Science of the Total Environment 669 (2019) 194–204

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Science of the Total Environment

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

AgI loading BiOI composites with enhanced photodegradation efficiency

for bisphenol A under simulated solar light
Jiaxin Lv a,b, Xuemin Liu a,b, Peicong Li a,b, Wei Jin c,⁎, Jiang Xu d, Yaping Zhao a,b,⁎
a
School of Ecological and Environmental Sciences, East China Normal University, Shanghai 200241, China
b
Institute of Eco-Chongming, Shanghai 200062, China
c
School of Environmental Science and Engineering, Tongji University, Shanghai 200071, China
d
Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Novel hierarchical AgI-BiOI microsphere

was synthesized via solvothermal
method.
• 1.25% AgI loading BiOI (AgI-BiOI(1–8))
greatly enhanced photodegradation of
BPA.
• Photogenerated h+ and O2•− radicals are
mainly responsible for BPA degradation.
• The eco-toxicity of AgI-BiOI(1–8) and
intermediates of BPA were evaluated.
• The photocatalytic mechanism of AgI
loading BiOI heterojuncture was
proposed.

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

Article history: Bismuth oxyiodide (BiOI) is a narrow band gap semiconductor which can be driven by visible irradiation. In order
Received 19 December 2018 to efficiently separate photo-generated carriers and utilization of visible light, a facile solvothermal approach was
Received in revised form 4 March 2019 used to synthesize a novel AgI loading BiOI 3D hierarchical composite (AgI-BiOI). The AgI-BiOI with Ag and Bi
Accepted 6 March 2019
molar ratio of 1:8 (AgI-BiOI (1–8)) showed great enhancement for photocatalytic degradation of bisphenol A
Available online 07 March 2019
(BPA) with pseudo-first degradation rate constant about 3.7 or 14.5 times than that of pristine BiOI or AgI
Editor: Shuzhen Zhang under simulated solar light. This synergistic enhancement for BPA degradation on AgI-BiOI(1–8) is mainly as-
cribed to enhancing the light absorption intensity and accelerating photo-generated carriers separation due to
Keywords: the formation of AgI-BiOI heterojunction. Free radical quenching experiments proved that positive holes (h+)
Bismuth oxyiodide and superoxide (O2•−) radicals were dominantly responsible for the degradation of BPA rather than singlet oxy-
Silver iodide gen (1O2) or hydroxyl radicals (•OH). The AgI-BiOI(1–8) hardly showed any ecotoxicity to C. elegans through le-
Photocatalytic degradation thal experiments. The luminance bacteria acute toxicity of degradation intermediates of BPA increased before
Bisphenol A 30 min then reduced significantly with reaction. The good durability and environmental-friendly characteristics
Heterojuncture
make AgI-BiOI(1–8) catalyst to be a good solar light-driven candidate.
© 2019 Published by Elsevier B.V.

1. Introduction

⁎ Corresponding authors. Nowadays the natural water resources are deteriorated by various
E-mail addresses: tjjinwei@tongji.edu.cn (W. Jin), ypzhao@des.ecnu.edu.cn (Y. Zhao). intensified anthropological activities. A large amount of organic

