Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-018-1305-y

REDUCING AIR AND SOIL POLLUTION IN CHINA: ISSUES IN ENVIRONMENTAL TECHNOLOGIES AND
MANAGEMENT

Photocatalytic removal of SO2 using natural zeolite modified by TiO2

and polyoxypropylene surfactant
Nasibeh Amini 1 & Mohsen Soleimani 1 & Nourollah Mirghaffari 1

Received: 25 October 2017 / Accepted: 15 January 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Air pollution due to emission of various hazardous gases such as SO2 into the atmosphere and its control is an important
environmental issue. Application of photocatalysts is considered as a suitable process to control the gaseous pollutants. In this
study, the efficiency of clinoptilolite as a natural zeolite (Ze) modified by TiO2 (Ze-Ti) and a polymeric surfactant
polyoxypropylene (Ze-Ti-POP) for removal of SO2 was investigated. The nanocomposites were characterized by SEM, EDX,
and BET analyses. The photocatalytic oxidation experiments of SO2 by the nanocomposites and natural zeolite were done under
UV irradiation with initial SO2 concentration of 500 ppm in a photoreactor. The effects of different factors including reaction
time, catalyst dose, UV irradiation intensity, humidity content, and calcination temperature and dose of TiO2 were studied. The
modification of clinoptilolite by TiO2 and POP increased considerably the BET specific surface area of the nanocomposites. The
results showed that maximum removal efficiencies of SO2 by Ze-Ti and Ze-Ti-POP under the optimum experimental conditions
were 82.1 and 87.4%, respectively. Adsorption kinetics data well fitted with the Langmuir–Hinshelwood model. Moreover,
reusing of nanocomposites after three regeneration cycles indicated that application of Ze-Ti and Ze-Ti-POP nanocomposites
could be a promising approach for SO2 removal.

Keywords Air pollution . Photocatalyst . Nanocomposites . Clinoptilolite . Sorption . TiO2

Introduction atmosphere and is a precursor to acid rain and stratospheric

Increase of fossil fuel combustion due to industrial activities
and transportation has resulted in an excessive release of ni-
trogen oxides (NOx) and sulfur dioxide (SO2) into the atmo-
sphere in recent years. These pollutants lead to formation of
secondary pollutants such as photochemical smog and ozone
in the presence of sunlight and could adversely affect urban air
quality. SO2 is well known as one of the noxious gases in the
Responsible editor: Suresh Pillai
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11356-018-1305-y) contains supplementary
material, which is available to authorized users.
* Mohsen Soleimani
m.soleimani@cc.iut.ac.ir
1
Department of Natural Resources, Isfahan University of Technology,
Isfahan, Iran
ozone destruction and is harmful for human health through
asthma and respiratory diseases (Niu et al. 2011; Su et al.
2013). Therefore, removal of SO2 from the atmosphere has
been a significant challenge, particularly in developing
countries.
There are several technologies available for removal of
SO2 emissions. Some of these technologies that are used for
removal of SO2 require complex systems and high cost
implementing. Compared to other techniques, photocatalytic
oxidation using the titanium dioxide (TiO2) nanoparticles has
been shown a successful approach in air pollution control
(Anpo and Kamat 2010). TiO2 photocatalysts have been in-
tensively studied and widely applied to environmental purifi-
cation in recent years. Having high specific surface area, fa-
vorable chemical properties, high stability, low cost, and high
efficiency, they are effective for controlling air pollutants
(Anpo and Kamat 2010). Furthermore, mechanism of TiO2
photoreaction only occur under ultraviolet (UV) irradiation,
a drawback for any application where the UV region only

