Advanced Powder Technology 29 (2018) 94–105

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Advanced Powder Technology

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

Original Research Paper

Magnetically recoverable highly efficient visible-light-active g-C3N4/

Fe3O4/Ag2WO4/AgBr nanocomposites for photocatalytic degradations of
environmental pollutants
Mitra Mousavi, Aziz Habibi-Yangjeh ⇑
Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, P.O. Box 179, Ardabil, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Herein, magnetically recoverable g-C3N4/Fe3O4/Ag2WO4/AgBr (gCN/M/AgW/AgBr) nanocomposites, as

Received 16 June 2017 greatly efficient visible-light-active photocatalysts, were fabricated by successive decoration of Fe3O4,
Received in revised form 15 October 2017 Ag2WO4, and AgBr over g-C3N4 (gCN) and they were characterized by XRD, EDX, SEM, TEM, HRTEM,
Accepted 17 October 2017
UV–vis DRS, FT-IR, PL, TG, and VSM analysis. Visible-light-induced photocatalytic performances were
Available online 31 October 2017
studied by degradations of RhB, MB, MO, and fuchsine pollutants. It was confirmed that the nanocompos-
ites are effective in the reduction of e
/h+ recombination through the matched interactions between
Keywords:
energy bands of gCN, Fe3O4, Ag2WO4, and AgBr semiconductors. The highest photocatalytic degradation
g-C3N4/Fe3O4/Ag2WO4/AgBr
g-C3N4-based photocatalysts
efficiency was observed for the gCN/M/AgW/AgBr (30%) nanocomposite when it was refluxed for 30 min.
Magnetic nanocomposites Activity of this nanocomposite is almost 21, 41, 94, and 10-folds greater than those of the gCN toward the
Heterojunction degradations of RhB, MB, MO, and fuchsine pollutants, respectively. Additionally, a mechanism for the
superior photocatalytic performances was proposed using reactive species scavenging experiments and
characterization results.
Ó 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
At the moment, the earth is facing with two main challenges of
energy shortage and environmental pollution [1–3].
Semiconductor-based photocatalysts are promising materials to
address these challenges using solar energy [4,5]. At the present,
these photocatalysts are applied in photodegradation of wide-
spread hazardous compounds, photocatalytic water splitting to
produce hydrogen gas, photosynthesis of fuels by reduction of car-
bon dioxide, synthesis of various organic compounds, and disinfec-
tion of microorganisms [6–9]. After about 40 years of enormous
researches about heterogeneous photocatalysts, semiconductors
such as TiO2 and ZnO and their composites have been widely
employed in the photocatalytic processes [10,11]. However, wide
band gaps of these semiconductors restrict effective utilization of
the solar light in these processes, because sun light contains almost
43 and 4% of the energy in visible and ultraviolet ranges, respec-
tively. Hence, these semiconductors have much lower quantum
efficiency under the solar-energy illumination. As a consequence,
design and fabrication of visible-light-driven (VLD) photocatalysts
⇑ Corresponding author.
E-mail address: ahabibi@uma.ac.ir (A. Habibi-Yangjeh).
are active research area to provide opportunity for using the solar
energy in environmental and energy crises [12–21]. In the field of
searching for effective VLD photocatalysts, graphitic carbon nitride
(g-C3N4, denoted as gCN) was introduced to the research commu-
nity in 2009 [22]. This organic semiconductor has displayed poten-
tial to apply in photocatalytic process under visible light, as one of
the effective next generation photocatalyst [23–26]. This poly-
meric semiconductor, with narrow band gap, is simply prepared
by polymerization of cheap compounds with ‘‘earth-abundant”
elements [23]. In spite of many appealing properties of gCN, activ-
ity of this photocatalyst is not high enough to utilize it in practical
applications, owing to some drawbacks including low visible-light
absorption and fast recombination of photoinduced e
/h+ pairs
[23–26]. One of the most effective methods to overcome these
shortcomings is fabrication of heterojunctions between gCN sheets
and other narrow/wide band gap semiconductors [24–28].
Silver tungstate (Ag2WO4) is one of the metal tungstates with a
wide band gap of almost 3.1 eV, which extensively applied in pho-
tocatalytic processes [21,29–32]. This large band gap semiconduc-
tor has appropriate valence band (VB) and conduction band (CB)
energies to help separation of the photogenerated e
/h+ pairs in
gCN through migration of electrons from CB of gCN to that of
Ag2WO4 [30]. On the other hand, silver bromide (AgBr) is a small

