Applied Surface Science 258 (2012) 3771–3778

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Applied Surface Science
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Microemulsion synthesis, characterization of bismuth oxyiodine/titanium
dioxide hybrid nanoparticles with outstanding photocatalytic performance
under visible light irradiation
Zhang Liu
a
, Xiaoxin Xu
a
, Jianzhang Fang
a,∗
, Ximiao Zhu
a
, Jinhui Chu
a
, Baojian Li
b,∗∗
a
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China
b
Department of Chemistry, The University of Hong Kong, PokfulamRoad, Hong Kong, China
a r t i c l e i n f o
Article history:
Received 29 September 2011
Received in revised form3 December 2011
Accepted 4 December 2011
Available online 13 December 2011
Keywords:
Microemulsion
BiOI/TiO
2
heterostructure
Visible light
Methyl orange
Degradation
a b s t r a c t
Reverse microemulsions, consisting of n-hexanol, Triton X-100, Cyclohexane and aqueous salt solutions,
were used to synthesize BiOI, TiO
2
and BiOI/TiO
2
hybrid nanoparticles at room temperature. The particles
had been characterized by X-ray powder diffraction, FT-IR spectra, TG-DSC analysis, nitrogen sorption,
electron microscopy, and UV–vis diffuse reflectance spectroscopy. The photocatalytic properties of those
particles were evaluated by degradation of methyl orange under visible light irradiation. The BiOI/TiO
2
composites showed about 5 times higher photocatalytic performances than BiOI when the mole ratio
of BiOI to TiO
2
was 75%. The remarkable enhancement in the visible light photocatalytic activities of
the BiOI/TiO
2
heterostructures could be first attributed to the effective electron–hole separations at
the interfaces of the two semiconductors, which facilitated the transfer of the photoinduced carriers.
Meanwhile, the heterojunction formed between BiOI and TiO
2
would further retard the recombination
of photoinduced carriers. In addition, high degree of crystallization, bimodal porous structure, relative
large specific surface area, and appropriate energy band gap have great contribution to the enhancement
of photocatalytic performance.
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
Over the past decade, much attention has been paid to both
the preparation and properties of photocatalytic nanocrystalline
materials. The majority of the work in this field, to the best of
our knowledge, has focused on oxides [1,2], sulfides [3], nitrides
[4], and oxynitrides [5,6], because they provide a promising strat-
egy for environmental pollution control or hydrogen generation.
Amongthevarious photocatalysts, titaniumdioxide(TiO
2
) has been
known as the most preferable photocatalyst owing to its chemical
stability, non-toxicity, and low cost. However, the low separation
rate of the photoexcited electrons and holes in TiO
2
leads to its lim-
itedquantumefficiency. Moreover, pure bulk TiO
2
, whose bandgap
energy is 3.0–3.2eV, becomes active solely under ultraviolet light
region, which is only a small part (3–5%) of solar irradiation. Hence,
much effort has been devoted to prepare a TiO
2
photocatalyst that
is capable of efficient generation and separation of photoinduced
electron–hole pairs and utilization of visible light, mainly includ-

