Journal of Environmental Chemical Engineering 6 (2018) 218–227

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Journal of Environmental Chemical Engineering

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Synthesis a novel multilamellar mesoporous TiO2/ZSM-5 for photo-catalytic T

degradation of methyl orange dye in aqueous media
⁎
Hussein Znada, , Khalid Abbasa, Sufia Henaa, Md. Rabiul Awualb
a
Department of Chemical Engineering, Curtin University, GPO Box U 1987, Perth, WA 6845, Australia
b
RENESA, Japan, 3-3-22 Sakuraguchi-cho, Nada-ku, Kobe-shi, Hyogo 657-0036, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: TiO2 photocatalyst hybridized with new multilamellar vesicles (MLVs) mesoporous ZSM-5 substrate (TiO2/ZSM-
Methyl orange 5) were prepared by the direct templating technique for decolorization and minerlization of methyl orange (MO)
Mesoporous TiO2/ZSM-5 dye effluent. The synthesized materials were characterized by X-ray diffraction (XRD), Field-emission scanning
Photo-catalytic electron microscopy (FE-SEM), Fourier-transformed infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller
Wastewater treatment
(BET). It was found that the specific surface area (SBET) of the synthesized TiO2/ZSM-5 was 1151 m2 g−1. The
results also indicated that the zeolite structure conserves mesoporous structure after the removal of surfactant
templates. Several parameters were also investigated such as the effect of catalyst types, pH, adsorption/pho-
tocatalysis phenomenon and contact time. Under 180 min solar irradiation, MO dye was efficiently decolorized
and mineralized to be 99.55% and 99%, respectively, at an initial MO concentration of 20 mg L−1. Furthermore,
the photocatalysis kinetic fit the pseudo-second-order model well and a great potential for saving energy as-
sociated with its recyclability. Therefore, the synthesized TiO2/ZSM-5 could be used as a promosing photo-
catalysis for fast removal and treatment of coloured wastewater.

1. Introduction complexometric methods produce by-products such as sulfonate,

In recent years, the environmental pollution caused by industrial
wastewater has become a common threat for most of the countries. The
presence of both organic and inorganic pollutants in water bodies due
to industrial activities led to deteriorate the quality of surface water.
However, the organic pollutants are more concern due to their carci-
nogenic and mutagenic effects even after exposure to minute con-
centrations [1–3]. Among all sources that cause water pollution is the
release of recalcitrant organic pollutants from textile, food colouring,
printing, cosmetic and paper making industries [4]. Methyl orange
(MO) (4-[4-(dimethylamino) phenylazo] benzene sulfonic acid,
C14H14N3NaO3S) represents one of the most important dyes, which is
widely used as a colouring agent in textile and leather industries and as
an indicator in coulometric method for the analysis of fenoterol in the
presence of other anti-asthmatic medicines and in kinetic assay method
for cyproheptadine in pharmaceutical industries [5].
Recently, several techniques have been developed to remove many
recalcitrant organic compounds along with methyl orange [6]. Physical
treatments such as adsorption, coagulation, reverse osmosis, and
membrane filtration are expensive and incompetent techniques, while
chemical treatments such as reduction, oxidation, ion exchange, and
phenol and plenty of aromatic compounds which are more toxic than
the original contaminants [7–13].
Adavanced oxidation processes (AOPs) such as, TiO2 photocatalysts
iraddiated with UV or solar light, considered one of the promising
technology applied for wastewater treatemnt. TiO2 stable, inexpensive,
non-toxic and potentially reusable in water; however, recovery of spent
TiO2 from aqueous media is remained a challenging issue [14].
Therefore, the key challenge of using TiO2 for advanced treatment of
industrial dyes mediated wastewater is to provide a plausible solution
via immobilising the semiconductor photo-catalysts on larger im-
mobiliser substrates to ease the process of post-separation and recovery
of catalyst from treated water [15]. Different immobiliser substrates
such as activated carbon [16], magnetite core [17], and clays [14,18]
have been used to enhance post-separation and recovery of photo-cat-
alyst from water. The black activated carbon is normally opaque ma-
terial, preventing the incident UV-radiation light to excite TiO2 [19,20].
Therefore, TiO2 immobilised on transparent and mesoporous scaffold
was desired [21–23].
In comparison with any synthetic porous materials, natural zeolites
are abundant, inexpensive and stable to synthesize functional semi-
conductor metal oxides [24]. Furthermore, zeolites possess crystalline

⁎
Corresponding author at: Curtin University, GPO Box U1987, Perth, WA 6845, Australia. Tel.: +61 8 9266 9893; Fax: +61 8 9266 3131.
E-mail address: h.znad@curtin.edu.au (H. Znad).

