Diamond & Related Materials 133 (2023) 109711

Contents lists available at ScienceDirect

Diamond & Related Materials

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

Photocatalytic destruction of Congo red dye in wastewater using a novel

Ag2WO4/Bi2S3 nanocomposite decorated g-C3N4 nanosheet as ternary
S-scheme heterojunction: Improving the charge transfer efficiency
Zaid H. Jabbar a, *, Ayah A. Okab b, c, Bassim H. Graimed c, Mohammed Abdullah Issa d,
Saad H. Ammar e, f
a
Building and Construction Techniques Engineering Department, Al-Mustaqbal University College, 51001 Hillah, Babylon, Iraq
b
College of Engineering, Al-Qasim Green University, 51002, Babylon, Iraq
c
Environmental Engineering Department, College of Engineering, University of Baghdad, Baghdad, Iraq
d
Department of Oil and Gas Economics, College of Administrative and Financial Sciences, Imam Ja’afar Al-Sadiq University, Baghdad, Iraq
e
Chemical Engineering Department, Al-Nahrain University, Baghdad, Iraq
f
College of Engineering, University of Warith Al-Anbiyaa, Karbala, Iraq

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

Keywords: Herein, a novel S-scheme g-C3N4/Ag2WO4/Bi2S3 (CN/AW/BS) heterojunction was fabricated using multistep
Water treatment approaches. The successful construction of CN/AW/BS was verified using XRD, XPS, HRTEM technologies. The g-
Ternary photocatalyst C3N4 support demonstrated its vital contribution for improving the surface characteristics of CN/AW/BS by
Semiconductor characterization
inhibiting the aggregation impacts of immobilized Ag2WO4/Bi2S3 nanorods. The DRS, photocurrent, EIS, and PL
Congo red degradation
Dual-S-scheme mechanism
spectra stated that the coupling of g-C3N4 nanosheets with Ag2WO4/Bi2S3 exhibited a dramatic improvement in
Stability studies the optical and photoelectrochemical properties as compared with bare g-C3N4 nanosheets. The photo­
degradation activity was examined by degrading Congo red under 140 W of LED illumination. The ternary
photocatalyst exhibited the best degradation performance (98 % in 60 min), which is about 2.86, 4.09, 6.19, and
1.67 times greater than g-C3N4, Ag2WO4, Bi2S3, CN/AW/BS, respectively. The environmental parameters that
affect the photoreaction, such as CN/AW/BS loading, Congo red concentration, and solution pH, were also
evaluated. The photostability of the CN/AW/BS composite was demonstrated by maintaining 85 % of its original
efficiency after five subsequent Cong red degradation cycles. The suggested dual-S-scheme electron pathway was
justified by trapping and ESR results, which certify that •OH, •O−2 , and h+ played a vital role in Congo red
oxidation. In addition, the Congo red degradation pathways were well explained, and the degraded intermediates
were also identified. According to comparison studies, efficient Congo red degradation can be achieved in a short
period of time and with a lower power consumption. The dual-S-scheme heterojunction proved its superiority by
providing a perfect dual S-scheme path for electrons and holes migration in the ternary system.

1. Introduction infections, allergic dermatitis, cancer, etc., by accumulating massively in

In the past decade, the environment and human health have suffered
from the rapid development of modern agriculture and industries
through the discharge of organic wastewater such as surfactants, pesti­
cides, pharmaceuticals, and organic dyes [1,2]. Because of their low
biodegradability and high toxicity, organic dyes from food industries,
paper, tanning, and textiles have been identified as a significant problem
in the aquatic environment [3,4]. Congo red is a typical water-soluble
anionic dye, which has many adverse impacts, such as respiratory
organisms’ bodies [5]. Thus, the sufficient removal of Congo red from
wastewater is of vital importance [6]. This class of hazardous organic
compounds in the wastewater was significantly removed by conven­
tional techniques such as ultraviolet oxidation, biological treatment, and
adsorption. Unfortunately, these treatment processes are also harmful to
the environment due to the production of some secondary byproducts or
intermediates [7,8].
Previous studies showed that the semiconductor-based photo­
catalysts were coupled into the most useful strategy for purifying dyes in

* Corresponding author.
E-mail address: z.jabbar1011@coeng.uobaghdad.edu.iq (Z.H. Jabbar).

https://doi.org/10.1016/j.diamond.2023.109711
Received 25 November 2022; Received in revised form 6 January 2023; Accepted 16 January 2023
Available online 21 January 2023
0925-9635/© 2023 Elsevier B.V. All rights reserved.
Z.H. Jabbar et al.
Scheme 1. Graphical design of the synthesis steps of g-C3N4/Ag2WO4/Bi2S3 nanocomposite
Scheme 2. A schematic representation of the designed batch reactor used in
the current work.
wastewater. Because of its ability to consume visible light irradiation,
photocatalysis has become one of the most feasible and inexpensive
water treatment technologies [9,10]. Therefore, the application of
semiconductors in environmental remediation was somewhat hindered
by some unsatisfactory aspects. Thus, semiconductors with wide
bandgap energy cannot exploit the light in visible regions, whereas some
photocatalysts with high photocatalytic efficiency can effectively absorb
visible light, but they are inevitably limited by photo-induced charge
carriers recombining [11,12]. The construction of heterojunctions be­
tween semiconductors such as conductive carbon materials and metal
oxides has shown considerable potential for enhancing photocatalytic
properties. It can expand the light absorption in the visible region and
provide sufficient photo-induced charge carriers (electrons and holes)
by interfacial effects [13,14]. In this regard, it’s necessary to develop a
stable, cheap, and highly active photocatalyst with efficient photo-
generated charge separation, lower recombination rate, and no sec­
ondary pollution.
Graphite carbon nitride (g-C3N4) is a metal-free polymer, n-type
semiconductor, and one of the most investigated semiconductors due to
its ability to harvest solar energy, high thermal stability, simple syn­
thesis, available, cheap, reliable chemical inertness, and its innocuity
[15–17]. Despite that, the photocatalytic activity of pristine g-C3N4 is
still limited by recombining the photo-induced electrons and holes,
2
Diamond & Related Materials 133 (2023) 109711
which is attributed to the weak interaction force (Van-Der-Waals)
among adjacent graphite carbon nitride layers and poor conductivity,
hindering their large-scale practical applications [18,19]. Consequently,
various modification strategies, including constructing a semiconductor
heterojunction (Type I, Type II, Z-scheme, n-n, p-n, n-p-n, S-scheme
heterojunctions), doping with non-metals or with metal elements, and
surface modification, were developed to improve the above shortcom­
ings [20,21]. Among them, the development of semiconductor-
semiconductor heterojunction has aroused a great interest and
concern in the photocatalytic degradation of organic pollutants. The
band-band transfer heterojunction systems such as Type I, Type II, and
p-n heterojunction exhibited successful electron and hole separation
with lower recombination rates, but they suffered from reduced redox
ability [22]. Fortunately, S-scheme heterojunctions will not suffer from
this phenomenon because of the unique migration path of the photo­
generated charge carriers, as evidenced by previous studies about S-
scheme heterojunctions based on g-C3N4 [23].
On the other hand, bismuth-based semiconductors such as Bi2WO6
[24], Bi2MoO6 [25], BiFeO3 [26], BiOX (X = I [27], Br [28], Cl [29]),
and Bi2S3 [30] are also widely applied in the treatment of different
environmental pollutants due to their controlled morphology, small
band gap, broad photo response, and good chemical stability. Further­
more, the decrease in the bandgap and an increase in charge carrier
mobility can be achieved through overlapping between the Bi 6s and the
O 2p orbitals caused by the lone pair distortion of the Bi 6s orbitals [31].
Among them, the Bi2S3 semiconductor has attracted wide attention in
several important applications that have a narrow direct bandgap of
approximately 1.3 eV [32]. Nevertheless, it can easily consume the light
in the visible region, but also the photo-induced electrons and holes are
readily recombined. Thus, the formation of heterogeneous structures
such as Bi2S3/Bi2WO6 [33], Bi2S3/TiO2/Au [34], Bi2O3/Bi2S3 [35], and
Bi2S3/CdS [36] was an excellent choice to hinder the recombination rate
and promote charge transfer, improving the photocatalytic activity.
Silver tungstate (Ag2WO4) is an important silver-based semi­
conductor with a wide bandgap energy of about 3.1 that has been har­
vested for use in a variety of environmental remediations like bacterial
growth inhibition, photocatalysis, and photoluminescence (PL) [37].
The co-precipitation and hydrothermal methods were developed for the
fabrication of Ag2WO4 nanostructures [38]. Because it has weak solar
light absorption, the Ag2WO4 photocatalyst should be coupled with
other photoactive materials in one system to achieve acceptable pho­
tocatalytic performance (like ZnS/Ag2WO4 [39], Sb2S3/α-Ag2WO4 [40],
and Ag/Ag2WO4/RGO [41]). Guangyu et al. [42] developed a g-C3N4/
Ag2WO4/WO3 heterojunction and it was investigated for methylene blue
(MB) degradation. The g-C3N4/Ag2WO4/WO3 photocatalyst showed
superior photoactive performance (98.68 % of MB was removed in 180
min) due to the synergistic effect among the three photocatalysts by
developing Type II heterojunction. In another investigation [43], Z-
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

# (A)
+
+# ** +
#
* * CN/AW/BS

Intensity (a.u.)
#
** * * CN/AW
# # g-C3N4 (JCPDS 87-1526)

# *+ Ag2WO (JCPDS 33-1195)

4
Bi S (JCPDS 84-0279)
2 3

g-C3N4

10 20 30 40 50 60 70 80
2θ (degree)

(B)
CN/AW/BS
Trasmittance (%)

808 cm-1

CN/AW
808 cm-1

Pure g-C3N4

3000-3300 cm−1 808 cm-1

−1
1700-1200 cm

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm -1)

Fig. 1. Structural analysis of fabricated photocatalysts: (A) XRD patterns; (B) FTIR spectra. XPS wide spectra of the CN/AW/BS composite: (C) Survey spectra; (D) C
1s spectra; (E) N 1s spectra; (F) Ag 3d spectra; (G) O 1s spectra; (H) w spectra; (I) Bi 4f and S 2p spectra.

scheme AgBr/β-Ag2WO4 was synthesized using a one-step precipitation
strategy and was applied to Rhodamine (RhB) under visible light. The
AgBr/β-Ag2WO4-30 % heterojunction showed an enhanced photoactive
mechanism with a degradation rate of approximately 1.7 and 135.9
times compared with pure AgBr and β-Ag2WO4, respectively.
In previous studies, many researchers developed g-C3N4/Ag2WO4 for
the photocatalytic degradation of a series of organic pollutants. These
studies demonstrated improved photodegradation performance towards
these pollutants. The activity of hybrid heterojunction is depending on
photostability, surface area, morphology, composition, bandgap energy,
bandgap potential [44,45]. Unfortunately, the g-C3N4/Ag2WO4 is still
suffering from the high band gap energy, lower light absorption activity,
and small specific surface area. Thus, further modification is becoming a
crucial concept to address these drawbacks. Therefore, we believe that
coupling among g-C3N4, Ag2WO4, and Bi2S3 photocatalysts in one sys­
tem could encourage the migration of charge carriers in an efficient dual
path, forming a stable heterojunction with enhanced photooxidation
activity. In addition, it can extend the absorption of light at visible edges
and boost the surface characteristics. Herein, a novel photoactive S-
scheme g-C3N4/Ag2WO4/Bi2S3 (CN/AW/BS) heterojunction was fabri­
cated using a multistep approach. Different sophisticated techniques like
XPS, XRD, FTIR, EDS, SEM, HRTEM, TEM, elemental mapping, DRS, EIS,
PL, and photocurrent were performed to describe the synthesized het­
erojunction. The photodegradation performance of the as-fabricated
CN/AW/BS heterojunction was investigated against Congo red elimi­
nation under visible light illumination. In addition, the stability of the
synthesized photocatalyst was demonstrated by five cycling experiments
and confirmed by the repeated characterization of the reused photo­
catalyst. Finally, scavenging experiments, ESR, DRS, PL, photocurrent,
and EIS analysis were performed to explain the suggested dual-S-scheme
pathway behavior.
2. Experimental work
2.1. Materials
Melamine (C3H6N6), isopropanol (IPA, C3H8O), sodium tungstate
(Na2WO4⋅2H2O), silver nitrate (AgNO3), Ethylenediaminetetraacetic
acid disodium salt (EDTA-2Na, C10H14N2Na2O8), nitric acid (HNO3),
Ethanol (C2H5OH), Bismuth nitrate (Bi(NO3)3⋅5H2O), thioacetamide
(TAA), and1,4-benzoquinone (BQ, C6H4O2). The materials that
consumed in this work were used as-purchased from Alpha chemika
(India) without modification.
2.2. Fabrication of g-C3N4 (CN)
Based on previous literature [46], the g-C3N4 nanosheets were pre­
pared by placing 10 g of melamine in the semi-closed alumina crucible.
Then, the melamine sample was covered and heated to 550 ◦ C in a
muffle furnace for 2 h at a rate of 5 ◦ C min− 1. After that, light-yellow g-
C3N4 nanosheets were obtained, and the sample was left to cool at room
temperature and grinded into powder. The formed sample was washed
with nitric acid (0.1 M) and ethanol three times and dried for 12 h at
60 ◦ C.

