Environmental Science and Pollution Research (2022) 29:90191–90206

https://doi.org/10.1007/s11356-022-22100-1

RESEARCH ARTICLE

Boosted photocatalytic effect of binary AgI/Ag2WO4 nanocatalyst:

characterization and kinetics study towards ceftriaxone
photodegradation
Sabereh Salesi1 · Alireza Nezamzadeh‑Ejhieh1

Received: 20 May 2022 / Accepted: 14 July 2022 / Published online: 22 July 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
In modern chemistry, great interest has been paid to introducing outstanding photocatalysts for degrading organic pollutants.
Herein, a highly efficient binary AgI/Ag2WO4 photocatalyst was prepared from AgI and A ­ g2WO4 nanoparticles (NPs) and
characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), UV–Vis diffuse reflectance spectroscopy
(DRS), electrochemical impedance spectroscopy (EIS), and Fourier transform infrared (FT-IR) techniques. In the Scherrer
model, the average crystallite sizes of 34.9, 42.0, and 24.1 nm were estimated for the AgI, ­Ag2WO4, and the binary catalyst,
while the values were 91, 13, and 85 nm by the Williamson-Hall model. FTIR confirmed the presence of W–O–W, O–W–O,
Ag-I, and O–Ag–O bonds in the coupled material. DRS results showed absorption edge wavelengths of 451, 462, and 495 nm
(corresponding to the band gap values of 2.75, 2.68, and 2.51 eV) for A
­ g2WO4, AgI, and AgI/Ag2WO4 catalyst, respectively.
Synergistic photocatalytic activity of the coupled system was achieved towards ceftriaxone (CTX) in an aqueous solution
(about 33% 10 ppm CTX solution was degraded without any optimization in the initial conditions of catal dose 0.3 g/L
­(Ag2WO4:AgI with mole ratio 1:2 and 30 min abrasion time), and irrad. time 45 min, ­CCTX). This boosted effect depended
on the AgI:Ag2WO4 mole ratio and grinding time for the mechanical preparation of the binary catalyst (optimums: mole ratio
of 4:1 and time 30 min). The photodegradation kinetics obeyed the Hinshelwood model with the apparent first-order rate
constant (k) of 0.013 ­min−1 ­(t1/2 = 53.30 min). Performing the COD on the photodegraded CTX solutions got a Hinshelwood
plot with a slope of 0.019 ­min−1 ­(t1/2 = 36.5 min).

Keywords Antibiotic pollution · Heterogeneous photodegradation · Hinshelwood kinetics · Binary AgI/Ag2WO4 coupled
photocatalyst

Introduction pharmaceutical compounds (Martinez 2009; Moussavi et al.

Environmental pollution due to a wide variety of pollut-
ants is a great interest in the environmental research field
(Ahmadian-Fard-Fini et al. 2020; Chaker et al. 2021a, b;
Hosseini et al. 2018). A widely used class of health and care
products to improve human, animal, and even plant health is
Responsible Editor: Sami Rtimi
* Alireza Nezamzadeh‑Ejhieh
arnezamzadeh@iaush.ac.ir
Sabereh Salesi
ssabere40@gmail.com
1 or decreasing their levels in the corresponding effluents
Department of Chemistry, Shahreza Branch, Islamic
Azad University, P. O. Box 311‑86145, Shahreza, Isfahan,
Islamic Republic of Iran
2013; Petrie et al. 2015). For preventing or treating bacterial
infections, antibiotics have been known as the most used
drugs (Moussavi et al. 2013). Subsequently, high amounts
of antibiotics can be discharged into various water resources
by municipalities and pharmaceutical laboratories and other
sources. Thus, a relatively high amount of antibiotics can
be accumulated in the aquatic environment, especially via
the bio-accumulative process. Thus, they have been intro-
duced as critical water contaminants, and in general for the
recipient environment, dangerous chemicals, and increased
agents for bacterial resistivity (Harris et al. 2014; Verlicchi
et al. 2015).
Thus, the elimination of such hazardous pollutants
before they are discharged into the environment has been
adopted with great special attention by various chemists and