https://doi.org/10.1016/j.jece.2017.11.077
Received 7 August 2017; Received in revised form 27 November 2017; Accepted 30 November 2017
Available online 02 December 2017
2213-3437/ © 2017 Elsevier Ltd. All rights reserved.
H. Znad et al.
aluminosilicate, high ion exchange capacity, tectosilicates with micro-
porous channels [25,26]. Few researchers have reported the utilisation
of photo-catalyst immobilised on natural zeolites. For insteant, TiO2/
ZSM-5 zeolite [27] and TiO2/MOR zeolite [28] have been used effec-
tively the removal of volatile acetaldehyde compound from wastewater.
TiO2/Y-zeolite photo-catalyst has been efficiently prepared for removal
of benzene and toluene molecules [29]. Recently, TiO2/ZSM-5 nano-
composite has been prepared for the degradation of humic acid from
potable water sources [30]. The best way to synthesize a high specific
surface area material is to use multi-lamellar vesicles (MLVs) template
shape using surfactant and a hydrophobic additive. In MLVs template,
ZSM-5 aggregates in unit of cluster to form a high surface area scaffold
allowed TiO2 particles to immobilize onto different sites. Tanev et al.
[31] were the first who reported the feasibility of forming mesoporous
vesicular silica by utilizing Bola-type surfactants H2N(CH2)nNH2
(n = 12–22) in aqueous medium. Later Zhou et al. [32] found that the
morphology of mesoporous silica can be controlled by the molar ratio of
hydrophobic additive and surfactant (TIPB:P123), however, the highest
specific surface area they achieved was 518 m2 g−1. Therfore, the ob-
jective of the present study was to synthesize multi-lamellar meso-
porous photo-catalyst TiO2/ZSM-5 with a high specific surface area as
well as with good crystallinity for efficient MO degradation under solar
light irradiation via a simple and cost-effective direct template method.
The photo-degradation efficiency of proposed catalyst was compared
with different catalysts (ZnO/ZSM-5, TiO2-mesoporous). The influence
of pH, catalyst loading, reuses, and the kinetics studies were also in-
vistigated.
2. Materials and methods
2.1. Chemicals
Zeolite type ZSM-5(Si/Al = 1000, 311 m2 g−1 surface area, 2–3 μm
particle size, 2.4 nm pore size) was obtained from ACROS organics,
New Jersey, USA. Titanium dioxide (TiO2 Degussa, 99.7% anatase),
tetraethoxysilane (TEOS), Pluronic (P123) surfactant (poly (ethylene
oxide)-block-poly (propylene oxide)-block-poly (ethylene oxide),
EO20PO70EO20, Mw = 5800 g/mol), hydrochloric acid (HCl, 32%),
1,3,5-triisopropylbenzene (TIPB), Methyl orange (C14H14N3NaO3S),
and zinc oxide (ZnO) were supplied by Sigma-Aldrich Co., NSW,
Australia. All the aqueous solutions were prepared in deionised (DI)
water.
2.2. Preparation of photo-catalysts
The direct-templating method with slight modification was adopted
as mentioned earlier [32] to fabricate translucent TiO2 or ZnO with
Alumina-silica (ZSM-5) and surfactant monolithic mesoporous mate-
rials. 1 g of P123 was dissolved into 20 ml DI and 4 ml HCL (32%) using
magnetic stirring (500 rpm) at ambient temperature for 4 h, till the
mixture became homogeneously transparent solution. Then 0.85 g of
TIPB was added to solution drop wise (TIPB: P123 of 0.85:1 mass ratio)
and the mixture was continuously stirred for 20 h. Subsequently, ZSM-5
added directly to the above solution under vigorous stirring at 35 °C for
12 h and followed by the addition of TiO2 (or ZnO) at (ZSM-5: TiO2 or
ZnO) wt ratio of 2:1, into the same solution under stirring at 35 °C for
another 12 h, then white suspension was formed. The white suspension
mixture was put into a Teflon-lined autoclave at 121.90 °C and 122 kPa
for 45 min, the formed white viscous solution was dried at 50 °C for
24 h to get a white powder form. The dried white powders were washed
with DI for several times, filtered and dried. Finally, the TiO2/ZSM-5 or
ZnO/ZSM-5 powders were calcined at 500 °C for 4 h at a heating rate of
2 °C/min in a muffle furnace to remove the organic templates (see Fig.
S1). For comparison, TiO2-mesoporous photocatalyst was prepared by
the same above method, but ZSM-5 was replaced by TEOS and a mass
ratio of TIPB: P123 was 12:1.
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Journal of Environmental Chemical Engineering 6 (2018) 218–227
2.3. Synthesis of multilamellar mesoporous TiO2/ZSM-5
High surface area mesoporous TiO2/ZSM-5 can be synthesized by
the direct-templating method using P123 surfactant and a hydrophobic
additive 1, 3, 5-triisopropylbenzene (TIPB) to form a template struc-
ture. In this study, the ZSM-5 as a source of alumina/silica was con-
sidered the framework structure of proposed catalyst (TiO2/ZSM-5)
after the calcination process. The scaffold prepared by TIBP and P123 is
well studied by Zhou et al. [32] and it has been proved that the porosity
and morphology of frame totally depend upon the molar ratio of TIPB:
P123. It was observed previously that the morphology of the meso-
