Separation and Purification Technology 142 (2015) 25–32

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Separation and Purification Technology

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

Visible light-driven Bi2Sn2O7/reduced graphene oxide nanocomposite

for efficient photocatalytic degradation of organic contaminants
Hong Liu ⇑, Zhitong Jin, Yun Su, Yong Wang ⇑
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai 200444, PR China

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

Article history: In this work, a novel Bi2Sn2O7/reduced graphene oxide (RGO) nanocomposite was synthesized by a one-
Received 27 August 2014 step hydrothermal method. The prepared composite was characterized by means of powder X-ray dif-
Received in revised form 26 December 2014 fraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron micros-
Accepted 26 December 2014
copy (HRTEM), energy-dispersive X-ray spectrometry (EDS), Raman spectroscopy, X-ray photoelectron
Available online 8 January 2015
spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) emission
spectroscopy and electrochemical impedance spectroscopy (EIS). The photocatalytic activity of the Bi2-
Keywords:
Sn2O7/RGO composite was investigated by the degradation of rhodamine B (RhB) and phenol. An increase
Bi2Sn2O7
Graphene
in photocatalytic activity was observed for Bi2Sn2O7/RGO composite compared with pure Bi2Sn2O7 under
Photocatalysis visible light. The enhanced photocatalytic performance of the composite was mainly ascribed to the more
Visible light effective charge separations and the excellent adsorption capacity of RGO. The composite maintained its
Degradation ability to degrade pollutants efficiently, even after 4 cycles of photocatalysis. Further study proved that
both the holes and hydroxyl radicals were the active species in the degradation process.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction et al. [13] synthesized nano-Bi2Sn2O7 by a hydrothermal method

Photocatalysis has attracted worldwide attention because of its
potential applications in water splitting and the degradation of
organic compounds, and TiO2 is the most studied semiconductor
photocatalyst because of its high photocatalytic activity, low cost,
non-toxicity, and chemical stability [1–4]. However, its large band
gap (3.2 eV for anatase) determined that it was only active under
ultraviolet (UV) light irradiation. To take sufficient advantage of
solar energy, the development of photocatalysts capable of photo-
induced charge separation upon excitation in the visible spectral
region is emerging as an important research direction in this field
[5–9].
Bi2Sn2O7, a novel semiconducting material with a typical pyroch-
lore structure and a band gap of 2.5–2.8 eV, has received consider-
able attention in catalysis and gas sensors in recent years [10–12].
The crystal structure of Bi2Sn2O7 is constructed of octahedral SnO6,
and these octahedra connect to each other by sharing vertexes. A
network of corner-shared octahedra can facilitate the mobility of
the charged carriers, which may make Bi2Sn2O7 an efficient visible
light-driven photocatalytic material [13–15]. Very recently, Wu
⇑ Corresponding authors. Tel.: +86 21 66137487; fax: +86 21 66137725.
E-mail addresses: liuhong@shu.edu.cn (H. Liu), yongwang@shu.edu.cn (Y.
Wang).
and studied its photocatalytic activity in the degradation of methyl
orange. Tian et al. [14] reported the synthesis of Bi2Sn2O7 and its
application in photocatalytic removal of As (III). Xu et al. [15]
reported the photocatalytic activity of Bi2Sn2O7 in the degradation
of rhodamine B (RhB) under visible light irradiation. However, the
photocatalytic efficiency of individually Bi2Sn2O7 was relatively
very low. For practical use, the photocatalytic performance of
Bi2Sn2O7 should be further improved.
Combination of different types of carbon with semiconductor
has been suggested as a promising method for an enhanced photo-
catalytic performance [16–19]. In the past few years, graphene as a
novel carbonaceous nanomaterial has attracted more and more
interests due to its large specific surface area, remarkable electrical
conductivity, excellent adsorptivity, and high chemical and thermal
stability [17–19]. Furthermore, graphene can be easily produced at
a low cost from natural graphite through chemical oxidation–
dispersion–reduction procedures. Efforts have been made to com-
bine semiconductor and graphene or reduced graphene oxide
(RGO) to obtain hybrid materials with superior photocatalytic per-
formance [20–29]. For example, significant improvement has been
reported for metal oxides [22–26], metal sulfides [27,28], and non-
metal g-C3N4 [29] by using graphene (or RGO) as a synergistic cat-
alyst material. If Bi2Sn2O7 is coupled with graphene, it is possible to
improve the efficiency of photoinduced charge separation, leading