accounts for ~4% of the total solar energy. However, mecha-
nism of TiO2 photoreaction occurs at the presence of UV
irradiation with large band-gap energy of 3.2 eV (λ
≥365 nm) (Anpo and Kamat 2010). Generally, photocatalytic
oxidation of pollutants in the gas phase is more efficient than
the liquid phase (Shang et al. 2002). However, it has also been
reported that the homogeneous and heterogeneous photooxi-
dation reactions of SO2 gas occur upon UV irradiation in the
absence and presence of TiO2, respectively (Shang et al.
2002). A lot of studies were conducted on using of TiO2
photocatalysts to reduce air pollution in 1990 (Zhao et al.
2009). Afterwards, Japanese researchers investigated photo-
catalytic oxidation of NOx using TiO2 photocatalysts in the
ambient atmosphere (Ibusuki and Takeuchi 1994).
Photocatalytic oxidation of SO2 highly depends on some im-
portant factors such as UV irradiation intensity, type of TiO2
supporting materials, and ambient humidity (Ao et al. 2004;
Kachina 2008). It has been reported that the presence of H2O
molecules on the surface of TiO2 plays an important role on
photocatalytic oxidation of pollutants. So that, photocatalytic
activity of TiO2 could be properly maintained (Ibusuki and
Takeuchi 1994; Shang et al. 2002).
In recent years, many researchers reported that the effective-
ness of supported photocatalysts could improve photocatalytic
activity of pure TiO2 (Kachina 2008). However, some studies
have focused on various methods for increasing TiO2 efficien-
cy in removal of environmental pollutants. One of these impor-
tant approaches is incorporation of TiO2 nanoparticles with
porous materials such as silica gel, activated carbon, and clay
minerals, which are often used for adsorbing target contami-
nants (Carriazo et al. 2010; Kibanova et al. 2009; Nieto-Suárez
et al. 2009; Papoulis et al. 2010). Among these different porous
materials, clay minerals such as zeolites (Ze) have been widely
studied, because they are inexpensive and have a useful prop-
erties such as large specific surface area and excellent adsorp-
tion capacity (Hao et al. 2016; Nasonova and Kim 2013).
Additionally, natural zeolites are an interesting kind of alumi-
nosilicate minerals with unique structures, uniform pores, and
channels that they are commonly used as adsorbent (Weitkamp
2000). As a result, a synergetic effect arises between TiO2
nanoparticles and nanoclays can significantly influence the
adsorption and photocatalytic degradation of pollutants.
Torimoto et al. (1996) studied the role of porous solids with
various adsorption capacities such as zeolite, activated carbon,
silica, and alumina for the photocatalytic degradation of
propyzamide which revealed the role of valuable physicochem-
ical properties (e.g., cation exchange and molecular sieves) of
zeolite over other adsorbents on the pollutant removal (Liu
et al. 2014). Besides, several reports have published about
using of polymeric surfactant with high molecular weight such
as polyoxypropylene (POP) in synthesis of clay-TiO2 nano-
composites that can increase pore volume and pore diameter
of nanocomposites (Chou et al. 2003; Lin et al. 2001). Chen
Environ Sci Pollut Res
et al. (2012) synthesized montmorillonite-TiO2 composites in
the presence of POP and evaluated photocatalytic oxidation of
methylene blue in water. According to their results, presence of
POP into the structure of montmorillonite-TiO2 composites
could significantly increase the porosity and surface area of
the composites (Chen et al. 2012).
Zeolite-TiO2 (Ze-Ti) composites have been used for degra-
dation of volatile organic compounds (Jansson et al. 2015),
NOx removal (Hashimoto et al. 2001), and H2S removal and
methane production as well (Hao et al. 2016). The photocat-
alytic behavior of the composite materials consisted of miner-
al substrate and TiO2 was investigated for NOx oxidation
which showed different oxidation rates depending on the type
of substrates (Todorova et al. 2014). However, it seems that
there is a lack of information about photocatalytic removal of
SO2 using Ze-Ti nanocomposites. Sulfur dioxide is one of the
main air pollutants in metropolitan cities in Iran because of
industrial activities and diesel fuel consumption by vehicles.
Among the natural zeolites, clinoptilolite are abundant and
low-cost resources which are widely distributed in different
regions of Iran and have a high potential for water, soil, and air
pollution control (Hamidpour et al. 2010; Malekian et al.
2011). Therefore, the aim of this study was modification of
clinoptilolite obtained from the Semnan Mine in Iran as a
natural zeolite with TiO2 nanoparticles in the presence of a
polymeric surfactant (i.e., polyoxypropylene) for removal of
SO2 in a laboratory experiment. Besides, the factors affecting
the removal efficiency of SO2 were investigated to find the
optimal conditions for photocatalytic removal of the pollutant.
Experiment
Photocatalyst preparation
In this research, clinoptilolite as a natural zeolite from Semnan
Mine (Iran), titanium tetraisopropoxide (Aldrich, 97%) as the
precursor of TiO2 photocatalyst, and polyoxypropylene as a
polymeric surfactant were used. Preparation of zeolite samples
was implemented through two processes. At first, zeolite sus-
pension was obtained by dispersion of 2 g raw zeolite into
100 mL distilled water and stirring for 4 h. In the second
process, 2 g of raw zeolite was dispersed into the 100 mL
distilled water and 0.5 g POP was added into the zeolite sus-
pension; afterwards, reaction mixture was stirred for 4 h at
80 °C. TiO2 sol was prepared by the hydrolysis of titanium
tetraisopropoxide in distilled water. Therefore, 6 mL
isopropanol was added dropwise into 31 mL titanium
tetraisopropoxide for a period of 10 min with vigorous stir-
ring. Then, 200 mL distilled water and 2 mL nitric acid were
slowly added and subsequently mixed for 2 h at 80 °C with
vigorous stirring. Afterwards, TiO2 sol was mixed dropwise
with zeolite suspension for 30 min while was vigorously
Environ Sci Pollut Res
stirred. The Ti/clay ratio (mmol of Ti per gram of zeolite) was
3, 7, and 13 mmol/g, which corresponded to about 0.24, 0.56
and 1.04 g of TiO2 per gram of zeolite, respectively. The
suspensions were stirred to be homogenized using a magnetic
stirrer for 6 h and hydrothermally treated at 150 °C for 4 h.
Finally, the obtained suspensions were centrifuged and
washed with distilled water and dried at the 80 °C and then
calcined at different temperatures including 300, 400, and
500 °C for 4 h (Chen et al. 2012; Daniel et al. 2007;
Petkowicz et al. 2010) to find the influence of calcination
temperatures on SO2 removal efficiency of nanocomposites.
Details of experiments have been described in the
BExperimental setup and procedure^ section.
Physicochemical characterization of modified
photocatalysts
The nanocomposites and natural zeolite were characterized
via a series of complementary analytical techniques. The spe-
cific surface area of the samples was determined by nitrogen
adsorption-desorption isotherms (Belsorp mini II Japan). The
results obtained from the specific surface area and pore struc-
ture were characterized by Brunauer–Emmett–Teller and
Barrett–Joyner–Halenda methods. Surface morphology and
semiquantitative elemental analysis were characterized using
scanning electron microscopy (SEM) model PHILIPS XL30-
FEG combined with an energy-dispersive X-ray (EDX) spec-
trometer and operated at 20 kV.
Experimental setup and procedure
The photocatalytic oxidation was evaluated in a fixed bed
continuous flow photoreactor. The photoreactor was made of
a Pyrex glass with capacity of 50 mL and equipped with air
inlet, air outlet, UVA-light lamp and its holder, temperature
controller, mass flow controllers, cooler, and a protected con-
tainer (Fig. 1). The photoreactor was sealed to avoid the leak
of gas. The UV-light source was a 64-W m-2 tube with a
spectral peak centered at 365–380 nm. The nanocomposites
and raw zeolite as well as TiO2 as blank (0.5 g) were placed on
a sample board in the photoreactor and treated at room tem-
perature (25 °C) in an N2 stream to attain an equilibrium
adsorption of SO2. Thus, SO2 and N2 were mixed in a gas
blender and were adjusted by mass flow controllers and intro-
duced into the photoreactor under the pressure of 1 atm and
flow rate of 60 mL min-1. The inlet concentration of SO2
monitored before the experiment was up to 500 ppm.
Analyses of the SO2 concentration at inlet and outlet were
continuously measured using the flue gas analyzer online
(MRU VARIO plus SE, Germany). Details of the experimen-
tal apparatus are shown in Fig. 1.
The removal efficiencies were calculated by comparing the
concentrations of SO2 after and before the experiments. For
each sample, the experiment was repeated for three times.
Investigation of regeneration and reuse ability of the Ze-Ti
and Ze-Ti-POP nanocomposites was carried out at 3 cycles
after washing the samples with a solution of H2O2 (0.03% w/w
in H2O) for 15 min after each cycle at the presence of UVA
lamp with irradiation intensity of 1.6 mW cm−2. Afterwards,
samples were washed with distilled water and dried at the
80 °C. SO2 removal efficiency under UV light irradiation
was calculated according to the following equation:
 