3
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

(C)

(D) (E)

(F) (G)

Fig. 1. (continued).

4
Z.H. Jabbar et al.
(H)
Fig. 1. (continued).
2.3. Fabrication of g-C3N4/Ag2WO4 (CN/AW) nanocomposite
The CN/AW composites were fabricated by the in-situ growth of 15%
Ag2WO4 Wt. on the surface of CN nanosheets (Eq. (1)). Typically, “2 g of
as-prepared g-C3N4 nanosheets were ultra-sonicated in 100 mL of
deionized water for 30 min (Power sonic 410, Malaysia). After that, the
AgNO3 solution was prepared separately by dissolving 0.22 g of AgNO3
into 50 mL of deionized water. The AgNO3 solution was dropped on the
sonicated mixture with stirring for 1 h to reach Ag+ sorption equilib­
rium. In the same way, 0.19 g of Na2WO4⋅2H2O was added to 50 mL of
deionized water and dropwise to the above mixture. Finally, the pro­
duced g-C3N4/Ag2WO4 composites were centrifuged, washed, and dried
for 12 h at 60 ◦ C. The pristine Ag2WO4 nanostructure was fabricated
using the same procedure but without the addition of g-C3N4 nano­
sheets” [47].
Na2 WO4 + 2AgNO3 →Ag2 WO4 + 2NaNO3 (1)
2.4. Fabrication of g-C3N4/Ag2WO4/Bi2S3 (CN/AW/BS) heterojunction
Scheme 1 shows the preparation steps for the g-C3N4/Ag2WO4/Bi2S3
composite. Thus, 1.5 g of as-fabricated g-C3N4/Ag2WO4 was dispersed in
100 mL of deionized water under ultrasonication for 30 min (solution
A). To precipitate 10 % of Bi2S3 (Eq. (2)), 0.21 g of Bi(NO3)3⋅5H2O was
dissolved in 50 mL of deionized water and stirred for 30 min (solution
B). Similarity aside, the 50 mL of TAA solution was supplied by
dispersing 0.065 g of TAA in DI with stirring for 30 min (solution C).
After that, the solution B was dropped on the above-mentioned solution
A and stirred for 30 min. Then, the solution C was added above the
mixture and stirred for 3 h at room temperature. Finally, the formed CN/
AW/BS composites were centrifuged, washed with ethanol, and dried
for 12 h at 60 ◦ C. The sole Bi2S3 nanostructure was prepared by the same
steps but without utilizing CN/AW composites [48].
4Bi (NO3 )3 ⋅5H2 O + 90 HCl + 6C2 H5 NS→2Bi2 S3 + 9 N2 + 12CH4 + 36H2 O
+ 45Cl
(2)
2.5. Characterizations
The phase composition of fabricated photocatalysts was examined
using X-ray diffraction (XRD) with Cu-Kα radiation, λ = 1.5418 Å (XRD,
Shimadzu, Japan). The X-ray photoelectron spectroscopy (XPS) was
conducted using Thermo Scientific K-Alpha+, USA. The morphology,
elemental composition, and elemental mapping of fabricated
5
Diamond & Related Materials 133 (2023) 109711
(I)
photocatalysts were investigated using a scanning electron microscope
(SEM), an energy-dispersive X-ray spectroscope (EDS), and EDS-
mapping (SEM, Hitachi S–4800, Japan). The transmission electron mi­
croscopy (TEM) was developed to assess the structural features of
samples using Hitachi, H-7500, Japan. The specific surface area was
measured on (Micromeritics Instruments, USA) using Brunauer-Emmett-
Teller (BET) technique. The optical characteristics of the as-fabricated
photocatalysts were measured on Hitachi U-3900H (Japan) using
UV–vis diffuse-reflectance spectra (DRS) technique. Photoluminescence
(PL) emission was obtained at an excitement wavelength of 350 nm
utilizing (PL, Hitachi F-7000, Japan). The electrochemical impedance
spectra (EIS) measurement and transient photocurrent tests were per­
formed by (CHI660D, China). Finally, the Bruker A300 spectrometer
(visible light, λ ≥ 400 nm) was performed to investigate Electron spin
resonance (ESR) analysis.
2.6. Photocatalytic measurements
Typically, a Congo red solution containing 20 mg L− 1 was prepared
and placed in a 250 mL beaker as a photocatalytic batch reactor (Scheme
2). Then, 50 mg of different fabricated semiconductors (Ag2WO4, g-
C3N4, Bi2S3, CN/AW, and CN/AW/BS) were added to 100 mL of Congo
red solution and mixed for 60 min to investigate the adsorption per­
formance. The reactor was irradiated with visible light simulation (140
W LED lamps) from a distance of 10 cm at a light intensity of 111 mW
cm− 2. The photodegradation performance of fabricated photocatalysts
was examined for 90 min under a visible-light source. At selected times
(15 min), a 3 mL of treated Congo red sample was collected, centrifuged,
and the remaining Congo red concentration was tested by UV–vis
spectrophotometer (UV1200-Spectrophotometer, China) at a wave­
length of 497 nm. The degradation efficiency of a fabricated catalyst can
be calculated using the following equation (Eq. (3)):
DE (%) = (C0 − Ct )/C0 × 100 (3)
where Ct is the remained Congo red concentration at time t, C0 is the
initial Congo red concentration, and DE is the degradation efficiency.
The Congo red mineralization efficiency of the fabricated photocatalyst
was measured using total organic carbon (TOC) analysis (Shimadzu
TOC-VCSH analyzer, Germany). The stability measurements were
assessed in five photocatalytic degradation cycles against Congo red at
the same operating condition. The investigated catalyst was centrifuged
after each degradation experiment, washed three times with ethanol and
deionized water to remove contaminants, and dried to be ready for the
next run. This photocatalytic procedure was in compliance with studies
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

Fig. 2. SEM images of: (A) sole CN nanosheets; (B) bare Ag2WO4; (C) bare Bi2S3; (D) CN/AW nanocomposites; (E) CN/AW/BS nanocomposites; (F) TEM image of
CN/AW/BS nanocomposites; (G) HRTEM image of CN/AW/BS nanocomposites.

6
Z.H. Jabbar et al.
Fig. 3. Elemental mapping: (A) N, O, S, W, Ag, and C elements; (B) Ag; (C) C; (D) N; (E) O; (F) S; (G) W; (H) EDS spectrum of CN/AW/BS nanocomposites.
reported by [49,50]. Liquid chromatography–mass spectrometry
(LC–MS) analysis was performed on the photodegradation pathways of
Congo red using the Shimadzu LCMS 2010 instrument. For identifying
the various intermediates formed during the CR photocatalytic degra­
dation procedure, a liquid chromatography mass spectrometry (LC–MS)
method was applied.
3. Results and discussion
3.1. Structure characterization
Fig. 1A depicts the XRD patterns of CN, CN/AW, and the CN/AW/BS
photocatalysts. For pristine g-C3N4, two distinct signals centered at
27.47◦ and 13.08◦ are assigned to the existence of hexagonal g-C3N4 that
is indexed to the (002) and (100) planes (JCPDS 87-1526) [37]. The
peak at 27.47◦ is assigned to aromatic systems of interlayer stacking,
while the peak at 13.08◦ is correlated to tri-s-triazine units [51]. For g-
C3N4/Ag2WO4, the diffraction peaks located at 30.1◦ , 32.2◦ , 44.9, and
56.2◦ were associated with (022), (220), and (042) planes of Ag2WO4
(JCPDS 33–1195) [52,53]. Furthermore, the g-C3N4/Ag2WO4/Bi2S3
sample showed some additional weak diffraction peaks at 11.1◦ , 28.3◦ ,
and 33.8◦ , which corresponded to the (020), (021), and (221) planes of
Bi2S3 (JCPDS 84-0279), respectively [54,55]. Notably, the reduction in
g-C3N4 peak intensity in g-C3N4/Ag2WO4 and g-C3N4/Ag2WO4/Bi2S3
samples was attributed to X-ray absorption and inhibition by Ag2WO4
7
Diamond & Related Materials 133 (2023) 109711
and Bi2S3 species [56]. In addition, the good dispersion and low amounts
of Ag2WO4 and Bi2S3 species result in their weak XRD intensities in the
ternary CN/AW/BS [57]. From the above findings, the formation of
ternary g-C3N4/Ag2WO4/Bi2S3 was successfully confirmed.
Fig. 1B presents the FTIR spectra of the fabricated photocatalysts
(CN/AW, g-C3N4, and CN/AW/BS). For pure g-C3N4, the broad ab­
sorption band between 3000 and 3300 cm− 1 was ascribed to the O–H
and N–H bond vibrations of absorbed water [58]. In addition, the sharp
peak at 808 cm− 1 was assigned to the breathing mode of triazine units,
while the absorption peaks between 1700 and 1200 cm− 1 were associ­
ated with the typical stretching modes of C–N heterocycles [59]. The
FTIR spectra of g-C3N4/Ag2WO4 and CN/AW/BS photocatalysts were
similar to that of pure g-C3N4, but with a slight decrease in intensity. The
presence of all pure g-C3N4 absorption peaks in the CN/AW/BS spectra
indicates that the g-C3N4 species were preserved after Ag2WO4 and Bi2S3
species grew on the surface of g-C3N4 [60]. Thus, the XPS and HRTEM
analyses should be conducted to verify the presence of Ag2WO4/Bi2S3
the CN/AW/BS composite.
The XPS analysis was conducted to investigate the surface chemical
state and composition of the CN/AW/BS nanocomposite. The XPS sur­
vey in Fig. 1C showed that the CN/AW/BS composite consists of C, N,
Ag, W, O, Bi, and S. The XPS spectra of C 1s (Fig. 1D) revealed three
peaks with the binding energies of 288.0, 285.8, 284.3, and 285.0 eV,
assigning to the N– – C, C–N, and C–C bonds of g-C3N4, and the carbon
extraneous, respectively [61,62]. The high-resolution spectra of N 1s
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

80 1.00
g-C3N4 CN/AW
70
Adsorption
Desorption
Pure g-C3N4 (A) (A) Ag2WO4 CN/AW/BS
Bi2S3
60 0.75
Total pore volume = 0.1133 cm3/g
Volume cm3(STP) g-1

50 SBET = 14.696 m2/g

Absorbance
Average pore diameters = 30.124 nm
40 0.50

30

20 0.25

10

0 0.00

0.0 0.2 0.4 0.6 0.8 1.0

350 400 450 500 550 600 650 700 750 800
P/P0 Wavelength (nm)

140
8

120
Adsorption
Desorption CN/AW/BS nanocomposite g-C3N4
(B)
CN/AW
100 (B) Total pore volume = 0.1863 cm3/g 6 Ag2WO4
Volume cm3(STP) g-1

SBET = 22.21 m2/g

80 Average pore diameters = 32.123 nm

(αhν)2
4
Eg = 2.72 eV Eg = 2.82 eV
60

40 2

20 Eg = 3.04 eV

0
0

0.0 0.2 0.4 0.6 0.8 1.0 2.55 2.70 2.85 3.00 3.15 3.30 3.45
P/P0 hv (eV)

