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JIEC-1737; No. of Pages 6

Journal of Industrial and Engineering Chemistry xxx (2013) xxxxxx

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Journal of Industrial and Engineering Chemistry

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Environmental remediation of thiophene solution by photocatalytic

oxidation using NiO/AgInS2 nanoparticles
E. Baeissa *
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203 Jeddah 21589, Saudi Arabia

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

Article history: AgInS2 nanoparticles were prepared via a microwave method, while NiO was immobilized on the surface
Received 22 October 2013 of AgInS2 via an impregnation method. The samples produced were characterized using different
Received in revised form 5 November 2013 techniques. The catalytic performances of the AgInS2 and NiO/AgInS2 samples were carried out for
Accepted 2 December 2013
photocatalytic oxidation of thiophene under visible light. The maximum oxidation efciency achieved
Available online xxx
was 100% at 0.3 NiO/AgInS2 photocatalyst. The doping of NiO into the AgInS2 was useful in improving the
photocatalytic activity. The catalyst could be reused without any loss in activity during the rst ve
Keywords:
cycles.
NiO doping
AgInS2
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Visible photocatalyst reserved.
Oxidation of thiophene

1. Introduction
Photocatalytic degradation of harmful organic compounds is of
great interest and importance for environmental protection [15].
It has been demonstrated that many organic pollutants present in
water or air streams can be removed by means of photocatalytic
oxidation. Sulfur-containing organic compounds are a class of
pollutants in fuel oils, and the removal of these pollutants is
difcult [6]. However, thiophene, one of the main sulfur-contain-
ing compounds in gasoline, is the most difcult to oxidize using
conventional oxidative desulfurization processes. The inertness of
thiophene in the oxidative desulfurization is mainly due to the
aromaticity and the low electron density on the sulfur atom, which
makes the oxidation of the thiophene molecule more difcult.
Therefore, it is ideal to develop an effective photocatalyst for the
removal of sulfur-containing compounds in gasoline via photo-
catalytic oxidation.
TiO2 is by far the most popular photocatalyst for its higher
photocatalytic activity, good photostability, non-toxicity, and low
price. However, the effective commercial applications are hindered
by two serious disadvantages. The rst is the agglomeration of the
ultrane powders resulting in an adverse effect on catalyst
performance. The second is the large band gap of 3.2 eV, so
wavelengths below 400 nm are necessary for excitation, which
limits the usage efciency of solar energy. The large band gap of
TiO2 (3.2 eV) limits its photocatalytic applications to the UV range.
* Corresponding author. Tel.: +96626400000; fax: +966 2 6952292.
E-mail address: elhambaeissa@gmail.com
UV light is about 4% of the solar spectrum and can be easily ltered
by clear glass or pure water. Therefore, it is necessary to modify the
band gap of TiO2 to improve its optical properties. In the last
decades, doping with nonmetals has been performed to shift the
optical response of the catalytically active TiO2 from UV to the
visible light region. Mordenite [7], graphene [8], Ni [9], Pt [10], Au
[11], Ag [12], rare earth dopants [13], and Co, Cr, and Ag [14] have
been used to extend the photoresponse range of the TiO2 matrix.
Ternary chalcogenides of XYmZn (X = Cu, Ag, Zn, Cd; Y = Ga, In;
Z = S, Se, Te; m, n = integers) have attracted considerable attention
due to their excellent electrical and optical properties, and have
been applied in photovoltaic solar cells, linear and nonlinear
optical instruments, and photocatalysis [1519]. As one of the
most important ternary chalcogenides, AgInS2 is an intriguing
functional material because of its promising applications in
photovoltaic, optoelectronic, and photocatalytic elds [2023].
Tsuji et al. [23] reported that solid solutions consisting of
combinations of CuInS2, AgInS2, and ZnS showed high photo-
catalytic activities for H2 evolution from aqueous sulde and
sulte solutions under visible light irradiation. Additionally, they
found that ternary AgInS2 absorbs visible light. Thus, it is of great
interest to investigate the photocatalytic activity of AgInS2 for
thiophene pollutant degradation.
So far, many methods for preparing AgInS2 powder and lm
have been reported, such as the solvothermal synthesis approach
[23,24], the hot press method [25], and the spray pyrolysis
technique [20,26]. These approaches are important for under-
standing the formation process and mechanism of complex AgInS2.
However, these methods have some distinct disadvantages. First,
some of these methods relied on relatively high temperatures [27]

