Separation and Purication Technology 86 (2012) 98105

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Separation and Purication Technology

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

Enhanced photocatalytic performance of Bi2WO6 by graphene supporter

as charge transfer channel
Yu-Lin Min a,b, Kan Zhang c,, You-Cun Chen a,b, Yuan-Guang Zhang a,b
a
School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246011, PR China
b
Provincial Key Laboratory of Functional Coordination Compounds, Anqing Normal University, Anqing 246011, PR China
c
Department of Chemical Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746, Republic of Korea

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

Article history: Bi2WO6 is incorporated on graphene sheets using a facile reuxing method to improve its photocatalytic
Received 4 October 2011 performance. Remarkable three times enhancement in photodegradation of Rh.B is observed on Bi2WO6/
Received in revised form 17 October 2011 graphene composite compared with pure Bi2WO6 under visible light irradiation. This improvement is
Accepted 20 October 2011
attributed to the longer electron lifetime of excited Bi2WO6 as the electrons even if holes are injected
Available online 26 October 2011
to graphene instantly at the site of generation, leading to a maximized charge separation. This study dem-
onstrated that the graphene as supporter could provide an effective way for enhancing photocatalytic
Keywords:
performance of semiconductor photocatalysts by acting as charge transfer channel.
Graphene sheets
Visible light
2011 Elsevier B.V. All rights reserved.
Photocatalytic activity
Charge transfer

1. Introduction supporter in order to improve their photocatalytic performance

Since the discovery of photocatalytic degradation of organic
compounds using Bi2WO6 (Eg = 2.69 eV) under visible light irradia-
tion [13], Bi2WO6 has received much attention as a photocatalytic
material [4]. Recently, special efforts to synthesize Bi2WO6 hierar-
chical structures with different sharps but a higher order are war-
ranted due to the high physicochemical properties and more
abundant transport paths for small molecules. For instance,
Bi2WO6 nano- and micro-structures exhibited shape associated
optical properties and photocatalytic activity for the degradation
of rhodamine B (Rh.B) under visible light irradiation [5]. Synthe-
sized Bi2WO6 ower-like superstructures also exhibited excellent
visible-light-driven photocatalytic efciencies for the degradation
of Rh.B [6]. Square Bi2WO6 nanoplates and nanoplate-built hierar-
chical nest-like structures can also show higher photocatalytic
activity under visible light irradiation [2,7]. It is well known that
the photocatalytic activity is closely related to the diameter size,
surface area, efciency of electron-hole separation and the struc-
ture of photocatalysts [8]. However, the challenge of developing
approaches to tailoring the shape and structure of the visible
light-driven photocatalysts with high activity has met with limited
success [9].
Although many photocatalysts as TiO2 and ZnO were attached
much attention using fullerene (C60) or carbon nanotube (CNT)
Corresponding author.
E-mail address: zhangkan112255@hotmail.com (K. Zhang).
by increasing surface area and efciency of electron-hole separa-
tion [1015], multimetallic oxide photocatalysts modied by
nanocarbons is a rarity in report as far as we known. It can be con-
sidered that these multimetallic oxide photocatalysts is difcult for
coating or depositing on C60 and CNT surface due to larger size con-
trast in simple component metal oxide photocatalysts. Graphene, a
two-dimensional nanocarbon with a at monolayer, has attracted
a great deal of scientic interest due to its excellent electronic,
mechanical and thermal properties and high surface area [16
18]. Most prominently, planary graphene sheets with microscale
can greatly supported multimetallic oxide photocatalysts [19
21]. Because these multimetallic oxide can interact with the graph-
ene oxide (GO) through physisorption, electrostatic binding or
through charge transfer interactions [22]. GO, as obtained from
the oxidation of graphite powder, consists of graphite sheets cova-
lently bonded with oxygen containing functional groups like hy-
droxy and epoxide groups on basal planes and carboxyl groups at
the edges [17,23]. The presence of oxygen functionalities at GO al-
lows interactions with the cations and provides reactive sites for
the nucleation and growth of nanoparticle.
In this study, we used graphene as supporter that successfully
deposited with Bi2WO6 nanoparticles via in situ reuxing method.
The graphene sheets as charge transfer channel on Bi2WO6 easily
attracted electrons, retarding the charge pair recombination under
visible light irradiation and greatly facilitating the degradation of
Rh.B.