porous vesicle drastically changes from rod shape to multilamellar type
by changing the molar ratio of TIPB: P123 from 2.9:1 to 4.3:1. Further,
it was also noticed that the same multilamellar morphology was
maintained from the range of molar ratio 4.3:1to 34.8:1. To describe
the formation of multilamellar mesoporous frame in TiO2/ZSM-5, the
TIPB was simply dissolved into the hydrophobic core of the P123 cy-
lindrical micelle. Thereafter, TIPB was spread into the palisade layers
where, TIPB was the reason to transform the cylindrical micelle phase
into the multilamellar vesicles MLV phase [32].
In the present study, multilamellar vesicle-like silica (ZSM-5) sup-
ported TiO2 Degussa was synthesized by the direct templating method
described elsewhere [32] with little modification by replacing SBA-15
with ZSM-5. This procedure forms bonds such as TieOeSi units inside
and outside the structure of MLVs (for more details see Section 3.1.4)
that can improve the catalyst performance.
2.4. Characterization
The crystalline structures of all samples were analysed by X-ray
diffraction (XRD) using a Bruker D8 diffractometer with Cu-Kα radia-
tion (λ = 1.5418 0A) in the range of 2θ = 5–80° operating at 40 kV
and 40 mA with a scanning rate of 28 min−1. The specific surface area
was measured by the N2 adsorption-desorption isotherms
(Micromeritics, Tristar II Surface area and Porosity analyzer) according
to the Brunnauer-Emmett-Teller (BET) method, after degassing the
samples at high temperature (230 °C) for overnight while, the pore size
distributions were derived from the adsorption branches of isotherms
using the Barrett–Joyner–Halenda (BJH) model at liquid nitrogen
temperature. The surface morphologies of the ZSM-5, TiO2 or ZnO/
ZSM-5, TiO2 mesoporous catalysts were also determined by using Field
Emission Scanning Electron Microscope (FE-SEM) operation at 5 kV and
10 μA. Fourier-Transformed Infrared (FTIR) spectroscopy was con-
ducted to determine the functional groups of the different photo-cata-
lysts.
2.5. Photo-catalytic experiments
The photocatalytic activities were evaluated in a cylindrical photo-
catalytic reactor of 5.5 cm in diameter and 9 cm height. A fixed volume
of 100 ml methyl orange solution of 20 mg L−1 concentration was
taken as initial concentration for batch studies. The photo-reactor was
externally irradiated with a light intensity of 100 mW/cm2 using a solar
simulator (solar simulator 2000, 100 mW/cm2, 18–25 Amps, 550 W
Max Lamp, ABET Technologies). All the experiments were conducted at
the fixed temperature of 30 °C with various initial pH in the range of
2–9. Different dosages of the catalyst (1, 2, 2.5, 3 g L−1) were also in-
vestigated to evaluate the optimum amount of photocatalyst for a
specific concentration and volume of methyl orange solution.
For all batch studies of photo-catalytic activities, the dye solution
with photo-catalyst was magnetically stirred for 30 min in the dark to
achieve adsorption–desorption equilibrium, before the light turned on.
Each experiment was carried out for 180 min under light irradiation.
Samples were collected every 30 min from the suspension using syr-
inges and Whatman filter (pore size 2.5 μm) to remove the catalyst
before further analysis. The MO dye concentrations were measured by
H. Znad et al.
Fig. 1. X-ray diffraction patterns of ZSM-5, TiO2/ZSM-5, TiO2 Degussa, ZnO/ZSM-5 and
TiO2-mesoporous.
UV–vis spectrophotometer (JASCO/V-670) at the maximum absorption
wavelength (λ) of 462 nm. The removal efficiency (η %) of MO dye was
calculated using Eq. (1); where co and c are the initial and final MO
concentrations in the solution.
co − c
η (%) = × 100
co
The total organic carbon (TOC) was measured using SHIMADZU,
TOC-VcpH Scientific apparatus.
3. Results and discussion
3.1. Characterization of photocatalys
3.1.1. XRD
The XRD patterns of ZSM-5, TiO2/ZSM-5, TiO2 Degussa, ZnO/ZSM-5
and TiO2- mesoporous catalysts were investigated and the obtained
diffraction peaks are shown in Fig. 1. The diffraction peaks of ZSM-5
were observed at 7.5°, 8°, 13.2°, 13.9°, 14.7°, 15.5°, 23.1°, 29.8°, 45.0°,
45.2° and typically coincided with the data, reported in the literature
for sodium aluminium silicate (Na 1.5 Si 93 O 192) [33]. While, the
signals of TiO2 Degussa with high crystallinity were found at 25.4°,
37.5°,48.0°, 54.1°, 54.8°, and 62.6° indicated the d 101, d 004, d 200,
d106, d 211, and d 204 planes of anatase [34–36]. Moreover, the peaks
at 68.5°, 71.2°, 75.5° indicated the d110 plane of rutile. However, no
significant peaks shift were noticed after ZSM-5 was modified with TiO2
Degussa. Though, the peak intensity corresponds to crystallite meso-
ZSM-5/TiO2 was found less prominent than that of ZSM-5 itself due to
slight line broadening of the diffraction peaks. It is noteworthy that the
crystalline size of TiO2 was slightly changed from 21 nm to 21.27 nm
after its loading onto ZSM-5 framework. Although, in case of ZnO/ZSM-
5, few peaks correspond to ZSM-5 disappeared during ZnO loading such