1226-086X/$ see front matter 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.2013.12.008

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and pressures [25]. Second, certain apparatuses, such as Teon-
lined stainless-steel autoclaves, were indispensable [23,28]. Third,
many of the approaches made use of organic solvents (anisole [29],
ethylenediamine [24,30], and ethanol [29]) as the reaction
mediates. Fourth, most of these methods require a long reaction
time. Therefore, the challenge remains in ways to prepare the
AgInS2 nanostructure using a facile, mild, stable, non-secondary
pollutant, and time-saving method, and ways to decrease or
prevent the recombination rate of photogenerated carriers to
increase the photocatalytic activity of AgInS2.
Herein, we present the synthesis of a Ni doped AgInS2
photocatalyst. The effect of NiO content on the photocatalytic
activity of AgInS2 has been investigated in detail. It was found that
the presence of NiO could signicantly improve the photocatalytic
performance of AgInS2 towards thiophene photocatalytic oxida-
tion in visible light.
2. Experimental
2.1. Synthesis of AgInS2
All chemicals were analytical grade and used as received,
without further purication. One mili mole of Ag2SO4, 1 mmol of
InCl3-4H2O, and an excess of thioacetamide were dissolved in
20 mL of deionized water. Then the pH was adjusted to a value of 4
using 0.1 mol L1 HCl. This solution was added to a 70 mL glass
vessel and was maintained at 180 8C for 20 min using a microwave
system (ETHOS TC from Milestone Inc.). After the reaction was
completed, the product was collected by centrifugation and then
was washed several times with deionized water and absolute
ethanol. The nal sample was dried at 80 8C for 24 h. The produced
sample was named AgInS2.
2.2. Synthesis of NiO/AgInS2
The prepared AgInS2 nanoparticle was added to 20 mL of
distilled water containing an appropriate amount of NiCl2 in a
ceramic dish. The suspension was stirred using a glass rod during
the evaporation of water under the irradiation of an infrared light.
The resulting powder was collected and calcined in air at 400 8C for
1 h. The content of the NiO loading species varied at 0.1, 0.2, 0.3,
and 0.4% wt., and the produced samples were named 0.1, 0.2, 0.3,
and 0.4 NiO/AgInS2, respectively.
2.3. Characterization techniques
X-ray diffraction (XRD) analysis was carried out at room
temperature with a Bruker axis D8, using Cu Ka radiation
(l = 1.540 A). The specic surface area was calculated from
measurements of N2-adsorption using a Nova 2000 series
Chromatech apparatus at 77 K. Prior to the measurements, all
samples were treated under a vacuum at 250 8C for 2 h. The band
gap of the samples was identied using UVvis diffuse reectance
spectra (UVvisDRS) in air at room temperature in the
wavelength range of 200800 nm, using a UV/vis/NIR spectropho-
tometer (V-570, JASCO, Japan). Transmission electron microscopy
(TEM) was recorded with a JEOL-JEM-1230 microscope, and the
samples were prepared by suspending them in ethanol, followed
by ultrasonication for 30 min. A small amount of this solution was
then put onto a carbon-coated copper grid and dried before loading
the sample in the TEM. The X-ray absorption ne structure (XAFS)
analysis, X-ray absorption near edge structure (XANES), and
extended X-ray absorption ne structure (EXAFS) were performed
at the BL-7C facility of the Photon Factory at the National
Laboratory for High-Energy Physics in Tsukuba, Tokyo, Japan. The
K-edge XAFS spectra of Ni was measured in the uorescence mode
Please cite this article in press as: E. Baeissa, J. Ind. Eng. Chem. (2013), http://dx.doi.org/10.1016/j.jiec.2013.12.008
at 298 K and a Fourier transformation was performed on K3-
weighted EXAFS oscillations in the range of 110 A1.
2.4. Photocatalytic activity
The photocatalytic oxidation reactions of thiophene were
carried out in a Pyrex reaction cell with O2 bubbled in a constant
ow as an oxidant. The photocatalyst (1 g L1) was dispersed in an
acetonitrile solution containing thiophene ([sulfur content] initial
= 600 ppm). The suspension was stirred in the dark for 30 min to
establish adsorption/desorption equilibrium between the solution
and photocatalyst before being irradiated by a 125 W medium
pressure mercury lamp with a UV cut lter. The temperature of the
reaction solution was maintained at 12 8C by a ow of cooling