https://doi.org/10.1016/j.apt.2017.10.016
0921-8831/Ó 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105 95

band gap (2.6 eV) semiconductor applied in fabrication of numer- trophotometer. For providing PL spectra, the amount of photocata-
ous VLD photocatalysts [33–35]. Owing to narrow band gap and lyst was 0.07 g in 3.5 mL of water. In addition, the excitation
appropriate band potentials, AgBr could help to further increase wavelength was 300 nm. The UV–vis spectra for the degradation
photocatalytic activity of g-C3N4/Ag2WO4, denoted as gCN/AgW. reaction were plotted using a Cecile 9000 spectrophotometer.
Recently, significant attempts have been devoted to prepare mag- Magnetic properties of the samples were obtained using a VSM
netically recoverable photocatalysts to address difficulty of photo- instrument (Meghnatis Kavir Kashan Co., Iran). The ultrasound
catalyst separation from the treated systems [36,37]. These next radiation was performed using a Bandelin ultrasound processor
generation photocatalysts provide opportunity to avoid the treated HD 3100 (12 mm diameter Ti horn, 75 W, 20 kHz).
systems from secondary pollutions [37]. Therefore, by codeposition
of Ag2WO4 and AgBr over g-C3N4/Fe3O4, denoted as gCN/M, we can
2.3. Photocatalysis section
prepare magnetically recoverable photocatalyst with efficient pho-
tocatalytic performance.
Photocatalytic performance of the fabricated samples was
In these regards, we present a simple method for fabrication of
explored at 25 °C under visible-light illumination of an LED lamp
g-C3N4/Fe3O4/Ag2WO4/AgBr photocatalysts, denoted as gCN/M/
with 50 W. Concentrations of RhB, MB, and MO were 1  10
5 M
AgW/AgBr. The fabricated magnetic photocatalysts were charac-
and concentration of fuchsine was 0.77  10
5 M. Before the light
terized by XRD, EDX, FT-IR, SEM, TEM, HRTEM, UV–vis DRS, PL,
irradiation, a suspension containing 0.1 g of the photocatalyst
TG, and VSM instruments. Visible-light photocatalytic performance
and 250 mL aqueous solution of the pollutant was continuously
of the magnetic photocatalysts was studied by degradations of rho-
stirred in the dark for 60 min, to attain adsorption equilibrium.
damine B (RhB), methylene blue (MB), methyl orange (MO), and
Samples were taken from the reactor at regular intervals and the
fuchsine. Additionally, the effects of Ag2WO4 and AgBr contents,
photocatalyst removed before analysis by the spectrophotometer
the preparation time, and calcination temperature on the degrada-
at 553, 664, 477, and 540 nm corresponding to the maximum
tion performance were explored. Finally, the proposed mechanism
absorption wavelengths of RhB, MB, MO, and fuchsine,
for the enhanced photocatalytic activity of the gCN/M/AgW/AgBr
respectively.
nanocomposites was discussed.

