J Mater Sci (2014) 49:73257332
DOI 10.1007/s10853-014-8445-3
Polypyrrole/Bi2WO6 composite with high charge separation
efficiency and enhanced photocatalytic activity
Zhijie Zhang Wenzhong Wang Erping Gao
Received: 24 April 2014 / Accepted: 2 July 2014 / Published online: 15 July 2014
Springer Science+Business Media New York 2014
Abstract The recombination of photogenerated electrons
and holes is a crucial factor that limits the efficiency of
photocatalysis and dye-sensitized solar cells. Conducting
polymers are known to have high charge carrier mobility.
Herein, a polypyrrole (PPy)/Bi2WO6 composite with pro-
moted charge separation efficiency was designed by a
photocatalytic oxidative polymerization method. The
photo-degradation of a typical model pollutant, phenol,
demonstrated that the PPy/Bi2WO6 composite possessed
significantly enhanced photo-activity than pure Bi2WO6
under simulated sunlight irradiation. The higher photo-
activity was attributed to the synergetic effect between PPy
and Bi2WO6. The photogenerated holes on the valence
band of Bi2WO6 could transfer to the highest occupied
molecular orbital of PPy, leading to rapid photoinduced
charge separation and enhancing the photocatalytic activ-
ity. This work provided a new concept for rational design
and development of highly efficient polymer-semiconduc-
tor photocatalysts for environmental purification under
simulated sunlight.
Z. Zhang (&)
Department of Materials Science and Engineering, Shanghai
Institute of Technology, 100 Haiquan Road, Shanghai 201418,
China
e-mail: zjzhang@sit.edu.cn
W. Wang
E. Gao
State Key Laboratory of High Performance Ceramics and
Superfine Microstructures, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Dingxi Road,
Shanghai 200050, China
Introduction
The degradation of organic pollutants using semiconductor
photocatalysis is attracting attention as an alternative
technology to wastewater treatment [13]. Under photo-
excitation, semiconductors undergo charge separation that
initiates oxidation of organic compounds at the interface.
Since photocatalysis is tightly related to the photogenerated
charge carriers, success in the applications of photocata-
lysts relies on the transfer efficiency of electronhole pairs.
Unfortunately, the much faster recombination rate (nano-
seconds) than the interfacial transfer rate (microseconds to
milliseconds) seriously limits the overall quantum effi-
ciency for photocatalysis [4]. Therefore, to improve the
photocatalytic activity of the semiconductors, it is impor-
tant to control the recombination dynamics of the photo-
generated charge carriers.
Conducting polymers (e.g., polyaniline, polypyrrole,
and polythiophene) with delocalized conjugated structures
have been widely studied due to their rapid photoinduced
charge separation and relatively slow charge recombination
[5, 6]. Recently, organic conducting polymers have gained
considerable interest in the research of many practicable
applications, such as lithium ion batteries [7], photocatal-
ysis [8, 9], biosensors [10], and solid-state solar cells [11].
In particular, polypyrrole (PPy) with extended p-conju-
gated electron systems has recently shown great promises
owing to its unique electrical and optical properties, such
as high absorption coefficients in the visible light part of
the solar spectrum, high mobility of charge carriers, and
excellent stability [12, 13]. Furthermore, PPy is also an
efficient electron donor and good hole transporter upon
visible light excitation. It was proposed that polypyrrole
has the ability to channel the photoinduced holes from the
surface of the semiconductor to the polymer/solution
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interface at a fast rate, which can then oxidize the pollu-
tants [14, 15]. Some work have been carried out to inves-
tigate the photocatalytic activity of PPy-modified TiO2 and
found that the modification of PPy can effectively enhance
the photoactivity of TiO2 [1618]. Inspired by this, we
intended to design a composite photocatalyst by introduc-
ing PPy into a visible light-induced Bi2WO6 photocatalyst.