https://doi.org/10.1016/j.scitotenv.2019.03.077
0048-9697/© 2019 Published by Elsevier B.V.
 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204
pollutants is world widely disposed into the environment due to inef-
fective treatment. More than a hundred different organic aquatic pollut-
ants were detected in the U.S. and several European countries with the
concentrations higher than the detection limit (aus der Beek et al.,
2015) There are different types of organic pollutant substances for
chemical raw material, cosmetics, and pesticides which are considered
to be the source of environmental endocrine disrupters (Hlekelele
et al., 2018). BPA, a substance for the production of polycarbonate plas-
tic bottles and a common chemical additive, has been extensively re-
ported to be an endocrine disrupter (Chen et al., 2017; Pan et al.,
2015). Typical treatments methods for wastewater containing BPA
are not qualified due to the high operating costs and generating sec-
ondary pollutions (Wang et al., 2014). However, new alternative
methods including electrochemical oxidation process, Fenton oxida-
tion, and semiconductor photocatalysis have been successfully de-
veloped (Cho and Hoffmann, 2014; Liu et al., 2017c; Mantzavinos
and Psillakis, 2004). The photocatalytic technique has emerged as
one of the most promising way for organic contaminants removal
due to the solar light driven property, easy operation, and eco-
friendly features.
Many kinds of photocatalysts, such as bismuth oxyhalides, (Tian
et al., 2012) TiO2, (Repousi et al., 2017) Fe2O3, (Xu et al., 2016) and
ZnO, (Qurashi et al., 2013) have already been utilized in photocatalytic
degradation of BPA. Bismuth oxyhalides due to their layered structure
have been extensively studied (Ganose et al., 2016; Zhang et al., 2008;
Zhang et al., 2006). Some factors including (1.7–1.8 eV), poor quantum
yield, low visible light absorption efficiency, low photo-induced charges
separation efficiency and high photo-induced charges recombination
contribute to a low photocatalytic performance (Bai et al., 2016; He
et al., 2015; Wen et al., 2017). Accordingly, BiOI shows the worst photo-
catalytic capability under UV–visible irradiation (Lv et al., 2018; Ye et al.,
2014). In order to enhance the solar light driven catalytic activity of BiOI,
many modification methods have been employed, such as co-catalyst,
(Ye et al., 2013; Yu et al., 2010) loading, (Li et al., 2013) coupling,
(Zhang and Yang, 2015) sensitization, graphene loading, (Liu et al.,
2012) making defects (Chen et al., 2018; Huang et al., 2016a). Among
these methods, loading other materials into BiOI matrix to construct
the heterojunction could potentially ameliorate the light absorption
characteristics and charge separation efficiency (Liu et al., 2015; Wang
et al., 2018). There are several types of materials often used for loading,
such as semiconductor materials BiOBr, (Zhang and Yang, 2015) ZnO,
(Jiang et al., 2011) CeO2, (Wen et al., 2017) carbon-based materials
graphene, (He et al., 2015) g-C3N4,(Li et al., 2015) carbon quantum
dots, (Di et al., 2016) regular metal Bi (Chang et al., 2013; Liu et al.,
2017a; Wang et al., 2019), and some noble metal Au, (Bai et al., 2016)
Ag (Chen et al., 2013). For example, Jiang et al. doped ZnO onto the sur-
face of BiOI to build ZnO/BiOI heterojuncture, which exhibited higher
catalytic activity in methyl orange degradation than pure BiOI (Jiang
et al., 2011). Chang et al. synthesized Bi/BiOI composite with much
higher photocatalytic degradation and mineralization ability on BPA
than pristine BiOI (Chang et al., 2013).
It has been recently reported that silver halides can efficiently absorb
light with wavelength shorter than 530 nm (Huang et al., 2017; Wan
and Zhang, 2015). AgX has an excellent photocatalytic activity due to
the surface plasmon resonance (SPR) effect of noble metal nanoparti-
cles, moreover, by coupling AgX with other semiconductor the separa-
tion of photo-generated carriers of pristine single-component
semiconductor will improve. In Cheng's study, Ag/AgBr/BiOBr was syn-
thesized via an ion exchange process and showed superior catalytic ac-
tivity under visible irradiation, which might be associated with effective
transfer of photogenerated carriers (Cheng et al., 2011). Cui et al.
showed an enhancement of catalytic activity of pure AgI and BiOIO3
through synthesis of AgI/BiOIO3 nanohybrid resulting in minimizing
the recombination probability between photogenerated carriers (Cui
et al., 2016). Therefore, loading AgX into BiOI is an effective approach
for improving the light responsive catalytic activity (Cao et al., 2013;
195
Chen et al., 2013; Chen et al., 2015; Cheng et al., 2010; Cheng et al.,
2013; Li et al., 2013; Lin et al., 2014; Lv et al., 2013). The present study
aims to investigate the photocatalytic activity towards different chemi-
cal structural organic pollutants under different spectral radiation
thereby elucidate the enhanced synergistic catalytic mechanism by
loading AgI on BiOI.
Here, we prepared AgI-BiOI composites by solvothermal method.
The physical, chemical and optical characterizations of AgI-BiOI were
thoroughly characterized. In addition, the photocatalytic performances
of AgI-BiOI composites were thoroughly tested by the degradation of
BPA under simulated solar light and degradation mechanism of BPA in
as-constructed solar light responsive AgI-BiOI system was proposed. Fi-
nally, the toxicity of catalyst and degradation intermediates of BPA and
the durability of catalyst were evaluated.
2. Experimental
2.1. Materials
Bismuth nitrate pentahydrate (Bi(NO3)3•5H2O), silver nitrate
(AgNO3), polyvinylpyrrolidone ((C6H9NO)n, K30), bisphenol A
(C15H16O2), ethylene glycol (EG), orange ΙΙ (C16H11N2NaO4S), phenol
(C6H5OH) were bought from Sinopharm Chemical Reagent Company
(Shanghai, China). Sodium azide (NaN3), tetranitromethane (C(NO2)4),
coumarin (C9H6O2), 7-hydroxycoumarin (C9H6O3) are purchased from
Sigma-Aldrich Company (Shanghai, China).
2.2. Synthesis and characterization of AgI-BiOI
AgI-BiOI samples with different Ag-Bi molar ratio were prepared by
one step solvothermal method, i.e. 1.940 g sample of Bi(NO3)3•5H2O
and 0.8 g polyvinylpyrrolidone (PVP) was dissolved into a 40 mL EG
with stoichiometric amounts of KI, with the I to Bi elemental molar
ratio of 2:1. Then different amount of AgNO3 were added into the mix-
ture to keep the Ag-Bi molar ratio changed from 1:16 to 4:1. The solu-
tion was heated in 55 mL Teflon-lined stainless autoclave at 180 °C for
24 h. Then precipitates were purified with deionized water and ethanol
thoroughly, then centrifuged and dried at 60 °C. Pristine AgI or BiOI was
prepared by aforementioned process without Bi(NO3)3 or AgNO3,
respectively.
The physiochemical properties such as crystalline, morphology, par-
ticle size, surface elemental composition and photoluminescence
excitation-emission spectra of AgI, BiOI and AgI-BiOI samples were
characterized according to our previously report (Lv et al., 2018). Be-
