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Journal of Industrial and Engineering Chemistry

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Photocatalytic degradation of 4-nitrophenol with ZnO supported

nano-clinoptilolite zeolite
Alireza Nezamzadeh-Ejhieh *, Setareh Khorsandi
Department of Chemistry, Shahreza Branch, Islamic Azad University, P.O. Box 311-86145, Shahreza, Isfahan, Iran

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

Article history: Photocatalytic degradation of 4-nitrophenol aqueous solution was investigated using ZnO/nano-
Received 25 December 2012 clinoptilolite zeolite under UV irradiation. Nano-powders of clinoptilolite were prepared using a
Accepted 20 June 2013 planetary ball mill mechanically method. The photocatalyst was prepared by ion exchanging of nano-
Available online xxx
clinoptilolite in a 0.1 M zinc nitrate aqueous solution for 24 h followed by calcination at 450 8C for 12 h.
Samples were characterized by XRD, FT-IR, DRS, AAS, TG/DTG, SEM, TEM and BET. Effects of various key
Keywords: operating parameters on the degradation rate were studied. The COD and HPLC tests were also used to
Heterogeneous catalysis
confirm the degradation extent of the pollutant.
4-Nitrophenol
ZnO
ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Nano-clinoptilolite zeolite reserved.

1. Introduction electronic or g beams and various combinations of these methods

The pollution of drinking water reservoirs and aquatic
environment by chemicals has been a serious problem of the last
decades [1]. Nitrophenols are one of the most refractory
compounds due to their high stability and solubility in water
[2]. 4-Nitrophenol and its derivatives result from the production
process of pesticides, herbicides and synthetic dyes [3].
Different adsorbent and methods such as sonolysis, extraction,
adsorption and other methods have been used for removing
nitrophenol [4–10] and other pheonlic compounds [11,12]. All
these methods have significant disadvantages such as incomplete
removal, high-energy requirements and production of toxic sludge
or other waste products that require further disposal [13]. For
example, although, granular or powdered activated carbon (AC) is
the most widely used adsorbent for different organic pollutants
due to its high adsorption capacity, but using of AC is usually
limited due to its high cost [14]. The separation of sorbent like AC
from aqueous solution is another problem in these removal
methods.
Advanced oxidation processes (AOPs) generate very powerful
and non-selective oxidizing agents such as hydroxyl radicals (OH)
for the destruction of refractory and hazardous pollutants in
different water samples [15]. Common AOPs involve Fenton and
photo-Fenton processes, ozonation, electrochemical oxidation,
photolysis with H2O2 and O3, high-voltage electrical discharge
process, photocatalysis, radiolysis, water solution treatment by
* Corresponding author. Tel.: +98 321 3292515; fax: +98 321 3291018.
E-mail address: arnezamzadeh@iaush.ac.ir (A. Nezamzadeh-Ejhieh).
[16,17]. The common homogeneous Fenton systems is a cost-
effective source of hydroxyl radicals, but has some following major
drawbacks that limit the industrial applications of this technology:
(i) the tight range of pH in which the reaction proceed, (ii) the need
for recovering the precipitated catalyst after treatment and (iii)
deactivation by some ion-complexing agents like phosphate
anions. The resulting sludge may also contain organic substances
as well as heavy metals and has to be treated further, thus
increasing the overall costs [18].
Among the various AOP techniques, semiconductor mediated
photocatalysis has been accorded great importance over the last
few years due to its potential to destroy a wide range of organic
and inorganic pollutants at ambient conditions, without the
production of harmful products [19,20]. Semiconductor photo-
catalyst generates electron and hole pairs (e/h+) upon irradiation
of light energy that could be utilized in initiating oxidation and
reduction reactions [21,22]. Among various semiconductors, TiO2
and ZnO have been used as effective, inexpensive and nontoxic
semiconductors for producing of photocatalysts for the degrada-
tion of a wide range of different pollutants in recent years [23,24].
ZnO has also been found more efficient than TiO2 in the
photodegradation of pesticide carbetamide and herbicide triclo-
pyr [25]. The biggest advantage of ZnO in comparison with TiO2 is
that it absorbs over a larger fraction of UV spectrum (the
corresponding threshold of ZnO is 425 nm) [26–29]. Hence, it has
widely used as a suitable semiconductor in the heterogeneous
photocatalysis in recent years [30–36]. Due to the advantages of
semiconductor based photocatalysis, this method has been
widely used in recent years for phodegradation of different
phenolic compounds [36–40].