13
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90192
environmental researchers. Accordingly, various removal
techniques such as microbial degradation, purification by
adsorption through activated carbon, chlorination, ozonation
(Cheng et al. 2019), and UV irradiation have been applied
by researchers (Bessergenev et al., 2017; Cruz-Ortiz et al.
2017; Hallmich & Gehr 2010; Wang et al. 2015; Wang
et al. 2016). Overall, energy consumption, toxic by-prod-
uct production, low efficiency, incomplete removal due to
the transferring of the pollutant to another phase, etc. have
been considered major drawbacks which limit applications
of many techniques mentioned above. Therefore, it is criti-
cal to develop/introduce environment-friendly and higher
effective technologies such as advanced oxidation processes
(AOPs) to diminish such drawbacks in water pollution treat-
ments. AOPs have potential efficiency for relatively com-
plete removal of various organic pollutants during waste-
water treatment based on the generation of critical reactive
and nonselective oxidant hydroxyl radicals (•OH) (Pigna-
tello et al. 2006; Zazo et al. 2005). This radical can oxidize
various organic pollutants to ­CO2 and ­H2O.
Outstanding green technology for removing organic con-
taminants, as well as some inorganic ones, is the heterogene-
ous semiconductor photocatalysis with eco-friendly, low-
cost, and repeatable properties and a green technology future
especially a solar-driven catalyst used (Kuvarega et al. 2018;
Senthil et al. 2018; Yang et al. 2017; Zinatloo-Ajabshir et al.
2020). Under the semiconductor illumination with photon
energy (hν > band gap), its VB electrons (VB: valence band)
reach its CB (valence band) leaving the positive holes (­ h+)
behind. The induced ­e−/h+ pairs can attack the molecules
of the pollutant directly to degrade them. In another way,
the photoinduced electrons can produce superoxide radicals
by reducing the dissolved oxygen and producing hydroxyl
radicals via oxidizing water molecules. Both radicals are
powerful reagents for attacking the pollutants present in
the aqueous solution (EL Bekkali et al. 2018; Nguyen et al.
2020; Sonu et al. 2021).
Another effort to stabilize the photoexcited semiconduc-
tor is losing the energy of CB-e− and getting recombined
with VB-h+. The drawback critically reduces the overall
efficiency of the photodegradation process, and thus, to
improve high quantum photocatalytic efficiency, a combi-
nation of photocatalyst with others compounds (heterojunc-
tion systems) (Chai et al. 2009; Cheng et al. 2012; Dianat
2018; Hassani et al. 2018; Monsef et al. 2021; Shamaila
et al. 2011; Zhang et al. 2013; Zinatloo-Ajabshir et al.
2018; Zinatloo-Ajabshir & Salavati-Niasari 2019), use of
catalysts in nanoscale (Khairnar et al., 2018) (Eslami et al.,
2018; Zebardast et al. 2018), doping (Bordbar et al., 2018;
Chaker et al. 2021a, b; Elmi Fard & Fazaeli 2018), support-
ing (Karimi-Shamsabadi & Behpour 2021; Karimi Sham-
sabadi & Behpour 2021; Landi et al. 2019), and construct-
ing the plasmonic systems have been suggested/used. These
13
Environmental Science and Pollution Research (2022) 29:90191–90206
technologies drastically increase the degradation of pollut-
ants by reducing the recombination rate of the e­ −/h+ pairs
(Davar et al. 2010; Hassani et al. 2021; Madihi-Bidgoli et al.
2021; Motahari et al. 2015).
It has been reported that silver iodide (AgI) can act as
a potential photosensitizer. Accordingly, it can be used in
photocatalytic disinfection and degradation of some organic
pollutants (W. Jiang et al. 2014). But, the pristine AgI is
unstable because of this photosensitizing property. To dis-
solve this problem, it has been commonly combined with
other semiconductors, forming a heterojunction structure
in which AgI acts as a photosensitizer (Wen et al. 2017).
Fortunately, AgI possesses a high conduction band potential
position of about − 0.4 V, facilitating the expected spatial
charge carriers separation in its couples systems such as AgI/
CeO2, AgI/ ­Ag2WO4, etc. (Wen et al. 2017).
In environmental issues, a growing interest has been
focused on silver tungstate ­(Ag2WO4) (Li et al. 2016; Lv
et al. 2017; Mousavi & Habibi-Yangjeh 2018; Wang et al.
2013; Xu et al. 2018), which its pure crystals with a wide
energy gap of about 3.0 eV can only absorb photons in the
ultraviolet region (Xu et al. 2018). This limited application
drawback should be overcome by the introduction of novel
visible-light-responsive ­Ag2WO4–based photocatalysts. The
presence of suitable VB and CB positions in a semiconduc-
tor with a large band gap value often separates the photogen-
erated charge carriers (Mousavi and Habibi-Yangjeh 2018) .
In this study, the binary AgI/Ag2WO4 catalyst was con-
structed and its synergistic effect concerning the semicon-
ductors alone was evaluated toward the degradation of cef-
triaxone under visible light. AgI has been selected due to
possessing matched energy band levels for combining with
­Ag2WO4. Here, brief characterization results will illustrate
and then the photodegradation section will focus on the
kinetic aspect of the work.
Experimental
Materials and preparations
AgNO3, KI, N ­ a2WO4, and other chemicals, having an ana-
lytical grade in purity, were purchased from Sigma/Aldrich
Company. The commercial ceftriaxone (as sodium salt)
ampoule (1 g, Pars Nami Co.) was prepared from the local
drugstores and used without further purification. Aqueous
solutions/suspensions were obtained in distilled water.
In the synthesis of AgI NPs, 20 mL 75 mM ­AgNO3 aque-
ous solution was quickly added to 20 mL 75 mM KI aqueous
solution. The obtained suspension was vigorously stirred for
15 min. The solid product was separated by centrifugation
and left to dry during the day under dark conditions. Finally,
Environmental Science and Pollution Research (2022) 29:90191–90206 90193