sides, the photocurrent or electrochemical impedance spectroscopy
(EIS) was monitored with an electrochemical analyzer (CHI-660B,
China).
2.3. Photocatalytic experiments
Typically, 50 mg AgI-BiOI was added into 200 mL of 10 mg/L of BPA
in borosilicate reactor and stirred for 60 min in dark to ensure the
equilibrium of adsorption–desorption between the catalyst and
reactants. To simulate the solar light, a 350 W Xe lamp was hung on
20 cm above the solution in reactor with irradiation intensity of
120 mW/cm2 measured by the radio meter (Radiometer FZ-A, China).
After different irradiation intervals, 5 mL of solution was filtered by
0.45 μm filter to remove catalyst. High performance liquid chromatogra-
phy (HPLC, Shimadzu, LC-20AD, Japan) equipped with a C18 reversed
phase column (Shim-pack XR-ODS, 2.2 μm, 3.0 mm I.D. × 75 mm) and
a UV detector (Shimadzu, SPD-20AV, Japan) was employed to detect
the concentration of BPA at 278 nm. All experiments were carried out
in triplicate.
The effect of light sources on photocatalytic degradation of BPA by
AgI, AgI-BiOI, or BiOI was investigated, respectively. The light sources
were a 100 W high-pressure mercury lamp served as ultraviolet (UV)
196 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204
irradiation, aforementioned simulated solar light (350 W Xe lamp) was
used as UV–visible irradiation, and a UV cut-off filter (λ N 420 nm) was
equipped to this simulated solar light (350 W Xe lamp) used as visible
irradiation, respectively.
2.4. Radical quenching experiments and quantitative detection
To better know the ROS involved in the photodegradation of BPA on
AgI-BiOI, free radical quenching experiments were employed to explore
the roles of positive holes (h+), singlet oxygen (1O2) and superoxide
radicals (O2•−) and hydroxyl radicals (HO•) according to aforementioned
photocatalytic degradation experiments (Cao et al., 2012; Park et al.,
2014; Yin et al., 2009) 100 mg ethylene diamine tetra acetic acid
disodium salt (EDTA-2Na), 20 mg sodium azide (NaN3), 50 mg ascorbic
acid (VC), and 10 mg methanol (MeOH) were used in photocatalytic
system as corresponding scavengers for h+, 1O2, O2•−, and HO•, respec-
tively (Huang et al., 2015a). Quantitatively detection of O2•− and HO•
radicals generated in this photocatalytic system were determined by
100 mg/L tetranitromethane (TNM) and 1.0 mM coumarin, respectively
(Kim et al., 2015). The absorbance of TNM oxidation from nitroform was
measured at 350 nm using UV–visible spectrophotometer (UV-1102,
China). The main hydroxyl product of coumarin was measured by spec-
trofluorometer (Hitachi F-4500, Japan). The emission wavelength was
at 445 nm and the excitation wavelength was 332 nm (Ishibashi et al.,
2000).
2.5. Toxicity measurements
Toxicity of both AgI-BiOI and the intermediates produced during the
BPA photodegradation were investigated. AgI-BiOI suspension was pre-
pared in K-medium (32 mM KCl, 51 mM NaCl) and pure K-medium so-
lution was kept as control. Before exposure, the AgI-BiOI suspension
was sonicated at a 100 W/m2 ultrasonic bath for 1 h. The lethal experi-
ments were performed by exposing approximately 20 nematodes of
Caenorhabditis elegans (C. elegans) to AgI-BiOI solutions of 5, 10, 25,
50, and 100 mg/L in 24-well plates with 50 μl E. coli OP50. The suspen-
sions were shaken slightly for 30 min every 12 h in a table concentrator
at 20 °C. The numbers of dead nematodes were recorded within differ-
ent days (Li et al., 2017). Toxicity of degradation intermediates of BPA in
AgI-BiOI photocatalytic process at different irradiation time was evalu-
ated by using luminescent bacteria described in our previous work
(Liu et al., 2017b; Tian et al., 2012).
10 20 30 40 50 60 70
2Theta (degree)
PDF #09-0374
AgI-BiOI(4-1)
AgI-BiOI(2-1)
Intensity (a.u.)
AgI-BiOI(1-1)
AgI-BiOI(1-2)
AgI-BiOI(1-4)
AgI-BiOI(1-8)
AgI-BiOI(1-12)
AgI-BiOI(1-16)
PDF #73-2062
Fig. 1. The XRD of a series of AgI-BiOI with different Ag-Bi molar ratio (a) and AgI, AgI-BiOI(1–8), and BiOI samples (b).
3. Results and discussion
3.1. Properties of AgI-BiOI
The crystal structure and phase composition of series AgI-BiOI sam-
ples were determined through XRD (Fig. 1). The XRD patterns of AgI-
BiOI with Ag-Bi molar ratio from 1:16 to 4:1 showed more typical char-
acteristic peaks of pristine AgI. The XRD pattern of AgI showed five main
peaks at 2θ of 22.31°, 23.71°, 25.35°, 39.20° and 45.57° assigned to the
(100), (002), (101), (110) and (200) planes of the hexagonal structures,
respectively. While, XRD pattern of BiOI showed five main peaks at
9.68°, 29.74°, 41.90°, 45.49° and 55.30° indexed to (001), (012), (110),
(020) and (122) crystalline planes of the tetragonal structures, respec-
tively. They can be correspondingly ascribed to the hexagonal structures
of AgI (JCPDS File No. 09–0374) or tetragonal structures of BiOI (JCPDS
File No. 73–2062). In the case of AgI-BiOI with the molar ratio of 1:8 do-
nated as AgI-BiOI(1–8), the main peaks at 2θ of 9.68°, 29.74°, 41.90°,
45.49° and 55.30° are ascribed to the pure tetragonal structures BiOI.
Only three weak peaks at 2θ of 23.84°, 39.56°, and 46.68° can be found
and might be attributed to the (002), (110), and (200) planes of AgI
hexagonal structures, respectively. There were no obvious peaks of
Ag0 nanoparticles in XRD spectra of AgI-BiOI samples. The intensity of
diffraction peak of AgI-BiOI(1–8) composites was much weaker than
that of the pristine BiOI sample after AgI-loading. According to the
Scherrer equation, (Balouria et al., 2013; Holzwarth and Gibson, 2011)
the overall crystallite size of the AgI-BiOI(1–8) of 30.4 nm is bigger
than pristine BiOI of 28.0 nm, which might be due to the hybriding of
AgI with BiOI.
The morphology of AgI, AgI-BiOI(1–8), and BiOI samples was charac-
terized using SEM showing in Fig. 2. The pristine AgI particles exhibited
an irregular rock-like morphology with stacked layers with average size
of almost 5 μm in Fig. 2(c). The pure BiOI possesses a 3D hierarchical mi-
crosphere structure making up with ~100 nm nanoplates (Jahurul Islam
et al., 2016). These nanoplates are wrapped layer in layer to form
around 800 nm 3D hierarchical structures. The morphology of AgI-
BiOI(1–8) remains 3D hierarchical microspheres with rough surface
which is formed with densely aggregated nanoplates with size enlarged
to about 1.5 μm in Fig. 2(b). The change of surface properties such as
redox sites may enhance the adsorption capacity of the reactants. The
lattice images of AgI, AgI-BiOI(1–8), and BiOI samples were investigated
through TEM. The pristine AgI was very unstable and experienced struc-
tural changes irradiated by high-energy electron beams during TEM
analysis. Therefore, no appropriate TEM image of AgI was recorded.
The black area in the TEM image of AgI-BiOI(1–8) samples in Fig. 2
80
AgI
101002
110
(b) AgI
100
200
103
PDF #09-0374
Intensity (a.u.)
AgI-BiOI(1-8)
110
012
001
020
122
BiOI
013
220
114
PDF #73-2062
BiOI 10 20 30 40 50 60 70 80
2Theta (degree)
 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204 197