http://dx.doi.org/10.1016/j.seppur.2014.12.027
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.
26 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32
to high photocatalytic performance. However, to the best of our
knowledge, there is no report on the design and fabrication of cou-
pled Bi2Sn2O7/graphene heterostructure so far.
In this paper, a novel Bi2Sn2O7/RGO composite has been synthe-
sized by a one-step hydrothermal method for the first time. The pre-
pared sample was characterized, and the photocatalytic activity
under visible light irradiation (k > 420 nm) was evaluated by the
degradation of RhB and phenol. The result revealed that the Bi2Sn2-
O7/RGO composite exhibited an enchenced photocatalytic activity
in comparison with bare Bi2Sn2O7. The obtained Bi2Sn2O7/RGO pho-
tocatalyst displayed good cycling stability under visible light. Fur-
thermore, the mechanism of enhanced photocatalytic activity as
well as the main active oxygen species in the photocatalytic reaction
process was also investigated.
2. Materials and methods
2.1. Preparation of Bi2Sn2O7/RGO composite
All the chemicals were of analytical grade from the Sinopharm
Chemical Reagent Co., Ltd. Graphene oxide (GO) was prepared by
a modified Hummers method [30]. The Bi2Sn2O7/RGO composite
was prepared by a one-pot hydrothermal method. In a typical syn-
thesis, 0.73 g Bi(NO3)3
5H2O and 0.45 g K2SnO3
3H2O were added
into 50 mL of deionized water. Under vigorous stirring, the pH
value of the mixture was adjusted to 12 by using NaOH solution.
Meanwhile, 0.1 g GO was dispersed in 20 mL ethanol by sonication
for 1 h to get a homogenous suspension of exfoliated graphene
oxide. Then, the obtained GO solution was added to the reacted-
mixture gradually. After stirring continuously for 2 h at room tem-
perature, the mixture was transferred into a Teflon-lined autoclave
with a volume of 100 mL. Then, the autoclave was sealed, heated
under autogenous pressure at 180 °C for 24 h, and then cooled
down to room temperature naturally. The resulting precipitate
was filtrated, washed thoroughly, and vacuum dried at 60 °C over-
night. For comparison, pure Bi2Sn2O7 was prepared by using the
same method without the addition of GO.
2.2. Characterization
The crystalline phases of prepared samples were identified by
X-ray diffraction (XRD) on a D/MAX-2550 at 40 kV and 40 mA with
Cu Ka radiation (k = 0.15418 nm). Structure and morphology of as
prepared samples were evaluated by TEM (200CX) and HRTEM
(JEM-2010F). Raman spectra were recorded on a microscopic con-
focal Raman spectrometer (Renishaw, INVIA) with an excitation of
514.5 nm laser light. UV–vis diffuse reflectance spectra (DRS) of the
samples were obtained on an UV–vis spectrophotometer (Hitachi
U-3010) using BaSO4 as a reference. The photoluminescence (PL)
spectra were measured using a Hitachi F-7000 fluorescence spec-
trophotometer at room temperature. Electrochemical impedance
spectroscopy (EIS) measurements were performed on a CHI660E
electrochemical workstation in a standard three-electrode system
using the prepared samples as the working electrodes, a platinum
wire as the counter electrode, and an Ag/AgCl (saturated KCl) elec-
trode as the reference electrode over the frequency range from
0.01 Hz to 106 Hz. Na2SO4 (1 M) aqueous solution was used as
the electrolyte. The working electrodes were prepared as follows:
0.08 g of photocatalyst was grinded with 0.01 g of polytetrafluoro-