as 45.0° and 45.2° and few appeared less intensified such as 7.5°, 8°,
13.2°, 13.9°, 14.7°, 15.5°, 23.1°, 29.8° due to the formation of meso-
porous phase (Na 1.2 Al 1.1 Si 93.7 O 192). This phenomenon ex-
plained that the loading of ZnO onto ZSM-5 framework was less stable.
In TiO2- mesoporous catalyst the instability of TiO2 was observed due to
the destruction of anatase phase at 2θ = 25.40 and 480 as shown in
Journal of Environmental Chemical Engineering 6 (2018) 218–227
Fig. 1. This might have obtained due to the precursor thermal reaction
of TEOS on the surface of TiO2, and hence the condensation of TEOS on
TiO2 particles affected the crystallinity of TiO2 particles, which can be
proved by size of the crystal particle as discuss below.
The average crystal size of TiO2 particle in TiO2/ZSM-5 can be
calculated from the Debye-Scherer formula [37]. It was found that the
average anatase crystalline size was 21.27 nm.
3.1.2. BET surface areas and pore distribution
The specific surface area and pore structure of the ZSM-5, TiO2/
ZSM-5, TiO2-mesopoures and ZnO/ZSM-5 were characterized by
Brunauer-Emmett-Teller method (BET). Fig. 2a–d illustrates nitrogen
adsorption-desorption isotherms to describe the surface area while the
BJH pore size distribution of corresponding samples is shown in Fig. 2e.
For comparison, the results of BET surface areas and pore structures are
summarized in Table 1.
According to IUPAC classification, nitrogen adsorption-desorption
isotherms are ascribed as type IV isotherms. The isotherms of TiO2/
ZSM-5 and ZnO/ZSM-5 exhibit type H4 hysteresis loops at P/P0 ranges
0.1–0.3, and 0.4–0.99, suggesting the presence of abundant mesoporous
structure in the samples, which give BET surface area of 1151 and
305 m2/g, respectively, and uniform pore diameter around 5–11 nm as
shown in Fig. 3e. The hysteresis loop of TiO2-mesopoures catalyst was
also exhibited type H4 hysteresis loop at P/P0 range 0.5–0.99 with
disordered pore diameter distribution around 2–24 nm (Fig. 2e). This
disordered pore diameter could be affected by calcination temperature
and the hydrolysis process of TEOS, which largely caused the damage
and collapse of the mesoporous structure. On the other hand, the iso-
therms of ZSM-5 display very narrow and limited type H4 hysteresis
loops (Fig. 2d), indicating the presence of a small slit mesoporous in the
sample with 0.014 nm of pore volume as shown in Fig. 2e.
As shown in Table 1, the BET surface areas and pore volume of all
catalysts are much larger than the ZSM-5, suggesting that the direct
template process has effected actively on the porosity of ZSM-5 zeolite.
(1)
However, replacement of TiO2 by ZnO, caused a decrease in surface
area and pore volume from 1151 m2/g and 0.2 m3/g to 380 m2/g and
0.17 m3/g respectively, as shown in Table 1. The higher surface area of
TiO2/ZSM-5 can be explained by isotherms graph. The isotherms of
TiO2/ZSM-5 revealed type H4 hysteresis do not exhibit any limiting
adsorption at high P/P0, which is true with non-rigid aggregates of
plate-like particles giving rise to slit-shaped pores while the desorption
branch contained a steep region associated with a (forced) closure of
the hysteresis loop, due to the tensile strength as shown in Fig. 2a.
Furthermore, It is noteworthy that the low pressure hysteresis which
occurred at range 0.1–0.3 for TiO2/ZSM-5 catalyst may be associated
with the change in volume of the adsorbent, i.e. the swelling of non-
rigid pores or with the irreversible uptake of molecules in the pores of
about the same width as that of the adsorptive molecule. In addition,
chemisorption was also led to cause “open” hysteresis loops at the low
P/P0 range (0.01–0.1) [38]. This phenomenon was observed in the
isotherms of TiO2/ZSM-5 while it was absent in the isotherms of ZnO/
ZSM-5, (Fig. 2a and b). It can be concluded that the ZSM-5 modified
with TiO2 by using the direct template method was successfully
achieved with high specific surface area (1151 m2/g), large pore vo-
lume (0.2 m3/g) and pore size (5.2 nm). For better understanding and
comparison few catalysts from previous literature have been listed
down in Table 2 with property of surface area and preparation method.
3.1.3. SEM images
High magnification images of the ZSM-5, TiO2/ZSM-5, ZnO/ZSM-5
and TiO2-mesoporous catalyst were investigated using FESEM as shown
in Fig. 3. The surface of ZSM-5 was found to be relatively smooth
(Fig. 3a), however small particles can be clearly seen dispersing on the
surface of ZSM-5 when TiO2 particles were loaded onto ZSM-5 surface
(Fig. 3b). Nevertheless, clusters of large particles were observed due to
the aggregation of ZSM-5 particles and dispersion and attachment of
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Fig. 2. N2 adsorption-desorption isotherms of (a) ZSM-5, (b) TiO2/ZSM-5 (c) TiO2-mesopoures and (d) ZnO/ZSM-5 and also corresponding BJH pore size distribution curves of samples
(e).