Fig. 2. SEM images of AgI (a), AgI-BiOI(1–8) (b), BiOI (c); TEM image of AgI-BiOI(1–8) (d), HRTEM images of AgI-BiOI(1–8) (e), intensity profile along the black arrows (f); the
corresponding EDX elemental mapping of AgI-BiOI(1–8) (g-k) showing Ag (red), I (blue), and Bi (yellow) element mapping. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

(d) illustrated that both materials have a thicker 3D structure
reconfirmed the SEM results. The HRTEM image of the AgI-BiOI(1–8)
was performed in these monolithic regions on the edge of this sample.
The distinct lattice fringe in the HRTEM image is an indication of a
good crystallization of AgI-BiOI(1–8) samples. The fringe spacing of
AgI-BiOI(1–8) of 0.301 nm can be assigned to (012) lattice plane of
the pure BiOI. However, the AgI lattice plane was ambiguously observed
in the HRTEM image due to the high crystalline diffraction peaks of BiOI
and lower content of AgI in AgI-BiOI(1–8) (Huang et al., 2017). To fur-
ther explore the co-existence of AgI within the BiOI matrix of this hier-
archical AgI-BiOI(1–8) microsphere, energy dispersive X ray (EDX) was
performed to further explore the co-existance of AgI within the BiOI ma-
trix in Fig. 2(g). The red, blue, and yellow colors exhibited the elemental
mapping of silver, iodine, and bismuth, respectively, which clearly dem-
onstrated the homogenously distribution of Ag, I, and Bi within the ma-
trix of AgI-BiOI(1–8) samples in Fig. 2(h-j). In addition, Ag elemental
signals could be detected by EDX spectrum Fig. 2(K) which further dem-
onstrated the uniform dispersal of AgI in the matrix of BiOI. The quanti-
tative weight ratio of Ag in AgI-BiOI(1–8) is given about 1.25% based on
EDX results (Sun et al., 2010).
The chemical composition and the elemental valence states of as-
prepared AgI-BiOI(1–8) nanocomposites were characterized with XPS
in Fig. 3. The wide scan XPS spectrum of BiOI in Fig. 3(a) indicated
that the binding energies of 158.17, 529.17, and 618.17 eV arose from
the presence of corresponding Bi, O, and I elements in the AgI-BiOI
(1–8) samples, respectively. While the new peak generated with bind-
ing energies of 367.08 eV was attributed to Ag+ loading in the matrix
of AgI-BiOI(1–8). Two strong peaks at 158.3 and 163.6 eV with the
high-resolution XPS spectrum in Fig. 3 (b) were attributed to Bi 4f7/2
and Bi 4f5/2 of Bi3+ of AgI-BiOI(1–8), respectively (Liang et al., 2018).
In Fig. 3 (c), the surface oxygen species of AgI-BiOI(1–8) could be
deconvoluted into the peak around 529.1 eV originated from the
Bi\\O bond and the weak peak around 530.3 eV attributed to the
adsorbed H2O or OH– on the catalyst surface (Huo et al., 2012; Zhou
et al., 2015). Additionally, the binding energies of I 3d3/2 and 3d5/2 deriv-
ing from I− were found at 629.7 and 618.2 eV, respectively in Fig. 3(d).
The above values are in accordance with previous report for BiOI and
AgI·(Li et al., 2013). As shown in Fig. 3(e), the Ag 3d XPS spectrum fit
well with the Ag 3d5/2 at 367.43 eV and Ag 3d3/2 at 373.44 eV, which
are attributed to Ag+ coming from AgI (Tang et al., 2011). The XPS
198 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204

I 3d5/2

Bi 4F 7/2
B iO I

Bi 4f 5/2
A g I - B iO I

I 3d 3/2
(a )

Intensity (a.u.)

O 1s

C 1s
Ag 3d
1200 1000 800 600 400 200 0
B in d in g E n e r g y (e V )

(b) Bi 4f7/2 BiOI (c) BiOI

AgI-BiOI AgI-BiOI
158.30 BiOI O 1s
Bi 4f 529.03 O 1s
158.35
Bi 4f5/2
163.61
529.06
Intensity (a.u.)

Intensity (a.u.)
163.66
AgI-BiOI
530.38

530.29

520 525 530 535 540

Binding Energy (eV)

150 155 160 165 170 520 525 530 535 540
Binding Energy (eV) Binding Energy (eV)

(d) BiOI (e) Ag 3d5/2 AgI-BiOI

I 3d5/2
AgI-BiOI 367.43 eV Ag 3d
618.19
I 3d
618.22
I 3d3/2 Ag 3d3/2
629.65
Intensity (a.u.)

Intensity (a.u.)

