Journal of Cleaner Production 215 (2019) 123e130

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Journal of Cleaner Production

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Color removal from wastewater by photocatalytic process using

titanium dioxide-coated glass, ceramic tile, and stainless steel sheets
Krit Sirirerkratana a, Patiya Kemacheevakul a, b, *, Surawut Chuangchote c
a
Department of Environmental Engineering, Faculty of Engineering, King Mongkut's University of Technology Thonburi, 126 Pracha-uthit Rd, Bangmod,
Tungkru, Bangkok, 10140, Thailand
b
Center of Excellences on Hazardous Substance Management (HSM), Bangkok, 10330, Thailand
c
Department of Tool and Materials Engineering, Faculty of Engineering, King Mongkut's University of Technology Thonburi, 126 Pracha-uthit Rd, Bangmod,
Tungkru, Bangkok, 10140, Thailand

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

Article history: Dye pollutants from textile industries are a major wastewater problem because they have complex
Received 18 May 2018 chemical structures. Photocatalysis is a promising wastewater treatment method, which is used to
Received in revised form remove dyes under light irradiation in the presence of a photocatalyst. In this article, titanium dioxide
3 January 2019
(TiO2) photocatalyst was synthesized through sol-gel technique and coated on different substrates (i.e.
Accepted 5 January 2019
Available online 7 January 2019
transparent glass, glazed ceramic tile, and stainless steel) by doctor blade technique. The coated sub-
strates were used in an innovative reactor to remove colors in dye wastewater. The photocatalytic ac-
tivities of the designed reactor were determined using a synthetic dye wastewater (methylene blue)
Keywords:
Wastewater treatment
under UV irradiations (36W-UVA or 30W-UVC lamps). The results showed that the optimum substrate
Color removal yielded the highest color removal efficiency (93.03 ± 0.66%) was TiO2-coated glass under UVC irradiation.
Photocatalysis The recycling ability of TiO2-coated glass sheet was also evaluated. It was found that TiO2-coated glass
Titanium dioxide sheet provided the same efficiencies for 20 cycles. In addition, the actual wastewater from textile in-
Dye wastewater dustry was tested in this study with different pH values (i.e. pH ¼ 3e11). The maximum color removal
obtained was 87.86 ± 0.23% at pH value 11 on TiO2-coated glass under UVC irradiation. The color removal
was found to decrease with decreasing pH.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction contaminated wastewater is advanced oxidation processes (AOPs)

Wastewater is a major problem because human needs to use
water to sustain life and in other daily activities, such as growing
crops in agriculture, mining, and manufacturing. One of the most
important environmental contaminants in wastewater is dye pol-
lutants from textile industries. Dyes in wastewaters have complex
chemical structures which are difficult to be biodegraded by mi-
croorganisms (Chen et al., 2012). Moreover, they can cause toxic to
human being, aquatic life, and microorganisms. This problem is a
serious challenge for environmental scientists to reduce a discharge
of dye wastewaters to the environment and to treat dye wastewa-
ters after discharge (Forgacs et al., 2004).
One of the most interesting technologies for removal of dye-
* Corresponding author. Department of Environmental Engineering, Faculty of
Engineering, King Mongkut's University of Technology Thonburi, 126 Pracha-uthit
Rd, Bangmod, Tungkru, Bangkok, 10140, Thailand.
E-mail address: patiya.kem@kmutt.ac.th (P. Kemacheevakul).
(Gogate and Pandit, 2004). AOPs can generate highly reactive hy-
droxyl radicals (OH) with short life to remove low level persistent
organic pollutants and degrade recalcitrant chemicals present in
wastewater (Chen et al., 2012; Borges et al., 2016). Examples of
AOPs that use for degradation of organic pollutants in wastewater
are O3/UV, H2O2/UV, O3/H2O2/UV, photocatalyst/UV, and Fenton
process (Wang et al., 2015; Simonenko et al., 2015; Lucas et al.,
2010; Wang, 2000; Xie et al., 2016). Each AOP has some disad-
vantages. O3/UV is expensive due to operation costs of ozone
generator and harmful effect of high dosages of ozone on human
health (Gogate and Pandit, 2004; Bromberg, 2016). H2O2/UV needs
high concentration of H2O2 as well as high UV light intensity to
generate sufficiently high level of OH (Behnajady et al., 2006).
Moreover, H2O2 is also a scavenger of OH (Ebrahiem et al., 2017).
Fenton process is efficient only in the pH range of 2e4 (Benitez
et al., 2001). In contrast, heterogeneous photocatalysis is based
on the nanostructured semiconductor photocatalysts. Electron-
hole pairs in the semiconductor photocatalysts are activated by