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.06.026

Please cite this article in press as: A. Nezamzadeh-Ejhieh, S. Khorsandi, J. Ind. Eng. Chem. (2013), http://dx.doi.org/10.1016/
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Despite the positive attributes of photocatalysts, poor adsorp-
tion properties of semiconductors limit their application. To
circumvent this limitation, several attempts have been made to
improve the efficiency of photocatalysts using suitable supports
[41]. Among various supports, zeolites have been widely used due
to their unique uniform pores and straight channels [42,43]. Ion
exchange property of zeolites is due to the presence of non-
compensated negative charges, which originate from heterova-
lence substitution (Si4+ by Al3+ in tetrahedral positions) as well as
the presence of surface functional groups (mainly OH and H2O) in
crystalline lattice discontinuity points [44]. Considering the large-
scale utilizations, natural zeolites seem more ascendant than
synthetic ones, due to their low cost, abundant and less chemical
pollution during production [45]. Nano-crystalline zeolites have
higher external surface area and reduced diffusion path lengths
relative to conventional micrometer-sized zeolites [46]. Although,
different methods have been reported for synthesis of nano-
zeolites, but, as an alternative technique, the zeolite particle size
may be reduced mechanically using specially designed ball mills
[47].
The goal of the present work is increasing the photodegradation
efficiency of ZnO by supporting it onto the nano clinoptilolite
zeolite. For this purpose, first an Iranian natural clinoptilolite, as a
cheap and abundant zeolite in Iran, was pretreated and converted
to nano particles by mechanical method to increase effective
surface area. The prepared nano powder was ion exchanged in a
zinc aqueous solution to prepare Zn-clinoptilolite material. Finally,
the ion exchanged form was calcined at 450 8C to obtain ZnO-
clinoptiloite catalyst. The obtained catalyst was used in the
photodegradation of 4-nitrophenol aqueous solution (4-NP) under
UV irradiation in different experimental conditions. Use of natural
zeolite reduces the cost of the method with respect to synthetic
one by elimination of the synthesis procedure (always need the
expensive reagents) and time consuming. The natural clinoptilolite
is also an eco-friendly material.
2. Experimental
2.1. Materials
The natural clinoptilolite tuffs (CP) belong to Semnan region in
the north–east of Iran was purchased from Afrand Touska
Company (Isfahan, Iran). Other used analytical grade chemicals
were purchased from Merck. The pH of solutions was appropriately
adjusted with sodium hydroxide or hydrochloric acid solution.
Deionized water was used throughout the experiments.
2.2. Pretreatment of the zeolite and production of clinoptilolite nano-
particles
The natural clinoptilolite was mechanically pretreated, by
crushing in an agate mortar and sieving in analytical sieves for the
separation of <100 mm particle-size fractions. The obtained
powder was used to prepare nano-particles of zeolite using a
planetary ball mill (PM100; Retsch Corporation) under controlled
milling conditions such as: rotational speed, ball to powder ratio as
well as, grinding time, so the crystallinity retained during the size
reduction process [47]. The milling speed, milling duration and
balls to powder ratio were 600 rpm, 6 h and 4.0, respectively. In
order to remove any water soluble and magnetic impurities, the
obtained nano-particles were heated at 70 8C in distilled water for
8 h on a magnetic stirrer (n = 3). In order to reach fixed water
content, after filtration, washing and drying, the purified material
was stored in a dish in a desiccators (containing a saturated sodium
chloride solution instead of solid calcium chloride or other
common materials) for 2 weeks.
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2.3. Catalyst preparation
In ion exchange experiments, 5 g of the nano-clinoptilolite
powders was added to 250 mL 0.1 M Zn2+ solution (as nitrate salt)
and the suspension was shaken for 24 h in a polyethylene bottle at
room temperature. In order to prepare the ZnO-nanoclinoptilolite
catalyst (ZnO-NCP), the obtained Zn-exchanged nano-clinoptilolite
sample (Zn-NCP) was calcined at 450 8C in a furnace for 24 h. Bulk
ZnO was prepared in the same method by calcination of solid zinc
nitrate particles at 450 8C.
2.4. Characterization techniques
X-ray diffraction patterns of the samples were recorded using a
Bruker diffractometer (D8 Advance) with Ni-filtered copper radia-
tion (Ka = 1.5406 Å) in 2u range of 5–808. FT-IR spectra of the
samples were recorded on KBr pellets with a Nicolet single beam FT-
IR spectrometer (Impact 400D) in the range of 400–4000 cm1 at
room temperature. DRS spectra of samples were recorded using
Shimadzu UV 3600 equipped with an integrating sphere at room
temperature in the wavelength range of 200–900 nm. BaSO4 was
used as the reference material. The spectra were recorded at room
temperature in the wavelength range of 190–900 nm. The surface
morphology of samples was studied using a Philips XL30 scanning
electron microscope (SEM). The surface texture properties of
samples were determined in equipment Quantachrome Corporation
(model Nova 1200). Before this study, all samples were heated at
250 8C for 3 h. The amount of zinc in the catalysts was measured by
atomic absorption spectrometer, Perkin Elmer AAnalyst 300 (Air-
C2H2, l = 324.8 nm). For this goal, 2 mL 1:1 HNO3:HClO4 was added
to an accurate amount of each catalyst in polyethylene beakers and
heated until dried. This process was repeated 3 times and then 2 mL
HF was added and heated to destroy the zeolite framework. Finally,
10 mL diluted HCl was added and heated for 20 min. The obtained
solution was filtered and diluted in a 50 mL volumetric flask and
finally used for the determination of zinc. TG and DTG were recorded
for the samples using Model Setaram (STA) units in the range of 50–
700 8C with temperature rise of 10 8C min1. The TEM images of
samples were recorded using Transmission Electron Microscope S-
3500N with Absorbed Electron Detector S-6542 (Hitachi Science
System Ltd). The absorption spectra were registered on a double
beam spectrophotometer (Carry 100 Scan) in quartz cells with 1 cm
optical path length. The absorbance of samples before and after
irradiation process was used to calculate the degradation extent of
the pollutant.
The pH of point of zero charge of the catalyst, pHpzc, was
determined as follows [48]: The pH of a series of 50 mL 0.01 M NaCl
solutions was adjusted to a value between 2 and 12 by adding HCl
0.1 M or NaOH 0.1 M solution in closed Erlenmeyer flasks. Before
adjusting the pH, all solutions were degassed by purging N2 gas to
remove dissolved CO2. The pH of these solutions was recorded as
the initial pHs (pHI). Then, 0.2 g of ZnO-NCP was added and the
final pH (pHF) was measured after 48 h. Finally, the plots of pHF
versus pHI and also pHI versus pHI were constructed which the
intersection of these curves determines the pHpzc.
2.5. Photocatalytic degradation experiments
A cylindrical Pyrex-glass cell (5 cm inside diameter and 10 cm
height) was used as a reactor. A 20 mL solution of 10 ppm 4-
nitrophenol (NPh) at pH = 8 containing 0.25 g L1 catalyst was
introduced in the reactor. The suspension was irradiated with a
medium pressure Hg lamp (75 W, 253 nm, Philips, which was
positioned above the reactor) under continuous magnetic stirring.
The blank solution had the same condition of analyte solution
without the catalyst. During the irradiation, the suspension was
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sampled out at the regular time intervals. Then absorbance of the
clear solutions was recorded at the lmax = 400 nm and used to
calculate the degradation extent by the following equation:
A0  At
Degradation % ¼  100
A0
where A0 and At are the initial and final absorbance of the PHZ
solution. A0 and At relate to the initial (C0) and final (C)
concentrations according to the Beer–Lambert law, respectively.
It is important to mention that the photodegradation of 4-
nitrophenol follows the pseudo first-order kinetics according to
the Langmuir–Hinshelwood model, so the photodegradation rate
of NPh could be expressed by the following equation:
ln C
¼ kt
C0
The rate constants (k) were calculated from the slopes of the
straight-line portion of the plots of ln(C/C0) versus t as a function of
the used experimental parameters.
3. Results and discussion
hexagonal phase of ZnO. The low intensity of these peaks is due
to low loading of ZnO in the zeolite structure and overlapping of its
lines with the diffraction peaks of zeolite in this region.
Presence of the broad lines in the XRD patterns agrees with the
formation of nano particles during the ball-milling process. So, the
average sizes of NCP, Zn-NCP and ZnO-NCP samples were
respectively determined about 30.8, 33.3 and 39.4 nm using b,
the excess of width line of the diffraction peak in radians, and u, the
Bragg angle in degrees, and using following Scherrer equation [51].
0:89l
D¼
b cos u
3.1.2. FT-IR investigations
The FT-IR spectra of the NCP, Zn-NCP and ZnO-NCP samples are
shown in Fig. 2. The internal vibrations of T–O (considered
insensitive to zeolite structure) and the vibrations of the external
linkages between tetrahedral, correspond to topology and the
mode of structure arrangement are two groups of vibrations in all
zeolitic structures. The FT-IR band connected with the internal Si–
O(Si) and Si–O(Al) vibrations in tetrahedral or alumino- and silico-
oxygen bridges lies in the range of 1200–400 cm1, while the
bands due to the presence of zeolitic water lie in the range of 1600–