C inlet −C outlet
SO2 removal efficiency ð%Þ ¼  100 ð1Þ
C inlet
where Cinlet and Coutlet are the concentrations of SO2 in the
photoreactor inlet and outlet streams, respectively. The Cinlet
concentration tests were performed under simulated flue gas
condition and without the presence of photocatalyst.
Kinetic model simulation
Langmuir–Hinshelwood (L-H) model of monomolecular re-
action kinetics has been most commonly used for the expres-
sion to explain heterogeneously photocatalytic reactions
(Kachina 2008). Experimental data were also analyzed with
the L-H model which can be expressed as the following equa-
tions:
kKC
r¼ ð2Þ
1 þ KC
1 1 1 1
¼ þ ð3Þ
r k kK C
where r is the reaction rate (mol m−3 s), k is the L-H rate
constant (mol m−3 s), K is the Langmuir adsorption coefficient
(m3 mol), and C is the concentration of the reactant (mol m−3).
A linear plot of 1/r versus 1/C is often obtained, that the
value k as the L-H rate constant and K as the Langmuir ad-
sorption constant can be derived from the combination of the
intercept and the slope of the linear line from the SO2 in the
photocatalytic degradation reaction.
Results and discussion
Structure characteristics of nanocomposites
BET analysis
Generally, the photocatalytic properties of TiO2 are influ-
enced by physicochemical variable such as pore volume,
particle size, and surface area. Table 1 represents the spe-
cific surface area and pore structure information that ob-
tained from the nitrogen adsorption–desorption isotherm
data. From these results, it can be concluded that specific
 Environ Sci Pollut Res

Fig. 1 Schematic diagram of 4

experimental setup for SO2
removal. 1 SO2 cylinder, 2 N2
cylinder, 3 mass flow controller, 4 3 3 6 8
valve, 5 water bath, 6 barometer,
7 gas blender, 8 holder, 9 UV 9
lamp, 10 photoreactor, 11 gas 7 Mix
10
GAS
analyzer, 12 computer 4 3 4
4

3
SO 2 N2
H2O
4 11
12

5
1 2

surface area of Ze-Ti-POP nanocomposites enhanced sig-
nificantly compared to the zeolite particles. However,
when TiO2 nanoparticles and POP surfactant were intro-
duced, the porosity of the synthesized nanocomposites
was greatly increased. According to IUPAC classification,
nitrogen adsorption–desorption isotherms for Ze, Ze-Ti,
and Ze-Ti-POP nanocomposites were a typical type IV
isotherms and pore size distributions were in the mesopo-
rous region (S1).
SEM-EDX analysis
Figure 2 shows the SEM and EDX results of Ze, as well
as Ze-Ti, and Ze-Ti-POP nanocomposites, which indicates a
variation in surface morphology with intercalation TiO2 nano-
particles and polyoxypropylene surfactant. When TiO2 nano-
particles are intercalated into the zeolite, small particles be-
come dispersing on the surface and interlayer spacing of zeo-
lite, and this can be the reason of disordered structures of the
samples. In the image of Ze-Ti-POP nanocomposites, the larg-
er platelets with smooth surfaces can be observed compared to
natural zeolite and Ze-Ti nanocomposites (Fig. 2). More struc-
tural information of the samples was investigated using the
elemental analysis through EDX. By comparison of EDX
analyses of natural zeolite, Ze-Ti, and Ze-Ti-POP nanocom-
posites, it was revealed that with increasing Ti at nanocom-
posites, the amounts of Si, Al, and other metals were signifi-
cantly decreased (Fig. 2).

Table 1 Structural properties of

the natural zeolite (clinoptilolite) Sorbent BJH plot BET plot
and nanocomposites synthe-
sized at various calcination tem- Vp Sp P/P0 Vm dpore Sa
peratures (300, 400 and 500°C) (cm3 g−1) (m2 g−1) (cm3 g−1) (cm3 g−1) (nm) (m2 g−1)

Ze 0.116 30.18 0.120 6.06 18.17 26.41

TiO2 0.125 56.90 0.125 9.62 11.97 42.01
Ze-Ti-(3 mmol Ti/g 0.233 122.98 0.244 26.89 8.34 117.04
zeolite)
Ze-Ti-(7 mmol Ti/g 0.228 134.46 0.234 28.30 7.60 123.21
zeolite)
Ze-Ti-(13 mmol Ti/g 0.223 174.41 0.186 28.01 7.24 167.04
zeolite)
Ze-Ti-300 0.231 116.97 0.239 27.28 8.07 118.75
Ze-Ti-400 0.223 174.41 0.186 28.01 7.24 167.04
Ze-Ti-500 0.256 137.88 0.253 26.63 8.76 115.94
Ze-Ti-POP-300 0.237 198.07 0.237 44.68 4.88 194.49
Ze-Ti-POP-400 0.250 115.4 0.258 27.00 8.78 117.5