https://doi.org/10.1016/j.jclepro.2019.01.037
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
124 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130
light. This process is an eco-friendly process with effective appli-
cations in many fields for environmental protections and treat-
ments (Calia et al., 2017). It can treat wastewater from the industrial
section, such as heavy metal remediation, air purification, sterili-
zation, etc. (Le et al., 2012). This process is a versatile, low cost, and
environmentally friendly option (Borges et al., 2008; Rammohan
and Nadagouda, 2013).
In the heterogeneous photocatalysis, titanium dioxide (TiO2) has
the highest potential for treatment of dye wastewater because of its
low cost, chemical stability, non-toxicity, and photocorrosion
resistance. Moreover, it can use sunlight as an energy source (Ollis
et al., 1991; Gaya and Abdullah, 2008). In the past, most TiO2 studies
focused on using TiO2 powders for photocatalytic color removal
(also called decolorization) of synthetic wastewater, such as
methylene blue, direct red 23, acid chrome blue K, reactive brilliant
red K-2G, methyl orange, acid red B, reactive yellow 17, and reactive
red 239 (Wang, 2000; Sohrabi and Ghavami, 2008; Tariq et al.,
2009; Hsiung et al., 2008; Bergamini et al., 2009). Good photo-
catalytic activities were reported using TiO2 powders. However, an
additional separation process is needed to remove TiO2 powders
from the treated wastewater, which is a drawback (Hoffmann et al.,
1995). In order to overcome the drawback, many researchers have
tried to immobilization TiO2 on various kinds of supports, such as
activated carbon, coconut shell, zeolite, natural clay, and stainless
steel (Zhang et al., 2012; Le et al., 2012; Chong et al., 2015;
Hadjltaief et al., 2016; Permpoon et al., 2005). These methods can
solve the problem in post-separation and increase the TiO2 recov-
ery efficiency. There are many techniques to immobilize TiO2 onto a
solid support, such as doctor blade, dip-coating, sol-spraying, spin
coating, thermal treatment, and chemical vapor deposition (Barton
et al., 2016; Momeni et al., 2015; Mansilla et al., 2007; Yazawa et al.,
2009). Among these techniques, doctor blade is a very simple
procedure. In this process, a well-mixed slurry consisting of a
suspension of ceramic particles along with some additives is placed
on a substrate beyond the doctor blade. When a relatively constant
movement between the substrate and the blade is established, the
slurry is spread on the substrate to form a thin sheet, resulting in a
gel-layer upon drying (Berni et al., 2004). Doctor blade has many
advantages, for example, it can be applied on a large surface area
and the coating support can guide the coated layer with a desig-
nated film thickness. However, limited studies of photocatalysts
have been done on this technique. The aim of present study is to
design an innovative reactor for color removal from wastewater and
to determine the optimum factors for color removal by photo-
catalytic process using TiO2 coated on various substrates using
doctor blade coating. Transparent glass, glazed ceramic tile, and
304 stainless steel sheet are chosen to be substrates because they
can be calcined at 500  C. Furthermore, synthetic and actual dye
wastewaters were used in the photocatalytic tests. The wastewater
in the batch reactor is continuously flowed by a recirculation pump
under UV irradiation. In addition, the composition and morphology
of TiO2-coated materials were analyzed by scanning electron mi-
croscopy (SEM) with the energy dispersive x-ray spectroscopy
(EDS) and x-ray diffractometry (XRD).
2. Experimental
2.1. Materials
Titanium (IV) n-butoxide (Acros Organics), acetylacetone (ACA;
Carlo Erba Reagents), methanol (RCI Labscan), propanol (RCI Lab-
scan), and polyvinylpyrrolidone (PVP; Mw ¼ 1,300,000, Sigma-
Aldrich) were used as received without purification. Methylene
blue (Sigma-Aldrich) solution (as a synthetic dye wastewater) was
prepared to the desired concentration in deionized water. The
actual wastewater used in the experiments was collected from the
textile industry in Thailand. Table 1 shows characteristics of syn-
thetic and actual wastewaters used in this work. Three types of
substrate materials were used in this experiment, i.e. transparent
glass (thickness ¼ 2 mm), glazed ceramic tile (thickness ¼ 6 mm),
and 304 stainless steel (thickness ¼ 1 mm). Size of each substrate
was 13  20 cm2. They were used as received without etching.
2.2. Preparation of TiO2 coated substrates
Three types of substrate materials were cleaned by propanol.
They were dried inside an oven at 105  C for 10 min. TiO2 thin film
was prepared using a sol-gel method and coated by doctor blade
technique. PVP (0.8 g) was dissolved in methanol (20 mL). The
mixture was stirred at room temperature for 30 min. Titanium (IV)
n-butoxide (4 g) and ACA (1.175 g) were added into the mixture.
The mixture was stirred at room temperature for 30 min. The ob-
tained gel solution was then coated on the substrate by doctor
blade. Coated samples were dried inside an oven at 105  C for 2 h.
Afterwards, coated samples were heated from room temperature to
500  C for 50 min (10  C/min), and held at 500  C for 2 h. The coated
samples are shown in Fig. 1. The bare substrates were also heated at
500  C for 2 h as the blank cases for comparisons.
2.3. Characterizations
TiO2 film coated on the substrates were characterized by x-ray
diffractometry (XRD; BRUKER AXS: D8DISCOVER) with Cu-Ka ra-
diation (l ¼ 0.15,406 nm) operated at 40 kV and 40 mA to deter-
mine the crystalline structure of TiO2. The average crystallite size (t)
of TiO2 particles was estimated by Scherrer equation (Raj and
Viswanathan, 2009).
t ¼ 0.94 l / Bcos q (1)
Where t is average crystallite size, B is the width of the mean peak
at half maximum intensity (FWHM), l is the wavelength of the X-
ray radiation, and q is the Bragg angle.
The surface morphology and particle sizes of the prepared
samples were determined using scanning electron microscopy
(SEM; JEOL JSM-6610 LV) operated at 20 kV with the energy
dispersive x-ray spectroscopy (EDS; Oxford INCA-xart).
2.4. Photocatalytic reactor
The photocatalytic reactor in this work is shown in Fig. 2. It
consisted of a UV light source in a chamber. The chamber was
37.5  100  50 cm3 in dimensions. The UV light source was a 36 W
ultraviolet A (UVA) lamp (Silver Light, light intensity of 0.983 mW/
cm2 at 20 cm) or a 30 W ultraviolet C (UVC) lamp (Philips, light
intensity of 1.061 mW/cm2 at 20 cm) installed on the top of the
chamber. Inside the UV chamber, there were a magnetic stirrer bar
in a 250-mL beaker, a magnetic stirrer, and a peristaltic pump. The
frames in the reactor were made of pieces of angle irons. The pump
was used to circulate the wastewater passing through the TiO2
coated substrate. The TiO2 coated substrate was tiled under water
nozzles on the upper level of the reactor. A slanted acrylic plastic
gutter with a 15 slope was placed between the TiO2 coated sub-
strate and the beaker in order to return the wastewater that passed
the TiO2 coated substrate back to the beaker.
2.5. Photocatalytic color removal of synthetic and actual dye
wastewaters
For synthetic dye wastewater, methylene blue solution with
 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130 125

