Sustainable Chemistry and Pharmacy 19 (2021) 100367

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Sustainable Chemistry and Pharmacy

journal homepage: http://www.elsevier.com/locate/scp

Activation of potassium peroxymonosulfate for rhodamine B photocatalytic

degradation over visible-light-driven conjugated polyvinyl chloride/Bi2O3
hybrid structure
Huu-Huan Pham a, b, Sheng-Jie You c, Ya-Fen Wang c, Minh Thi Cao d, Van-Viet Pham a, b, *
a
Faculty of Materials Science and Technology, University of Science, VNU-HCM, 227 Nguyen Van Cu Street, District 5, Ho Chi Minh City, 700000, Viet Nam
b
Vietnam National University – Ho Chi Minh City, Thu Duc District, Ho Chi Minh City, 700000, Viet Nam
c
Department of Environmental Engineering, Chung Yuan Christian University, Chung-Li 320, Taiwan
d
Ho Chi Minh City University of Technology (HUTECH), 475A Dien Bien Phu Street, Binh Thanh District, Ho Chi Minh City, 700000, Viet Nam

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

Keywords: In this study, a conjugated polyvinyl chloride is supported hydrothermally synthesized Bi2O3 semiconductor
Conjugated polymer (cPVC/Bi2O3) by a simple, and straightforward method at low temperature. Results show that 2% cPVC/Bi2O3/
Hybrid materials PMS/Vis system being the best photocatalytic ability of RhB degradation (200 mg L− 1) with a complete
Photocatalysis
degradation after 150 min under visible light irradiation. The photocatalytic ability of cPVC/Bi2O3/PMS system
Polyvinyl chloride
Visible light
for RhB degradation has also compared to previous publications. Moreover, the trapping test results are com­
bined with the measurement of electron spin resonance (ESR) spectroscopy indicated that • SO−4 , and • OH are
primary parameters of the photocatalytic RhB degradation.

1. Introduction activate PMS, including both inorganic and organic semiconductors

Advanced oxidation processes (AOPs) have been considered a pri­
ority, a high performance, and a green technology to remove contami­
nants in wastewater. (Elmolla and Chaudhuri, 2010; Méndez-Díaz et al.,
2010; Benitez et al., 2011; Babuponnusami and Muthukumar, 2012;
Jung et al., 2012; Karci et al., 2012). AOPs are defined as oxidation
processes involving the generation of hydroxyl radicals (• OH) (Truong
et al., 2019) and sulfate radicals (• SO−4 ) (Ha et al., 2020); therein, the
redox potential of the anion sulfate (• SO−4 ) is much higher than that of
•
OHradicals, leading to extend the long life span and strong oxidation
(Deng and Zhao, 2015). It is indicated that the use of ⋅ SO−4 is preferred
than that of • OHin wastewater treatment recently (Chen et al., 2007).
There are many routes to activate • SO−4 from peroxydisulfate or perox­
ymonosulfate (PMS), for instance, thermal, photochemical, radiolytic,
photocatalysis, or redox decomposition. (Zhao et al., 2010). Therein, the
activation of PMS over visible-light-driven photocatalysis is an efficient
approach compared to other methods in reducing the energy con­
sumption and the dosage of catalysts. (Chi et al., 2015; Hu et al., 2017;
Lin et al., 2017).
Recently, there are many photocatalysts that are used to efficiently
such as TiO2 (Golshan et al., 2018), ZnO, SnO2 (Bang et al., 2018), and
g-C3N4 (Wang et al., 2019). Besides the individual semiconductors, the
coupling of semiconductors or the combination of a semiconductor with
metal nanoparticles such as Co, Ni, Mn, Ag, etc. have also been excitedly
studied (Lin et al., 2016; Nekouei et al., 2018). However, the limitations
of inorganic materials synthesized processes are intricately synthesized
procedures, using many toxic precursors, and expensive chemicals that
lead to the problematic application in the industry scale (Leonard et al.,
2002; Irmawati et al., 2004). Among inorganic semiconductors, Bi2O3
shows a high visible-light photocatalytic activity due to its narrow
bandgap (about 2–3.9 eV at room temperature). Also, the cost-effective
and straightforward synthesized processes, nontoxic nature, and the
easily control of the morphology, and crystal phase are its remarkable
properties. However, the rapid recombination of photoinduced
electron-hole pairs stills a drawback of Bi2O3 as a photocatalyst. To
enhance the photocatalytic activity of Bi2O3, the combination of Bi2O3
with semiconductors such as TiO2, ZnO, BiOCl, conductive polymers,
etc. is often mentioned (Balachandran and Swaminathan, 2012;
Gómez-Cerezo et al., 2014; Priya et al., 2016).
As we have known, polyvinyl chloride (PVC) is a useful polymer

