Applied Clay Science 166 (2018) 27–37

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Applied Clay Science

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

Research paper

Degradation of aqueous ketoprofen by heterogeneous photocatalysis using T

Bi2S3/TiO2–Montmorillonite nanocomposites under simulated solar
irradiation
Lila Djouadia, Hussein Khalafa, Horiya Boukhatema,b, Hocine Boutoumia, Amina Kezzimec,
⁎
J. Arturo Santaballad, Moisés Canled,
a
Laboratoire de Génie Chimique, Département de Génie des procédés, Faculté de Technologie, Université Saad Dahleb-, Blida 1, BP270-09000 Blida, Algeria
b
Département des Sciences de la Matière, Faculté des Sciences et de la Technologie, Université Djilali Bounaama de Khemis-Miliana, Route de Theniet El Had, 44001
Khemis- Miliana, Algeria
c
Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, BP 32, 16111 Algiers, Algeria
d
Universidade da Coruña, Grupo Reactividade Química e Fotorreactividade (React!), Departamento de Química, Facultade de Ciencias & CICA, E-15071 A Coruña, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: The photocatalytic degradation of Ketoprofen (KP), 2-(3-benzoylphenyl)-propionic acid was studied under near
Heterogeneous photocatalysis UV–Vis irradiation (NUV-Vis) using supported photocatalysts. Bi2S3/TiO2-montmorillonite (Bi2S3/TiO2-Mt)
Ketoprofen photocatalysts were synthesized using a two- step ion exchange and impregnation method, and characterized
Nanocomposites using different techniques: Fourier transform infrared spectra (FTIR), X-ray fluorescence (XRF), X-ray diffraction
Montmorillonite
(XRD), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) and photo-electrochemistry. Successful inter-
Bi2S3
calation of TiO2 and Bi2S3 in the montmorillonite (Mt) was carried out, and the corresponding energy diagram
TiO2
for the Bi2S3/TiO2 heterojunction has been proposed. The resulting Bi2S3/TiO2-Mt nanocomposites were able to
degrade KP under NUV–Vis irradiation. KP photodegradation was monitored by HPLC. The kinetics of photo-
catalytic transformation followed the Langmuir-Hinshelwood kinetic model. Pseudo-first-order kinetics ade-
quately fitted the experimental data (t½ca. 17 min at pH 11, t½ca. 44 min at pH 3. 0.5 g·L−1 Bi2S3/TiO2 (25/75)-
Mt nanocomposite). Factors affecting the kinetics of the process, such as the different Bi2S3/TiO2 ratio and initial
pH solution have been discussed. KP photoproducts were identified using HPLC-MS, and the corresponding
reaction mechanism has been proposed. Photodegradation of KP over Bi2S3/TiO2-Mt nanocomposites under
NUV-Vis irradiation starts with the decarboxylation of KP and subsequent hydroxylation by HO• and oxidation
by HO• and other reactive oxygen species (ROS) leads to the formation of photoproducts. TiO2 and Bi2S3 in-
tercalated in the montmorillonite are cheap and efficient nanocomposites for the abatement of persistent organic
pollutants (POP), such as KP, using NUV-Vis light.

1. Introduction be a solution for the elimination and degradation of PPCP (Burrows

In the past decade, there has been a growing interest in the occur-
rence of pharmaceuticals and personal care products (PPCPs) in aquatic
environments. Common wastewater treatment processes are not effi-
cient enough for the elimination of a variety of PPCP because of their
low biodegradability (Halling-Sørensen et al., 1998; Huber et al., 2003;
Petrović et al., 2005). Consequently, these compounds occur in sewage
treatment plant (STP) effluents, and are discharged into surface waters
(Halling-Sørensen et al., 1998; Huber et al., 2003; Petrović et al., 2003
and Petrović et al., 2005). Besides classical biological treatments,
photochemical processes and advanced oxidation processes (AOP) may
et al., 2002; Ternes et al., 2002).
Ketoprofen (2-(3-benzoylphenyl) propionic acid, KP -Scheme 1-, is
one of the worldwide most-used non-steroidal anti-inflammatory drugs
(NSAID), also used as analgesic and antipyretic. Anti-inflammatory and
analgesic effects are due to inhibition of prostaglandin synthesis, while
its antipyretic effect is attributed to a resetting of the hypothalamic
temperature-regulating center. These drugs are widely used as non-
prescription drugs (Abdel-Hamid et al., 2001; Dvorak et al., 2004;
Marco-Urrea et al., 2010).
Heterogeneous photocatalysis is an alternative remediation tech-
nology and has attracted attention of many research groups around the

⁎
Corresponding author.
E-mail address: moises.canle@udc.es (M. Canle).