Table 1
Characteristics of synthetic and actual wastewaters.

Parameter Synthetic wastewater (Methylene blue) Actual wastewater (Reactive purple)

Color (ADMI) 1235 1080

pH 7.7e7.8 8.9e9
sCOD (mg/L) ND 800
Cl (mg Cl/L) ND 34.42

*ND ¼ not detected.

Fig. 1. Photographs of TiO2 coated on (a) glass, (b) ceramic tile, and (c) stainless steel substrates.

Fig. 2. Schematic diagram of the photocatalytic reactor apparatus; A: coated materials, B: gutter, C: 250-mL beaker, D: magnetic stirrer, E: peristaltic pump, F: UV lamp, and G: water
nozzle.

concentration of 5 mg/L was prepared with deionized water
(American Dye Manufacturer's Institute (ADMI) wastewater co-
lor ¼ 1235). The coated samples (glass, ceramic tile, and stainless
steel) were soaked in the methylene blue solution for 1 h. The batch
experiments were carried out with 50-mL dye solutions. Coated
samples were placed in the reactor and photocatalytic experiments
were started. The solution was circulated in the reactor with a flow
rate of 30 mL/min (excepted for the study of wastewater flow rate,
three different flow rates of 15, 30, and 90 mL/min were used.) in
the dark until the full adsorption of dye on TiO2 thin film was
achieved. After turning on UVA or UVC light, 2 mL of methylene
blue solution was withdrawn at a regular interval of every 30 min
and the concentration (C) of methylene blue was monitored by the
absorbance obtained from a spectrophotometer at the wavelength
126 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130

of 664 nm. The initial concentration was assigned as C0. Color
removal (%) was determined using the following equation:
Color removal (%) ¼ (C0  C) / C0 x 100.
Furthermore, the synthetic wastewater was used to test pho-
tocatalyst recycling ability of the coated sample for 20 cycles.
For actual wastewater, the wastewater from textile industry in
Thailand (ADMI wastewater color ¼ 1080) was used. The main
composition in this actual dye wastewater was reactive purple. The
concentration of dye was monitored and color removal was
determined by the same processes as the synthetic wastewater.
3. Results and discussion
3.1. Characterizations of TiO2 thin films-coated on different
substrates
3.1.1. Surface morphology of TiO2 thin films
SEM images of three different substrates (i.e. glass, ceramic tile,
and stainless steels) and the substrates coated by TiO2 are shown in
Fig. 3. It was found that the surface of glass was relatively smooth
however the surfaces of ceramic tile and stainless steel were rough.
It is noted that the surface of stainless steel was rougher than that
of ceramic tile. After coating with TiO2, the surface of the samples
was covered with a thin film layer of TiO2 consisted of uniform,
sphere-liked TiO2 particles. Separated sphere-liked shape of TiO2
particles could be obtained in this work because PVP was added in
(2) the precursor solution in sol-gel process. PVP did not react with
TiO2 but covered and separated the growth of gel particles.
Therefore, after the calcination, uniform sphere-liked TiO2 particles
could be obtained. Wiranwetchayan et al. (2017) also reported that
PVP can play an important role in producing spherical nano-
particles. However, the particle size in this work is significantly
bigger than that reported by Wiranwetchayan et al. (2017) because
the molecular weight (Mw) of PVP in this work is significantly
higher (1,300,000 in contrast with 360,000). Larger size (in
micrometer size) TiO2 has an advantage of lower health risks
compared with the nanometer-sized ones (Bianchi et al., 2014).
This is an advantage of TiO2 in this work if the particles are released
from the substrates to environment. Average diameters of the
particles on glass, ceramic tile, and stainless steel were quite similar
(1.16 ± 0.25 mm, 1.13 ± 0.24 mm, and 1.32 ± 0.3 mm, respectively,
calculated from SEM images of 130 particles in each sample).
Cross-sectional images of the coated samples reveal that the
particles are not round spheres but they are in the shape of
squeezed sphere. This is because of the squeeze of TiO2 at gel state
during the doctor blade coating. The squeezed sphere particles of
TiO2 is a uniqueness in this contribution. The average thicknesses of
TiO2 films on the surface of glass, ceramic tile, and stainless steel