* Corresponding author. Faculty of Materials Science and Technology, University of Science, VNU-HCM, 227 Nguyen Van Cu Street, District 5, Ho Chi Minh City,
700000, Viet Nam.
E-mail address: pvviet@hcmus.edu.vn (V.-V. Pham).

https://doi.org/10.1016/j.scp.2020.100367
Received 16 September 2020; Received in revised form 16 December 2020; Accepted 20 December 2020
Available online 9 January 2021
2352-5541/© 2020 Elsevier B.V. All rights reserved.
H.-H. Pham et al.
which is widely used in many applications such as the plastic industry,
household appliances, construction materials, etc.(Bidoki and Witt­
linger, 2010)., PVC can be easily transferred to conjugated PVC (cPVC)
as a conductive polymer by a dehydrochlorination reaction, leading to
the formation of a new partial conjugated polymer chain (Michell, 1985;
Rogestedt and Hjertberg, 1993; Owen et al., 1994; Starnes and Ge,
2004). According to the best of our knowledge, this is the first-time
combination of Bi2O3 and cPVC was employed to activate PMS under
visible light for RhB degradation. Moreover, using cPVC is a potential
approach to utilize PVC waste and reduce the dispose of plastic waste
into the environment.
In this study, the cPVC/Bi2O3 composites are synthesized by a simple
method at low temperature. The characterizations of cPVC/Bi2O3
composites are investigated in detail by X-ray diffraction (XRD) pattern,
Fourier-transform infrared spectroscopy (FTIR), field emission scanning
electron microscopy (FESEM), UV–Vis diffuse reflectance spectroscopy
(UV–Vis DRS), Raman spectroscopy and electrochemical characteriza­
tions. The PMS activation over cPVC/Bi2O3 hybrid materials under
visible light irradiation is studied based on rhodamine B (RhB) degra­
dation, effect of the photocatalysts, the PMS concentration, the recycle
ability. Finally, trapping experiments and ESR studies are inspected to
determine the primary parameters affect degradation reactions. Also,
the ability to completely degrade RhB in cPVC/Bi2O3 system extremely
high concentration is shown.
2. Experimental
2.1. Materials
Commercial polyvinyl chloride (PVC), ethylene glycol
(EC2nH4n+2On+1 Merck, 99%), tetrahydrofuran (THF, 99.0%), Bismuth
nitrate pentahydrate (Bi(NO3)3⋅5H2O, 99%), hydrochloric acid (HCl,
37% concentration), sodium hydroxide (NaOH, Merck, 99%), potassium
iodide (KI, 99.99%), isopropyl alcohol (IPA; C3H8O, 99.99%), sodium
sulfate anhydrous (Na2SO4, Merck, 99%), potassium dichromate
(K2Cr2O7, 99.99%), tert-butanol (TBA; (CH3)3COH, 99.99%), Deionized
water (DI), and a rhodamine B (RhB) dye was used as a pollutant organic
dye indicator to evaluate the photocatalytic activity of cPVC/Bi2O3
materials.
2.2. Synthesis of materials
Bismuth oxide (Bi2O3) was synthesized based on the previous study
(Yan et al., 2014). Firstly, 2.91 g Bi(NO3)3⋅5H2O powder was dissolved
in 30 mL glycerol and 30 mL absolute ethanol solution. The mixture was
then treated with vigorous stirring and ultrasonic dispersion to form a
homogeneous and transparent solution. The solution as mentioned
above was transferred into a teflon lined stainless autoclave, and this
system was heated at 160 ◦ C for 3 h. Secondly, the autoclave was
naturally cooled to room temperature and filtered the precipitate with
deionized water and absolute ethanol several times, then dry at 80 ◦ C for
2 h. Finally, the residue was calcined at 350 ◦ C, with a heating rate of
2 ◦ C/min for 2 h to form Bi2O3 materials.
For the cPVC, according to the optimized parameters from our pre­
vious study (Bui et al., 2020). First, PVC was slowly added to a solution
containing 4 g of NaOH and 100 mL of ethylene glycol solution. Second,
the mixture was stirred for 60 min. Third, it was poured into a round
neck three-bottomed flask, then stirred magnetically, and was purged in
nitrogen gas at 190 ◦ C for 3 h. The solution was then thoroughly washed
with DI water and dried at 60 ◦ C for 24 h to obtain cPVC.
For the cPVC/Bi2O3 composites, the different amounts of cPVC and
1.0 g of Bi2O3 were mixed in 10 mL of THF solution to create different
ratios of cPVC and Bi2O3 (1:100, 2:100, 3:100, 5:100 and 7:100).
