Powder Technology 313 (2017) 417–426

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Powder Technology

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TiO2-zeolite photocatalysts made of metakaolin and rice husk ash for

removal of methylene blue dye
Naruemon Setthaya a, Prinya Chindaprasirt b, Shu Yin c, Kedsarin Pimraksa a,⁎
a
Department of Industrial Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Sustainable Infrastructure Research and Development Center, Faculty of Engineering, Khon Kaen University, Khon Kaen 40002, Thailand
c
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan

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

Article history: In this study, synthesized zeolites were performed by solvothermal method using metakaolin and rice husk ash
Received 27 September 2016 as starting materials. The TiO2-zeolites photocatalysts obtained from the solvothermal method was compared
Received in revised form 7 December 2016 with that obtained from impregnation method. The synthesized products were characterized using X-ray Fluo-
Accepted 5 January 2017
rescence spectrometer (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), the Fourier trans-
Available online 6 January 2017
form infrared (FTIR), ultraviolet -visible spectroscopy (UV–vis), particle size analyzer and surface area
Keywords:
measurement. The results showed that the incorporation of TiO2 in a form of transparent titanium solution
TiO2 into zeolites obtained from solvothermal method was very similar to that obtained from impregnation method
Zeolites confirmed by their mineralogical compositions, microstructures and specific surface areas. The adsorption and
Photocatalyst degradation efficiency of the TiO2-zeolites photocatalysts obtained from solvothermal method of 97.32% was
Metakaolin slightly lower than 99.43% of impregnation method. In addition, the synthesized TiO2-zeolites photocatalysts
Rice husk ash showed a greater adsorption and degradation of methylene blue than pure zeolites and pure TiO2 anatase.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction support materials to improve the regeneration efficiency of TiO2.

Textile dyeing industry produces a massive quantity of contaminat-
ed effluent which exerts serious harmful effect on photochemical phe-
nomena. The increasing demand for dye by the textile manufactures
resulted in a risk of highly contaminated environment. Textile wastewa-
ters normally need high chemical oxygen demand due to the high tox-
icity and high total suspended solids [1–3]. Consequently, various
technologies for the degradation of dyes from wastewater were
constantly improved to obtain the best methodology for wastewater
treatment.
Recently, a photocatalytic process has shown a high potential to re-
duce organic pollution since it provides the absolute decrement of toxic
substances [4,5]. Titanium dioxide (TiO2) is considered as the promi-
nent photocatalyst due to its superior photocatalytic oxidation, thermal
stability, nonphotocorrosion and nontoxicity properties. Its reasonable
price also makes its utilization in an industrial scale possible. Due to
its low adsorption ability as well as the low concentration of pollutants
in ambient water and air, the efficiency of TiO2 photocatalyst is often
limited [6–12]. One of the promising ways to lever this issue is to com-
bine the better adsorber to the TiO2 photocatalyst to improve adsorptive
ability. Many researchers have thus dedicated in search for appropriate
⁎ Corresponding author.
E-mail address: kedsarin.p@cmu.ac.th (K. Pimraksa).
Among various support materials, porous aluminosilicate material
called “zeolite” has been shown to be the most desirable supporting ma-
terial for TiO2 as a result of their unique properties [13–15]. Zeolites act
as electron donors and acceptors of moderate strength to the guest spe-
cies based on the adsorption site. They show excellent absorption abili-
ty, high specific surface area including uniform pores and channels with
unique structures [16,17]. Zeolites generally possess cages and channels
of 4–14°A that can confine substrate molecules to improve the photo-
catalytic reactivity [18]. Therefore, zeolite is selected as supporting ma-
terial for TiO2 in this research.
From our previous works, nanoscale faujasite and zeolite P1 could be
obtained from the solvothermal treatment using rice husk ash (RHA)
and metakaolin (MK) as sources of silica and alumina with SiO2/Al2O3
molar ratio of 4. The solvothermal treatments using alcohol as a media
affected the nucleation rate and crystal growth of zeolite [19]. The aim
of this study is therefore to propose the way to synthesize nanoactive
adsorber with TiO2-containing zeolite materials using MK and RHA as
the starting materials in order to improve the catalytic efficiency. The
TiO2-zeolite photocatalyst obtained from the solvothermal method
was compared with that obtained from impregnation method. The
solvothermal method is selected in this research as it points to the syn-
thesis above boiling point of water in nonaqueous solution at relatively
high temperatures under closed system. These techniques have been
accepted to obtain resulting materials with metastable structure,