3. Results and discussion

2. Experimental
2.1. Synthesis of the photocatalysts
The gCN powder was prepared by heating melamine (99.2%,
Loba Chemie) in an alumina crucible up to 520 °C. The gCN/M
nanocomposite was prepared using our previous report [38]. The
gCN/M/AgW (30%) nanocomposite, in which 30% is weight percent
of Ag2WO4, was prepared by refluxing method. Typically, 0.35 g of
the gCN/M was dispersed into 150 mL of water by ultrasonic irra-
diation for 5 min. Then, 0.109 g of silver nitrate (99.9%, Loba Che-
mie) was added to the suspension and stirred for 60 min. Then,
an aqueous solution of sodium tungstate (Na2WO4H2O, 99.8%,
Merck), which is prepared by dissolving 0.106 g in 20 mL of water,
was dropwise added to the suspension and refluxed for 60 min.
The resultant suspension was then centrifuged to get the precipi-
tate out and washed two times with water and ethanol and dried
in an oven at 60 °C for 24 h. Finally, the resulting powder was col-
lected and used for the next step.
For preparation of the gCN/M/AgW/AgBr (30%) nanocomposite,
where 30% is weight percent of AgBr, 0.35 g of the gCN/M/AgW was
dispersed into 150 mL of water by ultrasonic irradiation for 5 min.
Then, 0.135 g of silver nitrate was added and stirred for 60 min.
Afterwards, an aqueous solution of sodium bromide (NaBr, 99.8,
Merck), prepared by dissolution of 0.082 g in 20 mL of water,
was dropwise added to the suspension and refluxed for 30 min.
After centrifugation and washing, the light brown powder was col-
lected and dried (Scheme 1).
2.2. Instruments
The XRD analysis was carried out by a Philips Xpert X-ray
diffractometer with high-intensity Cu Ka radiation (k = 0.15406
nm). Morphology and purity of the samples were studied by LEO
1430VP SEM equipped with an EDX system. The TEM images were
observed by a Philips CM30 instrument with 150 kV of acceleration
voltage. The UV–vis DRS data were recorded by a Scinco 4100
apparatus. The structural information for samples was measured
by FT-IR spectroscopy (Perkin Elmer Spectrum RX I). The PL spectra
were provided using a Perkin Elmer (LS 55) fluorescence spec-
Crystal structure and phase composition of the prepared photo-
catalysts were analyzed and the XRD patterns are presented in
Fig. 1. The pattern of gCN displays two broad peaks at 2h = 13.2°
and 27.4°. The strong peak at 27.4° is ascribed to the stacking of
aromatic systems. The weak peak at 13.2° is related to the inter-
layer stacking [25,26]. For the gCN/M nanocomposite, beside char-
acteristic peaks of gCN, six distinct typical peaks of Fe3O4
nanoparticle were observed (JCPDS No. 89-0691) [39]. Further-
more, the diffraction patterns of gCN/M/AgW, gCN/M/AgBr (30%),
and gCN/M/AgW/AgBr nanocomposites were performed and they
are shown in Fig. 1. As seen, the characteristic peaks of gCN were
appeared in all nanocomposites, representing that the structure
of gCN did not change by adding Fe3O4, Ag2WO4, and AgBr counter-
parts. For the gCN/M/AgW nanocomposites, the characteristic
diffraction peaks of Ag2WO4 were indexed to (0 2 0), (0 2 2),
(2 2 0), (0 4 0), and (0 4 2) planes with a hexagonal structure (JCPDS
No. 33-1195) [40]. Also, after loading AgBr nanoparticles on the
gCN/M, the composite shows several new diffraction peaks, which
are assigned to the (1 1 1), (2 0 0), (2 2 0), (2 2 2), (4 0 0), and (4 2 0)
planes of AgBr crystalline phase (JCPDS file: 06-0438) [33,34]. In
addition, about the gCN/M/AgW/AgBr nanocomposites, all diffrac-
tion peaks corresponding to gCN, Fe3O4, Ag2WO4, and AgBr can be
visualized and no additional peaks belonging to other impurities
were observed.
The elemental compositions of photocatalysts were revealed by
EDX measurements. As shown in Fig. 2a, the main signals of C and
N elements for the spectrum of gCN sample, C, N, Fe, and O ele-
ments for the spectrum of gCN/M nanocomposite, C, N, Fe, Ag, W,
and O elements for the spectrum of gCN/M/AgW (30%) nanocom-
posite, C, N, Fe, Ag, Br, and O elements for the spectrum of
gCN/M/AgBr (30%) nanocomposite, and C, N, Fe, Ag, W, Br, and O
elements are simultaneously observed in the spectrum of gCN/M/
AgW/AgBr (30%) nanocomposite, offering evidence for purity of
these samples. Furthermore, the contents of gCN, Fe3O4, Ag2WO4,
and AgBr in the gCN/M/AgW/AgBr (30%) photocatalyst were calcu-
lated using EDX analysis to be 33, 16, 21, and 30 wt%, respectively,
which are similar to the preparation contents. In addition, the con-
tents of C, N, Fe, Ag, W, Br, and O elements were calculated to be 13,
20, 12, 26.7, 8.3, 13, and 6.9 wt%, respectively. To further explore
96 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105

