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Journal of the Taiwan Institute of Chemical Engineers

journal homepage: www.elsevier.com/locate/jtice

Synthesis, characterisation and application of TiO2 zeolite

nanocomposites for the advanced treatment of industrial dye
wastewater
Meng Nan Chong a,b,, Zhen Yang Tneu a, Phaik Eong Poh a,b, Bo Jin c, Rupak Aryal d
a
School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor Darul Ehsan 46150,
Malaysia
b
Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor Darul Ehsan 46150,
Malaysia
c
School of Chemical Engineering, The University of Adelaide, North Terrace Campus, Adelaide 5005, South Australia, Australia
d
School of Natural and Built Environments, University of South Australia, Mawson Lakes Campus, Mawson Lakes 5095, South Australia, Australia

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

Article history: Photocatalysis usually involves the utilisation of nano-sized semiconductor photocatalysts owing to their
Received 7 August 2014 higher specic surface area and surface reaction rate. However, the key challenges in the utilisation of nano-
Revised 9 December 2014
sized photocatalysts for advanced treatment of industrial dye wastewater are to enhance the post-separation
Accepted 14 December 2014
and recovery of spent photocatalysts to prevent them from diffusing into the environment. Thus, the main aim
Available online xxx
of this study was to synthesize a functional-form of titanium dioxide (TiO2 )zeolite nanocomposite through
Keywords: the modied two-step solgel method for enhanced application and separation after advanced industrial dye
Titanium dioxide wastewater treatment. The synthesized TiO2 zeolite nanocomposite was characterised using eld-emission
Zeolite scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX) analysis, Fourier-transformed in-
Nanocomposite frared spectroscopy (FTIR), particle size distribution analysis and BrunauerEmmettTeller (BET) specic
Industrial dye wastewater surface area and porosity analysis. Subsequently, the photoactivity of synthesized TiO2 zeolite nanocompos-
Reactive Black 5 dye
ite was measured and compared against the commercial TiO2 particles. It was found that the TiO2 zeolite
nanocomposite shows a high apparent pseudo-rst order reaction rate constant of 0.0419 min1 at lower
dye concentration. This showed that the synthesized TiO2 zeolite nanocomposite follows a more adsorption-
oriented photocatalytic degradation of water pollutants, which is useful for removing trace and untreated
dye compounds in the advanced industrial dye wastewater treatment stage.
2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction safeguard and prevent the bioaccumulation of synthetic dye com-

pounds in the natural environment, direct discharge of industrial
In recent years, rapid industrialisation has extended the use of dye wastewater euent to environmental waterways or even local
synthetic dyes in various industrial applications in order to meet the wastewater treatment plants (WWTPs) should be made illicit [3]. In-
escalating demands on consumer products to sustain the national stead, the industrial dye wastewater should be retained on-site for
economic growth. While this is a favourable and positive shift in an further purication before discharging to the local WWTPs [3]. This is
endeavour to shape the short-term or long-term economic outlook to ensure that most of the toxic and hazardous parent azo-aromatic
of a country; the environmental dimension of effective handling and synthetic dyes and their intermediate compounds are being treated
management of produced industrial dye wastewater was often be- to avoid this point source pollution from diffusing into the natural
ing neglected. Industrial dye wastewater is highly refractory, as it ecosystem.
is usually made up of high salt and organic contents that render its To date, various concerted efforts have been made to retain the
low biodegradability in the natural environment [1,2]. In order to industrial dye wastewater for on-site treatments such as by using
the natural pond and lagoon treatments; physico-chemical treat-
ments such as sedimentation, occulation, coagulation and adsorp-

Corresponding author at: School of Engineering, Chemical Engineering Discipline,
tion; biological treatments such as aerobic and anaerobic digestion
Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor Darul
Ehsan 46150, Malaysia. Tel.: +60 3 5516 1840; fax: +60 3 5514 6207. or even high-rate algal metabolism and chemical treatments such
E-mail address: [email protected], [email protected] as Fenton, photo-Fenton and ozonation [4,5]. However, the treat-
(M.N. Chong). ment of industrial dye wastewater is not straightforward as synthetic

http://dx.doi.org/10.1016/j.jtice.2014.12.013
1876-1070/ 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
ment of industrial dye wastewater, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.013
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2 M.N. Chong et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2014) 19

