Accepted Manuscript

Title: Microwave-assisted solvothermal synthesis of novel

hierarchical BiOI/rGO composites for efficient photocatalytic
degardation of organic pollutants

Authors: Jinfen Niu, Peixuan Dai, Qian Zhang, Binghua Yao,

Xiaojiao Yu

PII: S0169-4332(17)32190-6
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2017.07.190
Reference: APSUSC 36724

To appear in: APSUSC

Received date: 1-5-2017

Revised date: 17-7-2017
Accepted date: 20-7-2017

Please cite this article as: Jinfen Niu, Peixuan Dai, Qian Zhang, Binghua Yao, Xiaojiao
Yu, Microwave-assisted solvothermal synthesis of novel hierarchical BiOI/rGO
composites for efficient photocatalytic degardation of organic pollutants, Applied
Surface Sciencehttp://dx.doi.org/10.1016/j.apsusc.2017.07.190

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 Microwave-assisted solvothermal synthesis of novel hierarchical
BiOI/rGO composites for efficient photocatalytic degardation of
organic pollutants

Jinfen Niu, Peixuan Dai, Qian Zhang, Binghua Yao, Xiaojiao Yu

School of science, Xi’an University of Technology, Xi’an 710048, China

*
Correspondence: Email: niujinfen@xaut.edu.cn (J.N.)

Graphical abstract

Highlights
 The BG-2 composite has been synthesized by one-step rapid microwave

hydrothermal method.

 Enhanced visible light photocatalytic activity was observed in the BG-2

composites due to its special morphology.

 Graphene acted as an electron acceptor and transmitter to hinder the charge

recombination.

 The active species of the photocatalyst was h+ and e-.

1
Abstract

In the present paper, a novel composite of BiOI/rGO with excellent visible-light

photocatalytic activity was successfully fabricated via very different simple, fast and
mild rapid microwave hydrothermal method. The BiOI/rGO -1(BG-1) was donated as
a simple chemical mechanical and the BiOI/rGO -2(BG-2) was donated as one-step
rapid microwave hydrothermal method. The BG-1 were composed of the BiOI
microspheres with a diameter of about 1 μm and mixed heterogeneously with
graphene. While, the BG-2 were consist of the BiOI nanoplates with the thickness of
approximately 20 nm dispersed heterogeneously on the surface of rGO. The
degradation of 40 mg/L methylene blue (MB) and 20 mg/L levofloxacin (LEV) under
visible light irradiation can reach about 11 and 3 times than that of P25, respectively.
Furthermore,the reactive species of hole was determined to dominant the
photodegradation process. The intensive photocatlytic could ascribe to more effective
electron transportation and separations ， this conclusion was different with other
studies. A possible photocatalytic mechanism of BG-2 was also proposed.

Key words: BiOI; graphene; visible light; microwave hydrothermal;

1. Introduction

In recent years, the photocatalysts effective in the photodegradation of organic

compound in the wastewater which is deemed to be a potential method for solving
power shortages and environmental pollution problems has drawn intensive research
interests [1-7]. Compared with the traditional technology, photocatalysis is generally
believed to be environmental technology of the next generation due to its
environmental friendly, low cost, high rate of mineralization photosensitivity,
nontoxic nature and less secondary pollution [8]. Simultaneously, preparation of
visible-light composite photocatalysts with excellent performance has been
recognized [9-12], such as phosphorous-doped anatase TiO2 powders [13],
hierarchical Ag2O-ZnO-Fe3O4 composites [14], and so on. Be universally known, The
TiO2 was limited due to its narrow band gap (3.2 eV for anatase ) in practical
application [15]. Although composite TiO2 photocatalysts are positive to achieve
visible light absorption ability, the effect is still not ideal [16,9]. Consenquently,
ameliorating photocatalysts stimulated under visible-light is significative and essential
[4].
As a substitution, the bismuth oxyhalides pohotocatalysts have showed extensive
potential, owing to narrow band gaps and large space of layered structures. It
generally can be propitious to the inhibition separation of photo-induced electron-hole
pairs and promote the performance on photogradation reactions [17-21]. By
comparison, BiOI owns intensenly visible light response ability[16]. Nevertheless,
pure BiOI didn’t perform excellently from the point of easy recombination of photo-
generated electrons and holes [4].Consequently, multifarious BiOI-based
composites[22, 23], such as BiOI/TiO2 heterostructures synthesized via a simple low