it was water washed several times and sintered at 250 °C for (Ao) to calculate the CTX removal percentage by using the
5 h (Hawari & Johan 2011). following formula.
The following precipitation method was used to synthe- [( ) ] [( ) ]
size ­Ag2WO4 nanorods in which 10 mmol ­Na2WO4 (99.9%) Degradation% = Co − C ∕Co × 100 = Ao − A ∕Ao × 100
was dissolved in 100 mL water (solution A). 2.5 mmol (1)
­AgNO 3 was also dissolved in 100 mL water (solution
B). Solution B was dropped into solution A (10 mL/min
under magnetic stirring), and stirring was continued for
Results and discussion
2 h. Finally, the product was separated with centrifugation,
washed with water and ethanol, and dried at 80 °C for 4 h in
Characterization studies
an air atmosphere (Jing & Kang 2020).
For obtaining an AgI/Ag2WO4 binary catalyst having a
X‑ray diffraction (XRD) studies
certain AgI:Ag2WO4 mole ratio, a definite weight of each
component was used and hand-mixed completely in an agate
The diffraction patterns for ­Ag2WO4, AgI, and the binary
mortar for 30 min. The use of agate mortar is due to war-
­Ag2WO4/AgI catalysts are presented in Fig. 1. Pattern A
rant the no impurities add to the sample during the grinding
depicts the diffraction peaks for the as-synthesized A
­ g2WO4
process. Table SDT1 summarized all data and amounts used
NPs. According to PDF file no 34–0061, α-Ag2WO4 with
for preparing the coupled catalysts.
an orthorhombic crystallite phase can be confirmed with
the diffraction peaks positioned at 2θ values of 16° (011),
30.31° (002), 31° (231), 32.50° (400), 45.10°, (402),
Characterization methods
55° (361), and 57.80° (333) (Chen & Xu 2014). In con-
trast, the β -Ag2WO4 (the hexagonal crystallite phase with
The following instruments were used for the characteriza-
PDF#33–1195), can show typical diffraction peaks at 2θ
tion of the samples. Recoding XRD patterns was done by
positions of 18.54°, 30.13°, 31.64°, 32.40°, 44.84°, 52.66°,
an XRD diffractometer model X’PertPro (with a Ni-filtered
56.34°, and 59° which can be assigned to (020), (121), (022),
Cu-Ka radiation source at 1.5406 Å, 40 kV, i 30 mA; Neth-
(220), (042), (242), (060), and (224) crystal planes (Li et al.
erland). A UV–Vis diffuse reflectance spectrophotometer
2015; Lv et al. 2017). In the XRD pattern of the as-synthe-
(JASCO V 670, by using B ­ aSO4 as the reference material,
sized ­Ag2WO4, the diffraction angles appeared at 18.65°,
Japan) was used for recording DRS spectra. Fourier trans-
27.40°, 30.31°, 32.44°, 45.00°, 56.45°, 57.79°, and 59.36°
form infrared (FTIR) spectrophotometer (PerkinElmer Spec-
which agreed better with those for the β-Ag2WO4 hexagonal
trum 65) was used for recording FTIR spectra. MIRA3LMU
crystallite phase. Thus, the peaks were assigned to the cor-
scanning electron microscope (TESCAN Co Czech Repub-
responding hkl planes of (020), (121), (022), (220), (042),
lic) equipped with an energy-dispersive analyzer (EDX) was
(242), (060), and (224), respectively. According to the stand-
used for recording the SEM images and the EDX spectra
ard pattern for the cubic γ-Ag2WO4 (JCPDS No: 33–1197)
of the samples. Electrochemical impedance spectra were
(Alvarez-Roca et al. 2021; Roca et al. 2017), some peaks
recorded on an Autolab instrument (PGSTAT 302, Metrohm)
with lower intensity are present in the pattern of ­Ag2WO4
Instrument. A Jenway pH meter (model 3505) was used for
which were assigned.
pH adjustment.
A typical diffraction pattern for the as-synthesized AgI
NPs is depicted in Fig. 1B. Based on the standard JCPDS
file no 09–0374, the hexagonal β-AgI phase can be identified
Photodegradation experiments
by typical diffraction peaks positioned at the 2θ positions of
22.79° (100), 23.91° (002(, 39.62°(110), and 46.58° (112)
To investigate the photocatalytic activities of the obtained
of AgI (Cheng et al. 2010; Xu et al. 2021). Here, 2θ peaks
individual and coupled catalysts, photodegradation of cef-
of 22.29°, 23.66°, 25.20°,39.10° 42.52°, and 46.26° have
triaxone aqueous solution (10 mg/L) under irradiation by
appeared in the pattern of the as-synthesized AgI sample,
a 100-W tungsten lamp (located 10 cm above the cell) was
confirming the synthesis of a hexagonal β-AgI phase. Thus,
done. Accordingly, 0.3 g/L of the photocatalyst/ceftriaxone
the diffraction peaks have been assigned to their hkl planes.
suspension was used. Before the irradiation process, the
In the pattern of the coupled binary A ­ g2WO4/AgI system,
mixture was stirred at dark for 15 min and then irradiated for
all the peaks mentioned above have appeared with some
45 min. The absorbance (A) of the cleaned ceftriaxone solu-
overlapping and slight shifts. This may be related to some
tion (achieved via centrifugation) was recorded by a UV–Vis
interactions that occurred between the components due to
spectrophotometer at maximum absorbance wavelengths of
the mechanical force applied.
238 and 274 nm and compared with that of blank solution