ethylene (PTFE), 0.01 g of carbon black and 2 mL of isopropanol to
produce a slurry. The slurry was then coated onto a 1 cm  1.5 cm
titanium mesh electrode by the doctor blade method. Next, the
resulting electrodes were dried in vacuum at 60 °C for 24 h. All
electrodes studied had a similar film thickness.
2.3. Photocatalytic activity test
The photocatalytic activity of the as-prepared photocatalyst
was estimated by monitoring the degradation of RhB and phenol
in an aqueous solution under visible light irradiation. The reaction
was performed in a photochemical reactor (BL-GHX-V, Shanghai
Bilon Instruments Co., Ltd., China), equipped with a 500 W Xe lamp
combined with a 420 nm cut-off filter as a light source. All exper-
iments were conducted at room temperature in air. In a typical
photocatalytic experiment, 0.05 g of the photocatalyst was added
into 50 ml of 10 mg/L pollutant solution in a reaction cell with a
Pyrex jacket. Prior to irradiation, the suspension was magnetically
stirred in the dark for 1 h to reach an adsorption–desorption equi-
librium. Then, the suspension was exposed to visible light irradia-
tion under magnetic stirring. At given time intervals, about 5 ml
suspensions were collected and centrifuged (12,000 rpm, 6 min)
to remove the photocatalyst particles. Then, the pollutant concen-
tration of the obtained solution was analyzed by a UV–vis spectro-
photometer (Hitachi, U-3310) by checking the absorbance at
553 nm and 270 nm for RhB and phenol, respectively. To probe
the oxidizing species in the photocatalytic process, the disodium
ethylenediamine tetraacetate (EDTA-2Na), tert-butyl alcohol (t-
BuOH), or benzoquinone (BQ), was added in the solution. The con-
centrations of the quenching chemicals were at 1 mM.
3. Results and discussion
3.1. Structure and properties characterization
The XRD patterns of the pristine Bi2Sn2O7 and Bi2Sn2O7/RGO
composite are shown in Fig. 1. The XRD of Bi2Sn2O7 shows several
strong peaks at 2h = 28.8°, 33.4°, 47.9°, and 56.9°, which represent
the formation of a pure cubic phase of Bi2Sn2O7 (JCPDS No.
87-0284) [13,15]. It is found that the main diffraction peaks of
Bi2Sn2O7/RGO composite are similar to that of pristine Bi2Sn2O7,
and no apparent peaks of RGO are observed in the Bi2Sn2O7/RGO
composite, which might be due to the low amount of RGO
and relatively low diffraction intensity of RGO in the
composite. No apparent peaks of graphene oxide are observed in
the Bi2Sn2O7/RGO composite, indicating the successful reduction
of GO to RGO through the hydrothermal process.
The morphologies of the pristine Bi2Sn2O7 and Bi2Sn2O7/RGO
composite were investigated by TEM as shown in Fig. 2. Fig. 2a
shows that pure Bi2Sn2O7 is comprised of many irregular nano-
GO
Intensity (a. u.)
Bi2Sn2O7/RGO
Bi2Sn2O7
10 20 30 40 50 60 70 80
2 Theta (degree)
Fig. 1. XRD patterns of GO, Bi2Sn2O7 and Bi2Sn2O7/RGO.
 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32
particles with diameters ranging from 5 to 15 nm. From Fig. 2b, it
can be clearly observed that the RGO sheets are decorated by
irregular Bi2Sn2O7 nanoparticles, which confirmed the successful
attachment of Bi2Sn2O7 nanoparticles to RGO sheets. The HRTEM
image shows the characteristic lattice fringes of Bi2Sn2O7 in the
RGO nanosheets matrix (Fig. 2c). The lattice spacing is about
0.310 nm, which can be assigned to the (2 2 2) plane of cubic
Bi2Sn2O7 [13]. Fig. 2c also reveals the intimate contact between