TiO2 onto aggregated particles of ZSM-5 as shown in Fig. 3b. It was
predicted that ZSM-5 might have formed channels and cavities inside
and between the ZSM-5 particles during the aggregation process since
ZSM-5 forms multilamellar scaffold, as mentioned in Section 3.1, which
would have provide surplus space for TiO2 crystallites to bind inside
and out of the cavities and channels formed by ZSM-5 particles and
consequently formed heavy particles with high porosity. It was antici-
pated that this behaviour of TiO2/ZSM-5 catalyst can be exhibited ease
of post-operational separation of catalyst from treated wastewater. It
was interesting to note that the vesicular (spherical) ZSM-5 was tended

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Table 1 It can be observed that the TEOS condensed randomly around TiO2
Specific surface area (SBET), pore volume (V) and average pore diameter (d) for ZSM-5, particles to form dense grape-like network cluster, where vesicles like
TiO2 Degussa, TiO2/ZSM-5, ZnO/ZSM-5, and TiO2-mesoporous.
structure of silica were disordered and that might formed potentially
Sample SBET (m2/g)a V (cm3/g)b D (nm)c unstable TiO2 particles.

ZSM-5 311 0.014 8.6

TiO2 Degussa 45–55 – < 25 3.1.4. Fourier-transformed infrared spectroscopy (FTIR) analysis
TiO2/ZSM-5 1151 0.2 5.2 The functional groups present in TiO2/ZSM-5, ZnO/ZSM-5, TiO2 –
ZnO/ZSM-5 380 0.17 6.1
mesoporous and ZSM-5 was studied using the FTIR spectroscopy. From
TiO2-mesoporous 360 0.42 5.6
Fig. S2, it is observed that the TiO2/ZSM-5 exhibited similar FTIR
a
The specific surface area was calculated by BET method. spectra characteristics as of pure zeolite (ZSM-5) for extended band at
b
The pore volume was obtained from the BJH Desorption cumulative volume of pores 1064 cm−1 without clear shifting. This indicated that the zeolite
between 1.0000 nm and 50.0000 nm diameter. structure was not affected when TiO2 used as immobiliser onto ZSM-5
c
The average pore diameter was estimated using the desorption branch of the isotherm surface due to the high stable framework of ZSM-5 particles.
and BJH model.
However, ZnO/ZSM-5 showed the narrow band at 1064 cm−1 and
band at 838 cm−1 were disappeared which proved unsuitable of im-
to form grape-like clusters of aggregating vesicles rather than separate
mobilization of ZnO particles due to causing disturbance in framework
vesicular particles (Fig. 3b–d). The reason behind that is the high
and no interstitial binding with ZSM-5 structure. Whereas, TiO2 me-
condensation of silanol groups (SieOH) on the surface of the individual
soporous catalyst sample possessed broad band at 3429 cm−1 that was
silica particles, as discussed by earlier researchers [48,49]. More in-
related to the eOH stretching and bending vibrations of silanol groups
terestingly, The FESEM results were in agreement with the proposed
(SieOH) and due to the interaction between water molecules and
study as discussed in Section 3.1 and with the finding of XRD as there
eSieOH groups. Whilst, the small band at 1228 cm−1 is associated
was no major change in the structure of ZSM-5. Consequently, the di-
with the bending vibrations of HeOeH bonds in water molecules and
rect template method was proved to be suitable for the synthesis of a
eSieOH groups.
unique, stable structure and high surface area of TiO2/ZSM-5 catalyst
Besides, the sharp band of TiO2/ZSM-5 was observed at 838 cm−1
(Fig. 3b).
due to the AleOeAl or SieOeSi symmetric stretching vibrations in the
Whereas, the ZnO particles loading on the surface of ZSM-5 were
tetrahedral SiO4 and AlO4 structures, formed in ZSM-5 framework.
tended to aggregate predominantly together rather than on the surface
Previously Damin et al. [50] have reported that the immobilization of
of ZSM-5 particles, as a result, the silanol groups of ZSM-5 particles
TiO2 onto the ZSM-5 structure can be resulted in the asymmetric or
cannot formed bonds with ZnO (Fig. 3c) and thus have unstable and
antisymmetric for TiO2 and TieOeSi units at the infrared band range of
weak binding structure of ZnO/ZSM-5. In case of TiO2 – mesoporous
960–1097 cm−1. It was also noticed that the band intensity was pro-
catalyst, TEOS was used as a source of silica instead of ZSM-5 (Fig. 3d).
portional to the amount of Ti presenting in the ZSM-5 framework.

Fig. 3. SEM images of a) ZSM-5, b) TiO2/ZSM-5, c) ZnO/ZSM-5, d)TiO2-mesoporous.

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Table 2
Comparison of surface area among different catalysts.

Catalyst Preparation method BET surface area (m2/g) Ref.