Finally, the cPVC/Bi2O3 composites were magnetically stirred for 30
min and ultrasonicated for 30 min. Then, the composites were dried at
60 ◦ C for 60 min.
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2.3. Characterization of materials
Properties of materials, including the morphology, crystal structure,
functional groups, and chemical bonds, are measured by FESEM images,
XRD patterns, FTIR spectra. The XRD pattern is measured as 2θ in the
range of 10o–70◦ to match the crystal structure and crystal size of ma­
terials, the scanning rate of 1.25◦ /min, and the step size of 0.02◦ , using
samples XRD pattern (Bruker D8, Advance 5005). Subsequently, for
FTIR analysis, KBr was served as the reference sample; its weight
selected was 1% of the sample weight. The vibrations of the molecules
are expressed in the range of 480–4000 cm− 1, with a step size of 1 cm− 1,
using the FTIR spectrum (JASCO-4700). To determine the band energy
structure of material, UV–Vis DRS and Mott-Schottky plot were selected
for implementation. Therein, the absorption of light was investigated
when the wavelengths ran from 200 to 800 nm, using the DRS spectrum
(JASCO V-550), and electrochemical measurements were performed by
an electrochemical workstation (Biologic SP - 240). To convert the po­
tential vs. Ag/AgCl (3 M KCl) (EAgCl (V)) to NHE (ENHE (V)) at 25 ◦ C
(Eqn. (1)):
0
ENHE = EAg/AgCl + 0.21V (1)
where ENHE is the potential of a normal hydrolysis electrode, and
E0Ag/AgCl is the initial potential of the Ag/AgCl electrode.
For Raman analysis, samples were placed in the analytical position.
Then, bond fluctuations are recorded in 1000–4000 cm− 1 region using
Raman scattering spectroscopy (HORIBA) with laser excitation source at
532 nm. Finally, ESR signals were investigated by Bruker EMX Plus X-
Band spectrophotometer, generated during the photocatalytic process
with DMPO-based spin-trapped reagents. The source of irradiation
xenon short-arc lamp (Labguide® 150 W Mercury arc lamp, λ > 400
nm). Typical test conditions: temperature 298 K, central field 3483 G,
sweep width 200 G, frequency 9755 GHz, modulation amplitude 1.00 G,
microwave power 20 mW, sample concentration 400 ppm, 1000 ppm
DMPO.
2.4. Evaluation of the photocatalytic activity of materials
Initially, the catalysts were taken with a dosage of 0.33 g L− 1 of 20
mg L− 1 RhB dye solution. After that, 0.5 mM PMS was added to this
solution and stirred magnetically in the dark for 1.5 h to achieve
adsorption/desorption. The mixture was illuminated under visible light
from simulated solar light (Osram Ultra-Vitalux 300 W) using UV cutting
glass. At intervals of 30 min, the suspension was withdrawn and
centrifuged rapidly to extract the solution. The absorption spectra of the
solutions were measured using a UV–Vis spectrophotometer (U2910,
HITACHI, Japan). The photocatalytic efficiency of cPVC/Bi2O3 com­
posites and their photocatalytic reaction rates were calculated as Eqn.
(2) and Eqn. (3):
C0 − Ct
η= × 100% (2)
C0
Ct
= e− kt
(3)
C0
where η is the photocatalytic degradation efficiency of RhB (%), C0 is the
initial concentration of RhB, Ct is the concentration of RhB at time t, and
k is the reaction rate calculated from the Langmuir-Hinshelwood (L – H)
model (min− 1).
The trapping test experiments were carried out to determine the
primary aspects of the RhB photocatalytic degradation with scavengers
including KI, K2Cr2O7, TBA were used as trapping agents h+ , e− ,
•
OHradical, respectively. Meanwhile, IPA is a scavenger for trapping
both • SO−4 , and • OHradicals. The concentration of the scavengers was 1
mM to the initial photocatalyst. The experimental conditions for these
H.-H. Pham et al.
experiments are similar to the photocatalysis test. The stability of cat­
alysts was investigated by the evaluation of the photocatalytic RhB
degradation over materials after 4 cycles and catalysts were analyzed by
the FTIR spectrum.
3. Results and discussion
Fig. 1 (a) exhibits a broadband of the wavenumber at around
3400–3500 cm− 1, associating to the stretching vibrations of hydrogen-
bonded surface water molecules and hydroxyl groups. The vibration