Fig. 3. SEM images of different bare substrates: (a) glass, (b) ceramic tile, and (c) stainless steel surface; and the substrates coated with TiO2. Numbers 1e3 refer to surface images of
bare substrates, surface images of TiO2-coated substrates, and cross-sectional images of TiO2-coated substrates, respectively.
 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130
sheet were 1.93 mm, 1.90 mm, and 1.03 mm, respectively. Stainless
steel showed a thinner TiO2 film because there is no hydroxyl group
on the surface of stainless steel to react with TiO2 (hydrogen
bonds). So, some areas of the film can be peeled off.
3.1.2. Crystalline structure of TiO2 films
XRD patterns of bare substrates (glass, ceramic tile, and stainless
steel) and the coated samples are shown in Fig. 4. It can be seen that
all three coated samples contain a characteristic peak of TiO2
anatase phase (2q ¼ 25.4 ). There is no rutile or other TiO2 phases.
This anatase phase will provide higher photocatalytic activity than
rutile because of the higher adsorptive affinity of anatase to organic
compounds and its lower electron-hole recombination rates
(Sakthivel et al., 2006).
Crystallite size of TiO2 thin film coated glass, ceramic tile, and
stainless steel were 14.11 nm, 17.84 nm, and 20.37 nm, respectively.
It is noted that particle sizes were larger than these crystallite sizes
because crystallite from the primary particles agglomerated to form
the larger particles. The results show that TiO2 coated on glass has
the smallest crystallite size, which implies that the surface area of
TiO2 coated on glass should be the highest compared with those of
the ceramic tile and the stainless steel samples as Raj and
Viswanathan (2009) reported that surface area was found to
decrease with increasing crystallite size. TiO2 coated stainless steel
had the largest crystallite size because stainless steel was a metal.
When it was calcined at 500  C, it had the highest thermal con-
duction compared with those of glass and ceramic tile (Chung,
2001). Therefore, TiO2 crystallize growth rate on the stainless
steel was the highest, resulted in the largest size.
3.2. Color removal of synthetic wastewater by photocatalytic
process
3.2.1. Effect of substrate material
Before photocatalytic experiments, photolytic degradation
(alteration of chemicals by only light without any catalyst) of
methylene blue solution under UVA irradiation was investigated on
all bare substrates. The solution was circulated with a flow rate of
30 mL/min. From the experiments of 180 min, the photolytic
degradation of methylene blue on glass, ceramic tile, and stainless
steel were less than 10% (9.85%, 8.43%, and 8.88%, respectively), as
Fig. 4. XRD patterns of different bare substrates (glass, ceramic tile, and stainless steel)
and the substrates coated with TiO2.
127
shown in Fig. 5. This is in agreement with the work previously
reported by Franco et al. (2009), which indicated that less than 20%
of methylene blue (20 mg/L) was degraded under UVA irradiation
(450-W medium-pressure mercury-vapor lamp) after 120-min
photolysis.
Photocatalytic degradation of methylene blue solutions under
UVA irradiation was investigated in all TiO2 coated samples. The
solution was circulated with a flow rate of 30 mL/min. From the
experiments, degradation of methylene blue solution on TiO2
coated glass, ceramic tile, and stainless steel sheets after 180 min
were 98.25 ± 0.29%, 98.34 ± 0.62%, and 18.63 ± 5.72%, respectively,
as shown in Fig. 5. Moreover, methylene blue reaction rates
calculated from the Langmuir-Hinshelwood kinetic model (Chong
et al., 2015) on TiO2 coated glass, ceramic tile, and stainless steel
sheets were 0.025, 0.027, and 0.001 min1, respectively. The results
confirmed that TiO2 was the active photocatalyst under UVA irra-
diation. When it absorbs energy greater than its energy band gap
from the light source, hydroxyl radicals (OH) are generated on the
surface of TiO2 to degrade the organic compounds as shown in
Equations (3)e(7) (R is an organic compound) (modified from Le
et al., 2012).
TiO2 þ hv / TiO2 (e) þ TiO2 (hþ) (3)
hþ þ R / intermediates / CO2 þ H2O (4)
H2O þ hþ/ OH þ Hþ (5)
OH þ hþ/ OH (6)
OH þ R / intermediates / CO2 þ H2O (7)
TiO2 coated on glass and on ceramic tile have better color
removal efficiencies than on stainless steel because the crystallite
size of TiO2 coated on glass and on ceramic tile are smaller than that
on stainless steel. The smaller size resulted in higher surface area
for photocatalytic activities (Pardeshi and Patil, 2009; Chuangchote
et al., 2009). On the other hand, TiO2 coated stainless steel has no
significant effect on color removal of dyes compared with those
coated on glass and ceramic tile because, during the calcination
process, Fe2þ ions may diffuse from stainless steel substrate to the
TiO2 thin film and retard photogenerated hole transfer toward the
Fig. 5. Color removal of synthetic wastewater (5 mg/L methylene blue solution, 50 mL)
under UVA irradiation on bare substrates and the substrates coated with TiO2.
128 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130