http://dx.doi.org/10.1016/j.powtec.2017.01.014
0032-5910/© 2017 Elsevier B.V. All rights reserved.
418 N. Setthaya et al. / Powder Technology 313 (2017) 417–426

condensed and aggregation statuses, controllable morphology and par-

ticle size, and dopant ions directly in synthetic reaction [20,21]. As a re-
sult, solvothermal process is referred to incorporating of Ti species
during solvothermal treatment of zeolite production. For impregnation
method, Ti species are introduced later after zeolite production has been
done.
Kaolin, a hydrated aluminium silicate mineral with the chemical
composition of Al2O3·2SiO2·2H2O, when calcined, undergoes dehy-
droxylation resulting in a collapse of kaolin structure, called
“metakaolin (Al2O3·2SiO2)” [22,23]. Metakaolin is readily dissolved in
alkaline solution and is thus a good precursor for zeolite synthesis
[24–26]. RHA, a combustion by-product rich in silica is very reactive to
alkaline solution and forms sodium silicate gel which is used in the syn-
thesis of zeolite [27–30].
The main objectives of the present work were to synthesis zeolites
(faujasite and zeolite P1), to prepare the TiO2-containing zeolite com-
posites using solvothermal method compared with impregnation meth-
od and to determine the photocatalytic activities of the samples. The
comparison of photocatalytic activities was also carried out for the syn-
thesized zeolites and pure anatase TiO2. A series of complementary
techniques: X-ray diffraction (XRD), Field emission scanning electron
microscopy (SEM), Fourier transform infrared spectroscopy (FTIR),
UV–visible diffuse reflectance spectroscopy (UV–vis DRS) were used
to characterize the synthesized TiO2 containing zeolite composites.
The photocatalytic activities of samples were evaluated by the degrada-
tion of methylene blue dye (MB) in water as a representative dye in
water. The findings from this work would help in the finding of environ-
mental cleaning up materials.
2. Experimental
2.1. Materials
Kaolin clay was supplied from Sibelco Mineral (Thailand) Co., Ltd.
Rice husk was collected from paddy fields in Chiang Mai, a province in
Northern Thailand. China clay and rice husk were subjected to calcina-
tion at temperatures of 750 °C and 700 °C, respectively for 3 h with
the heating rate of 5 °C/min in an oxidizing atmosphere resulting in
MK and RHA, respectively. After that, they were ground and passed
through a sieve No.325 [19,31]. The chemical compositions, average
particle sizes and specific surface area of MK and RHA were character-
ized using X-ray fluorescence (XRF), Zetasizer nanoparticle analyzer
and Brunauer–Emmett–Teller (BET) analysis, respectively and show in
Table 1. The mineralogical compositions and morphology were detected
by X-ray diffractometer (XRD) and field-emission scanning electron mi-
croscope (FE-SEM), and show in Figs. 1 and 2. Anatase TiO2 was a re-
agent grade supplied from Sigma Aldrich with 99.7% of purity and less
than 25 nm of particle size. Titanium (IV) butoxide was a reagent
grade supplied from Sigma Aldrich with 97% of purity.
Table 1
Characteristics of starting materials and synthesized products.
Characteristics MK RHA Zeolite
Fig. 1. XRD patterns of starting materials. I; Illite, Q; Quartz, M; Microcline.
2.2. Preparation of zeolite and TiO2-containing zeolite catalysts
The TiO2-zeolite photocatalysts were prepared using titanium (IV)
butoxide (Ti(OC4H9)4) as the titanium source. The transparent titanium
solution was prepared using the method modified from the method re-
ported by Li et al. [13] and Son et al. [32]. The 10 ml Ti(OC4H9)4 and
40 ml absolute ethanol was gradually instilled and then slowly dripped
into an aqueous solution containing 40 ml ethanol, 4 ml acetic acid and
3 ml distilled water under vital stirring to obtain the transparent titani-
um solution.
Zeolites (Z) and TiO2 containing zeolite composites (ZS) were pre-
pared by a solvothermal method. An alkaline solution used in this meth-
od was prepared using 10% ethanol in aqueous NaOH solution. The SiO2/
Al2O3 molar ratio of 4 was used for preparing a precursor gel. In the first
step, MK or RHA was mixed with the alkaline solution at solid to liquid
ratio of 1:8 with continuous stirring at 220 rpm for 48 h at room tem-
perature to obtain precursor gel. To prepare zeolites, the precursor gel
was then treated using solvothermal reactor at 120 °C for 6 h in the sec-
ond step. For the preparation of ZS, the transparent titanium solution
was added to the precursor gel at the precursor gel solid to transparent
titanium solution ratio of 1:3 to obtain 5% TiO2. The prepared mixture
was then treated with solvothermal reactor under the same condition.
After that, the precipitates were separated by filtration and thorough
washing with distilled water until the solution pH reached 10 before
being dried at 60 °C to obtain dried zeolite powders. The dried ZS pow-
ders were then calcined at 480 °C for 3 h to get rid of residual chemicals.
TiO2 containing zeolite composites prepared from impregnation meth-
od (ZI) were prepared by mixing 1 g of the synthesized zeolite (Z) in
3 and 12 ml of transparent titanium solutions to obtain 5% and 20%
TiO2, respectively. The resulting colloidal suspension was stirred for
2 h and aged for 48 h to form gel. The gel was dehydrated in an oven
at 80 °C for 48 h and calcined at 480 °C for 3 h to obtain the ZI powders.
ZI ZS