2
temperature soft-chemical process[3], BiOMxR1-x solid solutions synthesized through
a low-temperature precipitation [12], have been synthesized to enhance the
photocatalytic activity. Graphene and its derivatives have aroused numerous attention
due to its special structure and remarkable feature, such as robust but flexible
structure, outstanding electron mediator and high carrier mobility. Many researchers
have devoted themselves to enhancing the photodegradation actives of catalysts by
preparing graphene-based hybrid composites[4, 24-30].These composites can improve
the photocatalytic process of BiOI by promoting charge separation, but there are a
series of disadvantages, like long reaction time, more power consumption, difficulty
in handling the process and high temperatures[31-33]. Hence, it’s still necessary to
develop a new synthetic method to deal with these problems. Microwave irradiation
technique is a facile, rapid, time-saving, highly efficient, environmentally friendly and
economical synthetic method [13, 34-37].
In this paper, we report a simple one-step rapid microwave hydrothermal method
to prepared BG-1 and BG-2 composites with different synthesized route. The
photocatalytic performance of BG-1 and BG-2 were evaluated by photocatalytic
degradating methylene blue (40 mg/mL) and levofloxacin (20 mg/mL) under visible-
light irradiation. And this study tries to build up a relationship between the
synthesized route of BG-1 and BG-2 composites and their photocatalytic activity by
comparing the crystal structure, morphologies, optical properties, specific surface area,
electrons-holes separation effect, respectively. The obtained results may provide
important information for preparing high photocatalytic activity photocatalysts via
microwave hydrothermal method.