thin film surface and ruin the photocatalytic activity (Permpoon

et al., 2005). Momeni et al. (2015) also reported that diffusion of
Fe ions into the photocatalysts was encouraged by increasing
calcination temperature from 400  C to 600  C.
Fig. 6 presents color removal of synthetic wastewater under UVC
irradiation on bare substrates and the substrates coated with TiO2.
At 60 min, color removal efficiencies of methylene blue solution on
bare glass, ceramic tile, and stainless steel were 7.78%, 6.12%, and
3.40%, respectively. Color removal efficiencies of methylene blue
solution on TiO2 coated glass, ceramic tile, and stainless steel sheets
for reaction time of only 60 min (3 times shorter than UVA cases)
were 93.03 ± 0.66%, 91.65 ± 0.88%, and 38.72 ± 2.35%, respectively.
The results of different substrates showed the same trend
compared with UVA irradiation. It can be concluded that UVA and
UVC lights can be used as light sources for color removal of syn-
thetic wastewater (degradation of methylene blue). However, UVC
light has more efficiency than UVA light. This is because the
wavelength of the UVC was lower than that of the UVA, so the
photon energy to activated TiO2 was higher causing generation of
higher hydroxyl radicals (OH). Fig. 7. Color removal of synthetic wastewater (5 mg/L methylene blue solution, 50 mL)
under UVC irradiation on TiO2-coated glass substrate with different solution flow rates
of 15, 30, and 90 mL/min.
3.2.2. Effect of wastewater flow rate
Fig. 7 shows color removal of synthetic wastewater under UVC
irradiation on TiO2-coated glass substrate with different solution of photocatalytic color removal of dyes after twenty cycles (color
flow rates of 15, 30, and 90 mL/min. It shows that the higher removal efficiency ~ 96%) as shown in Fig. 8. A SEM image of 20-
wastewater flow rate decreased detention time of wastewater un- cycle used substrate revealed no change of size and density of
der UV irradiation (at a time of flow). However, it increased con- TiO2 particles (not shown here) and no particle was found in the
tacted time of wastewater and TiO2 surface (with a higher number tested methylene blue solution. This could be ascribed to the sta-
of time that the wastewater passed the photocatalytic substrate). bility of TiO2 coated glass. Li et al. (2014) also reported that the
Therefore, the initial rate of color removal was found to increase, photocatalytic degradation of Rhodamine B on photocatalysts for
while the overall color removal was found to slightly increase with 12 h could maintain more than 91.0% for five-cycle degradations. In
increasing flow rate of wastewater. contrast, Bouarioua and Zerdaoui (2017) reported that the degra-
dation efficiency of TiO2 coated films after 5 cycles of reuse was
3.2.3. Photocatalyst recycling ability test slightly decreased.
Recycling ability is one of the important parameters for deter-
mining the efficiency of the photocatalytic reactor. In order to 3.3. Color removal of actual wastewater by photocatalytic process
assess the recycling ability of the TiO2 thin film, the color removal of
methylene blue solution (5 mg/L, 50 mL) was repeated up to twenty 3.3.1. Color removal of actual wastewater
cycles on another TiO2 coated glass (TiO2 film thickness ¼ 2.30 mm) The actual wastewater from textile industry in Thailand was
under UVC irradiation (flow rate ¼ 30 mL/min). After each cycle, a used for photocatalysis. The maximum UVevis absorption of the
new methylene blue solution was replaced in the reactor. It was wastewater is found at a wavelength of 561 nm. NaCl and Na2CO3
found that the color removal efficiency still maintained a high level from the textile process were also found in the wastewater. The