TiO2 nanoparticales supported on natural zeolite (TI-ZE). A simple hydrolysis 80.04 [39]
TiO2 nanoparticles supported on zeolite type 13X. Two steps sol-gel 324.1 [15]
TiO2 nanoparticales supported on zeolite type ZSM-5. Sol-gel 343 [40]
TiO2 (25%) nanoparticles supported on zeolite type MCM-41molecular sieve. Hydrothermal 669 [41]
TiO2 nanoparticles Supported on HZSM-11 Zeolite (10%). Hydrothermal crystallization 365 [42]
HB zeolite-supported TiO2 (amount of TiO2 (g) per gram of HB 0.01) Sol-gel 545 [43]
1.5% Pt- TiO2/natural zeolite Sol-gel 118.7 [44]
Cr/TiO2/zeolite (10%Cr) Sol-gel 205 [45]
Beta zeolite supported TiO2 Sol-gel 31 [46]
N-Ti/13X/MCM-41 Templating 664 [47]
TiO2 –Zeolite type ZSM-5 Templating 1151 This study

3.2. Photocatalyst activities
3.2.1. Effects of catalyst type
To find the best catalyst for the degradation of methyl orange (MO)
in aqueous solution under solar irradiation, three types of catalysts
were synthesized TiO2/ZSM-5, TiO2-mesoporous, and ZnO/ZSM-5. TiO2
Degussa (99% anatase) and ZSM-5 were also used for comparison. The
initial concentration of MO in aqueous solution was 20 mg L−1. The
photo-catalysts loading were controlled at 2 g L−1 and the pH was kept
at the initial value of 7.5. The results show (Fig. 4) that the best catalyst
was TiO2/ZSM-5 because of the maximum decolouration of MO
achieved (99.55%) during 180 min of solar irradiation. Fig. 4 shows
that the decolouration rate of MO increased rapidly within the first
60 min, however, it continued up to 150 min till it reached in the state
of equilibrium. The photo-degradation of MO using TiO2 Degussa and
TiO2- mesoporous were also studied, it can be observed that the de-
gradation efficiency of MO after 180 min were 80.7% and 83.4% re-
spectively as a shown in Fig. 4. However, the high degradation per-
centage of TiO2 Degussa and TiO2-mesoporous were proved inefficient
due to post-operation recovery of these catalysts from the aqueous so-
lution as shown in Fig. 4.
On the basis of the results and discussion of the structural properties
described in previous sections, the reasons behind TiO2/ZSM-5 as an
efficient catalyst where high specific surface area (1151 m2/g) which
provided additional active sites on the surface of TiO2/ZSM-5 and
perfect distribution of TiO2 particles onto the morphology of ZSM-5
vesicles, which in turn enhanced the photo-degradation efficiency of
the catalyst. Moreover, the wide pore size of TiO2/ZSM-5 was increased
the solar light penetration directly without any reflection light intensity
outside the bulk solution. The photocatalysis ability of ZnO/ZSM-5 was
also studied, where it was noticed that the degradation efficiency of MO
after 180 min was only 50.71% (Fig. 4). In case of ZnO/ZSM-5, the
decoloration of MO increased slowly up to 90 min which was re-
markably slower than the rate achieved by TiO2/ZSM, TiO2-Meso-
poures and TiO2 Degussa, however the degradation remained continue,
but the rate of degradation gradually decreased till it reached in the
state of equilibrium at 120 min. The low specific surface area 380 m2/g
and disordered distribution of ZnO onto ZSM-5 surface make this cat-
alyst less efficient. Nevertheless, ZSM-5 was exhibited completely in-
efficient catalyst; there was no perceptible color change in MO dye.
Thus, the results above demonstrated that the TiO2/ZSM-5 was the
excellent catalyst in comparison to others prepared via direct template
method.
3.2.2. Effect of pH on photo-degradation for TiO2/ZSM-5 catalyst
The pH value has a crucial influence on the photocatlytic de-
gradation process, its affects the generation of the oxidizing species (%
OH, O2%−, H2O2 and HO2%) that result in photodegradtion [51], thus it
is necessary to study the effect of the pH on the methyl orange photo-
degradation process. Experiments were carried out at pH values of 2, 4,
6, 7, 7.5, 8 and 9, with 20 mg L−1 of MO, 2 g/L dosage of TiO2/ZSM-5
in 100 ml reaction volume, for 180 min reaction time and the pH was
adjusted by using 1 M KOH and HCL solution.
In the presence of TiO2/ZSM-5 catalyst, the degradation increased
with the increase of pH from 2.0 to 7.5, and reached to its maximum
MO removal efficiency at 7.5 but started to decrease with the increase
of pH from 7.5 and beyond (Fig. 5). The highest removal of MO at
almost neutral pH (7.5) was a great achievement since after treatment
there was no need to adjust the pH of water before joining the water
bodies.
It is to be believed that the surface of TiO2/ZSM-5 is positively

Fig. 4. UV–vis/spectrophotometer of MO dye decolourization using TiO2/ZSM-5, TiO2-

mesopoures, TiO2 Degussa, ZnO/ZSM-5 and ZSM-5. Fig. 5. Effect of pH on removal efficiency of MO.