water. The products and byproducts were analyzed by GC-FPD
(Agilent 7890, FFAP column) and GC-MS after separation of the
catalyst particles from the reaction system by centrifugation.
The adsorption capacities of the catalysts are determined as
with photocatalytic activity measurements, the only difference is
that the adsorption process was conducted without light irradia-
tion. Adsorption of the thiophene by the AgInS2 and doped NiO/
AgInS2and P25 over the same time period was approximately zero.
3. Results and discussion
3.1. Structural, morphological, and compositional characterizations
The XRD patterns of each parent AgInS2 and NiO/AgInS2
nanoparticle samples are compared in Fig. 1. The structural
characteristics of AgInS2 and NiO/AgInS2 are primarily composed
of orthorhombic phase AgInS2 (JCPDS Card: 25-1328), which
indicates that the AgInS2 structure remained after the doping of
NiO. However, no diffraction peaks of Ni or NiO in the patterns of
NiO/AgInS2 samples appeared. This is probably attributable to the
low NiO doping content. Moreover, the data may imply that the
NiO is well dispersed within the AgInS2 phase. NiO played a
prominent role in the process of crystallization, as can be seen from
the XRD patterns, showing that the orthorhombic AgInS2 phase
characteristic diffraction peaks became broad and the diffraction
peaks intensity decreased with increased NiO loading. The average
crystallite sizes of AgInS2 were calculated by Scherers equation
using the full width at half the maximum of the X-ray diffraction
peaks at u = 26.68, corresponding to the most intense orthorhombic
AgInS2 peak. The crystallite size of the AgInS2, 0.1, 0.2, 0.3, and 0.4
AgInS2
Intensity, a.u.
0.1 NiO/ AgInS2
0.2NiO/ AgInS2
03 NiO/ AgInS2
0.4 NiO/ AgInS2
20 30 40 50 60 70
2-Theta/ degree
Fig. 1. XRD pattern of AgInS2 and NiO/AgInS2 nanoparticles.
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NiO/AgInS2 were 12, 11, 10, 9, and 7 nm, respectively. Therefore,
the particle size became smaller as the NiO concentration
increased.
To investigate the nature of the Ni introduced into the
composite, we performed extended X-ray absorption ne structure
(EXAFS) measurements. Fig. 2 shows the EXAFS analysis for 0.3
NiO/AgInS2. The presence of the peaks assigned to the Ni-O at
about 2.08 A indicates the formation of nano-sized Ni-O.
TEM images of AgInS2 and NiO/AgInS2 nanoparticles are shown
in Fig. 3. The results reveal that NiO dispersed on the surface of the
catalyst and the diameter of the NiO increased with increases in the
wt. percentages of NiO.
3.2. Surface area analysis
The specic surface area (SBET) of the parent AgInS2 and NiO/
AgInS2 nanoparticles were determined. The SBET values were 8, 7.5,
6.9, 6.5, and 6.4 m2/g for the AgInS2, 0.1, 0.2, 0.3, and 0.4 NiO/
AgInS2, respectively. The surface area of the parent AgInS2 and NiO/
AgInS2 nanoparticles are collected in Table 1. The surface area of
AgInS2 is higher than that of the NiO/AgInS2 samples, due to the
blocking of some pores by the doping of NiO.
3.3. Optical characterization
The UVvis diffuse reectance spectra of the AgInS2 and NiO/
AgInS2 nanoparticles are displayed in Fig. 4. The loading of NiO into
the AgInS2 caused a red shift toward higher wavelengths from 566
to 685 nm for different loadings of NiO, compared to a wavelength
of AgInS2 at about 508 nm. The direct band gap energy for the
AgInS2 and NiO/AgInS2 nanoparticles was calculated from their
reection spectra based on a method suggested by Kumar et al.
[31]; the results are tabulated in Table 2. It is clear that the energy
gap decreased with the increase in the NiO. The band gap values
were 2.44; 2.19; 2.03; 1.92 and 1.82 2 eV for the AgInS2, 0.1, 0.2,
0.3, and 0.4 Ni/AgInS2 respectively. This result indicates that the
NiO doping can narrow the band gap of catalysts, which may be
benecial for improving the photocatalytic activity of the catalysts.
Photoluminescence (Pl) emission spectra have been used to study
the transfer of the photogenerated electrons and holes and to
understand the separation and recombination of photogenerated
charge carries. In order to investigate the photoelectric properties
of the prepared samples, the Pl spectra were detected for the
different samples, excited at 270 nm at room temperature, as
shown in Fig. 5. It is clear that the Pl intensity greatly decreased