Fig. 6. Color removal of synthetic wastewater (5 mg/L methylene blue solution, 50 mL) Fig. 8. Recycle ability of TiO2-coated glass substrate for color removal of synthetic
under UVC irradiation on bare substrates and the substrates coated with TiO2. wastewater (5 mg/L methylene blue solution, 50 mL) under UVC irradiation.
 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130
initial condition of actual wastewater was used as received. The
photolysis and photocatalysis of actual wastewater (pH of the
wastewater ¼ 9) on TiO2 coated film under UVC irradiation are
shown in Fig. 9. The results show that the photolysis degradation
was only 7.52%. So, the degradation was negligible even the
wastewater was illuminated with UVC light for 5 h. On the other
hand, the photocatalytic color removal efficiency was 92.19 ± 2.03%
after 5 h. The result showed that the photocatalytic reactor made of
TiO2-coated glass was a promising candidate for treatment of the
actual dye wastewater.
3.3.2. Effect of solution pH
Wastewater from textile industries usually has a wide range of
pH values. Therefore, effect of solution pH is taken into consider-
ation. The pH depends on the type of dye used and the chemical
compounds added to the dye during the process (Dhanya and
Aparna, 2016).
The effects of solution pH of the actual wastewater from textile
wastewater has been investigated in the pH range of 3e11. Photo-
catalytic treatment was performed on TiO2 coated glass under UVC
irradiation. The pH values were adjusted using 1 M NaOH or 1 M
HCl. The color removal was found to be the highest at pH 11 and
decreased with decreasing pH, as shown in Fig. 10. The highest
efficiency of degradation in alkaline pH at the highest pH values
could be attributed to more efficient generation of hydroxyl radicals
by TiO2 with increasing concentration of hydroxide ion (Faisal et al.,
2007). In Thailand, the environmental law allows industries to
discharge wastewater with pH in the range of 5.5e9 to the water-
course. The color removal efficiency at pH 9 was not significantly
different from that of pH 11. Therefore, the optimum pH of the
actual wastewater in the photocatalytic wastewater treatment
should be at 9.
4. Conclusions
TiO2 was synthesized through sol-gel technique and coated on
transparent glass, glazed ceramic tile, and stainless steel by doctor
blade technique. The coated substrates were characterized by SEM,
EDS, and XRD. It was found that substrate materials influenced the
surface morphology and structure of TiO2 films. SEM images
Fig. 9. Color removal of actual wastewater (50 mL) under UVC irradiation on TiO2-
coated glass substrate. Inset is a photographical image of actual wastewater before and
after photocatalytic treatment for 5 h. (For interpretation of the references to color in
this figure legend, the reader is referred to the Web version of this article.)
129
Fig. 10. Color removal of actual wastewater (50 mL) at different pH values (3e11)
under UVC irradiation on TiO2-coated glass substrate.
showed that the micrometer size particles were agglomerated to
form thin film and shape of the particles were squeezed sphere-
liked shape. XRD patterns showed that TiO2 thin films on all sub-
strate materials were pure anatase phase with different crystallite
sizes depending on substrate materials. The coated substrates were
used to fabricate an innovative reactor for color removal of dye
wastewater. The photocatalytic activities of the designed reactor
were determined using a synthetic dye wastewater (methylene
blue) under UV irradiations. The results shows that the better
substrate (transparent glass) and light source (UVC) yielded the
highest color removal efficiency (93.03 ± 0.66%). It was observed
that TiO2-coated glass sheet has negligible change in efficiency after
20 cycles of uses. In addition, the actual wastewater from textile
industry was tested with different pH values (i.e. pH ¼ 3e11). The
maximum color removal observed at pH value 11 was found to
decrease with decrease in pH.
Acknowledgements
The authors express gratitude to the Thailand Research Fund
and Office of the Higher Education Commission (grant no.
MRG5980109) and the 55th Anniversary Commemorative Fund of
King Mongkut's University of Technology Thonburi for financial
supports. This research was also supported by Research Strength-
ening Project of the Faculty of Engineering, KMUTT. Technical
support from the Department of Environmental Engineering, Fac-
ulty of Engineering, KMUTT, is also gratefully acknowledged. The
author (K. Sirirerkratana) would like to acknowledge the Petchra