dye compounds are usually having very good water solubility. To- it is anticipated that photocatalytic water treatment technology
gether with the highly stable azo-aromatic structures of synthetic utilising TiO2 zeolite nanocomposite can provide a technically feasi-
dyes, these made the industrial dye wastewater even more dicult ble and cost effective solution for advanced industrial dye wastewater
to be degraded naturally or via bio-assisted degradation processes. In treatment.
addition, the breakdown of synthetic dye compounds would release
by-products such as benzidine, naphthalene and other aromatic com- 2. Materials and methods
pounds that are toxic, carcinogenic and mutagenic not only to marine
living organisms but also affecting human beings through the food 2.1. Materials
chain. For instance, Lupica [6] reported the toxicological effects of
synthetic dyes could have on the shape and size of red blood cells of Titanium (IV) butoxide (97% gravimetric, SigmaAldrich) and ab-
shes. In addition, it was also reported that the untreated synthetic solute ethanol (Kollin Chemicals) and zeolites (particle size < 45 m,
dyes can cause the reduction of reproductive organs of rat up to 44%, SigmaAldrich, Product code: 96096) were used as received. Nitric
decrease in total protein concentration by 70% and cholesterol was acid (Kollin Chemicals), sodium hydroxide (Kollin Chemicals) and Re-
depleted up to 91% [6]. active Black 5 dye (C26 H21 N5 Na4 O19 S6 , 55% SigmaAldrich) were pre-
Photocatalysis is an emerging branch of advanced oxidation tech- pared to the nal desired concentration via the addition of deionised
nologies used for water and wastewater treatment that has been water.
widely documented for its ability to degrade indiscriminately almost
all water pollutants [4]. Nano-sized semiconductor photocatalysts 2.2. Preparation of TiO2 zeolite nanocomposites
are usually being used owing to their higher specic surface area
and thus, giving yields to a higher surface reaction rate during the The modied two-step solgel synthesis method for TiO2 zeolite
degradation of water pollutants. The utilisation of nano-sized pho- nanocomposites was in accordance to Chong et al. [7] in exception
tocatalysts in the advanced treatment of industrial dye wastewater that kaolinite was replaced by zeolite particles. Briey, 25 mL of tita-
is, however, remained highly challengeable owing to the problems nium (IV) butoxide was mixed with 30 mL of absolute ethanol under
associated with post-separation and recovery of spent photocatalysts vigorous magnetic stirring. The mixture was denoted as mixture A.
[7]. Even with the additional post-separation and recovery stage; the Then 60 mL of diluted nitric acid was added drop wise into mixture
photo-eciency of catalysts, recovery eciency of photocatalysts and A. During the mixing process, the mixture A was stirred continu-
unit treatment cost of photocatalysis are the major factors that inhibit ously until the dispersion rst became milky white and eventually
the large scale application of photocatalytic water treatment technol- transparent homogeneous sol with no visible precipitation. The stir-
ogy [8]. Thus, the key challenge in the utilisation of nano-sized pho- ring was continued for another 30 min to ensure the homogeneity in
tocatalysts for advanced treatment of industrial dye wastewater is to transparent homogenous sol formed. Following this, the zeolite parti-
provide a bespoke solution by immobilising the nano-sized semicon- cles were made into suspension via the addition of 100 mL deionised
ductor photocatalysts on larger immobiliser substrates to alleviate water and the zeolite suspension was set in ask immersed in wa-
the post-separation and recovery eciency. Different immobiliser ter bath with temperature set at 37 C. The prepared transparent sol
substrates such as magnetite core [9], activated carbon [10] and clays was added drop wise into the zeolite suspension and the mixture
[7,11] have been used to enhance their post-separation and recovery was continuously stirred for 4 h. Subsequently, the nal mixture was
from bulk water. cooled to room temperature and aged for 1316 h. After the aging pro-
In comparison, natural zeolites are abundant, easily available and cess, the mixture was ltered and washed repeatedly for three times
inexpensive as the immobiliser substrate to synthesize functional with deionised water and then the ltrate was dried at 6570 C for
nanocomposites with semiconductor metal oxides [12]. More inter- 24 h. Finally, the ltrate containing TiO2 zeolite nanocomposites
estingly, zeolites are having crystalline aluminosilicates with differ- was annealed at different temperatures before it was used as the pho-
ent cavity structures and high ion exchange capacity, tectosilicates tocatalysts for the treatment of synthetic industrial dye wastewater.
with microporous channels, pore spaces, molecular sieving, adsorp-
tion and catalysis capacity [13,14]. Recently, the titanium dioxide 2.3. Characterisation of TiO2 zeolite nanocomposites
(TiO2 )zeolite nanocomposite has been studied for the removal of hu-
mic acid from drinking water source [12]. Thus, the main aim of this Field-emission scanning electron microscopy images were ob-
study was to design a functional-form of TiO2 zeolite nanocompos- tained using the Hitachi SU8010 electron microscope at an acceler-
ite by varying the acid concentrations, zeolite loadings and annealing ating voltage of 5 kV. Similarly, the energy dispersive X-ray analysis
temperatures used in the modied two-step solgel synthesis pro- was carried out using the same electron unit after the samples were
cess for subsequent application in the advanced treatment of indus- coated with platinum for ease of analysis of percentages of atomic
trial dye wastewater. In this instance, nano-sized TiO2 crystals were element and element weight, respectively.
synthesized and immobilised on submicron sized zeolite particles to BrunauerEmmettTeller specic surface area of the TiO2 zeolite
enable the functionality of nanoparticles while presenting a mi- nanocomposites was determined by using adsorption isotherms ob-
crostructure for ease of post-separation and recovery after industrial tained from the Micromeritics BET ASAP 2020 (surface area and poros-
dye wastewater treatment. Following this, further characterisations ity analyser) at 77 0.5 K in liquid nitrogen and by using the BET equa-
on the physicochemical properties and photoactivity of TiO2 zeolite tion. Sample vessels were degassed at high temperatures overnight
nanocomposite were carried out using eld-emission scanning elec- before being analysed for SSA, pore volume and pore size of the TiO2
tron microscopy (FE-SEM), energy dispersive X-ray (EDX) analysis, zeolite nanocomposites.
Fourier-transformed infrared spectroscopy (FTIR), particle size distri- The functional groups on TiO2 zeolite nanocomposites were anal-
bution analysis and BrunauerEmmettTeller (BET) specic surface ysed using Thermo Scientic FTIR Nicolet iS10 while particle size dis-
area and porosity analysis. Finally, the effects of catalysts loading, an- tribution were determined using Malvern Mastersizer 3000.
nealing temperature and initial dye concentration on the photodegra-
dation kinetics of surrogate model Reactive Black 5 dye compound 2.4. Photocatalytic experiments on aqueous Reactive Black 5 solution
were investigated. The UVvis absorbance scans from 400 to 700 nm
were also being carried out to monitor the cleavage and disappear- The photoactivity of synthesized TiO2 zeolite nanocomposites
ance of characteristic system linked to the azo bonds and the was tested on the degradation of a surrogate indicator, Reactive Black
possible appearance of other reaction by-products. With this study, 5 dye, which is commonly found in industrial dye wastewater. The

