Applied Catalysis B: Environmental 68 (2006) 125–129

www.elsevier.com/locate/apcatb

Study of the electronic structure and photocatalytic activity

of the BiOCl photocatalyst
Ke-Lei Zhang a, Cun-Ming Liu a, Fu-Qiang Huang a,*, Chong Zheng b,*, Wen-Deng Wang a
a
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, PR China
b
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Received 8 December 2005; received in revised form 24 July 2006; accepted 4 August 2006
Available online 7 September 2006

Abstract
A novel bismuth oxychloride (BiOCl) was synthesized by a hydrolysis method. The powder sample was characterized by X-ray diffraction,
field emission scanning electron microscope and UV–vis spectrophotometer. The layered compound BiOCl was the first oxyhalide to be used
as a photocatalyst. The prepared material has an optical indirect band-gap of 3.46 eV. For its photocatalytic reactivity, the methyl orange (MO)
dye degradation was chosen to be investigated. In a comparison of a three-cycle measurement of BiOCl with that of TiO2 (P25, Degussa), it
was found that BiOCl had better performance than P25 at every recycle. The calculated electronic structure of BiOCl confirms that it has an
indirect band-gap, and the Cl 3p and Bi 6p states dominate the highest occupied molecular orbitals (HOMO) and the lowest unoccupied
orbitals (LUMO), respectively. The open crystal structure and indirect optical transitions of BiOCl play important roles in its excellent
photocatalytic activity.
# 2006 Elsevier B.V. All rights reserved.

Keywords: Photocatalyst; UV–vis; BiOCl; Band-gap; Methyl orange

1. Introduction
Heterogeneous photocatalysis through semiconductor solid
systems has become an exciting and rapidly growing area of
research in the last few years [1,2]. It can be used to decompose
organic compounds into inorganic substances for the purpose of
purifying textile dye wastewater from industries [3,4], and to
split water into hydrogen and oxygen gases for clean energy
production [5]. There are numerous papers on the photo-
degradation of organic compounds and the splitting of water,
and the reported photocatalysts include oxides, nitrides,
sulfides, etc., but most of them are focused on TiO2-based
photocatalyst [6,7].
Very recently, anion-doped titanium oxide systems have
been intensively investigated. Asahi et al. reported that TiO2
doped by nitrogen (N) exhibited higher photocatalytic activity
in such reactions as photodegradation of methylene blue [8].
* Corresponding authors.
E-mail addresses: huangfq@mail.sic.ac.cn (F.-Q. Huang),
zheng@cz.chem.niu.edu (C. Zheng).
0926-3373/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2006.08.002
Khan et al. described that substitution of carbon (C) for oxygen
in TiO2 caused higher photoconversion efficiency for water
splitting [9]. Modified titanium dioxide through co-doping with
bromine (Br) and chlorine (Cl) was also studied as a
photocatalyst for water splitting under UV light [10]. Although
a lot of progress has been achieved, the photocatalytic activity
enhancement was observed in TiO2-based materials. Few other
types of anion-doped oxides have been investigated as
photocatalysts. In order to achieve maximum photocatalytic
activity, it is indispensable to develop new hybrid oxide
photocatalysts.
In this paper, the oxychloride photocatalyst BiOCl was
synthesized using a hydrolysis method. Its photocatalytic activity
was evaluated by the photodecomposition of MO in aqueous
medium under UV lamp, and a comparison of the three-cycle
measurement on BiOCl and TiO2 (P25, Degussa) was presented.
BiOCl is a known tetragonal structure with lattice constants
a = 3.890 Å and b = 7.890 Å [11]. To understand the electronic
structure of BiOCl, theoretical calculations were performed
using a density functional method (TB-LMTO). To our
knowledge, this is the first investigation of photocatalytic
activity of an oxyhalide.