Bi2Sn2O7 nanoparticles and RGO. This intimate contact is in
favour of the electronic interaction between Bi2Sn2O7 and
RGO and improves the charge separation and the photocatalytic
activity. The EDS spectrum of Bi2Sn2O7/RGO (Fig. 2d) exhibits
the presence of Bi, Sn, O and C elements.
The X-ray photoelectron spectroscopy (XPS) was used to evalu-
ate the surface elemental compositions of Bi2Sn2O7 and Bi2Sn2O7/
RGO. The survey XPS spectra (Fig. 3a) reveal that both Bi2Sn2O7
and Bi2Sn2O7/RGO are composed of Bi, Sn, O and C, which is in good
agreement with the EDS results. The Bi 4f XPS spectra in Fig. 3b
shows that the binding energies of Bi 4f7/2 and Bi 4f5/2 for Bi2Sn2O7
occur at 158.8 and 164.2 eV, respectively, which are indicative of
Bi3+ in Bi2Sn2O7 [8,9,20]. The Sn 3d spectrum of Bi2Sn2O7 (Fig. 3c)
shows two peaks at 486.7 and 495.0 eV, indicating the presence of
Sn4+ [31]. The peaks corresponding to Bi 4f and Sn 3d in the XPS
spectra of the as-prepared Bi2Sn2O7/RGO composite slightly shift
toward higher binding energies as compared to pure Bi2Sn2O7. This
kind of shift in XPS measurement indicates that there is a strong
interaction between Bi2Sn2O7 and RGO sheets in the nanohybrid
[32,33]. The intense interaction may result in the formation of elec-
tron transfer channel, which is beneficial to the improvement of
(a)
(c)
Fig. 2. TEM images of Bi2Sn2O7 (a) and Bi2Sn2O7/RGO (b), HRTEM image of Bi2Sn2O7/RGO (c) and EDS spectrum of Bi2Sn2O7/RGO (d).
27
photoinduced charge separation rate during the photocatalytic pro-
cess [33]. In addition, the high-resolution spectra in Fig. 3d shows
that the peak binding energies of 530.4 eV is assigned to O 1s [34].
The XPS spectrum of C1s from GO (Fig. 3e) can be deconvoluted into
three smaller peaks, which are ascribed to the following functional
groups: sp2 bonded carbon (CAC, 284.8 eV), epoxy/hydroxyls (CAO,
286.8 eV), and carboxyl (OAC@O, 288.8 eV) [35], indicating the high
percentage of oxygen-containing functional groups. In Fig. 3f,
although the three types of carbon species can still be seen in the
Bi2Sn2O7/RGO composite, the XPS peaks corresponding to CAO
and OAC@O are severely weakened in comparison to Fig. 3e, indi-
cating that GO has been highly reduced during the hydrothermal
synthesis. Besides, no any peak corresponding to the BiAC bond
(at 281.2 eV in C 1s spectrum [36]) is observed, suggesting no car-
bon doping in the lattice of Bi2Sn2O7.
The Raman spectra of GO and Bi2Sn2O7/RGO are presented in
Fig. 4. In Raman spectra, both samples exhibit two strong peaks,
denoted as the disorder peak (D, centered at 1359 cm 1) and the
graphitic peak (G, at 1606 cm 1) [37,38]. Compared with GO,
Bi2Sn2O7/RGO displays an increased D/G intensity ratio, indicating
the presence of localized sp3 defects within the sp2 carbon network
upon reduction of the exfoliated GO [39].
The UV–vis diffuse reflectance spectra of the synthesized sam-
ples are shown in Fig. 5a. Compared to pure Bi2Sn2O7, Bi2Sn2O7/
RGO composite shows an increased absorption in both UV and vis-
ible range and an obvious red-shift in the absorption edge, which
can be attributed to the presence of carbon in the composites,
reducing reflection of light [22,40]. Similar phenomenon has been
noted in previous studies [3,9,20,27,40,41]. The band gap energy
(b)
(d)
Cu
Itensity (a.u.)
C Bi
Sn
O Sn Cu Bi Bi
0 2 4 6 8 10 12 14
Energy (keV)
28 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32