https://doi.org/10.1016/j.clay.2018.09.008
Received 14 June 2018; Received in revised form 4 September 2018; Accepted 6 September 2018
Available online 13 September 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
L. Djouadi et al.
O OH
O Bi2S3/TiO2 content in the nanocomposites.
CH3
Scheme 1. Chemical structure of ketoprofen (KP).
World (Canle et al., 2017). This technique has often been reported to
offer a number of key advantages, including the potential use of sun-
light irradiation, operation at ambient conditions, and potential reuse
of the catalyst. Hetereogeneous photocatalysis of KP with TiO2 has been
thoroughly investigated previously by some of us (Martínez et al.,
2013). A number of studies are available summarizing the funda-
mentals of heterogeneous photocatalytic degradation processes,
(Konstantinou and Albanis, 2004; Canle et al., 2017) and it is widely
accepted that the primary step is the adsorption of the substrate on the
support (Konstantinou and Albanis, 2004; Canle et al., 2017). The
second step concerns the photo-redox reactions between the adsorbed
substrate and TiO2. The photocatalytic process is initiated when a
photon with energy (hν) equal to or higher than the band gap energy
(Eg) reaches the photocatalyst, with transfer of electrons (e−) to the
conduction band (CB) and subsequent formation of positive holes (h+)
in the valence band (VB). The so-formed e−/h+ pairs can recombine
and dissipate energy as heat, get trapped in metastable surface states or
migrate to the surface to react with electron donors and acceptors ad-
sorbed on the semiconductor surface or within the immediate sur-
rounding electrical double layer of the charged particles. Free hydroxyl
radicals (HO●) are directly produced by reaction of h+ with H2O or
OH– at the surface of the catalyst. HO● radicals are extraordinarily
reactive, highly unselective species, exhibiting second order rate con-
stants ca. 106–109 M−1·s−1, and very high electrophilicity (Ling et al.,
2015; Valdés et al., 2015).
The use of TiO2 as photocatalyst for water treatment is well docu-
mented (Hermann, 1999; Konstantinou and Albanis, 2004). Never-
theless, the practical recovery of the powder when used as an aqueous
dispersion still remains difficult. TiO2 supported on different minerals
or TiO2 thin films therefore appeared to be a promising way to enlarge
application fields, and to overcome TiO2 recovery problems (Zhiyong
et al., 2008). TiO2, intercalated in the interlayer spaces of montmor-
illonite (Mt), could have high photocatalytic activity because of its
dispersion. The adsorption capacity of clays, related to their high sur-
face area, could facilitate the retention of pollutants and their inter-
mediate products of photocatalytic degradation. Finally, clays easily
flocculate (Khalaf et al., 1997). On the other hand, organophilic clays
can also be used for adsorbing poorly soluble pollutants, and the con-
taminated clay can be treated subsequently by photocatalysis over TiO2
(Ilisz et al., 2002).
Since TiO2 can be activated by UV light of λ < 365 nm, it can make
use of only about 4% of sunlight at ground level. Different strategies
have been adopted to improve its photocatalytic efficiency, such as ion
doping (Reddy et al., 2006), dye- sensitization (Kaur and Singh, 2007),
polymer-sensitization (Khalfaoui-Boutoumi et al., 2013) and doping
with junction semiconductors (Bessekhouad et al., 2005 and
Bessekhouad et al., 2006; Brahimi et al., 2007; Brahimi et al., 2008;
Bessekhouad et al., 2012; Brahimia et al., 2012; Khalfaoui-Boutoumi
et al., 2013). However, these doping processes modify other physical
properties such as the lifetime of e−–h+ pairs, adsorption character-
istics and photoelectrochemical stability (Table 1).
Bi2S3 is an important III–VI semiconductor that has been the subject
of intensive research over the last decades owing to its small band gap
Egca. 1.3 eV (Huaqiang et al., 2006; Zhou et al., 2008; Yang et al.,
2011;), optoelectronic properties and low cost (Bessekhouad et al.,
2004a, 2004b).
28
Applied Clay Science 166 (2018) 27–37
Table 1
Nanocomposite Bi2S3 (%) TiO2 (%)
Bi2S3/TiO2 (25/75)-Mt 25 75
Bi2S3/TiO2 (50/50)-Mt 50 50
Bi2S3/TiO2 (75/25)-Mt 75 25
The aim of this work is to extend the absorption spectra of TiO2 to
the visible region by using the expected advantages of the TiO2/Bi2S3
junction to increase sunlight absorption efficiency. The obtained na-
nocomposites were characterized by Fourier transform infrared (FTIR),
X-ray fluorescence (XRF), X-ray diffraction (XRD), UV–Vis diffuse re-
flectance spectroscopy (UV– Vis DRS) and photo-electrochemistry. The
photocatalytic activity of these nanocomposites was tested by the
photocatalytic degradation of KP under near UV–Vis irradiation. The
supported photocatalysts, Bi2S3/TiO2-Mt nanocomposites, were syn-
thesized using a two-step ion exchange and impregnation method. The
effect of various operating parameters such as the load of nano-
composite and initial pH of the dispersion was studied. Reaction in-
termediates produced during the photodegradation process were de-
tected, and a suitable mechanism is proposed for the degradation of KP
based on HPLC/MS analysis.
2. Experimental
2.1. Materials
A bentonite clay sample from the Roussel deposit of Maghnia
(Algeria) was used. It was purified using a sedimentation process to
obtain purified bentonite with high montmorillonite (Mt) content.
Some samples of pure bentonite were modified through cation ex-
change with 1 M sodium chloride solution to obtain NaeMt (Khalaf
et al., 1997). Hydrochloric acid (HCl) was purchased from Chiminova.
Titanium (IV) isopropoxide ((Ti(OC3H4)4) (100%) and thiourea
(SC(NH2)2) were acquired from Fluka. Bi(NO3)3·5H2O was obtained
from Panreac Quimica S.A. Experimental KP VETRANAL®, analytical
standard, was purchased from Sigma–Aldrich. All reagents were used
without further purification. Milli-Q water was obtained from a Milli-
pore apparatus with a resistivity of 18.2 MΩ·cm at 298.0 K, and a
measured total organic carbon (TOC) ≤ 5 μg·L−1 (ppb). Triply distilled
water was also used for washing purposes.
2.2. Synthesis of nanocomposites
2.2.1. Preparation of TiO2 pillaring solution
A “sol-gel method” was used, where a colloidal solution was pre-
pared by the addition of (Ti (OC3H4)4 and 1 N HCl, with a molar ratio
[HCl]:[Ti] = 4 (Damardji et al., 2009a; Damardji et al., 2009b). The
mixture was stirred for 3 h at room temperature (ca. 293 K).
2.2.2. Preparation of Bi2S3 pillaring solution
SC(NH2)2 was dissolved in water, and then Bi(NO3)3·5 H2O was
added to this solution and stirred for 30 min at room temperature (ca.
298 K).
2.2.3. Synthesis of Bi2S3/TiO2-Mt nanocomposites
1 g of Mt. was dispersed into 100 mL of water with vigorous stirring
for 18 h to obtain 1.0% (mass) Mt. dispersion. The Bi2S3 pillaring so-
lution was added dropwise to this dispersion, with vigorous stirring, for
24 h, to have 25% Bi2S3. The mixture was autoclaved at 120 °C for
30 min. After cooling to room temperature, the obtained solution was
centrifuged and washed several times with water to remove impurities.
A TiO2 solution was added dropwise to the Mt-Bi2S3 solution, with
strong stirring for 24 h, to 75% TiO2. The resulting mixture was
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