Fig. 4. The N2 sorption isotherm: (A) bare g-C3N4; (B) CN/AW/BS 6

nanocomposites. g-C3N4/Ag2WO4/Bi2S3
Bi2S3
(C)
5
(Fig. 1E) presented several XPS peaks centered at 401.7, 400.4, 398.7
eV, corresponding to N–H [63], N–(C)3 [62], and C– – N–C [61] bonds
2 4
of sp -hybridized nitrogen, respectively, revealing the successful for­
(αhν)2

mation of g-C3N4. As depicted in Fig. 1F, the Ag 3d spectrum displayed

Eg = 1.3 eV
two XPS peaks located at 374.1 eV and 368.0 eV, which were attributed 3

to Ag 3d3/2 and Ag 3d5/2 of the Ag element in Ag2WO4 [64]. In the XPS

spectra of O 1s (Fig. 1G), the peak sited at 530.9 eV was connected to the 2
oxygen in Ag2WO4, while the peak located at 529.9 eV was correlated to
the oxygen in –OH [65]. Furthermore, the XPS spectra of W (Fig. 1H)
1 Eg = 1.43 eV
showed two peaks centered at 37.3 eV and 35.2 eV binding energies,
which were related to W 5p and W 4f, respectively, indicating the ex­
istence of Ag2WO4 in the CN/AW/BS composite [66]. Fig. 1I illustrates 0

the XPS spectra of S 2p and Bi 4f in the CN/AW/BS sample. The XPS 1.20 1.35 1.50 1.65 1.80 1.95

peaks within Bi 4f located at 163.13 eV and 157.83 eV binding energies hv (eV)

were linked to Bi 4d5/2 and Bi 4f7/2 of Bi3+ in spin–orbit components of
Bi2S3. Additionally, the peak at 161.73 eV was related to S 2p3/2, while
the peak at 160.68 eV was matched to S 2p1/2, implying the perfect
formation of Bi2S3 in the CN/AW/BS composite [67].
3.2. Morphological studies
The SEM and TEM analyses were performed in order to investigate
the morphology details of the g-C3N4/Ag2WO4/Bi2S3 photocatalyst.
Based on the SEM image of Fig. 2A, the pure g-C3N4 nanosheets can be
clearly observed in stacked and agglomerated flat layers [68]. Fig. 2B
depicts the SEM image of pristine Ag2WO4, which was observed in a 3D
rectangular structure (aggregated with each other) with nanosized
Fig. 5. (A) DRS spectra of fabricated samples; (B) Tauc plot of g-C3N4, Ag2WO4,
and CN/AW; (C) Tauc plot of bare Bi2S3, and CN/AW/BS.
cross-section dimensions. As illustrates in the SEM image in Fig. 2C, the
pristine Bi2S3 was detected in agglomerated nano-rod arrays (urchin-like
structure) with a diameter of <20 nm. According to SEM images of CN/
AW and CN/AW/BS nanocomposites (Fig. 2D and E), the Ag2WO4 and
Bi2S3 nanostructures were distributed homogeneously on the surface of
g-C3N4 nanosheets. Thus, a more reactive heterojunction interface was
obtained by inhibiting the agglomeration of Ag2WO4 and Bi2S3 nano­
structures, which can improve the surface characteristics of g-C3N4/
Ag2WO4/Bi2S3 [54].

8
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

corresponding to the (002), (042), and (200) planes of the g-C3N4 [71],
g-C3N4/Ag2WO4/Bi2S3
(A) Ag2WO4 [65], and Bi2S3 [54], respectively, verifying the ideal con­
g-C3N4/Ag2WO4
struction of the CN/AW/BS composite.
g-C3N4
The elemental mapping analysis was performed to further demon­
strate the distribution of Bi2S3 and Ag2WO4 nanostructures in the g-
Iintensity (a.u.)

C3N4/Ag2WO4/Bi2S3 nanocomposite (Fig. 3A–G). The elements of N, O,

S, W, Ag, and C were detected in elemental mapping images of the g-
C3N4/Ag2WO4/Bi2S3 nanocomposite. Furthermore, these elements
appeared in the same location and shape, indicating the uniform depo­
sition of Ag2WO4 of Bi2S3 species on the CN nanosheet surface [72]. The
EDS analysis was conducted to further provide information about the
elemental composition of the g-C3N4/Ag2WO4/Bi2S3 nanocomposite.
The percentages of N, O, Bi, S, W, Ag, and C elements in g-C3N4/
Ag2WO4/Bi2S3 nanocomposite can be noted, as illustrated in Fig. 3H.
These results agree with SEM and TEM observations.
375 400 425 450 475 500 525 550 575 600
Wavelength (nm)
3.3. N2 sorption studies

The N2 sorption isotherm was developed to study the surface char­

(B) acteristics of the CN/AW/BS composite, and the results are presented in
Fig. 4A and B. The sorption isotherms of CN and CN/AW/BS samples are
clearly classified as Type IV with an H3 hysteresis loop, indicating that
they have unevenly distributed and large mesopores [73]. Importantly,
it was noted that the BET surface area (SBET) of the CN/AW/BS com­
posite (22.21 m2/g) was dramatically improved compared with pure CN
(16.523 m2/g) after the deposition of Ag2WO4 and Bi2S3 species on the
CN nanosheet surfaces. These findings were attributed to the important
role of CN in inhibiting the aggregation impacts of immobilized nano­
particles and increasing the void spaces between CN nanosheet and
deposited nanoparticles, reflecting a positive effect on the photo­
degradation performance [74–76].

3.4. Optical properties

(C)
Fig. 6. Photoelectrochemical properties of fabricated photocatalysts: (A) PL
spectra; (B) Transient photocurrent response; (C) EIS Nyquist plots.
Fig. 3F represents the TEM image of the ternary CN/AW/BS photo­
catalyst. The CN nanosheets can be observed in two-dimension nano­
sheet layers [69]. The g-C3N4 nanosheets presented a small
agglomeration and were stacked on each other, which can be recognized
by the light gray color. Obviously, the rectangular-like Ag2WO4 nano­
structures and Bi2S3 nanorods were well distributed on the g-C3N4
nanosheet surfaces, which can inhibit the aggregation of deposited
nano-species (Ag2WO4 and Bi2S3) [70]. The TEM image agreed with
SEM images, which verified the morphology of g-C3N4/Ag2WO4/Bi2S3
nanocomposite. The HRTEM image of the CN/AW/BS composite depicts
the lattice fringes of CN, Ag2WO4 and Bi2S3 NPs as presented in Fig. 2G.
Clearly, the lattice fringes of 0.34 nm, 0.32 nm, and 0.36 nm were
Fig. 5A shows the DRS spectra of pure g-C3N4, Ag2WO4, Bi2S3, CN/
AW, and CN/AW/BS nanocomposites. Notably, the pure g-C3N4 and
Ag2WO4 captured only UV light with a wavelength of <450 and 400 nm,
respectively, which had negligible absorption in the visible spectrum.
Contrarily, the broadest absorption was revealed for the Bi2S3 photo­
catalyst, which was attributed to its narrower band gap energy [77].
When the g-C3N4 was coupled with Ag2WO4, the absorption edge of the
CN/AW nanocomposite was expanded to 460 nm. The absorption
spectra of CN/AW/BS were significantly expanded to the visible region
after the hybridization of g-C3N4 with Ag2WO4 and Bi2S3 in one system.
This result was ascribed to the superior absorption coefficient of Bi2S3
photocatalyst, which can dramatically enhance the photodegradation
behavior of the g-C3N4/Ag2WO4/Bi2S3 composite [78].
The Tauc formula (Eq. (4)) was performed to examine the band gap
energy (Eg) of fabricated samples by plotting the (αhν)2 vs. energy (hν) as
presented in Fig. 5B and C [79]. Thus, the estimated band gaps are 2.82,
3.04, and 1.3 eV for pure g-C3N4, Ag2WO4 and Bi2S3, respectively. A
slight enhancement in the measured band gap of pure g-C3N4 was
detected when modified with Ag2WO4, while a severe improvement in
the optical properties of CN/AW/BS was revealed by forming a band gap
energy of 1.4 eV. It can concluded that the CN/AW/BS has excellent
visible light harvesting, which can generate a significant number of
electron/hole pairs.
( )n/2
αhν = A hν − Eg (4)
3.5. Photoelectrochemical properties
The photoelectrochemical properties of the g-C3N4/Ag2WO4/Bi2S3
nanocomposite were investigated using EIS, transient photocurrent
response, and PL analysis. The fate of photo-excited charge carriers in
fabricated samples was examined using PL analysis, as depicted in

9
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

Adsorption Photocatalysis
1.0 (A)
0.8

0.6

C/C0
Photolysis
0.4 g-C3N4
Ag2WO4
Bi2S3
0.2 g-C3N4/Ag2WO4
g-C3N4/Ag2WO4/Bi2S3
0.0
-45 -30 -15 0 15 30 45 60 75 90
Time (min)

Photolysis
100
g-C3N4
g-C3N4/Ag2WO4
(B) 98
g-C3N4/Ag2WO4/Bi2S3
Ag2WO4
Congo red removal efficiency (%)

85
80
70

62
60
55

40

20

0
Illumination time (60 min)

80

Adsorption (C)
Photocatalysis
70
g-C3N4/Ag2WO4/Bi2S3
TOC removal efficiency (%)

60

50

40

30

20

10

0
-45 -30 -15 0 15 30 45 60 75 90
Time (min)

4.0
g-C3N4
Ag2WO4
(D)
3.5
Bi2S3
3.0 g-C3N4/Ag2WO4
g-C3N4/Ag2WO4/Bi2S3
2.5
-ln (C/C0)

2.0

1.5

1.0

0.5

0.0

-10 0 10 20 30 40 50 60 70 80
Time (min)

(caption on next page)