1. Chemical composition (wt%)

SiO2 58.03 94.52 46.23 45.71 46.58
2.3. Characterization
Al2O3 32.69 1.34 24.49 23.15 20.67
CaO 0.28 0.46 0.78 0.90 0.56 The crystalline phases of synthesized products were detected by X-
K2O 2.84 1.83 1.42 1.29 1.29 ray diffractometer (XRD, Bruker AXS D2 Phaser) using graphite-
Na2O 0.06 0.05 11.28 11.20 12.44
monochromized CuKα radiation. The chemical compositions were
Fe2O3 1.65 0.28 1.19 1.08 0.84
MgO 0.55 0.03 0.51 0.59 0.35 identified by X-ray fluorescence (XRF) using a Philips Magix Pro. The
TiO2 0.07 0.02 0.06 6.43 6.79 morphology observation and elemental analysis were detected using a
LOI 3.39 0.56 0.13 0.11 0.11 field-emission scanning electron microscope (FE-SEM, SU-6600,
2. Average particle size (μm) 1.31 2.81 0.621 0.704 0.663 Hitachi) and an energy dispersive X-ray spectrometer (EDS, Inca x-act,
3. Specific surface area by BET (m2/g) 15.10 23.34 487.10 437.60 442.10
Oxford Instruments), respectively. The specific surface area was
 N. Setthaya et al. / Powder Technology 313 (2017) 417–426 419

Fig. 2. FE-SEM photomicrographs of starting materials (a) MK and (b) RHA.