autoclaved at 120 °C for 30 min. After cooling to room temperature, the

solids from the final solution were centrifuged and washed several
times with water. The solid product was dried at 120 °C for 10 min and
calcinated at 400 °C for 10 min in a microwave oven, since this proce-
dure is known to lead to photocatalytic materials with higher activity
than that obtained by conventional heating (Damardji et al., 2009a;
Houari et al., 2005; Pichat et al., 2005). The so-obtained photocatalyst,
with 25% Bi2S3 and 75% TiO2 was named Bi2S3/TiO2 (25/75)-Mt.

2.2.4. Synthesis of Bi2S3 semiconductor

The obtained Bi2S3 bridged solution (black precipitate) were cen-
trifuged and purified several times with distilled water, then it was
dried in an oven at 40 °C for 48 h to eliminate the water which it
contains, then finely ground.

2.3. Nanocomposites characterization

FTIR spectra were recorded with a Shimadzu FTIR-8900 spectro-

meter using a KBr pellet technique for solid samples. The chemical
compositions of the natural and modified materials were determined
with X-ray fluorescence (XRF) analysis, which was performed with a
Phillips PW4025 X-fluorescence spectrophotometer and X-ray powder
diffraction (XRD) was carried out on a Bruker D8 ADVANCE, X-ray
diffractometer operating at 40 kV and 40 mA with Cu Kα radiation. N2
adsorption-desorption isotherms were measured using a Coulter
Omnisorp 100 CX apparatus. The morphology of the samples was re-
corded using scanning electron microscopy (SEM). SEM images and
semiquantitative XEDS microanalyses were taken on a HitachiTM-1000.
UV–Vis diffuse reflectance (UV–vis DRS) spectra were obtained with a
SPECORD® 200 plus analytic Jena spectrophotometer, equipped with
an integrating sphere accessory. The data were transformed to the ex-
tinction coefficient (α) using the Kubelka- Munk (K-M) equation
(Azimia and Nezamzadeh-Ejhieh, 2015). For the photo- electrochemical
(PEC) measurements, the semiconductor powder (Bi2S3) was pressed
into pellets by applying a pressure of 3 bars and sintered at 120 °C. A
copper wire was soldered to one side of the pellet with a conductive
silver paint. A conventional cell was used for the PEC characterization
including a Pt auxiliary electrode, a saturated calomel electrode (SCE)
and the working electrode (WE). The current-potential (J-V) measure-
ments were recorded with a Voltalab potentiostat galvanostat PGZ301
using a tungsten lamp (200 W; Osram).