1383-5866/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2011.10.025
 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
2. Experimental
2.1. Materials
Bismuth nitrate (Bi(NO3)3) and sodium tungstate (Na2WO4) was
purchased from Aldrich. Hydrogen peroxide (H2O2, 35%), ethylene
glycol (EG), nitric acid (HNO3) and ammonia solution (NH3H2O,
3 mol/L) was purchased from Junsei chemicals, Japan. The Rhoda-
mine B (Rh.B) was purchased from Samchun Pure Chemical Co.,
Ltd., Korea.
2.2. Synthesis of Bi2WO6/graphene photocatalyst
The preparation of graphite oxide (GO) suspensions was similar
with the Hummers method [24]. The synthesis of the Bi2WO6/
graphene photocatalyst involved two steps. In the rst step, 0.3
mol Na2WO4 was added into solution containing the superuous
HNO3, and was reuxed and maintained at 83 C for 3 h in oil bath,
whereafter yellow H2WO4 precipitates was obtained and named as
solution A, which is conrmed by XRD (Fig. S-1). Solution B con-
taining 0.6 mol Bi(NO3)3 was dispersed into 200 mL distilled H2O.
Subsequently, solutions A and B were mixed. The mixture was re-
uxed and stirred at 98 C in oil bath, pH value of the solution was
simultaneously adjusted to about 7 by adding NH3H2O. After being
stirred for 24 h, the resulting precipitation was collected, washed
with de-ionized water, vucuum-dried at 50 C and annealed at
500 C for 5 h to obtain Bi2WO6. In the second step, GO was ultr-
asonicated in a two-neck round-bottom ask 50 mL of EG to dis-
perse it well; after that, 0.5 g of as-prepared Bi2WO6 was added
to the calculated amount of the above GO solution to prepare 1,
2.5, 5, 10, and 15 wt.% Bi2WO6/graphene with different weight
addition ratios of graphene. The mixing solution was aged with
vigorous stirring for 2 h to obtain a homogeneous suspension.
Then, this suspension was transferred onto oil bath and reuxed
at 180 C for 48 h. The resulting precipitation was collected,
washed with acetone and vucuum-dried at 50 C in succession.
Fig. 1. Tapping-mode AFM image of graphene oxide.
99
2.3. Analysis instruments
Diffuse reectance UVvisible absorption spectra were re-
corded using a spectrophotometer (Shimadzu UV-2401PC) with
an integrating sphere attachment. BaSO4 was used as the reference.
XRD patterns were obtained with a diffractometer on Riguka, Ja-
pan, RINT 2500 V using Cu Ka radiation. Raman spectra were car-
ried out by a Horiba Jobin Yvon LabRAM (WITEC, Germany) using a
100 objective lens with a 532 nm laser excitation. Fourier trans-
form-infrared (FT-IR) spectra were recorded in KBr pellets with
Bruker FTIR. XPS analysis was performed with an ESCALAB-220I-
XL (THERMO-ELECTRON, VG Company) device. Transmission elec-
tron microscopy (TEM) observations were performed on a JEOL,
JEM-2010 (Japan) electron microscope with an accelerating voltage
of 200 kV. The working electrode was a thin lm with a working
area of 1.05 cm2 on ITO, platinum as counter electrode, Ag/AgCl
as reference electrode, and Na2SO4 (0.5 M) as electrolyte. A 300
W Xe lamp (Oriel) with a 420 nm cut-off lter was used for excita-
tion with external 0.5 V. Measurements of the photocurrent col-
lected were carried out using a potentiostat (CHI660C). The UV
vis absorption spectra were recorded using a (S-3100, Sainco. Co.
Ltd., Korean) spectrometer.
2.4. Photocatalytic activity
In order to analyze the photocatalytic effect, the decomposition
reaction of Rh.B in water was followed. Powdered Bi2WO6/graph-
ene of 0.03 g was dispersed in the 50 mL Rh.B solution
(2  105 M) under ultrasonication for 3 min. For irradiation sys-
tem, the visible light (k > 420 nm, LED lamp) was used at the dis-
tance of 100 mm from the solution in darkness box. The
suspension was irradiated with light source as a function of irradi-
ation time. Samples were then withdrawn regularly from the reac-
tor and removal of dispersed powders through centrifuge. The
clean transparent solution was analyzed by UVvis spectroscopy.
The concentration of Rh.B in the solution was determined as a
100 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105