obtained from the Brunauer–Emmett–Teller (BET) method using a
Quantachrome Autosorp-1. Average particle size was performed using
a Malvern Zetasizer nano ZS. Fourier transform infrared spectra (FTIR)
were analyzed using a Perkin Elmer Spotlight 400. The UV–vis diffuse
reflectance spectra (DRS) were measured using a JASCO's V-670, UV–
VIS-NIR spectrophotometer.
2.4. Methylene blue removal efficiency and photocatalytic activity test
The removal efficiency and photocatalytic degradation of methylene
blue (MB) solution were studied using 0.1 g of TiO2-zeolite catalyst
suspended in 100 ml of 20 ppm MB solution. In addition, the MB degra-
dation using 0.1 g of anatase TiO2 was also studied to compare the
quality of the products. Specific surface area of anatase TiO2 was
55 m2/g. The initial MB concentration was analyzed by measuring
its maximum absorbance (λmax = 664 nm) using a JASCO's V-670,
UV–VIS-NIR spectrophotometer. The suspension was stirred at 500 rpm
in a dark chamber for 30 min to reach the adsorption equilibrium. Then
the obtained suspension was illuminated under a 300 W HAL-302
xenon light source with UV lamp (250–385 nm) at room temperature.
UV lamp (300–365 nm; Osram Ultra Vitalux 300 W) was also used to
compare degradation performances of ZI and ZS samples in different
UV wavelengths. The illuminated suspension was then collected and cen-
trifuged at 5000 rpm to obtain the clear solution. The remaining concen-
tration of MB was also analyzed using a UV-VIS-NIR spectrophotometer
at a wavelength of 664 nm. The MB degradation efficiency (X) was cal-
culated by the following equation:
X ¼ ½ðC0 −Ct Þ=C0   100
where C0 and Ct represent the initial concentration of MB solution and
the concentration of MB analyzed at t time of illumination, respectively.
3. Results and discussion
3.1. Characterization of starting materials
The chemical compositions of MK and RHA are shown in Table 1. MK
composed of 58.03% SiO2 and 32.69% Al2O3 contents, corresponding to a
SiO2/Al2O3 molar ratio of 3.02. The main components of RHA was

Fig. 3. XRD patterns of synthesized products prepared by different method. F: Faujasite, N: Zeolite Nu-5, P: Zeolite P1, S: Zeolite SSZ16.
420 N. Setthaya et al. / Powder Technology 313 (2017) 417–426

Fig. 4. FE-SEM photomicrographs and EDS of synthesized products prepared by different method (a) zeolites, (b) ZI and (c) ZS.

94.52 wt% of SiO2. The mineralogical compositions of MK and RHA are
shown in Fig. 1. MK consisted mainly of amorphous aluminosilicate,
resulting from dehydroxylation that driven off water from kaolinite.
Some quartz, illite and muscovite were also found together with MK
due to their inert phases showing no disruptive structures on calcina-
tion. RHA consisted of amorphous silica as indicated by the strong
broad peaks of pure silica in the range of 2θ ≈ 22–23°. The average par-
ticle size of ground MK and ground RHA were 1.31 and 2.81 μm, respec-
tively and the specific surface areas of MK and RHA were 15.10 and
23.34 m2/g, respectively. The FE-SEM image of MK and RHA as shown
in Fig. 2 indicated that the MK particles composed of stacks of platelets
with hexagonal shape and the RHA particles were very irregular parti-
cles with the remains of porous cellular fabric of rice husk, thus leading
to a high surface area of RHA in comparison with that of MK.
3.2. Characterization of zeolite and TiO2-containing zeolite catalysts
X-ray powder diffraction was used to discover the existences of TiO2
and zeolite as shown in Fig. 3. Diffraction peaks of the synthesized zeo-
lites corresponded to zeolite faujasite; Na2Al2Si3.3O10.6(H2O)7 (major
phase), zeolite P1; Na6Al6Si10O32(H2O)12 and zeolite SSZ16; Na3.06
H4.14(Si40.80Al7.20O96). It was obvious that the XRD patterns of ZS and
 N. Setthaya et al. / Powder Technology 313 (2017) 417–426 421