2.4. Photocatalytic degradation experiments

Photocatalysis experiments with KP were carried out at room tem-

perature (ca. 293 K) in aqueous solution upon NUV–Vis irradiation
(Fig. 1). Experiments were carried out in a 300 mL glass immersion
photochemical reactor (Ø = 6.5 cm) charged with 200 mL of disper-
sion, and the irradiation lamp, located axially in the reactor inside a
quartz immersion tube. The reactor was equipped with a Heraeus TQ
150 medium-pressure Hg-vapor lamp, for which the more intense
emission lines occur at λexc = 254, 313, 366, 405, 436, 546 and
578 nm. The UV emission lines at λexc < 366 nm were filtered out
using a DURAN 50® glass jacket, filled with water to keep the tem-
perature of dispersion within 293 ± 1 K, limiting the irradiation to
near UV- Visible (NUV-vis). The photon flux at 366 nm was 2.38·10−6
Einstein·s−1 as determined by potassium ferrioxalate (K3[Fe(C2O4)3])
actinometry (Kuhn et al., 2004).
For detection reasons, the initial concentration (C0) of the substrate
was set at 15 mg·L−1 (15 ppm). Although this concentration is much
higher than typical environmental values, it would not induce any
change in the reaction mechanism, in the kinetics of the process, or in
the reaction products (Santaballa et al., 2006). In a typical experiment
the load of catalyst was 0.5 g·L−1. Photocatalyst dispersions were
magnetically stirred for 30 min to allow the adsorption– desorption
equilibrium to be established. A first sample was taken out at the end of
Fig. 1. Scheme of the photoreactor: (1) Magnetic stirrer, (2) magnetic stirring
bar, (3) UV/Vis lamp, (4) reactor, (5) gas inlet, (6) power source, (7) lamp
cooling by circulation of thermostated water, (8) sample collection.
this adsorption period, just before the lamp (previously ignited and
warmed up for sufficient time) was inserted, to determine the con-
centration of KP in solution, which was hereafter considered as the
initial concentration (C0). Then, the dispersions were irradiated with
NUV– Vis light, keeping the stirring speed constant. Samples (3 mL)
were withdrawn at different times from the reactor, and immediately
filtered through Sartorius NY 0.45 μm filters.
2.5. Photodegradation kinetics
UV–Vis photocatalytic degradation processes can be adequately
described using a modified Langmuir-Hinshelwood kinetic model, as in
Eq. (1):
KLH ·C
r = kLH ·Θ = kLH ·
1 + KLH ·C (1)
where C is the KP concentration once the adsorption equilibrium has

29
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

a) an electrospray interface operating both in positive (ESI+) and nega-

b) tive (ESI-) ion mode. A Phenomenex Kinetex XB- C18 (100 × 2.10 mm,
2.6 μm) column was used, operated at 40 °C with the elution solvents A
c)
(aqueous 0.1% formic acid) and C (methanol 0.1% formic acid) and a
d) flow-rate of 200 μL min−1. The gradient is described as follow: 0–1 min,
95–95% A and 5–5% C; 1–8 min, 95–5% A and 5–95% C, 8–10 min,
1635 cm-1
5–5% A and 95–95% C; 10–11 min, 5–95% A and 95–5% C; 11–15 min,
3465 cm-1
3647 cm-1 620 cm-1
95–95% A and 5–5% C. The injection amount was 20 μL. Analyses were
carried out using full-scan data dependent MS scanning from m/z 50 to
T (%)

500. The reaction kinetics were monitored by measuring the change in

UV–Vis absorbance at 260 nm using a Biochrom Libra S 70 spectro-
photometer. Total organic carbon (TOC) was quantified using a
Shimadzu TOC-5000A analyser on samples withdrawn at from the re-
actor at 120 min of reaction, and immediately filtered through Sartorius
1036 cm-1 NY 0.45 μm filters.
2349 cm-1
4000 3600 3200 2800 2400 2000 1600 1200 800 400 3. Results and discussion

Wavenumber / cm-1
Fig. 2. Infrared Spectra spectra of the different nanocomposites: (a) NaeMt, (b)
Bi2S3/TiO2 (25/75)-Mt, (c) Bi2S3/TiO2 (50/50)-Mt and (d) Bi2S3/TiO2/(75/25)-
Mt.
been established, kLH (mol s−1 cm−2) is the apparent kinetic rate con-
stant per unit of surface area, and Θ (cm2) accounts for the catalyst
surface covered by KP. KLH is the Langmuir-Hinshelwood adsorption
constant. Assuming KLH·C < < < 1 (see below, section 3.1), eq. (1)
yields the typical expression for a first order kinetic model Eq. (2):
r = kapp·C
kapp ≈ kLH ·KLH
where kapp, Eqs. (2) & (3), is the limiting apparent first order kinetic
rate constant when KLH·C < < < 1.
Since heterogeneous photocatalysis depends on the initial con-
centration of the organic substrate, [KP]0 was kept constant at
15 mg·L−1 (15 ppm).
Integration of eq. (3) between t = 0 and t leads to Eq. (4):
Ct = C0·e−kapp·t
from which apparent first-order rate constants were obtained through
non-linear unidimensional optimization of (Ct/C0) vs. t plots.
2.6. Characterization of the photoproducts
The change in KP concentration was monitored using a Thermo
Fisher HPLC system, equipped with a UV 6000 LP detector, AS 3000
autosampler and P4000 solvent pump, the stationary phase consisted in
a Kromaphase C18 column (4.6 mm × 250 mm × 5 μm). The elution
was made with a (30:70, V/V) ultrapure water-acetonitrile with a
1 mL·min−1 flow rate, injecting 50 μL at room temperature. Qualitative
identification of the photoproducts was carried out by HPLC/MS, using
a Thermo Scientific, LTQ Orbitrap Discovery apparatus, equipped with
3.1. Catalysts characterization
The presence of the two semiconductors (TiO2 and Bi2S3) in the
nanocomposites was confirmed by FTIR analysis (Fig. 2). The intensity
of the IR peaks at 915, 1049 (stretching vibration Si–O-Si) and
1630 cm−1 decreases with decreasing amounts of TiO2 (montmor-
illonite), while the intensity of IR peaks at 624 and 2349 cm−1 attrib-
uted to the presence of Bi2S3 and increases with the percentage of Bi2S3.
The band centered at 1630 cm−1 is attributed to the deformation vi-
brations of H2O molecules adsorbed between layers of montmorillonite
(Boukhatem et al., 2013). The intensity of the IR peak at 915 cm−1,
(2) attributed to the vibration of Si–Oδ−……δ+–Ti (TiO2 combined with
SiO2 in montmorillonite), increases with the amount of TiO2.
(3) The ratio of SiO2/Al2O3 is ca. 3.08 for NaeMt (Table 2), indicating
that Mt. is an aluminosilicate. The Na2O ratio is reduced from 4.3% for
NaeMt to 0.04% for Bi2S3/TiO2 (25/75)-Mt nanocomposite (Table 2),
which evidences the cationic exchange of the Na+ ions of Mt. by the
complex cations, and it is similar for the other two nanocomposites
(Boukhatem et al., 2013).
This suggests that this element is not strongly bound to the sheet,
and is easily exchanged. This confirms that it is eliminated after the
(4) intercalation process and participates in the cation exchange capacity of
Mt. It is also noted that formation of TiO2/Bi2S3 - montmorillonite
nanocomposite is justified by the presence of TiO2, Bi2S3, and SO2 in the
analysis of the samples.
XRD of NaeMt and TiO2/Bi2S3(75/25)-Mt nanocomposite (Fig. 3
a,b) show the important decrease of the Mt. reflection at 2θ = 7.159°
with a basal spacing of 12.349 Å. On the other hand, the suppression of
Mt. reflections from the other two nanocomposites (Fig. 3c and Fig. 3d)
and the increasing intensity of the reflections ascribed to the presence
of crystallized bismuthinite can be explained by the formation of an
exfoliated nanocomposite involving dispersed few-layer of montmor-
illonite. Some of these aggregates Bi2S3 could be in orthorhombic
structure (parameters of the unit cell a = 11.13 Å, b = 11.27 Å and
c = 3.97 Å) according to reference code 00–002-0391, and to the pre-
sence of TiO2 anatase reflections according to JCPDS files № 38–517