2. Experimental

2.1. Composites preparation

Adopting a modified Hummers method, Graphene oxide (GO) was success fully
prepared in the laboratory[38]. The BG-1 and BG-2 composite materials were
acquired by a rapid microwave solvothermal method. A representative BG-2 synthesis:
0.0723 g of GO was scattered in ethanol (10 mL) to obtain the homogenous
suspension of exfoliated GO under ultrasonic for 1 h. Meanwhile, 0.4851 g of bismuth
nitrate pentahydrate was added in 15 mL of ethanediol (EG), then the solution was
transferred to 5 ml of EG solution dissolving 0.1660 g of KI under magnetically
stirring. Then the GO suspension was transferred slowly to the as-acquired reacting
mixture. Then the mixture was heated in a MDS-6 microwave hydrothermal system
under temperature-controlling model at 160 °C for 20 min. The deposit was collected
after the autoclave reaching to room temperature. The solid precipitate was purged
three times using ethyl ethanol and deionized water, then dried under 60 °C for 24 h,
as illustrated by Fig. 1. Pure BiOI was obtained in the same way without the existing
of GO. With 0.4500 g of BiOI dissolved in 10 ml of EG, then mixed with the as-
obtained GO solution, the remaining steps were same as above, it is BG-1.
2.2. Sample characterization
Powder X-ray diffraction was documented on X-ray diffractometer (XRD-7000s)
with Cu Kα under the condition of tube current 40 mA and tube voltage 40 kV. The
morphology images of samples were recorded on a scanning electron microscopy
3
(JEOL-7800) and transmission electron microscope(TEM-3010). X-ray photoelectron
spectroscopy (XPS) was done on K-Alpha System (Thermo Electron, USA) with Al
Kα radiation operated at 250 W. Diffuse reflectance spectra (DRS) were recorded on
a UV-vis-NIR spectrometer (TU-1901) .Raman spectroscopy was performed using a
microscopic confocal Raman spectrometer (RENISHAW, inVia) with an excitation of
514 nm laser light. Photoluminescence (PL) spectra were recorded on PL
spectrometer (Horiba, Japan) at room temperature. Nitrogen adsorption-desorption
isotherms and Brunauer-Emmett-Teller (BET) were obtained on JW-BK-122W
sorptometer at liquid nitrogen temperature. Fourier transform infrared (FT-IR) spectra
were collected in FT-IR spectrometer (FTIR-8900). The thermal behavior of samples
was performed on thermogravimetric analyzer (ZCT-B TG/DTA) at controlled
heating rate of 10℃ ·min-1(25 to 1000 ℃under air atmosphere). Photoelectrochemical
properties were performed in CHI660B electrochemical system in a three electrode
cell system. The working electrode were prepared on ITO conducting glass which was
coated by the sample,while a platinum wire was acted as counter electrode, a
saturated calomel electrode (SCE) was employed as the reference electrode,
respectively. The electrolyte solution was Na2SO4(1.0 mol/L) aqueous.
2.3. Photocatalytic reaction
To evaluate the photocatalytic performance of the as-obtained catalysts, the
photocatalytic reaction was carried out under visible light illuminate taking methyl
blue (MB, 40 mg/L) and levofloxacin (LEV, 20 mg/L) as model reactant. In every
photocatalytic experiments, products (50 mg) were dispersed in 50 mL MB solution
(or LEV solution) and ultrasonically vibrated for 40 min without the lamp to achieve
absorption–desorption equilibrium between the catalysts and model reactants. Then
the suspension was illuminated with a halogen-tungsten lamp (150 W) which was
placed in the center of the reactor with a cooling water system. Air was bubbled into
the suspension to ensure constant supply of oxygen. A 5 mL of suspension solution
were sampled and separated after 20 min intervals.The degradation efficiency is
calculated based on the changes of absorbance MB at 664 nm (or LEV at 294 nm ).
2.4 Analysis of reactive species
Photo-induced active radical trapping experiments were carried out to measure
the reactive species during the photo-degradation MB process. The isopropanol (IPA),
bromic acid potassium (KBrO3), benzoquinone (BZQ) and disodium
ethylenediaminetetraacetate (EDTA-2Na) are served as the hydroxyl radical (•OH),
electron (e-), superoxide radical (•O2−) and hole (h+) scavenger, respectively. The
dosage of scavenger (concentration) was 0.01 times of MB[39-41].

3. Results and discussion

3.1. Structure and properties characterization

The XRD results of BiOI, BG-1, BG-2 GO and Graphite were presented in Fig.2. A
series of characteristic peaks of BiOI at around 2θ of 24.3°, 29.7°, 31.8°, 45.8° and
55.3° are related to the reflection of (0 1 1), (0 1 2), (1 1 0), (2 0 0), and (2 1 2) planes
of BiOI, in accordance with the typical tetragonal structure (JCPDS-ICDD No. 73-
2062). These peaks are sharp and intense, indicating the well crystallized structure of
4
BiOI microspheres. All of them (BG-1, BG-2 and BiOI) match perfectly with it. As
for GO sheet, the XRD pattern shows that, the diffraction peak at 10.8° (2θ) is
observed, which is assigned to the (0 0 1) planes of GO [37]. As shown in Fig. 2b, no
characteristic peaks of GO are detected own to low content of GO and weak peaks of
nanocrystals. It also illustrates that rGO has few influences on the phase structure and
crystallinity of BiOI [4].
The morphologies information of BG-1 and BG-2 were revealed in SEM and
TEM images (Fig. 3). The graphene is smooth with lamellar structure and the BiOI
microspheres have a spherical shape with a rough surface and a relative uniform grain
size of around 1 μm in diameter, as shown in Fig. 3a. Fig. 3c displays that the BiOI
sample indicates the similar result as the SEM. As revealed in Fig. 3b, the as-acquired
BiOI block are homodispersed on the elegant graphene sheets with heterogeneous
nanoplates, and the BiOI nanoplates with a thickness of approximately 20 nm (inset in
Fig. 3b), which consisting with the results from TEM (Fig. 3d). The morphology of
the BG-2 composite is further observed by magnification (inset in Fig. 3b). Further
observation shows that it’s the role of microwave, so BiOI is no longer separated in
the microsphere. The clear diffraction rings (inset in Fig. 3d) reveals the
polycrystalline nature of tetragonal BiOI, and it agrees with the results of XRD. From
the HRTEM image(Fig. 3e), it showed that the lattice interlinear spacing is 0.286 nm,
corresponds to the (1 1 0) plane of BiOI.