Table 2 surface areas of 487.1, 452.1 and 437.6 m2/g as shown in Table 1. The av-
Weight/atomic percent of Si, Al and Ti elements from EDS in synthesized products pre- erage particle size was in good agreement with specific surface area
pared by different methods.
being that material with smaller particles had higher specific surface
Position Element Zeolite (a) ZI (b) ZS (c) area. The decreases in specific surface areas of ZS and ZI was due to
Wt% At% Wt% At% Wt% At% the deposition of TiO2 particles on the zeolite surfaces that filled up
the pore, and the TiO2 agglomeration/growth phenomena during the
A Si 12.45 7.98 11.86 10.02 3.05 8.50
Al 7.20 3.54 6.28 5.53 0.88 2.55 calcination treatments [17].
Ti – – 3.21 1.59 2.15 3.51 Fig. 4a–c shows the FE-SEM photomicrographs and EDS spectrum of
B Al 4.95 3.92 12.52 9.33 13.13 7.98 synthesized products (a) synthesized zeolites, (b) ZI and (c) ZS with the
Si 8.75 9.66 9.88 7.66 5.60 3.54 data of weight and atomic percent of Si, Al and Ti elements from EDS
Ti – – 2.80 1.22 4.13 1.47
analysis as shown in Table 2. It can be seen that the morphology of zeo-
lite faujasite composed of various sizes of agglomerated particles with
ZI mainly contained faujasite phase incorporating with zeolite Nu-5 as octahedral shapes [19,35] with a SiO2/Al2O3 molar ratio of 3.33 as
minority. With the presence of TiO2, zeolite P1 and zeolite SSZ16 obtain- shown in Fig. 4a. This was slightly lowered than deviated from the
ed from the TiO2-absenced system were transformed into faujasite and used starting SiO2/Al2O3 molar ratio of 4.0. The other particles with pris-
zeolite Nu-5; Na0.14Al2Si70O143.07(H2O)0.97. It should be noted here that matic shape corresponded to the zeolite P1 [19,36] with a SiO2/Al2O3
ZS and ZI were subjected to calcinations at high temperature while the molar ratio of 3.41. The obtained SiO2/Al2O3 molar ratios was similar
pure zeolite was only dried in electric oven. Diffraction peaks of TiO2 the values of 3.21 and 3.33 detected by XRF and XRD, respectively.
phase was not detected in ZS and ZI samples. Similar results were also From the EDS in Fig. 4b, the octahedral shape of faujasite phase of ZI
reported by Li et al. [13] and Faghihian and Bahranifard [33] showing sample encompassed TiO2 in the range of 4.67–5.36 wt%. While, the
no TiO2 peak, although using different zeolite types. Li et al. used com- EDS in Fig. 4c showed TiO2 content of ZS sample, in the range of 3.59–
mercially natural clinoptilolite and Faghihian and Bahranifard used zeo- 6.89 wt%. This result was also similar to results obtained from the XRF
lite X synthesized using metakaolin and sodium silicate as starting analysis. In addition, it can be observed that the surface morphology of
materials. However, synthesized temperature and time of this present ZI and ZS sample showed nanoparticles of spherical TiO2 in the range
work were different from Faghihian and Bahranifard in that 120 °C 100–200 nm and its clusters attached onto the surfaces of zeolites as
and 6 h for this work and 90 °C and 24 h for Faghihian and Bahranifard. also reported by Gomez et al. [17].
The framework structure of zeolite was not destroyed with the loading The results of FTIR Spectroscopy as shown in Fig. 5 were used to ex-
of TiO2. It was also probable that after the calcination step, the clusters of amine the chemical structures of the synthesized products. The
TiO2 formed were too small to give clear diffraction patterns for ZS and stretching and bending vibration bands of hydroxyl groups in zeolites
ZI samples [34]. As detected by using XRF, the chemical compositions of were s observed at 3470 cm− 1 and 1650 cm−1, respectively. The
ZS and ZI contained 6.79 and 6.43 wt% of TiO2, respectively as shown in broad band around 991 cm−1 was assigned to the internal asymmetric
Table 1. Synthesized zeolites with TiO2-absenced system, on the other stretching vibration of Si\\O\\T (T = Si or Al) in zeolite [29,37] The
hand, consisted mainly of SiO2 and Al2O3 with 46.23 and 24.49 wt%, re- presences of adsorption modes at 747 and 564 cm−1 were due to the
spectively and extremely low TiO2 contents of only 0.06 wt%. The exis- external symmetric stretching of Si\\O\\T, while the absorption
tence of TiO2 in the TiO2-absenced zeolite was from MK and RHA. bands at 683 and 463 cm−1 corresponded to the Si\\O\\Al symmetric
The average particle size of the synthesized zeolite, ZS and ZI were stretching and symmetric bending, respectively [37,38]. For the FTIR
0.621, 0.663 and 0.743 μm, respectively with corresponding specific spectra of TiO2-zeolite photocatalysts, no band of Si-O-Ti antisymmetric

Fig. 5. FTIR spectra of synthesized products prepared by different method.