function of irradiation time from the absorbance region at a wave- images of the Bi2WO6/graphene (Fig. 2c) and the corresponding
length line of 555 nm. elemental mapping (Fig. 2df) show homogeneous distribution of
C, Bi and W in the entire range.
To better study the interface structure between the two phases,
3. Results and discussion
the Bi2WO6/graphene was further examined with high-resolution
transmission electron microscopy (HR-TEM). The well-crystallized
3.1. Surface characteristics and element analysis
structure with lattice spacing of 0.223 nm corresponds to the
(1 0 1) planes of the orthorhombic Bi2WO6 (Fig. 3a), It can be fur-
The tapping mode AFM image (Fig. 1) of GO shows macro size
ther seen from Fig. 3b that the graphene sheet with the basal plane
sheets and the height prole of thickness indicates formation of
is perfectly bridged with Bi2WO6. For comparison, the Bi2WO6/CNT
single layer GO.
was synthesized using similar reuxing method and TEM image of
The structure of Bi2WO6/graphene is investigated by TEM. The
Bi2WO6/CNT indicates that a separated phases of Bi2WO6 and CNT
2D graphene sheets and Bi2WO6 nanoparticles are clearly observed
(Fig. S-3). Most recently, Xu et al. reported a systematic compari-
in Fig. 2a. Bi2WO6 nanoparticles are randomly distributed on the
son study between graphene/TiO2 photocatalysts and their ana-
surface and edges of the graphene sheets, which is further con-
logues CNTTiO2 [25], which demonstrated that the role of
rmed by SEM images (Fig. S-2). TEM image of Bi2WO6/graphene
graphene is much the same way as its carbon forebears. Subse-
in Fig. 1b shows irregular Bi2WO6 nanoparticles containing square
quently, the authors claimed that full and intimate coverage of
Bi2WO6 nanoplates. The square nanoplates can be attributed to
the individual 2D sheet of graphene with TiO2 can maximize the
anisotropic growth in the crystalline-ripened process. The STEM

Fig. 2. The TEM images (a and b), STEM image (c) and elemental mapping images (df) of Bi2WO6/graphene.
 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105 101

Fig. 3. The HR-TEM and SAED images of Bi2WO6/graphene.

Fig. 4. (a) The XRD patterns and FT-IR spectra of GO, Bi2WO6 and Bi2WO6/graphene. (c) The Raman spectra of GO and Bi2WO6/graphene and (d) the UVvis diffuses
reectance spectra of Bi2WO6 and Bi2WO6/graphene.