3.1. Characterization

3.1.1. XRD patterns

X-ray diffraction (XRD) patterns of the nanoclinoptilolite (NCP),
Zn-exchanged nanoclinoptilolite (Zn-NCP) and ZnO nanoclinopti-
lolite (ZnO-NCP) samples were recorded and the corresponding
patterns are shown in Fig. 1. The characteristic lines at 2u values of
10, 11.4, 17.4, 23, 26, 28.2, 30.2 and 328 (in the pattern ‘a’ in Fig. 1)
can be indexed to clinoptilolite crystalline structure data in the
library of the instrument [JCPDS No. 39-1383]. Good agreement
between the results shows that the original natural zeolite
includes clinoptilolite structure as major component. XRD pattern
also showed that the used zeolite tuff includes slight amounts of
quartz (3.5%) and cristobalite (7.8%) phases as impurities.
Comparing the XRD patterns shows no considerable shifts at
the peaks position in the XRD patterns of the raw and treated
samples. But, decrease in the intensity of the calcined sample is due
to possible formation of some amorphous structure [49]. As shown
in Fig. 1a, the peak corresponding to the (0 2 0) plane of the zeolite,
has the highest intensity variation because its intensity is mainly
associated with differences in the nature, amount and position of
the extra-framework species in the clinoptilolite channels [50].
The weak diffraction peaks in the pattern (c) especially in the 2u
range between 30 and 408 are in agreement with the JCPDS file for
ZnO (JCPDS 36-1451), which can be indexed as a wurtzite

Fig. 1. XRD patterns of NCP (a), Zn-NCP (b) and ZnO-NCP (c). Fig. 2. FT-IR spectra of NCP (a), Zn-NCP (b) and ZnO-NCP (c).