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
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Fig. 1. Effects of different HNO3 concentration on the textural and gelation characteristics of TiO2 solgel formed.

reaction solution was placed in a beaker on a magnetic stirrer under a Chong et al. [7]. The Ti-precursor solution was rst hydrolysed in a
UV illumination of approximately 300 W/cm2 . Air ventilation in the hydrolysis reaction followed by condensation. Through this synthesis
reactor box was controlled using a vacuum pump with the ventilation method, it is possible to control the homogeneity of TiO2 solgel as
rate set at 2 L/min. Sampling was done during the reaction using a well as tune the microstructures of eventual TiO2 crystallites formed.
micropipette. In order to yield nanosized TiO2 crystallites, the control on the ex-
During the initiation of photocatalytic experiment, 100 mL of the tent of hydrolysis reaction is essential. In this study, the hydrolysis
reaction solution was placed in the beaker with certain photocat- of Ti-precursor was carried out in two stages, where a partially hy-
alysts loading. The reaction solution was then magnetically stirred drolysed state was rst targeted by adding absolute ethanol to the
for 30 min to ensure homogeneous mixing before the UV illumina- Ti-precursor. Chong and Jin [8] explained that this partially hydrol-
tion was turned on. Subsequently, the samples were collected every ysed state is to provide non-hydrolysable ligands of Ti for better TiO2
30 min up until 180 min of reaction time. The collected samples were cluster-to-cluster growth during condensation, as well as to provide
centrifuged (ScanSpeed Mini, Labogene, Denmark) at 12,000 rpm for better molecular homogeneity. Due to the low functionality range
15 min before the supernatants were being separated and ltered for of ethanol in the hydrolysis of Ti-precursor, the true extent of hy-
analysis. A triplicate of the reaction solution was sampled where the drolysis reaction was controlled by the second HNO3 acid-catalysed
absorption spectra were scanned using a UVvis spectrophotometer hydrolysis reaction.
(Genesys 10uv, Thermo Electron Corporation). The monochromatic Fig. 1 shows the effects of varying HNO3 concentration during the
maximum wavelength of 597 nm from the UVvis scanning was used, acid-catalysed hydrolysis reaction step on the textural and gelation
to determine the concentration of Reactive Black 5 dye in the samples. characteristics of TiO2 solgel formed. The range of studied HNO3
In order to evaluate for the photoactivity of TiO2 zeolite nanocom- concentration was between 0.05 M and 1 M. In this instance, the vari-
posites, the raw data on concentrationtime was tted with the ation in the HNO3 concentration resulted in TiO2 solgel of different
LangmuirHinshelwood model as given in Eq. (1). The reason for se- uidity and precipitation. Previously, Chong et al. [7] reported that
lecting this kinetic model to represent the heterogeneous photocatal- the optimum HNO3 concentration lies in the range of 0.250.30 M
ysis reaction was due to that the model dye compound is thought to without any temperature and humidity controls during the synthe-
adsorb on the catalysts surface before being degraded and nally, the sis experiments. From Fig. 1, however, it was observed that there are
products will be desorbed from the catalysts surface [4]. Depending some precipitations in lumps still occur at HNO3 concentration below
on the dye concentration, Chong et al. [15] found that the Langmuir 0.35 M. Precipitation was observed at low acid concentration due to a
Hinshelwood model could be further simplied when the KC-value is very high gelation rate that resulted in precipitates in the TiO2 poly-
less than 1 to the simplied pseudo-rst order kinetic model as given meric gel network. For the synthesis of TiO2 zeolite nanocomposites,
in Eq. (2). precipitates are not favourable for the immobilisation of TiO2 crys-
tallites onto the external surface of zeolite due to its low degree of
dC kKC
r= = (1) uidity (i.e. non-owing hardened TiO2 solgel). When the acid con-
dt 1 + KC
centration of 0.300.35 M was used, it was found the hardening of gel
  occurred almost instantaneously after the addition and stirring with
C0
ln = kKt = kapp t (2) HNO3 . No precipitation was observed for HNO3 concentration above
C
0.35 M where instead, a clear hard gel was formed at acid concen-
where r is the reaction rate, k is the reaction rate constant, K is the tration range of 0.350.40 M. As for high HNO3 concentration above
dynamic Langmuir adsorption constant, C is the dye concentration 0.5 M, no gelation occurred even after long ageing time and Ti-sol
and kapp is the apparent pseudo-rst order reaction rate constant. presented a very high uidity characteristic. It was understood that
high acid concentration would slow down the condensation rate and
3. Results and discussion thus, affecting the formation of TiO2 polymeric gel.
When the acid concentration of 0.38 M was used, the gel formed
3.1. Effects of nitric acid concentration hardened at a lower rate allowing the Ti-sol to be added drop-wise
into the zeolite suspension in later stage. Thus, the optimum HNO3
The synthesis of TiO2 solgel constitutes the rst step in the mod- concentration found in this study which showed a good gelation be-
ied two-step solgel synthesis method as previously reported by haviour with acceptable uidity level and no precipitation occurred