10
Z.H. Jabbar et al.
Fig. 7. (A) The photocatalytic activity in term of C/C0 at operation parameters (catalyst concentration = 0.5 g/L, Congo red concentration = 20 mg L− 1, pH = 7.1 to
7.3); (B) Time-dependent photo-removal efficiency; (C) TOC removal efficiency for g-C3N4/Ag2WO4/Bi2S3; (D) The first-order kinetic plots for fabricated
photocatalysts.
Fig. 6A. Clearly, the single g-C3N4 exhibited a strong emission peak
located at 438 nm, indicating the possibility of rapid charge recombi­
nation [80]. Consequently, the g-C3N4/Ag2WO4 composite showed a
remarkable decrease in PL intensity compared with pure g-C3N4, which
was ascribed to the heterojunction between g-C3N4 and Ag2WO4 pho­
tocatalysts, improving charge transfer efficiency. Importantly, the syn­
thesized ternary g-C3N4/Ag2WO4/Bi2S3 heterojunction showed
enhanced charge transfer and restrained recombination rate by exhib­
iting the weakest PL intensity [81]. These results can be supported
through Congo red degradation experiments.
Fig. 6B illustrates the transient photocurrent response of pure g-
C3N4, pristine Ag2WO4, pristine Bi2S3, CN/AW, and CN/AW/BS heter­
ojunctions. The pristine Bi2S3 showed the lowest photocurrent response
compared to other samples, suggesting a high number of its charge
carriers can be readily recombined [82]. As expected, a noticeable
improvement in photocurrent density was explored in the CN/AW/BS
sample, which was 11, 4.5, 2.5, and 1.5 times greater than that of Bi2S3,
g-C3N4, Ag2WO4, CN/AW, and CN/AW/BS, respectively, indicating the
vital role of heterojunction in inhibiting the charge recombination rate
[83]. The EIS analysis was conducted to further confirm the transfer
properties and the electron migration (Fig. 6C). The Nyquist plots of the
g-C3N4/Ag2WO4/Bi2S3 photocatalyst showed a narrower semicircle
radius compared with other samples, suggesting a lower electrolyte
interface and small charge transfer resistance between the ternary g-
C3N4/Ag2WO4/Bi2S3 photocatalyst, which can enhance the photo­
catalytic activity [84].
3.6. Evaluation of adsorption and photocatalytic performance
The photocatalytic efficiency of as-fabricated catalysts was investi­
gated against Congo red under LED lamp illumination. As shown in
Fig. 7A and B, the Congo red degradation treatment can be completely
ignored without using catalysts, where only 9 % of Congo red was self-
degraded in 75 min of LED illumination, confirming that the photo­
catalytic process was actually responsible for the Congo red degradation
[85]. All synthesized samples showed significant adsorption perfor­
mance towards Congo red g-C3N4 (20 %), Ag2WO4 (25 %), Bi2S3 (32 %),
g-C3N4/Ag2WO4 (23 %) and g-C3N4/Ag2WO4/Bi2S3 (27 %) during the
first 45 min of the dark control. It can be noted that bare Bi2S3 had the
highest adsorption activity, which can improve the g-C3N4/Ag2WO4/
Bi2S3 adsorption performance.
After 75 min of light illumination, the pristine g-C3N4, Ag2WO4, and
Bi2S3 exhibited Congo red photodegradation ratios of 80 %, 71 %, and
66 %, respectively. For binary CN/AW nanocomposite, the photo­
degradation activity was remarkably enhanced (97.5 % in 75 min) by
coupling the Ag2WO4 nanostructure with g-C3N4 nanosheets. There are
two suggested reasons behind the increase in the photodegradation ef­
ficiency of CN/AW. Firstly, the binary CN/AW heterojunction can pro­
vide a sufficient path for charge carriers separation, and the other reason
is that the g-C3N4 nanosheets can inhibit the Ag2WO4 agglomeration
[86]. The separation path and adsorption performance of CN/AW were
improved after devolving ternary CN/AW/BS nanocomposites by
precipitating 10 % of Bi2S3 on the surface of the CN/AW composite. This
observation was demonstrated by shifting the Congo red photo-removal
efficiency from 85 % to 98 % in 60 min of light illumination and
increasing the adsorption efficiency from 23 % to 27 % after stirring for
45 min in the dark control. These findings may provide a new horizon
for developing other g-C3N4/Ag2WO4-based ternary heterojunctions for
improved Congo red elimination. The extent of Congo red mineraliza­
tion was revealed for ternary g-C3N4/Ag2WO4/Bi2S3 nanocomposites
11
Diamond & Related Materials 133 (2023) 109711
using TOC measurement. According to Fig. 7C, the CN/AW/BS exhibited
a 72 % TOC removal efficiency after 75 min of visible-light illumination.
It was revealed that a considerable percentage of TOC was simplified to
environmentally harmless products [87].
The kinetics plots corresponding to Congo red photodegradation in
the presence of CN/AW, Bi2S3, CN/AW, and CN/AW/BS are viewed in
Fig. 7D. It was noted that the Congo red photocatalysis reaction was well
explained by a pseudo–first–order model based on Eq. (5), where k is the
reaction rate constant, while C0 and C are ascribed to Congo red con­
centration at times equal to zero and t. Therefore, the rate constant
values of g-C3N4, Ag2WO4, Bi2S3, CN/AW, and CN/AW/BS were eval­
uated to be 0.01899, 0.01328, 0.00878, 0.03234, and 0.05433 min− 1,
respectively (Table 1). Clearly, the degradation rate constant of CN/
AW/BS heterojunction was revealed to be 2.86, 4.09, 6.19, and 1.68
times greater than g-C3N4, Ag2WO4, Bi2S3, and CN/AW, respectively.
However, the CN/AW/BS heterojunction demonstrated its performance
attributed to the synergistic effects of ternary heterojunction. Finally,
the photodegradation activity of samples could be ordered as: CN/AW/
BS > CN/AW > g-C3N4 > Ag2WO4 > Bi2S3.
ln (C/C0 ) = − kt (5)
3.7. Experimental conditions affecting the photocatalytic performance
3.7.1. Effect of CN/AW/BS loading
The effect of CN/AW/BS loading on photodegradation activity
against CR was investigated by trying different amounts of CN/AW/BS
catalyst (0.25, 0.5, 1, and 2 g/L) at pH = 7.2 and a dye concentration of
20 mg L− 1. As shown in Fig. 8A, by increasing the catalyst dosage from
0.25 to up to 1 g/L, the CR removal efficiency was improved to 83 % in
45 min. This improvement refers to the provision of sufficient active
sites for CR adsorption and the formation of enough ROS during the
photodegradation reaction via an adequate catalyst amount [88].
Contrarily, a further increase in CN/AW/BS dosage above 2 g/L could
dramatically reduce the degradation efficiency. This adverse behavior
can be associated with the reduction in solution transparency and the
ability for light absorption at large catalyst dosages, leading to hindered
photodegradation performance [89].
3.7.2. Impact of CR concentration
The impact of CR concentration on the photoreaction performance of
ternary CN/AW/BS nanocomposites (0.5 g/L, pH = 7.2) was covered by
repeating the photocatalytic process at different CR concentrations (10,
20, 30, and 40 mg/l). Fig. 8B revealed that the photoreaction perfor­
mance was adversely affected by increasing the CR concentration from
10 up to 40 mg L− 1. These findings suggest that increasing CR concen­
tration can stymie photodegradation by increasing solution turbidity,
which reduces the amount of photo-quantum harvested by the photo­
catalyst. Also, more dye molecules can clog the effective sites of the
catalyst surface, causing a shortage in the generated ROS [90].
Table 1
The degradation rate constant for constructed photocatalyst (g-C3N4, Ag2WO4,
Bi2S3, CN/AW, and CN/AW/BS).
Photocatalyst k/min R2
g-C3N4 0.01899 0.95098
Ag2WO4 0.01328 0.93851
Bi2S3 0.00878 0.92727
g-C3N4/Ag2WO4 0.03234 0.88360
g-C3N4/Ag2WO4/Bi2S3 0.05433 0.85616
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

Adsorption Photocatalysis
1.0
CN/AW/BS composite
(A)
0.8 0.25 g/L
0.5 g/L
1 g/L
0.6 2 g/L

C/C0
0.4

0.2

0.0
-45 -30 -15 0 15 30 45 60 75 90
Time (min)

Adsorption
1.0 Photocatalysis
(B)
CN/AW/BS composite

0.8
10 mg/L
20 mg/L
30 mg/L
0.6
C/C0

40 mg/L

0.4

0.2

0.0
-45 -30 -15 0 15 30 45 60 75 90
Time (min)

Adsorption Photocatalysis pH = 3
1.0 (C) pH = 5
pH = 7.2
pH = 9
0.8
pH = 11
CN/AW/BS nanocomposite
0.6
C/C0

0.4

0.2

0.0
-45 -30 -15 0 15 30 45 60 75 90
Time (min)
60

Zeta potential curve of CN/AW/BS nanocomposite

40

20
Zeta Potential

-20

-40
PZC = 7.07
0 2 4 6 8 10 12

pH

Fig. 8. Operational parameters affecting the photoreaction performance towards CR degradation: (A) Effect of CN/AW/BS loading; (B) Effect of CR concentration;
(C) Effect of pH; (D) Zeta potential plot for the CN/AW/BS composite.

12
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

3.7.3. Effect of solution pH g-C3N4/Ag2WO4/Bi2S3 heterojunction

The acidity and alkalinity conditions of the aqueous dye solution are
100
(A)

Photocatalytic Removal Efficiency (%)

considered one of the important parameters in the photocatalytic reac­
tion [91]. Therefore, the effect of the solution pH was examined on the 80

photocatalytic ability of the CN/AW/BS nanocomposite (0.5 g/L) to­

wards CR (20 mg L− 1) at the selected pH values (3, 5, 7.2, 9, and 11). 60

From an overview of Fig. 8C, the highest photocatalytic performance

was achieved at the lowest solution pH, and the opposite is correct. This 40
overview explains that the photocatalytic performance of CR is
improved in acidic conditions and inhibited in an alkaline environment. 20
These findings were attributed to the effect of solution pH on the CR
molecules’ adsorption behavior over the surface of the CN/AW/BS
nanocomposite [92]. For more details, the point of zero charge (PZC) of
0
0 1 2 3 4 5 6
the CN/AW/BS nanocomposite was analyzed to be pH = 7.07 (Fig. 8D). Cycle number
When the solution pH is less than PZC, the CN/AW/BS surface will be
positive, while it will be negative when the solution pH is more than
(B) Recycled g-C3N4/Ag2WO4/Bi2S3
PZC. Because the CR is an anionic azo dye, the electrostatic attraction Fresh g-C3N4/Ag2WO4/Bi2S3
was apparent between the CR molecules and the positively charged CN/
AW/BS in the acidic environment. In contrast, at alkaline conditions, the

Intensity (a.u.)
lowest photodegradation performance was detected due to the electro­
static repulsion between the anionic CR molecules and the negatively
charged CN/AW/BS [93].

3.8. Stability investigation

The photocatalytic degradation cycles were conducted to estimate

the photostability of the CN/AW/BS heterojunction during the degra­ 10 20 30 40 50 60 70 80

dation reaction against Congo red dye. Five identical successive degra­ 2θ (degree)

dation experiments were performed on 20 mg L− 1 of Congo red using 1

g/L of CN/AW/BS for 75 min. After each experiment, the photocatalyst (C)
was centrifuged, cleaned with DI, and dried at 60 ◦ C for the subsequent Fresh g-C3N4/Ag2WO4/Bi2S3
operation [94]. As shown in Fig. 9A, a slight reduction in photoreaction Recycled g-C3N4/Ag2WO4/Bi2S3
activity was evidenced after the fifth run, where the removal efficiency
was still maintained at 85 %. This drop in catalytic activity may be
Absorbance

likened to the mass loss around the centrifuge and cleaning processes of
the photocatalyst [95]. The structure, morphology, and optical charac­
teristics of the CN/AW/BS heterojunction were investigated after the
final cycle using XRD, DRS, SEM, and TEM techniques (Fig. 9B, C, D, and
E). Notably, a negligible variation and high match between the fresh and
reused samples were revealed, confirming that the g-C3N4/Ag2WO4/
Bi2S3 heterojunction possesses a remarkable photostability during the
photoreaction processes [96].
350 400 450 500 550 600 650 700 750 800
Wavelength (nm)

3.9. Suggested mechanism Fresh Recycled

(D)
The major reactive species that drive the photoreaction were
discovered to draw the photocatalytic enhanced mechanism of the CN/
AW/BS heterojunction. In these experiments, the reactive radicals (•OH
and •O−2 ) and holes (h+) were captured using 1 mM of isopropanol (IPA),
1,4-benzoquinone (BQ), and EDTA-2Na scavengers, respectively [97].
As presented in Fig. 10A, the Congo red removal efficiency was hindered
to 76 % (after 75 min) when EDTA-2Na was added to the reaction,
suggesting that the h+ possesses a minimum participation in the Fresh Recycled
photoreaction. After the addition of IPA, a drastic inhibition in Congo
(E)
red degradation was revealed (35 % in 75 min), indicating that the •OH
is the dominant oxidant. In similarity, the •O−2 radical was also proved to
be an important oxidant by reducing the Congo red removal efficiency to
46 % (in 75 min) after BQ addition to the reaction solution. However,
the role of oxidants in Congo red degradation can be ordered as: •OH >
O2 > h+.
• −

The ESR analysis was performed to further explore the reactive

species in the CN/AW/BS reaction under visible light illumination and
dark conditions. Thus, 5-dimethyl-1-pyrroline-N-oxide (DMPO) was
Fig. 9. (A) Stability experiments of CN/AW/BS heterojunction. Characteriza­
employed as •OH and •O−2 trapping reagent [98]. As shown in Fig. 10B
tion of fresh and recycled CN/AW/BS heterojunction: (B) XRD; (C) DRS spectra;
and C, no ERS signals were revealed for DMPO-•OH and DMPO-•O−2 in (D) SEM; (E) TEM.
the dark environment. After 15 min of visible light irradiation, stronger

13
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

99.8 Without scavenger

100
1,4-benzoquinone (•O2−) (A)

Photocatalytic removal efficiency (%)

•
Isopropanol ( OH)
80 EDTA-2Na (h+) 76

60

46
40
35

20

(B) (C)

(D)

(E)

Fig. 10. (A) scavenger results of g-C3N4/Ag2WO4/Bi2S3; (B) ESR analysis for DMPO-•OH; (C) ESR analysis for DMPO-•O−2 ; (D) Conventional photocatalytic mech­
anism; (E) Dual S-scheme mechanism.

14
Z.H. Jabbar et al. Diamond & Related Materials 133 (2023) 109711

Scheme 3. Suggested degradation pathways of CR over g-C3N4/Ag2WO4/Bi2S3 after 75 min of visible light irradiation.