373.44 eV
629.70

610 615 620 625 630 635 640 360 365 370 375 380
Binding Energy (eV) Binding Energy (eV)

Fig. 3. Survey-scan XPS spectra of BiOI and AgI-BiOI(1–8) (a), Bi 4f (b), O 1 s with inset of O 1 s spectra after quantifying (c), I 3d XPS spectra of BiOI and AgI-BiOI(1–8) (d), and Ag 3d (e) at
high resolution.

spectrum of Ag 3d indicated that almost no Ag0 nanoparticles were de- composite photocatalysts showed considerable influence on the
posited on the surface of AgI-BiOI(1–8) microspheres. The XPS analysis photo-degradation of BPA under the same conditions due to the loading
successfully proved the incorporation of Ag I into the matrix of AgI-BiOI of AgI into the matrix of BiOI. A small amount of AgI is capable to signif-
(1–8) composites. icantly enhance the photocatalic performance of BiOI. The pseudo-first
order kinetic model was applied to quantitatively assess the degrada-
3.2. Enhanced photocatalytic performances of AgI-BiOI tion of BPA over series of AgI-BiOI nanomaterials through Eq. (2):
 
The photocatalytic degradation performance for BPA by AgI-BiOI C0
ln ¼Kt ð2Þ
samples with various Ag-Bi molar ratios from 1:16 to 4:1 was evaluated Ct
under Xe lamp irradiation shown in Fig. 4(a). In control experiment only
4% BPA was removed after 2 h irradiation, indicating that BPA is not where C0 and Ct are the concentrations of BPA at time 0 and t, respec-
prone to direct photolysis. The adsorption ratio of BPA on AgI-BiOI sam- tively. K is the pseudo-first-order kinetic rate constant. The pseudo-
ples with various Ag-Bi molar ratio were almost within 10% after 1 h first-order kinetic rate constants for photocatalytic degradation of BPA
adsorption-desorption equilibrium process. Pristine AgI exhibited very by AgI-BiOI samples were assayed in Fig. 4(b). The photocatalytic activ-
slow photocatalytic activity with only 46% of BPA removed after 2 h ir- ities of BiOI greatly depend on the dose of AgI. When the Ag-Bi molar
radiation. Prinstine BiOI exhibited high degradation efficiency with ratio increased from 1:16, 1:12 to 1:8, subsequently, the photocatalytic
92.4% BPA removal ratio after 2 h irradiation. Moreover AgI-BiOI activity for BPA gradually enhanced. However, further increase of the
 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204
1.0
(a)
0.8
0.6
C/C0
Blank
BiOI
AgI
0.4 AgI-BiOI(1-16)
AgI-BiOI(1-12)
AgI-BiOI(1-8)
0.2 AgI-BiOI(1-4)
AgI-BiOI(1-2)
AgI-BiOI(1-1)
AgI-BiOI(2-1)
0.0
0 30 60 90 120
Time (min)
Fig. 4. Photodegradation activity (a) and the pseudo-first-order degradation kinetic rate constants (b) of BPA on the AgI-BiOI materials with various Ag-Bi molar ratios.
Ag-Bi molar ratio from 1:4 to 4:1 resulted in continuous deterioration
for BPA photo-catalytic activities. For instance, when Ag-Bi molar ratio
goes from 1:8 to 4:1, the pseudo-first order kinetic photodegradation
rate of BPA by AgI-BiOI decreased 40%, which could be due to the ag-
glomeration of AgI nanoparticles on the surface of BiOI. Excessive load-
ing of AgI will significantly affect the size, dispersion and light
absorbance of AgI-BiOI materials. Meanwhile, the larger size of AgI
nanoparticle on AgI-BiOI samples could weaken the anchored force be-
tween AgI and BiOI leading to destruct the heterojunction structure and
decrease of photocatalytic activity (Xu et al., 2013). Kong et al. reported
similar phenomenon in which series AgBr-BiOBr heterojunction
photocatalytsts with varying AgBr loadings were synthesized. AgBr-
BiOBr with lower AgBr loading (up to 0.5 wt%) showed superior photo-
catalytic activities for target pollutants, while AgBr-BiOBr with higher
AgBr loading amount (N0.5 wt%) produced isolated AgBr particles and
reduced photocatalytic performance (Kong et al., 2012) AgI-BiOI(1–8)
showed the highest photo-degradation activity with pseudo-first-
order rate constant of 0.0725 min−1, which is nearly 3.7 fold that of pris-
tine BiOI. Therefore, AgI-BiOI(1–8) was chosen in this study for photo-
catalytic degradation of BPA.
3.3. The effect of environmental factors
3.3.1. The effectiveness in degradation of various structural organics
The physiochemical properties of the target organic pollutants, such
as steric structure, surface charge might play a vital role and lead to dif-
ferent kinetics and dynamics of adsorption or photocatalytic degrada-
tion. ((Kerkez-Kuyumcu et al., 2015; Khataee and Kasiri, 2010); Liu
et al., 2017d) To investigate the universality of AgI-BiOI(1–8) samples,
the adsorption and photocatalytic degradation activities of anionic dye
orange II (OII), cationic dye methylene blue (MB), and neutral molecu-
lar phenol and BPA were evaluated under Xe lamp irradiation shown in
Fig. S1. AgI-BiOI(1–8) significantly improved the photodegradation effi-
ciency for aforementioned organic contaminants in comparison with
that of pristine AgI or BiOI. Furthermore, the charges and physiochemi-
cal structures of those contaminants influenced the adsorption capacity
on each type of the catalysts leading to the different photodegradation
efficiency. AgI-BiOI showed about 16% adsorption ratio towards OII
due to electrostatic repulsion with negatively charged OII and exhibited
efficient photodegardation of OII afterwards (79%). AgI-BiOI(1–8)
displayed about 67% adsorption ratio of the MB due to electrostatic at-
traction with positively charged MB and exhibited insignificant
photodegradation of MB afterwards (~34%) caused by deterioration of
light absorbance. It was shown that negatively charged organic OII
would be more easily degraded by AgI-BiOI(1–8). As for neutral or-
ganics, AgI-BiOI(1–8) was more efficient for the photodegradation of
hydrophobic BPA. The photocatalytic degradation was shown to be a
199
0.08
(b)
0.07
0.06
K constant (min )
-1
0.05
0.04
0.03
0.02
0.01
0.00
I 6) 2) 8) 4) 2) 1) 1) 1) Ag
I
BiO I(1-1 I(1-1 I(1- I(1- I(1- I(1- I(2- I(4-
-BiO -BiO I-BiO I-BiO I-BiO I-BiO I-BiO I-BiO
I I Ag Ag Ag Ag Ag Ag
Ag Ag
surface catalyzed reaction which will be beneficial for the adsorption
of hydrophobic compounds. AgI-BiOI(1–8) showed good universality
in photocatalytic degradation of pollutants with various charge and
structural characteristics. Our previous work about degradation effi-
ciencies of various charged organic structures in α-Fe2O3@GO+H2O2
+ UV system is in line with above result suggesting the same kind of or-
ganics follow the same degradation trend (Liu et al., 2017b).
3.3.2. The effect of various environmental factors
The influence of initial pH on photocatalytic degradation of BPA in
AgI-BiOI(1–8) system was evaluated in Fig. S2 (a). It was revealed that
the Ag-BiOI(1–8) had the best photocatalytic activity when the initial
pH of BPA was 6.5. While, acidic or alkaline pH significantly impacted
on photocatalytic activity. Additionally, the initial pH of 4 caused dam-
age to the surface structure resulting in deterioration of photocatalytic
activity. Hence, this material can be effectively used in a wide pH
range without acidification (Xu et al., 2013).
Fig. S2 (b) shows the effect of the AgI-BiOI(1–8) dosage on photocat-
alytic degradation of BPA. Accordingly, the degradation rate of BPA con-
siderably increased with the increase of catalyst dosage. The
photodegradation ratio of BPA was 28.7% when the concentration of
AgI-BiOI(1–8) is 62.5 mg/L. in addition, the concentration of 250 mg/L
almost degraded all the BPA within 1 h. When the dosage of Ag-BiOI
(1–8) increased from 250 mg/L to 500 mg/L, the photocatalytic degra-
dation rate remains unchanged due to the inhibition of light penetration
by nanoparticles.
The effect of initial BPA concentrations on photocatalytic perfor-
mance of AgI-BiOI(1–8) was compared in Fig. S2 (c). The photocatalytic
degradation of BPA reduced following the increase of the initial concen-
tration of BPA in AgI-BiOI system which was involved in adsorption and
the subsequent surface redox reaction (Luo et al., 2015). Hence the ad-
sorption and catalytic sites might be limited and saturated when the
dosage of the catalyst is already given.
3.3.3. The effect of different types of illumination
Light absorption capacity and the charge separation and transfer dy-
namics play vital roles in determining the photoreactivity of the semi-
conductors (Hoffmann et al., 1995). Therefore, the effect of light
sources on the photodegradation of BPA was analyzed. In order to ex-
plore the enhanced mechanism of photocatalytic capability of AgI-BiOI
(1–8), UV–Vis DRS are used to detect the optical properties of the semi-
conductor materials in Fig. 5(a). The optical absorption edge is about
449, 681 and 698 nm for AgI, Ag-BiOI(1–8), and pure BiOI, respectively.
The light absorbance of AgI exhibited a sharp decline on the wavelength
above 450 nm. While, it increased substantially in the ultraviolet re-
gions. The absorption edge of AgI-BiOI(1–8) had a slightly blue shift
compared with the pristine BiOI. Moreover, the absorption intensity of
200 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204