Different from TiO2 in which both hydroxyl radicals and
holes are active species, the main active species in Bi2WO6
photocatalyst are photogenerated holes [19]. Coincidently,
as an excellent hole conductor, PPy can transport the
valence band holes of Bi2WO6 to the polymer/solution
interface quickly to participate in the oxidation of pollu-
tants. In other words, PPy and Bi2WO6 are expected to be
better partners. Recently, Duan et al. [20] have synthe- persed in 100 mL deionized water by bath-sonication for
sized PPy/Bi2WO6 composite by in situ deposition oxida-
tive polymerization of pyrrole, and evaluated its
photocatalytic activity by degradation of two kinds of dyes,
rhodamine B (RhB), and methylene blue (MB). However,
in this method, the Bi2WO6 nanoparticle only acts as a
template for the organic PPy phase but does not play an
active role in its formation, and the polymer layer simply
deposits on the surface of Bi2WO6 semiconductor. An
alternative approach is to employ in situ photocatalytic
oxidative polymerization method, in which the photo-
generated holes of the semiconductor act as initiator for
surface-mediated polymerization, and the reaction can be
initiated at any point of the semiconductor. Thus the
polymer could be in good contact with the semiconductor,
and the strong interfacial binding favors charge migration
for the composite materials [21, 22], which can lead to an
enhanced photocatalytic activity.
In this study, a photocatalytic oxidative polymeriza-
tion method was used to synthesize the PPy/Bi2WO6
composite. The photo-activity evaluation, via the photo-
catalytic degradation of phenol under simulated sunlight,
demonstrated that the PPy/Bi2WO6 composite exhibited
much enhanced photocatalytic activity than pure Bi2WO6.
By photoelectrochemical measurement and oxidative spe-
cies scavengers experiment, the reasons for improving the
photocatalytic activity of PPy/Bi2WO6 composite were
explored.
Experimental
Synthesis of Bi2WO6 photocatalyst
Bi2WO6 photocatalyst was prepared by a hydrothermal
method. In a typical process, 2 mmol of Bi(NO3)3
5H2O
and 1 mmol of Na2WO4
2H2O were dissolved in 4 M nitric
acid and 30 mL of deionized water, respectively. After
that, these two solutions were mixed together and a white
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J Mater Sci (2014) 49:73257332
precipitate was formed. After being stirred for 1 h, the
suspension was transferred into a 50 mL Teflon-lined
stainless steel autoclave up to 80 % of the total volume.
The autoclave was heated at 160 C for 20 h, and then
cooled to room temperature naturally. The resulting pro-
ducts were separated by filtration, washed with deionized
water and absolute alcohol for several times, and then dried
at 60 C for 12 h.
Synthesis of PPy/Bi2WO6 composite
The PPy/Bi2WO6 composite was prepared by a photo-
catalytic oxidative polymerization process as follows:
1 mmol of the obtained Bi2WO6 photocatalyst was dis-
30 min. Then 5 lL of pyrrole was injected into the above
suspension with constant stirring. Photo-oxidation was
proceeded under a 500 W Xe lamp for 3 h during which
pyrrole monomers were oxidized into polypyrrole by the
photoinduced holes of Bi2WO6. The obtained PPy/Bi2WO6
composite was then washed with deionized water, and
dried in an oven at 60 C for 12 h.
Characterization
The phase and composition of the as-prepared samples
were measured by X-ray diffraction (XRD) studies using
an X-ray diffractometer with Cu Ka radiation under 40 kV
and 100 mA and with the 2h ranging from 20 to 70
(Rigaku, Japan). The morphologies and microstructures of
the as-prepared samples were investigated by transmission
electron microscopy (TEM, JEOL JEM2100F). The
energy-dispersive X-ray analysis (EDX) of the samples
was also performed during the TEM measurements. UV
Vis diffuse reflectance spectra (DRS) of the samples were
recorded with an UVVis spectrophotometer (Hitachi U
3010) using BaSO4 as reference. Fourier transform infrared
(FTIR) spectroscopy was performed with a spectropho-
tometer (Nicolet 380, Thermo, USA) with the KBr pellet
technique.
Photoelectrochemical measurement
The electrodes were prepared by electrophoretic deposition
in an acetone solution (50 mL) containing Bi2WO6 or PPy/
Bi2WO6 powder (40 mg) and iodine (10 mg). A FTO
electrode and a Pt wire as counter electrode were immersed
in the solution with a 1015 mm separation, and a 10 V
bias was applied between the two for 3 min under poten-
tiostat control.
Photoelectrochemical measurements were carried out
using a CHI 660C electrochemical workstation at room
temperature. The cell was a three-electrode-type system
J Mater Sci (2014) 49:73257332
Fig. 1 XRD patterns of the products
using Pt wire and saturated calomel electrode (SCE) as the
counter and reference electrodes, respectively. A Na2SO4
aqueous solution (pH 6) was used as the electrolyte. The
light source was a 500 W Xe lamp.