13
90194
Fig. 1  XRD patterns of ­Ag2WO4 NPs (A), AgI NPs (B), and binary AgI/Ag2WO4 (C) catalysts; typical Williamson-Hall plot obtained by XRD
data of the binary AgI/Ag2WO4 sample
The full width (β: FWHM) of the diffraction peaks and
the diffraction angle θ were used for calculating the crystal-
lite size (d) using the below Scherrer formula (Ramasamy
et al. 2012). In this formula, the Scherrer constant or the
shape factor k commonly gets a value of about 0.9, and the
X-ray wavelength is commonly Cu-Kα at 1.5406 Å (Lotfian
et al. 2020; Maharana & Sen 2022).
D = kλ∕βcosθ (2)
All data used and the crystallite sizes obtained are sum-
marized in Tables SDT2–4 (see supplementary data). The
average crystallite sizes of about 34.9, 42.0, and 24.1 nm
were estimated for the AgI, A­ g2WO4, and the binary catalyst,
respectively.
Scherrer’s method uses the peak width derived from the
X-ray pattern or the size broadening for estimating the crys-
tallite size. The peak width in a diffraction pattern depends
on the size of the crystalline particle, inhomogeneous strain,
and instrumental factor. Accordingly, the accurate crys-
tallite size determination from powder diffraction data is
13
Environmental Science and Pollution Research (2022) 29:90191–90206
complicated. Thus, many indirect methods have been often
used, among them the Williamson–Hall (W–H method) is
more famous (Williamson & Hall 1953). This method adds
the effect of the induced lattice strain (ε) to the peak broad-
ening as shown by formula (3). Thus, the W–H formula
confirms that the peak width includes the size broadening
(the Scherrer formula) and the strain broadening (Collu
et al. 2022; Pourshirband et al. 2020; Xu et al. 2021).
βcosθ = (kλ∕d) + 4εsinθ (3)
Typical plots of βcosθ-sinθ were constructed as depicted
in Fig. 1D and SDF2-4. From the y-intercept of the fitted
W–H line, the crystallite size can be estimated. The aver-
age sizes of 91, 13, and 85 nm were obtained for the AgI,
­Ag2WO4, and the coupled photocatalyst, respectively.
FTIR spectra
The characteristic chemical bonds for the as-prepared AgI,
­Ag2WO4, and AgI/ ­Ag2WO4 catalysts were evaluated by
Environmental Science and Pollution Research (2022) 29:90191–90206
Fig. 2  A–D FT-IR spectra for as-prepared ­Ag2WO4 NPs, AgI NPs, and binary AgI/Ag2WO4 catalyst at different washing/drying conditions
FT-IR absorption spectrophotometry which spectra are
depicted in Fig. 2. Three washing/drying samples were
compared in the recorded spectra. First, the as-prepared
sample was air subjected to FTIR directly. The dried sam-
ple means that the as-prepared sample was oven-dried at
75 °C for 1 h and then the FTIR spectrum was recorded.
The washed sample means that the as-prepared sample was
stirred in H
­ 2O-Ethanol (1:1) for 1 h and then oven-dried at
75 °C for 1 h before recording the FTIR spectrum.
For all samples, the broad stretching vibration around
3400 ­c m −1 and the bending adsorption band around
1650 ­cm−1 have appeared belonging to the adsorbed phys-
ically water molecules or hydroxyl groups (Amiri et al.
2017; Davoodi et al. 2022; Salavati-Niasari & Davar 2006;
Yosefi & Haghighi 2018).
Typical absorption spectra for the as-prepared silver
tungstate are shown in Fig. 4A. Based on the literature,
W–O–W and O–W–O asymmetric stretching vibration
90195
modes in tetrahedral tungstate can appear intense absorp-
tion bands at 591, 761, and 828 ­c m −1 (Sreedevi et al.
2016). Figure 4B shows the absorption FTIR spectra for
AgI. Commonly, typical IR absorption peaks for Ag–X
(X = Cl and I) sample have appeared at the positions of
595 and 640 ­cm−1 belonging to the stretching vibration of
the bonds (Choi et al. 2015).
In the spectrum of the binary catalyst (Fig. 4C), the bands
mentioned above for ­Ag2WO4 and AgI have appeared, but
the band intensities are relatively weaker than those for the
systems alone. This can be related to the loading of each
component to the other in the coupled system. Similar find-
ings have been reported for AgX-loaded A ­ g2WO4 catalysts,
proving the good dispersion of AgX nanocrystals on the sur-
face of A
­ g2WO4 nanorods (Tang et al. 2012; Xu et al. 2013).
The slight shifts in the band positions can be attributed to
particle size, preparation procedures used, and distortions
on O–W–O and O–Ag–O bonds (Cavalcante et al. 2012).
13
90196 Environmental Science and Pollution Research (2022) 29:90191–90206

UV–Visible optical spectroscopy results
To estimate the change in the band gap energy variation
during the coupling of the semiconductors, the UV–Vis
diffuse spectra (DRS) were recorded (Hassani et al. 2021;
Landi et al. 2022a, b; Tehubijuluw et al. 2022). Due to the
importance and critical role of the visible-light active pho-
tocatalyst in the photocatalysis field, having some knowl-
edge about the band gap energy of the semiconductors
used is of great importance (Sabzehmeidani et al. 2020).
The absorption spectra for the AgI, ­Ag 2WO 4 NPs, and
the binary AgI/Ag2WO4 catalyst are depicted in Fig. 3A.
The absorption edge wavelength (λAE) was obtained via
the extrapolation of the rising slope of absorption spectra
towards the x-axis. The values of 451, 462, and 495 nm for
­Ag2WO4, AgI, and AgI/Ag2WO4 catalyst, respectively. The
λAE values obtained were then substituted in this empiri-
cal formula: E­ g = 1240/λ (Yang et al. 2019), to estimate
the band gap (Eg) of the samples (Landi et al. 2022a, b).
The Eg values of 2.75, 2.68, and 2.51 eV were achieved