422 N. Setthaya et al. / Powder Technology 313 (2017) 417–426
stretching vibration in the region near 960 cm− 1 was detected. Ac-
cordingly, the replacement of the tetrahedral Si sites with Ti did
not take place for both ZS and ZI samples. It was demonstrated
that titanium compound was deposited on the surfaces of zeolites
in a form of TiO2 rather than the Ti incorporated into the SiO4 frame-
work [1,17].
The results of UV–vis diffuse reflectance spectra (UV–vis DRS) of the
synthesized products and anatase TiO2 are shown in Fig. 6a. It could be
clearly seen that zeolite with no TiO2 had the lowest intensity absorp-
tion band compared with TiO2-zeolite photocatalysts and anatase
TiO2. The broad absorption band of ZI was found at 268.4 nm which
was slightly lower than the 263.6 nm of ZS. While using pure anatase
TiO2 provided the highest intensity absorption band at 335.2 nm. The
diffuse reflectance spectra presented that TiO2-zeolite photocatalysts
have a significant shift to longer wavelengths and an extension of the
absorption in the visible range in comparison with that of anatase
TiO2. This result was in agreement with previous finding of Wang
et al. [39]. The band gap energies of the catalysts were obtained from
the Kubelka Munk theory which could be evaluated by a plot of
[F(R)hν]2 as a function of hν [40] as shown in Fig. 6b. The calculated
band-gap energies of pure anatase TiO2, ZI and ZS were 3.24, 3.20 and
3.45 eV, respectively. These results implied that TiO2-zeolite
photocatalysts had the photocatalytic performance of TiO2.
Fig. 6. Graphical representation of (a) absorbance versus wavelength and (b) Kubelka-
Munk (F(R)hν)2 versus energy of synthesized products and anatase.
3.3. Methylene blue removal efficiency and photocatalytic activity test
The degradation of MB dye was measured in the solution system to
assess the photocatalytic activity of the synthesized catalysts. The acti-
vation of TiO2 by UV light generated electron (e−) - hole (h+) pairs on
the surfaces of material that reacted with bound O2 or H2O in order to
generate reactive oxygen species like hydroxide radicals (OH−), super-
oxide radicals (O2−) and hydrogen peroxide (H2O2) in various chain re-
actions. These active species worked for disruption of organic molecule
structures. In the degradation of MB (C16H18N3SCl), the OH– obtained
from the oxidation of adsorbed water or adsorbed OH– played a great
role on the elimination of MB. For an absolute reaction, the final prod-
ucts of the reaction are CO2 and H2O [41,42] as shown in the following
equation.
 