Table 2
XRF-analysis expressed as oxides, of NaeMt and Bi2S3/TiO2-Mt nano-composites.
Nanocomposite Composition (wt%)

SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O TiO2 Bi2O3 SO2 LOI

Na-Mt 55.22 17.90 2.06 0.81 4.55 4.3 1.62 0.55 – 0.20 12
Bi2S3/TiO2 (25/75)-Mt 36.31 13.32 1.52 0.06 2.50 0.04 2.30 29.52 0.40 3.02 12
Bi2S3/TiO2 (50/50)-Mt 36.20 12.98 1.85 0.05 2.30 0.03 1.44 15.25 3.51 12.52 13
Bi2S3/TiO2 (75/25)-Mt 38.22 13.40 1.20 0.03 2.56 0.05 1.56 2.10 5.50 22.39 13

LOI: Loss on ignition at 900 °C

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L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

Fig. 3. X-ray diffraction pattern of: (A) NaeMt, (B) Bi2S3/TiO2 (25/75)-Mt, (C) Bi2S3/TiO2 (50/50)-Mt and (D) Bi2S3/TiO2 (75/25)-Mt; (■) Montmorillonite
(bentonite), (•) TiO2 anatase, (▲) Bi2S3.

31
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

30 and reference code = 00–002-0406.

The average crystal size of the particles could be estimated from the
widths of Bi2S3 (orthorhombic) reflections by using the Scherrer for-
mula, L = 0.89·λ/(β·cosθ), where λ (1.5413 Å) is the wavelength, θ is
20 the Bragg angle (°), L is the average crystallite size (nm) and β is the full
width at half-maximum. The calculated data indicates that the average
2

crystal sizes for the three nanocomposites are approximately 13 nm.

(α h ν)

SEM images and XEDS spectra for TiO2/Bi2S3(75/25)-Mt nanocompo-

10 site (Fig. SI2) show evidence for agglomeration in the nanocomposite,
but the real structure and arrangement of layers of the nanocomposites
are not recognizable.
Eg = 1.331 eV N2 adsorption-desorption studies showed a type IV isotherm with a
0 H3 hysteresis loop profile (Fig. SI1 -Supplementary Data-), without a
1.24 1.28 1.32 1.36 1.40 limiting adsorption at high (P/P°) values (Sing et al., 1985). This profile
hν / eV suggests a physisorption process, with formation of a multilayer of
adsorbate and formation of aggregates. BET surfaces of 45.97 m2/g for
Fig. 4. Tauc plot for Bi2S3. Bi2S3/TiO2 (25/75)-Mt, and 17.23 m2/g for Bi2S3/TiO2 (75/25)-Mt
were obtained. The mean pore sizes (BET) measured were ca. 80 Å and
97 Å, respectively, typical of mesoporous materials. Finally, the ob-
tained Freundlich slopes, ca. 2 in both cases, are consistent with a co-
1 operative adsorption. (Kumar and Sharma, 1998) Additional adsorption
and porosity data in Supplementary Data, Table SI1.
DRS was used to determine the optical properties of pure Bi2S3. The
V (V) band gap was determined by plotting (α·h·ν)nversus hν and extrapolating
0
-2.0 -1.5 -1.0 -0.5 0.0 0.5 the linear portion which intercept the energy axes hν·α is the absorp-
tivity coefficient, which depends on the wavelength, n can take the
values 1/2 or 2 for indirect and direct optical transitions, respectively.
-1 It should be noted that α is proportional to ln[(Rmax − Rmin)/
Von= 0.12 V (R − Rmin)], where reflectance decreased from Rmax to Rmin due to the
semiconductor absorption (Kumar and Sharma., 1998).The direct op-
J (mA.cm-2)