Sn 3d
(a) Survey (b) Bi 4f
Bi 4f7/2

Bi 4f
O 1s
Bi 4f5/2

Sn 3p
Sn 3p
Sn

Bi 4d
Sn 3s

Bi 4p

Intensity (a. u.)

Intensity (a. u.)

Bi 4d
O

C 1s

O 2s
Bi 5d
Bi2Sn2O7

Bi2Sn2O7

Bi2Sn2O7/RGO
Bi2Sn2O7/RGO

1000 800 600 400 200 0 168 166 164 162 160 158 156 154
Binding energy (eV) Binding energy (eV)

(c) Sn 3d (d) O 1s
Sn 3d5/2
Sn 3d3/2

Intensity (a. u.)

Intensity (a. u.)

Bi2Sn2O7
Bi2Sn2O
7

Bi2Sn2O7/RGO
Bi2Sn2O /RGO
7

500 498 496 494 492 490 488 486 484 482 540 538 536 534 532 530 528 526 524
Binding energy (eV) Binding energy (eV)

(e) C 1s C-O (f) C 1s

Intensity (a. u.)

C-C
Intensity (a. u.)

C-C

O-C=O
O-C=O O-C

292 29 0 28 8 28 6 28 4 282 292 290 288 286 284 282

Binding energy (eV) Binding energy (eV)
Fig. 3. XPS spectra of Bi2Sn2O7 and Bi2Sn2O7/RGO: (a) survey, (b) Bi 4f, (c) Sn 3d, (d) O 1s, (e) C 1s of GO, and (f) C 1s of Bi2Sn2O7/RGO.

can be estimated by the following formula: a h m = A(h m–Eg)n/2,
where a, h, m, Eg, and A are the absorption coefficient, Planck con-
stant, the light frequency, the band gap, and a constant, respec-
tively. And n is the electron transitions depending on the
semiconductor characteristics (direct transition n = 1 and indirect
transition n = 4). For Bi2Sn2O7, the value of n is 4 for the indirect
transition [13]. Fig. 5b plots the relationship of (a h m)1/2 versus
photon energy (h m), and shows that the bandgap energy of pure
Bi2Sn2O7 is 2.48 eV, whereas this value is reduced to 1.85 eV by
decorating with RGO. This phenomenon is possibly ascribed to
the interaction between Bi2Sn2O7 and RGO [3,20,22,29], which
has been evidenced by XPS analysis as described above.
3.2. Photocatalytic activity
The photoactivity of the Bi2Sn2O7/RGO composite was evalu-
ated by photocatalytic degradation of RhB and phenol under visible
light irradiation, and the results are shown in Fig. 6. It can be seen
that both RhB and phenol are very stable under visible light irradi-
ation without the catalyst. Fig. 6a shows that the RhB removal rate
is about 95.8% after irradiation for 125 min in the presence of Bi2-
Sn2O7/RGO composite, while the value of pristine Bi2Sn2O7 is only
83.7%. Meanwhile, the degradation rate of phenol on Bi2Sn2O7/RGO
composite reaches 81.1% after irradiation for 200 min, whereas
only 64.4% of phenol is removed by pristine Bi2Sn2O7 after same
 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32 29

Table 1
Pseudo first-order rate constants of the photocatalytic decomposition of different
pollutants.
G Catalyst RhB Phenol
D
1
k (h ) R2 k (h 1
) R2
GO
Intensity (a. u.)

ID/IG= 0.667 Bi2Sn2O7 0.8382 0.9777 0.3093 0.9976

Bi2Sn2O7/RGO 1.5350 0.9872 0.5146 0.9907

Bi2Sn2O7/RGO
800 1200
Raman
Fig. 4. Raman spectra of the Bi2Sn2O7/RGO composite and GO.
irradiation time (Fig. 6b). These results indicate clearly that the
introduction of RGO can enhance the photocatalytic performance
of Bi2Sn2O7. Notably, the photocatalytic activity of the obtained Bi2-
Sn2O7/RGO composite on the degradation of organic pollutant RhB
and phenol is higher than the Bi2Sn2O7-based materials reported
previously [42,43]. These photocatalytic properties are also better
than various graphene-based composites [20,28,44–52]. For
detailed analysis the photocatalysis kinetics of the pollutants deg-
radation, the pseudo-first order model was applied. This model is
generally used for photocatalytic degradation process if the initial
concentration of pollutant is low [53]. The rate constants were
evaluated from the data plotted in Fig. 6a and b and summarized
ID/IG= 0.924 in Table 1. The rate constant for Bi2Sn2O7/RGO composite to
remove RhB is 1.54 h 1, which is 1.83 times as large as that of
pristine Bi2Sn2O7 (0.8382 h 1). This value for the composite is also
1.66 times larger than pristine Bi2Sn2O7 for the degradation of
phenol.
1600 2000
In addition to photocatalytic activity, the stability of photocata-
Shift (cm-1) lysts is another important issue for their practical applications. To
confirm the stability of the Bi2Sn2O7/RGO photocatalyst, the circu-
lating runs in the photocatalytic degradation of RhB and phenol in
the presence of Bi2Sn2O7/RGO under visible-light was checked. In
the work, Bi2Sn2O7/RGO was recycled for four times in the same
photocatalytic reactions. After each reuse cycle which lasted for
125 min (for degradation of RhB) or 200 min (for degradation of
phenol), the photocatalyst was separated from the aqueous sus-
pension by filtration, washed with deionized water and ethanol,
dried, and weighed for the next reuse cycle. It can be seen from
Fig. 7, after four recycles for the photodegradation of RhB and phe-
nol, the catalyst do not exhibit any significant loss of activity, indi-
cating the good stability of the Bi2Sn2O7/RGO composite during
photocatalytic degradation of model pollutant.

(b) 3.0
(a) 1.6
2.5 Bi2Sn2O7/RGO
Adsorbance (a.u.)

