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Synergistic eect of crystal and electronic structures on the

visible-light-driven photocatalytic performances of Bi2O3 polymorphsw
Hefeng Cheng,a Baibiao Huang,*a Jibao Lu,b Zeyan Wang,a Bing Xu,a
Xiaoyan Qin,a Xiaoyang Zhanga and Ying Daib
Received 15th July 2010, Accepted 31st August 2010
DOI: 10.1039/c0cp01189d
Three polymorphs of Bi2O3 were selectively synthesized via solution-based methods. The phase
structures of the as-prepared samples were conrmed by X-ray powder diraction (XRD) and
X-ray photoelectron spectroscopy (XPS). UV-vis diuse reectance spectroscopy was employed to
study the optical properties of Bi2O3 polymorphs, and the band gaps were estimated to be 2.80,
2.48, and 3.01 eV for a-Bi2O3, b-Bi2O3, and d-Bi2O3, respectively. The photocatalytic
performances of the oxides were investigated by decomposing methyl orange and 4-chlorophenol
under visible irradiation at room temperature. It was observed that b-Bi2O3 displayed much
higher photocatalytic performance than N-doped P25. Among the three polymorphs of Bi2O3, the
photocatalytic activities followed the order: b-Bi2O3 > a-Bi2O3 > d-Bi2O3, which was in good
accordance with the photoluminescence spectra measurement results. The synergistic eect of the
crystal and electronic structures on the photocatalytic performances of Bi2O3 polymorphs was
investigated. The much better photocatalytic activity of b-Bi2O3 was considered to be closely
related to its smaller band gap, higher crystallinity and unique tunnel structure.

1. Introduction
The past several decades have witnessed the exponential
increase of studies on semiconductor photocatalysts, which
were employed for energy conversion and environmental
decontamination.15 TiO2, one of the most extensively studied
semiconductors, was regarded as an outstanding candidate
and usually used as a reference material for photocatalytic
evaluation owing to its unique photochemical features.2
However, lack of visible absorption hinders the practical
applications of TiO2, which only captures less than 4% of
the sunlight. Therefore, to make the best of the solar energy or
indoor illumination, it is indispensable to exploit visible-lightdriven photocatalysts. To date, substantial eorts have been
devoted to expanding the absorption spectra of the photocatalysts into the visible range by energy band engineering and
two approaches have been well developed. One of the
approaches is the modication of TiO2, which involves metal6,7
and/or non-metal ions doping.3,810 Nonetheless, the doped
materials usually could not endure thermal stability, and the
dopants always perform as the recombination sites of the
photoinduced electrons and holes.6 Another access is to seek
new semiconductor photocatalysts working under visible
irradiation.1115 Among them, the Bi-based multimetal oxides
with a 6s2 conguration, such as CaBi2O4,16 BiVO4,17 have
shown to be active under visible illumination, which can be
a

State Key Lab of Crystal Materials, Shandong University,

Jinan 250100, Peoples Republic of China.
E-mail: bbhuang@sdu.edu.cn; Fax: +86-531-8836-5969;
Tel: +86-531-8836-6324
b
School of Physics, Shandong University, Jinan 250100,
Peoples Republic of China
w Electronic supplementary information (ESI) available: Adsorptivity
of dye on catalysts; SEM images; photocatalytic activity comparison.
See DOI: 10.1039/c0cp01189d

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ascribed to their fresh-constructed, well-dispersed valence

bands by the hybridization of Bi 6s and O 2p orbitals.
Due to its particular dielectric, optical, and ion-conductive
properties, bismuth trioxide (Bi2O3) has been extensively
applied in gas sensors, optoelectronics devices, and catalysts.1820
Recently, Bi2O3 as an undoped and single oxide semiconductor
sensitive to visible irradiation has also been found to exhibit
good photocatalytic performance, which originates from its
appropriate band gap.21 Generally, Bi2O3 has four dierent
polymorphs, denoted as monoclinic a, tetragonal b, bodycentered cubic g, and face-centered cubic d. Among these, the
low-temperature a-phase and the high-temperature d-phase
are stable; while the other two phases are high-temperature
metastable.19 So far, Bi2O3 nano/microstructures have been
prepared by various ways, and dierent synthetic procedures
could lead to dierent phases of Bi2O3.2224 As is known, the
photocatalytic performance of a photocatalyst is closely
related to its corresponding structural and photochemical
features.25,26 For example, as a result of their dierent band
and crystal structures, monoclinic BiVO4 shows much better
photocatalytic properties than tetragonal BiVO4.17 Since each
polymorph of Bi2O3 possesses a special crystal and electronic
structure, there is good reason to believe that the activities of
Bi2O3 polymorphs will dier from each other. Although the
photocatalytic activities of Bi2O3 have been reported,21,24 to
the best of our knowledge, few studies have been devoted to
exploring the correlation between the crystal structures,
electronic structures, and the photocatalytic properties of the
Bi2O3 polymorphs.
In the present work, we have prepared three dierent
polymorphs of Bi2O3 through the solution-based routes by
varying the experimental conditions. The photocatalytic
performances of the Bi2O3 polymorphs were evaluated by
decomposing methyl orange and 4-chlorophenol under visible
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light irradiation. A systematical synergistic eect of crystal