The surface components and chemical states of BG-1 and BG-2 composites are
analyzed by XPS. The whole XPS spectrogram of the BG-1 and BG-2 composites can
be investigated in Fig. 4a. Bi, O, I and C are expectation in the samples. Fig. 4b
reveals the high-resolution XPS spectrogram of the Bi 4f. The peaks for the Bi 4f7/2
and Bi 4f5/2 are observed at 159.5 and 164.8 eV (binding energy) respectively [42],
which belong to of Bi3+ ion in BiOI compared to the standard data. As to the high-
resolution spectrogram of I 3d (Fig. 4c), two peaks with binding energy of 619.1 eV
and 630.7 are ascribed to I 3d5/2 and I 3d3/2 respectively, may be attributed to I− ion in
BG-1 and BG-2 [43].The O 1s wide peaks are fitted into two peaks associating with
the oxygen (529.4 eV, 530.4 eV) in the Bi-O bonds in [Bi2O2] of BiOX layered
structure and other components (531.3 eV,532.0 eV) like the water molecules,
hydroxyl groups on the surface of the composites [24] (Fig. 4d). The C 1s of GO (Fig.
4f) can be fitted into two peaks, which own the binding energy at 284.6 eV (C-C) and
287.0 eV (C-O). As to the BG-1 and BG-2 (Fig. 4e), the peak of C-O is significantly
weaken. Compared to the ratio of C-O and C-C, GO was higher than BG-1and BG-2,
indicating the BG-1 and BG-2 had more thermal reduction of the C-O group and
combined with rGO perfectly.
\The optical properties of the samples were studied via the UV-vis diffuse
reflectance.It could be observed in Fig. 5 that the BG-1 and BG-2 samples showed an
increased absorption in visible light range and two composite samples showed an
obvious red-shift relative to the pure BiOI sample in Fig. 5a. And the band gap
energy of them could be calculated from Kubelka-Munk equation (Fig. 5b) [5]. The
reaults are written in Table 1.

5
 The porous structure and BET surface areas of the BG-1 and BG-2 composites
and pristine BiOI are investigated by N2 adsorption-desorption. As showed in Fig. 6,
the pore size distributions (Fig. 6a) of the composites exhibit broader pore size
distribution from 2 nm to 10 nm, further proving the existing of micropore. The
isotherm of BiOI and BG-1 and BG-2 composites exhibited type IV with a H3
hysteresis loop (Fig. 6b), which suggesting the presence of meso-porous in materials
[37]. Table 1 reveals the specific surface areas. It can be observed that BG-1 and BG-
2 composites have larger specific surface areas comparing to that of undoped BiOI,
that is way the BG-1 and BG-2 composites owned higher photocatalytic performance.