Fig. 3  A Absorption spectra

obtained in DRS characteriza- 1.4 Catalyst λ (nm) Eg (eV)
tion of ­Ag2WO4 NPs, AgI NPs, a: AgI/Ag2WO4 495 2.51
and binary AgI/Ag2WO4 cata- b: Ag2WO4 451 2.75
lyst; B typical EIS spectra for 1.2 c: AgI 462 2.68
the modified glassy carbon elec-
trodes with the individual and a
binary AgI/Ag2WO4 catalysts 1.0
(amplitude 10.0 mV, frequency
10 MHz to 100 kHz, electro-
0.8
Abs.

lyte 0.1 M ­Na2SO4, potential

0.0 V versus Ag/AgCl, counter c
electrode Pt) b
0.6
a: AgI/Ag 2 WO 4
0.4 b: Ag 2 WO 4
c: AgI
0.2

0.0
800 700 600 500 400 300 200
A
Wavelength (nm)
30000
a: GC/Ag2WO4
25000 b: GC/AgI
c: GC/AgI/Ag2WO4
a

20000 b
Z" (Ohm)

15000 c

10000

5000

0
0 5000 10000 15000 20000 25000
B
'
Z (Ohm)

13
Environmental Science and Pollution Research (2022) 29:90191–90206
Fig. 4  A–B Some SEM images for the as-synthesized ­Ag2WO4 catalyst
for ­Ag2WO4, AgI, and AgI/Ag2WO4 catalyst, respectively.
This study proves that the bond gap energy of the coupled
system was relatively red shifted to longer wavelengths.
Electrochemical impedance spectroscopy (EIS) study
Corresponding EIS spectra for the modified glassy carbon
(GC) electrodes with AgI NPs, A ­ g2WO4 NPs, and the binary
AgI-Ag2WO4 catalyst are compared in Fig. 3B. As shown,
in the case of the modified GC electrode with the binary
catalyst, a semicircle Nyquist plot was achieved, confirm-
ing lower resistance for charge transfer. This decrease in the
resistance confirms that the charge carriers in the coupled
system can migrate with more efficiency. Thus, it would be
expected that this coupled binary catalyst shows better pho-
tocatalytic activity than the individual systems.
SEM–EDX, X‑ray mapping results
Figure 4A–B show SEM images for the individual A ­ g2WO4
catalyst. As shown, A­ g2WO4 NPs have an original spherical
shape and their aggregates formed both spherical and rod
morphologies. Some SEM pictures for the binary catalyst
are also presented in Fig. 5A-B. As shown, some smaller
spherical species have dispersed on the larger species. Simi-
lar observations have been reported for the dispersion of AgI
on the surface of A­ g2WO4 (Xu et al. 2018). The relatively
90197
bright spots can be related to AgI, confirming its high ionic
conductivity (Pourshirband et al. 2020). Comparing SEM
images of ­Ag2WO4 and the coupled system confirms that
the rod-like aggregates of ­Ag2WO4 were relatively disap-
peared or relatively converted to the more bulky rod-like
aggregates.
The X-ray maps for the binary catalyst are also shown
in Fig. 5C and SDF2, confirming the good distribution of
each constituent element (Ag, I, W, and O) thorough the
catalyst. Figure 4D shows the typical EDX spectrum for the
as-prepared binary AgI/Ag2WO4 sample. All constituent ele-
ments of the binary catalyst have appeared in the spectrum.
Photocatalytic degradation studies
Initial removal experiments
Figure 6A shows the UV–Vis absorption spectra obtained
for the effects of direct photolysis, surface adsorption, and
photocatalytic degradation in the CTX removal. As shown,
the maximum absorbance was decreased during the tech-
niques mentioned above. As the results show, direct pho-
tolysis by direct light irradiation has no critical role in CTX
removal. This confirms a relatively high stabile CTX mol-
ecules against the arrived photons. No considerable radicals
were formed by the CTX irradiation during the illumination
13
90198 Environmental Science and Pollution Research (2022) 29:90191–90206