Pra Jom Klao Master's Degree Research Scholarship from King
Mongkut's University of Technology Thonburi. Prof. S. Seraphin was
acknowledged for the English editing of this article.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.01.037.
References
Barton, I., Matejec, V., Matousek, J., 2016. Photocatalytic activity of nanostructured
TiO2 coating on glass slides and optical fibers for methylene blue or methyl
orange decomposition under different light excitation. J. Photochem. Photobiol.,
A 317, 72e80.
130 K. Sirirerkratana et al. / Journal of Cleaner Production 215 (2019) 123e130
Behnajady, M.A., Modirshahla, N., Fathi, H., 2006. Kinetics of decolorization of an
azo dye in UV alone and UV/H2O2 processes. J. Hazard Mater. B136, 816e821.
Benitez, F.J., Acero, J.L., Real, F.J., Rubio, F.J., Leal, A.I., 2001. The role of hydroxyl
radicals for the decompositionof p-hydroxy phenylacetic acid in aqueous so-
lutions. Water Res. 35 (5), 1338e1343.
Bergamini, R.B.M., Azevedo, E.B., Araújo, L.R., 2009. Heterogeneous photocatalytic
degradation of reactive dyes in aqueous TiO2 suspensions: decolorization ki-
netics. Chem. Eng. J. 149 (1e3), 215e220.
Berni, A., Mennig, M., Schmidt, H., 2004. Doctor blade. In: Aegerter, M.A.,
Mennig, M. (Eds.), Sol-Gel Technologies for Glass Producers and Users. Springer,
Boston, MA, pp. 89e92.
Bianchi, C.L., Colombo, E., Gatto, S., Stucchi, M., Cerrato, G., Morandi, S., Capucci, V.,
2014. Photocatalytic degradation of dyes in water with micro-sized TiO2 as
powder or coated on porcelain-gre s tiles. J. Photochem. Photobiol., A 280,
27e31.
Borges, M.E., Alvarez-Galva n, M.C., Esparza, P., Medina, E., Martín-Zarz, P.,
Fierro, J.L.G., 2008. Ti-containing volcanic ash as photocatalyst for degradation
of phenol. Energy Environ. Sci. 1, 364e369.
Borges, M.E., Sierra, M., Cuevas, E., García, R.D., Esparza, P., 2016. Photocatalysis with
solar energy: sunlight-responsive photocatalyst based on TiO2 loaded on a
natural material for wastewater treatment. Sol. Energy 135, 527e535.
Bouarioua, A., Zerdaoui, M., 2017. Photocatalytic activities of TiO2 layers immobi-
lized on glass substrates by dip-coating technique toward the decolorization of
methyl orange as a model organic pollutant. J. Environ. Chem. Eng. 5,
1565e1574.
Bromberg, P.A., 2016. Mechanisms of the acute effects of inhaled ozone in humans.
Biochim. Biophys. Acta 1860 (12), 2771e2781.
Calia, A., Lettieri, M., Masieri, M., Pal, S., 2017. Limestones coated with photocatalytic
TiO2 to enhance building surface with self-cleaning and depolluting abilities.
J. Clean. Prod. 165, 1036e1047.
Chen, C.Y., Cheng, M.C., Chen, A.H., 2012. Photocatalytic decolorization of remazol
black 5 and remazol brilliant orange 3R by mesoporous TiO2. J. Environ. Manag.
102, 125e133.
Chong, M.N., Tneu, Z.Y., Poh, P.E., Jin, B., Aryal, R., 2015. Synthesis, characterization
and application of TiO2-zeolite nanocomposites for the advanced treatment of
industrial dye wastewater. J. Taiwan Inst. Chem. Eng. 50, 288e296.
Chuangchote, S., Jitputti, J., Sagawa, T., Yoshikawa, S., 2009. Photocatalytic activity
for hydrogen evolution of electrospun TiO2 nanofibers. ACS Appl. Mater. In-
terfaces 1 (5), 1140e1143.
Chung, D.D.L., 2001. Materials for thermal conduction. Appl. Therm. Eng. 21 (16),
1593e1605.
Dhanya, A., Aparna, K., 2016. Synthesis and evaluation of TiO2/chitosan based
hydrogel for the adsorptional photocatalytic degradation of azo and anthra-
quinone dye under UV light irradiation. Proc. Technol. 24, 611e618.
Ebrahiem, E.E., Al-Maghrabi, M.N., Mobarki, A.R., 2017. Removal of organic pollut-
ants from industrial wastewater by applying photo-Fenton oxidation technol-
ogy. Arab. J. Chem. 10 (2), S1674eS1679.
Faisal, M., Abu Tariq, M., Muneer, M., 2007. Photocatalysed degradation of two
selected dyes in UV-irradiated aqueous suspensions of titania. Dyes Pigments
72, 233e239.
Forgacs, E., Cserh ati, T., Oros, G., 2004. Removal of synthetic dyes from wastewaters:
a review. Environ. Int. 30 (7), 953e971.
Franco, A., Neves, M.C., Ribeiro Carrott, M.M.L., Mendonç, M.H., Pereiraa, M.I.,
Monteiro, O.C., 2009. Photocatalytic decolorization of methylene blue in the
presence of TiO2/ZnS nanocomposites. J. Hazard Mater. 161, 545e550.
Gaya, U.I., Abdullah, A.H., 2008. Heterogeneous photocatalytic degradation of
organic contaminants over titanium dioxide: a review of fundamentals, prog-
ress and problems. J. Photochem. Photobiol. C Photochem. Rev. 9 (1), 1e12.
Gogate, P.R., Pandit, A.B., 2004. A review of imperative technologies for wastewater