Raman spectrum is an available tool to analyze graphene and graphen-based

materials, primarily for identifying defects and disordered structures[44]. As showed
in the Raman spectra (Fig. 7a) of GO, two characteristic bands of GO could be seen at
1590 cm-1 (G band) and 1354cm-1 (D band) [7]. The D band is assigned to disorders
sp2 carbon, and the G band is usually attributed to the E2g phonon of sp2 bonds of
carbon atoms [24]. Significantly, the two characteristic peaks of GO are observed in
the Raman spectrogram of BG-2, which indicate the existence of GO in composites.
The change in Raman shifts in BG-1 and BG-2 composite shows a strong interaction
between the GO and BiOI matrix[24]. In comparison with pure GO, the BG-1 and
BG-2 samples have an increased ID/IG intensity ratio. This change suggests the
existence of graphene sheets in the BG-1 and BG-2 composites[26, 45-47] , Cai [45]
had the same result with us. Fig. 7b shows the FT-IR spectra of acquired samples. the
FT-IR spectrum exhibits peaks at 3410 cm-1, 1560 cm-1, 1404 cm-1 and 1045 cm-1,
corresponding to -OH in hydroxyl and carboxyl, C=C, O-H and C-O[37]. Compared
to spectrum of GO, the BG-1 and BG-2 composites showed decreased peaks intensity
at C-OH (3410 cm-1, 1404 cm-1), C-O (1045 cm-1), C=O (1730 cm-1), indicating that
GO can be successfully reduced by microwave hydrothermal process.
To determine the amount of GO introduced in the BiOI/rGO composites, the
thermalgravim and differential thermal analysis (TG-DTA) were conducted from 25
to 1000 ℃. As shown in Fig.8, the TG-DTA of three samples show obviously weight
lost. By comparing the TG-DTA of three samples, it may be deduced that the weight
drop from 300 to 440℃ corresponding the decomposition of rGO[45]. The contents
of rGO in BG-1 and BG-2 are almost the same, being 14.5% and 15.3%, respectively.
The results is close to their theoretical content 10%(GO). These results testify again
that the BiOI/rGO composite has been acquired successfully.

PL spectrum can be applied to investigate the transfer and recombination process

of photoexcited electron–hole pairs for semiconductors [46-49]. The PL spectra of
BiOI, BG-1 and BG-2 samples are depicted in Fig. 9a，which measured under the
excitation of 450 nm. As can be seen in Fig. 9, the intensities of BG-1 and BG-2 are
obviously reduced in comparison with BiOI, and the BG-2 has the lowest PL emission
intensity. It suggests that the presence of GO can effectively enhance charge transfer
ability and lower the recombination probability of e-h+ pairs, and thus promoting their
lifetime. The photocurrent response and electrochemical impedance spectra (EIS)
were record to affirm the promoted charge transfer efficiency, the result was shown in
the Fig. 9b and Fig. 9c. Fig.9b shows the transient photocurrent response for as-
6
prepared different composite photocatalysts. All the photocatalysts display reversible
photocurrent response with light on-off. Among then, BG-2 exhibits the stronger
photocurrent intensity than that of BG-1. The EIS curve was shown in the Fig. 9c, it
can be found that BG-2 shows the smallest simicircle among three samples in the EIS
Nynquist plots. The smaller the arc simicircle is, the faster the interfacial charge
transfers. This results from the photoelectrochemical measurements are in accord with
with photophotocatalytic experiments, which reveal that photo-generated electron and
hole pairs transfer and separation efficiency is primarily crucial to the photocatalytic
activity of these as-prepared photocatalysts.