peaks located at 1637 and 879 cm− 1 wavenumber that were strength­
ened to confirm the formation of = C–H and C–H bonds, respectively.
The vibration peaks at 1386-1287 cm− 1 region, and 1459 cm− 1 repre­
sent the C–O prolonged vibration, and the C–H bending vibration,
respectively, indicating the presence of the organic solvents as ethanol
and glycerol in the product (Xiong et al., 2008; Wang et al., 2009). In
addition, the vibration peak at 844 cm− 1 is due to the symmetrical
elongation of the Bi–O–Bi bonding of the Bi2O3 (Irmawati et al., 2004;
He et al., 2011) and the regions at 700–400 cm− 1 wavenumber represent
oxygen-metal vibrations that could be assigned to the existence of Bi2O3
in the product (Wang et al., 2015). XRD patterns of materials (Fig. 1 (b))
provide the crystallinity, phase existence, and a confirmation of the
formation’s materials in the FTIR analysis. Results show that the typical
diffraction peak of cPVC at 2θ = 25◦ is appeared and existed when cPVC
and Bi2O3 are combined in the composite materials. Besides, Fig. 1 (b)
shows that there are typical diffraction peaks at 2θ = 25.86, 27.07,
27.54, 28.17, 33.19, 35.13, 37.17, 42.44, 46.22, 48.88, 53.25, 54.94,
57.16, and 58.11◦ , corresponding to the diffraction peaks of the (002),
(111), (120), (012), (121), (022), (112), (122), (311), (113), (321),
(241), (222), and (024) planes of the α monoclinic phase of Bi2O3 ma­
terials, respectively (JCPDS No. 76–1730). In addition, the typical
diffraction peaks at 2θ = 27.64◦ and 30.4◦ , corresponding to the
diffraction of (310) and (222) planes of the β-Bi2O3, respectively (JCPDS
No.74–1375). Also, the XRD patterns of cPVC/Bi2O3 composites existed
all typical peaks that characterized to Bi2O3 phase and cPVC materials.
Fig. 1. FTIR spectra (a) and XRD patterns (b) of the cPVC/Bi2O3 composites.
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Sustainable Chemistry and Pharmacy 19 (2021) 100367
The results demonstrated that the as-prepared materials are not the
secondary phase. It can be concluded that the successful synthesis of
α-phase is the most stable phase of both Bi2O3 and the cPVC/Bi2O3
composites.
Raman spectroscopy was added to provide information on the exis­
tence of cPVC and Bi2O3 (Fig. 2). The Raman spectroscopy analysis of
PVC shows that there are 4 positions of Raman signals including C–Cl
bonds (636 and 694 cm− 1) (Solodovnichenko et al., 2016a) and C–H
(1430 and 2918 cm− 1) (Solodovnichenko et al., 2016b). After the
dichlorination process, these four peaks have a significant lower in­
tensity, which clearly shows a decrease in the existence of C–Cl and C–H
bonds in the sample. In addition, major peaks appeared at 1123 and
1513 cm− 1, corresponding to the elongation of variation (C–C) and
(C–
– C) of polyene, respectively (Ellahi et al., 1995; Zhang et al., 2016;
Bui et al., 2020). These results concluded that the cPVC has been suc­
cessfully synthesized from chlorination of PVC. For the Bi2O3 and 2%
cPVC/Bi2O3, the Raman peaks observed at 319 and 452 cm− 1 are due to
the presence of Bi2O3 (In et al., 2011; Wang et al., 2012, 2014). For the
2% cPVC/Bi2O3 sample, characteristic peaks of C–C and C– – C at 1123
and 1513 cm− 1 in cPVC and distinct peaks of Bi2O3 also exist in this
composite.
The surface morphology of the samples was observed by FESEM
images that are exhibited in Fig. 3. First, the morphology of cPVC is
aggregated particles with the particle size from 500 nm to 1 μm (Fig. 3(a
and b)) while Bi2O3 has the nanosheets structure that is formed over­
lapping and alternating sheets (Fig. 3(c and d)). For combining the two
materials, cPVC and Bi2O3 together, the existence of cPVC particles in
the composite sample is presented clearly in Fig. 3 (e). However, the
particle boundary of cPVC particles is no longer clear. The presence of
Bi2O3 is confirmed in Fig. 3 (f) that the nanosheet shape is observed
clearly at high magnify.
Moreover, elements mapping was performed to express the
elemental surface distribution in the cPVC/Bi2O3 composite. Fig. 4
shows the presence of the elements, including Bi, O, and C in the 2%