Table 2
The photodegradation activity of different semiconductor heterojunctions that compared with this work.
Composite Dosage Pollutant concentration Light source Key oxidants Time (min) Degradation efficiency (%) References
− 1
Fe2O3/porous SiO2 1 g/L Congo red (20 mg L ) Metal halide lamp (400 W) •
OH 180 88 [106]
CuInSe2–ZnO 0.5 g/L Congo red (10 mg L− 1) Mercury-vapor lamp (400 W) h+ and •OH 120 99.8 [107]
SnO2/CeO2 1 g/L Congo red (10 mg L− 1) Xenon lamp (500 W) •
OH and •O−2 120 90 [108]
AgI-Ag2S@g-C3N4 0.5 g/L Congo red (10 mg L− 1) Xenon lamp (500 W) h+ 50 94.2 [109]
Cu2O/ZnO-PANI 1 g/L Congo red (30 mg L− 1) LED light source (100 W) h+ and •O−2 30 100 [110]
CN25 photocatalyst 10 mg Tetracycline (40 mg L− 1) Visible-light irradiation 1
O2 and •O−2 100 81.3 [111]
20-PACN 10 mg Rhodamine B (40 mg L− 1) Visible-light irradiation h+, •O−2 and 1O2 100 91 [112]
PCN/PEI 10 mg Tetracycline (30 mg L− 1) Visible-light irradiation 1
O2 and •O−2 100 80 % [113]
g-C3N4/Ag2WO4/ 0.5 g/L 20 LED lamp (140 W) •
OH, •O−2 , and h+ 60 98 This work
Bi2S3

peaks were ascribed to •OH radicals and slightly weaker signals were
explored for •O−2 radicals. These findings indicate that the two radicals
have significant participation in the Congo red reaction and that the •OH
is the major active radical. The ESR analysis was well matched with
trapping experiments.
A dual S-scheme mechanism was proposed to describe the electrons
and holes separation pathways among g-C3N4, Ag2WO4, and Bi2S3
photocatalysts during the photocatalytic reaction of the g-C3N4/
Ag2WO4/Bi2S3 composite. The valence (VB) and conduction (CB) bands
of bare photocatalysts were determined using Eqs. (6)–(8) [99]. Ac­
cording to previous report [100], the electronegativity (χ ) of elements
was selected to be 6.27, 7.3, 4.44, 4.4, 7.54, 4.69, and 6.22 eV for C, N,
Ag, W, O, Bi, and S, respectively, while the free electron constant (Ee) is
4.5 eV with respect to the hydrogen scale (NHE), and was calculated
from DRS spectra (pure g-C3N4 = 2.82 eV, Ag2WO4 = 3.04 eV, and Bi2S3
= 1.3 eV). Depending on the above considerations, the VB of Bi2S3,
Ag2WO4, and g-C3N4 is 1.706, 3.02, and 1.672 eV (vs. NHE), whereas the
CB is 0.406, − 0.02, − 1.148 eV (vs. NHE), respectively.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
χ (Am Bn Cl ) = m+n+l χ mA χ nB χ lC (6)
VB = χ –Ee + 0.5Eg
CB = VB − Eg
The electrons and holes were generated in the VB and CB, respec­
tively, after the g-C3N4, Ag2WO4, and Bi2S3 photocatalysts were irradi­
ated with LED light. Based on the conventional mechanism (Fig. 10D),
the CB of g-C3N4 and Ag2WO4 is more negative than the Bi2S3 CB. As a
result, the photo-induced electrons would accumulate in the CB of the
Bi2S3 photocatalyst. Because the VB of g-C3N4 is the most positive, the
associated holes could be transferred from the VB of Ag2WO4 to that of
Bi2S3, then accumulated in the VB of the g-C3N4 semiconductor.
Importantly, the •OH and •O−2 radicals could not be generated because
the energy potentials of g-C3N4 VB and Bi2S3 CB were less than the
potentials of OH− /•OH = 2.38 eV and O2/•O−2 = − 0.33 (vs. NHE),
respectively [101]. It can be concluded that the conventional mecha­
nism is inconsistent with trapping and ESR results. In the dual S-scheme
pathways (Fig. 10E), the stacked electrons in the CB of g-C3N4 would be
migrated to the VB of Ag2WO4 and Bi2S3 semiconductors and recom­
bined with their stacked holes. In these pathways, a superior negative
potential (− 1.148 eV) and a suitable positive potential (3.02 eV) could
be achieved on the CB of g-C3N4 and the VB of Ag2WO4, respectively
[114]. Thus, the dissolved oxygen and H2O or/and OH− can be captured
by free electrons and holes, respectively, in the redox reactions, gener­
ating •OH, •O−2 as well as H2O2 oxidants, which are able to degrade the
Congo red dye to simple products (Eqs. (9)–(13)) [102,103].
The LC-MS analysis was performed to identify the photodegradation
pathways of CR dye over the g-C3N4/Ag2WO4/Bi2S3 composite. As
(7) illustrated in Scheme 3, the Congo red with an anionic form of m/z =
650 was dissociated into different intermediate values (from m/z = 447
(8) to 215), in which the benzene ring and –N– – N– bonds were attacked
by generated radicals and cleaved. As the reaction proceeded, the ter­
tiary species could be formed (from m/z = 208 to 110) by degrading the
secondary intermediates via aromatic-ring opening reactions into