and electronic structures on the visible-light-driven photocatalytic performances of Bi2O3 polymorphs was discussed.

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2. Experimental
2.1

Samples preparation

All the reagents employed in the experiments were analytical

grade and used without any further purication.
(1) a-Bi2O3. In the preparation of a-Bi2O3, Bi(NO3)3
5H2O
(1.94 g, 4 mmol) was rst dissolved in dilute HNO3 (1 mol L 1,
20 mL) to give a clear solution. Then NaOH (4 mol L 1,
80 mL) aqueous solution was added with continuous stirring.
The suspension was heated and maintained at 60 1C for 6 h.
The nal products were ltered, washed, and dried at 60 1C in
vacuum for several hours.
(2) b-Bi2O3. To synthesize b-Bi2O3, Bi(NO3)3
5H2O was
dissolved in dilute HNO3, then the solution was added
dropwise to the excessive Na2CO3 solution with constant
stirring for 2 h to obtain Bi2O2CO3.27 Then the as-derived
Bi2O2CO3 precipitation was ltered, washed, dried in vacuum,
and nally annealed at 380 1C for 10 min to yield b-Bi2O3.28
(3) d-Bi2O3. The preparation procedure of d-Bi2O3 was
similar to that of a-Bi2O3, except that equal stoichiometric
amount of NH4VO3 was introduced, which modulated the
phase formation of d-Bi2O3.24
2.2

Samples characterization

Powder X-ray diraction (XRD) patterns were recorded on a

Bruker AXS D8 advance powder diractometer (Cu-Ka X-ray
radiation, l = 0.154056 nm). X-Ray photoelectron spectroscopy

(XPS) measurements were performed on a Thermo Fisher

Scientic Escalab 250 spectrometer with monochromatized
Al Ka excitation, and C 1s (284.6 eV) was used to calibrate
the peak positions of the elements. The scanning electron
microscopy (SEM) images were obtained on a Hitachi
S-4800 microscope with an accelerating voltage of 7.0 kV. A
Micromeritics ASAP 2020 analyzer was employed to measure
the BrunauerEmmettTeller (BET) surface areas of the
samples at liquid nitrogen temperature. The photoluminescence
(PL) was carried out on a Hitachi F-4500 uorescence spectrophotometer at room temperature. UV-vis diuse reectance
spectra were collected on a Shimadzu UV 2550 recording
spectrophotometer, which was equipped with an integrating
sphere.
2.3 Photocatalytic performance evaluation
The photocatalytic performances of the as-prepared products
were evaluated by decomposition of methyl orange (MO) and
4-chlorophenol (4-CP) under visible light irradiation at room
temperature. A 300 W Xe arc lamp (PLS-SXE300, Beijing
Trusttech Co., Ltd.) was used as the light source and equipped
with an ultraviolet cuto lter to provide visible light
(l Z 400 nm). The distance between the liquid surface
of the suspension and the light source was set about 10 cm.
The photodegradation experiments were performed with the
sample powder (100 mg) suspended in MO or 4-CP aqueous
solution (20 mg L 1, 100 mL) with constant stirring. Prior to
irradiation, the suspensions were stirred in the dark for 1 h to
ensure the adsorption/desorption equilibrium. At the given
time intervals, about 5 ml of the suspension was taken for the
following analysis after centrifugation. The MO and 4-CP

Fig. 1 Scheme crystal structures of the Bi2O3 polymorphs: (a) a-Bi2O3, (b) b-Bi2O3 and (c) d-Bi2O3.

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photodegradation were then analyzed at 464 and 225 nm,

respectively, as a function of irradiation time on a UV-vis
spectrophotometer (Shimadzu UV 2550).