excellent electron conductivity of graphene [26]. Because the supe-
rior and easily accessible structure directing role of GO (the pre-
cursor of graphene) in an aqueous phase is able to be utilized easy
and sufciently compared to CNT. As a result, the GO as starting
materials can promote interaction of Bi2WO6 and GO through
physisorption, electrostatic binding or through charge transfer
[27].
3.2. Crystal and optical properties
The XRD patterns of GO, Bi2WO6, and Bi2WO6/graphene are
shown in Fig 4a. The diffraction peak at 10.45 in the XRD pattern
of the GO corresponds to the layer-to-layer distance (d-spacing) of
0.78 nm. All the peaks for the Bi2WO6 are readily indexed to the
orthorhombic phase of Bi2WO6 (JCPDS card no. 73-1126). It is also
found that the main diffraction peaks of Bi2WO6/graphene are sim-
ilar to that of pure Bi2WO6. No obvious diffraction peak attribute to
GO or graphene is observed, which suggests that low content and
the stacking of the graphene sheets disordered.
The FT-IR spectra of GO, Bi2WO6, and Bi2WO6/graphene are
shown in Fig 4b. The representative absorption peaks of GO includ-
ing those at 3400 cm1 (OH stretching vibration), 1736 cm1
(C@O stretching vibration of COOH groups), 1396 cm1 (tertiary
COH stretching vibration), and 1072 cm1 (CO stretching vibra-
102 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
Fig. 5. The C1s XPS spectra of GO and Bi2WO6/graphene.
Fig. 6. Photocurrent transient responses of Bi2WO6 and Bi2WO6/graphene under
visible light irradiation.
tion), are in good agreement with previous work [28]. The Bi2WO6
has main absorption peaks between 500 and 1200 cm1, which can
be attributed to stretching vibration of BiO and WO, and bending
vibration of WOW [29,30]. Obvious decreases in intensity or
even disappearance after solvothermal reduction in FT-IR spec-
trum of Bi2WO6/graphene indicate that the oxygen-containing
functional groups in GO are decomposed in the solvothermal envi-
ronment [31]. The absorption band appearing at 1689 cm1 clearly
shows the skeletal vibration of the graphene sheets, indicating the
formation of graphene in Bi2WO6/graphene.
As shown in Fig. 4c, the Raman spectrum of GO contains both G
(the E2g mode of sp2 carbon atoms) and D (the symmetry A1g
mode) bands at 1582 and 1352 cm1, respectively. Also of note,
the frequencies of the G (1595 cm1) and D (1352 cm1) bands in
the Bi2WO6/graphene are very similar to that observed in the
GO; however, with an increased D/G intensity ratio (0.889) com-
pared to that in GO (0.829) [32]. This change suggests a decrease
in the size of the in-plane sp2 domains and a partially ordered
crystal structure of the Bi2WO6/graphene. Furthermore, the 2D
and D + G bands are shifted into higher wavenumbers compared
to GO, which may be ascribed to highly disordered and randomly
arranged graphene akes.
The typical UVvis diffuse reection spectra (UVvis DRS) of
Bi2WO6 and Bi2WO6/graphene are shown in Fig. 4d. The Bi2WO6
displays photoabsorption properties from the UV light region to
the visible light absorption shorter than 470 nm, while the
Bi2WO6/graphene shows an intense, broad background absorption
in the visible light region, indicating the same absorption and iden-
tical band gap energy. The increase of absorption in the visible light
region is due to the reintroduction of black body properties typical
of graphite-like materials [33], indicating the existence of graph-
ene in Bi2WO6/graphene.
3.3. Chemical bonds analysis
X-ray photoelectron spectroscopy (XPS) was used to conrm
the formation of graphene from GO during the solvothermal treat-
ment, as shown in Fig. 5. Five peaks located at 284.6, 285.6, 286.7,
287.7 and 288.4 eV observed from the C1s deconvolution spectrum
of GO correspond to the CC, COH, CO, C@O, and OC@O (COO
) groups, respectively. Compared with GO, the intensity of the CO
peak in Bi2WO6/graphene is dramatically decreased, while the
peak intensity due to COH is increased. The results indicate that
most of the oxygen-containing functional groups are removed after
reduction by EG [34].
3.4. Electrochemical properties
The photochemical behaviors of Bi2WO6/graphene were also
investigated using a Bi2WO6/graphene-coated electrode. The pho-
tocurrent responses were recorded upon excitation of Bi2WO6/
ITO and Bi2WO6/graphene/ITO electrodes with visible light
(k > 420 nm) as shown in Fig. 6. It was found that the photocurrent
on Bi2WO6/graphene is about ve times higher than that of
Bi2WO6. The improved photocurrent response can be ascribed to
the following two aspects: (1) graphene can serve as an acceptor
of the generated electrons of Bi2WO6 and effectively retard the
charge recombination due to its excellent conductivity [16,35].
(2) The distributing Bi2WO6 on graphene sheets plays an important
role in enhancing visible light response.
3.5. Photocatalytic activity and mechanism
The photocatalytic degradation of Rh.B under visible light irra-
diation is utilized to evaluate the photocatalytic performance of
the Bi2WO6/graphene, as shown in Fig. 7. It can be seen that Rh.B
is very stable under visible light irradiation without any catalyst
or in the presence of graphene sheets in Fig. 7a. The degradation
of Rh.B can be obviously occurred over Bi2WO6, mixed Bi2WO6
and graphene, and 5 wt.% Bi2WO6/graphene, suggesting the excita-
tion of the Bi2WO6 under visible light, and the Bi2WO6 and 5 wt.%
Bi2WO6/graphene can be greatly dispersed in Rh.B solution before
and after visible light irradiation (Fig. S-4). The mixture of graph-
ene and Bi2WO6 shows slightly higher photocatalytic activity than
that of pure Bi2WO6. It has been found that the 5 wt.% Bi2WO6/
graphene exhibit higher photocatalytic activities than Bi2WO6
 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105 103