3.2. Photocatalytic activity

Photo degradation of MB tests have carried out under visible light to observe the
photocatalytic activity of different materials. The rGO was found to have a
remarkable influence on the absorption efficiency. The blank test indicates that it have
few degradation under visible light irradiation without photocatalysts (Fig. 10a). The
result suggests that these contaminants are relatively stable in the test environment.
Fig. 10a reveals the variation of MB concentration against illumination time over
different composites. Under visible light, BiOI, P25, BG-1 and BG-2 can remove 43%,
6%, 37% and 68% of MB in 2 h, respectively. It’s found easily that the photocatalytic
composites made better performances than commodity P25. In Fig. 10b, the same
results can be found that the photodegradation of LEV in the presence of over BG-2
displays much better activity than pristine BiOI, BG-2 and P25. The Fig. 10c and 10d
reveal that the photodegradation process over all the catalysts follows pseudo-first-
order kinetics. The results are summarized in Table 2. The rate constant for BG-2 to
decompose MB is two times as large as pristine BiOI(in table 2). To further
investigate the rGO amounts in the composites affecting the photocatalytic activity,
the rGO amounts in the composites have been modified form 3%,10%,15% and 20%
in BG-2 sample. Fig. 10e shows the changes of MB degradation rate against
irradiation time over different catalysts. The photocatalytic activity of BG-2
composite is found to be related with the content of GO. Obviously, the BG-2(10%)
exhibits the highest MB removal. The repeated photocatalysis of BG-2 was
investigated relative to MB degradation for five times. The degradation activity of
MB at different recycle times was shown in Fig. 10f. The results showed that BG-2
was rather stable and after five times recycling remained about 50%.
3.3. Photocatalytic mechanism
Why the same composite owned different photocatalytic performance? BG-2 not
possessed the biggest specific surface area and the least band gap, but it had more
thermal reduction of the C-O group indicating it combined with rGO perfectly from
XPS. Therefore, we should explore the causes in essence.
Be widely known, in the photocatalytic processes, reactive species are the prime
participants during organic compound degradation process. When BiOI is illuminated
by visible light, electrons-holes pairs are produced, which could rapidly recombine.
The residual impactful holes (h+) could directly take part in the oxidation process for
organic compound, meanwhile the other reactive species formed via electrons (e−)
may also oxidize contaminants [5,8]. So analyzing reactive species is important to
explore the photocatalytic process mechanism.
7
 Degradation efficiency of MB under these scavengers is displayed in Fig. 11. The
degradation rate of MB which adds different scavenger has been written in the Table
3 (use the formula (1)). It can be influenced that the photo-degradation was affected
by IPA, EDTA-2Na, KBrO3 and BZQ for both BiOI and BG-1 composites, indicating
that •OH, h+, e− and •O2− are used for the degradation. The organic pollutants could
be impactful oxidize via these radicals to water and carbon dioxide. What's more, the
photo-degradation of MB shows an obvious decrease after adding EDTA-Na2. This
indicates that h+ was the primary active specie for the BiOI and BG-1. The probable
photocatalytic mechanism is that the holes created in the VB are caused from the
exciting of electron from VB to the CB under visible light illumination. Then the
photo-generated electrons of BG-1 can transfer from the CB to the graphene in virtue
of the good fluidity performance. During this process, activated •O2− can be quickly
formed on the surface of graphene, which generates form the photo-generated
electrons transfer to surface absorbed oxygen. Meanwhile, hydroxyl radical(•OH)
can be also quickly formed, which rise from the holes accumulated at the VB reacting
with surface adsorbed H2O or OH− [16]. For pure BiOI catalyst, without the addition
of graphenea, the photo-generated charge carriers will recombinate rapidly, so the
photocatalytic activity is not better than BG-1.
But photocatalytic mechanism of BG-2 is not similar to the above photocatalysts.
While when IPA and BZQ was added, the photo-degradation of MB showed a little
increase, that could be caused by the fact that when •OH and •O2− is captured by IPA
and BZQ, more h+ and e- can participant in the photodegradation reaction and the
degradation efficiency is enhanced. The possible mechanism of BG-2 can be
explained as follows (Fig. 12)[50-53]. Wang[54] had the similar experimental
phenomena with us in their literature.