cPVC/Bi2O3 composite showing the coexistence of cPVC and Bi2O3 in
H.-H. Pham et al.
Fig. 2. Raman spectra of PVC, cPVC, Bi2O3, and 2% cPVC/ Bi2O3 composite.
the product after the synthesis process.
The optical property of materials are measured through UV–vis DRS
to verify their optical characterization and the optical bandgap. Fig. 5
(a) shows a typical UV–vis DRS of cPVC, Bi2O3, and 2% cPVC/Bi2O3
composite. It can be seen that the absorption edge of cPVC at 650 nm
range of wavelength while the absorption edge of Bi2O3 and 2% cPVC/
Bi2O3 composite is located at wavelength 470 nm and 475 nm, respec­
tively. The combination of cPVC and Bi2O3 did not significantly change
the shape and position of the absorption spectrum of the composite
sample compared to pure Bi2O3. Also, the Tauc-plots (Eqn. (4)) (Tauc
et al., 1966) is calculated to determine the optical band gap of cPVC,
Bi2O3, and 2% cPVC/Bi2O3 composite with the values 2.0 eV, 2.4 eV,
and 2.3 eV, respectively (Fig. 5 (b)). This result indicated the excellent
visible light response of 2% cPVC/Bi2O3 composite.
( )2
αhν = A hν − Eg (4)
where α, h, ν, A, and Eg are the absorption coefficient, Plank’s constant,
frequency of the light, a continuous, and direct bandgap energy,
respectively.
Determining the band structure of cPVC/Bi2O3 composite, Mott-
Schottky plot is measured to determine the conduction band (CB) of
Bi2O3, the lowest unoccupied molecular orbital (LUMO) of cPVC, and
the CB of 2% cPVC/Bi2O3 composite (Fig. 5 (c)). The CB potential of
Bi2O3 and the LUMO level of cPVC are 0.2 eV and 0 eV, respectively. The
CB potential position of 2% cPVC/Bi2O3 composite is at – 0.18 eV, and
its bandgap measured by DRS spectrum, which can illustrate in Fig. 5
(d). The valence band (VB) and the highest occupied molecule orbital
(HOMO) levels of Bi2O3 and cPVC are 2.63 and 2.02 eV, respectively.
The VB potential is near H2O/• OH(2.7 V vs. NHE (Li et al., 2016) that
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Sustainable Chemistry and Pharmacy 19 (2021) 100367
may oxidize H2O and OH− to • OHradicals. However, the CB potential
level is more favorable than the O2/• O−2 (– 0.33 V vs. NHE) potential that
to partially produce O2 (Li et al., 2016). These results will be discussed
more in the photocatalytic activity and photocatalytic mechanism of
cPVC/Bi2O3 composite.
Firstly, we conduct the optimization of the content of cPVC for the
RhB photocatalytic degradation ability under visible light irradiation.
Fig. 6 (a) shows the RhB degradation ability of cPVC/Bi2O3 composites
with different contents of cPVC. In the without catalyst case, RhB is
almost not degraded by visible light irradiation (blank sample) and this
has also occurred similarly for pure cPVC. The presence of cPVC in the
cPVC/Bi2O3 composites has improved significantly of the RhB photo­
catalytic degradation. Detailly, the RhB photocatalytic degradation ef­
ficiency achieved 56% and 59%, corresponding to 1% cPVC/Bi2O3
composite and the 2% cPVC/Bi2O3 composite. However, when the
content of cPVC increases from 3% wt to 7% wt, the RhB photocatalytic
degradation efficiency of these composites decreased significantly, even
they are lower than that of the pure Bi2O3. This can be explained that the
RhB decomposition occurred mainly on both the surface of Bi2O3 and
cPVC. Besides, in our previous mention, cPVC contributes as a mem­
brane helping to accelerate the charge transfer (Bui et al., 2020).
Increasing the content of cPVC will lead to covering the surface of the
Bi2O3 and reduce the efficiency of RhB decomposition. The L - H model
is used to fit the reaction kinetics of materials and provided for a more
quantitative comparison in Fig. 6 (b). Under visible light irradiation, 2%
cPVC/Bi2O3 composite is the highest reaction rate (k = 1.21 × 10− 4
min− 1), equaling 1.3 times, and 12.4 times over pure Bi2O3, and pure
PVC, respectively. The order of the reaction rates was consistent with the
results of the photocatalytic performance of cPVC/Bi2O3 composites that
were mentioned above. Also, the 2% cPVC/Bi2O3 composite has also
H.-H. Pham et al. Sustainable Chemistry and Pharmacy 19 (2021) 100367