(a) AgI (b) AgI

AgI-BiOI(1-8) AgI-BiOI(1-8)
BiOI BiOI
Absorbance (a.u.)

Intensity (a.u.)
2.0

1.5
( hv)2/(eV)2

1.0

0.5

0.0
2 3 4
hv/eV

200 300 400 500 600 700 800 -5 0 5 10 15

Wavelength (nm) Binding Energy (eV)

light off light on light off light on

1.0 1.0
(c) (d)
0.8 0.8

0.6 0.6
C/C0

C/C0

0.4 0.4

0.2 0.2
BiOI BiOI
AgI AgI
AgI-BiOI(1-8) AgI-BiOI(1-8)
0.0 0.0
-60 -30 0 30 60 90 120 -60 -30 0 30 60 90 120
Time (min) Time (min)

0.08
light off light on AgI
Pseudo-first-order rate constant (min )

(f) 0.0725
-1

1.0 BiOI
(e) AgI-BiOI(1-8)

0.8 0.06
0.054
0.047
0.6 0.0424
C/C0

0.04 0.036

0.4
0.0198 0.0194
0.02
0.2
BiOI
AgI 0.005
AgI-BiOI(1-8) 0.0029
0.0
-60 -30 0 30 60 90 120 0.00
Time (min) UV UV-Vis Vis

Fig. 5. UV–visible DRS of AgI, AgI-BiOI(1–8), and BiOI; The upper right inset shows the photographs of the corresponding samples. The lower left inset shows the plot of (αhv)2 versus hv
for AgI, AgI-BiOI(1–8), and BiOI samples (a). The valence band (VB)-XPS of AgI, AgI-BiOI(1–8), and BiOI (b). The photocatalytic degradation of BPA by AgI, AgI-BiOI(1–8) and BiOI under UV
irradiation (c), UV–visible irradiation (d), and visible irradiation (e), and the histogram of the first-order kinetic rate constants of corresponding degradation of BPA on AgI, AgI-BiOI(1–8)
and BiOI under different irradiation sources (f).

AgI-BiOI(1–8) was higher than pure BiOI in UV–visible region. The ab-
sorption edge wavelength of semiconductor can be calculated through
band gap energy based on Eq. (3):
E ¼ h  c=λ
where E stands for the band gap energy, c is velocity of light (3 × 108 m/s),
h is Planck's constant (6.626 × 10−34 Js) and λ is wavelength (nm). The
band gap energy of prinstine AgI, Ag-BiOI(1–8) and pristine BiOI was
found to be 2.76, 1.82, and 1.78 eV, respectively. The valence bands (VB)
of prinstine AgI, Ag-BiOI(1–8) and pristine BiOI were obtained through
XPS valence spectra in Fig. 5(b). The edge of the maximum energy was
at approximately 0.89, 0.42, and 0.42 eV for AgI, AgI-BiOI(1–8), and
ð3Þ BiOI, respectively. According to the optical absorption spectrum, The con-
duction band (CB) minimum of AgI, AgI-BiOI(1–8), and BiOI would occur
at approximately −1.87, −1.40, and − 1.36 eV based on the difference
between valence band maximum and band gap energy, respectively.
The AgI loading slightly changed the band gap characteristic of BiOI,