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
ment of industrial dye wastewater, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.013
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at 0.38 M. This was not in agreement with the previous nding re- of TiO2 particles. Since the amount of Ti added remains unchanged
ported by Chong et al. [7] and this was deduced to be owing to higher throughout the synthesis experiments, both the weight and atomic
temperature and local humidity level in the present experiment set- percentages of Ti in the TiO2 zeolite nanocomposites are measured
tings. A systematic study should be carried out in order to understand (using EDX) to be approximately 23.83% and 10.02%, respectively.
the effects of temperature and humidity on the eventual textural and
gelation characteristics of TiO2 solgel formed. Apart from getting the
3.3. Characterisation of TiO2 zeolite nanocomposites
right textural and gelation characteristics of TiO2 solgel, it was also
known that the optimum condition will also affect the TiO2 crystal-
3.3.1. BET adsorption isotherm analysis
lites size formed. In this study, since the volume of acid used was kept
By analysing the adsorption isotherms of nitrogen on the meso-
constant while the molarities were varied, the predominant synthesis
porous zeolite surface at an increasing relative pressure, the BET sur-
parameter was related to the pH. Su et al. [16] also reported that the
face area, pore size and volume were determined. Fig. 3 shows the
TiO2 crystallite particles in aqueous solution possess surface charges
adsorption and desorption isotherms of TiO2 zeolite nanocompos-
that are highly dependent on pH. When the surface charges of TiO2
ites for zeolite loading of 5% w/v and annealing treatment at 400 C.
particles are high, strong repulsive forces exert among the particles
From Fig. 3, it can be observed that the adsorption and desorption
making them less likely to form aggregates and thus, resulting in more
isotherms are not the same for a specied region of relative pressures.
stable Ti-sol with smaller particle sizes. It was also reported that large
This phenomenon is known as a hysteresis loop and is commonly ex-
TiO2 particles sizes are formed between pH 5 and pH 8 where white
hibited in mesoporous adsorbents such as zeolite particles used in
precipitates were formed. Clear Ti-sol formed at low pH was reported
this study. With the adsorption and desorption isotherm characteris-
to form nano-sized TiO2 particles at pH less than pH 3. This is consis-
tics, the observed isotherms can be classied as the Type IV isotherm
tent with the results obtained in this study where, the optimum TiO2
in accordance to the IUPAC isotherm classications [17].
solgel condition chosen was clear and contained no precipitates.
Table 2 shows the effects of zeolite loading and annealing tempera-
ture on the BET surface area, pore size and pore volume distribution. It
3.2. Effects of zeolite loading
was observed that an increase in zeolite loading from 5% to 10% (w/v)
in suspension is accompanied by an increase in BET surface area, as
In the modied two-step solgel synthesis method for
the mesoporous zeolite structure is porous. At the zeolite loading of
TiO2 zeolite nanocomposites, the latter part was to coat TiO2 solgel
5% (w/v), it was found through FE-SEM imaging (Fig. 2(f)) that TiO2
onto the external surfaces of zeolite before subjected to controlled an-
crystallites were dispersed more frequently on the zeolite surface due
nealing treatment. During the optimisation of TiO2 solgel condition,
to lesser nucleation sites. When the pore volume was examined for
the acid-catalysed hydrolysis reaction was manipulated to produce
mass loadings of zeolite at 5% and 10% (w/v), two potential hypothe-
solgel with optimal uidity to enable drop wise addition into the
ses can be portrayed. Firstly, the immobilisation of TiO2 crystallites
zeolite suspension. This was done to enable the proper and more uni-
on the external surface of zeolite is causing blockage of zeolite pores
form coating of positively-charged TiO2 solgel dispersed onto the
and resulted in an attenuation of pore volume from 0.223379 cm3 /g
negatively-charged aluminosilicate framework of zeolite. It is theo-
to 0.201215 cm3 /g. Secondly, the immobilised TiO2 layer on zeolite