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3700 cm1 [52]. Changes of the characteristic bands took place
between the host zeolite NCP (the values in the parentheses) and the
host–guest materials Zn-NCP and ZnO-NCP. For the Zn-NCP, the
characteristic bands are seen at 471 (472) cm1, 675 (671) cm1,
876 (887) cm1 and 1072 (1076) cm1 that show slight shifts for
some bands compared with the bands of the NCP zeolite (Fig. 2a and
b). The same shifts can be shown for the ZnO-NCP at 477 (472) cm1,
675 (671) cm1, 799 (796) cm1 and 1049 (1076) cm1. In addition,
some changes observed for the structural OH vibrations bands in the
region between 3500 and 3700 cm1 which relates to the bridging
OH groups in BBAl–OH–SiBB and other hydrogen atoms on different
framework oxygen atoms of NCP. These changes indicate that there
is complete coverage between ZnO and OH groups existing in the
intra-channels and extra-channels surfaces of NCP. In the other
word, because of the presence of OH groups inside and outside of the
channels in the NCP structure, and regarding the complete
disappearance of the OH characteristic absorption peak in the
spectrum of the ZnO-NCP (compare Fig. 2a and c), it can be
concluded that there are complete interactions between all OH
groups and ZnO [53]. Based on the results of the FT-IR study, we
conclude that during the calcination process a certain amount of ZnO
reacts with the surface –OH of the raw zeolite, and creates the new
bonds like Zn–O–Si and Zn–O–Al. The bond stress is strong enough to
keep the ZnO caught on the zeolite during the photodegradation
process and even the recycling process.
Breck demonstrated that when a transition metal cation enters
into a zeolitic structure during an ion exchange process, the zeolite
structure remains unchanged and only some slight shifts occur at
the peaks where located at the right side of the framework Si(Al)–O
stretching vibration band [54]. Comparing the spectrum (a) and (b)
in Fig. 2 shows slight shifts in the peaks positions which are in
accordance with Bercks’ results, confirming incorporation of zinc
cation to zeolite channels during the ion exchange process. Same
shifts were also observed for calcined sample. These observations
confirm sufficient loading of Zn2+ and ZnO inside the zeolite during
the ion exchange and calcination processes.
be noted that, unlike the synthetic zeolites, the spectrum of natural
clinoptilolite can be change under calcination [56] which shows a
red shift in the band-gap transition.
3.1.4. Thermal analysis studies
Water in the silicate minerals present in two forms as intact
molecules and as OH groups formed on dissociation of water
interacting with metal (Si4+, Al3+, B3+) and O2 ions. Physically
adsorbed water is mainly eliminated at T < 100 8C. Hydroxyls are
removed through the associative desorption mechanism at 100–
300 8C or higher hydroxyls groups leave the surface mainly at 200–
500 8C, moreover the isolated OH groups are eliminated at higher
temperatures [52]. At temperatures higher than 400 8C almost all
OH-groups on the silicate surface are isolated. The presence of
different exchangeable cations in zeolites leads to changes in the
required temperature for elimination zeolitic water, which is held
in a few stages [52]. The TG/DTG curves of the CP, NCP, Zn-NCP and
ZnO-NCP samples are shown in Fig. 4 which respectively shows the
weight losses of 10%, 9.5%, 8.9% and 4.4%. These results show a
smaller weight loss for ZnO-NCP than the other samples, which in
turn show lower hydration of the ZnO-NCP sample due to
conversion of Zn2+ to ZnO.
3.1.5. SEM, TEM and textural investigations
The surface texture properties of the raw clinoptilolite (CP),
NCP, ZnO supported clinoptilolte (ZnO-CP) and ZnO-NCP samples
were determined by N2 adsorption and the obtained results are
summarized in Table 1. As shown, the surface area of the micro
sized CP increased when it was changed to nano-particles, while
the total pore volume decreased. This is due to elimination of
distance space between micro and meso sized particles by

3.1.3. DRS studies

The UV–vis/DRS was also used to probe the band structure (or
molecular energy levels) in the materials since UV–vis light
excitation creates photogenerated electrons and holes [55]. The
UV–vis DRS spectra of the CP, NCP, Zn-NCP and ZnO-NCP samples
are shown in Fig. 3. The spectrum of CP shows an absorption band
about 700 nm due to impurities of the CP, because the synthetic
clinoptilolite does not absorb in the range of l > 300 nm [56]. Also,
zeolites usually have substantial intrinsic absorption in the range
of l < 350 nm. The absorption bands in the short-wavelengths are
inherent in different types of zeolites and they can originate from
the charge transfer O2 ! Al3+ with participation of aluminum
atoms at specific locations (surface, corners, defects, etc.). It should

Fig. 3. Diffuse reflectance spectra of CP (a), NCP (b), Zn-NCP (c) and ZnO-NCP (d). Fig. 4. Thermal analysis curves of CP (a), NCP (b), Zn-NCP (c) and ZnO-NCP (d).

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changing to nano particles. Loading of ZnO semiconductor by both
micro and nano sized clinoptilolite decreases the surface area and
also the total pore volume due to probable blocking of some zeolite
pores by ZnO. In general, the surface texture data is in coherence
with the XRD data of particle size. The formation of ZnO in the
zeolite channels and surface leads to an increase in the solid
particle size and it accompanied by a decrease in surface area and
pore volume.
The surface morphology of the NCP (a–c), Zn-NCP (d) and ZnO-
NCP (e,f) was studied by scanning electron microscopy and the
corresponding SEM pictures are presented in Fig. 5. The crystallites
of the unloaded zeolite have a very well defined layered like
crystals. The images of the loaded samples also show the same
crystals that indicate the zeolite crystallites are not affected by
Zn2+ and ZnO loading. Although, there are some particles with
micro-dimension in the SEM pictures of the raw NCP, but the major
particles have nano dimension covering the range from 43 to
65 nm. The particles size of the nano particles of Zn-NCP showed a
small increase in the range of 48–70 nm. According to the SEM
images of the ZnO-NCP, it seems that the pores of nano zeolite were
blocked by ZnO and porosity of the catalyst decreased. This causes
an increase in the particles size of the ZnO-NCP catalyst to 50–
85 nm. This also confirms that the surface ZnO in the ZnO-NCP
catalyst take part in the photocatalysis phenomena.
To have more precise estimation about the particle size of the
prepared samples, TEM images of NCP and ZnO-NCP were also
recorded and the corresponding images are respectively shown in
Fig. 5g and h. As shown, major particles of clinoptilolite have sizes
less than 100 nm. According to images, clinoptilolite particles retain
its dimension less than 100 nm after loading of ZnO particles.
3.2. Effect of the experimental parameters on the photodegradation
efficiency
3.2.1. Effect of support
In preliminary experiments, the surface adsorption and also
photolysis extents were determined and the results showed
maximum 2–3.5% surface adsorption in removing of the pollutant.
As shown in Fig. 6, direct photolysis does not show considerable
degradation for 4-NPh which in turn confirms the effective role of
the used catalyst in the photodegradation process.
In order to determine the role of the zeolite in the
photodegradation process, some experiments were carried out
using the bulk ZnO, ZnO-NCP and ZnO-supported micro-sized
clinoptilolite (particle size <10 mm, ZnO-MCP). The amount of
loaded ZnO into the zeolite was measured by atomic absorption
spectroscopy (by determination of Zn2+) and was found 6.71 mg
ZnO per gram of the catalyst (equal to 2.07% ZnO). To determine
whether the degradation of 4-nitrophenol by ZnO takes place or
not, a suspension containing 6.71 mg L1 ZnO (10 ppm 4-
nitrophenol, pH = 8) was prepared and the degradation extent of
the pollutant was studied. The obtained results, which are shown
in Fig. 6, indicate that the unsupported ZnO show the smaller
degradation efficiency with respect to the supported ZnO. On the
other hand, in the case of ZnO-supported onto zeolite surface, the
adsorption capacity of the zeolite enhances the chance of OH
radicals attacking the adsorbed 4-nitrophenol, resulting in faster
Table 1
Some surface characteristics of samples.
Sample SBET (m2/g) Vp (cm3/g)
CP 53.14 0.12
NCP 115.23 0.09
Zn-NCP 103.12 0.08
ZnO-NCP 45.51 0.05
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5
degradation. Also, zeolite enhances the photocatalytic efficiency by
preventing the electron/hole recombination [41]. In addition, the