Vp primary mesopore volume, Sp specific surface area of primary mesopores, P/P0 total pore volume, Vm mono-
layer volume, dpore mean pore diameter, Sa BET specific surface area, Ze zeolite, Ti TiO2, POP polyoxypropylene
Environ Sci Pollut Res

Fig. 2 SEM images with EDX Ze

spectrum results of zeolite (a), Ze-
Ti (b), and Ze-Ti-POP (c) (Ze ze-
olite, Ti TiO2, POP
polyoxypropylene)

Ze-Ti

Ze-Ti-POP

Effect of different content of TiO2 in nanocomposites Ti nanocomposites decreased with increasing the calcination
on SO2 removal efficiency temperature from 400 to 500 °C (Table 1). Generally, in-
creasing the calcination temperatures could lead to phase
The photocatalytic removal of SO2 using Ze-Ti nanocompos- transformation of anatase to rutile which affects specific sur-
ites having different TiO2 contents is shown in Fig. 3. The SO2 face area (Hussain et al. 2011). Figure 4 shows the removal
removal efficiency was enhanced by increasing TiO2 content efficiency of SO2 by Ze-Ti nanocomposites which enhanced
of nanocomposites probably because of increasing specific by increasing calcination temperature from 300 to 400 °C
surface area (Table 1) which could provide more surface ac-
tive sites and improved the adsorption ability of the nanocom-
posites (Kachina 2008). So, Ze-Ti nanocomposites synthe-
sized with 13 mmol Ti/g clay ratio showed the highest surface
area and SO2 removal efficiency. Furthermore, pore size dis-
tribution was also investigated using BJH plot and results
showed that the maximum distributed pore size of nanocom-
posites was up to 2.10 nm (S2).

Effect of different calcination temperature

of nanocomposites on SO2 removal efficiency

Based on the obtained results, increasing the calcination tem-

peratures from 300 to 400 °C led to increasing and decreas-
ing the specific surface area of Ze-Ti and Ze-Ti-POP nano-
composites, respectively. It revealed that Ze-Ti composites
had a good thermal stability in comparison to Ze-Ti-POP
nanocomposites. However, the specific surface area of Ze-
Fig. 3 Effect of different content of TiO2 in Ze-Ti nanocomposites on
SO2 removal efficiency (conditions: SO2 concentration, 500 ppm;
photocatalyst dose 1.3 g m−3, gas flow, 60 mL min−1, run time 25 min,
UVA irradiation intensity, 6.4 mW cm−2). Ze zeolite, Ti TiO2

Fig. 4 Effect of different calcination temperatures (300, 400 and 500 °C)
of Ze-Ti and Ze-Ti-POP nanocomposites on SO2 removal efficiency
(conditions: SO2 concentration, 500 ppm; photocatalyst dose 1.3 g m−3
gas flow, 60 mL min−1, run time 25 min, UVA irradiation intensity,
6.4 mW cm−2). Ze zeolite, Ti TiO2, POP polyoxypropylene
and then decreased from 400 to 500 °C. However, the re-
moval efficiency of all samples was more than 80%. In the
case of Ze-Ti-POP nanocomposites, increasing calcination
temperature from 300 to 400 °C led to decreasing removal
efficiency of SO2 from 87.4 to 76.5%. It has been reported
that increasing the calcination temperatures more than
500 °C can decrease surface area of composites and conse-
quently has an adverse effect on photocatalytic activity (Sun
et al. 2015; Turki et al. 2014). In this study, Ze-Ti-POP nano-
composites calcined at temperature of 300 °C showed the
highest specific surface area (up to 194 m2 g−1) compared
to the other nanocomposites (Table 1). It seems that increas-
ing temperature from 300 to 400 °C could reduce thermal
stability of Ze-Ti-POP nanocomposites and therefore de-
creased their specific surface area and consequently reduced
the SO2 removal efficiency (Fig. 4).
Kinetic model of SO2 removal by nanocomposites
To assess the photocatalytic performance of natural zeolite
and prepared nanocomposites, the removal rate of SO2 was
calculated over the time. Figure 5 shows the removal percent-
age of SO2 by Ze, Ze-Ti-POP, and Ze-Ti nanocomposites un-
der UV irradiation (UV intensity; 6.4 mW cm-2). The results
showed that the removal efficiencies of SO2 by Ze, Ze-Ti, and
Ze-Ti-POP nanocomposites were 17.5, 82.1, and 87.4%, re-
spectively, whereas the removal efficiency of blank (i.e., TiO2)
was about 46.3%. During the whole process (25 min), SO2
removal rate indicated only a slight difference between Ze-Ti
and Ze-Ti-POP nanocomposites, which demonstrated the high
adsorption capacity of both sorbents. In fact, the synergic ef-
fects between zeolite adsorption and TiO2 photocatalysts was
the main reason for much more efficiency of the Ze-Ti and Ze-
Ti-POP nanocomposites in comparison to the natural zeolite
Environ Sci Pollut Res
Fig. 5 SO2 removal efficiency of sorbents in various times (conditions:
SO2 concentration, 500 ppm; photocatalyst dose 1.3 g m−3 gas flow,
60 mL min−1, UVA irradiation intensity, 6.4 mW cm−2). Ze zeolite, Ti
TiO2, POP polyoxypropylene
which led to further oxidation of SO2. The key process in the
photocatalytic reaction rate is the interaction between ac-
tive oxygen species, such as hydroxyl radical and superox-
ide anion radicals and SO2 that occurs on the surface of the
TiO2 (Campostrini et al. 1994). The removal of SO2 is
usually done through physical adsorption leading to the
formation of strong bonds between SO2 molecules and
TiO2 surface, but chemical absorption may occur through
weak bonds between SO2 molecules and oxidizing species
on the TiO2 surface. As a result of this chemical reaction,
SO3 molecules that remain on the TiO2 surface subsequent-
ly react with water from humid air and convert into H2SO4
on the TiO2 surface (Zhao et al. 2009). According to the
results achieved from the study of Shang et al. (2002)) in
the SO2–O2–N2 system under UV irradiation, SO2 mole-
cules produced singlet-state (1SO2) and triplet-state (3SO2)
species, and this demonstrated that 3SO2 molecules was
mainly dominant species in the photochemical reactions.
The reaction mechanism of SO 2 removal by TiO 2
photocatalysts according to results of previous investiga-
tions is as follows (Sanchez and Augustynski 1979; Shang
et al. 2002; Zhao et al. 2009):
TiO2 þ hv→TiO2 þ e− ðCBÞ þ hþ ðVBÞ ð5Þ
O2 ðgÞ →O2 ðadsÞ →2OðadsÞ ð6Þ
OðadsÞ þ e− →O−ðadsÞ þ hþ →O*ðadsÞ ð7Þ
O* →O−ðadsÞ þ hþ →O*ðadsÞ ð8Þ
O* þ H2 OðadsÞ →2OH* ðadsÞ ð9Þ
Moreover, homogeneous photooxidation reactions of SO2
without nanocomposites and zeolite in the presence of UV
irradiation may occur. The SO2 removal efficiency under ho-
mogeneous photooxidation reactions was about 7%.
Environ Sci Pollut Res