rised that the TiO2 solgel will only be immobilised on the external
could form a microporous structure that could increase the pore vol-
surfaces of zeolite without being dispersed into its pores or cavities.
ume of TiO2 zeolite nanocomposites. It was however, from the BET
Fig. 2(a) and (b) shows the FE-SEM images showing the changes
analysis that the zeolite pore sizes were ranged between 2 and 3 nm
in surface morphology of zeolite, both before and after TiO2 loading.
while the TiO2 crystallites were measured from 10 to 100 nm. Thus,
From Fig. 2(a) and (b), it can be observed that a distinct change in
the difference in zeolites pore size and TiO2 crystallites size conrmed
surface morphology occurred when TiO2 was heterogeneously im-
that the second hypothesis is valid whereas a microporous TiO2 layer
mobilised on the zeolite surface. In order to further investigate the
was formed on the external zeolite surface.
effects of zeolite loadings on TiO2 dispersion, different mass loadings
When the effect of annealing temperatures was studied between
of zeolite in suspensions of 5%, 10% and 15% w/v was mixed with a
300 C and 600 C, the TiO2 zeolite nanocomposites were found to ex-
constant volume of Ti-sol prepared from the rst synthesis procedure.
hibit a wide rangeability of behaviour in terms of the BET surface area,
Fig. 2(c)(e) shows the FE-SEM images of TiO2 zeolite nanocompos-
pore size and volume. By ensuring the mass loading of zeolite was con-
ites synthesized under three different mass loadings of zeolite at 5%
stant at 5% (w/v), the increase in annealing temperature from 300 C
(w/v), 10% (w/v) and 15% (w/v), respectively. From Fig. 2(c)(e), the
to 400 C was observed to have negligible effect on the BET surface
analysis of three different mass loadings of zeolite used revealed that
area but a slight increase in both the pore size and volume. However,
the TiO2 particles were not evenly distributed over the zeolite sur-
when the annealing temperature was increased to 600 C, an abrupt
face and many sections of the zeolite surface still remained bare and
reduction in the BET surface area from 279.5122 1.1593 m2 /g to
uncovered by TiO2 particles. When a low zeolite loading of 5% (w/v)
38.1123 1.2562 m2 /g was observed. Vimonses et al. [18] reported
was mixed with constant volume of Ti-sol, the TiO2 layer on zeolite
that there exists a small endothermic peak at 600 C in zeolite that cor-
surface was found to be thick and layered coating (Fig. 2(c)). This was
responds to the dehydroxylation process in zeolite. This endothermic
possibly due to the aggregation of TiO2 particles during the immobil-
peak was the potential reason for the abrupt reduction in BET sur-
isation process and is believed to cause a reduction in the effective
face area as observed when the annealing temperature was increased
surface area of TiO2 particles that had immobilised on the zeolite
from 400 C to 600 C. Simultaneously, an increase in both the pore
surface. It was however, at higher mass loadings of zeolite, the TiO2
size and volume was observed and this is in close agreement with the
layer on the zeolite surface showed a consistent and layered coating
observed endothermic peak in zeolite at 600 C.
and this coating appeared to become thinner when the zeolite load-
ing was increased (i.e. 15% w/v). This was attributed to the higher
amount of crystal nucleation sites available for TiO2 binding when 3.3.2. Fourier-transformed infrared spectroscopy (FTIR)
higher zeolite loading was used. Finally, an energy dispersive X-ray The functional groups that present in TiO2 zeolite nanocompos-
analysis was carried out to validate the presence and composition of ites were studied using the FTIR spectroscopy. Fig. 4 shows the com-
Ti in the prepared TiO2 zeolite nanocomposites. Table 1 shows the parison of FTIR spectra of pure zeolite and TiO2 zeolite nanocompos-
quantied elemental composition of prepared TiO2 zeolite nanocom- ites. From Fig. 4, it can be observed that the samples of pure zeolite
posites from EDX analysis and this conrmed that the layered coating and TiO2 zeolite nanocomposites annealed at 500 C and 600 C ex-
formed on the zeolite surface was indeed due to the immobilisation hibited similar FTIR spectra characteristics of zeolite. This indicated