Photocatalytic test
Photocatalytic activity of the PPy/Bi2WO6 composite
photocatalyst was evaluated by photo-degradation of phe-
nol under simulated sunlight irradiation provided by a
500 W Xe lamp. The experiments were performed at room
temperature as follows: 0.05 g of photocatalyst was added
into 50 mL of phenol solution (20 mg L-1). Prior to irra-
diation, the suspensions were magnetically stirred for an
hour in the dark to ensure the adsorption/desorption equi-
librium between phenol and photocatalyst powders. At
given time intervals, 2 mL of suspension was sampled and
centrifuged to remove the photocatalyst particles. Then, the
absorption spectrum of the centrifugated solution was
recorded using a Hitachi U3010 UVVis spectropho-
tometer. The concentration change of phenol was deter-
mined by monitoring the optical intensity of absorption
spectra at 270 nm.
Results and discussion
Crystal structure
XRD patterns of pure Bi2WO6 and PPy/Bi2WO6 composite
were recorded to investigate the phase structures of the
products, as shown in Fig. 1. All the peaks can be indexed
to the orthorhombic phase of Bi2WO6 according to the
JCPDS card no. 39-0256 and no other crystalline phase can
be detected. Compared with the XRD pattern of pure
Bi2WO6, no distinct difference was observed on the PPy/
7327
Bi2WO6 composite due to the amorphous structure of PPy.
In other words, the introduction of PPy did not alter the
phase of the Bi2WO6.
Morphology
The morphology and microstructure of the PPy/Bi2WO6
composite was revealed by the transmission electron
microscope (TEM) images. The panoramic view shown in
Fig. 2a indicates that the as-prepared products exhibit
sheet-like morphology, decorated with nanoparticles on the
surface. Close observation on an individual nanoplate
revealed by high magnification TEM image (Fig. 2b)
shows that the nanoparticles are monodisperse with size of
about 10 nm. In order to further confirm the existence of
PPy, the marked area with the nanoparticles was selected
for energy-dispersed X-ray (EDX) microanalysis. Accord-
ing to Fig. 2c, signals corresponding to Bi, W, O, N, and C
elements were detected, which indicated that the nano-
particles dispersed on the surface of nanosheets were PPy.
UVVis diffuse reflectance spectra
The UVVis diffuse reflectance spectrum of PPy/Bi2WO6
composite is compared with that of pure Bi2WO6, as shown
in Fig. 3. According to the spectrum, pure Bi2WO6 sample
presents the photoresponse property from the UV light
region to visible light until 450 nm, which is similar to our
previous results [23, 24]. Pure PPy shows photo-absorption
in the whole visible light region, which is attributed to
pp* (HOMOLUMO) transition of the PPy backbones.
Therefore, after the modification of PPy, the photoresponse
property of Bi2WO6 is enhanced greatly. As shown in
Fig. 3, the PPy/Bi2WO6 composite shows an intense
absorption in the visible light region. This indicates that the
presence of PPy component strongly enhances the
absorption in the visible light region, which might favor the
enhancement of the photocatalytic activity of PPy/Bi2WO6
composite.
FTIR spectra analysis
Molecular structures of the resulting samples were char-
acterized by FTIR spectra in the range from 4000 to
400 cm-1. The FTIR spectra of PPy and PPy/Bi2WO6
composites are shown in Fig. 4. For PPy sample, the bands
at 3450 and 1639 cm-1 are attributed to NH stretching
mode and bending mode, respectively. The bands at 1560
and 1470 cm-1 are assigned to the characteristic C=C
stretching of the pyrrole rings, and the band at 1295 cm-1
corresponds to =CH band in-plane vibrations. The peak at
1184 cm-1 is associated with the NC stretching vibration.
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7328
Fig. 2 a and b TEM image of
the PPy/Bi2WO6 composite;
c EDX microanalysis spectrum
of PPy/Bi2WO6
Fig. 3 UVVis diffuse reflectance spectra of the as-prepared samples
The FTIR peak observed at 901 cm-1 may be assigned to
the =CH out of plane vibration, indicating the polymeri-
zation of pyrrole [25, 26]. For the PPy/Bi2WO6 composite,
besides the characteristic peaks of PPy, main absorption
bands at 4001000 cm-1, which are attributed to BiO,
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J Mater Sci (2014) 49:73257332
PPy
PPy/Bi2WO6
Fig. 4 FTIR spectra of PPy and PPy/Bi2WO6 composite
WO stretching, and WOW bridging stretching modes
are also observed, which indicated that the composite is
composed of PPy and Bi2WO6. Compared with the spec-
trum of PPy, the characteristic peaks of PPy in the PPy/
Bi2WO6 composite shift to higher wave numbers,
J Mater Sci (2014) 49:73257332 7329

Fig. 5 a Raman spectra of the

as-prepared samples; b high
resolution of spectra in the
region of 100180 cm-1

indicating that a strong interaction exists at the interface

between Bi2WO6 and PPy.