FT/a.u.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
Distance, A
Fig. 2. Fourier transforms of Ni LIII-edge EXAFS spectra for 0.3 NiO/AgInS2.
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3
with the increase in the percentage of NiO. NiO acts as a trapping
site to capture photogenerated electrons from the conduction
band, thus separating the photogenerated electron-hole pairs. It is
generally accepted that the incorporation of noble metal nano-
particles into the semiconductor-based catalysts could enhance
the light absorption of the catalysts in the visible-light region. This
leads to a shift of the absorption edge toward longer wavelengths,
indicating a decrease in the band gap energy, and that more
photogenerated electrons and holes could participate in the
photocatalytic reactions. In the case of NiO, NiO seems to modify
the interface of AgInS2 in a way that alters the mechanism in which
photogenerated charge carriers undergo recombination or surface
reactions. This would force AgInS2 to be activated more in the
visible region. The shift in emission position could be attributed to
the charge transfer between the NiO generated band and the
conduction band of AgInS2 as a semiconductor.
3.4. Photocatalytic activity
3.4.1. Effect of catalyst type on photocatalytic conversion of thiophene
Fig. 6 shows the photocatalytic conversion of thiophene by
AgInS2 and NiO/AgInS2 samples under visible light and the
experiment carried out under the following conditions: 600 ppm
of thiophene, 500 ml of thiophene solution, and 0.4 g of the
catalyst. The results indicate that AgInS2 has small photocatalytic
activity under visible light. In addition, the photocatalytic activity
of NiO/AgInS2 increased in the following order 0.1 NiO/AgInS2
<0.2 NiO/AgInS2 <0.3 NiO/AgInS2 0.4 NiO/AgInS2, which is in
agreement with XRD, TEM, and band gap.
AgInS2 is a visible light photocatalyst absorbing wavelengths
shorter than 508 nm. The electrons in AgInS2 valence band are
excited and transfer to a conduction band under visible light
irradiation. Then the oxidative species OH and photogenerated
holes form and decompose the organic compounds. However, the
high recombination rate of photogenerated carriers leads to the
low photoactivity of pure AgInS2. When the NiO species is
introduced into the AgInS2 samples, the NiO particles can act as
electron traps, promoting the electron-hole separation and
subsequent transfer of the trapped electron to the adsorbed O2,
which is acting as an electron acceptor on the surface of the AgInS2.
The holes remain in the AgInS2 valence band after the migration of
the excited electrons. Therefore, the recombination of electron-
hole pairs is restrained, and the photocatalytic reaction can be
enhanced greatly. It has been reported that the surface of some
noble metals and compounds on some photocatalysts can be
excited by visible light [3235], enhancing the surface electron
excitation and electron-hole separation. In this experiment, we
deduced that the NiO dopant might act in another role to enhance
the visible light photoactivity of the NiO/AgInS2 nanoparticle
photocatalysts, as shown in the left of Fig. 7. The acceptor surface
state forms in the forbidden band of AgInS2 because of the NiO
doping, and the electron in the valence band of AgInS2 can be
excited by visible light and migrate into the NiO particles, then the
doped NiO species reaches a surface excitation state. The electrons
on the surface of the excited NiO particles can react with O2 to
produce O2. The newly formed intermediates can interact to
produce OH. Therefore, the NiO in the composite photocatalysts
has a benecial role in improving charge separation and extending
AgInS2 in response to visible light.
To examine the photoproducts, the gas from the outlet of the
products was introduced to a NaOH aqueous solution (0.2 M) for
further analysis. A white precipitate was produced when a
6.0 Ba(NO3)2 aqueous solution (0.2 M) was added into the NaOH
aqueous solution after the reaction (denoted as precipitate 1).
Fig. 8a shows the XRD pattern of the white precipitate. The XRD
pattern was assigned to BaCO3, which is in good agreement with
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Fig. 3. TEM images of AgInS2 and NiO/AgInS2 nanoparticles, where wt.% of NiO is 0.0 (A); 0.1(B); 0.2 (C); 0.3(D); and 0.4 (F).