126 K.-L Zhang et al. / Applied Catalysis B: Environmental 68 (2006) 125–129
2. Experimental
2.1. Synthesis
BiOCl powder was synthesized by a hydrolysis method. The
reagent Bi2O3 (AR, Shanghai) was dissolved in excessive
concentrated hydrochloric acid (AR, Shanghai) to obtain a
BiCl3–HCl aqueous system. A white colloid appeared when the
pH value of the solution was adjusted between 2 and 3 with
ammonia (AR, Shanghai). After the colloid was heated at 40 8C
for half an hour, a powdery BiOCl material consisting of small
plate-like crystals was obtained. The product was purified by
filtration, washed by distilled water until no Cl was left in
the solution as tested by silver nitrate (AgNO3) and then
dried at 40 8C in a vacuum dry oven for 6 h before further
characterization.
2.2. Characterization
X-ray powder diffraction patterns of the prepared samples
were recorded on a Rigaku D/MAX-2550 V at 40 kV and
40 mA (Cu Ka radiation). FE-SEM images were obtained on a
JSM-6700F field emission scanning electron microscope at
10.0 kV. The UV–vis absorption spectra were measured by a
Hitachi U-3010 spectrophotometer.
2.3. Electronic structure calculation
Electronic structure of BiOCl was calculated by the TB-
LMTO program, which is a self-consistent, scalar relativistic
linearized muffin-tin orbital program by Andersen and Jepsen
within the atomic sphere approximation [12,13]. This method
splits the crystal space into overlapping atomic spheres
(Wigner-Seitz spheres) whose radii are chosen to fill
completely the crystal volume. In the present calculations,
the von Barth–Hedin exchange-correlation potential was used
within the local density approximation (LDA) [14]. All k-space
integrations were performed with the tetrahedron method
[15,16]. The basis sets consisted of the valence 6s and 6p states
for Bi, 2s and 2p states for O, 3s and 3p states for Cl, and 1s
states for empty spheres. The 6d states for Bi, 3d states for O
and Cl, and p–d states for empty spheres were downfolded by
means of the technique described by Löwdin [17]. Within the
Brillouin zone of the cell, 144 irreducible k points were used.
The respective high-symmetry points are G (0,0,0), X (1/2,0,0),
Z (0,0,1/2), M (1/2,1/2,0), R (1/2,0,1/4), and A (1/2,1/2,1/4) in
terms of the reciprocal basis vectors [18].
2.4. Photocatalytic measurement
A photocatalytic reaction system consisting of a 300 W
ultraviolet high-pressure mercury lamp with a maximum
emission at 365 nm and a water filter was used. The filter was
placed between the mercury lamp and the reaction cell to prevent
the thermal catalytic effect. The photocatalytic property of
BiOCl was evaluated by decomposing 10 mg/L methyl orange
(MO) in aqueous medium inside a batch photocatalytic reactor.
0.2 g powder BiOCl was suspended in 100 mL MO solution. The
slurry of the photocatalyst and the MO solution was stirred by a
magnetic bar in dark for 45 min to achieve adsorption–
desorption equilibrium of the suspension. At specific time
intervals, 3 mL of the reactive solution was withdrawn by a
syringe. The solution was centrifuged to remove the BiOCl
powder before being analyzed by the U-3010 spectrophotometer.
For comparison, three cycles of measurements were performed
for both BiOCl and TiO2 (P25, Degussa), respectively.
3. Results and discussion
3.1. XRD and FE-SEM analysis
The XRD pattern of as-prepared BiOCl, as shown in
Fig. 1(a), indicates that the single phase of BiOCl (JCPDS
ICDD no. 73-2060) was synthesized. The narrow broadening of
the peaks implies a well-crystallized BiOCl powder material.
To test the stability of the sample during the photocatalytic
process, we analyzed it again at the end of the process by XRD.
Fig. 1(b) shows the XRD pattern of BiOCl after the
photocatalytic reaction. As shown in the figure, the pattern
did not change after the reaction. Thereby, the photocatalyst is
stable during the reaction and can be repeatedly used. The FE-
SEM images of the samples are shown in Fig. 2. Clearly, the
morphology of BiOCl is dominated with plates, and the longest
dimension of the plates is between 100 and 300 nm.
3.2. UV–vis diffuse reflectance spectroscopy
Reflectance spectra of BiOCl and TiO2 (P25) are shown in
Fig. 3. The absorption edge of BiOCl occurs at about 361 nm,
and the band-gap energy is estimated to be 3.46 eV by the
formula lg = 1239.8/Eg [19], which is slightly larger than that
of TiO2 (3.23 eV). Pure bulk bismuth oxide has a direct band-
gap of 2.6 eV [19], much narrower than that of BiOCl.