223
H. Znad et al.
charged under acidic conditions pH < 6 by the adsorbed H+ ions on
the semiconductor surface, whereas, it is negatively charged under al-
kaline conditions pH > 7.5 by the adsorbed OH− ions on the semi-
conductor surface. The photodegradation efficiency affects by an an-
ionic or cationic form of the MO dye. Two reaction mechnasims
contribute to MO dye degradation such as direct oxidation by positive
holes, and direct reduction by electrons. It was observed that the de-
gradation efficiency of MO in acidic to neutral (pH of 2, 4, 6, 7, 7.5) was
significantly increased than the basic solution of pH 9 which is made
the catalyst surface negatively charged. Therefore, in acidic to neutral
media, a strong adsorption of MO on the composite particles is pre-
ferred as a result of the electrostatic attraction of the positively charged
particles toward the MO to be a higher at neutral region. However, in
basic solutions of pH = 9, MO dye dissociated forming sodium ions that
can react with the adsorbed OH− ions, which reduced the amount of
OH- radicals [55].
3.2.3. Adsorption and photodegradtion of MO
In order to investigate the adsorption and photodegradtiton of MO
separatly, experiments were conducted under the optimimum condi-
tions of pH 7.5, catalyst dose 2 g L−1, and concentration dye 20 mg L−1
in the dark and solar light irradiation for 180 min. It was noticed (Fig.
S3) that the adsorption equilibrium of MO was achieved at about
120 min and the maximum adsorption efficiency of TiO2/ZSM-5 was
10% after 180 min treatment in the dark compared with 99.55% of
photodegradation. In spite of the high specific surface area of TiO2/
ZSM-5, it has minimum MO decolorization contribution vai adsorption,
however, TiO2/ZSM-5 provided a plenty of active sites for photo-cata-
lytic degradation of MO in aqueous media.
3.2.4. Kinetics studies
In order to evaluate the kinetics of photo-degradation of MO via
TiO2/ZSM-5 catalyst were simulated using pseudo-first order and
pseudo-second order model and the best fitted model was selected
based on the highest correlation coefficient R2 value. The pseudo first
order model of photo-degradation reaction can be described by
Langmuir-Hinshelwood kinetic model, which can be simplified to an
apparent first order equation as shown in Eq. (2). Chong et al. [52]
found that the Langmuir-Hinshelwood model could be simplified when
the KC-value is less than 1 to pseudo-first order kinetic model as given
in Eq. (3).
dC kKC
= =r
dt 1+KC (2)
Co
ln = k K t = kapp t
C (3)
Where r is the reaction rate, k is the reaction rate constant, K is the
dynamic Langmuir adsorption constant, C is the dye concentration and
kapp is the obvious pseudo-first order reaction rate constant. The plot ln
(C0/C) versus t for photo-degradation of MO by TiO2/ZSM-5 catalysts at
different dosages described a linear behaviour as shown in Fig. 6. The
variation of the k values with TiO2/ZSM-5 are shown in the insert of
Fig. 6.
The experimental data were also analysed with pseudo-second order
model, using he linear Eq. (4)
t qt = 1 k2 qe 2 + 1 qe t
(4)
where k2 is the reaction rate constant for pseudo-second order model, qe
is the amount of MO at equilibrium and qt is the amount of MO photo-
degraded at time t. The plot t/qt versus t for photo-degradation of MO
by TiO2/ZSM-5 catalysts at different dosages described a linear beha-
viour as shown in Fig. 7. The variation of the k2 values with TiO2/ZSM-
5 are shown in the insert of Fig. 7.
The values of correlation coefficients R2 indicated a better fit of
pseudo-second order model with dosage 2 mg L−1 of TiO2/ZSM-5
224
Journal of Environmental Chemical Engineering 6 (2018) 218–227
catalysts.
Catalyst loading is a significant factor in photo-catalytic wastewater
treatment processes [53]. The optimum photo-catalyst loading not only
preventing unnecessary excess use of applied catalysts but also gives a
maximum photo-activity. It was noticed that photo-activity increased
with increase of TiO2/ZSM-5 loading and achieved the maximum
photo-activity at 2 g L−1 due to the availability of more reactive radi-
cals for surface reaction and also high number of active sites. However,
catalyst loading more than 2 g L−1 caused cloudiness in the reaction
solution which blocked the penetration of solar illumination.
Mahadwad et al. [54] have explained that the increase in catalyst
concentration caused deactivation of molecules due to collisions. Thus,
the optimum TiO2/ZSM-5 mesoporous loading for the photocatalytic
degradation of 20 ppm model MO dye in aqueous solution was 2 g L−1.
3.2.5. TOC removal
The mineralization of total organic carbon (TOC) from MO dye
(20 mg L−1) solution using TiO2/ZSM-5, TiO2-mesoporous, ZnO/ZSM-5
and TiO2 Degussa were investigated. The results were presented in
Fig. 8, indicated that TiO2/ZSM-5 managed to remove completely
(99%) TOC of MO in 180 min of solar irradiation, however, some of the
intermediate by-products (1%) reminded in the solution even after its
treatment of 180 min. The photocatalytic degradation proposal path-
ways and intermediates are discussed in section 3.2.5. As reflected in
Fig. 4, it can be fairly concluded that MO dye was decoloured via