15
Z.H. Jabbar et al.
smaller molecular masses like succinic acid and maleic acid. These
products can be formed after the cleavage of each C–C, C–N, C–S
2−
4 , SO4 , NO3 , CO2, and water
bonds, which can be mineralized into NH+ −
[104,105].
g − C3 N4 /Ag2 WO4 /Bi2 S3 + LED→electrons + holes (9)
electrons in CB of g − C3 N4 + H+ or O2 →(O˙2 − + H2 O2 ) radicals (10)
˙ radical
(OH− or H2 O) + holes in VB of Ag2 WO4 →OH (11)
H2 O2 orO˙2 − + electron→OH
˙ radical (12)
˙ O˙2 − ,holes, H2 O2 ) + Congo red→CO2 + H2 O + intermediates
(OH, (13)
3.10. Comparative studies
On the basis of degradation duration, principal reactive species, light
source, Congo red concentration, and catalyst dosage, the photoreaction
ability of CN/AW/BS against Congo red was compared to past studies
(Table 2). Depending on the above comparison, four crucial advantages
can be argued for this work as follows:
1. The CN/AW/BS heterojunction showed satisfactory Congo red
degradation activity in a reasonable time (60 min).
2. This catalyst can absorb light with low energy (140 W).
3. The fabricated catalyst contains no precious metals, which might
considerably reduce costs.
4. Both •OH and •O−2 were generated during the catalyst reaction.
4. Conclusions
An efficient ternary dual-S-scheme CN/AW/BS heterojunction was
successfully constructed via a multistep approach. All peaks related to g-
C3N4, Ag2WO4, and Bi2S3 NPs were discovered in XRD and XPS spectra,
implying the perfect construction of the CN/AW/BS photocatalyst. The
morphological studies evidenced the existence of g-C3N4 nanosheets
integrated with Ag2WO4/Bi2S3 nanorods in a ternary heterojunction
system. The g-C3N4 nanosheets acted as sufficient support structure,
which exhibited an important role in inhibiting the agglomeration im­
pacts of Ag2WO4/Bi2S3 nanorods and improving the specific surface area
of CN/AW/BS nanocomposite. The DRS spectra of CN/AW/BS were
dramatically expanded into the visible region compared with pure g-
C3N4 and Ag2WO4 semiconductors. The synthesized ternary CN/AW/BS
photocatalyst showed enhanced charge transfer and a restrained
recombination rate, which were confirmed using PL, transient photo­
current, and EIS analyses. The g-C3N4/Ag2WO4/Bi2S3 composite dis­
played an improved photocatalysis process by exhibiting 98 % of CR
degradation in 60 min. The photocatalytic experiments and TOC anal­
ysis revealed that a high percentage of TOC (72 %) was converted into
environmentally harmless products. The Congo red photoreaction ki­
netics were well explained by a pseudo–first–order model. The photo­
degradation parameters like catalyst loading, pH, and CR concentration
exhibited a significant impact on the degradation reaction. The stability
studies confirmed that the g-C3N4/Ag2WO4/Bi2S3 heterojunction pos­
sesses remarkable photostability during the photoreaction processes.
The trapping experiments and ESR findings indicated that the •OH and
O2 radicals have significant participation in the Cong red reaction, and
• −
the •OH is the key active radical in the CR photoreaction. The photo­
degradation pathways declared that a high part of the CR pollutant was
converted to simple products. The suggested mechanism was well
described by dual-S-scheme heterojunction, which was agreed with
trapping and ESR findings. Finally, this study may provide a new hori­
zon for developing other g-C3N4/Ag2WO4-based ternary heterojunctions
for improved Congo red elimination.
16
Diamond & Related Materials 133 (2023) 109711
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
The authors are grateful to the University of Al-Qadisiyah, college of
science for their support.
References
[1] M.A. Issa, H. Zentou, Z.H. Jabbar, Z.Z. Abidin, H. Harun, N.A.A. Halim, M.
M. Alkhabet, M.Y. Pudza, Ecofriendly adsorption and sensitive detection of hg (II)
by biomass-derived nitrogen-doped carbon dots: process modelling using central
composite design, Environ. Sci. Pollut. Res. 1–14 (2022).
[2] X. Yuan, F. Pei, X. Luo, H. Hu, H. Qian, P. Wen, K. Miao, S. Guo, W. Wang,
G. Feng, Fabrication of ZnO/Au@Cu2O heterojunction towards deeply oxidative
photodegradation of organic dyes, Sep. Purif. Technol. 262 (2021), 118301,
https://doi.org/10.1016/j.seppur.2021.118301.
[3] J.H. Al-Baidhani, Z.H. Khadafy, Treatment of water and wastewater by using
roughing filter technology of local materials, Int. J. Curr. Eng. Technol. 6 (2016)
2192–2198.
[4] Z.H. Jabbar, S. Esmail Ebrahim, Highly efficient visible-light-driven
photocatalytic degradation of organic pollutants by using magnetically separable
supported heterogeneous nanocomposites (SiO2/Fe3O4/Ag2WO4), Environ.
Nanotechnol. Monit. Manag. (2021), 100554, https://doi.org/10.1016/J.
ENMM.2021.100554.
[5] J.H. Al-baidhani, Z.H.A.-. Khafajy, Pre-treatment of water by using broken marble
and ceramic wastes as up-flow roughing filter media, Int. J. Curr. Eng. Technol. 7
(2017) 74–81.
[6] J. Xie, N. Guo, A. Liu, Y. Cao, J. Hu, D. Jia, Simple solid-state synthesis of BiOCl/
Bi2O2CO3 heterojunction and its excellent photocatalytic degradation of RhB,
J. Alloys Compd. 784 (2019) 377–385.
[7] M. Abdullah Issa, Z.Z. Abidin, S. Sobri, S. Abdul-Rashid, M.A. Mahdi, N.
A. Ibrahim, M.Y. Pudza, Fabrication, characterization and response surface
method optimization for quantum efficiency of fluorescent nitrogen-doped
carbon dots obtained from carboxymethylcellulose of oil palms empty fruit
bunch, Chin.J. Chem. Eng. 28 (2020) 584–592, https://doi.org/10.1016/j.
cjche.2019.04.003.
[8] D. Huang, Z. Li, G. Zeng, C. Zhou, W. Xue, X. Gong, X. Yan, S. Chen, W. Wang,
M. Cheng, Megamerger in photocatalytic field: 2D g-C3N4 nanosheets serve as
support of 0D nanomaterials for improving photocatalytic performance, Appl.
Catal. B Environ. 240 (2019) 153–173.
[9] Z.H. Jabbar, S.H. Ammar, S. Esmail Ebrahim, Enhanced visible-light
photocatalytic bacterial inhibition using recyclable magnetic heterogeneous
nanocomposites (Fe3O4@SiO2@Ag2WO4@Ag2S) in core/shell structure,
Environ. Nanotechnol. Monit. Manag. 16 (2021), 100601, https://doi.org/
10.1016/J.ENMM.2021.100601.
[10] Z.H. Jabbar, B.H. Graimed, A.A. Okab, M. Abdullah, S.H. Ammar, H.J. Khadim, Y.
A. Shafiq, A review study summarizes the main characterization techniques of
nano-composite photocatalysts and their applications in photodegradation of
organic pollutants, Environ. Nanotechnol. Monit. Manag. 19 (2023), 100765,
https://doi.org/10.1016/j.enmm.2022.100765.
[11] Z.H. Jabbar, S.E. Ebrahim, Synthesis, characterization, and photocatalytic
degradation activity of core/shell magnetic nanocomposites (Fe3O4@SiO2@
Ag2WO4@Ag2S) under visible light irradiation, Opt. Mater. (Amst) (2021),
111818, https://doi.org/10.1016/J.OPTMAT.2021.111818.
[12] C. Xu, K. Yan, P. Wang, X. Zhou, T. Zhang, Y. Fu, Q. Yan, CuBi2O4 and rGO co-
modified 3D hierarchical flower-like Bi5O7I nanoflakes as Z-scheme
heterojunction for enhanced photocatalytic performance, Sep. Purif. Technol. 257
(2021), 117935, https://doi.org/10.1016/j.seppur.2020.117935.
[13] Z.H. Jabbar, S.E. Ebrahim, Recent advances in nano-semiconductors
photocatalysis for degrading organic contaminants and microbial disinfection in
wastewater: a comprehensive review, Environ. Nanotechnol. Monit. Manag. 17
(2022), 100666.
[14] Z.H. Jabbar, B.H. Graimed, Recent developments in industrial organic
degradation via semiconductor heterojunctions and the parameters affecting the
photocatalytic process: a review study, J. Water Process Eng. 47 (2022), 102671.
[15] M.A. Issa, Z.Z. Abidin, S. Sobri, S. Rashid, M.A. Mahdi, N.A. Ibrahim, M.Y. Pudza,
Facile synthesis of nitrogen-doped carbon dots from lignocellulosic waste,
Nanomaterials 9 (2019), https://doi.org/10.3390/nano9101500.
[16] F. Guo, X. Huang, Z. Chen, L. Cao, X. Cheng, L. Chen, W. Shi, Construction of
Cu3P-ZnSnO3-g-C3N4 p-n-n heterojunction with multiple built-in electric fields
for effectively boosting visible-light photocatalytic degradation of broad-
Z.H. Jabbar et al.
spectrum antibiotics, Sep. Purif. Technol. 265 (2021), 118477, https://doi.org/
10.1016/j.seppur.2021.118477.
[17] S. Wang, J. Wang, Magnetic 2D/2D oxygen doped g-C3N4/biochar composite to
activate peroxymonosulfate for degradation of emerging organic pollutants,
J. Hazard. Mater. 423 (2022), 127207.
[18] F. Guo, L. Wang, H. Sun, M. Li, W. Shi, High-efficiency photocatalytic water
splitting by a N-doped porous gC 3 N 4 nanosheet polymer photocatalyst derived
from urea and N, N-dimethylformamide, Inorg. Chem. Front. 7 (2020)
1770–1779.
[19] Z. Chen, W. Chen, G. Liao, X. Li, J. Wang, Y. Tang, L. Li, Flexible construct of N
vacancies and hydrophobic sites on g-C3N4 by F doping and their contribution to
PFOA degradation in photocatalytic ozonation, J. Hazard. Mater. 428 (2022),
128222.
[20] G. Fan, B. Du, J. Zhou, W. Yu, Z. Chen, S. Yang, Stable Ag2O/g-C3N4 pn
heterojunction photocatalysts for efficient inactivation of harmful algae under
visible light, Appl. Catal. B Environ. 265 (2020), 118610.
[21] A. Wang, S. Guo, Z. Zheng, H. Wang, X. Song, H. Zhu, Y. Zeng, J. Lam, R. Qiu,
K. Yan, Highly dispersed Ag and g-C3N4 quantum dots co-decorated 3D
hierarchical Fe3O4 hollow microspheres for solar-light-driven pharmaceutical
pollutants degradation in natural water matrix, J. Hazard. Mater. 434 (2022),
128905.
[22] H. Yin, Y. Cao, T. Fan, P. Li, X. Liu, Construction of AgBr/β-Ag2WO4/g-C3N4
ternary composites with dual Z-scheme band alignment for efficient organic
pollutants removal, Sep. Purif. Technol. 272 (2021), 118251, https://doi.org/
10.1016/j.seppur.2020.118251.
[23] Z. Li, C. Jin, M. Wang, J. Kang, Z. Wu, D. Yang, T. Zhu, Novel rugby-like g-C3N4/
BiVO4 core/shell Z-scheme composites prepared via low-temperature
hydrothermal method for enhanced photocatalytic performance, Sep. Purif.
Technol. 232 (2020), 115937.
[24] S. Li, J. Chen, S. Hu, W. Jiang, Y. Liu, J. Liu, A novel 3D Z-scheme heterojunction
photocatalyst: Ag 6 Si 2 O 7 anchored on flower-like Bi 2 WO 6 and its excellent
photocatalytic performance for the degradation of toxic pharmaceutical
antibiotics, Inorg. Chem. Front. 7 (2020) 529–541.
[25] S. Li, S. Hu, W. Jiang, J. Zhang, K. Xu, Z. Wang, In situ construction of WO3
nanoparticles decorated Bi2MoO6 microspheres for boosting photocatalytic
degradation of refractory pollutants, J. Colloid Interface Sci. 556 (2019)
335–344.
[26] S. Bera, S. Ghosh, S. Shyamal, C. Bhattacharya, R.N. Basu, Photocatalytic
hydrogen generation using gold decorated BiFeO3 heterostructures as an efficient
catalyst under visible light irradiation, Sol. Energy Mater. Sol. Cells 194 (2019)
195–206.
[27] X. Hao, X. Yu, H. Li, Z. Zhang, Y. Wang, J. Li, The preparation of full-range BiOBr/
BiOI heterojunctions and the tunability of their photocatalytic performance
during the synthesis of imines under visible light irradiation, Appl. Surf. Sci. 528
(2020), 147015.
[28] S. Li, J. Chen, W. Jiang, Y. Liu, Y. Ge, J. Liu, Facile construction of flower-like
bismuth oxybromide/bismuth oxide formate pn heterojunctions with
significantly enhanced photocatalytic performance under visible light, J. Colloid
Interface Sci. 548 (2019) 12–19.
[29] W. Liu, Q. Yang, Z. Wang, X. Lv, Z. Yang, Photocatalytic degradation of
trichloroethylene over BiOCl under UV irradiation, Appl. Organomet. Chem. 32