To distinguish the transition character (direct or indirect) of
the sharp absorption edge, we analyzed its shape. In
semiconductors, the square of absorption coefficient is linear
Fig. 1. The XRD patterns of BiOCl (a) before and (b) after the photocatalytic
reaction.
 K.-L Zhang et al. / Applied Catalysis B: Environmental 68 (2006) 125–129
Fig. 2. The FE-SEM images of BiOCl.
with energy for direct optical transitions in the absorption edge
region; whereas the square root of absorption coefficient is
linear with energy for indirect transitions. Data plots of
absorption2 versus energy and absorption1/2 versus energy in
the absorption edge region are shown in the inset of Fig. 3. The
absorption1/2 versus energy plot is nearly linear, while the
absorption2 versus energy deviates from the fitted straight line.
This feature suggests that the absorption edge of BiOCl is
caused by indirect transitions.
3.3. Band calculation of BiOCl
The electronic structure of BiOCl was calculated by using the
TB-LMTO code in order to clarify the distribution of valence
states of Bi, O, and Cl atoms near the Fermi level. The band
structure of BiOCl is displayed in Fig. 4. The lowest unoccupied
states are found along the G (0,0,0) point to X (1/2,0,0), and near
the R (1/2,0,1/4) point. The highest occupied state is at the Z
(0,0,1/2) point. The LDA calculations confirm the indirect nature
Fig. 3. The absorption spectra of BiOCl and TiO2. The inset shows the plots of
absorption2 vs. energy (unfilled circles for experimental data and the dashed line
for a linear fit) and absorption1/2 vs. energy in the absorption edge region for
BiOCl.
127
Fig. 4. Band structure of BiOCl. The respective high-symmetry points are G
(0,0,0), X (1/2,0,0), Z (0,0,1/2), M (1/2,1/2,0), R (1/2,0,1/4), and A (1/2,1/2,1/4)
in terms of the reciprocal basis vectors.
of the band-gap of BiOCl. Fig. 5 shows total and partial (Bi, Bi
6p, O, Cl) densities of states (DOS) of BiOCl. The order of the
states from 20 eV to 10 eV starts with mainly O 2s states
( 18.5 to 16 eV), then localized Cl 3s states ( 13.5 to
12.5 eV), Bi 6s ( 10 to 7 eV), O 2p and Cl 3p ( 5 to
0 eV), and Bi 6p (2.8–7.5 eV). The Cl 3p states contribute
considerably to the DOS beneath the Fermi level, whereas the Bi
6p states just make significant contribution above the Fermi level.
Some O 2p and Cl 3p states appear above the Fermi level (2.8–
7.5 eV), and some Bi 6s and Bi 6p states appear from 5 to 0 eV.
The state mixing in the figure indicates that Bi, O 2p, and Cl 3p
states hybridize slightly. The highest occupied orbitals (HOMO),
Cl 3p states, are rather localized. The lowest unoccupied orbitals
(LUMO), Bi 6p, O 2p, and Cl 3p states (antibonding states of Bi–
O and Bi–Cl) are much more dispersed. LUMO is mainly Bi 6p.
3.4. Photocatalytic behavior
The MO decomposition catalyzed by BiOCl was investi-
gated. As a comparison, the MO photodegradated by TiO2
(P25) was also performed. The blank experiment without the
photocatalyst was investigated under the same conditions. The
Fig. 5. (a) Total Cl and O DOS of BiOCl, and (b) Bi (6s, 6p) and Bi (6p) DOS.
128 K.-L Zhang et al. / Applied Catalysis B: Environmental 68 (2006) 125–129
Fig. 6. MO degradation by BiOCl and TiO2 (P25) ((a) the first cycle; (b) the
second cycle; (c) the third cycle; C0, initiatial concentration of MO; C, residual
concentration of MO).