-2 tical transition was found at ca. 1.331 eV (Fig. 4), corresponding to the
band gap energy. This result suggests that Bi2S3 (1.331 eV) is more
in the dark
adequate for solar light harvesting than TiO2, whose well known band
under illumination
-3 gap is 3.20 eV.
Photoelectrochemical characterization was performed to determine
Fig. 5. J-V curves of Bi2S3/0.1 M Na2SO4/Pt in the dark and under illumination. the flat band potential (Von) and to confirm the p-type character of
Scan rate 10 mV/s at room temperature. Bi2S3, from J-V curves both in the dark and under illumination Fi.
The position of the valence band of Bi2S3 (p-type) (Fig. 6) is

Fig. 6. Energy diagram of Bi2S3/TiO2 heterojunction at pH = 7.42.

32
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

obtained from the relation (Bessekhouad et al., 2012):

VVB = eVon + Eσ (5)
The position of the Bi2S3 conduction band is calculated with respect
to the vacuum from the following formula (Bessekhouad et al., 2012):
VCB = eVVB − Eg (6)
For an n-type semiconductor, here TiO2, and taking into account the
level of the vacuum, the position of the conduction band can be pre-
dicted from the following equation:
VCB = eVon − ∆Eσ (7)
The position of the valence band of TiO2 is calculated with respect
to the vacuum as:
VVB = Eg + eVCB (8)
The potential of the valence band EVB and of the conduction band
ECB are calculated using the following relationships:
EVB = −(VVB + 4.75 ) (9)
Fig. 7. Energy diagram illustrating charge transfers between Bi2S3/TiO2 junc-
tion under near UV–Visible light irradiation. ECB = −(VCB + 4.75 ) (10)
The energy ΔEσ (= 0.10 eV) for Bi2S3 is simply equal to the differ-
(a) ence of energy between the Fermi level and the valence band. In gen-
1.0 (b) eral, the higher the difference between conduction bands of two
(c) semiconductors, the higher the driving forces of electron injection
(Fig. 5).
0.8

3.2. Photocatalytic degradation of KP in the presence of different

0.6 nanocomposites
C/C0

Using two semiconductors in contact with different redox energy

0.4 levels of their corresponding conduction and valence bands can be
considered as one of the most promising methods to improve charge
separation, to increase the lifetime of charge carriers, and therefore to
0.2
enhance the efficiency of the interfacial charge transfer to adsorbed
substrates. When the two semiconductors are excited under UV–Vis
0.0
irradiation, the electrons are injected from Bi2S3 to TiO2. This results in
0 20 40 60 80 100 120 an increased concentration of electrons in the conduction band of TiO2,
t (min) due to the injection of Bi2S3 electrons in addition to those naturally
generated in TiO2. The TiO2/electrolyte interface is therefore very rich
Fig. 8. Photodegradation of 15 mg·L−1 aqueous KP onto 0.50 g·L−1 of the dif- in electrons.
ferent nanocomposites under UV–Vis irradiation: (a) Bi2S3/TiO2(25/75)-Mt, (b) On the other hand, the holes generated in the TiO2 valence band are
Bi2S3/TiO2(50/50)-Mt and (c) Bi2S3/TiO2 (75/25)-Mt. T ca. 293 K. transferred to the Bi2S3 valence band, which also results in a high
concentration of holes at the Bi2S3/electrolyte interface. Electrons and
holes can react to produce free radicals (O2•- and HO•) able to degrade
1.0 KP (Fig. 7). Nanocomposites Bi2S3/TiO2(50/50)-Mt and Bi2S3/TiO2(75/
25)-Mt show lower degradation rates than that of Bi2S3/TiO2(25/75)-
Mt (Fig. 8). First order decay model appropriately fit the obtained ki-
0.8
(a) netic data, with R2 values always higher than 0.97 (Table 3).
(b) The lower activity with increasing the Bi2S3 concentration beyond
(c) certain limit may be explained by possible formation of a film which
0.6
encapsulates TiO2 particles, thus blocking the transfer of electrons
C/C0

flowing from excited Bi2S3 to the TiO2 conduction band; therefore less
0.4 radicals are produced and the KP photodegradation rate decreases.

3.3. Effect of pH
0.2
The photodegradation yield increases with pH (Fig. 9 and Table 3),
this is attributed to electron injection from the CB-Bi2S3 to the CB-TiO2
0.0 band (vide supra).
0 20 40 60 80 100 120
By increasing the pH, the energy gap between the CB-TiO2 band and
t (min) CB-Bi2S3 band decreases. This is explained according (Nozik and
Memming, 1996) by the pH independence of the CB and VB bands of
Fig. 9. Photodegradation of 15 mg·L−1 aqueous KP onto 0.50 g·L−1 of the na-
nocomposite Bi2S3/TiO2 (25/75)-Mt under UV–Vis irradiation at different pH
Bi2S3, unlike TiO2, which undergoes a shift of the potential towards the
values: (a) pH = 11, (b) pH = 7 and (c) pH = 3. T ca. 293 K. cathodic or anodic side as a function of the acidity of the medium
(Fig. 10). In addition to the described effect speciation of KP should be

33
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

Fig. 10. Efect of pH on the VB and CB of Bi2S3 and TiO2.