the standard card of ICDD-PDF No. 05-0378. This result indicates LogCc kt LogCo
that thiophene can be photocatalytically oxidized to CO2 and
trapped in the NaOH aqueous solution. Very interestingly, when where, [C]o and [C]t represent the concentration of the substrate in
we added HNO3 (aq.) to the precipitate 1, there was still some solution at time zero and t time of illumination respectively, and k
white precipitate that existed, which could not be dissolved in represents the apparent rate constant (min1).
HNO3 (aq.), denoted as precipitate 2. The XRD pattern of precipitate
2, shown in Fig. 8b, can be readily assigned to BaSO4, which is in
good agreement with the standard card of ICDD-PDF No. 24-1035.
This indicates that the sulfur in thiophene can be photocatalyti- AgInS2
cally oxidized to SO3. Namely, thiophene can be oxidized to CO2 0.1 NiO/AgInS2
and SO3 in the photocatalytic oxidation reaction.Therefore, the
photocatalytic conversion of thiophene will be 0.2 NiO/AgInS2
0.3 NiO/AgInS2
Absorbance, a.u.

Thiophene photocatalyst ! CO2 SO3 H2 O 0.4 NiO/AgInS2

The reaction order with respect to thiophene was determined

by plotting reaction time versus log [thiophene] according to the
following equation for AgInS2 and NiO/AgInS2 samples.

Table 1
BET surface area of AgInS2 and NiO/AgInS2 nanoparticles.

Samples SBET(m2/g)

AgInS2 8
NiO/AgInS2 7.5 300 400 500 600 700 800 900
NiO/AgInS2 6.9
Wavelength, nm
NiO/AgInS2 6.5
NiO/AgInS2 6.4
Fig. 4. UVvis absorption spectra of AgInS2 and NiO/AgInS2 nanoparticles.

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Table 2
Band gap energy of AgInS2 and NiO/AgInS2 nanoparticles.

