experiments
were carried out and the result is presented in Fig. 12. For each new
cycle, photocatalysts were reused for the decolorization of a fresh
MO solution under similar conditions after the photocatalyst samples
were filtered and dried. After 4 h of simulated solar irradiation, the
decolorization percentage of MO solution (15 mg L − 1) was 38.2%
and 29.5% at the 5th use by TiO2/chitosan NTFs and ZnO/chitosan
100
decolorization percentage (%)
NTFs, respectively. Obviously, the photocatalytic activities of both
TiO2/chitosan NTFs and ZnO/chitosan NTFs were low for the decolor-
ization of MO dye when used at the 5th use. However, in the presence
of TiO2/ZnO/chitosan NTF, the decolorization percentage of MO
solution for 5 times use were 97.8%, 86.0%, 78.2%, 72.7% and 73.7%
after 4 h of simulated solar irradiation, respectively. The results
showed that the catalytic activity of the TiO2/ZnO/chitosan NTF had
an obvious decrease in the second use and subsequently maintained
relative stability. The decrease of decolorization percentage may be
due to the adsorption of intermediate products on the photocatalyst
active sites, which rendered them unavailable for decolorization
of fresh dye solution. However, 73.7% of MO was decolorized success-
fully for the 5th use of the photocatalysts, which indicated that the
TiO2/ZnO/chitosan NTFs catalyst could be reused.
4. Conclusions
TiO2/ZnO/chitosan NTFs were prepared by a solution casting tech-
nology under mild conditions and used to perform adsorption–
photocatalytic decolorization of MO under simulated solar irradia-
tion. Results of the XRD and SEM analyses indicated that titanium
dioxide and zinc oxide were embedded in the nanocomposite films
using chitosan as the induced matrix. The decolorization of MO in
the presence of the TiO2/ZnO/chitosan NTFs and simulated solar irra-
diation were significantly influenced by key operational factors,
including initial dye concentration, catalyst dosage, and initial solu-
tion pH. Over 97% decolorization of a 15 mg L − 1 MO solution at
natural pH and 0.5 g L − 1 photocatalyst dosage was achieved after

80
4 h of irradiation by simulated solar light. TiO2/ZnO/chitosan NTFs
could be reused, which meant that the adsorption-photocatalytic
60 decolorization process could be operated at a relatively low cost.
The results obtained in the study can be useful and helpful in design-
ing an upscalable, practical process for dye wastewater treatment.
pH 2.0
40 pH 6.0
pH 8.0 Acknowledgement
pH 10.0
20 pH 12.0
Financial support for this study was provided by the Natural
Science Foundation of China (N0.21007044 and N0.21106091)
and the Key Research Foundation of Taizhou University (NO.
0 2011PY16).
0 50 100 150 200 250 300
Time (min) References
Fig. 11. Effect of initial pH on MO decolorization. (MO concentration: 15 mg L− 1; TiO2/ [1] H. Park, W. Choi, Visible light and Fe (III)-mediated degradation of acid orange
ZnOchitosan NTF dosage: 0.5 g L− 1). 7 in the absence of H2O2, J. Photochem. Photobiol. A 159 (2003) 241–247.
48 H. Zhu et al. / Desalination 286 (2012) 41–48
[2] U.G. Akpan, B.H. Hameed, Parameters affecting the photocatalytic degradation of
dyes using TiO2-based photocatalysts: a review, J. Hazard. Mater. 170 (2009)
520–529.
[3] M. Makita, A. Harata, Photocatalytic decolorization of rhodamine B dye as a model
of dissolved organic compounds: influence of dissolved inorganic chloride salts in
seawater of the Sea of Japan, Chem. Eng. Process. 47 (2008) 859–863.
[4] M. Stylidi, D.I. Kondarides, X.E. Verykios, Visible light-induced photocatalytic
degradation of acid orange 7 in aqueous TiO2 suspensions, Appl. Catal., B 47
(2004) 189–201.
[5] S. Kaur, V. Singh, Visible light inducing sonophotocatalytic degradation of
Reactive Red dye 198 using dye sensitized TiO2, Ultrason. Sonochem. 14 (2007)
531–537.
[6] W. Liu, S. Chen, W. Zhao, S. Zhang, Study on the photocatalytic degradation of tri-
chlorfon in suspension of titanium dioxide, Desalination 249 (2009) 1288–1293.