Fig. 5  A–B Some SEM images for the binary AgI/Ag2WO4 catalyst; C typical X-ray map of the binary AgI/Ag2WO4 catalyst for showing all
constituent element distribution, D typical EDX spectrum for the binary AgI/Ag2WO4 catalyst

process. Furthermore, surface adsorption by the semicon-
ductors alone or the coupled binary catalyst has a more
intense role in CTX removal concerning direct photolysis. In
general, the adsorption of pollutants on the surface of pho-
tocatalysts plays a critical role in the overall efficiency that
has been illustrated in the literature (Hassani et al. 2020).
Concerning the direct photolysis and the surface adsorption,
the heterogeneous photodegradation by the semiconductors alone
and the binary catalyst showed relatively high removal efficiency.
Despite the direct photolysis, in the case of heterogeneous pho-
tocatalysis, some photo-induced reactive species of e­ −/h+, •OH,
• −
O2 , and hydrogen peroxide may be formed that participate
in the photocatalytic reaction. Among the catalysts, the binary
system showed a boosted photocatalytic activity. This can be
related to the higher charge carriers’ separation in this system,
resulting in the rate of ­e−/h+ recombination. Thus, the binary
system was used in the next photodegradation runs. Based on
the results obtained, to eliminate the role of surface adsorption
in CTX removal, the suspensions were shaken at dark for 20 min
and then the illumination process began.
In the next step, the effect of the various mole fractions in the
binary catalyst was tested toward CTX photodegradation. The
experiment runs were done in triplicates and the average results
are depicted in Fig. 6B (corresponding UV–Vis spectra in SDF3).
Generally, the photodegradation activity of the binary catalyst
depends on the ­e−/h+ production extent, the ­e−/h+ recombination

13
Environmental Science and Pollution Research (2022) 29:90191–90206 90199

Fig. 6  A Decrease in the UV– C/Co Removal%

Sample/Method
Vis spectra of CTX solutions λ238 λ274 λ238 λ274
during the mentioned removal a: Blank 1 1 - -
processes (conditions: catal b: photolysis 0.88 0.88 12 11
c: Sur Ads Ag2WO4 0.81 0.76 18 24
dose, 0.3 g/L ­(Ag2WO4:AgI d: Deg AgI 0.81 0.80 19 20
with mole ratio 1:2 and 30 min e: Sur Ads AgI 0.80 0.79 20 21
abrasion time); irrad. time, f: Deg Ag2WO4 0.79 0.75 21 25
45 min; ­CCTX, 10 ppm); B the g: Sur Ads AgI/Ag2WO4 0.76 0.72 24 28
effect of AgI:Ag2WO4 mole 0.8 h: Deg AgI/Ag2WO4 0.71 0.67 29 33
a
ratio in the photocatalytic activ-
ity towards CTX at the condi-
b
tions in case A; C the effect of
the grinding time to prepare 0.6 c
the binary catalyst with the d
e

Absorbance
­Ag2WO4:AgI mole ratio of 1:4 g f
for the CTX photodegradation h
0.4

0.2

200 220 240 260 280 300 320 340

A Wavelength (nm)

1.0
Ag2 WO4 :AgI mole ratio
238 nm

274 nm
4: 1
2: 1
0.8 1: 2 3: 1
Blank

1: 1
1: 3

0.6 1: 4
C/C0

0.4

0.2

0.0
Catalysts with various Ag2WO4: AgI mole ratios
B
a

0.6 b
d e c
f a: 30 min
e f d
g
g b:10min
Absorbance

h
h
c: 20min
0.4 Sample/Grinding C/Co D%
time (min) λ238 λ274 λ238 λ274 d: 5min
a: Blank 1 1 - -
e: 15min
b: 20 0.80 0.76 19 24
c: 10 0.80 0.75 20 25 f : blank
0.2 d: 5 0.79 0.73 21.4 26
e: 15 0.78 0.73 21.7 26 g: 1 h
f: 60 0.74 0.70 26 30
h: 45min
g: 45 0.71 0.68 29 32
0.0 h: 30 0.70 0.66 30 34
200 220 240 260 280 300 320
C Wavelength (nm)