Corresponding author. Tel.: +86 20 39314646.
∗∗
Corresponding author. Tel.: +852 51311961.
E-mail addresses: liuzhang0126@126.com(Z. Liu), fangjzh@scnu.edu.cn(J. Fang),
h0992052@hku.hk (B. Li).
ing doping withcationor anionions [7–9], coupling TiO
2
withother
semiconductors, among which, Cu
2
O [10,11], Bi
2
O
3
[12,13], Fe
x
O
y
[14], CdS [15,16], and so on, have been reported to be efficient
photocatalysts under visible light irradiation.
In the past few years, BiOX (X=Cl, Br, I) compounds, which
are important V–VI–VII ternary compounds with layer structures
and all crystallize in the tetragonal matlockite structures, were
exploited and exhibited attractive photocatalytic activity on degra-
dation of organic pollutants [17–22]. As a member of bismuth
oxyhalide family, bismuth oxyiodine (BiOI) has attracted more
interest [23–25] and made it an ideal option as a new visible-
light photocatalyst because of its estimated narrow band gap of
about 1.77eV and a coral red material, leading to easily excitation
in visible light region (>420nm). However, it seems difficult to syn-
thesize pure BiOI withlarge specific surface area [17,18,22–24], and
also pure BiOI is not a powerful visible-light-driven photocatalyst
[17,20–22].
The present work is based on the idea that heterostructures of
BiOI coupling with TiO
2
would perform outstanding visible-light-
induced photocatalytic properties. Since the complex process of
nucleation and nanocrystal growth is difficult to control, reverse
microemulsions, which consist of aqueous droplets of 2–20nm in
diameter, encapsulated by surfactant molecules and surrounded
by an oil phase, are considered as an excellent reaction mediumfor
0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.12.025
3772 Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778
the preparation of nanoparticles. In this paper, x% BiOI/TiO
2
(x =0,
25, 50, 75, 100) hybrid nanoparticles were synthesized in reverse
microemulsions systemat roomtemperatureandambient pressure
without the necessity of subsequent thermal treatments. The pho-
tocatalytic activity of these samples was evaluated and compared
withthe mechanicallymixedsample BiOI +TiO
2
onthe degradation
of an inflexible azo dye methyl orange (MO) in aqueous solution
under visible light irradiation. The role of the BiOI amount in the
visible-light-induced photocatalytic property was discussed, and
the possible origin of the highly enhanced performance was also
proposed based on characterization results.
2. Experimental
2.1. Preparation of photocatalysts
The BiOI/TiO
2
nanostructured composites were prepared in a
reverse microemulsion approach. Triton X-100 (chemically pure,
CP) was chosen as the surfactant, n-hexanol (CP) was chosen as
cosurfactant, and the oil phase was Cyclohexane (analytically pure,
AP). Microemulsions involved above oil, surfactant, cosurfactant,
andwater (deionizedwater) withaqualityratioof 15:6:4:4, respec-
tively. A typical synthetic route of BiOI/TiO
2
composites was as
follows (Scheme 1). One aqueous phase (denoted as A) of the
microemulsions involving certain amounts of bismuth nitrate pen-
tahydrate (Bi(NO
3
)
3
·5H
2
O, AP) and tetrabutyl titanate (TBOT, AP)
with various molar ratios dissolved by appropriate amounts of
dilute nitric acid solutions, and the other aqueous phase (denoted
as B) of the microemulsions containing certain amounts of KI with
molar amount equivalent to that of Bi(NO
3
)
3
·5H
2
O dissolved by
appropriate amounts of dilute ammonia hydroxide solution were
dropped into the mixed solvent of the same contents of oil, surfac-
tant and cosurfactant (15:6:4) respectively with constant stirring
until they became transparent. The obtained microemulsions were
identified as ME-A, ME-B. Afterwards, ME-A was added to ME-B.
It is worth noting that after mixing the microemulsions together,
the particle formationoccurs by intermicellar exchange of the reac-
tants. The resultant suspension, of which pHwas adjusted to 10–11
was stirredfor 3h. Thesolidproducts wereseparatedinacentrifuge
at 4000rpm and washed with anhydrous ethanol (AP) and deion-
ized water to remove the residual organic compounds adsorbed
on the particles, and then dried in an oven at 80

C for 24h. The
final products were milled before characterization. The samples
with original Bi/Ti molar ratios of 0, 0.25, 0.50, 0.75, and 1.0 were
denoted as 0%, 25%, 50%, 75%, and 100% BiOI/TiO
2
, respectively.
Samples were labeledas x%BiOI/TiO
2
, where x%was the molar ratio
of BiOI to TiO
2
. Pure TiO
2
and BiOI were also prepared in the same
method. All the products were synthesized at room temperature
and ambient pressure without thermal treatment, if not otherwise
stated.
2.2. Characterization of photocatalysts
The crystalline phases of the synthesized catalysts were
analyzed by X-ray powder diffraction (XRD) using a Bruker
D8 ADVANCE X-ray diffractometer with Cu K␣ radiation
(=0.154060nm) at a high voltage of 40kV in the range
10