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2.4

Theoretical calculations

The theoretical calculations in our study were performed by

using the standard CASTEP package, which is a plane-wave
pseudopotential total energy calculation method based on the
density functional theory (DFT). The lattice parameters of the
a-Bi2O3, b-Bi2O3 and d-Bi2O3 models were optimized, and
then these models were used to calculate the ground-state
energy band. The exchangecorrelation potential was depicted
by the generalized gradient approximation (GGA) with the
PerdewBurkeErnzerhof (PBE) scheme.29 The Brillouin
zones were separately sampled at 5  3  4, 3  3  4 and
4  4  4 MonkhorstPack k-points for the a, b and d phase.30
The electronic wave functions were expanded in a plane-wave
basis set up to a 380 eV cuto, while the self-consistent eld
(SCF) tolerance was all 5  10 7 eV/atom.

3. Results and discussion

3.1

Structure analysis

Fig. 1 illustrates the scheme crystal structures of the Bi2O3

polymorphs. In a-Bi2O3 structure (see Fig. 1a), the layers of
bismuth atoms are parallel to the (100) crystal plane of the
monoclinic cell, which are separated by the layers of oxygen
ions in a zigzag manner.31,32 In b-Bi2O3 (see Fig. 1b),
tunnels lie in the structure along the crystallographic c axis.33
However, in the uorite-type structure of d-Bi2O3 (see Fig. 1c), a
large number of oxygen defects result in its high degree of
disorder.32
X-Ray powder diraction (XRD) is a useful tool to
characterize the phase structure of the materials. Fig. 2 shows
the XRD patterns of the as-prepared Bi2O3 polymorphs. The
identications of the diraction peaks of the samples can
be indexed well to the single phases, which are monoclinic

a-Bi2O3 (JCPDS No. 41-1449), tetragonal b-Bi2O3 (JCPDS

No. 27-0050), and cubic d-Bi2O3 (JCPDS No. 52-1007),
respectively. The sharp diraction peaks of a-Bi2O3 and
b-Bi2O3 indicate their high crystallinity. However, in the case
of d-Bi2O3, the diraction peaks become much broader and
weaker, which suggests its low crystallinity along with the
decreased crystallites. Furthermore, the lattice parameters
were also deduced from the cell renement of the compounds
and listed in Table 1.
To elucidate the oxidation states of the Bi2O3 polymorphs,
X-ray photoelectron spectroscopy (XPS) was conducted.
Fig. 3 demonstrates the high-resolution XPS spectra of Bi 4f
and O 1s states of the dierent polymorphs of Bi2O3 products.
All the three dierent Bi2O3 polymorphs exhibit narrow
Gauss-shaped symmetrical Bi 4f7/2 and Bi 4f5/2 core spectra
(see Fig. 3a). The characteristic binding energy values of
Bi 4f7/2 for a-Bi2O3, b-Bi2O3, and d-Bi2O3 are 158.5, 158.4,
and 158.6 eV, respectively, which are in agreement with the
reported values.34,35 Moreover, no related peaks of bivalent,
tetravalent, or pentavalent states were found on the Bi 4f7/2
shoulder, which indicates that Bi exists as Bi(III) oxidation
state in all the samples.34 However, in the XPS spectra of O 1s
peaks (see Fig. 3b), notable asymmetry and broadening can be
observed. In all the Bi2O3 samples, the O 1s spectra can be
deconvoluted into two peaks, which are the BiO in the crystal
lattice with lower binding energy and the absorbed oxygen
(OH or CO32 groups) on the surface with higher energy.35
The binding energies of BiO in a-Bi2O3, b-Bi2O3, and d-Bi2O3
are accordingly found to be 530.1, 530.5, and 530.1 eV, and
this diversity could result from their dierent crystal
structures.
The typical microstructure information of the Bi2O3
polymorphs was obtained by the SEM images (see Fig. 4).
As Fig. 4a shows, the a-Bi2O3 products are presented as
ower-like architectures, which consist of interlaced microrods that are 24 mm in length and about 1 mm in thickness.
The b-Bi2O3 products are composed of the worm-like structures
with numerous pores (see Fig. 4b). In Fig. 4c, plenty of
nanoparticles with an average size of ca. 20 nm are found in
d-Bi2O3 products.
As a signicant index to the photocatalytic activity, the
BrunauerEmmettTeller (BET) surface areas of the Bi2O3
products were executed and listed in Table 1. The BET surface
area was only 1.10 m2 g 1 for a-Bi2O3, and this was attributed
to its big crystallites. The smaller grain size and the porous
structures enabled b-Bi2O3 to have a bigger BET surface area
of 8.55 m2 g 1. The BET surface area of d-Bi2O3 reached as
high as 39.2 m2 g 1, which stemmed from its much smaller
crystallites.
3.2 Photophysical properties

Fig. 2 XRD patterns of the a-Bi2O3, b-Bi2O3, and d-Bi2O3 products.