while it greatly improved the optical adsorption intensity of AgI-BiOI
(1–8). The AgI modified BiOI can utilize solar light irradiation more effec-
tively according to the yellow area which showed the relative intensity
distribution of the solar spectrum (ASTM, 2000).
In order to figure out the impact of the optical properties, we mea-
sured the photocatalytic degradation efficiencies of BPA on AgI, AgI-
BiOI(1–8) or BiOI under UV, UV–visible and visible irradiations, respec-
tively in Fig. 5(c-e). The corresponding first-order kinetic rate constants
of BPA under different light sources are shown in Fig. 5(f). Under UV ir-
radiation, AgI-BiOI(1–8) presented the highest photocatalytic degrada-
tion ability and the reaction rate constant of AgI-BiOI(1–8) is 1.2 and 1.5
times that of the pristine AgI and BiOI, respectively. Pristine AgI per-
formed faster photocatalytic degradation rate than the pure BiOI,
which may be ascribed to the fact that AgI has good optical absorption
ability in the UV region. Likewise, under UV–visible irradiation or visible
irradiation, the reaction rate constant of AgI-BiOI(1–8) is faster than
that of pure AgI and BiOI. When it comes to the AgI, the photocatalytic
degradation efficiency of BPA is quite poor either under UV–visible or
visible irradiation. It can be seen that the loading of AgI into BiOI can ef-
fectively improve the photocatalytic capacity of BPA in the entire spec-
tral range, especially under the UV–visible irradiation.
3.4. Photoelectrochemical properties
It is widely accepted that the photoluminescence (PL) emission, tran-
sient photocurrent response, and electrochemical impedance spectros-
copy (EIS) are often applied to investigate the migration efficiencies of
photogenerated carriers (Cui et al., 2010; Li et al., 2015). Generally, a
higher PL intensity indicates the higher recombination of the photo-
generated carriers which is ascribed to the higher production rate or
amount of photogenerated carriers (Huang et al., 2014; Wang et al.,
2013). Therefore, the separation and transfer of photo-generated carriers
of AgI, AgI-BiOI(1–8), and BiOI samples by PL emission were investigated
in Fig. 6 (a). The PL intensity is in the order of AgI b BiOI b AgI-BiOI(1–8).
Accordingly, after loading of AgI, the PL intensity of AgI BiOI(1–8) in-
creased successively even above 440 nm within BiOI matrix. Meanwhile,
in Fig. 6(b) the transient photocurrent responses obviously show the
great increase of the charge separation and transfer of BiOI due to the
loading of AgI, which is consistent with the aforementioned PL result.
The stable transient photocurrent responses of AgI-BiOI(1–8) shows sta-
ble photocatalytic activity due to the loading of AgI rather than the grad-
ual decreasing photocatalytic activity of prinstine BiOI. In Fig. 6(c), the EIS
turn out the same consequence indicating the decrease of the charge
transfer resistence of BiOI by AgI loading. However, the charge recombi-
nation efficiencies of AgI-BiOI(1–8) have been improved apparently com-
pared with that of AgI or BiOI proved by PL, transient photocurrent
responses and EIS. However, in our system, the obviously enhanced
photodegradation efficiency of BPA by AgI-BiOI(1–8) further confirmed
the role of photogenerated carriers separation would be more obvious
than that of the recombination of charge carriers. The similar situation
has also appeared in previous report. Huang et al. doped CoFe2O4 onto
(a)
AgI
AgI-BiOI(1-8)
BiOI
PL Intensity (a.u.)
280 320 360 400 440
Wavelength (nm)
Fig. 6. The PL spectra (a), transient photocurrent responses (b), and EIS Nyquist plots (c) of AgI, AgI-BiOI(1–8), and BiOI samples.
J. Lv et al. / Science of the Total Environment 669 (2019) 194–204 201
Ag3PO4 to enhance the photocatalytic performance, while the carrier sep-
aration efficiency have been slashed after CoFe2O4 were incorporated
(Huang et al., 2017).
3.5. Radical formation involved in this system
Photocatalytic reactions usually involve various kinds of ROS, such as
hole (h+), singlet oxygen (1O2), superoxide radicals (O2•−) and so on
being responsible for the degradation of organic contaminants. EDTA-
2Na, NaN3, VC, and MeOH were used as scavengers for h+, 1O2, O2•−
and HO• during the photocatalytic process to explore the presence and
roles of ROS, respectively. The results of radical quenching experiments
were shown in Fig. S3 (a). The photocatalytic degradation of BPA de-
creased slightly with the addition of NaN3 and MeOH, indicating that
1
O2 and HO• were not the main ROS responsible for BPA degradation.
The photodegradation efficiencies of BPA were apparently suppressed
by the addition of EDTA-2Na and VC, suggesting that h+ and O2•− are
most likely the main ROS responsible for BPA degradation. Comparing
with the oxidation potential of O2•−, photo-generated h+ should play a
dominated role in AgI-BiOI(1–8) photocatalytic oxidation of BPA,
which shows that AgI-BiOI(1–8) photocatalytic process should be a
hole-initiated radical-propagated oxidation reaction. To further verify
aforementioned conclusions obtained from the radical quenching ex-
periments, the formation of O2•− and HO• radicals were quantitatively
determined using radical trapping test in Ag-BiOI(1–8) photocatalytic
systems shown in Fig. S3 (b). It can be seen that the formation concen-
tration of O2•− and HO• radicals were different in AgI-BiOI(1–8) photo-
catalytic system. The concentration of HO• radicals reach 0.11 mM
after 120 min irradiation which is too low to play main role towards or-
ganic contaminants degradation even if HO• radicals have high oxida-
tion potential (+2.80 eV versus NHE). The intensity of O2•− radicals
increased significantly with time showing the dominant role in