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
ment of industrial dye wastewater, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.013
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Fig. 2. FE-SEM images showing changes in the surface morphology of zeolite (a) before TiO2 loading; (b) after TiO2 loading; (c) with 5% w/v zeolite; (d) with 10% w/v zeolite;
(e) with 15% w/v zeolite and (f) measured TiO2 crystallites size on zeolite.

that zeolite is high suitable to act as TiO2 immobiliser, as the structure While the small band at 1619 cm1 is a characteristic of the bending
is not affected by the high annealing temperatures used. vibrations of HOH bonds in water molecules associated with ze-
The broad band occurring at 3286 cm1 in both annealed TiO2 olite particles. Following these, the sharp intense peak observed at
zeolite nanocomposites samples was linked to the OH stretching and 958 cm1 was due to the SiOSi or AlOAl non-symmetric stretch-
bending vibrations of silanol groups (SiOH), which was formed due ing vibrations in the tetrahedral SiO4 and AlO4 structures that form
to the interaction between Si groups in zeolite and water molecules. the zeolite framework and thus, explaining its band intensity being

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
ment of industrial dye wastewater, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.013
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Fig. 3. Adsorption and desorption isotherms of TiO2 zeolite nanocomposites for zeo-
lite loading of 5% w/v and annealing treatment at 400 C.
Fig. 4. Comparison of the FTIR spectra of pure zeolite and TiO2 zeolite nanocompos-
ites.
Table 1
Elemental composition of prepared TiO2 zeolite nanocom-
posites from EDX analysis. channels, as compared to the at surfaces of zeolite particles. With
Element Weight% Atomic%
such a nanocomposites structure of TiO2 and zeolite, it is anticipated
that they could be exhibiting the nano-scale effects while a sub-
O 65.1181 81.9005 micron sized microstructure for ease of separation after wastewater
Al 5.34493 3.98998
treatment.
Si 5.7023 4.08635
Ti 23.8347 10.0231
Total 100 100 3.4. Photoactivity evaluation of TiO2 -zeolite nanocomposites