Fig. 1. XRD patterns for the (a) gCN, gCN/M, and gCN/M/AgW with different weight percents of Ag2WO4 and (b) gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr
nanocomposites with different compositions.

the detailed elemental distributions, elemental mappings of C, N,
Fe, Ag, W, Br, and O in the gCN/M/AgW/AgBr (30%) nanocomposite
were constructed (Fig. 2b–i). As shown, all of the elements were
uniformly distributed. Hence, it was concluded that Fe3O4, Ag2-
WO4, and AgBr counterparts have uniformly deposited over surface
of the gCN sheets.
The SEM and TEM instruments were used to evaluate morphol-
ogy of the gCN/M/AgW/AgBr (30%) nanocomposite, as the images
are displayed in Fig. 3. As shown, spherical particles of the Fe3O4,
Ag2WO4, and AgBr have deposited on the surface of gCN. In the
TEM image, sheet of gCN (light section) and particles of Fe3O4, Ag2-
WO4, and AgBr (dark parts) are clearly observed (Fig. 3b). Although
before TEM analysis, the sample was undergone long sonication,
the deposited particles over gCN are clearly observed, representing
firm connection between these particles and surface of the gCN. In
addition, the HRTEM image confirms heterostructure formation in
the gCN/M/AgW/AgBr (30%) nanocomposite, where g-C3N4 sheet
serve as a support to bind with Fe3O4, Ag2WO4, and AgBr nanopar-
ticles in the resulting nanocomposite (Fig. 3c). Lattice fringes for g-
C3N4 (0.326 nm, corresponding to 0 0 2 plane), Fe3O4 (0.24 nm, cor-
responding to 3 1 1 plane), Ag2WO4 (0.310 nm, corresponding to
3 0 1 plane), and AgBr (0.285 nm, corresponding to 2 0 0 plane)
are observed in this nanocomposite.
Additionally, structure of the gCN, gCN/M, gCN/M/AgW (30%),
gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) samples was fur-
ther studied using FT-IR spectroscopy. As seen in Fig. S1(a), all of
 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105 97

Scheme 1. Schematic procedure for preparation of the gCN/M/AgW/AgBr nanocomposites.