Fig. 7. (a) Photocatalytic degradation of Rh.B under visible light (k > 420 nm) as a function of irradiation time by the graphene, Bi2WO6, mixture of Bi2WO6 and graphene, and
5 wt.% Bi2WO6/graphene. (b) The kinetics of photocatalytic degradation of Rh.B by the Bi2WO6 and 5 wt.% Bi2WO6/graphene. (c) Photocatalytic degradation of Rh.B under
visible light (k > 420 nm) as a function of irradiation time by the Bi2WO6 and 5 wt.% Bi2WO6/graphene in presence of H2O2 (2  105 M). (d) Photocatalytic degradation
efciencies of Rh.B under visible light (k > 420 nm) as a function of irradiation time by the Ag2WO4, 5 wt.% Ag2WO4/graphene, BiVO4, 5 wt.% BiVO4/graphene, CdS, and 5 wt.%
CdS/graphene.

and mixture of graphene and Bi2WO6 both. The pseudo-rst-order
kinetics of photocatalytic degradation ratio for the Bi2WO6 and
5 wt.% Bi2WO6/graphene in Fig. 7b show that the Bi2WO6/graphene
is about three times greater than Bi2WO6. Previous study had dem-
onstrated that direct hole oxidation and O 2 oxidation reaction
mainly govern the photocatalytic process by adding holes and hy-
droxyl radicals scavengers in graphene/semiconductors system
[21,36]. Herein, addition of H2O2 as electron accepting agents is
used to evaluate effective separation of electron/hole pairs in pres-
ence of graphene sheets, the effect on the degradation kinetics of
Rh.B is illustrated in Fig. 7c. It is obvious that the degradation rate
of Rh.B on 5 wt.% Bi2WO6/graphene is accelerated. However, on
pure Bi2WO6, degradation of Rh.B is slightly slower in the presence
of H2O2. It can be considered that the OH radical formation on
Bi2WO6 in presence of H2O2 can be decreased by the process of
recombination of holes, which is formed on Bi2WO6 surface after
its excitation with electrons due to supplying H2O2 [37]. The differ-
ent behavior of degradation of Rh.B on Bi2WO6/graphene can be
supposed to prior adsorbed H2O2 on the graphene surface, there-
fore the amounts of OH radical formed main due to reacted with
transferred electrons is higher on Bi2WO6/graphene. Additionally
OH radical formation on the surface of Bi2WO6 is suppressed by
the scavenging of the free carriers by H2O2. Based on the above re-
sults, the photocatalytic activity enhancement can be attributed to
the introduction of graphene as charge transfer channel, resulting
in an effective separation of photogenerated electron/hole pairs
and fast interfacial charge transfer to the electron donor/electron
acceptor. To further verify the electron transfer by graphene sup-
porter, more semiconductor photocatalysts, such as Ag2WO4,
BiVO4 and CdS combined with graphene in 5 wt.% content are syn-
thesized for degradation of Rh.B. Synthesis route is similar to
Bi2WO6/graphene in an EG solvent by a hydrothermal reaction,
their FT-IR, XRD and UVvis DRS analysis show true composites
with obvious visible light response (Fig. S-5). As shown in Fig. 7d,
all graphene based semiconductor photocatalysts show 23 times
greater than individual semiconductor in photocatalytic perfor-
mances. It suggests that the graphene sheets as charge transfer
channel can effectively transfer electrons, even holes for semicon-
ductor with different band gaps.
Degradation of Rh.B are further carried out for 120 wt.% graph-
ene supported Bi2WO6 to optimize graphene loading in Bi2WO6.
The photocatalytic performances enhance in the degradation of
Rh.B up to 5 wt.% graphene loading, after which it starts decreasing
(Fig. 8a). It can be deduced that the gap of degradation perfor-
mance among Bi2WO6/graphene with different graphene contents
is mainly related to weakening photon absorption ability, which
have been conrmed in graphene based photocatalysts by previous