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As the direct recombination consequence of the photogenerated

electrons and holes, photoluminescence emission spectra are
usually employed to determine the separation eciency of the
charge carriers.36 Fig. 5 shows the room temperature PL
spectra of the Bi2O3 polymorphs with the excitation wavelength
at 300 nm. We can observe that both a-Bi2O3 and d-Bi2O3
show a strong broad emission peak around 460 nm,37 implying
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Table 1

The lattice parameters, band gaps and BET surface areas of the Bi2O3 polymorphs

Sample

Crystal structure

Space group

Lattice parameters

Eg/eV

d/nma

SBET /m2 g

a-Bi2O3

monoclinic

P21/c

2.80

80.8

1.10

b-Bi2O3

tetragonal

P421c

2.48

47.1

8.55

d-Bi2O3

cubic

Fm3m

a = 5.849 A
b = 8.165 A
c = 7.509 A
g = 113.01
a = 7.731 A
b = 5.628 A
a = 5.520 A

3.01

19.3

39.2

the mean sizes of the samples obtained according to the Scherrer formula.

Fig. 3 High-resolution XPS spectra of (a) Bi 4f and (b) O 1s states of

the dierent polymorphs of Bi2O3 products.

the high recombination rates of the photoinduced carriers.

However, b-Bi2O3 shows a rather lower intensity, which
means the ecient separation rate of the carriers in b-Bi2O3
structure.38 The PL intensity of the samples follows the order:
d-Bi2O3 > a-Bi2O3 > b-Bi2O3, indicating the relative amounts
of trapping sites for the free carriers in the crystal structures of
the Bi2O3 polymorphs.
Fig. 6 displays the UV-vis diuse reectance spectra of the
Bi2O3 polymorphs. As Bi2O3 behaves the direct absorption
dependence, its band gap can be extrapolated by the following
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Fig. 4 Typical SEM images of (a) a-Bi2O3, (b) b-Bi2O3, and

(c) d-Bi2O3 samples.

equation39 ahn = A(hn

Eg)1/2, where a, n, Eg, and A are
the absorption coecient, light frequency, band gap, and a
constant, respectively. As shown in the insert, the band gaps
are deduced from the plot (ahn)2 versus (hn) and estimated to
be 2.80, 2.48, and 3.01 eV for a-Bi2O3, b-Bi2O3, and d-Bi2O3,
respectively.
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PL spectra of the dierent Bi2O3 polymorphs (lexc = 300 nm).

Fig. 5

Fig. 6 UV-vis diuse reectance spectra of the Bi2O3 polymorphs:

(a) a-Bi2O3, (b) b-Bi2O3, and (c) d-Bi2O3; Insert: the corresponding
plots of (ahn)2 versus energy (hn).

3.3

Photocatalytic properties

The photocatalytic performances of the dierent Bi2O3

polymorphs were investigated by decomposing MO and
4-CP under visible irradiation (l Z 400 nm). Fig. 7 represents
the photodegradation of MO as a function of irradiation time
over dierent photocatalysts. As shown, after irradiation for
90 min, the photodegradation eciency of MO on a-Bi2O3
was 13.9%, which was negligible for d-Bi2O3. However, for
b-Bi2O3, the photodegradation eciency could reach 87.3%
when subjected to illumination only for 60 min. As the MO
photodegradation follows the pseudo-rst-order reaction, it is
worth noting that the MO photodegradation rate over b-Bi2O3
(1.7505 h 1) was almost 16 times faster than that of a-Bi2O3
(0.1098 h 1). The photocatalytic activity of the Bi2O3 polymorphs
followed the order: b-Bi2O3 > a-Bi2O3 > d-Bi2O3. For
comparison, after irradiation for 90 min, N-doped P25 displayed
a low degradation rate of 9.8%.
As a precondition for photocatalytic performance, the
adsorptivity of MO dye on catalysts was studied after the
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Fig. 7 Photodegradation of MO with time over dierent photocatalysts under visible irradiation.