MO concentrations versus the reaction time in both the BiOCl
and TiO2 (P25) systems as well as the blank experiment are
plotted, respectively, in Fig. 6. MO was completely photo-
decomposed catalyzed by BiOCl in 10 min, but 5% MO
remained in the reaction by TiO2 (P25). MO photolysis without
the photocatalyst could almost be neglected. Therefore, BiOCl
had better photocatalytic activity in MO degradation reaction
than TiO2 (P25). To evaluate the stability of BiOCl in the
photocatalytic reaction, BiOCl and TiO2 (P25) were reclaimed
and re-examined for two extra cycles. As shown in Fig. 6(b and
c), BiOCl again completely decomposed MO in 10 min in the
following two cycles, but the photocatalytic activity of TiO2
(P25) decreased. These experimental results indicate that
BiOCl is more stable and has better photocatalytic performance
on the degradation of MO than TiO2 (P25).
3.5. Structure–property relationship
The unit cell of BiOCl is displayed in Fig. 7. The crystal
structure [11] can derive from the fluorite (CaF2) structure. The
Bi atom is coordinated to a square antiprism with four O atoms
in one base and four Cl atoms in another. The O atom is
tetrahedrally coordinated to four Bi atoms. The Cl atom is
bonded with four Bi atoms in a planar square to form a pyramid
and with its nonbonding (lone pair) electrons pointing to the
other side of the square. These nonbonding electrons convert
the three-dimensional fluorite-like structure into a two-
dimensional layered structure. In the three-dimensional
Bi2O3, the Bi atoms are coordinated to six O atoms. This
structural difference between them is the major reason for
BiOCl to have a wider optical band-gap.
As shown in the figure, the [BiOCl] layers are stacked
together by the nonbonding (van der Waals) interaction through
the Cl atoms along the c-axis. Therefore, the structure is not
closely packed in this direction. When one photon excites one
electron from Cl 3p states to Bi 6p states in BiOCl, one pair of a
hole and an excited electron appear. The layered structure
BiOCl can provide the space large enough to polarize the
related atoms and orbitals. The induced dipole can separate the
Fig. 7. The unit cell of BiOCl viewed along [1 0 0].
hole–electron pair efficiently, enhancing photocatalytic activ-
ities. BiOCl has an indirect-transition band-gap so that the
excited electron has to travel certain k-space distance to be
emitted to valence band. This reduces the recombination
probability of the excited electron and the hole. Both the open
(loose packed) structure and indirect transitions may benefit the
hole–electron separation and the charge transport. Thus, these
features are both favorable to the photocatalytic reactions. The
conclusion may also be derived from the different phases of
TiO2. Both anatase and rutile are three-dimensional structures.
The density is 3.84 g/cm3 for anatase [20] and 4.26 g/cm3 for
rutile [20]. Obviously, anatase has a more open structure than
rutile. The optical transitions are indirect for anatase [21,22]
and direct for rutile [21,23]. Better photocatalytic activity in
anatase may result from the more open structure and indirect
transitions. It is probably the same reasons for BiOCl to be a
good photocatalyst for MO degradation. Note that Bi 6p
orbitals in BiOCl and 3d orbitals in TiO2 dominate LUMO.
Much more dispersed Bi 6s and 6p states than Ti 3d is easier for
an excited electron to travel a longer distance. This might also
be one of the reasons for its better catalytic capability.
4. Conclusions
Bismuth oxychloride (BiOCl) powders were synthesized by
a hydrolysis method. The layered compound BiOCl was
investigated as a photocatalyst for the first time. The material
has an indirect-transition optical band-gap of 3.46 eV. In
photocatalytic reactions of methyl orange (MO) dye degrada-
tion, BiOCl had better performance than TiO2 (P25). The
electronic structure of BiOCl calculated by the TB-LMTO
program shows that BiOCl has an indirect-transition band-gap,
and Cl 3p states and Bi 6p states dominate the highest occupied
orbitals and the lowest unoccupied orbitals, respectively. The
 K.-L Zhang et al. / Applied Catalysis B: Environmental 68 (2006) 125–129
open crystal structure and indirect optical transitions of BiOCl
play important roles in its excellent photocatalytic activity.
Acknowledgements
This research was supported by National Science Founda-
tion of China Grant B010504-20471068. We thank Dr. Wei
Tong for his help.
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