The effect of reaction time on SO2 removal efficiency
is shown in Fig. 4. SO2 removal by the natural zeolite
exhibited different trend and was the highest during the
first 5 min of reaction time. Then, it was reduced because
of zeolite surface saturation by sulfate. Compared to zeo-
lite, Ze-Ti and Ze-Ti-POP nanocomposites showed more
than 97% SO2 removal efficiency after 5 min and then it
showed a constant trend. This revealed the significant ef-
fect of zeolite modification by TiO2 and POP on the gas
removal.
However, Langmuir-Hinshelwood kinetic model was
used to explain the heterogeneous photocatalytic mecha-
nisms of SO2 oxidation using Ze-Ti, Ze-Ti-POP nanocom-
posites, and clinoptilolite. Table 2 shows the k, K, and R2
values for SO2 oxidation via the L-H simulation. The R2
values obtained from the L-H kinetic model ranged be-
tween 0.92 and 0.97. The comparing values obtained from
the L-H kinetic model indicated that the adsorption con-
stant (K) for Ze-Ti and Ze-Ti-POP nanocomposites was
approximately the same and it was more than the adsorp-
tion constant of the natural zeolite. But the reaction rate
(k) value of the zeolite was more than that of Ze-Ti and
Ze-Ti-POP nanocomposites. This explains that higher ad-
sorption constant cannot indicate a higher reaction rate
(Boulamanti et al. 2008). Chiu et al. (2015) explained that
higher R2 values obtained from the L-H kinetic model
could indicate impregnated surface of photocatalyst. By
the way, results of the current study revealed that the
experimental data had a good agreement with Langmuir-
Hinshelwood kinetic model.
Table 2 Langmuir–Hinshelwood parameters obtained from SO2
photocatalytic removal experiments using various sorbents
Sorbents L-H kinetic model
k (mol m−3 s−1) K (m3 mol−1) R2
Ze 154,548 3.8 × 10−9 0.97
−6
Ze-Ti 3 × 10 5.2 × 10−12 0.92
Ze-Ti-POP 5 × 10−6 1.8 × 10−12 0.97
k reaction rate constant, K Langmuir adsorption coefficient, R2 correlation
coefficient, Ze zeolite, Ti TiO2, POP polyoxypropylene
Effect of humidity on SO2 removal efficiency
The effect of humidity on SO2 removal efficiency was studied
at different humidity contents (Fig. 7). The SO2 removal effi-
ciency of Ze-Ti and Ze-Ti-POP nanocomposites increased
with increasing the humidity content from 0 to 2%, and a
further increase in the humidity content to 5% resulted in a
decrease of SO2 removal. It is known that the increasing ad-
sorption of water on the irradiated TiO2 surface leads to re-
combination of the photogenerated electrons and holes and
decreases photocatalytic reactivity (Park et al. 2001). The re-
sults showed that the maximum SO2 removal efficiency of
71.6 and 77.6% were achieved for Ze-Ti and Ze-Ti-POP nano-
composites with 2% humidity, respectively. This could be in
account of SO2 oxidizing by active radicals such as ·OH, ·O2−,
and .O on TiO2 surface. The overall mechanism of photocat-
alytic oxidation in the presence of H2O molecules can be
described by the following reactions (Zhao et al. 2009):