Fig. 2. (a) EDX spectra for the gCN, gCN/M, gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) samples. (b)–(i) EDX mapping of the gCN/M/AgW/AgBr (30%)
nanocomposite.
98 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105
Fig. 3. (a) SEM image of the gCN/M/AgW/AgBr (30%). (b) TEM image of the gCN/M/AgW/AgBr (30%) nanocomposite. (d) HRTEM image of the gCN/M/AgW/AgBr (30%)
nanocomposite with lattice fringes.
gCN containing samples show three different absorption peaks,
which correspond to the tri-s-triazine structure (808 cm
1), hep-
tazine heterocycles (1200–1600 cm
1), and unreacted amino
group and adsorbed H2O molecules (3100–3300 cm
1) [25,26]. In
addition, FT-IR spectrum of the gCN/M nanocomposite shows an
intense peak at 570 cm
1, which is assigned to stretching vibration
of FeAO bonds in Fe3O4 [41–43]. Compared with the gCN and gCN/
M samples, a new peak at 860 cm
1 was observed in the gCN/M/
AgW (30%) nanocomposite, which is attributed to the asymmetric
stretching vibration of OAWAO group [44]. The spectrum of gCN/
M/AgW/AgBr (30%) nanocomposite is similar to that of the gCN/M/
AgW (30%) nanocomposite, and the characteristic peaks of gCN,
Fe3O4, and Ag2WO4 are observed in the spectrum. Similar to
AgBr-based photocatalysts, any absorption peaks were not
detected for AgBr [45,46].
UV–vis DRS technique was applied to characterize optical
behavior of the photocatalysts, as shown in Fig. S1(b). As can be
seen, the gCN/M and gCN/M/AgW nanocomposites show much
more absorption in visible region compared to the gCN sample,
due to the presence of magnetite (M) in their structures. More
importantly, in the gCN/M/AgBr and gCN/M/AgW/AgBr nanocom-
posites, intensity of the absorption in visible region became stron-
ger than the other samples, due to the presence of narrow band gap
AgBr, indicating potential of these nanocomposites to produce
more charge carriers in this region.
The amounts of gCN in the final products were determined by
TG analysis by heating in air atmosphere with rate of 20 °C min
1.
Fig. 4a presented the TGA curves of gCN, gCN/M, gCN/M/AgW
(30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) samples.
The pure gCN exhibited two regions in the TGA curves. The first
weight loss occurred at around 25–400 °C due to evaporation of
surface adsorbed water. The later weight loss from 400 °C to 650
°C was because of gCN combustion. Although the nanocomposites
have TGA curves similar to the pure gCN, with decoration of Fe3O4,
Ag2WO4, and AgBr over the gCN, the starting degradation temper-
atures considerably decreased. Similar observations have been pre-
viously reported about gCN-based composites [47,48]. The
corresponding amounts of gCN in the gCN/M, gCN/M/AgW (30%),
 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105
Fig. 4. (a) TG curves for the gCN, gCN/M, gCN/M/AgW (30%), gCN/M/AgBr (30%), and
gCN/M/AgW/AgBr (30%) samples. (b) VSM plots for the Fe3O4 and gCN/M/AgW/AgBr
(30%) samples.
gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) samples were
estimated from the remained weights at 700 °C to be about 68,
53, 46, and 23 wt%, respectively.
To magnetically collect and reuse the photocatalysts after pollu-
tant treatment, they should have good superparamagnetic proper-
ties [36,37]. For this purpose, magnetic properties of the Fe3O4 and
gCN/M/AgW/AgBr (30%) samples were studied by VSM instrument
and the curves are shown in Fig. 4b. The saturation magnetizations
of Fe3O4 and gCN/M/AgW/AgBr (30%) samples were found to be
55.5 and 9.61 emu g
1, respectively. The magnetic separability of
the nanocomposites was also explored by placing a magnet near
the glass bottle containing its aqueous suspension. Obviously, the
brown particles were rapidly attracted toward the magnet
(Fig. 4b, inset), revealing that the gCN/M/AgW/AgBr (30%)
nanocomposite possesses excellent magnetic properties. Hence,
this gCN-based magnetic nanocomposite may be an excellent can-
didate for potential environmental applications.
Fig. 5a shows degradations of RhB over the gCN, gCN/M, and
gCN/M/AgW photocatalysts under visible-light illumination. As
99
Fig. 5. (a) Photodegradations of RhB over the gCN, gCN/M, and gCN/M/AgW with
different compositions of Ag2WO4. (b) Photodegradation of RhB over the gCN, gCN/
M, gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr with different
compositions of AgBr.
control experiment shows, concentration of RhB was slightly chan-
ged in the presence of the light irradiation (without using any pho-
tocatalyst), representing that RhB is considerably stable in this
study. It is clear that photocatalytic activity of the gCN and gCN/
M samples is not high enough and activity of gCN/M/AgW
nanocomposites increases with weight percent of Ag2WO4 up to
30%. To further increase photocatalytic performance of the gCN/
M/AgW (30%) nanocomposite, AgBr particles were decorated over
this nanocomposite and the results are displayed in Fig. 5b. As
we can see from Fig. 5b, with combining AgBr semiconductor with
gCN/M/AgW (30%) nanocomposite, remarkable enhancements of
the photocatalytic activity was observed. Among these samples,
the gCN/M/AgW/AgBr (30%) nanocomposite displayed the superior
activity and RhB was completely degraded within 150 min of the
light irradiation. Moreover, in order to show the role of gCN on
the photocatalytic activity, the M/AgW/AgBr (30%) nanocomposite
was prepared and its activity was evaluated and shown in Fig. 5b. It
is clear that this photocatalyst does not have good activity, in com-
parison with the gCN/M/AgW/AgBr (30%) nanocomposite. Hence, it
was concluded that combination of g-C3N4, Ag2WO4, and AgBr have
vital role in the enhanced activity.
The degradation rate constants (kobs) of RhB over the gCN, gCN/
M, gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr
(30%) samples were calculated to be 12.2  10
4, 13.1  10
4,
100 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105

codeposition of AgBr and Ag2WO4 over the gCN/M nanocomposite,

the lowest PL intensity was observed for the gCN/M/AgW/AgBr
(30%) nanocomposite. Thus, it was concluded that among the pre-
pared photocatalysts, the gCN/M/AgW/AgBr (30%) nanocomposite
has the highest separation efficiency for the photoinduced e
/h+
pairs, which is beneficial in enhancing photocatalytic performance.
Hence, it was concluded that codeposition of AgBr and Ag2WO4

o
Fig. 7. A plausible diagram for enhanced photocatalytic activity of the gCN/M/AgW/
AgBr nanocomposites.