adsorption/desorption equilibrium in the dark. As shown in

the ESI (see Fig. S1),w the bar plot illustrated the remaining
concentration of MO over dierent photocatalysts. Among
the photocatalysts, b-Bi2O3 showed the best adsorption
capacity, and the remaining concentration of MO dye was
ca. 83%. Since the BET area of b-Bi2O3 is far lower than that
of d-Bi2O3 or N-doped P25, the adsorptivity of MO dye would
not merely stem from the simple physical absorption. The
better adsorptivity of MO dye on b-Bi2O3 is believed to be
largely associated with the selective absorption of aromatic
dye.40
Given that MO has considerable absorption in the visible
light region, we have also tested the photodecomposition
of 4-CP under visible irradiation to exclude the possible
inuential factors such as dye sensitization. Fig. 8 shows the
photodecomposition of 4-CP in the presence of the dierent
photocatalysts. As an aromatic compound to show resonance
stability, 4-CP was dicult to decompose. After visible
irradiation for 90 min, about 12.3% of 4-CP molecules were
decomposed over a-Bi2O3, and the photodecomposition
eciency of d-Bi2O3 was only 6.5%. In particular, b-Bi2O3
displayed much higher decomposition eciency, which could

Fig. 8 Photodegradation of 4-CP with time over dierent photocatalysts under visible irradiation.

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Fig. 9 Electronic structures of (a) a-Bi2O3 and (b) b-Bi2O3.

reach 80% after irradiation for 90 min. The photocatalytic

performances of the Bi2O3 polymorphs also obeyed the
sequence b-Bi2O3 > a-Bi2O3 > d-Bi2O3. Besides, about
21.7% of the 4-CP molecules were decomposed over N-doped
P25 sample under the same conditions. It was found that the
4-CP photodecomposition rate over b-Bi2O3 (0.8543 h 1) was
much faster than that of a-Bi2O3 (0.0783 h 1) and N-doped
P25 (0.0816 h 1) by a factor of about eleven.
As the BET area of b-Bi2O3 (8.55 m2 g 1) is ca. 8 times
larger than that of a-Bi2O3 (1.10 m2 g 1), one could conceive
that larger BET area of a-Bi2O3 will lead to higher photocatalytic performance. To elucidate the inuences of BET
surface area on the photocatalytic performance, we also
prepared a-Bi2O3 by calcination treatment and the product
was labeled as a-Bi2O3 (CT). Firstly, Bi(NO3)3
5H2O was
dissolved in dilute HNO3, then NH3
H2O was introduced
dropwise to the solution and the pH value was adjusted to
7.0. The white suspension was ltered, washed, dried, and
nally calcined at 500 1C for 1 h. The as-prepared a-Bi2O3
(CT) products consist of irregular nanoparticles with an
average diameter of about 1 mm (see Fig. S2 in the ESI).w
The BET area of a-Bi2O3 (CT) products (6.53 m2 g 1) is about
6 times larger than that of a-Bi2O3, however, the corresponding
photocatalytic activity improved slightly a little (see Fig. S3
in the ESI).w The above results suggest that the dramatic
dierence in the photocatalytic activities of a-Bi2O3 and
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b-Bi2O3, under the maintenance of similar crystallinity and

BET area, can be attributed to their crystal and electronic
structure dierences..
3.4 Synergistic eects of the crystal and electronic structures
on the photocatalytic performances
In general, the photocatalytic capacity of a semiconductor
photocatalyst is mainly dependent on two factors, which are
the separation eciency of the photoinduced carriers and the
light absorption range. Among the Bi2O3 polymorphs, their
photocatalytic activities for decomposing MO and 4-CP both
follow the order b-Bi2O3 > a-Bi2O3 > d-Bi2O3. The crystal
structures have an important eect on the corresponding
photocatalytic performances.2,25,26 d-Bi2O3 exhibits much
structural disarrangement, which could readily become the
recombination sites of the carriers. In addition, the rather low
crystallinity of d-Bi2O3 gives rise to many defects on the
surface or in the volume, which leads to its high recombination
rate of the electronhole pairs and the negligible photocatalytic
activity. This was also conrmed by its highest PL intensity of
d-Bi2O3 among the Bi2O3 polymorphs. In contrast, the high
crystallinity of a-Bi2O3 and b-Bi2O3 could be propitious to
decreasing the recombination sites of the free carriers, which
results in a higher photocatalytic eciency. Whereas the dramatic
dierences in the photocatalytic activities of a-Bi2O3 and
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b-Bi2O3 still remain, and these could be associated with their