H2 O↔Hþ þ OH− ð10Þ

Effect of UV irradiation intensity on SO2 removal
efficiency OH− þ hþ ðVBÞ→∙OH ð11Þ
þ þ
H2 O þ h ðVBÞ↔H þ ∙OH ð12Þ
As it is seen in Fig. 6, when UV irradiation intensity
increased from 3.2 to 6.4 mW cm−2, SO2 removal effi-
ciency enhanced significantly from 45.2 to 72.6% and
from 60.9 to 77.6% for Ze-Ti and Ze-Ti-POP, respective-
ly. Besides, SO2 removal efficiency without UV irradia-
tion was only 14.9 and 25.1% for Ze-Ti and Ze-Ti-POP,
respectively. However, comparison of the results indicated
that UV irradiation intensity played an important role on
the photocatalytic reaction. The effects of the UV irradia-
tion intensity on SO2 removal efficiency can be explained
by two main reasons. On the one hand, after activation,
the surface of TiO2 by UV irradiation could lead to the
transfer of electrons from the valence band to the conduc-
tion band and therefore electron–hole pairs on TiO2 would
be generated (Sun et al. 2015). Moreover, increasing the
UV irradiation intensity could enhance production of pho-
Fig. 6 Influence of the UVA irradiance on the SO2 removal efficiency
toexcited active species on the surface of TiO2 and sub- (conditions: SO2 concentration, 500 ppm; photocatalyst dose 0.6 g m−3
sequently the photocatalytic activity would increase (Yuan gas flow, 60 mL min−1, run time 25 min). Ze zeolite, Ti TiO2, POP
et al. 2012). polyoxypropylene
 Environ Sci Pollut Res

Fig. 7 Influence of the humidity content on the SO2 removal efficiency

(conditions SO2 concentration, 500 ppm; photocatalyst dose 0.6 g m−3, Fig. 8 Influence of the photocatalyst dose on SO2 removal efficiency
gas flow 60 mL min−1, run time 25 min, UVA irradiation intensity, (conditions: SO2 concentration, 500 ppm; photocatalyst dose 0.6 g m−3,
6.4 mW cm−2). Ze zeolite, Ti TiO2, POP polyoxypropylene gas flow 60 mL min−1, run time 25 min, UVA irradiation intensity,
6.4 mW cm−2). Ze zeolite, Ti TiO2, POP polyoxypropylene

∙OHðadsÞ þ SO2ðadsÞ →HOSO2ðadsÞ ð13Þ Regeneration ability and reuse of the photocatalysts

SO3ðadsÞ →SO3ðgÞ ð14Þ During the photocatalytic processes, sulfur dioxide is convert-
ed into sulfur trioxide, which accumulated on the surface of
TiO2 catalyst and leads to gradual disappearance of catalytic
activity (Shang et al. 2002). Therefore, the adsorbent stability
The results also showed that with increaseing the hu-
and regeneration of Ze-Ti and Ze-Ti-POP nanocomposites is
midity content from 0 to 5%, the SO2 removal efficiency
very important factor for SO2 removal by adsorption and pho-
by zeolite decreased from 10.5 to 4.4%. It was reported
tocatalytic oxidation. The regeneration results of Ze-Ti and
that SO2 removal efficiency decreased due to the inhibi-
Ze-Ti-POP after 3 cycles are indicated in Fig. 9. It was seen
tory effect of H2O molecules into the zeolite pores (Rouf
that the regenerated Ze-Ti and Ze-Ti-POP showed an excellent
and Eić 1998). Furthermore, excess of H 2O molecules
adsorption and high photocatalytic capacity as the fresh sor-
which occupy the active sites on the surface of TiO2 com-
bents after three regeneration cycles with only a slight de-
pete with the gas molecules and reduce photocatalytic
crease in efficiency. The SO2 removal efficiency of the regen-
reaction rate and removal efficiency (Kachina 2008).
erated Ze-Ti and Ze-Ti-POP was about 66.1 and 76.3%,
However, it should be considered that a certain amount
of humidity is necessary to maintain hydroxylation and to
prevent saturation of TiO2 surface by partially oxidized
products (Maira et al. 2001).