Sample Band gap energy (eV)

AgInS2 2.44
NiO/AgInS2 2.19
NiO/AgInS2 2.03
NiO/AgInS2 1.92
NiO/AgInS2 1.82

AgInS2
0.1 NiO/AgInS2
0.2 NiO/AgInS2
0.3 NiO/AgInS2 Fig. 7. Photocatalytic mechanism of NiO/AgInS2 composite photocatalysts under
0.4 NiO/AgInS2 visible light irradiation.
Intensity /a.u.

observed with an increase in the catalyst amount from 0.8 g L1 to

1.2 g L1, respectively. However, further increases of the photo-
catalyst amount above 1.2 g L1 increased the reaction time again
to 150 min. The increase in the photocatalyst amount increased the
number of active sites on the photocatalyst [36]. Consequently, the
number of nitrate molecules and photons absorbed increased.
However, at photocatalyst dosages above 1.2 g L1, the reaction
450 500 550 600 650 time required to reduce the nitrate ions increased due to the
Wavelength /nm

Fig. 5. Pl spectra of AgInS2 and NiO/AgInS2 nanoparticles.

a

The apparent rate constants are summarized in Table 3. The

results show that the reaction followed rst order kinetics with
respect to thiophene and the rate constants were found in the
Intensity, a.u.

range of 10  104182  104 min1. The rst order rate

equation for thiophene is given by: R = k [thiophene]

3.4.2. Effect of photocatalyst amount on photocatalytic conversion of

thiophene
The photocatalyst amount was another important parameter of
the photocatalytic conversion of the thiophene solution under
visible light irradiation. Amounts of 0.3 NiO/AgInS2, ranging from
0.4 to 2.0 g L1 in 600 mg L1 thiophene solutions, were employed
in this study. As shown in Fig. 9, a decrease in reaction time, which
5 10 15 20 25 30 35 40 45 50 55 60 65 70
was required to oxidize thiophene, from 150 to 90 min was
2-Theta
110
b
AgIn S2 500
100 0.1 NiO/AgInS2
0.2 NiO/AgInS2
90 0.3 NiO/AgInS2
400
0.4 NiO/AgInS2
Conversion of thiophene, %

80

70
300
Intensity, a.u.

60

50
200
40

30
100
20

10
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
2-Theta
Reaction time, min
Fig. 8. a. is the XRD pattern of the precipitate 1. b. is the XRD pattern of the
Fig. 6. Effect of type of catalyst on photocatalytic conversion of thiophene. precipitate 2.

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100 photocatalyst is effective, and thus the photocatalyst is stable

90 and is promising for environmental remediation.

80 4. Conclusions
Conversion of thiophene, %

70
In summary, the NiO/AgInS2 photocatalyst was successfully
60 synthesized and was proven a promising catalyst due to its high
reduction efciency of the pollutant under visible light. The red
50
0.4g/l shift phenomenon was found to depend on the percentage of wt. of
40 0.8g/l NiO doped on AgInS2, which has been observed in the UVvis
1.2 g/l spectra of AgInS2 and NiO/AgInS2 samples. Photocatalytic mea-
30
1.6 g/l surements through the photocatalytic oxidation of thiophene
20 2.0 g/l solutions showed that NiO/AgInS2 nanoparticles with a 0.3% wt. of
NiO exhibited the highest catalytic activities and efcient
10 photocatalytic properties in water purication, and may nd
0 potential applications in related elds. Optimization of reaction
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 conditions led to the conclusion that 0.3 NiO/AgInS2 and the use of
Reaction time, min 1.2 g of the catalyst in a 1000 mL, 600 mg/L thiophene solution
yielded 99% oxidation of the thiophene solution, with 90 min of
Fig. 9. Effect of loading of 0.3 NiO/AgInS2 on photocatalytic conversion of thiophene.
irradiation of visible light. The results of re-use of the catalyst
revealed that the present photocatalyst remains effective and
active after ve cycles, which indicates the promising recyclability
Photocatalytic conversion of thiophene %

of the NiO/AgInS2 photocatalyst.

100 References

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Please cite this article in press as: E. Baeissa, J. Ind. Eng. Chem. (2013), http://dx.doi.org/10.1016/j.jiec.2013.12.008