Table 3 under ESI+ and ESI− ionization modes, with mass to charge (m/z)
Pseudo-first-order rate constants for KP photodegradation over Bi2S3/TiO2-Mt values: 210, 242, 228, 226 and 316 were identified (Table 4). The
composites under UV–Vis irradiation. [KP]0 = 15 mg·L−1; [Bi2S3/TiO2- product with (m/z) = 210 was also found by MS (Martínez et al.,
Mt]0 = 0.5 g·L−1;T ca. 293 K. 2013;Kosjek et al., 2011; Illés et al., 2014), and is identified as 3-
kapp/min−1 ethylbenzophenone. The products with (m/z) = 242 and 226 corre-
spond to 3-(1-droperoxyethyl) benzophenone, 3-(1-hydroxyethyl)ben-
Nanocomposite Bi2S3/TiO2(25/75)-Mt Bi2S3/TiO2 Bi2S3/TiO2(75/ zophenone, respectively. They were identified in the literature based on
(50/50)-Mt 25)-Mt
pH natural pH = 11 0.0378 ± 0.0008 0.030 ± 0.003 0.030 ± 0.003
chromatographic and spectroscopic evidences (Boscá and Miranda.,
pH = 7 0.0396 ± 0.0009 1998; Bagheri et al., 2000; Nakajima et al., 2005; Musa et al., 2007;
pH = 3 0.022 ± 0.002 Real et al., 2009; Kosjek et al., 2011; Szabó et al., 2011).
0.015 ± 0.002 Peaks with (m/z) = 316 and 228 were also detected by MS and are
proposed to correspond to (3-(1-hydroxy-1-phenylpropan-2-yl)phenyl)
(phenyl)methanone and 1-[3-(hydroxy-phenyl-methyl)- phenyl]-
considered as its pKa is ca. 4.7 (Martínez et al., 2013), this means than ethanol, respectively. HO• produced under NUV–Vis irradiation during
at pH > 7, KP mainly exists in its anionic form, which makes easier its
heterogeneous photocatalysis over Bi2S3/TiO2-Mt is likely the main
decarboxylation. degrading species of KP.
Considering the identified photoproducts and related literature data
(Martínez et al., 2013; Musa et al., 2007; Matamoros et al., 2009),
3.4. Reaction mechanism
Scheme 2 shows the proposed reaction mechanism for KP aqueous
photodegradation over Bi2S3/TiO2-Mt nanocomposites upon NUV-Vis
The products of the photocatalyzed degradation of KP in aqueous
irradiation. The first degradation step is the decarboxylation of KP re-
solution over Mt. nanocomposites under NUV-Vis irradiation were
sulting in formation of 3-ethylbenzophenone (2) (Musa et al., 2007).
analyzed by HPLC. According to Figs SI3 and SI4 (Supplementary Data),
Likely, the decarboxylation will be easier when pH > 5 as pKa (KP) ca.
two degradation products with retention times 3.848 min (b) and
4.7 (Martínez and Scaiano, 1997), and therefore KP will be mainly in its
4.943 min (c) were identified. The photoproduct (b) disappeared at
anionic form. The formation of photoproducts can be explained by
80 min of the reaction, while the photoproduct (c) stayed stable till the
subsequent reactions of 3-ethylbenzophenone (2) and/or its radical
end of the reaction (120 min).The main transformation products were
(2●) with HO● and other reactive oxygen species (ROS) like O2●- and
identified by HPLC-MS (Fig. SI5 –Supplementary Data–), with elution
with O2. Hydroxylation of (2), and/or (2●) leads to 3-(1-hydroxyethyl)
times 0.98, 6.60, 8.19, 8.67 and 8.86 min, respectively. Ion peaks,

Table 4
KP degradation products formed upon heterogeneous photocatalysis under NUV-Vis radiation (120 min) over Bi2S3/TiO2-Mt nanocomposites, as identified by HPLC/
MS. T ca. 293 K.
Compound Ion Formula Mass Name tR/min Reference
m/z

(1) [M-2H]− C22H20O2 (3-(1-hydroxy-1-phenylpropan-2-yl) 0.98 proposed

314.09 316 phenyl)(phenyl)methanone
(2) [M + H]+ C15H14O 3-ethylbenzophenone 6.60 (Kosjek et al., 2011; Martínez et al., 2013; Illés et al., 2014; Assaf et al., 2017;
211.14 210 Koumaki et al., 2015; Wang et al., 2017; Li et al., 2017).
(3) [M-H]− C15H14O3 3-(1-hydroperoxyethyl) benzophenone 8.17 (Boscá and Miranda, 1998; Bagheri et al., 2000; Nakajima et al., 2005; Musa
241.09 242 et al., 2007; Real et al., 2009; Kosjek et al., 2011; Szabó et al., 2011; Koumaki
[M + H]+ et al., 2015; Li et al., 2017)
243.10
(4) [M-H]− C15H164O2 1-[3-(hydroxy-phenyl-methyl)-phenyl]- 8.67 Proposed
227.11 228 ethanol
[M + H]+
229.11
(5) [M-H]− C15H14O2 3-(1-hydroxyethyl) benzophenone 8.84 (Boscá and Miranda, 1998; Bagheri et al., 2000; Nakajima et al., 2005; Musa
225.09 226 et al., 2007; Real et al., 2009; Kosjek et al., 2011; Szabó et al., 2011; Koumaki
[M]+ et al., 2015; Assaf et al., 2017; Wang et al., 2017; Li et al., 2017)
226.09

34
L. Djouadi et al. Applied Clay Science 166 (2018) 27–37

Scheme 2. Proposed reaction mechanism for the photocatalytic degradation of KP aqueous solution over Bi2S3/TiO2-Mt under NUV–Vis radiation.