13
90200
rate, and the type of the semiconductor whose CB and VB posi-
tions involved the photogenerated ­e−/h+ pairs. On the other
hand, the VB and CB potential position plays a drastic role in
the photodegradation efficiency of the pollutant used. The factors
mentioned above vary with the semiconductor’s amounts used in
the coupled system. The change in the moles’ fraction changed
the photodegradation efficiency, and the highest efficiency (the
lowest C/Co value) was reached when the moles of AgI were 4
times greater than ­Ag2WO4. This study proves that the change in
the mole fraction changes the yield of the e­ −/h+ production, as
well as the yield of ­e−/h+ recombination. On the other hand, at
this optimized mole ratio, the highest ­e−/h+ pairs may be induced
and the lowest rate for ­e−/h+ recombination may have occurred
(Singh et al. 2018). Thus the coupled system with this mole ratio
(AgI:Ag2WO4 mole ratio of 4:1) was used in the next steps.
The next step of the photodegradation experiments was the
study of the effect of the grinding time on the photodegrada-
tion efficiency of the binary coupled catalyst. The change in the
UV–Vis absorption spectra for the photodegraded CTX solu-
tions as a function of the grinding time spent for preparing the
binary catalyst is presented in Fig. 6C. As shown, the grinding
time affected the efficiency of the prepared binary catalysts,
and with elongation of the grinding time to a certain amount
(from 5 to 30 min) the photodegradation efficiency of the
prepared catalyst was increased. This proves that the induced
mechanical force to the catalyst component was increased
over time and the components were better diffused to others.
Thus, the interface between the semiconductors coupled was
shorten, resulting in a better charge carries’ separation. After
45 min, no considerable change in the degradation efficiency
was achieved with respect to 30 min, but elongation of the
grinding time for 60 min caused a relative decrease in the
degradation efficiency. This may be due to aggregation of the
catalyst particles because of the heat created under grinding.
In general, in a smaller catalyst particle more the number of
atoms positioned at the surface. Furthermore, higher effective
surface area (surface to volume ratio) would be expected for
smaller species (Mohamed et al. 2012; Ong et al. 2013). Thus,
the available surface active sites and the rate of the interfacial
charge-carrier transfer would be expected to increase, leading
to higher photocatalytic performance (Martin et al. 1994).
Comparison of the photodegradation and mineralization
rates
When a typical photodegradation process both the initial pol-
lutant and the degradation products can absorb the illumi-
nated photons based on the Beer-Lambert law, the rate of the
photodegradation process can be followed by the following
Grotthus-Drapers law. Here, the initial and final concentrations
of the pollutant used are C­ o and C, while the rate constant is
­k1. Furthernore, the absorption coefficients for the parent pol-
lutant and the degradation products are k­ 2 and k­ 3, respectively
13
Environmental Science and Pollution Research (2022) 29:90191–90206
(Lu et al. 2014). When the degradation intermediates cannot
absorb the illuminated photons, ­k3 is about zero.
( [ ( ( ))])[ ( ( ))]
−dC∕dt = k1 1 − exp − k2 C + k3 Co − C k2 C∕ k2 C + k3 Co − C
(4)
When the reactant is present at a high concentration, a
zero-order kinetic can well process the reaction kinetics.
A pseudo-first-order reaction rate (not a first-order one)
can well process the reaction kinetic for a case in which
the reactants and the degradation products have a similar
absorption spectrum (means that ­k 3 ~ ­k 2). Thus, Eq. (4)
can be summarized in Eq. (5), in which the pseudo-first-
order reaction rate constant is k. The integrated form of
this equation is shown as Eq. (6) that has known as the
pseudo-first-order reaction confirmed by Hinshelwood (Bi
et al. 2021; Collu et al. 2022; Fei et al. 2022; Matsuura
et al. 1990; Pavlović et al. 2022; Pourshirband et al. 2021;
Xie et al. 2013).
(5)
( [ ])( )
−dC∕dt = k1 1 − exp −k2 Co C∕Co = kC
(6)
( )
ln(C∕Co) = −kt orCt = Co e−kt
In general, knowing the experimental kinetics helps
us to identify the photodegradation mechanism for the
pollutant. The effect of the illumination time in the CTX
photodegradation by the binary catalyst was followed.
The results in Fig. 6A confirm that the C/Co values were
decreased during the illumination of the suspensions,
proving the decrease in the CTX molecules. The data
obtained were then substituted in the Langmuir–Hinshel-
wood model which typical plot is presented in the inset
of Fig. 7A. The plot equation plot of y = 0.034–0.013x
(r 2 = 0.9648) was obtained for the linear plot which its
slope of 0.013 ­m in −1 shows the apparent first-order
rate constant (k) for the CTX photodegradation. Sub-
stituting the k value in the t­1/2 = (0.693/k) formula gives
­t 1/2 = 53.30 min. On the other hand, half of a 3.5 mg/L
CTX solution can be photodegraded by the proposed
binary catalyst and the applied conditions for 53.30 min.
In the next step, the photodegraded CTX solutions
were subjected to the chemical oxygen demand (COD)
approach to evaluate the relative mineralization of CTX
during the photodegradation process. However, COD
gives us a measure of the pollution extent of the sub-
jected sample, and thus, a low COD confirms a lower
polluted water sample used. On the other hand, lower
pollution consumes lower oxygen to be oxidized during
the COD experiment. As shown in Fig. 7B, the remained
COD for the photodegraded CTX solutions was decreased
with elongation of the photodegradation process. This
means that more CTX and the degradation products
were mineralized to water, carbon dioxide, etc., and thus,
Environmental Science and Pollution Research (2022) 29:90191–90206 90201

Fig. 7  A The C/Co values 1.0

obtained from CTX photodeg-
radation in various irradiation
times; inset: typical Hinshel-
wood plot obtained from the
results, ­(CCTX = 3.5 mg/L,
pH 9, amount of the AgI/ 0.9
Ag2WO4 (mole ratio 4:1 cata-
lyst) = 1 g/L). B Remained COD 0.0
in the photodegraded CTX
solutions obtained in the case

C/Co
-0.1
A to study the mineralization of 0.8
CTX; inset: resulted Hinshel-

ln(C/Co)
wood plot from COD results -0.2

-0.3 y= -0.013 X+0.034

2
0.7 r = 0.9648
-0.4

0 5 10 15 20 25 30
Time (min)
0.6
0 5 10 15 20 25 30
A Time (min)
500

450
Remained COD (mg O2/L)

400
0.0
ln ([COD]/[COD]o )

-0.1

350 -0.2
-0.3
-0.4 y = -0.019 X+ 0.113
300 -0.5 r2= 0.9425
-0.6
0 5 10 15 20 25 30
Time (min)
250
0 5 10 15 20 25 30
B Time (min)

lower oxygen requires to oxidize the remained species. applied conditions, the CTX photodegradation intermedi-
The inset of this figure shows the Hinshelwood plot ates rapidly mineralize to inorganic species.
obtained from the COD results with the equation plot of
y = 0.113–0.019x (r2 = 0.9425). The slope is 0.019 ­min−1 Catalyst stability and reusability
corresponding to ­t1/2 = 36.5 min. The comparison of the
results confirms that the mineralization extent of the CTX The reusing experiments for the binary AgI/Ag2WO4 cata-
molecules during the photodegradation run is high and lyst were carried out in the conditions of the dose of the
lower CTX molecules and their photodegradation inter- catalyst: 1 g/L, initial pH 9, ­CCTX 3.5 mg/L, and irradiation
mediates remained in the photodegraded solution. In the time 85 min in CTX photodegradation. At the end of each