Table 1
The values of the v, CB, and VB potentials for g-C3N4, Fe3O4, Ag2WO4, and AgBr.

Material v Eg (eV) ECB (eV) EVB (eV)

g-C3N4 4.73 2.7
1.13 +1.57
Fe3O4 5.76 0.1 +1.21 +1.31
Ag2WO4 5.98 3.1
0.07 +3.03
AgBr 5.80 2.6 +0.00 +2.60

Fig. 6. (a) The degradation rate constants of RhB over the gCN, gCN/M, gCN/M/AgW
gCN/M/AgBr (30%), and gCN/M/AgW/AgBr nanocomposites. (b) PL spectra for the
gCN, gCN/M, gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%)
samples.

97.3  10
4, 43.5  10
4, and 226  10
4 min
1, respectively

(Fig. 6a). Therefore, photocatalytic performance of the gCN/M/
AgW/AgBr (30%) nanocomposite is about 18.6, 17.3, 2.30, and
5.20 times higher than those of the gCN, gCN/M, gCN/M/AgW
(30%), and gCN/M/AgBr (30%) samples, respectively. Therefore, it
was concluded that combination of gCN with Fe3O4, Ag2WO4, and
AgBr significantly enhanced photocatalytic activity of the
nanocomposite.
Heterogeneous photocatalytic activity mainly depends on gen-
eration and separation efficiency of e
/h+ pairs. In PL spectrum of
a semiconductor, the peak intensity relates to e
/h+ recombination
rate. An intensive peak shows high rate for recombination of these
charges [46,49]. In order to evaluate recombination rate of the pho-
togenerated charge carriers, PL spectra of the gCN, gCN/M, gCN/M/
AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) sam-
ples were provided and they displayed in Fig. 6b. As can be
observed, after deposition of Fe3O4, the PL intensity of gCN/M
was decreased when compared with the gCN photocatalyst. The
decrease of PL intensity continuous with depositing AgBr or Fig. 8. The degradation rate constants of RhB over the gCN/M/AgW/AgBr (30%)
Ag2WO4 over the gCN/M nanocomposite. Interestingly, with nanocomposite in the presence of various scavengers.
 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105 101