treatment I: oxidation technologies at ambient conditions. Adv. Environ. Res. 8
(3), 501e551.
Hadjltaief, H.B., Zina, M.B., Galvez, M.E., Costa, P.D., 2016. Photocatalytic degradation
of methyl green dye in aqueous solution over natural clay-supported ZnO-TiO2
catalysts. J. Photochem. Photobiol., A 315, 25e33.
Hoffmann, M.R., Martin, S.T., Choi, W., Bahnemann, D.W., 1995. Environmental ap-
plications of semiconductor photocatalysis. Chem. Rev. 95 (1), 69e96.
Hsiung, T.L., Wang, H.P., Lin, H.P., 2008. Chemical structure of photocatalytic active
sites in nanosize TiO2. J. Phys. Chem. Solid. 69, 383e385.
Li, D., Zheng, H., Wang, Q., Wang, X., Jiang, W., Zhang, Z., Yang, Y., 2014. A novel
double-cylindrical-shell photoreactor immobilized with monolayer TiO2-
coated silica gel beads for photocatalytic degradation of Rhodamine B and
Methyl Orange in aqueous solution. Separ. Purif. Technol. 123, 130e138.
Le, H.A., Linh, L.T., Chin, S., Jurng, J., 2012. Photocatalytic degradation of methylene
blue by a combination of TiO2-anatase and coconut shell activated carbon.
Powder Technol. 225, 167e175.
Lucas, M.S., Peres, J.A., Li Puma, G., 2010. Treatment of winery wastewater by ozone-
based advanced oxidation processes (O3, O3/UV and O3/UV/H2O2) in a pilot-
scale bubble column reactor and process economics. Separ. Purif. Technol. 72
(3), 235e241.
Mansilla, H.D., Mora, A., Pincheira, C., Mondaca, M.A., Marcato, P.D., Dura n, N.,
Freer, J., 2007. New photocatalytic reactor with TiO2 coating on sintered glass
cylinders. Appl. Catal., B 76 (1e2), 57e63.
Momeni, M., Golestani-Fard, F., Saghafian, H., Barati, N., Khanahmadi, A., 2015.
Development of visible light activated TiO2 thin films on stainless steel via sol
spraying with emphasis on microstructural evolution and photocatalytic ac-
tivity. Appl. Surf. Sci. 357, 1902e1910.
Ollis, D.F., Pelizzetti, E., Serpone, N., 1991. Photocatalyzed destruction of water
contaminants. Environ. Sci. Technol. 25 (9), 1522e1529.
Pardeshi, S.K., Patil, A.B., 2009. Effect of morphology and crystallite size on solar
photocatalytic activity of zinc oxide synthesized by solution free mechano-
chemical method. J. Mol. Catal. Chem. 308, 32e40.
Permpoon, S., Fallet, M., Berthome , G., Baroux, B., Joud, J.C., Langlet, M., 2005. Photo-
induced hydrophilicity of TiO2 films deposited on stainless steel via sol-gel
technique. J. Sol. Gel Sci. Technol. 35 (2), 127e136.
Raj, K.,J.A., Viswanathan, B., 2009. Effect of surface area, pore volume and particle
size of P25 titania on the phase transformation of anatase to rutile. Indian J.
Chem. 48A, 1378e1382.
Rammohan, G., Nadagouda, M.N., 2013. Green photocatalysis for degradation of
organic contaminants: a review. Curr. Org. Chem. 17 (20), 2338e2348.
Sakthivel, S., Hidalgo, M.C., Bahnemann, D.W., Geissen, S.-U., Murugesan, V.,
Vogelpohl, A., 2006. A fine route to tune the photocatalytic activity of TiO2.
Appl. Catal., B 63, 31e40.
Simonenko, E., Gomonov, A., Rolle, N., Molodkina, L., 2015. Modeling of H2O2 and
UV oxidation of organic pollutants at wastewater post-treatment. Procedia Eng
117, 337e344.
Sohrabi, M.R., Ghavami, M., 2008. Photocatalytic degradation of direct red 23 dye
using UV/TiO2: effect of operational parameters. J. Hazard Mater. 153 (3),
1235e1239.
Tariq, M., Chuncheng, C., Lili, L., Dan, Z., Wanghong, M.A., Jun, L., Jincai, Z., 2009.
Effect of dye-metal complexation on photocatalytic decomposition of the dyes
on TiO2 under visible irradiation. J. Environ. Sci. 21 (2), 263e267.
Wang, Y., 2000. Solar photocatalytic degradation of eight commercial dyes in TiO2
suspension. Water Res. 34 (3), 990e994.
Wang, M.Y., Lu, Y.W., Wu, F., Zhang, X.J., Yang, C.X., 2015. Photocatalytic decom-
position of formaldehyde by combination of ozone and AC network with
UV365nm, UV254nm and UV254þ185nm. Procedia Eng 121, 521e527.
Wiranwetchayan, O., Promnopas, S., Thongtem, T., Chaipanich, A., Thongtem, S.,
2017. Effect of alcohol solvents on TiO2 films prepared by solegel method. Surf.
Coating. Technol. 326, 310e315.
Xie, Y., Chen, L., Liu, R., 2016. Oxidation of AOX and organic compounds in phar-
maceutical wastewater in RSM-optimized-Fenton system. Chemosphere 155,
217e224.
Yazawa, T., Machida, F., Kubo, N., Jin, T., 2009. Photocatalytic activity of transparent
porous glass supported TiO2. Ceram. Int. 35, 3321e3325.
Zhang, Z., Xu, Y., Ma, X., Li, F., Liu, D., Chen, Z., Zhang, F., Dionysiou, D.D., 2012.
Microwave degradation of methyl orange dye in aqueous solution in the
presence of nano-TiO2-supported activated carbon (supported-TiO2/AC/MW).
J. Hazard Mater. 209e210, 271e277.