MB þ OH→products CO2 þ H2 O þ NH4þ þ NO3 − þ SO4 2− þ Cl
−
Fig. 7a–d shows the UV–vis absorption spectra of 20 ppm MB solu-
tion under the illumination with UV light at 250–385 nm for different
durations of time with 4 catalysts viz., (a) anatase TiO2, (b) zeolite,
(c) ZI and (d) ZS. The characteristic absorption spectrum of MB at
663.8 nm was examined as a function of the UV light revelation time.
The results revealed that the major peak of MB gradually was reduced
over time accompanied by a significant shift of the peak in the case of
using anatase TiO2 as a photocatalyst similar to Nagarjuna et al.'s work
[43] and Zuo et al.'s work [44]. While using zeolite powder with no
TiO2, the absorption peak of MB decreased by a half from initial concen-
tration of MB indicating the adsorption capacity of zeolite alone could
not hand on the photocatalytic performance. However, adsorption of
the MB on the photocatalyst surface was one of the significant reaction
steps in degradation [33]. In using ZI and ZS as the photocatalysts, the
intensity of an absorption peak of MB from initial concentration (2.78)
was obviously reduced after adsorption in the dark or 0 min of UV illu-
mination time demonstrating not only the adsorption capacity of zeolite
but also TiO2 in comparison with anatase TiO2. In addition, the photocat-
alytic activity could be enhanced by TiO2-containing zeolite at low con-
centration (calculated as 7.6 mg and 7.1 mg of TiO2 for ZS and ZI,
respectively) while the amount of anatase TiO2 was 0.1 g in this test.
The intensity of an absorption peak of MB gradually decreased with
time as shown in Fig. 7c and d. It was worth noting here that the ZI sam-
ple showed slightly better MB degradation performance than ZS sample.
This was due to the incorporation of TiO2 chiefly on the external surface
of zeolite in the impregnation method which was slightly better than
the solvothermal synthesis method. To prove photodegradation perfor-
mance, MB decolorization experiments of ZI and ZS under illumination
of longer wavelength UV lamp (300–365 nm; Osram Ultra Vitalux
300 W) were carried out at room temperature. The results proved that
under illumination with longer wavelength (300–365 nm), the main
peak of MB was higher than that illuminated under shorter wavelength
(250–385 nm) in every illumination time as shown in Fig. 8. This result
indicated the photodegradation effect of ZI and ZS. Shorter UV wave-
length carried more energy thus affecting the MB degradation. The
photodegradation of ZI and ZS using different sources of illumination
reflected the influence of wavelengths and light intensity on the reac-
tion rates of degradation [45]. Moreover, to reveal a TiO2-doping limita-
tion of the photocatalysts, effect of TiO2 doped contents in ZI composite
on photodegradation performance were studied, as shown in Fig. 9. Ab-
sorption peak of MB of 20wt% TiO2 doped ZI was compared with that of
5wt% TiO2 doped ZI under 300–365 nm illumination. It is obvious that
without illumination, the absorption peaks of MB of both samples
were similar that resulted from only adsorption phenomena. For 3 h
of illumination time with wavelength of 300–365 nm, absorption peak
of MB of 20 wt% TiO2 doped ZI sample slightly lowered than 5wt%
TiO2 doped ZI sample indicating the doping limitation of photocatalysts.
Therefore, effect of TiO2 content on photocatalytic rate of MB dye was
 N. Setthaya et al. / Powder Technology 313 (2017) 417–426 423

Fig. 7. UV–vis absorbance spectra of MB as a function of illumination times with (a) anatase, (b) zeolite, (c) ZI and (d) ZS.

Fig. 8. UV–vis absorbance spectra of MB as a function of illumination times with difference of UV wavelengths (a) ZI; 250–385 nm, (b) ZI; 300–365 nm, (c) ZS; 250–385 nm and (d) ZS;
300–365 nm.
424 N. Setthaya et al. / Powder Technology 313 (2017) 417–426

Fig. 9. UV–vis absorbance spectra of MB as a function of illumination times with difference of TiO2 doping contents in ZI (a) 5 wt% and (b) 20 wt% under illumination with 300–365 nm of
UV wavelength.