13
90202 Environmental Science and Pollution Research (2022) 29:90191–90206

Table 1  Some previously published papers on CTX photodegradation

Catalyst Rad. source CTX deg.% Conditions Ref

ZnO/TiO2-nanorod Vis 99 Dose: 10 mg/mL, time = 180 min, CTX (Abbas et al. 2022)
conc. = 5 mg/L
CdSe QDs@MoS2 Vis 85 180 min, 20 ppm CTX (Zhou et al. 2021)
Ag-doped ­TiO2/cellulose-derived carbon 500 W Xe lamp 83% 25 ppm CTX at pH 8, 7 g/L of the catalyst (Yang and Luo 2021)
beads (350 mg/50 mL)
Bi2WO6/g-C3N4 300 W Xe lamp 94 40%-BW/CNNs, 10 ppm CTX (Zhao et al. 2018b)
Bi2WO6 nanoflowers 300 W Xe lamp 70 10 mg/mL CTX, 1 g/L of catalyst, HPLC (Zhao et al. 2018c)
detection
Ag NPS ZnSe quantum dots/g-C3N4 300 W Xe lamp 89 90 min, 10 mg/mL CTX, 1 g/L of catalysts, (Zhao et al. 2018a)
Bi2WO6 by Ti doping Vis 74 - (Arif et al. 2021)
Biotic and abiotic degradation of 4 cephalo- - - HPLC detection (Jiang et al. 2010)
sporin antibiotics
Zn1-xIn2x/3S solid solution 300 W xenon 59 0.5 g/L of the catalyst, 10 ppm CTX, (Zheng et al. 2021)
120 min

photodegradation run, the recycled catalyst was washed and
dried at 70 °C for 15 min and then used in the next run.
Based on triplicate photodegradation experiments for each
run, the average C/Co values of 0.38 ± 0.01, 0.40 ± 0.01,
0.43 ± 0.02, and 0.45 ± 0.02 were obtained for the first to
4th run. Comparing the results confirm that the binary cata-
lyst retained above 82% of its photocatalytic activity after
four reusing runs.
Comparison of the work with other previously published
works
As far as we know, comparing other antibiotics, there are
only a few published works on CTX photodegradation.
Table 1 summarized some published works in this regard
(Abbas et al. 2022; Arif et al. 2021; Jiang et al. 2010; Yang
& Luo 2021; Zhao et al. 2018a, b, c; Zheng et al. 2021;
Zhou et al. 2021). Some catalysts used such as titanium
dioxide are UV-active light. Some detecting techniques
such as HPLC are expensive and need some special sol-
vents for the mobile phase. The catalysts used here are vis-
ible light active with suitable VB and CB potential posi-
tions to couple them for reaching a satisfying e/h pairs
separation.
the relative interaction of the components. The red-
shift of absorption edge (451, 462, and 495 nm, cor-
responding to the band gap values of 2.75, 2.68, and
2.51 eV for A ­ g 2 WO 4 , AgI, and AgI/Ag 2 WO 4 catalyst)
for the coupled system proves the enhancement of
its photocatalytic activity in the visible region of the
light. Synergistic photocatalytic activity of the coupled
system and its dependence on the AgI:Ag 2 WO 4 mole
ratio and grinding time confirm better charge carri-
ers’ transfer in the coupled system which varies with
the mole ratio of the components. Longer grinding
time until 30 min confirms better interactions of the
mechanical force-induced. Comparing the rate constants
(k) of 0.013 ­m in −1 ­( t 1/2 = 53.3 min) and 0.019 ­m in −1
­( t 1/2 = 36.5 min) obtained from the photodegradation
and COD experiments confirms a high CTX minerali-
zation during the photodegradation process.
Supplementary Information The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 11356-0​ 22-2​ 2100-1.
Author contribution Alireza Nezamzadeh-Ejhieh: conceptualization,
methodology, supervision, software, writing (reviewing and editing),
validation, formal analysis, supervision.
Sabereh Salesi: data curation, writing (original draft0, visualization,
investigation, resources, investigation.

Data availability Not applicable.

Conclusion
Declarations
The relative change in the average crystallite sizes of
34.9, 42.0, and 24.1 nm (by the Scherrer model) and Ethical approval Not applicable.
91, 13, and 85 nm (by the Williamson-Hall model) for
the AgI, ­Ag 2WO 4, and the binary catalyst, confirms the Consent to participate Not applicable.
relative effect of the induced strain in peak broadening. Consent to publish All authors agree to publish.
The presence of W–O–W, O–W–O, Ag-I, and O–Ag–O
bonds in the coupled material by the FTIR confirms Competing interests The authors declare no competing interests.

13
Environmental Science and Pollution Research (2022) 29:90191–90206 90203

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