[7] K.M. Parida, N. Sahu, N.R. Biswal, B. Naik, A.C. Pradhan, Preparation, characteriza-
tion and photocatalytic activity of sulfate-modified titania for degradation of
methyl orange under visible light, J. Colloid Interface Sci. 318 (2008) 231–237.
[8] E. Leyva, C. Montalvo, E. Moctezuma, Photocatalytic degradation of pyridine in
water solution using ZnO as an alternative catalyst to TiO2, J. Ceram. Proc. Res. 9
(2008) 455–462.
[9] J. Nishio, M. Tokumura, H.T. Znad, Y. Kawase, Photocatalytic decolourization of
azo-dye with zinc oxide power in an external UV light irradiation slurry photo-
reactor, J. Hazard. Mater. 138 (2006) 106–115.
[10] M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic
degradation of C.I. Acid Yellow 23 by ZnO photocatalyst, J. Hazard. Mater. 133
(2006) 226–232.
[11] S.K. Kansal, M. Singh, D. Sud, Studies on TiO2/ZnO photocatalysed degradation of
lignin, J. Hazard. Mater. 153 (2008) 412–417.
[12] D.L. Liao, C.A. Badour, B.Q. Liao, Preparation of nanozied TiO2/ZnO composite
catalyst and its photocatalytic activity for degradation of methyl orange, J.
Photochem. Photobiol. A 194 (2008) 11–19.
[13] X.D. Yu, Q.Y. Wu, S.C. Jiang, Y.H. Guo, Nanoscale ZnO/TiO2 composites: prepara-
tion, characterization and visible-light photocatalytic activity, Mater. Charact.
57 (2006) 333–341.
[14] A.A. Aal, M.A. Barakat, R.M. Mohamed, Electrophoreted Zn–TiO2–ZnO nanocom-
posite coating films for photocatalytic degradation of 2-chlorophenol, Appl.
Surf. Sci. 254 (2008) 4577–4583.
[15] A. Deshpande, P. Shah, R.S. Gholap, N.M. Gupta, Interfacial and physico-chemical
properties of polymer-supported CdS–ZnS nanocomposites and their role in the
visible-light mediated photocatlytic splitting of water, J. Colloid Interface Sci.
333 (2009) 263–268.
[16] W.S. Wan Ngah, S. Fatinathan, Adsorption of Cu(II) ions in aqueous solution using
chitosan beads, chitosan–GLA beads and chitosan–alginate beads, Chem. Eng. J.
143 (2008) 62–72.
[17] D. Chauhan, N. Sankararamakrishnan, Highly enhanced adsorption for decontam-
ination of lead ions from battery.wastewaters using chitosan functionalized with
xanthate, Bioresour. Technol. 99 (2008) 9021–9024.
[18] A.H. Chen, S.C. Liu, C.Y. Chen, C.Y. Chen, Comparative adsorption of Cu(II), Zn(II),
and Pb(II) ions in aqueous solution on the crosslinked chitosan with epichlorohy-
drin, J. Hazard. Mater. 154 (2008) 184–191.
[19] H.Y. Zhu, R. Jiang, L. Xiao, Y.H. Chang, Y.J. Guan, X.D. Li, G.M. Zeng, Photocatalytic
decolorization and degradation of Congo Red on innovative crosslinked chitosan/
nano-CdS composite catalyst under visible light irradiation, J. Hazard. Mater. 169
(2009) 933–940.
[20] R. Jiang, H.Y. Zhu, X.D. Li, L. Xiao, Visible light photocatalytic decolourization of
C. I. Acid Red 66 by chitosan capped CdS composite nanoparticles, Chem. Eng. J.
152 (2009) 537–542.
[21] X.H. Wang, Y.M. Du, S. Ding, L.H. Fan, X.W. Shi, Q.Q. Wang, G.G. Xiong, Large two-
photon absorbance of chitosan–ZnS quantum dots nanocomposite film, Physica E
30 (2005) 96–100.
[22] R. Khan, A. Kaushik, P.R. Solanki, A.A. Ansari, M.K. Pandey, B.D. Malhotra, Zinc
oxide nanoparticles–chitosan composite film for cholesterol biosensor, Anal.
Chim. Acta 616 (2008) 207–213.