photodegradation. Similar observations have reconfirmed the role of
O2•− in photodegradation of organic pollutants using ESR technique
(Huang et al., 2016b; Huang et al., 2015b).
The possible pathway for photocatalytic degradation of BPA on AgI-
BiOI(1–8) is shown in Scheme 1. Both AgI and BiOI of AgI-BiOI(1–8)
heterojunction could directly be excited to generate photoelectron-hole
pairs under UV–visible radiation. The photoexcited electrons in the con-
duction band (CB) of AgI (−1.87 eV) will quickly transfer to the CB of
BiOI (−1.40 eV) which will react with oxygen adsorbed on the surface
of AgI-BiOI(1–8) to produce O2•−. At the same time, the photogenerated
holes of AgI (0.89 eV) will accumulate in the valence band (VB) of BiOI
(0.42 eV) acting as the dominant active species to effectively oxidize
BPA adsorbed on the catalyst surface (Park et al., 2014). The proposed
photocatalytic mechanism of AgI-BiOI(1–8) was shown in Scheme 1.
3.6. Stability of AgI-BiOI(1–8)
As indicated in literatures, photochemical-corrosion is a big problem
for Ag based materials for practical application (Chen et al., 2015; Dai
2.00E-007 300
(b) (c)
AgI AgI
AgI-BiOI(1-8) 250 AgI-BiOI(1-8)
1.50E-007 BiOI BiOI
200
Current (A)
Z"/ohm
1.00E-007 150
100
5.00E-008
50
0.00E+000 0
480 0 100 200 300 400 0 100 200 300 400 500 600 700
Time (sec) Z'/ohm
202 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204
Scheme 1. Proposed photocatalytic degradation mechanism of BPA on AgI-BiOI(1–8).
et al., 2012; Yu et al., 2016). The stability of pristine AgI, BiOI, and AgI-BiOI
(1–8) was studied in degradation of BPA under UV–visible irradiation for
five cycles shown in Fig. 7(a). The photocatalytic activities of the three
materials all decreased with the cycling runs. The photodegradation of
BPA by AgI-BiOI(1–8) remained at 80% after three cycling runs. Gradual
deactivation of AgI-BiOI(1–8) (about 50%) is noticed from first to fifth
run. AgI-BiOI(1–8) has almost similar degradation efficiency in the fifth
photocatalytic cycles with that of BiOI showing the gradual deactivation.
In order to explore the reasons for the decrease in catalyst performance,
the XRD pattern of AgI-BiOI(1–8) after five recycling runs was measured
shown in Fig. 7(b). The XRD pattern of used AgI-BiOI(1–8) remains quite
similar to that of the phase and structure of pristine BiOI. While the
heterojunction structures between AgI and BiOI might be destroyed due
to the deactivation of AgI leading to the deterioration of AgI-BiOI(1–8)
photocatalytic performance (Lin et al., 2012).
3.7. Toxicity and environmental applications
After exposure to a series of concentrations of AgI-BiOI(1–8), the sur-
vival percentages of nematodes were shown in Fig. S4 (a) in order to eval-
uate the toxicity of AgI-BiOI(1–8). The survival percentages curve didn't
show obvious dose-responsive relationship in the AgI-BiOI(1–8) suspen-
sions. The results showed that there was no impact lethal effects on the
survival of nematodes even at 100 mg/L AgI-BiOI(1–8). There was almost
no difference in survival rate compared with the blank control group. The
potential adverse effect of degradation intermediates of BPA was assessed
by monitoring the luminosity of luminescent bacteria and the result is
shown in Fig. S4 (b) (Liu et al., 2017c). The relative luminosity ratio de-
creased from 60% to 27% after 30 min UV–visible irradiation exposure.
Thereafter, it gradually increased to about 57% which almost same as
the initial value. The reduction of the acute toxicity of the BPA photocata-
lytic degradation samples produced no second pollution. This eco-toxicity
1.0 (a)
0.8
0.6
C/C0
0.4
0.2
AgI
AgI-BiOI(1-8)
0.0 BiOI
round 1 round 2 round 3 round 4 round 5
0 120 240 360 480
Time (min)
Fig. 7. Cycling experiments in the photocatalytic degradation of BPA in presence of BiOI, AgI, and AgI-BiOI(1–8) (a), and the XRD pattern of AgI-BiOI(1–8) before and after five cycling
photodegradation (b).
curve is typical form in advanced oxidation processes presumably due to
the formation of early-stage more toxic transformation products followed
by progressively converting to less harmful compounds with reaction
(Mantzavinos and Psillakis, 2004; Repousi et al., 2017).
4. Conclusions
In this work, AgI-BiOI composites were synthesized by a facile
solvothermal method and the photocatalytic performance of BPA were
thoroughly tested under various situations. The enhanced photocata-
lytic activity of BPA by AgI-BiOI under UV–Vis irradiation is generally re-
lated to formation of AgI-BiOI heterojunctions, which may lead to the
extended light absorption intensity and accelerate the separation of
photogenerated carriers. The radical quenching experiments showed
that h+ and O2•− radicals play the dominated role in BPA photocatalytic
degradation on the surface of AgI-BiOI(1–8). The AgI-BiOI(1–8) and the
intermediates produced during BPA photocatalytic degradation process
have low ecotoxicity without producing secondary pollutants in envi-
ronment. This work provides an alternative strategy to improve the cat-
alytic efficiency and visible response of pristine BiOI by incorporation of
small amount of AgI. The AgI-BiOI composite can be a promising solar
light-driven catalyst for organic contaminants elimination in the future.
Acknowledgements
We very appreciated for the support from Natural Science Founda-
tion of China (NO. 21377039).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2019.03.077.
(b) AgI-BiOI(1-8) before
Intensity (a.u.)
AgI-BiOI(1-8) after
600 10 20 30 40 50 60 70 80
2Theta (degree)
 J. Lv et al. / Science of the Total Environment 669 (2019) 194–204
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