reports [36,38]. After conrming the fact that graphene supported
Bi2WO6 should serve as an advanced photocatalyst that assists the
charge separation, the degradation of Rh.B also indicates if
104 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
Fig. 8. (a) Photocatalytic degradation efciencies of Rh.B over Bi2WO6/graphene
with different graphene contents. (b) Repeated runs of Rh.B degradation by 5 wt.%
Bi2WO6/graphene.
Fig. 9. Proposed mechanism of light irradiating to graphene based semiconductor
photocatalysts.
graphene supporter can enhance photocatalytic performance of
semiconductors with different band gap. Incidentally, the photo-
catalytic performances of graphene/semiconductor photocatalysts
are usually tested by monitoring the degradation of dyes as target
substrates [33,39]. However, the dye is not a suitable test substrate
to evaluate the photocatalytic activity since the dye degradation is
much affected the sensitized path, which complicates the mecha-
nism of dye degradation. As shown in this case, the photocatalytic
activity of Bi2WO6/graphene is maintained through the repeated
cycles of Rh.B degradation with showing a signicant deactivation
of the photocatalyst (Fig. 8b). There is debate over the exact rea-
sons for the change of photocatalytic activity, but it is generally
agreed upon its adsorption afnity to graphene. Due to zero band
semiconductor with symmetric K and K0 [40] the energy level of
graphene can create a matching midgap between conduction band
and valence band of semiconductors. Therefore, the exited elec-
trons or holes can quickly inject to grapheen sheets and then re-
acted with adsorbed O2 or H2O on the graphene to produce OH
or O2
2 radicals. The possible charge transferring mechanism of
graphene based semiconductor photocatalyst is proposed in
Fig. 9. This study demonstrates that graphene supporter can act
as charge transfer channel to enhance photocatalytic activity of
semiconductors with different band gap, and it is necessary to pass
judgment on the stable adsorption afnity of graphene.
4. Conclusions
In this work, the Bi2WO6/graphene photocatalysts were suc-
cessfully prepared via in situ reuxing method in the presence of
GO. The photocatalytic activity of Bi2WO6/graphene is greatly en-
hanced compared to pure Bi2WO6. Analogous case was also found
in other semiconductors with different band gap deposited on
graphene supporter. The enhanced photocatalytic activity could
be attributed to that graphene as charge transfer channel readily
accepts electrons or even holes transfer due to special properties
of graphene, but it is not very informative in understanding the
stable adsorption afnity of graphene. This work not only provides
an example of a Bi2WO6/graphene photocatalyst and demonstrated
that graphene is a very promising candidate for development of
high performance photocatalysts, but also opens new possibilities
to provide some insight into the design of semiconductor modied
photocatalysts with high activity for wastewater purication and
solar cell applications.
Acknowledgements
The present work was supported by the special funding support
from Natural Science Foundation of Anhui Province (Nos.
KJ2010ZD07 and KJ2008B172) and the National Science Founda-
tion of China (NSFC) (Grants No. 20871005).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.seppur.2011.10.025.
References
[1] J. Tang, Z. Zou, J. Ye, Photocatalytic decomposition of organic contaminants by
Bi2WO6 under visible light irradiation, Catal. Lett. 92 (2004) 5356.
[2] C. Zhang, Y.F. Zhu, Synthesis of square Bi2WO6 nanoplates as high-activity
visible-light-driven photocatalysts, Chem. Mater. 17 (2005) 35373545.