≤2 ≤80

with a step of 0.02

. The average crystallite size was
calculated according to the Scherrer equation. FT-IR spectra were
recorded using a Shimadzu IRPrestige-21 Fourier transform spec-
trometer by blending the sample into a KBr pellet. The sample
powder was ultrasonically dispersed in ethanol and dropped onto
carbon–copper grids for transmission electron microscopy (TEM)
and high-resolution transmission electron microscopy (HRTEM)
analysis using a JEM-2100HR (JEOL, Japan) operated at 200kV
equipped with an energy-dispersive X-ray spectroscope (EDX)
which was operated at an acceleration voltage of 20kV. FE-SEM
images were obtained on a JSM-6700F field emission scanning
electron microscope at 20.0kV. The thermogravimetric analyses
of final powder were measured using a STA449c/1/41G thermal
analyzer. A Micromeritics ASAP 2010 nitrogen adsorption appa-
ratus was used to determine the structural properties of samples
including Brunauer–Emmett–Teller (BET) surface area, pore vol-
ume, and Barrett–Joyner–Halenda (BJH) pore size and distribution,
based on nitrogen adsorption and desorption isotherms. Diffuse
reflectance ultraviolet–visible light (UV–vis) spectra of the pow-
ders were measured at room temperature on a HITACHI U-3010
spectrophotometer.
2.3. Photocatalytic studies
The photocatalytic activity of BiOI/TiO
2
heterostructures was
evaluated by the degradation of MO in aqueous solution under vis-
ible light irradiation, while pure TiO
2
, BiOI and mechanically mixed
sample BiOI +TiO
2
were used for comparison. For all photocatalytic
experiments, a 250Whalogen lamp and a 420nmcutoff filter were
employed to provide visible light with wavelengths shorter than
420nm, a cylindrical glass was used as the reactor, in which 0.1g
of photocatalysts was addedinto 200mL of MO solutionwitha con-
centration of 10mg/L. Prior to illumination, the suspensions were
stirred in the dark for 30min to achieve adsorption–desorption
equilibrium of MO on the catalysts surface. During the course of
irradiation, 5.0mL of suspensions was withdrawnperiodicallyfrom
the reactor and centrifuged at 4000rpm. The upper liquid was
used for absorbency analysis. Wavelength sweeping with UV–vis
8500spectrophotometer (Shanghai Tianmei Science Apparatus Ltd.
Co., China) in the range from 200nm to 800nm on MO solution
confirmed that the maximum absorption wavelength occurred at
464nm.
3. Results and discussion
3.1. Application of microemulsions for synthesizing hybrid
BiOI/TiO
2
nanomaterial
A two-microemulsion approach was used for the synthesis of
hybrid BiOI/TiO
2
particles in reverse micelles. The method can be
considered as a coalition process of ionic precipitation and hydrol-
ysis, taking place in the core of reverse micelles as nanoscale
hydrophilic cavities. Four major steps can be identified during
the process (Scheme 1). First, two separate microemulsions are
prepared: one containing acid salts solutions of bismuth nitrate
pentahydrate and tetrabutyl titanate, the other containing alkaline
solutions of the counterions of iodine to precipitate BiOI (Step (1)).
Onaccount of the rapidly movedreverse micelles, the nanodroplets
containing the reactants can diffuse through the continuous phase
and collide with each other after mixing, and then the droplets coa-
lesce and merge with each other (Step (2)), resulting in the rise of
pH and the formation of TiO
2
and BiOI (Step (3)). These reactions
can be represented as follows [18,26]:
Ti(OBu)
4
+4H
2
O → Ti(OH)
4
+4n-BuOH (1)
Ti(OH)
4
→ TiO
2
·nH
2
O + (2−n)H
2
O (2)
Bi(NO
3
)
3
+KI + H
2
O → BiOI + NaNO
3
+HNO
3
(3)
The precipitates collide and aggregate with each other, subse-
quently nucleate and grow to form hybrid BiOI/TiO
2
composites
(Step (4)). Owning to faster aggregating and growing speed of BiOI,
the fine TiO
2
particles are mainly dispersed and grafting onto the
Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778 3773
Scheme 1. Schematic illustration of synthesis of BiOI/TiO
2
hybrid nanoparticles via a two-microemulsion approach.
surface of BiOI. This inference would be supported by the subse-
quent characterization analysis.
3.2. Materials characterization
3.2.1. TG-DSC measurement
The TG-DSC curves of 75% BiOI/iO
2
are shown in Fig. 1. In the
present study a temperature range of 25–700

C was used and at
the end of the analysis around 17% weight loss was observed. The
TG results indicated that the sample weight lose slowly from25