1.2
2.0
(αhν)1/2

0.8 1.5
Bi2Sn2O7/RGO 1.0 Bi2Sn2O7
0.4 Bi2Sn2O7
0.5

0.0 0.0
200 300 400 500 600 700 800 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Wavelength (nm) Photo energy (eV)
Fig. 5. (a) UV–vis spectra of Bi2Sn2O7 and Bi2Sn2O7/RGO composite and (b) plots of the (a h m)1/2 versus photon energy (h m) for as-synthesized samples.

(a) 1.0 (b) 1.0

Bi2Sn2O7
0.8 0.8
Bi2Sn2O7 Bi2Sn2O7/RGO
0.6 Bi2Sn2O7/RGO blank
0.6
C/C0

C/C0

blank
0.4
0.4
0.2
0.2
0.0
0 25 50 75 100 125 0 40 80 120 160 200
Time (min) Time (min)
Fig. 6. Photocatalytic activities of as-prepared samples on the degradation of RhB (a) and phenol (b) under visible-light irradiation.
30 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32

(a) 1.0 1.00

1 st run 2 nd run 3 rd run 4 th run
0.8 Bi2Sn2O7
0.96
Bi2Sn2O7/RGO
0.6
C/C0

0.92
0.4

C/C0
0.2 0.88

0.0
0 125 125 125 125
0.84
Time (min)
0 10 20 30 40 50 60
(b) 1.0
1 st run 2 nd run 3 rd run 4 th run Time (min)
0.8 Fig. 9. Absorption activities of Bi2Sn2O7 and Bi2Sn2O7/RGO.

0.6
C/C0

implying that the recombination of photogenerated electrons and

0.4
0.2
0.0
0 200 200
Time (min)
Fig. 7. The cyclic test of as-prepared Bi2Sn2O7/RGO composite on the degradation of
RhB (a) and phenol (b).
3.3. Mechanism on enhancement of photocatalytic activity
The photocatalytic activity of semiconductors is closely related
with the recombination rate of the photoinduced electrons and
holes. To investigate the efficiency of charge carrier trapping,
migration, and transfer in the as-prepared Bi2Sn2O7 and Bi2Sn2O7/
RGO, the photoluminescence (PL) emission spectra of these sam-
ples were measured. Fig. 8a presents PL emission spectra of pure
Bi2Sn2O7 and Bi2Sn2O7/RGO photocatalyst monitored at an excita-
tion wavelength of 350 nm. It can be seen that the pure Bi2Sn2O7
shows a broad PL emission band, which is ascribed to lumines-
cence from localized surface states due to recombination of photo-
generated electron–hole pairs. The Bi2Sn2O7/RGO composite
exhibits a much lower emission intensity than pure Bi2Sn2O7,
holes is inhibited greatly in the Bi2Sn2O7/RGO system. The
improved efficiency in inhibiting the recombination of photogener-
ated charge carriers of Bi2Sn2O7 by the use of RGO can be further
supported by the electrochemical impedance technique which is
a reliable way to characterize electrical conductivity. Fig. 8b shows
the electrochemical impedance spectra (EIS) of Bi2Sn2O7 and
200 200 Bi2Sn2O7/RGO. It is clear that the Bi2Sn2O7/RGO photocatalyst has
smaller arc as compared to the pristine Bi2Sn2O7, suggesting the
more efficient interfacial charge transfer over Bi2Sn2O7/RGO.
Graphene or RGO as a two-dimensional sheet of carbon atoms
has superior electrical conductivity, which would make it an excel-
lent electron-transport material in the process of photocatalysis.
The photogenerated electrons of excited Bi2Sn2O7 were transferred
instantly from the conduction band of Bi2Sn2O7 to RGO, resulting in
a minimized charge recombination and offering an enhanced
photocatalytic activity.
In addition, adsorption performance of the targeted substance is
also very important for the surface reaction. To evaluate the
adsorption ability of Bi2Sn2O7 and Bi2Sn2O7/RGO, the residue rate
of RhB after 60 min stirring in the dark was determined. As shown
in Fig. 9, the residue rate of RhB in the solution with Bi2Sn2O7 as the
adsorbent is 87.4%, whereas that of Bi2Sn2O7/RGO as the adsorbent
is 84.6%. It is obviously that the adsorption ability of Bi2Sn2O7 was
enhanced by introduction of RGO, which is also a prequisite for
good photocatalytic activity.
To understand the photocatalytic mechanism, the main active
oxidant in the photocatalytic reaction process should be identified.

50
(a) (b)
Relative intensity (a. u.)