3.4.1. Effect of catalyst loading

the highest. Previous study by Smirnov and Graaf [19] and Damin et al. Catalyst loading is an important parameter in photocatalytic water
[20] reported that the insertion of Ti into the zeolite structure would treatment processes [21]. The optimum catalyst loading enables the
result in the TiOSi bonds at the infrared band of 960 cm1 . It was maximum photoactivity while preventing the unnecessary excess use
also reported that the band intensity is proportional to the amount of of applied catalysts. Fig. 7 shows the plot of pseudo-rst order rate
Ti present in the zeolite framework. However, the FTIR spectra at the constant of model Reactive Black 5 dye against TiO2 zeolite nanocom-
intense band of 958 cm1 that represents the Si and Al tetrahedral posites loadings used. Control experiment showed that in the absence
bonding was found to overshadow the potential Ti band formed. This of UV irradiation, the photocatalytic degradation of Reactive Black 5
observation indicated that the amount of Ti that presents in the TiO2 dye was very low to negligible. In the other control experiment with
zeolite nanocomposites could be minimal and again proven that the the absence of TiO2 zeolite nanocomposites photocatalyst, the direct
microporous TiO2 crystallites layer is surface-bounded without any UV photolysis of Reactive Black 5 was still evident with a measured
interstitial binding into the zeolite structure. pseudo rst-order rate constant of 0.0035 min1 (data not shown).
From Fig. 7, it was found that the optimum TiO2 zeolite nanocom-
3.3.3. Particle size distribution posites loading required is 0.3 g/L that yields the pseudo-rst order
Previously, the TiO2 crystallites on nanocomposites were mea- rate constant of 0.0102 min1 . Primarily the increase in photoactivity
sured as shown in Fig. 2(f). From the average TiO2 crystallites size when the TiO2 zeolite nanocomposites loading was increased from
estimation over sampling through FE-SEM image, the size range was 0.1 g/L to 0.3 g/L was attributed to the higher number of active sites
found between 10 nm and 80 nm. While Fig. 5 shows the particle and more reactive radicals available for surface reaction. However, the
size distribution of TiO2 zeolite nanocomposites measured using the reduction in photoactivity of TiO2 zeolite nanocomposites was ob-
laser light diffraction method. From Fig. 5, it was observed that the served at higher catalysts loadings owing to the increasing cloudiness
size rangeability of TiO2 zeolite nanocomposites varied from 0.4 to in the reaction solution that prevents penetration from UV illumina-
200 m with the majority of the nanocomposites particles in the size tion. Mahadwad et al. [22] also explained that the increase in catalysts
range of 510 m. The larger particle sizes measured were due to concentration will result in the deactivation of activated molecules
the aggregation of zeolite particles and this is shown in the FE-SEM due to collisions with ground state molecules. Thus, the optimum
imaging in Fig. 6. In Fig. 6, it was observed that the zeolite aggregates TiO2 zeolite nanocomposites for the photocatalytic degradation of
formed were composed of cubes arranged in a random and disorgan- 10 ppm model Reactive Black 5 dye in aqueous solution were 0.3 g/L.
ised manner. As for the particle size distribution below 5 m, this
was found to be owing to the non-aggregated single cubes of zeolite. 3.4.2. Effect of annealing temperature
It was also observed that when the zeolite cubes aggregate, they will Fig. 8 shows the effects of annealing temperature on TiO2 zeolite
form cavities and channels in between the cubes. In this instance, the nanocomposites on its photoactivity in degrading the model Reac-
TiO2 crystallites were seen to bind more frequently to the cavities and tive Black 5 dye in aqueous solution. It was interesting to note that

Table 2
Effects of different zeolite loading and annealing temperature on the BET surface area, pore size and pore volume.

Zeolite loading Annealing temperature (C) BET surface area (m/g) Pore size (nm) Pore volume (cm/g)

5% zeolite 400 279.4826 1.6744 2.87983 0.201215

10% zeolite 400 324.0927 1.7259 2.75698 0.223379
5% zeolite 300 279.5122 1.1593 2.79353 0.195206
5% zeolite 600 38.1123 1.2562 4.32126 0.831245

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Fig. 5. Particle size distribution of TiO2 zeolite nanocomposites.

Fig. 6. FE-SEM images showing (a) large aggregates of zeolite and/or TiO2 zeolite nanocomposites; (b) non-aggregated single cube of zeolite and/or TiO2 zeolite nanocomposites.