insignificant when added greater than 5 wt%. However, TiO2 doping
limitation reported in Wang et al.’s work [1] was at 20 wt% TiO2. It
was worth noting here that zeolite types used were different in that
faujasite and Na-Y zeolites were used in this work and Wang's work, re-
spectively. The limitation was due to a reduction in specific surface area
of TiO2 doped zeolites.
Fig. 10 shows the adsorption and photocatalytic degradation of MB
with time with various synthesized catalysts. MB removal efficiency
was calculated by the remaining concentration of MB in the solution
after illumination at 1, 2 and 3 h. The decolorization rates after 30 min
of the adsorption equilibrium in dark conditions of MB solution for
both of ZI and ZS were faster than that with zeolite and anatase TiO2.
It was worth noting here that the MB degradation with zeolite without
TiO2 took place only via adsorption phenomena not via photocatalytic
process. In the adsorption process before UV illumination, the adsorp-
tion capacity of MB by anatase TiO2 was relatively low and was signifi-
cantly improved by zeolite adsorption. More than 90% of MB was
removed by TiO2-containing zeolites within 30 min as shown in
Fig. 11, ascribing to its high surface area and high adsorbability of zeolit-
ic characteristics. In the process of photodegradation, anatase TiO2 was a
high potential photocatalysts achieving 82% of MB photodegradation in
3 h. Nevertheless, the degradation by pure anatase TiO2 was lower than
that of TiO2-zeolite photocatalyst. The high decolorization rate was
caused by the high porosity and proper pore sizes of zeolites. MB dye
had an effective molecular diameter of approximately 0.77 nm which
was smaller than that of synthesized zeolite with the average pore
size of approximately 1.36 nm [19]. MB could be stored in the large in-
ternal surfaces and on the external surfaces of both zeolite and TiO2. The
MB removal efficiency was 99.43% and 97.32% at 3 h illumination while
the adsorption efficiency (without illumination) was 95.2% and 92.0% at
20 ppm MB concentration using ZI and ZS samples, respectively. When
compared with Faghihian and Bahranifard's finding [33], MB removal
efficiency using zeolite X was 90% as a concern of similar zeolite to MB
solution ratio. For using natural clinoptilolite of Li et al.’s work, the re-
moval efficiency test was performed using methyl orange as a tester
and the result was 85–95% removal efficiency. In addition to the ad-
sorption, the adherence of MB on zeolite could be from cation ex-
change capacity of zeolite [2]. This proposed that the total rate of
the adsorption procedure was controlled by chemisorption which
complicated valency forces through exchange or sharing of elec-
trons between the sorbent (zeolite) and sorbate (MB solution)
[46]. It was quite obvious that MB removal of ZI and ZS samples

Fig. 10. Adsorption and photocatalytic degradation of MB from initial concentrations of 20 mg/l with time with different photocatalysts.
 N. Setthaya et al. / Powder Technology 313 (2017) 417–426
Fig. 11. The percent of adsorption and photodegradation of MB from initial concentrations of 20 mg/l with different photocatalysts.
was mainly from adsorption process and was slightly increased by
photodegradation. However, the total photocatalytic activity of ZI
and ZS samples was not yet measured in term of quantity which
would be figured out in the next phase. It was worth noting here
that the used TiO 2 contents in ZI and ZS samples were 16 times
lower than pure TiO2 anatase.
4. Conclusion
Synthesized TiO2-zeolite photocatalyst using solvothermal method
was successfully prepared with metakaolin and rice husk ash as starting
materials and transparent titanium solution as TiO2 source. The synthe-
sized TiO2-zeolite photocatalyst using impregnation method (ZI) was
also performed for the comparison. The photodegradation efficiency of
synthesized TiO2-zeolite photocatalyst was found to be better TiO2-
absenced zeolites. The band gap energy of ZI was lower than ZS
(3.20 eV for ZI and 3.45 eV for ZS). The MB removal efficiency was
99.43% and 97.32% at 20 ppm MB concentration using ZI and ZS sam-
ples, respectively. While these were 82.37% and 47.21% at 20 ppm MB
concentration using pure TiO2 anatase and pure synthesized zeolites, re-
spectively. It was demonstrated that association of the adsorption and
photocatalytic degradation enhanced the removal efficiency. The syn-
thesis of zeolite nanocrystals using natural raw materials viz., rice
husk and kaolin clays is economical advantageous and thus offers valu-
able option for cleaning up the contaminated environment.
Acknowledgements
This work was financially supported by the Thailand Research Fund
(TRF) through the Royal Golden Jubilee Ph.D. program, (Grant No. PHD/
0011/2557), the Graduate School, Chiang Mai University, and the Khon
Kaen University and TRF under TRF Senior Research Scholar Contract
No. RTA5780004.
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