OH radicals on the surface of ZnO is easily transferred onto the
surface of zeolite. This means that the organic pollutants, which
have already been adsorbed on the nonphotoactive zeolite, have a
chance to be degraded due to the appearance of OH resulting in
the enhancement of the photodegradation performance of ZnO-
zeolite [57]. Based on the results, ZnO-NCP showed 22% enhance-
ment in the efficiency with respect to ZnO-MCP.
The catalytic efficiency of the NCP toward 4-nitrophenol
degradation was also studied at above-mentioned conditions
and no considerable degradation observed, while the Zn-NCP
showed a better photoreactivity. We believe that some Zn2+
cations in Zn-NCP bind to framework oxygen atoms and exhibit as
semi-ZnO semiconductor which increases the degradation extent
of the pollutant. The results demonstrate that the active centers are
ZnO in the zeolite structure.
The photoreactivity of the used catalyst was also compared with
TiO2. As shown, the proposed catalyst has good efficiency with
respect to TiO2. Also the used method is very cheap and economic.
3.2.2. Effect of ZnO loading
The ZnO loading in slurry processes is a significant factor that
can affect performance of the used catalyst [58]. The influence of
the ZnO loading onto the NCP toward 4-NPh degradation was
studied using the same above-mentioned experimental conditions
(10 ppm of 4-NPh, pH = 8, 0.1 g L1 of the ZnO/NCP catalyst). Four
catalysts were prepared by ion exchanging of the NCP in 0.1, 0.2,
0.3 and 0.5 M of Zn2+ aqueous solutions. According to the results of
atomic absorption of zinc determination, the ZnO content of the
obtained catalysts was obtained as: 2.07, 2.45, 2.61 and 3.71%,
respectively which respectively showed the degradation efficien-
cies of 33.2, 25.4, 16.7 and 10.8% during 150 min irradiation time.
The obtained results showed the maximum activity for the ZnO/
NCP containing 2.07% ZnO and thereafter decreased. On the other
hand, following factors affect the degradation of 4-NPh beyond this
ZnO loading. At high ZnO loading, particles may tend to aggregate
which reduces the interfacial area between the reaction solution
and the photocatalyst, and hence it decreases the number of active
sites on the catalyst surface [59]. Also, the excess of ZnO particles
may mask some parts of the photosensitive surface and
consequently hinder or even reflect light penetration [58]. In
these aggregates, deactivation of activated molecules due to
collision with the ground state ZnO molecules can also reduces the
degradation extent. Hence an optimum amount of the ZnO has to
be added in order to avoid unnecessary excess and also ensure total
absorption of light photons for efficient photo-mineralization [60].
3.2.3. Effect of pH
It is well known that the pH of solution has a significant
influence on the degradation rate of some organic compounds in a
photocatalytic process [61,62]. The effect of pH in the range of 2–
12 on the degradation efficiency of 4-NPh is presented in Fig. 7.
Based on the results, the degradation efficiency increased from pH
2 to 8 and thereafter decreased. Generally, the effect of pH on the
organic degradation assisted by the semiconductor oxides has
been related to the establishment of acid–base equilibria govern-
ing the surface chemistry of metal oxides in water according to the
following reactions [26]:
dp (nm) ZnOH2 þ $ ZnOH þ Hþ
2180
ZnOH þ OH $ ZnO þ H2 O
35
41
The pH at which the surface of an oxide is uncharged is defined
68
as the zero point charge (pHPZC). It has been reported that the pH of
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Fig. 5. SEM pictures of raw NCP (a–c), Zn-NCP (d) and ZnO-NCP (e and f), TEM images of NCP (g) and ZnO-NCP (h).