Fig. 8. Effects of annealing temperature on the photocatalytic degradation of model

Reactive Black 5 dye in aqueous solution. Initial dye concentration: 10 ppm; pH 5 and
Fig. 7. Plot of pseudo-rst order rate constants of model Reactive Black 5 dye against
TiO2 zeolite nanocomposites loading: 0.3 g/L.
TiO2 zeolite nanocomposites loadings used.

the TiO2 zeolite nanocomposites sample annealed at 600 C showed ity in TiO2 zeolite nanocomposites sample annealed at 600 C could
higher photoactivity than those annealed at 300 C, albeit lower BET be attributed to the formation of higher pore size and volume as
specic surface area for sample annealed at 600 C. The apparent discussed in Section 3.3.1. Another physicochemical property that
pseudo-rst order rate constants at both 300 C and 600 C were contributes to the higher photoactivity is due to the presence of pho-
0.0056 min1 and 0.0102 min1 , respectively. The higher photoactiv- toactive TiO2 phases, of whether pure anatase or rutile TiO2 or a

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
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Fig. 9. Comparison plot between TiO2 zeolite nanocomposites and commercial TiO2 particles in apparent pseudo-rst order rate constants against initial dye concentration. Inset:
Percentage degradation of dye against UV illumination time at initial dye concentration: 1 ppm; pH 5 and catalyst loading of 0.3 g/L.

mixture of the two photoactive phases. From our previous study,

we found that the pure anatase TiO2 photoactive phase dominates
where the mixed anatase/rutile phase only appears when annealed at
650 C [7].

3.4.3. Effect of initial dye concentration

Fig. 9 shows the comparison plot of apparent pseudo-rst order
rate constants between TiO2 zeolite nanocomposites and commer-
cial TiO2 particles on photocatalytic degradation of different initial
dye concentrations. From Fig. 9, it was found that the TiO2 zeolite
nanocomposites exhibited a higher apparent pseudo-rst order
rate constant of 0.0419 min1 than the commercial TiO2 particles
(i.e. 0.0297 min1 ) at a low dye concentration of 1 ppm. This was
comparatively higher than the apparent pseudo-rst order rate con-
Fig. 10. Absorbance of Reactive Black 5 reaction solution samples taken at 30 min
stants obtained at higher dye concentrations for both TiO2 zeolite intervals from 400 to 700 nm (10 ppm initial dye concentration, pH 5, 25 C, 0.3 g/L
nanocomposites and commercial TiO2 particles. At low dye concen- catalyst).
tration, dye molecules are dynamically adsorbed, reacted and des-
orbed from the external surface of TiO2 zeolite nanocomposites. As
the dye concentration increases, cumulative amount of dye molecules trace water pollutants in the advanced water/wastewater treatment
are adsorbed onto the TiO2 zeolite nanocomposites that reduces stages.
the penetration of UV illumination and rate of surface reaction, re-
spectively. Simultaneously, the absorption of UV illumination by the 4. Conclusion
surface-adsorbed dye molecules also attenuates the photon trans-
missivity to the catalyst surface. The inset in Fig. 9 shows the com- In conclusion, the modied two-step solgel method was success-
parison plot in photocatalytic degradation kinetics of Reactive Black fully adopted to synthesize TiO2 zeolite nanocomposite with surface
5 dye at 1 ppm for both TiO2 zeolite nanocomposites and commer- covered TiO2 crystallites size of 10100 nm and zeolite immobilis-
cial TiO2 particles. From the kinetics plot, it was observed that a com- ers size of 510 m. This enables the functionality of nano-sized
plete degradation of Reactive Black 5 dye was achieved in 95 min effect for TiO2 while presenting sub-micron zeolite microstructure
and 120 min using the TiO2 zeolite nanocomposites and commercial platforms to allow for the ease of post-separation and recovery af-
TiO2 particles, respectively. While at higher initial dye concentra- ter advanced industrial dye wastewater treatment. During the rst
tion of 10 ppm, it was observed that the commercial TiO2 particles solgel synthesis step, the optimum acid concentration was found to
(i.e. 0.0128 min1 ) performed better than the TiO2 zeolite nanocom- be 0.350.40 M HNO3 that yielded a homogeneous, clear and hard
posites (i.e. 0.0102 min1 ). Fig. 10 shows the attenuation in UVvis TiO2 solgel with no precipitation formed. Subsequently, the TiO2
absorbance peak at max value of 597 nm at 30 min interval, as a result solgel was coated onto different mass loadings of zeolite and the
of the cleavage and disappearance of characteristic system linked physical structural existence of TiO2 zeolite nanocomposite was suc-
by the azo bonds (NN). Based on these ndings, it can be con- cessfully characterised and proven using FE-SEM and EDX analysis.
cluded the TiO2 zeolite nanocomposites exhibited more adsorption FE-SEM images showed that a consistent layer of TiO2 crystallites was
oriented photocatalytic degradation that could be useful to remove present on the zeolite surface, while the EDX analysis conrmed the

Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
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Please cite this article as: M.N. Chong et al., Synthesis, characterisation and application of TiO2 zeolite nanocomposites for the advanced treat-
ment of industrial dye wastewater, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2014.12.013