photocatalytic degradation process using TiO2/ZSM-5 and at the same
time the by-products were efficiently mineralized. Fig. 8 also depicted
that the relative concentration of TOC reduced quickly within 90 min
and it remained decreased, but with lower rates than before till 180 min
without showing any obvious equilibrium. However, in case of TiO2-
mesoporous, it was noticed that the TOC removal was 42% under solar
irradiation after 180 min as shown in Fig. 8. The ZnO/ZSM-5 and TiO2
Degussa catalysts were just able to remove 28% and 17% TOC for the
same time span of 180 min, respectively. Among all catalysts studied in
this study, TiO2 Degussa reached to its equilibrium state within 60 min,
which was considered as quite before in respect of others. Hence it
could be concluded that some of intermediate by-products and few
percentage of MO itself cannot be degraded by TiO2 Degussa. ZnO/
ZSM-5 and TiO2-mesoporous have not acquired their equilibrium event
at 180 min, however the rate was extremely low and from application
point of view, it would not be suggested to use these catalysts for MO
mediated wastewater treatment.
Combining the results depicted in Figs. 4 and 8, it would be easily
understood that TiO2-mesoporous, ZnO/ZSM-5 and TiO2 Degussa were
better with decolouration of MO than their efficiency to degrade TOC.
Finally, it was speculated that the TiO2/ZSM-5 has strong reduction-
oxidation ability as a result of the hole-pair electron recombination,
which given high activation cites on the surface of the catalyst and
consequently proved to be the most appropriate catalyst for TOC re-
moval from MO mediated wastewater.
3.2.6. Regeneration of the TiO2/ZSM-5 photocatalyst
Studying regeneration and reuses of the photo-catalyst were im-
portant aspects in terms of potential practical applications, cost effec-
tiveness and eco-friendly nature of proposed catalyst. After the end of
first complete photo-catalyst cycle, the catalyst was filtrated, washed
with deionized water, dried at 100 °C, and followed by the calcination
process at 400 °C for 3hr to remove adsorbed MO dye and its inter-
mediate molecules, if any present onto the surface of TiO2/ZSM-5 cat-
alyst. The same above mentioned procedure was conducted after every
cycle of usage.
The degradation efficiency of MO dye is shown in Fig. S4. At the end
of the six cycles, a slight reduction from 99.55% to 95.16% in the de-
gradation efficiency was noticed. It was likely due to the accumulation
of the intermediate by-products on the surface of the catalyst or might
be because of slight leaching of TiO2 particles.
H. Znad et al.
In order to study the durability of the TiO2/ZSM-5 catalyst, the
surface area of the recycled catalyst after six complete cycles of usage
was tested by N2 adsorption – desorption analyzer and the surface was
characterized by XRD spectra. The results clarified that the specific
surface area, XRD and FTIR (Fig. S5a–c) results of regenerated catalyst
after complete six cycles possessed no significance changes which in-
dicated the durability and feasibility of TiO2/ZSM-5. It can be noticed
that the TiO2/ZSM-5 exhibited high structural stability even after multi-
cycles usage.
Based on these findings, it can be concluded that the TiO2/ZSM-5
225
Journal of Environmental Chemical Engineering 6 (2018) 218–227
Fig. 6. Influence of the TiO2/ZSM-5 loading on the pseudo-first-order re-
action rate constant.
catalyst has unique adsorption photocatalytic ability, which is highly
recommended in the advanced wastewater treatment.
4. Conclusion
TiO2 immobilised onto a new multilamellar vesicles (MLVs) meso-
porous ZSM-5 substrate were fabricated by the direct templating ap-
proach. The synthesized TiO2/ZSM-5 catalyst shows an effective re-
moval of MO from wastewater under solar light irradiation. The
decolorization and minerlization removal effectiveness can reach
Fig. 7. Influence of the TiO2/ZSM-5 loading on the pseudo-second-order
reaction rate constant.
H. Znad et al.
Fig. 8. TOC removal of 20 mg L−1 methyl orange dye by using different types of catalyst.
99.55% and 99%, respectively, for initial MO concentration of
20 mg L−1. The special multilamellar vesicles morphology can effec-
tively enhance the utilisation of light through a multiple interior spaces.
The high specific surface area of the TiO2/ZSM-5 (1151 m2 g−1) en-
sures a high photocatalysis efficiency of MO dye. TiO2/ZSM-5 meso-
porous was compared with different catalysts such as TiO2 Degussa,
ZSM-5, ZnO/ZSM-5, and TiO2-mesoporous·The XRD analysis confirmed
the anatase phase mostly in the synthesized TiO2/ZSM-5 mesoporous.
Moreover, SEM images showed that TiO2 crystallites were present on
the multilamellar vesicles ZSM-5. The kinetic study follows the pseudo-
second-order model. TiO2/ZSM-5 was regenerated six times, with its
degradation efficiency remained as high as 95.16%. The results de-
monstrate that the TiO2/ZSM-5 multilamellar vesicles mesoporous ex-
hibits promosing potential application as a new photocatalyst mor-
phology for coloured wastwater purification.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.jece.2017.11.077.
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