Table 5 phenylpropan-2-yl)phenyl)(phenyl)methanone (1).

Total carbon and total organic carbon determined for KP aqueous solution
heterogeneous photocatalysis over different Bi2S3/TiO2-Mt nanocomposites
after 120 min of NUV-Vis irradiation. T ca. 293 K. 3.5. Total organic carbon and extent of mineralization
Total carbon/mg·L−1 Total organic carbon/mg·L−1
Total organic carbon (TOC) measurements were carried out to check
KP 11.90 11.80 the extent of mineralization achieved (Table 5).
Bi2S3/TiO2 (25/75)-Mt 10.67 10.57
Bi2S3/TiO2 (50/50)-Mt 10.09 9.85
From the obtained results, increasing the proportion of TiO2 im-
Bi2S3/TiO2 (75/25)-Mt 10.08 9.93 proves the mineralization, but only up to Ti/Bi (50/50). However, the
low TOC reduction (mineralization, ca. 16%) found confirms the need
to increase the time of treatment by far > 2 h. KP is initially trans-
benzophenone (5) which after further hydroxylation produces either 1- formed into the different intermediates and products (Table 4 and
[3-(hydroxy-phenyl-methyl)-phenyl]-ethanol (4) or 3-(1-hydro- Scheme 2), but some of them are highly persistent and contribute to
peroxyethyl) benzophenone (3), which might also be generated by re- slow TOC reduction. This makes necessary to take into account the
action of (2) or (2●) with O2●- or even O2. A bimolecular radical chain congeners of KP and not only the parent compound in what regards
termination would explain formation of (3-(1-hydroxy-1- regulation of KP levels in the environment.

35
L. Djouadi et al.
4. Conclusions
The photodegradation of KP has been investigated, a widely used
pharmaceutical product, onto new nanocomposite materials containing
TiO2, Bi2S3 and montmorillonite under near UV–Vis irradiation. The
effective and low-cost nanocomposites were obtained by simple im-
pregnation, and characterized by FTIR, XRF, XRD, and UV-Vis DRS,
montmorillonite being successfully modified by the two semi-
conductors. Successful intercalation of TiO2 and Bi2S3 in the mon-
tmorillonite was carried out, and the corresponding energy diagram for
the Bi2S3/TiO2 heterojunction has been proposed. KP was successfully
degraded, showing the efficiency of the photocatalytic process. The
decay of KP in aqueous over Bi2S3/TiO2 (25/75)-Mt nanocomposites
under NUV-Vis irradiation, monitored by HPLC, followed pseudo-first-
order kinetics according to the Langmuir-Hinshelwood kinetic model.
Bi2S3/TiO2(25/75)-Mt was the most efficient nanocomposite in terms of
KP degradation. KP photodegradation was higher and faster at basic pH
than at acidic pH. Complete KP disappearance took place after 120 min
of irradiation (t½ca. 17 min) at pH 11, whereas just 80% of KP dis-
appeared, also after two hours irradiation, (t½ca. 44 min) at pH 3.
Likely the existence of KP in its anionic form facilitates its photo-
degradation (pKa(KP) ca. 4.7). The photodegradation products are ra-
ther refractory, so although KP disappears, the extent of mineralization
is low.
Some KP photoproducts were identified by using HPLC-MS, and the
corresponding reaction mechanism was proposed. Photodegradation of
KP over Bi2S3/TiO2-Mt nanocomposites under NUV-Vis irradiation
starts with the decarboxylation of KP, subsequent hydroxylation by
hydroxyl radical and oxidation by other reactive oxygen species (ROS)
leads to the photoproducts detected by HPLC-MS: (3-(1-hydroxy-1-
phenylpropan-2- yl)phenyl)(phenyl)methanone, 3-ethylbenzophenone,
3-(1-hydroperoxyethyl)benzophenone, 1-[3-(hydroxy-phenyl-methyl)-
phenyl]-ethanol, 3-(1-hydroxyethyl) benzophenone. Intercalation TiO2
and Bi2S3 in the montmorillonite has been proved as an appropriate
strategy to prepare cheap and efficient supported nanocomposites for
the abatement of organic pollutants from aqueous solution using NUV-
Vis light.
Acknowledgements
The authors would like to thank Prof. M. Trari and Dr. R. Brahimi
from University of Science and Technology Houari Boumediene, Algeria
for his technical assistance and Dr. A. Boucherit from Saad Dahlab
University, Algeria for proofreading the manuscript.
This research was partially supported by the Group of Chemical
Reactivity & Photoreactivity (React!) at University of A Coruña, with
financial support from Ministerio de Economía y Competitividad (Spain)
through project CTQ2015-71238-R (MINECO/FEDER) and Xunta de
Galicia through Grupo Potencial Crecemento (GPC) ED431B 2017/59.
Conflicts of interest
All authors declare that they have no conflicts of interest
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2018.09.008.
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