4. Conclusions

According to the experimental results, the most significant conclusions can be

combined and summarized as follows:
1. BG-1 and BG-2 were obtained by a simple chemical mechanical and one-step
rapid microwave hydrothermal route respectively.
2. BG-2 composite exhibits a higher visible light photodegradtion efficiency and
adsorption ability than BG-1 and BiOI for methyl bule(MB) and levofloxacin (LEV),
which is about 1.6 times and 7.3 times compared to that of the BiOI. In the
photocatalytic mechanism study, the photo-degradation is dominant by the h+
oxidation process.
3. Based on the characterization results, the BG-2 provided high
photodegradation performance was ascribed to the special morphology and larger
specific surface area of BiOI for more effective charge transportation and separations.
It is suggested that this study may provide a new strategy for the design of different
morphology of high–performace photocatalyst via microwave hydrothermal method.
8
Acknowledgement

We gratefully acknowledge the National Natural Science Foundation of China

(No.21576220), Shaanxi Natural Science Foundation(No. 2017JQ2033), Natural
Science Foundation of Shaanxi Provincial Department of Education (No.16JK1546),
International Science Technology Cooperation Program of China
(2015DFR50350),the Innovation of Science and Technology Foundation from Xi’an
University of Technology(No.2016CX014), and Starting and Innovation Team
Foundation of Xi’an University of Technology.

9
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14
Fig. 1. Illustration of the preparation method of BG-2

Fig. 2. XRD patterns of (a) GO and Graphite, (b) BiOI, BG-1 and BG-2.

15
Fig. 3. SEM images of (a) BG-1, (b) BG-2, TEM images of (c) BG-1, (d) BG-2 (inset: selected area electron
diffraction pattern) and (e) HRTEM of BG-2.

16
Fig. 4. XPS spectrogram of BG-1 and BG-2: (a) survey spectrum, (b) Bi 4f, (c) I 3d, (d) O 1s, (e) C 1s; (f) C 1s
XPS spectra of GO.

Fig. 5. (a) DRS spectra of BiOI, BG-1 and BG-2 and (b)Kubelka-Munk transformation for as-synthesized samples.

17
Fig. 6. BJH pore size distribution curve of the (a) as-synthesized composites and (b) The Nitrogen adsorption-
desorption isotherm.

18
Fig. 7. (a) Raman spectrogram ;(b) FT-IR spectrogram of GO, BG-1 and BG-2 composites.

19
Fig. 8. TG-DTA curve of different samples (25 to 1000 ℃ under air atmosphere) (a)BiOI;(b) BG-1 and(c)BG-2.

20
Fig. 9. (a) PL spectra of BiOI, BG-1 and BG-2 samples ;(b) Transient photocurrent response of the sample
electrodes of BG-1 and BG-2 composites; (c) EIS Nyquist plots of BiOI, BG-1 and BG-2.

21
Fig. 10 Photocatalytic activity of different composites toward (a) MB and (b) LEV degradation, kinetics of (c) MB
and (d) LEV degradation for different photocatalyst,(e) photocatalytic activity of BG-2 with different GO contents
on the degradation of MB, (f) recycling test of BG-2 in photodegradation of MB (all the experiment under visible
light irradiation).

22
Fig. 11. The histograms of different trapping agents on photocatalytic reaction effect about BiOI, BG-1 and BG-2

Fig. 12. Photocatalytic mechanism of BG-2 composites.

23
Table 1 Textural parameters and band gaps of as-obtained composite.

Sample SBET (m2/ g) Pore volume Average pore size Band gap
(cm3/g) (nm) Eg (eV)
BG -1 36.101 0.063 6.432 2.21
BG-2 45.572 0.193 5.364 1.58
BiOI 32.212 0.169 5.208 2.31

24
Table 2 Parameters of Pseudo first-order kinetic model of the photocatalytic degradation of MB and LEV

MB LEV
Catalysts η(%) η(%)
k (min-1) k (min-1)
P25 0.00006 6 0.00148 18
BiOI 0.00479 43 0.00104 7
BG-1 0.00242 37 0.00065 8
BG-2 0.00921 68 0.00612 51

25
Table 3 The different degradation rates of MB.

Catalyst Blank (%) •OH (%) h+ (%) e− (%) •O2−

BiOI 43.2 31.7 19.2 37.9% 24.0
BG-1 37.3 19.4 15.8 17.5% 23.5
BG-2 67.6 81.3 46.0 56.6% 78.2

26