[3] H.B. Fu, C.S. Pan, W.Q. Yao, Y.F. Zhu, Visible-light-induced degradation of
rhodamine b by nanosized Bi2WO6, J. Phys. Chem. B 109 (2005) 2243222439.
[4] A. Kudo, S. Hijii, H2 or O2 evolution from aqueous solutions on layered oxide
photocatalysts consisting of Bi3+ with 6s2 conguration and d0 transition
metal ions, Chem. Lett. 28 (1999) 11031104.
[5] L.S. Zhang, W.Z. Wang, Z. Lin, H.L. Xu, Bi2WO6 nano- and micro-structures:
shape control and associated visible-light-driven photocatalytic activities,
Small 3 (2007) 16181625.
 Y.-L. Min et al. / Separation and Purication Technology 86 (2012) 98105
[6] L.S. Zhang, W.Z. Wang, Z.G. Chen, L. Zhou, H.L. Xu, W. Zhu, Fabrication of
ower-like Bi2WO6 superstructures as high performance visible-light driven
photocatalysts, J. Mater. Chem. 24 (2007) 25262532.
[7] J. Wu, F. Duan, Y. Zheng, Y. Xie, Synthesis of Bi2WO6 nanoplate-built
hierarchical nest-like structures with visible-light-induced photocatalytic
activity, J. Phys. Chem. C 111 (2007) 1286612871.
[8] J.Q. Yu, A. Kudo, Effects of structural variation on the photocatalytic
performance of hydrothermally synthesized BiVO4, Adv. Funct. Mater. 16
(2006) 21632169.
[9] L. Ren, L.L. Ma, L. Jin, J.B. Wang, M.Q. Qiu, Y. Yu, Template-free synthesis of
BiVO4 nanostructures: II. Relationship between various microstructures for
monoclinic BiVO4 and their photocatalytic activity for the degradation of
rhodamine B under visible light, Nanotechnology 20 (2009) 405602405611.
[10] W.C. Oh, F.J. Zhang, Z.D. Meng, K. Zhang, Relative photonic properties of Fe/
TiO2-nanocarbon catalysts for degradation of MB solution under visible light,
Bull. Korean Chem. Soc. 31 (2010) 11281134.
[11] N. Bouazza, M. Ouzzine, M.A. Lillo-Rdenas, D. Eder, A. Linares-Solano, TiO2
nanotubes and CNTTiO2 hybrid materials for the photocatalytic oxidation of
propene at low concentration, Appl. Catal. B: Environ. 92 (2009) 377383.
[12] W. Zhou, K. Pan, Y. Qu, F.F. Sun, C.G. Tian, Z.Y. Ren, G.H. Tian, H.G. Fu,
Photodegradation of organic contamination in wastewaters by bonding TiO2/
single-walled carbon nanotube composites with enhanced photocatalytic
activity, Chemosphere 81 (2010) 555561.
[13] Tawk A. Saleh, M.A. Gondal, Q.A. Drmosh, Z.H. Yamani, A. AL-yamani,
Enhancement in photocatalytic activity for acetaldehyde removal by
embedding ZnO nano particles on multiwall carbon nanotubes, Chem. Eng. J.
166 (2011) 407412.
[14] C. Martnez, M. Canle L, M.I. Fernndez, J.A. Santaballa, J. Faria, Kinetics and
mechanism of aqueous degradation of carbamazepine by heterogeneous
photocatalysis using nanocrystalline TiO2, ZnO and multi-walled carbon
nanotubes-anatase composites, Appl. Catal. B: Environ. 102 (2011) 563571.
[15] O. Akhavan, M. Abdolahad, Y. Abdi, S. Mohajerzadeh, Synthesis of titania/
carbon nanotube heterojunction arrays for photoinactivation of E. coli in
visible light irradiation, Carbon 47 (2009) 32803287.
[16] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Electric eld effect in atomically thin carbon lms,
Science 306 (2004) 666669.
[17] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. 6 (2007) 183191.
[18] S. Park, R.S. Ruoff, Chemical methods for the production of graphenes, Nat.
Nanotechnol. 4 (2009) 217224.
[19] Y.H. Ng, A. Iwase, A. Kudo, R. Amal, Reducing graphene oxide on a visible-light
BiVO4 photocatalyst for an enhanced photoelectrochemical water splitting, J.
Phys. Chem. Lett. 1 (2010) 26072612.
[20] E.P. Gao, W.Z. Wang, M. Shang, J.H. Xu, Synthesis and enhanced photocatalytic
performance of graphene-Bi2WO6 composite, Phys. Chem. Chem. Phys. 13
(2011) 28872893.
[21] X.F. Zhang, X. Quan, S. Chen, H.T. Yu, Constructing graphene/InNbO4 composite