point of zero charge for ZnO is about 9 [26]. In our idea, a layer of
ZnO particles has formed around the clinoptilolite nano-particles
and hence pHPZC of the composite is about 9. At the pH values lower
than 9, the attractive forces between the positive excess charges on
the surface of the catalyst (due to specific adsorption of H+ ions)
and free electrons of nitrogen and oxygen atoms of 4-NPh favor the
approach of pollutant molecules to the catalyst surface [63].
Accordingly, the best photodegradation results are desirable at
stronger acidic pHs, while such result was observed at pH 8.0. In
the strong acidic pHs, chloride anions (due to adding of HCl) react
with OH radicals and produce OCl radicals with less reactivity than
the OH radicals. Due to partial protonation of free electrons of 4-
NPh at stronger acidic conditions, by increasing the repulsive
forces of protonated oxygen on nitrogen atoms with positive
surface catalyst, less pollutant molecules can reach the catalyst
surface where hydroxyl radical will form. Hence the degradation
efficiency decreases [64]. Also, these acidic conditions may
dissolve the ZnO from the catalyst surface and reduces the
photodegradation efficiency. To confirm this, the leached zinc
extent was determined as a function of solution pH by atomic

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UV min1) as a function of the catalyst weight on the degradation of 4-

NCP NPh are also collected in Table 2. It is clear that the photodegrada-
60 Zn-NCP
tion rate increases with increasing in the weight of the catalyst,
ZnO
50 reaches the highest value at 0.25 g L1 and thereafter decreased.
ZnO-NCP
When the concentration of the catalyst rises, more active ZnO
Degradation (%)

TiO 2
40 centers is available for receiving photons to produce electron/hole
pairs, consequently increases the photodegradation rate, but
30 beyond the optimum value, the solid particles increasingly block
the penetration of the photons. So the overall number of the
20 photons that can be reached to catalyst particles and the
production of OH radicals decreased with the loading of the
10
catalyst [25]. Also, the aggregation of solid particles when a large
amount of catalyst used, reduces the effective surface area of the
0
20 40 60 80 100 120 140 160 180 catalyst [65]. In the aggregates, deactivation of activated ZnO
molecules due to collision with the ground state ZnO molecules
time (min)
reduces the photogenerated hydroxyl radicals. Light scattering by
Fig. 6. Effect of zeolite on the photocatalytic activity: 10 ppm of 4-NP concentration, the particles may also be other reason for the decrease in the
pH = 8, irradiation time = 180 min. degradation rate at higher amounts of the used catalyst [64].

3.2.5. Effect of the initial concentration of 4-NPh

absorption determination of zinc. The results showed that an The substrate level is one of the defining factors of the
increase in the leached zinc cations in pH = 2. Because of low guarantee for effective transformation of a pollutant [66]. The
concentration of the leached zinc cations it was only followed photocatalytic degradation of 4-NPh at initial concentrations
qualitatively. The higher leached zinc extent at pH = 2 causes a covering the range from 3 to 30 ppm was investigated under the
decrease in the degradation efficiency which in turn confirms that optimized conditions (catalyst weight = 0.25 g L1, pH = 8). Fig. 9
the lower efficiency of the homogeneous photocatalysis by zinc shows the maximum photocatalytic removal of 4-NPh at initial
cations toward the degradation of 4-NPh. concentration of 10 ppm. Increasing initial 4-NPh concentration
When the pH > pHzpc, the surface of the catalyst is negatively enhances the rate of the liquid phase reaction, and surface reaction
charged and 4-NPh molecules may be repelled, resulting in no as well, at least of the initial steps of the complex degradation
adsorption of 4-NPh which hinders the degradation of 4-NPh [19]. mechanism. On the other hand, increasing in the initial concen-
While it is desirable to increase the degradation efficiency at tration of 4-NPh bring more pollutant molecules near the catalyst
stronger basic pHs due to present higher hydroxyl anions, but a surface, where the hydroxyl radicals will form. In this case,
reverse trend was observed. Same results were observed in our hydroxyl radicals that have short few nano-second lifetime
previous work [42] which confirms that in presence of high immediately react with 4-NPh molecules [67]. Meanwhile, the
hydroxyl anions concentration, deactivation of produced hydroxyl experimental results show that the negative effects of the 4-NPh
radicals with hydroxyl anions is considerable, resulting less other concentration depress the positive ones [23]. By increasing in the
reactive radicals. Also, radical–radical reaction may take place at concentration of 4-NPh, some of the UV photons were absorbed by
higher basic pHs between hydroxyl radicals due to high the substantial amount of 4-NPh molecules. This in turn reduces
concentration of the produced radicals [44]. the quantity of the absorbed effective photons by the surface of the
The rate constant values, k (min1), as a function of solution pH
were calculated from the straight-line portion of the first-order
Table 2
plots and the obtained results are listed in Table 2. Reaction rate constants of 4-NP degradation as a function of some experimental
parameters.
3.2.4. Effect of the catalyst weight
Parameter Value k  1000 (min1)
The effect of the photocatalyst weight in the range of 0.25–
5 g L1 was studied on the photodegradation of 4-NPh and the pH 2 0.2
4 1.2
obtained results are presented in Fig. 8. The rate constant values (k,
8 2.0
10 0.9
40 12 0.5
pH=2
Catalyst mass (g L1) 0.05 0.5
pH=4
0.25 2.8
30 pH=8 0.5 1.8
pH=10 2.5 1.4
Degradation (%)

5.0 1.2
pH=12
Concentration of 4-NP (ppm) 3 0.5
20
5 0.6
7 1.7
10 2.6
10 15 1.4
20 0.8
C (H2O2) (mM) 1 1.4
0 5 2.2
15 2.3
25 17
20 40 60 80 100 120 140 160 180 50 6.7
C (KBrO3) (mM) 0.5 1.2
time (min)
1 1.6
5 11.8
Fig. 7. Effect of pH on photodegradation efficiency: 0.1 g L1 of catalyst, 10 ppm of
10 7.2
4-NP concentration, irradiation time = 180 min.