specic crystal structures. The tunnels in b-Bi2O3 can provide
the channels for the transfer of the photogenerated electrons
and holes to prevent the excessive recombination of them,
which could enable more free carriers to participate in the
photodecomposition process. Since the formed internal
electric eld between the two layers benets the transfer of
the photoinduced carriers, the layered compounds could
eectively improve the separation eciency.13 Nonetheless,
for a-Bi2O3, its zigzag-type conguration increases the
recombination rates of the carriers, leading to its higher PL
intensity than that of b-Bi2O3. Therefore, b-Bi2O3 shows much
higher photocatalytic performance than a-Bi2O3. The results
conrmed that while maintaining similar crystallinity and
BET surface areas, b-Bi2O3 also exhibited much better photocatalytic property than a-Bi2O3, and this could be explained by
their dierence in crystal structure.
Fig. 9 illustrates the band structure and density of states of
monoclinic a-Bi2O3 and tetragonal b-Bi2O3. As is known, due
to the deep energy position of O 2p orbital in valence band,
TiO2 has a wide band gap only responsive to UV light.4 For
the Bi(III)-based oxides, the hybridized valence band (VB)
composed of Bi 6s and O 2p orbitals is thought to narrow
the band gaps into the visible region, and its large dispersivity
is favorable to the mobility of the photogenerated carriers.1517 It
can be observed that in both a-Bi2O3 and b-Bi2O3, the top of
VBs is mainly comprised of O 2p and Bi 6s orbitals, which
makes a-Bi2O3 and b-Bi2O3 sensitive to visible light irradiation,
while the bottom of conduction bands (CBs) is dominantly
constructed by Bi 6p orbital. It is noted that b-Bi2O3 exhibits a
more dispersive band structure than a-Bi2O3, which is more
suitable for the transfer of the photoinduced electrons and
holes. In addition, The VBs of a-Bi2O3 and b-Bi2O3 are
similar, yet the bottom of CB of b-Bi2O3 shifts to a more
negative potential, resulting in Eg(b-Bi2O3) o Eg(a-Bi2O3).
The calculated nding turns out to be in accordance with the
measured band gaps of b-Bi2O3 (2.48 eV) and a-Bi2O3
(2.80 eV), which demonstrates that b-Bi2O3 can absorb more
visible light than a-Bi2O3. The mentioned two points above
give an electronic structure explanation why b-Bi2O3 shows a
much better photocatalytic performance than a-Bi2O3.
However, with regard to d-Bi2O3, we failed to optimize the
semiconductor electronic structure on account of its high ionic
conductivity.32,41 Nonetheless, derived from the wide band
gap of d-Bi2O3 (3.01 eV), it could only respond to visible
light in a small proportion, which also resulted in its low
photocatalytic eciency.

4. Conclusions
In this work, we have synthesized three dierent phases of
Bi2O3 through the solution-based routes. The band gaps of the
Bi2O3 polymorphs were estimated to be 2.80, 2.48, and
3.01 eV for a-Bi2O3, b-Bi2O3, and d-Bi2O3, respectively. In
the photocatalytic experiments of decomposing methyl orange
and 4-chlorophenol, it was observed that b-Bi2O3 displayed
much higher photocatalytic performance than N-doped P25.
Furthermore, the photocatalytic activities of Bi2O3 polymorphs
followed the order: b-Bi2O3 > a-Bi2O3 > d-Bi2O3, which was
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in good accordance with the photoluminescence spectra

measurement results. The layered structure of a-Bi2O3 and
tunnel structure of b-Bi2O3 favor the transfer of the photoinduced carriers, while a mass of defects in d-Bi2O3 increase
the recombination rates of the carriers. Moreover, deduced
from the electronic structures calculations, b-Bi2O3 has smaller
band gap than a-Bi2O3, and this is in good agreement with the
measured values. The higher crystallinity, smaller band gap,
and tunnel structure are believed to be associated with the
excellent photocatalytic activity of b-Bi2O3. Our study reveals
b-Bi2O3 as a highly ecient visible-light-driven photocatalyst,
and appropriate microstructure modulation may lead to
higher photocatalytic performance. In addition, this work
provides theoretical and experimental evidence for the
synergistic eects of the crystal and electronic structures on
the photocatalytic properties, which could be applied to other
semiconductor photocatalysts with polymorphs, such as WO3,
In2O3, CdS and so on.

Acknowledgements
This work was nancially supported by a research Grant from
the National Basic Research Program of China (973 Program,
Grant 2007CB613302), the National Natural Science
Foundation of China under Grants (Nos. 20973102,
50721002 and 10774091), and China Postdoctoral Science
Foundation funded project (20090461200).

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