Fig. 9. (a) The degradation rate constants of RhB over the gCN/M/AgW/AgBr (30%) nanocomposite prepared with different refluxing time. (b)–(c) SEM images, and (d) PL
spectra for the gCN/M/AgW/AgBr (30%) nanocomposite refluxed for 30 and 120 min.
102 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105
semiconductors synergistically participate in suppression of the
charge carriers from the unwanted recombination reaction. As a
result, based on the DRS and PL spectra, the higher photocatalytic
activity of the gCN/M/AgW/AgBr (30%) nanocomposite relative to
its counterparts ascribed to stronger absorption in the visible
region, due to the presence of AgBr, and higher efficiency for sep-
aration and transmission of the photoinduced e
/h+ pairs, due to
synergistic participation of the deposited particles over the gCN
sheets.
In this step, a probable mechanism for enhancement photocat-
alytic activity of the gCN/M/AgW/AgBr nanocomposites was pro-
posed, as shown in Fig. 7. It is important to say that band
positions for constituents of a photocatalyst have strong effect on
the photocatalytic performance. The band gap energies (Eg) of
gCN, Fe3O4, Ag2WO4, and AgBr are 2.7, 0.1, 3.1, and 2.6 eV, respec-
tively. The ECB and EVB edge potentials for the counterparts of the
nanocomposites were estimated using Eqs. (1) and (2) [50]:
(b)
Fig. 10. (a) The degradation rate constants of RhB over the gCN/M/AgW/AgBr (30%)
nanocomposite calcined at different calcination temperature. (b) PL spectra for the
gCN/M/AgW/AgBr (30%) nanocomposite without calcination and the sample
calcined at 400 °C for 2 h.
EVB ¼ v
Ee þ 0:5Eg ð1Þ
ECB ¼ EVB
Eg ð2Þ
where v and Ee are electronegativity of the semiconductor and the
free electrons’ energy on the hydrogen scale (Ee value is about 4.5
eV/NHE). The v, ECB, and EVB values of gCN, Fe3O4, Ag2WO4, and
AgBr are listed in Table 1. The proposed mechanism for degradation
of pollutants over the gCN/M/AgW/AgBr nanocomposites is
schematically shown in Fig. 7. Firstly, under visible-light illumina-
tion, gCN and AgBr are excited to produce e
/h+ pairs, because of
their small band gaps. Owing to well-matched band edge potentials
and heterojunction formation between the semiconductors, the
photoinduced electrons on the CB of gCN simply transfer to the
CB of Fe3O4, Ag2WO4, and AgBr. Additionally, the excited holes pro-
duced over AgBr are transferred into the VB of gCN, resulting in
enhanced e
/h+ separations. Subsequently, the electrons on the CB
of Ag2WO4 and AgBr are trapped by adsorbed O2 to produce OH
radicals (E0(O2/H2O2) = +0.695 eV vs. NHE) [27]. It should be noted
that OH radicals are not produced through oxidation of OH
and
Fig. 11. (a) Reusability of the gCN/M/AgW/AgBr (30%) nanocomposite. (b) XRD
patterns of the nanocomposite before and after utilization.
 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105
H2O species, because the VB potentials of gCN (+1.57 eV/NHE) is not
enough for oxidation of OH
(E°-OH/OH° = +2.38 eV) and H2O (E°H2O/
OH° = +2.72 eV) [27]. Also, the electrons on the CB of gCN react with
O2 to form O
2 radicals, because the CB position of gCN is more neg-
ative than the potential of O2/O
0 

2 (E (O2/ O2 ) =
0.33 eV/NHE) [27].
Finally, the produced reactive species react with the adsorbed pol-
lutant molecules to oxidize it and produce different products. In
summary, the synergistic effect and efficient charge transfer in
the gCN/M/AgW/AgBr nanocomposite make it an efficient photocat-
alyst under visible-light irradiation.
The trapping experiments were performed to determine the
major active species by using benzoquinone (BQ, quencher of


O2 ), ammonium oxalate (AO, a quencher of h+), and 2-PrOH (a
quencher of OH). Fig. 8 shows that in the presence of BQ, the
degradation rate constant decreased from 226  10
4 min
1 to
40.0  10
4 min
1. Besides, with the addition of AO and 2-PrOH,
the degradation rate constants were decreased to 173  10
4 and
121  10
4 min
1, respectively. Hence, it was concluded that the
role of O