Effect of photocatalyst dose on SO2 removal

efficiency

The amount of removed SO 2 increased monotonously

with increasing photocatalyst dose (Fig. 8). Maximum re-
moval efficiency of SO 2 achieved to 17.5, 82.1, and
87.2% for Ze, Ze-Ti, and Ze-Ti-POP, respectively. One
main reason for increasing the removal rate of SO2 is
generation of more photocatalytic reactive sites for the
oxidation of SO2 into SO2− 4 (Kamegawa et al. 2013).
However, it should be considered that increasing the
photocatalyst dose may also lead to particle aggregation Fig. 9 SO2 removal efficiency of Ze-Ti and Ze-Ti-POP nanocomposites
in three reuse cycles (conditions: SO 2 concentration, 500 ppm;
and formation of multilayers which are not accessible to
photocatalyst dose 1.3 g m−3, gas flow 60 mL min−1, run time 25 min,
the reaction and decreases the exposed surface area of UVA irradiation intensity, 6.4 mW cm−2). Ze zeolite, Ti TiO2, POP
sorbents (Fida et al. 2015). polyoxypropylene
Environ Sci Pollut Res
respectively, while the efficiency of original samples was 82.1
and 87.4%, respectively. The regeneration could be due to
formation of •OH radicals from H2O2 aqueous solutions under
UVA irradiation which react with the pollutants on
photocatalyst surface and play the most relevant role for the
successful regeneration (Miranda-García et al. 2014).
However, H2O2 in the presence of UVA irradiation might
affect the structure and surface of the nanocomposites.
Conclusions
This study showed that modification of clinoptilolite as a
natural zeolite with TiO2 and POP surfactant could signifi-
cantly affect SO2 removal efficiency through the changing the
sorbent structure properties (specific surface area and pore
volume) as well as improving photocatalytic oxidation.
Furthermore, the factors affecting the gas removal efficiency
including calcination temperature, reaction time, dose of
photocatalysts, water content, and UV irradiation intensity
were optimized. The L-H kinetic model was successfully
fitted with the obtained data from the experiments.
Regeneration process of the sorbents revealed that they could
be reused as promising photocatalysts for SO2 oxidation. By
the way, in practical point of view, the economic aspects of
using these modified photocatalysts, interactions of other pol-
lutants in real conditions, and management of the by-products
of the process should be considered.
Acknowledgements The current work was financially supported by the
Iran Nanotechnology Initiative Council (INIC-84100) under the project
entitled BApplication of TiO2-clay nanocomposites for removal of SO2 as
a pollutant gas,^ which is appreciated. The authors gratefully acknowl-
edge Dr. Ali Ashrafi for his great help to set up the photoreactor equip-
ment for laboratory experiments.
References
Anpo M, Kamat PV (2010) Environmentally benign photocatalysts: ap-
plications of titanium oxide-based materials. Springer Science &
Business Media, Berlin. https://doi.org/10.1007/978-0-387-48444-0
Ao C, Lee S, Zou S, Mak C (2004) Inhibition effect of SO2 on NOx and
VOCs during the photodegradation of synchronous indoor air pol-
lutants at parts per billion (ppb) level by TiO2. Appl Catal B Environ
49(3):187–193. https://doi.org/10.1016/j.apcatb.2003.12.011
Boulamanti AK, Korologos CA, Philippopoulos CJ (2008) The rate of
photocatalytic oxidation of aromatic volatile organic compounds in
the gas-phase. Atmos Environ 42(34):7844–7850. https://doi.org/
10.1016/j.atmosenv.2008.07.016
Campostrini R, Carturan G, Palmisano L, Schiavello M, Sclafani A
(1994) Sol-gel derived anatase TiO2: morphology and photoactivity.
Mater Chem Phys 38:277–283
Carriazo J, Moreno-Forero M, Molina R, Moreno S (2010) Incorporation
of titanium and titanium–iron species inside a smectite-type mineral
for photocatalysis. Appl Clay Sci 50(3):401–408. https://doi.org/10.
1016/j.clay.2010.09.007
Chen D, Zhu Q, Zhou F, Deng X, Li F (2012) Synthesis and photocata-
lytic performances of the TiO2 pillared montmorillonite. J Hazard
Mater 235:186–193
Chiu CH, Hsi HC, Lin HP (2015) Multipollutant control of Hg/SO /NO
from coal-combustion flue gases using transition metal oxide-im-
pregnated SCR catalysts. Catal Today 245:2–9
Chou C-C, Shieu F-S, Lin J-J (2003) Preparation, organophilicity, and self-
assembly of poly (oxypropylene) amine-clay hybrids. Macromolecules
36(7):2187–2189. https://doi.org/10.1021/ma025773h
Daniel LM, Frost RL, Zhu HY (2007) Synthesis and characterisation of
clay-supported titania photocatalysts. J Colloid Interface Sci 316(1):
72–79. https://doi.org/10.1016/j.jcis.2007.08.023
Fida H, Guo S, Zhang G (2015) Preparation and characterization of bi-
functional Ti–Fe kaolinite composite for Cr (VI) removal. J Colloid
Interface Sci 442:30–38
Hamidpour M, Kalbasi M, Afyuni M, Shariatmadari H, Holm PE,
Hansen HCB (2010) Sorption hysteresis of Cd (II) and Pb (II) on
natural zeolite and bentonite. J Hazard Mater 181:686–691
Hao X, Hou G, Zheng P, Liu R, Liu C (2016) H2S in-situ removal from
biogas using a tubular zeolite/TiO2 photocatalytic reactor and the
improvement on methane production. Chem Eng J 294:105–110
Hashimoto K, Wasada K, Osaki M, Shono E, Adachi K, Toukai N,
Kominami H, Kera Y (2001) Photocatalytic oxidation of nitrogen
oxide over titania–zeolite composite catalyst to remove nitrogen
oxides in the atmosphere. Appl Catal B Environ 30(3-4):429–436.
https://doi.org/10.1016/S0926-3373(00)00258-7
Hussain M, Russo N, Saracco G (2011) Photocatalytic abatement of VOCs
by novel optimized TiO2 nanoparticles. Chem Eng J 166:138–149
Ibusuki T, Takeuchi K (1994) Removal of low concentration nitrogen
oxides through photoassisted heterogeneous catalysis. J Mol Catal
88(1):93–102. https://doi.org/10.1016/0304-5102(93)E0247-E
Jansson I, Suárez S, Garcia-Garcia FJ, Sánchez B (2015) Zeolite–TiO2 hy-
brid composites for pollutant degradation in gas phase. Appl Catal B
Environ 178:100–107. https://doi.org/10.1016/j.apcatb.2014.10.022
Kachina A (2008) Gas-phase photocatalytic oxidation of volatile organic
compounds. Lappeenranta University of Technology, Lappeenranta
Kamegawa T, Kido R, Yamahana D, Yamashita H (2013) Design of TiO2-
zeolite composites with enhanced photocatalytic performances under
irradiation of UV and visible light. Microporous Mesoporous Mater
165:142–147. https://doi.org/10.1016/j.micromeso.2012.08.013
Kibanova D, Trejo M, Destaillats H, Cervini-Silva J (2009) Synthesis of
hectorite–TiO2 and kaolinite–TiO2 nanocomposites with photocata-
lytic activity for the degradation of model air pollutants. Appl Clay
Sci 42(3-4):563–568. https://doi.org/10.1016/j.clay.2008.03.009
Lin J-J, Cheng I-J, Wang R, Lee R-J (2001) Tailoring basal spacings of
montmorillonite by poly (oxyalkylene) diamine intercalation.
Macromolecules 34(26):8832–8834. https://doi.org/10.1021/ma011169f
Liu S, Lim M, Amal R (2014) TiO2-coated natural zeolite: rapid humic
acid adsorption and effective photocatalytic regeneration. Chem Eng
Sci 105:46–52
Maira A, Yeung KL, Soria J, Coronado J, Belver C, Lee C, Augugliaro V
(2001) Gas-phase photo-oxidation of toluene using nanometer-size
TiO2 catalysts. Appl Catal B Environ 29(4):327–336. https://doi.
org/10.1016/S0926-3373(00)00211-3
Malekian R, Abedi-Koupai J, Eslamian SS, Mousavi SF, Abbaspour KC,
Afyuni M (2011) Ion-exchange process for ammonium removal and
release using natural Iranian zeolite. Appl Clay Sci 51(3):323–329.
https://doi.org/10.1016/j.clay.2010.12.020
Miranda-García N, Suárez S, Maldonado MI, Malato S, Sánchez B
(2014) Regeneration approaches for TiO 2 immobilized
photocatalyst used in the elimination of emerging contaminants in
water. Catal Today 230:27–34
Nasonova A, Kim K-S (2013) Effects of TiO2 coating on zeolite particles
for NO and SO2 removal by dielectric barrier discharge process.
Catal Today 211:90–95. https://doi.org/10.1016/j.cattod.2013.03.
006