with excellent adsorptivity and charge separation performance for enhanced
visible-light-driven photocatalytic ability, Appl. Catal. B: Environ. 105 (2011)
237242.
[22] G. Williams, B. Seger, P.V. Kamat, TiO2-graphene nanocomposites. UV-assisted
photocatalytic reduction of graphene oxide, ACS Nano. 2 (2008) 14871491.
105
[23] M.J. Allen, V.C. Tung, R.B. Kaner, Honeycomb carbon: a review of graphene,
Chem. Rev. 110 (2010) 132145.
[24] W. Hummers, R. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc. 80
(1958) 1339.
[25] Y. Zhang, Z.R. Tang, X. Fu, Y.J. Xu, TiO2-graphene nanocomposites for gas-phase
photocatalytic degradation of volatile aromatic pollutant: is TiO2-graphene
truly different from other TiO2-carbon composite materials?, ACS Nano 4
(2010) 73037314.
[26] Y. Zhang, Z.R. Tang, X. Fu, Y.J. Xu, Engineering the unique 2D mat of graphene
to achieve graphene-TiO2 nanocomposite for photocatalytic selective
transformation: what advantage does graphene have over its forebear
carbon nanotube?, ACS Nano 5 (2011) 74267435.
[27] A.V. Moholkar, S.M. Pawar, K.Y. Rajpure, Saleh N. Almari, P.S. Patil, C.H.
Bhosale, Solvent-dependent growth of sprayed FTO thin lms with mat-like
morphology, Sol. Energy Mater. Sol. Cells 92 (2008) 14391444.
[28] J.I. Paredes, S. Villar-Rodil, A. Martinez-Alonso, J.M.D. Tascon, Graphene oxide
dispersions in organic solvents, Langmuir 24 (2008) 1056010564.
[29] D.K. Ma, S.M. Huang, W.X. Chen, S.W. Hu, F.F. Shi, K.L. Fan, Self-assembled
three-dimensional hierarchical umbilicate Bi2WO6 microspheres from
nanoplates: controlled synthesis, photocatalytic activities, and wettability, J.
Phys. Chem. C 113 (2009) 43694374.
[30] L.H.M. Krings, W. Talen, Wet chemical preparation and characterization of
electrochromic WO3, Sol. Energy Mater. Sol. C 54 (1998) 2737.
[31] A.V. Murugan, T. Muraliganth, A. Manthiram, Facile microwave-solvothermal
synthesis of graphene nanosheets and their polyaniline nanocomposites for
energy storage, Chem. Mater. 21 (2009) 50045006.
[32] J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang, S. Guo, Reduction of graphene
oxide via L-ascorbic acid, Chem. Commun. 46 (2010) 11121114.
[33] L.W. Zhang, H.B. Fu, Y.F. Zhu, Efcient TiO2 photocatalysts from surface
hybridization of TiO2 particles with graphite-like carbon, Adv. Funct. Mater. 18
(2008) 21802189.
[34] P. Wang, T.F. Jiang, C.Z. Zhu, Y.M. Zhai, D.J. Wang, S.J. Dong, One-step,
solvothermal synthesis of graphene-CdS and graphene-ZnS quantum dot
nanocomposites and their interesting photovoltaic properties, Nano Res. 3
(2010) 794799.
[35] X. Wang, L.J. Zhi, K. Mullen, Transparent, conductive graphene electrodes for
dye-sensitized solar cells, Nano Lett. 8 (2008) 323327.
[36] T.G. Xu, L.W. Zhang, H.Y. Cheng, Y.F. Zhu, Signicantly enhanced photocatalytic
performance of ZnO via graphene hybridization and the mechanism study,
Appl. Catal. B: Environ. 101 (2011) 382387.
[37] B. Tryba, A.W. Morawski, M. Inagaki, M. Toyoda, The kinetics of phenol
decomposition under UV irradiation with and without H2O2 on TiO2, Fe
TiO2 and FeCTiO2 photocatalysts, Appl. Catal. B: Environ. 63 (2006) 215
221.
[38] T.G. Xu, L.W. Zhang, H.Y. Cheng, Y.F. Zhu, Appl. Catal. B: Environ. 101 (2011)
382387.
[39] D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu, C. Wang, L.V. Saraf, J. Zhang,
I.A. Aksay, J. Liu, Self-assembled TiO2-graphene hybrid nanostructures for
enhanced Li-ion insertion, ACS Nano. 3 (2009) 907914.
[40] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, M.I. Katsnelson, I.V.
Grigorieva, S.V. Dubonos, A.A. Firsov, Two-dimensional gas of massless Dirac
fermions in graphene, Nature 438 (2005) 197200.