2 species on the degradation reaction is greater than those
of OH and h+ species. Additionally, degradation rate constant of
RhB was considerably decreased by N2 bubbling in the reaction
Fig. 12. The degradation rate constants of RhB, MB, MO, and fuchsine over the gCN, gCN/M/Ag2WO4 (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr (30%) samples.
103
system, confirming the important role of dissolved O2 in scaveng-
ing electrons from the CB of g-C3N4 [51,52].
As an important operational parameter, preparation time of
photocatalyst could have remarkable effect on the photocatalytic
performance. So, we investigated the effect of refluxing time on
photoactivity of the gCN/M/AgW/AgBr (30%) nanocomposite
(Fig. 9a). As seen, when the refluxing time increased from 15 to
30 min, the photoactivity increased and then with further increas-
ing the preparation time to 240 min, the degradation rate constant
was decreased. Fig. 9b and c display SEM images of the gCN/M/
AgW/AgBr (30%) nanocomposite fabricated by refluxing for 30
and 120 min. As clearly observed, aggregation of the deposited
counterparts over gCN for the prepared photocatalyst by refluxing
for 120 min is higher than that of the sample prepared by refluxing
for 60 min. Additionally, from Fig. 9d it can be found that the sam-
ple prepared within 120 min refluxing time shows a strong PL
emission band, which attributed to the high recombination of
charge carriers. Therefore, decrease of the photocatalytic activity
for the nanocomposite fabricated in higher refluxing time is
ascribed to recombination of the e
/h+ pairs with high rate, due
to breaking up the formed heterojunctions between constituents
104 M. Mousavi, A. Habibi-Yangjeh / Advanced Powder Technology 29 (2018) 94–105
of the nanocomposite, which results decreasing of the photocat-
alytic activity.
In this study, we studied dependence of photocatalytic activity
to the calcination temperature of the gCN/M/AgW/AgBr (30%)
nanocomposite ranging from 100 to 400 °C. It can be visualized
that the degradation rate constant significantly decreased with
increasing the calcination temperature (Fig. 10a). To disclose this
decrease, separation efficiency of the charge carriers was explored
by PL spectra. It is observable that after calcination of the
nanocomposite at 400 °C, recombination of the e
/h+ pairs was
greatly increased, leading to decrease of the activity. In fact, by cal-
cination of the photocatalysts, size of the decorated particles of
Fe3O4, Ag2WO4, and AgBr over the gCN is enlarged. Hence, in the
calcined photocatalyst, by aggregation of the deposited particles,
the heterojunctions between constituents of the nanocomposite
decreased. As a result, the photogenerated charge carriers are not
efficiently separated from each other, which leads to decrease of
the activity. Thus, the photocatalyst prepared by refluxing for 30
time without any calcination displayed the highest photocatalytic
activity.
In consideration of the practical applications, it is important to
show reusability of the nanocomposite during the photocatalytic
reactions. So, the recycling experiments were performed for the
degradation of RhB over the gCN/M/AgW/AgBr (30%) nanocompos-
ite under visible light. Fig. 11a displays that activity of the photo-
catalyst does not show a significant decrease after four cycles,
indicating that the nanocomposite has acceptable durability for
practical purposes. Additionally, to display stability of the
nanocomposite during the photocatalytic reactions, XRD patterns
of the photocatalyst before and after RhB degradation were shown
in Fig. 11b. No apparent change is observed before and after cycling
experiments, confirming that the nanocomposite possesses good
photostability without structural changes during the photocat-
alytic reaction.
Wastewaters containing organic dyes are known as difficult-to-
treat wastes. These wastes usually contain various dyes. To show
ability of the optimized photocatalyst to degrade different pollu-
tants, degradations of RhB, MB, MO, and fuchsine over the gCN,
gCN/M/AgW (30%), gCN/M/AgBr (30%), and gCN/M/AgW/AgBr
(30%) samples were evaluated, as shown in Fig. 12a–d. From the
degradation rate constants, we can see that photocatalytic activity
of the gCN/M/AgW/AgBr (30%) nanocomposite is about 21.0, 41.1,
94.7, and 10 times greater than that of gCN for photodegradations
of RhB, MB, MO, and fuchsine under the visible-light illumination,
respectively. As a result, the gCN/M/AgW/AgBr (30%) nanocompos-
ite, as a magnetically separable photocatalyst, has promising abil-
ity to degrade different water pollutants. Therefore, this
magnetically separable photocatalyst can be used in environmen-
tal remediation.
4. Conclusions
In summary, novel gCN/M/AgW/AgBr nanocomposites with
well-designed structure were prepared by a facile methodology.
Excellent visible-light activity of the gCN/M/AgW/AgBr nanocom-
posites for photodegradations of RhB, MB, MO, and fuchsine in
comparison with the gCN, gCN/M/AgW, and gCN/M/AgBr (30%)
samples was confirmed. It was showed that contents of Ag2WO4
and AgBr in the nanocomposites have major effect on the photocat-
alytic performance. At the optimal Ag2WO4 and AgBr contents, the
as-prepared sample exhibited enhanced activity for degradation of
MO by a factor of 94.7, 17.4, and 26.7 relative to the gCN, gCN/M/
AgW (30%), and gCN/M/AgBr (30%) samples, respectively. The
active species trapping experiments showed that superoxide anion
radicals are the main active species in decomposition of RhB.
Additionally, the nanocomposite displayed considerable stability
during successive runs. The synergistic effects in the nanocompos-
ite favor for considerable visible-light absorption and effective sep-
aration of the charge carriers, resulting in enhanced photocatalytic
performance.
Acknowledgement
The authors genuinely appreciate University of Mohaghegh
Ardabili–IRAN, for financial support of this project.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.apt.2017.10.016.
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