(2018), e4354.
[30] S. Bera, S. Ghosh, R.N. Basu, Fabrication of Bi 2 S 3/ZnO heterostructures: an
excellent photocatalyst for visible-light-driven hydrogen generation and
photoelectrochemical properties, New J. Chem. 42 (2018) 541–554.
[31] H. Cui, S. Dong, K. Wang, M. Luan, T. Huang, Synthesis of a novel Type-II In2S3/
Bi2MoO6 heterojunction photocatalyst: Excellent photocatalytic performance
and degradation mechanism for Rhodamine B, Sep. Purif. Technol. 255 (2021),
117758, https://doi.org/10.1016/j.seppur.2020.117758.
[32] L. Guo, Q. Zhao, C. Wang, H. Shen, X. An Han, K. Zhang, D. Wang, F. Fu,
Magnetically recyclable Fe3O4@SiO2/Bi2WO6/Bi2S3 with visible-light-driven
photocatalytic oxidative desulfurization, Mater. Res. Bull. 118 (2019), 110520,
https://doi.org/10.1016/j.materresbull.2019.110520.
[33] A. Rauf, M.S.A. Sher Shah, G.H. Choi, U. Bin Humayoun, D.H. Yoon, J.W. Bae,
J. Park, W.J. Kim, P.J. Yoo, Facile synthesis of hierarchically structured Bi2S3/
Bi2WO6 photocatalysts for highly efficient reduction of Cr(VI), ACS SustainChem.
Eng. 3 (2015) 2847–2855, https://doi.org/10.1021/acssuschemeng.5b00783.
[34] S. Paul, S. Ghosh, D. Barman, S.K. De, Maximization of photocatalytic activity of
Bi2S3/TiO2/Au ternary heterostructures by proper epitaxy formation and
plasmonic sensitization, Appl. Catal. B Environ. 219 (2017) 287–300.
[35] L. Chen, J. He, Q. Yuan, Y. Liu, C.-T. Au, S.-F. Yin, Environmentally benign
synthesis of branched Bi 2 O 3–Bi 2 S 3 photocatalysts by an etching and re-
growth method, J. Mater. Chem. A 3 (2015) 1096–1102.
[36] L.-X. Hao, G. Chen, Y.-G. Yu, Y.-S. Zhou, Z.-H. Han, Y. Liu, Sonochemistry
synthesis of Bi2S3/CdS heterostructure with enhanced performance for
photocatalytic hydrogen evolution, Int. J. Hydrog. Energy 39 (2014)
14479–14486.
[37] B. Zhu, P. Xia, Y. Li, W. Ho, J. Yu, Fabrication and photocatalytic activity
enhanced mechanism of direct Z-scheme g-C3N4/Ag2WO4 photocatalyst, Appl.
Surf. Sci. 391 (2016) 175–183, https://doi.org/10.1016/j.apsusc.2016.07.104.
[38] A.C.S. Jucá, F.H.P. Lopes, H.V. Silva-Júnior, L.K.R. Silva, E. Longo, J.C. Szancoski,
L. Cavalcante, Structure, morphology features and photocatalytic properties of
α-Ag2WO4 nanocrystals-modified Palygorskite clay, J. Photocatal. 02 (2021)
114–129, https://doi.org/10.2174/2665976x02666210210163001.
[39] S. Kokilavani, S.A. Al-Farraj, A.M. Thomas, H.A. El-Serehy, L.L. Raju, S.S. Khan,
Enhanced visible light driven photocatalytic and antibacterial activities of
17
Diamond & Related Materials 133 (2023) 109711
Ag2WO4 decorated ZnS nanocomposite, Ceram. Int. 47 (2021) 12997–13006,
https://doi.org/10.1016/j.ceramint.2021.01.163.
[40] C. Ayappan, V. Jayaraman, B. Palanivel, A. Pandikumar, A. Mani, Facile
preparation of novel Sb2S3 nanoparticles/rod-like α-Ag2WO4 heterojunction
photocatalysts: continuous modulation of band structure towards the efficient
removal of organic contaminants, Sep. Purif. Technol. 236 (2020), 116302,
https://doi.org/10.1016/j.seppur.2019.116302.
[41] G. Wu, W. Xing, J. Han, P. Li, Fabrication of silver-based visible-light-driven
photocatalyst and degradation of organic pollutants in wastewater, Fresenius
Environ. Bull. 29 (2020) 445–453.
[42] G. Wu, Synthesis of Silver-based Composite Photocatalysis Material and Its
Visible-light-driven Photocatalytic Degradation of Dye Pollutants, 2021.
[43] H. Yin, M. Zhang, J. Yao, Y. Luo, P. Li, X. Liu, S. Chen, Surfactant-assisted
synthesis of direct Z-scheme AgBr/β-Ag2WO4 heterostructures with enhanced
visible-light-driven photocatalytic activities, Mater. Sci. Semicond. Process. 105
(2020), 104688.
[44] S. Iqbal, A. Bahadur, M. Javed, O. Hakami, R.M. Irfan, Z. Ahmad, A. AlObaid, M.
M. Al-Anazy, H.B. Baghdadi, H.S.M. Abd-Rabboh, Design Ag-doped ZnO
heterostructure photocatalyst with sulfurized graphitic C3N4 showing enhanced
photocatalytic activity, Mater. Sci. Eng. B 272 (2021), 115320.
[45] A. Bahadur, S. Iqbal, H.O. Alsaab, N.S. Awwad, H.A. Ibrahium, Designing a novel
visible-light-driven heterostructure Ni–ZnO/SgC 3 N 4 photocatalyst for coloured
pollutant degradation, RSC Adv. 11 (2021) 36518–36527.
[46] D. Ayodhya, G. Veerabhadram, Synthesis and characterization of g-C 3 N 4
nanosheets decorated Ag 2 S composites for investigation of catalytic reduction of
4-nitrophenol, antioxidant and antimicrobial activities, J. Mol. Struct. 1186
(2019) 423–433, https://doi.org/10.1016/j.molstruc.2019.03.048.
[47] R.A. Senthil, S. Osman, J. Pan, A. Khan, V. Yang, T.R. Kumar, Y. Sun, Y. Lin,
X. Liu, A. Manikandan, One-pot preparation of AgBr/α-Ag2WO4 composite with
superior photocatalytic activity under visible-light irradiation, Colloids Surf A
Physicochem. Eng. Asp. 586 (2020), 124079, https://doi.org/10.1016/j.
colsurfa.2019.124079.
[48] L. Yan, Y. Wang, H. Shen, Y. Zhang, J. Li, D. Wang, Photocatalytic activity of Bi 2
WO 6 /Bi 2 S 3 heterojunctions: the facilitation of exposed facets of Bi2WO6
substrate, Appl. Surf. Sci. 393 (2017) 496–503, https://doi.org/10.1016/j.
apsusc.2016.10.039.
[49] H. Liu, B. Wang, M. Chen, H. Zhang, J. Peng, L. Ding, W. Wang, Simple synthesis
of BiOAc/BiOBr heterojunction composites for the efficient photocatalytic
removal of organic pollutants, Sep. Purif. Technol. 261 (2021), 118286, https://
doi.org/10.1016/j.seppur.2020.118286.
[50] Z. Chen, J. Zhao, J. Chen, Y. Zhang, D. Chen, Q. Wang, D. Xia, UiO-66/BiOBr
heterojunction functionalized cotton fabrics as flexible photocatalyst for visible-
light driven degradation of dyes and Cr(VI), Sep. Purif. Technol. 258 (2021),
118007, https://doi.org/10.1016/j.seppur.2020.118007.
[51] B. He, Y. Du, Y. Feng, M. Du, J. Wang, J. Qu, Y. Liu, N. Jiang, J.J. Wang, X.Y. Sun,
Fabrication of novel ternary direct Z-scheme + isotype heterojunction
photocatalyst g-C3N4/g-C3N4/BiOBr with enhanced photocatalytic performance,
Appl. Surf. Sci. 506 (2020), https://doi.org/10.1016/j.apsusc.2019.145031.
[52] Z.H. Jabbar, S.E. Ebrahim, S.H. Ammar, Supported heterogeneous
nanocomposites (SiO2/Fe3O4/Ag2WO4) for visible-light-driven photocatalytic
disinfection against E. coli, Mater. Sci. Semicond. Process. 141 (2022), 106427.
[53] Y. Li, Y. Li, S. Ma, P. Wang, Q. Hou, J. Han, S. Zhan, Efficient water disinfection
with Ag2WO4-doped mesoporous g-C3N4 under visible light, J. Hazard. Mater.
338 (2017) 33–46.
[54] H. Jiang, Z. Xing, Z. Li, K. Pan, Z. Yang, K. Wang, M. Guo, S. Yang, W. Zhou,
Wide-spectrum response urchin-like Bi2S3 spheres and ZnS quantum dots co-
decorated mesoporous g-C3N4 nanosheets heterojunctions for promoting charge
separation and enhancing photothermal-photocatalytic performance, Appl. Surf.
Sci. 527 (2020), 146653, https://doi.org/10.1016/j.apsusc.2020.146653.
[55] J. Feng, T. Jiang, Y. Han, O.K. Okoth, L. Cheng, J. Zhang, Construction of dual Z-
scheme Bi2S3/Bi2O3/WO3 ternary film with enhanced visible light
photoelectrocatalytic performance, Appl. Surf. Sci. 505 (2020), 144632, https://
doi.org/10.1016/j.apsusc.2019.144632.
[56] A. Meng, J. Zhang, D. Xu, B. Cheng, J. Yu, Enhanced photocatalytic H2-
production activity of anatase TiO2 nanosheet by selectively depositing dual-
cocatalysts on 101 and 001 facets, Appl. Catal. B Environ. 198 (2016) 286–294.
[57] X. Chen, W. Zhang, L. Zhang, L. Feng, J. Wen, J. Yang, C. Zhang, J. Jiang,
H. Wang, Effective photocatalytic salicylic acid removal under visible light
irradiation using Ag2S/AgI-Bi2S3/BiOI with Z-scheme heterojunctions, Appl.
Surf. Sci. 481 (2019) 1335–1343, https://doi.org/10.1016/j.apsusc.2019.03.214.
[58] A.A. Okab, A.I. Alwared, A dual S-scheme g-C3N4/Fe3O4/Bi2WO6/Bi2S3
heterojunction for improved photocatalytic decomposition of methylene blue:
proposed mechanism, and stability studies, Mater. Sci. Semicond. Process. 153
(2023), 107196.
[59] J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Ultrathin 2D/2D WO3/g-C3N4 step-scheme
H2-production photocatalyst, Appl. Catal. B Environ. 243 (2019) 556–565.
[60] R.S. Das, S.K. Warkhade, A. Kumar, G.S. Gaikwad, A.V. Wankhade, Graphitic
carbon nitride@ silver zirconate nanocomposite (gC3N4@ Ag2ZrO3): a type-II
heterojunction for an effective visible light photocatalysis and bacterial photo-
inactivation, J. Alloys Compd. 846 (2020), 155770.
[61] Z. Wang, J. Lv, J. Zhang, K. Dai, C. Liang, Facile synthesis of Z-scheme BiVO4/
porous graphite carbon nitride heterojunction for enhanced visible-light-driven
photocatalyst, Appl. Surf. Sci. 430 (2018) 595–602.
[62] Z. You, C. Wu, Q. Shen, Y. Yu, H. Chen, Y. Su, H. Wang, C. Wu, F. Zhang, H. Yang,
A novel efficient gC3N4@BiOI p–n heterojunction photocatalyst constructed
through the assembly of gC3N4 nanoparticles, Dalt. Trans. 47 (2018) 7353–7361.
Z.H. Jabbar et al.
[63] K. Dai, L. Lu, C. Liang, G. Zhu, Q. Liu, L. Geng, J. He, A high efficient graphitic-
C3N4/BiOI/graphene oxide ternary nanocomposite heterostructured
photocatalyst with graphene oxide as electron transport buffer material, Dalt.
Trans. 44 (2015) 7903–7910.
[64] Z. Zhu, F. Zhou, S. Zhan, Enhanced antifouling property of fluorocarbon resin
coating (PEVE) by the modification of g-C3N4/Ag2WO4 composite step-scheme
photocatalyst, Appl. Surf. Sci. 506 (2020), 144934.
[65] L. Zhou, Y. Li, S. Yang, M. Zhang, Z. Wu, R. Jin, Y. Xing, Preparation of novel 0D/
2D Ag2WO4/WO3 Step-scheme heterojunction with effective interfacial charges
transfer for photocatalytic contaminants degradation and mechanism insight,
Chem. Eng. J. 420 (2021), 130361, https://doi.org/10.1016/j.cej.2021.130361.
[66] Y. Li, B. Zhu, J. Yu, W. Ho, P. Xia, Fabrication and photocatalytic activity
enhanced mechanism of direct Z-scheme gC3N4/Ag2WO4 photocatalyst, Appl.
Surf. Sci. 391 (2016) 175–183.
[67] J. Cao, J. He, J. Ye, K. Ge, Y. Zhang, Y. Yang, Urchin-like Bi2S3/Ag
nanostructures for photocatalytic reduction of Cr(VI), ACS Appl. Nano Mater. 4
(2021) 1260–1269, https://doi.org/10.1021/acsanm.0c02858.
[68] F. Guo, Y. Cai, W. Guan, H. Huang, Y. Liu, Graphite carbon nitride/ZnIn2S4
heterojunction photocatalyst with enhanced photocatalytic performance for
degradation of tetracycline under visible light irradiation, J. Phys. Chem. Solids
110 (2017) 370–378.
[69] B. Luo, M. Chen, Z. Zhang, J. Xu, D. Li, D. Xu, W. Shi, Highly efficient visible-
light-driven photocatalytic degradation of tetracycline by a Z-scheme g-C3N4/
Bi3TaO7 nanocomposite photocatalyst, Dalt. Trans. 46 (2017) 8431–8438,
https://doi.org/10.1039/c7dt01250k.
[70] S. Fentie Tadesse, D.H. Kuo, W. Lakew Kebede, G. Sisay Wolde, Visible light
driven Nd2O3/Mo(S, O)3–x⋅0.34H2O heterojunction for enhanced photocatalytic
degradation of organic pollutants, Appl. Surf. Sci. 569 (2021), 151091, https://
doi.org/10.1016/j.apsusc.2021.151091.
[71] D. Wang, X. Yu, Q. Feng, X. Lin, Y. Huang, X. Huang, X. Li, K. Chen, B. Zhao,
Z. Zhang, In-situ growth of β-Bi2O3 nanosheets on g-C3N4 to construct direct Z-
scheme heterojunction with enhanced photocatalytic activities, J. Alloys Compd.
859 (2021), 157795.
[72] W.E.T. Dou, Y. Zhu, J. Liu, L. Jing, Improved photocatalytic activities of
recyclable porous Fe2O3 nanotubes by modifying with nano-sized SiO2 and g-
C3N4 for degrading 2-chlorophenol, Mater. Res. Bull. 142 (2021), 111416,
https://doi.org/10.1016/j.materresbull.2021.111416.