Nieto-Suárez M, Palmisano G, Ferrer ML, Gutiérrez MC, Yurdakal S,
Augugliaro V, Pagliaro M, del Monte F (2009) Self-assembled tita-
nia–silica–sepiolite based nanocomposites for water decontamina-
tion. J Mater Chem 19(14):2070–2075. https://doi.org/10.1039/
b813864h
Niu S, Han K, Lu C (2011) Release of sulfur dioxide and nitric oxide and
characteristic of coal combustion under the effect of calcium based
organic compounds. Chem Eng J 168(1):255–261. https://doi.org/
10.1016/j.cej.2010.10.082
Papoulis D, Komarneni S, Nikolopoulou A, Tsolis-Katagas P,
Panagiotaras D, Kacandes H, Zhang P, Yin S, Sato T, Katsuki H
(2010) Palygorskite-and halloysite-TiO2 nanocomposites: synthesis
and photocatalytic activity. Appl Clay Sci 50(1):118–124. https://
doi.org/10.1016/j.clay.2010.07.013
Park D-R, Ahn B-J, Park H-S, Yamashita H, Anpo M (2001)
Photocatalytic oxidation of ethylene to CO2 and H2O on ultrafine
powdered TiO2 photocatalysts: effect of the presence of O2 and H2O
and the addition of Pt. Korean J Chem Eng 18(6):930–934. https://
doi.org/10.1007/BF02705621
Petkowicz DI, Pergher SB, Da Silva CDS, Da Rocha ZN, Dos Santos JH
(2010) Catalytic photodegradation of dyes by in situ zeolite-
supported titania. Chem Eng J 158(3):505–512. https://doi.org/10.
1016/j.cej.2010.01.039
Rouf SA, Eić M (1998) Adsorption of SO2 from wet mixtures on hydro-
phobic zeolites. Adsorption 4(1):25–33. https://doi.org/10.1023/A:
1008883219403
Sanchez J, Augustynski J (1979) X-ray photoelectron spectroscopic study
of the interaction of various anions with the oxide-covered titanium
metal. J Electroanal Chem Interfacial Electrochem 103(3):423–426.
https://doi.org/10.1016/S0022-0728(79)80366-6
Shang J, Zhu Y, Du Y, Xu Z (2002) Comparative studies on the deacti-
vation and regeneration of TiO2 nanoparticles in three photocatalytic
oxidation systems: C7H16, SO2, and C7H16–SO2. J Solid State Chem
166(2):395–399. https://doi.org/10.1006/jssc.2002.9613
Environ Sci Pollut Res
Su C, Ran X, Hu J, Shao C (2013) Photocatalytic process of simultaneous
desulfurization and denitrification of flue gas by TiO2–polyacrylo-
nitrile nanofibers. Environ Sci Technol 47(20):11562–11568.
https://doi.org/10.1021/es4025595
Sun Q, Hu X, Zheng S, Sun Z, Liu S, Li H (2015) Influence of calcination
temperature on the structural, adsorption and photocatalytic proper-
ties of TiO2 nanoparticles supported on natural zeolite. Powder
Technol 274:88–97. https://doi.org/10.1016/j.powtec.2014.12.052
Todorova N, Giannakopoulou T, Karapati S, Petridis D, Vaimakis T,
Trapalis C (2014) Composite TiO2/clays materials for photocatalytic
NOx oxidation. Appl Surf Sci 319:113–120. https://doi.org/10.1016/
j.apsusc.2014.07.020
Torimoto T, Ito S, Kuwabata S, Yoneyama H (1996) Effects of adsorbents
used as supports for titanium dioxide loading on photocatalytic deg-
radation of propyzamide. Environ Sci Technol 30(4):1275–1281.
https://doi.org/10.1021/es950483k
Turki A, Guillard C, Dappozze F, Berhault G, Ksibi Z, Kochkar H (2014)
Design of TiO2 nanomaterials for the photodegradation of formic
acid—adsorption isotherms and kinetics study. J Photochem
Photobiol A Chem 279:8–16. https://doi.org/10.1016/j.
jphotochem.2014.01.008
Weitkamp J (2000) Zeolites and catalysis. Solid State Ionics 131(1-2):
175–188. https://doi.org/10.1016/S0167-2738(00)00632-9
Yuan Y, Zhang J, Li H, Li Y, Zhao Y, Zheng C (2012) Simultaneous
removal of SO2, NO and mercury using TiO2-aluminum silicate
fiber by photocatalysis. Chem Eng J 192:21–28. https://doi.org/10.
1016/j.cej.2012.03.043
Zhao Y, Han J, Shao Y, Feng Y (2009) Simultaneous SO2 and NO re-
moval from flue gas based on TiO2 photocatalytic oxidation.
Environ Technol 30(14):1555–1563. https://doi.org/10.1080/
09593330903313786