Fig. 3. FESEM images of cPVC (a–b), Bi2O3 (c–d), and 2% cPVC/Bi2O3 composite (e–f).

shown the highest quantum efficiency with a 12 × 10− 4% valuation in concentration, the formation of the reactive radicals such as ⋅ SO−4
the weight of catalyst samples (Dcat = 0.33 g L− 1). The enhancement of and. OHis too much that will occur the reactions with HSO−5 to produce
the RhB photocatalytic degradation of 2% cPVC/Bi2O3 composites is the less oxidative ⋅ SO−5 radicals (Zhang et al., 2013) as Eqn. (5).
explained by the photocurrent response results in Fig. 6 (c). Results show / /
that the photocurrent response of cPVC, Bi2O3, and cPVC/Bi2O3 com­
⋅
SO−4 . OH + HSO−5 →⋅ SO−5 + SO2−4 + H+ /OH − (5)
posites indicated the stability and fast of the composite sample with 5 Or ⋅ SO−4 self-combination forming S2 O2−
8 (Eqn. (6)).
cycles and each extended cycle for 30 s of the on-off status. The
photocurrent density of 2% cPVC/Bi2O3 composite is much higher than ⋅
SO−4 ​ + ⋅ SO−4 →S2 O2−8 (6)
that of cPVC, Bi2O3, and other composites materials, which is consistent
Fig. 7 (b) shows that the highest photocatalytic reaction rate was
with the photocatalytic results of RhB decomposition in Fig. 6 (a) and
achieved with 3 mM PMS under visible light irradiation (k = 6.68 ×
(b). Therefore, we can conclude that the 2% cPVC/Bi2O3 material
10− 4 min− 1). In addition, the shape of the UV–Vis absorption spectra of
composite performance the best optical response among the rest of the
RhB is maintained during 150 min irradiation with the catalyst presence
composites.
(Fig. 7 (c)). This demonstrated the RhB complete degradation by 2%
The PMS concentration is changed from 0.1 to 5 mM to investigate its
cPVC/Bi2O3/PMS/Vis instead of forming intermediate complexes.
effect on the RhB degradation (200 mg L− 1) over 2% cPVC/Bi2O3
To determine the stability and reusability of the 2% cPVC/Bi2O3/
composite under visible light presented in Fig. 7. It can see clearly that
PMS/Vis system, the photocatalytic activity of RhB decomposition was
the RhB degradation ability of 2% cPVC/Bi2O3 composite increases
tested 4 times and shown in Fig. 8 (a). The RhB degradation ability of 2%
significantly when PMS concentration increases from 0.1 mM to 3 mM
cPVC/Bi2O3/PMS/Vis system after 4 cycles achieve 77% for 180 min
(Fig. 7 (a)). After that, when PMS concentration increase from 4 to 5
under visible light irradiation. This result indicated a good photo­
mM, the RhB degradation decreases gradually. The decrease of the RhB
catalytic efficiency of 2% cPVC/Bi2O3/PMS/Vis system. Moreover, the
degradation ability of 2% cPVC/Bi2O3 composite at high PMS concen­
FTIR spectra in Fig. 8 (b), the FTIR spectra show 2% cPVC/Bi2O3
trations (4 and 5 mM) can be explained as due to at high PMS