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50 The influence of hydrogen peroxide in the photocatalytic

degradation of 4-NPh is presented in Fig. 10. According to the
0.05 g/L
0.25 g/L
straight segment of plots of ln C/C0 versus time, the rate constant
40
0.5 g/L values, k (min1), were calculated as a function of hydrogen
2.5 g/L peroxide dose and the results are listed in Table 2. The degradation
Degradation (%)

30 5 g/L rate of 4-NPh increased with increasing in the H2O2 concentration

up to 25 mM and thereafter decreased. This is because of the
reaction of hydrogen peroxide with conduction band electrons and
20 the superoxide radical anion to yield hydroxyl radicals and anions
as follows [58]:
10
H2 O2 þ e ! OH þ HO
0
20 40 60 80 100 120 140 160 180 200 220
time (min) H2 O2 þ O2  ! OH þ HO þ O2

Fig. 8. Effect of catalyst weight on photocatalytic activity: 10 ppm of 4-NP These reactions enhance the reactivity due to the formation of
concentration, pH = 8, irradiation time = 210 min. additional oxidizing species and also the suppression of e/h+
recombination. Since hydrogen peroxide is a better electron
acceptor than the molecular oxygen, it could act as an alternate for
catalyst. Hence, the quantity of the excited ZnO electrons produced
oxygen and hence enhances the degradation efficiency. When
by effective photons was decreased, making the generating holes
H2O2 is in excess, it acts as a powerful hydroxyl scavenger [69] as
lessened. Simultaneously, a large amount of impurities, interme-
shown in the following equations:
diate and other organic substances may probably adsorbed on the
surface of the catalyst, making it more difficult for holes to enter
the solution contact to the catalyst surface. Finally fewer hydroxyl H2 O2 þ  OH ! HO2  þ H2 O
radicals will form at higher 4-NPh concentration [68]. The rate
constant values, k (min1), as a function of the initial 4-NPh
concentration, which have calculated from the results of the plot of HO2  þ  OH ! H2 O þ O2
ln C/C0 versus time, are listed in Table 2.
These reactions have a negative effect on the hydroxyl radicals,
3.2.6. Effect of hydrogen peroxide because of consuming the produced hydroxyl radicals and also
The photocatalytic degradation of organic pollutants depends changing the more reactive hydroxyl radicals to the less reactive
upon their reactions with the OH radicals. Therefore, the electron HO2 [67]. Thus, addition of optimal concentration of H2O2 shows a
acceptors have been used to enhance the degradation rates since beneficial effect on the photocatalytic degradation of 4-NPh.
they generate more OH radicals [59]. Also, the electron–hole
recombination is one of the main drawbacks in the application of 3.2.7. Effect of KBrO3
photocatalysis as it causes waste of energy. In the absence of a Potassium bromate as another electron acceptor was also added
suitable electron acceptor or donor, recombination step is into the suspension in order to enhance the formation of hydroxyl
predominant, and thus, it limits the quantum yield. Thus, it is radicals and also to inhibit e/h+ pairs recombination [70]. The
crucial to prevent the electron–hole recombination to ensure effect of KBrO3, in the photocatalytic degradation of 4-NPh is
efficient photocatalysis [69]. Hydrogen peroxide as an electron shown in Fig. 11. Based on the rate constant values in Table 2, it can
scavenger accepts a photo-generated electrons from the conduc- be seen that the degradation rate for the decomposition of the
tion band and thus prevents electron–hole recombination forming pollutant increased with increasing in the concentration of KBrO3.

OH radicals. In addition, UV photons (from the radiation source) The enhancement of the removal rate is due to the reaction
facilitate the decomposition of hydrogen peroxide, forming between BrO3 and eCB which reduces the recombination of
hydroxyl radicals [25]. electron-hole pairs according to the following reactions [71]:
BrO3  þ e CB þ 2Hþ ! BrO2  þ 3H2 O

50

3 ppm 100
40 5 ppm
90
7 ppm
Degradation(%)

1 mM H2O2
Degradation(%)

30 10 ppm 80
5 mM H2O2
15 ppm 15 mM H2O2
70
20 20 ppm 25 mM H2O2
60 50 mM H2O2
10
50

0 40
20 40 60 80 100 120 140 160 180 20 40 60 80 100 120 140 160 180
time (min) time (min)

Fig. 9. Effect of initial concentration of 4-NP on the photodegradation efficiency: Fig. 10. Effect of H2O2 on the photodegradation efficiency: 0.25 g L1 of catalyst,
0.25 g L1 of catalyst, pH = 8, irradiation time = 180 min. 10 ppm of 4-NP, pH = 8, irradiation time = 180 min.