[73] X. Zhang, X. Wang, J. Meng, Y. Liu, M. Ren, Y. Guo, Y. Yang, Robust Z-scheme g-
C3N4/WO3 heterojunction photocatalysts with morphology control of WO3 for
efficient degradation of phenolic pollutants, Sep. Purif. Technol. 255 (2021),
117693, https://doi.org/10.1016/j.seppur.2020.117693.
[74] Z.H. Jabbar, B.H. Graimed, M. Abdullah, S.H. Ammar, S. Esmail, H.J. Khadim, A.
A. Okab, Photocatalytic degradation of Congo red dye using magnetic silica-
coated Ag2WO4/Ag2S as Type I heterojunction photocatalyst: stability and
mechanisms studies, Mater. Sci. Semicond. Process. 153 (2023), 107151, https://
doi.org/10.1016/j.mssp.2022.107151.
[75] M.S. Athar, M. Danish, M. Muneer, Fabrication of visible light-responsive dual Z-
Scheme (α-Fe2O3/CdS/g-C3N4) ternary nanocomposites for enhanced
photocatalytic performance and adsorption study in aqueous suspension,
J. Environ. Chem. Eng. 9 (2021), 105754, https://doi.org/10.1016/j.
jece.2021.105754.
[76] J. Luo, P. Lin, P. Zheng, X. Zhou, X. Ning, L. Zhan, Z. Wu, X. Liu, X. Zhou, In suit
constructing S-scheme FeOOH/MgIn2S4 heterojunction with boosted interfacial
charge separation and redox activity for efficiently eliminating antibiotic
pollutant, Chemosphere 298 (2022), 134297.
[77] Y. Cui, Q. Jia, H. Li, J. Han, L. Zhu, S. Li, Y. Zou, J. Yang, Photocatalytic activities
of Bi2S3/BiOBr nanocomposites synthesized by a facile hydrothermal process,
Appl. Surf. Sci. 290 (2014) 233–239, https://doi.org/10.1016/j.
apsusc.2013.11.055.
[78] S. Vadivel, A.N. Naveen, V.P. Kamalakannan, P. Cao, N. Balasubramanian, Facile
large scale synthesis of Bi 2 S 3 nano rods-graphene composite for photocatalytic
photoelectrochemical and supercapacitor application, Appl. Surf. Sci. 351 (2015)
635–645, https://doi.org/10.1016/j.apsusc.2015.04.101.
[79] D. Wu, S. Yue, W. Wang, T. An, G. Li, H.Y. Yip, H. Zhao, P.K. Wong, Boron doped
BiOBr nanosheets with enhanced photocatalytic inactivation of Escherichia coli,
Appl. Catal. B Environ. 192 (2016) 35–45, https://doi.org/10.1016/j.
apcatb.2016.03.046.
[80] M. Zhu, H. Chen, Y. Dai, X. Wu, Z. Han, Y. Zhu, Novel n-p-n heterojunction of
AgI/BiOI/UiO-66 composites with boosting visible light photocatalytic activities,
Appl. Organomet. Chem. 35 (2021) 1–16, https://doi.org/10.1002/aoc.6186.
[81] A.M. Taddesse, M. Alemu, T. Kebede, Enhanced photocatalytic activity of p-n-n
heterojunctions ternary composite Cu2O/ZnO/Ag3PO4under visible light
irradiation, J. Environ. Chem. Eng. 8 (2020), 104356, https://doi.org/10.1016/j.
jece.2020.104356.
[82] C. Zhu, T. Gong, Q. Xian, J. Xie, Graphite-like carbon nitride coupled with tiny Bi
2 S 3 nanoparticles as 2D/0D heterojunction with enhanced photocatalytic
activity, Appl. Surf. Sci. 444 (2018) 75–86, https://doi.org/10.1016/j.
apsusc.2018.03.021.
[83] H. Li, Y. Zhang, Q. Zhang, Y. Wang, Y. Fan, X. Gao, J. Niu, Boosting visible-light
photocatalytic degradation of indomethacin by an efficient and photostable
Ag3PO4/NG/WO3 composites, Appl. Surf. Sci. 490 (2019) 481–491, https://doi.
org/10.1016/j.apsusc.2019.06.072.
[84] H. Fang, Y. Pan, H. Yan, X. Qin, C. Wang, L. Xu, C. Pan, Facile preparation of Yb3
+/Tm3+ co-doped Ti3C2/Ag/Ag3VO4 composite with an efficient charge
separation for boosting visible-light photocatalytic activity, Appl. Surf. Sci. 527
(2020), https://doi.org/10.1016/j.apsusc.2020.146909.
18
Diamond & Related Materials 133 (2023) 109711
[85] J. Liu, J. Chen, Z. Wu, K. Zhu, J. Wang, Z. Li, G. Tai, X. Liu, S. Lu, Enhanced
visible-light photocatalytic performances of ZnO through loading AgI and
coupling piezo-photocatalysis, J. Alloys Compd. 852 (2021), 156848, https://doi.
org/10.1016/j.jallcom.2020.156848.
[86] M. Sher, S.A. Khan, S. Shahid, M. Javed, M.A. Qamar, A. Chinnathambi, H.
S. Almoallim, Synthesis of novel ternary hybrid g-C3N4@Ag-ZnO nanocomposite
with Z-scheme enhanced solar light-driven methylene blue degradation and
antibacterial activities, J. Environ. Chem. Eng. 9 (2021), 105366, https://doi.
org/10.1016/j.jece.2021.105366.
[87] S. Guo, H. Luo, Y. Li, J. Chen, B. Mou, X. Shi, G. Sun, Structure-controlled three-
dimensional BiOI/MoS2 microspheres for boosting visible-light photocatalytic
degradation of tetracycline, J. Alloys Compd. 852 (2021), 157026, https://doi.
org/10.1016/j.jallcom.2020.157026.
[88] H.J. Khadim, A. Al-Farraji, S.H. Ammar, Boosted visible-light-driven
photocatalytic degradation of lomefloxacin over α-Ag2WO4/NiSx
nanocomposites, Environ. Nanotechnol. Monit. Manag. 18 (2022), 100722.
[89] A. Namdarian, A.G. Tabrizi, N. Arsalani, A. Khataee, A. Mohammadi, J. Ind. Eng.
Chem. (2019), https://doi.org/10.1016/j.jiec.2019.09.012.
[90] M.B. Shekardasht, M.H. Givianrad, P. Gharbani, Z. Mirjafary, A. Mehrizad, Diam.
Relat. Mater. (2020), 108008, https://doi.org/10.1016/j.diamond.2020.108008.
[91] M.H.H. Ali, M.E. Goher, A.D.G. Al-Afify, S.M. El-Sayed, A facile method for
synthesis rGO/Ag nanocomposite and its uses for enhancing photocatalytic
degradation of Congo red dye, SN Appl. Sci. 4 (2022) 1–15.
[92] Z.H. Jabbar, B.H. Graimed, M.A. Issa, S.H. Ammar, S.E. Ebrahim, H.J. Khadim, A.
A. Okab, Photocatalytic degradation of Congo red dye using magnetic silica-
coated Ag2WO4/Ag2S as Type I heterojunction photocatalyst: stability and
mechanisms studies, Mater. Sci. Semicond. Process. 153 (2023), 107151.
[93] L. Chen, Y. Chuang, T.B. Nguyen, J. Chang, S.S. Lam, J. Alloys Compd. (2020),
156448, https://doi.org/10.1016/j.jallcom.2020.156448.
[94] J. He, Y. Cheng, T. Wang, D. Feng, L. Zheng, D. Shao, W. Wang, W. Wang, F. Lu,
H. Dong, R. Zheng, H. Liu, Enhanced photocatalytic performances and magnetic
recovery capacity of visible-light-driven Z-scheme ZnFe2O4/AgBr/Ag
photocatalyst, Appl. Surf. Sci. 440 (2018) 99–106, https://doi.org/10.1016/j.
apsusc.2017.12.219.
[95] Y. Lin, H. Cai, H. Chen, H. Luo, One–pot synthesis of Bi4V2O11/BiVO4
heterostructure with enhanced photocatalytic activity for dye degradation, Appl.
Surf. Sci. 544 (2021), 148921, https://doi.org/10.1016/j.apsusc.2020.148921.
[96] M. Joy, B.N. Nair, A.A.P. Mohamed, K.G. Warrier, U.N.S. Hareesh, One-pot
hydrothermal synthesis of visible-light-responsive MoS2/g-CNO heterostructures
for organic-pollutant degradation, Eur. J. Inorg. Chem. 2016 (2016) 3912–3920,
https://doi.org/10.1002/ejic.201600232.
[97] H. Zhao, J. Zhang, H. Zheng, Facile preparation of dual Z-scheme Bi2O3/g-C3N4/
Ag6Si2O7 photocatalyst for highly efficient visible-light photocatalytic
degradation of organic pollutants, Appl. Surf. Sci. 527 (2020), 146901, https://
doi.org/10.1016/j.apsusc.2020.146901.
[98] D. Peng, Y. Zhang, X. Huang, Highly Efficient Visible-Light Induced
Photocatalytic Capacity Towards Cyclohexane Oxidation of Mg3al0. 5cr0. 5o4. 5
Coupled with N-Doped Tio2, Available SSRN 4151492. (n.d.).
[99] J.-C. Sin, S.-M. Lam, H. Zeng, H. Lin, H. Li, A.K. Kumaresan, A.R. Mohamed, J.-
W. Lim, Z-scheme heterojunction nanocomposite fabricated by decorating
magnetic MnFe2O4 nanoparticles on BiOBr nanosheets for enhanced visible light
photocatalytic degradation of 2, 4-dichlorophenoxyacetic acid and Rhodamine B,
Sep. Purif. Technol. 250 (2020), 117186.
[100] R.G. Pearson, Absolute electronegativity and hardness: application to inorganic
chemistry, Inorg. Chem. 27 (1988) 734–740, https://doi.org/10.1021/
ic00277a030.
[101] J. He, Y. Cheng, T. Wang, D. Feng, L. Zheng, D. Shao, W. Wang, W. Wang, F. Lu,
H. Dong, Enhanced photocatalytic performances and magnetic recovery capacity
of visible-light-driven Z-scheme ZnFe2O4/AgBr/Ag photocatalyst, Appl. Surf. Sci.
440 (2018) 99–106.
[102] P. Raizada, A. Sudhaik, P. Singh, A. Hosseini-Bandegharaei, P. Thakur,
Converting type II AgBr/VO into ternary Z scheme photocatalyst via coupling
with phosphorus doped g-C3N4 for enhanced photocatalytic activity, Sep. Purif.
Technol. 227 (2019), 115692, https://doi.org/10.1016/j.seppur.2019.115692.
[103] B. Szczepanik, Photocatalytic degradation of organic contaminants over clay-
TiO2 nanocomposites: a review, Appl. Clay Sci. 141 (2017) 227–239, https://doi.
org/10.1016/j.clay.2017.02.029.
[104] W.A. Aboutaleb, R.A. El-Salamony, Effect of Fe2O3-CeO2 nanocomposite
synthesis method on the Congo red dye photodegradation under visible light
irradiation, Mater. Chem. Phys. 236 (2019), 121724, https://doi.org/10.1016/j.
matchemphys.2019.121724.
[105] B.H. Graimed, A.A. Okab, Z.H. Jabbar, M. Abdullah, S.H. Ammar, Highly stable
β-Bi2O3/Ag decorated nanosilica as an efficient Schottky heterojunction for
ciprofloxacin photodegradation in wastewater under LED illumination, Mater.
Sci. Semicond. Process. 156 (2023), 107303, https://doi.org/10.1016/j.
mssp.2022.107303.
[106] S. Mandal, S. Adhikari, S. Pu, X. Wang, D.H. Kim, R.K. Patel, Interactive Fe2O3/
porous SiO2 nanospheres for photocatalytic degradation of organic pollutants:
kinetic and mechanistic approach, Chemosphere 234 (2019) 596–607, https://
doi.org/10.1016/j.chemosphere.2019.06.092.
[107] M. Bagheri, A.R. Mahjoub, B. Mehri, Enhanced photocatalytic degradation of
congo red by solvothermally synthesized CuInSe2-ZnO nanocomposites, RSC Adv.
4 (2014) 21757–21764, https://doi.org/10.1039/c4ra01753f.
[108] A. Mohammad, M.E. Khan, M.H. Cho, T. Yoon, Adsorption promoted visible-light-
induced photocatalytic degradation of antibiotic tetracycline by tin oxide/cerium
Z.H. Jabbar et al.
oxide nanocomposite, Appl. Surf. Sci. 565 (2021), 150337, https://doi.org/
10.1016/j.apsusc.2021.150337.
[109] S. Velmurugan, S. Balu, S. Palanisamy, T.C.K. Yang, V. Velusamy, S.W. Chen, E.S.
I. El-Shafey, Synthesis of novel and environmental sustainable AgI-Ag2S
nanospheres impregnated g-C3N4 photocatalyst for efficient degradation of
aqueous pollutants, Appl. Surf. Sci. 500 (2020), 143991, https://doi.org/
10.1016/j.apsusc.2019.143991.
[110] A.M. Mohammed, S.S. Mohtar, F. Aziz, M. Aziz, A. Ul-Hamid, Cu2O/ZnO-PANI
ternary nanocomposite as an efficient photocatalyst for the photodegradation of
Congo Red dye, J. Environ. Chem. Eng. 9 (2021), 105065, https://doi.org/
10.1016/j.jece.2021.105065.
[111] T. Zhou, T. Li, J. Hou, Y. Wang, B. Hu, D. Sun, Y. Wu, W. Jiang, G. Che, C. Liu,
Tailoring boron doped intramolecular donor–acceptor integrated carbon nitride
skeleton with propelling photocatalytic activity and mechanism insight, Chem.
Eng. J. 445 (2022), 136643.
19
Diamond & Related Materials 133 (2023) 109711
[112] T. Zhou, J. Shi, G. Li, B. Liu, B. Hu, G. Che, C. Liu, L. Wang, L. Yan, Advancing n-
π* electron transition of carbon nitride via distorted structure and nitrogen
heterocycle for efficient photodegradation: Performance, mechanism and toxicity
insight, J. Colloid Interface Sci. 632 (2023) 285–298.
[113] L. Yan, J. Hou, T. Li, Y. Wang, C. Liu, T. Zhou, W. Jiang, D. Wang, G. Che,
Tremella-like integrated carbon nitride with polyvinylimine-doped for enhancing
photocatalytic degradation and hydrogen evolution performances, Sep. Purif.
Technol. 279 (2021), 119766.
[114] Z.H. Jabbar, A.A. Okab, B.H. Graimed, M. Abdullah, S.H. Ammar, Fabrication of
g-C3N4 nanosheets immobilized Bi2S3/Ag2WO4 nanorods for photocatalytic
disinfection of Staphylococcus aureus cells in wastewater: Dual S-scheme charge
separation pathway, J. Photochem. Photobiol. A Chem. 438 (2023) 114556,
https://doi.org/10.1016/j.jphotochem.2023.114556.