Raman spectra analysis

Raman spectra were carried out to investigate the bond

interaction in the composite, as shown in Fig. 5a. The
strongest Raman modes in the range of 790830 cm-1 are
assigned to the symmetric and asymmetric stretching
modes of the WO6 octahedra. The bands in the
180500 cm-1 region originate from the bending modes of
the WO6 octahedra coupled with stretching and bending
modes of the bismuthoxygen polyhedra, and the modes
below 150 cm-1 are assigned to translations of the tung-
sten and bismuth ions. The peaks at 1355 and 1551 cm-1
are assigned to the C=C backbone stretching and ring
stretching of PPy, respectively. Moreover, high resolution
of the spectra in the region of 100180 cm-1 shows that
Raman mode of Bi2WO6 in the composite exhibits a red
shift in wavenumber (Fig. 5b), which suggests a covalent-
like interaction between PPy and Bi2WO6 [21, 27]. The
strong interaction is expected to facilitate the charge sep-
aration in the PPy/Bi2WO6 composite.
Photoelectrochemical measurement
Generally, photocurrent reflects indirectly the semicon-
ductors ability to generate and transfer the photogenerated
charge carriers, which correlates with the photocatalytic
activity [28, 29]. To demonstrate that the PPy/Bi2WO6
composite was preferred for efficient charge separation, the
photoresponses of PPy/Bi2WO6 and Bi2WO6 electrodes
were studied and the results are shown in Fig. 6. Fast and
uniform photocurrent responses of PPy/Bi2WO6 and
Bi2WO6 electrodes can be observed in Fig. 6. After mod-
ifying with PPy, the photocurrent of Bi2WO6 was enhanced
by 2.7 times under simulated sunlight irradiation, which
indicates the modification of PPy can effectively promote
the charge carrier transfer and inhibit the electronhole
recombination. It is assumed that interactions between
Fig. 6 Photocurrent of PPy/Bi2WO6 and Bi2WO6 electrodes under
visible light irradiation. [Na2SO4] = 0.1 M
Bi2WO6 and PPy are favorable for enhancing the photo-
catalytic activity of the PPy/Bi2WO6 composite.
Photocatalytic activity
The photocatalytic activity of the PPy/Bi2WO6 composite
was evaluated in terms of phenol degradation in aqueous
solution under simulated sunlight, and the pure Bi2WO6
sample was also tested for comparison. Phenol was selec-
ted as the model pollutant instead of dyes because it has no
light absorption property in the visible light region and the
photo-sensitization effect can be excluded. Figure 7 shows
the photo-degradation rate of phenol as a function of time,
where C was the concentration of phenol after irradiation
and C0 was the concentration after the adsorption equilib-
rium on the photocatalyst particles before irradiation. It
was found that phenol exhibited little photolysis under
simulated sunlight illumination only without photocatalyst,
which indicated that phenol is stable under simulated
sunlight. In contrast, phenol was completely degraded in
the presence of PPy/Bi2WO6 composite under simulated
sunlight illumination after 120 min reaction, while only
72.4 % of phenol was degraded by pure Bi2WO6 within the

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Fig. 7 Degradation efficiency of phenol as a function of time by the
as-prepared samples under visible light irradiation
Fig. 8 EIS Nyquist plots of PPy/Bi2WO6 and Bi2WO6 electrodes in
0.1 M Na2SO4 solution
same time period. This result indicated that the modifica-
tion of PPy could significantly enhance the photocatalytic
activity of Bi2WO6.