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H.-H. Pham et al. Sustainable Chemistry and Pharmacy 19 (2021) 100367

Fig. 4. FESEM–EDS elemental mapping images of 2% cPVC/Bi2O3 (a–b), and elemental mapping with Bi (c), O (d), and C (e).

Fig. 5. UV–Vis DRS (a) of cPVC, Bi2O3, and 2% cPVC/Bi2O3 composite and their Tauc plots (b), Mott–Schottky plots (c), and the energy band alignment of ma­
terials (d).

composite before and after 4 cycles of the visible-light irradiation of the cm− 1, representing to Bi–O–Bi of Bi2O3 were not significantly different.
photocatalysis. The typical vibration peaks of Bi2O3 and cPVC did not This demonstrated that cPVC/Bi2O3 composite is a stable photocatalyst
change significantly. Detailly, the wavenumber at 1637 cm− 1, corre­ consistent with the color change in Fig. 8 (b). Therein, the typical yellow
sponding to the = C–H bond of cPVC, and the vibration peak at 844 color of the 2% cPVC/Bi2O3 composite was not almost changed

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Fig. 6. Photocatalytic activity of materials under visible light without the assistance of PMS (a), the fitted data for the reaction kinetic (b) with photocatalytic
reaction rate and quantum efficiency of cPVC, Bi2O3 and cPVC/Bi2O3 composites (c) photocurrent responses of cPVC, Bi2O3 and cPVC/Bi2O3 composites in Na2SO4
(0.5 M) aqueous solution. [RhB] = 20 mg L− 1; Dcat = 0.33 g L− 1.

compared to its original color. and holes (Eqn. (7)). The photogenerated electrons transfer from VB to
Fig. 9 (a) shows the effects of four different radical scavengers in the CB of Bi2O3 and they will also occur a transition from the HOMO level to
2% cPVC/Bi2O3/PMS/Vis system. With the addition of IPA, the RhB LUMO level of cPVC. Because the difference of the potential levels of CB
decomposition was thoroughly decreased, demonstrating that the• SO−4 of Bi2O3 and LUMO energy level position of cPVC, some electrons will
and • OHradicals are the primary factors for RhB degradation over cPVC/ migrate from LUMO of cPVC to the CB of Bi2O3. Herein, these electrons
Bi2O3/PMS/Vis system because IPA is a scavenger for trapping both will active PMS to generate • SO−4 or react dissolved oxygen molecules to
•
SO−4 and • OHradicals. Meanwhile, Fig. 9 (a) shows that with the form the • O−2 radicals (see Eqn. (8) and Eqn. (9)). Similarly, the holes
addition of KI and K2Cr2O7, trapping e− and h+ in the reaction process, transfer from the VB of Bi2O3 to HOMO level of cPVC and directly react
the RhB decomposition are less than the addition of IPA. This shows the with the hydroxyl anion to produce • OH radicals (Eqn. (11)), which will
role of h+ and e- in forming • SO−4 radicals (via Eqns. (8), (11) and (13)). oxidize pollutants due to its strong oxidizing capacity. Clearly, the
To compare the role of the • SO−4 and • OH, the TBA scavenger is added to photogenerated holes contribute in two processes, including oxidizing
investigate the RhB degradation. It is found that TBA scavenger RhB directly and forming • SO−5 radicals via their reaction with PMS
(• OHtrapping) is insignificantly decreased the RhB degradation effi­ (Eqn. (12)). Besides, • SO−4 anion radicals can form by other reaction
ciency, indicating the primary role of • SO−4 in decomposing RhB over pathways (Eqn. (14–16)) (Das, 2001) (Choe et al., 2020). The formation
cPVC/Bi2O3/PMS/Vis system. To clarify the presence of the active of • O−2 , • OH, and • SO−4 radicals is consistent with presence of their
radicals in the cPVC/Bi2O3/PMS system, the ESR analysis is an efficient signals in the ESR result (Fig. 9 (b)). As a result, • O−2 -, • OH, and
method to evaluate that. We conduct the ESR measurement to identify •
SO−4 contributed to excellent catalytic degradation activity in
the radicals such as superoxide radicals in methanol, hydroxyl and sul­ cPVC/Bi2O3/PMS with the aid of visible light (Eqn. (17)).
fate anion radicals in water (Fig. 9 (b)). Results show that the signals of
•
OH, SO−4 •, and • O−2 presences are barely clear at dark condition for the cPVC/ Bi2O3 + hν → cPVC/ Bi2O3 (e– + h+) (7)
both DMPO-H2O and DMPO-methanol. However, the photogenerated e + −
HSO−5 •
→ SO−4 + OH −
(8)
electrons will be formed and migrated to the CB of Bi2O3 and LUMO
level of cPVC while the photogenerated holes in the VB of Bi2O3 will e− + O2 →• O−2 (9)
transfer to HOMO level of cPVC. In the next step, the electrons will
active PMS to form sulfate anion radicals (Eqn. (8)). In addition, the •
O−2 + H2 O→• O H + H + (10)
photogenerated holes can also directly oxidize H2O, OH− to produce
•
OH radicals (Eqn. (11)). The • OHradicals also will contribute for the h+ + OH − →• O H + H + (11)
formation of • SO−4 (Eqn. (13)).
Based on the above results, the photocatalytic reaction mechanism h+ + HSO−5 →• SO−5 + H + (12)
for cPVC/Bi2O3/PMS/Vis system is proposed and presented in Fig. 10.
The excitation of visible light will form the photogenerated electrons HSO−5 + • O H→• SO−4 + OH − (13)