[23] J.Y. Chen, P.Z. Zhou, J.L. Li, Y. Wang, Study on the photocatalytic performance of
Cuprous oxide/chitosan nanocomposites activated by visible light, Carbohydr.
Polym. 72 (2008) 128–132.
[24] Q. Li, H.J. Su, T.W. Tan, Synthesis of ion-imprinted chitosan–TiO2 adsorbent and its
multi-functional performances, Biochem. Eng. J. 38 (2008) 212–218.
[25] C.G.T. Neto, J.A. Giacometti, A.E. Job, F.C. Ferreira, J.L.C. Fonseca, M.R. Pereira, Ther-
mal analysis of chitosan based networks, Carbohydr. Polym. 62 (2005) 97–103.
[26] D. Yang, J. Li, Z.Y. Jiang, L.Y. Lu, X. Chen, Chitosan/TiO2 nanocomposite pervapora-
tion membranes for ethanol dehydration, Chem. Eng. Sci. 64 (2009) 3130–3137.
[27] D.E.S. Santos, C.G.T. Neto, J.L.C. Fonseca, M.R. Pereira, Chitosan macroporous
asymmetric membranes — preparation, characterization and transport of drugs,
J. Membr. Sci. 325 (2008) 362–370.
[28] Y. Zhiyong, H. Keppner, D. Laub, E. Mielczarski, J. Mielczarski, L. Kiwi-Minsker, A.
Renken, J. Kiwi, Photocatalytic discoloration of methyl orange on innovative
parylene–TiO2 flexible thin films under simulated sunlight, Appl. Catal. B 79
(2008) 63–71.
[29] Y. Zang, R. Farnood, Photocatalytic activity of AgBr/TiO2 in water under simulated
sunlight irradiation, Appl. Catal. B 79 (2008) 334–340.
[30] C.C. Chen, Degradation pathways of ethyl violet by photocatalytic reaction with
ZnO dispersions, J. Mol. Catal.,A 264 (2007) 82–92.
[31] N. Daneshvar, M.H. Rasoulifard, A.R. Khataee, F. Hosseinzadeh, Removal of C.I.
Acid Orange 7 from aqueous solution by UV irradiation in the presence of ZnO
nanopowder, J. Hazard. Mater. 143 (2007) 95–101.
[32] S.K. Kansal, M. Singh, D. Sud, Studies on TiO2/ZnO photocatalysed degradation of
lignin, J. Hazard. Mater. 141 (2007) 581–590.
[33] H.H. Wang, C.S. Xie, W. Zhang, S.Z. Cai, Z.H. Yang, Y.H. Gui, Comparison of dye
degradation efficiency using ZnO powders with various sized scales, J. Hazard.
Mater. 141 (2007) 645–652.
[34] T. Sauer, G. Cesconeto Neto, H.J. José, R.F.P.M. Moreira, Kinetics of photocatalytic
degradation of reactive dyes in a TiO2 slurry reactor, J. Photochem. Photobiol. A
149 (2002) 147–154.
[35] B. Tryba, A.W. Morawski, M. Inagaki, M. Toyoda, The kinetics of phenol decompo-
sition under UV irradiation with and without H2O2 on TiO2, Fe–TiO2 and Fe–C–
TiO2 photocatalysts, Appl. Catal. B 63 (2006) 215–221.
[36] M. Saquib, M.A. Tariq, M.M. Haque, M. Muneer, Photocatalytic degradation of
disperse blue 1 using UV/TiO2/H2O2 process, J. Environ. Manage. 88 (2008)
300–306.
[37] A. Franco, M.C. Neves, M.M.L. Ribeiro Carrott, M.h. Mendonca, M.I. Pereira, O.C.
Monteiro, Photocatalytic decolorization of methylene blue in the presence of
TiO2/ZnO nanocomposites, J. Hazard. Mater. 161 (2009) 545–550.
[38] J. Wang, B.D. Guo, X.D. Zhang, Z.H. Zhang, J.T. Han, J. Wu, Sonocatalytic degrada-
tion of methyl orange in the presence of TiO2 catalysts and catalytic activity com-
parison of rutile and anatase, Ultrason, Sonnochem. 12 (2005) 331–337.
[39] H.Y. Wang, J.F. Niiu, X.X. Long, Y. He, Sonophotocatalytic degradation of methyl
orange by nano-sized Ag/TiO2 particles in aqueous solutions, Ultrason. Sonnochem.
15 (2008) 386–392.