40 Bi2Sn2O7
Bi2Sn2O7/RGO
-Z''(ohm)

Bi2Sn2O7
30

20

Bi2Sn2O7/RGO 10

0
380 400 420 440 460 480 500 520 540 560 580 10 15 20 25 30 35 40 45 50
Wavelength (nm) Z'(ohm)
Fig. 8. (a) PL spectra and (b) Nyquist impedance plots of Bi2Sn2O7 and Bi2Sn2O7/RGO composite.
 H. Liu et al. / Separation and Purification Technology 142 (2015) 25–32 31

(a) 1.0 (b) 1.0

0.8 Bi2Sn2O7/RGO 0.8

+ EDTA-2Na
0.6 + t-BuOH 0.6

C/C0
C/C0
+ BQ
0.4 0.4
Bi2Sn2O7/RGO
+ EDTA-2Na
0.2 0.2
+ t-BuOH
+ BQ
0.0 0.0
0 25 50 75 100 125 0 40 80 120 160 200
Time (min) Time (min)
Fig. 10. Photocatalytic degradation of RhB (a) and phenol (b) with the addition of hole and radical scavenger.

4. Conclusion

A novel Bi2Sn2O7/RGO photocatalyst has been synthesized via a

O2 - one-step hydrothermal method in this study. Under visible irradi-
e- · O2 Pollutants ation, the Bi2Sn2O7/RGO photocatalyst was found to exhibit higher
e- photocatalytic activities than pure Bi2Sn2O7 in the degradation of
RhB and phenol. The photocatalytic activity of Bi2Sn2O7/RGO in
e- CB e- degradation of RhB and phenol was 1.83 and 1.66 times that of
pure Bi2Sn2O7, respectively. The enhanced photocatalytic perfor-
Bi2Sn2O7 Oxidized mance of the composite was mainly ascribed to the more effective
charge separations and the excellent adsorption capacity of RGO.
products
h+ h+ h+ h+ Both the holes and hydroxyl radicals were the active species in
the degradation process. In addition, Bi2Sn2O7/RGO displayed an
VB
Pollutants excellent stability during four reaction cycles, indicating Bi2Sn2O7/
RGO has a potential application in water purification.

Acknowledgments

The authors gratefully acknowledge Natural Science Foundation

Scheme 1. Photocatalytic mechanism of the Bi2Sn2O7/RGO composite under visible
light irradiation.
It is well-known that the oxidants generated in the photocatalytic
process can be measured through trapping by t-BuOH (a scavenger
of hydroxyl radicals), EDTA-2Na (a scavenger of holes) or BQ (a
scavenger of O2 ). It can be clearly seen from Fig. 10 that the addi-
tion of EDTA-2Na greatly reduces the photodegradation rate of RhB
and phenol in the Bi2Sn2O7/RGO suspension, whereas the addition
of BQ has little effect on the photodegradation rate of RhB and phe-
nol. In addition, the addition of t-BuOH as hydroxyl radicals’ scav-
enger causes a minor change in the photocatalytic degradation of
the above pollutants. It indicates that both the holes and hydroxyl
radicals are the active species in the photocatalytic degradation of
RhB and phenol, while O2 can be negligible in the reaction.
Based on the experimental results, a schematic mechanism for
the degradation of RhB and phenol with Bi2Sn2O7/RGO as the pho-
tocatalyst is illustrated in Scheme 1. As irradiated, the Bi2Sn2O7
particles were excited and generated holes and electrons. Due to
the higher work function of RGO than that of Bi2Sn2O7, the excited
electrons quickly transported to RGO and then reacted with the
adsorbed O2 on the RGO surfaces to form superoxide radical anions
(O2 ), which could further react with H+ or H2O to produce OH rad-
icals responsible for the degradation of the pollutants [5,54].
Meanwhile, holes left on Bi2Sn2O7 surfaces participated in the deg-
radation of pollutants either by direct oxidation or by OH radicals
produced during the reaction of holes with the adsorbed H2O or
OH [5,54].
of Shanghai (12ZR1410300), the follow-up Program for Professor of
Special Appointment in Shanghai (Eastern Scholar), the National
Natural Science Foundation of China (51271105), Shanghai Munici-
pal Government (11JC1403900, 11SG38, IRT13078) for financial
support. The authors also thank Lab for Microstructure, Instrumen-
tal Analysis and Research Center, Shanghai University, for materi-
als characterizations.
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