7
H.-H. Pham et al. Sustainable Chemistry and Pharmacy 19 (2021) 100367

Fig. 7. RhB degradation ability of 2% cPVC/Bi2O3/PMS/Vis system versus different PMS concentrations (a), the fitted data for the reaction kinetic rate (b), and
UV–Vis spectra of RhB solution with the presence of 2% cPVC/Bi2O3 composite under visible light. [RhB] = 200 mg L− 1, Dcat = 0.33 g L− 1.

Fig. 8. Photocatalytic ability of 2% cPVC/Bi2O3/PMS/Vis throughout cycle tests (a) and the FTIR spectra of a 2% cPVC/Bi2O3 composite before and after 4 cycles.

cPVC and Bi2O3 enhanced the visible–light photoactivity and created the
•
SO−4 + OH − →SO2−4 + • O H (14)
preferred redox potentials for the RhB photocatalytic degradation. The
•
SO−5 + • SO−5 →2• SO−4 + O2 (15) cPVC/Bi2O3/PMS/Vis system with 3 mM PMS degraded completely 200
mg L− 1 RhB solution after 150 min. Also, cPVC/Bi2O3/PMS/Vis system
expressed the stability and reusability after 4 cycles of the photocatalytic
SO2−4 + • O H + H + →• SO−4 + H2 O (16)
reaction.
/• /•
•
OH O−2 SO−4 + RhB→Degradation Products (17)
Author contributions

4. Conclusion
Pham Huu Huan: Methodology, Visualization, Writing-Original
Draft.
In this study, we have successfully synthesized cPVC/Bi2O3 com­
Cao Minh Thi: Validation, Data curation, Investigation.
posite by a friendly and straightforward method. The combination of
Thi Minh Cao: Resources, Formal analysis, Supervision.

8
H.-H. Pham et al.
Fig. 9. The trapping test of 2% cPVC/Bi2O3/PMS/Vis (a), DMOP-ESR spectra in 2% cPVC/Bi2O3/PMS/Vis system of DMPO-• SO−4 and DMPO-• OH, and DMPO-
O2 (b).
• −
Fig. 10. The proposed mechanism of the photocatalytic reaction for cPVC/Bi2O3/PMS/Vis system.
Sheng-Jie You: Resources, Formal analysis.
Ya-Fen Wang: Resources, Formal analysis.
Pham Van Viet: Chemical Conceptualization, Supervision, Funding
acquisition, Project administration.
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.
Acknowledgements
The authors would like to acknowledge the support from the Viet­
nam National University Ho Chi Minh City and the CM Thi Laboratory.
This research is funded by Vietnam National University Ho Chi Minh
City (VNU-HCM) under grant number 562-2020-18-05.
9
Sustainable Chemistry and Pharmacy 19 (2021) 100367
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