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BrO3  þ 6e CB þ 6Hþ ! ½BrO2  ; HOBr ! Br þ 3H2 O
Due to reduction potential of bromate ions ðe BrO =BrO ¼
3 2
1150 mV; e O =O  ¼ 155 mVÞ BrO3 is more oxidizing agent
2 2
than the oxygen. Bromate ions may also change the mechanism of
the reaction. Although reduction of bromate by electrons prevents
direct production of hydroxyl radicals, but bromate ions act as an
oxidizing reagent. Hence it can produce other oxidizing agents like
BrO2 and HOBr [67].
3.2.8. Reusability of the photocatalyst
Reusability of the catalyst for the degradation of 4-NPh was also
evaluated. The catalyst was separated from the solution by
filtration, washed with water and dried at 100 and 200 8C. The
dried catalysts were used for the degradation of 4-NPh, employing
similar experimental conditions. The degradation extents after
four runs are about: 33, 24, 14 and 6% for drying temperature of
100 8C and 35, 29, 21 and 14 for temperature drying of 200 8C. The
decrease in the degradation percentage is explained by adsorption
of organic intermediates and by-products of the photodegradation
process in the cavities and on the surface of the photocatalyst that
influences the surface activity of the catalyst [41]. Hence, for the
dried catalyst at 200 8C, the decreasing of the degradation
percentage is lower than the other case. On the other hand, at
higher temperature the excess of adsorbed molecules on the
surface was disappeared and the excess of degradation centers was
released. Thus the photocatalyst has higher effective surface. Also,
in both case, the leached zinc cations into the solution decreases
the semiconductor as the active sites on the catalyst surface. This in
turn reduces the photoreactivity of the remained catalyst. In
addition, in repetitive uses of the catalyst, a loss was occurred in
the amount of the reused catalyst particles. Hence it decreases the
degradation efficiency in the later runs.
3.2.9. Confirm the photodegradation results
To confirm the carrying the photdegradation of 4-NPh based on
the UV–vis spectra, chemical oxygen demand (COD) and HPLC
were used. The chemical oxygen demand test has been widely used
as an effective technique to measure the organic strength of
wastewater. The test allows the measurement of waste in terms of
the total quantity of required oxygen for the oxidation of organic
matter to CO2 and water [72]. The COD of the 4-NPh solution before
and after treatment was determined. The results showed a
decrease in the remaining COD values as 784, 512 and 120 mg L1
1 for irradiation times of 0, 90 and 150 min, respectively. This
decrease confirms the mineralization of 4-NPh molecules.
The degradation extent of the 4-NPh pollutant was also
confirmed by the conventional HPLC measurement [73]. The HPLC
100
80
Degradation(%)
60
40
20
20 40 60 80 100 120 140 160
time (min)
Fig. 11. Effect of KBrO3 on the photodegradation efficiency: 0.25 g L1 of catalyst,
10 ppm of 4-NP, pH = 8, irradiation time = 150 min.
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j.jiec.2013.06.026
9
chromatograms of 4-NPh solutions are presented in Fig. 12. A sharp
peak of 4-NPh solution was detected before the degradation
process (Fig. 12a) and the decreasing in the peak intensity was
observed after the degradation process (Fig. 12b). This observation
also confirms the degradation of 4-NPh by ZnO/NCP catalyst.
The changes in the absorption spectra of the 4-NPh solution
during the photocatalytic degradation at different irradiation times
are also presented in the inset of Fig. 12. The 4-NPh shows a band with
a maximum absorption at 400 nm. The decrease in the absorption
peak intensity actually indicates the degradation of 4-NPh.
According to the obtained results, the proposed mechanism for
4-NPh degradation by using the ZnO/NCP photocatalyst is
suggested as follows:
During the photocatalytic process, the adsorption of photon by
semiconducting ZnO leads to the promotion of an electron from the
valence band to the conduction band producing electron–hole pair
(Eq. (1)). Recombination of the photogenerated electrons and holes
may occur (Eq. (2)) and indeed it has been suggested that pre-
adsorption of 4-NPh substrate onto the photocatalyst is a
prerequisite for highly efficient degradation. The holes at the
ZnO valence band can oxidize adsorbed water or hydroxide ions to
produce hydroxyl radicals (Eqs. (3) and (4)).
ZnO þ hy ! e þ hþ (1)
 þ
e þ h ! heat (2)
hþ þ H2 Oads !  OHads þ Hþ (3)
hþ þ OHads  !  OHads (4)
The photo-generated electrons in the conduction band may
react with oxygen to form superoxide ions (O2) (Eq. (5)). This
radical may form organic peroxides or hydrogen peroxide in the
presence of organic scavengers (Eqs. (6) and (7)). The hydroxyl
radical is a powerful oxidizing agent and attacks to organic
compounds and intermediates (Int.) are formed. These intermedi-
ates react with hydroxyl radicals to produce final products (P).
(Eq. (8)) [3,18]:
e þ O2 ! O2  (5)
O2  þ H2 O þ Hþ ! H2 O2 þ O2 (6)
 
O2 þ 4-NPh ! 4-NP-OO (7)

OHads þ 4-NPh ! Int: ! P (8)
0.5 mM KBrO 3
1 mM KBrO3
5 mM KBrO3
10 mM KBrO3
180
Fig. 12. The HPLC chromatogram of 4-NP solution before degradation (a) and after
degradation (b), conditions of degradation: 0.25 g L1 of catalyst, 10 ppm of 4-NP
concentration, pH = 8, irradiation time = 150 min (inset: decrease in the absorbance
intensity of 4-NP during the photodegradation experiments).
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4. Conclusions
The photocatalytic degradation of 4-NPh using the ZnO/NCP
catalyst and UV light was found to be an efficient technique. The
obtained results indicated that the photodegradation rate of 4-NPh
was affected by the initial 4-NPh concentration, the pH of solution
and the amount of catalyst. The proper addition of hydrogen
peroxide and potassium bromate as electron acceptors could
improve the photodegradation rate which bromate is more
effective than the hydrogen peroxide due to using of smaller dose
of bromate. The zeolite bed showed an important role in the
photodegradation process and the pure ZnO and zeolite did not
have significant photodegradation efficiency. The photocatalytic
degradation of 4-NPh followed the pseudo first-order kinetics
according to the Langmuir–Hinshelwood model. The reduction in
COD and HPLC confirm the destruction of the organic molecules.
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