Mechanism of enhanced photoactivities
The competition between the charge separation process and
the charge recombination process is a determination factor
for photocatalysis efficiency. Desired photocatalysts are
expected to promote the charge transfer process while
suppressing recombination process. The electronhole
recombination rate, in turn, depends mainly on the charge
transport properties. The charge transport properties of
Bi2WO6 and PPy/Bi2WO6 were investigated by electro-
chemical impedance spectra (EIS). Figure 8 showed the
EIS Nyquist plots of Bi2WO6 and PPy/Bi2WO6 photocat-
alysts at open-circuit potential. The radius of the arc on the
EIS spectra reflects the reaction rate occurring at the
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J Mater Sci (2014) 49:73257332
Visible light
CB
LUMO
H H
N N
N
n
H
Bi2WO6 HOMO
VB
: electron : hole
CB: conduction band
VB: valence band
Fig. 9 The energy level diagram for Bi2WO6 and PPy and the charge
transfer processes
surface of the electrode [3032]. The smaller arc radius on
the EIS Nyquist plot of PPy/Bi2WO6 indicates that a more
effective separation of photogenerated electronhole pairs
and a faster interfacial charge transfer had occurred. This
result indicated that the introduction of PPy into Bi2WO6
can effectively enhance the separation efficiency of
photogenerated electronhole pairs.
According to the relative energy level of PPy (p-orbital
and p*-orbital) and Bi2WO6 (conduction band, CB, and
valence band, VB) [33, 34], the lowest unoccupied
molecular orbital (LUMO) levels of the PPy polymer are
energetically higher than the conduction band edge of
Bi2WO6 and the highest occupied molecular orbital
(HOMO) levels of PPy are higher than the valance band
edge of Bi2WO6. So the charge transfer processes of the
conjugated polymer and Bi2WO6 can be illustrated in
Fig. 9. Under simulated sunlight irradiation, the polymer
can absorb photons and promote an electron from the
ground state into an excited state. Meanwhile, electrons can
be excited to the conduction band and leave holes in the
valence band of Bi2WO6. As an efficient electron donor,
the excitated electrons of PPy can be easily injected to the
conduction band of Bi2WO6. Simultaneously, the photo-
generated holes in valance band of Bi2WO6 can directly
transfer to the p-orbital of PPy. By this way, efficient
charge separation at the interface between Bi2WO6 and
PPy was realized.
More importantly, the main oxidative species in the
Bi2WO6 photocatalysis system are photogenerated holes
while PPy is an efficient hole conductor. This can be ver-
ified by adding oxidative species scavengers into the
reaction system, as shown in Fig. 10. It was found that the
addition of 2-propanol, a well-known scavenger of
OH
radicals [19, 35], into the photoreaction system did not
J Mater Sci (2014) 49:73257332
Fig. 10 Photocatalytic degradation of phenol by PPy/Bi2WO6 with
different scavengers (10-4 mol L-1 2-propanol, 0.005 mol L-1
sodium oxalate)
H H
N N
N
N H
H
h+
e- h+ e-
Bi2WO6 H H
N N
N
N
H
H Chem Rev 95:6996
Fig. 11 Mechanism of the hole transport process through PPy
cause apparent changes in the degradation of phenol. This
indicated that
OH radicals could not be the main reactive
oxygen species in this photochemical process. However,
with the introduction of a hole scavenger, sodium oxalate
[36], the photo-degradation of phenol was depressed by a
large extent, which implied that holes are the main oxi-
dative species in the PPy/Bi2WO6 photocatalysis system.
Due to the conjugated structure of PPy, the photogenerated
holes can be transported easily through the p-conjugated
bond, as shown in Fig. 11. This is in accordance with the
result in Fig. 8, which showed that PPy/Bi2WO6 composite
had better charge transport properties. Then the holes that
migrated to polymer/solution interface can oxidize the
adsorbed contaminations directly. As a result, the PPy/
Bi2WO6 composite exhibits excellent photocatalytic
performance.
Conclusions
Bi2WO6 was modified with PPy by a photocatalytic oxi-
dative polymerization process. The photo-degradation of
phenol under simulated sunlight, demonstrated that the
7331
modification of Bi2WO6 with PPy could greatly enhance
the photocatalytic activity of Bi2WO6. The introduction of
PPy could not only facilitate the separation of charge car-
riers, but also channel the photogenerated holes to the
polymer/solution interface at a rate much faster than the
self-oxidation of the semiconductor. This work opens new
possibilities to provide some insights into the design of
new modified photocatalysts with high activity for envi-
ronmental purification and other applications.
Acknowledgements We acknowledge the financial support from
the Shanghai Science and Technology Committee (14YF1410700)
and the scientific research funds of Shanghai Institute of Technology
(10120K146024-YJ2014-24).
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