C
to 280

C, which could be attributed to volatilization of physically
10 20 30 40 50 60 70 80
BiOI
TiO2
25%BiOI/TiO2
50%BiOI/TiO2
75%BiOI/TiO2
100%BiOI/TiO2
i
n
t
e
n
s
i
t
y
(
a
.
u
.
)
2theta(deg.)
a
R
(
1
0
1
)
(
1
1
1
)
(
1
1
0
)
R R A
R
rutile
(
1
0
1
)
(
0
0
7
)
(
1
1
6
)
(
1
0
1
)
(
2
2
0
)
(
1
0
6
)
(
2
0
4
)
(
1
1
5
) (
2
1
2
)
(
1
1
4
)
(
0
0
5
)
(
0
0
4
)
(
0
0
2
)
(
1
0
2
)
(
1
1
0
)
(
0
1
3
)
(
2
0
0
)
anatase A
0.00 0.25 0.50 0.75 1.00
30
40
50
60
70
80
(004)
(102)
(110)
c
r
y
s
t
a
l
l
i
t
e

s
i
z
e

/

n
m
R
m
b
Fig. 1. TG-DSC curves of 75% BiOI/TiO
2
sample.
absorbed water and hexanol. A sharp weight loss of the sample
from280

C to 335

C was due to removal of surfactant (the boiling
point of Triton X-100 is 270

C), and this could be explained well
by a sharply exothermic peak detected in a DSC curve at 310

C.
As the temperature increased from 335

C to 480

C, the sample
exhibitedfurther slowweight loss, whichcorrespondedtothe crys-
talline phase transition of TiO
2
fromamorphismto anatase, and it
was also reflected in DSC curve that a broad and weak endothermic
peak appear after 400

C. Between 500 and 540

C, the BiOI began
to decompose, noticed as a sharp mass decrease. Beyond 540

C the
curve declined sluggishly, which might be ascribed to burning of
residual carbon elements. The DSC curve of the precursor showed
one main exothermic peaks, which was the burning of surfactant
as discussed above.
3.2.2. X-ray diffraction (XRD) analysis
Fig. 2 shows the XRDpatterns (Fig. 2A) and calculated crystallite
sizes (Fig. 2B) of the as-preparedparticles. Pure TiO
2
andTiO
2
inthe
BiOI/TiO
2
heterostructures synthesized in reverse microemulsions
without thermal treatment displayed no obvious diffraction peaks
and this was due to the too strong diffraction intensities of BiOI
and relatively weak intensities of TiO
2
. All the apparent diffraction
peaks of BiOI/TiO
2
can be well assigned to the tetragonal structure
of BiOI (space groupP4/nmm(129), JCPDS 10-0445), andthe strong
and sharp diffraction peaks revealed a high degree of crystalliza-
tion. Meanwhile, thecharacteristic peaks of BiOI werestrengthened
gradually with the BiOI amounts increasing in the BiOI/TiO
2
pow-
ders. No diffraction peaks of Bi were observed, indicating complete
conversion of Bi to BiOI [27]. Patterns for all particles of BiOI/TiO
2
and pure BiOI showed some degree of anisotropic peak broadening.
100 200 300 400 500 600 700
82
84
86
88
90
92
94
96
98
100
102
TG
Temperature/ºC
T
G
/
%
DSC
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
D
S
C
/
(
m
W
/
m
g
)
Fig. 2. XRD patterns of (A) pure TiO
2
, BiOI and BiOI/TiO
2
hybrid nanoparticles, and
(B) the crystallite sizes calculated frompeaks (102), (110), and (004) of pure BiOI
and BiOI/TiO
2
nanoparticles, Rm denotes half mole ratios of BiOI to TiO
2
, in case of
pure BiOI, Rm =1.0.
3774 Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778
500 1000 1500 2000 2500 3000 3500
1
3
8
1
6
9
2
1
3
3
8
1
6
2
1
TiO
2
BiOI
25%BiOI/TiO
2
50%BiOI/TiO
2
75%BiOI/TiO
2
100%BiOI/TiO
2
T
r
a
n
s
m
i
t
t
a
n
c
e
(
a
.
u
.
)
wavenumber/cm
-1
2
3
4
3
5
1
8
1
5
5
4
Fig. 3. FT-IR spectra of pure TiO
2
, BiOI and BiOI/TiO
2
composites.
Interestingly, a mixed crystal of anatase and rutile phase was
observed in the sample 25% BiOI/TiO
2
, presumably because BiOI
crystallite was around by abundant TiO
2
and acted as rutile nuclei
that reduced the surface energy to provide a crystal plane with low
surface energy which forced those amorphous TiO
2
grow to form
the tetragonal rutile particles, as similarly demonstrated by Qi et al.
[28]. The (101) and(110) peaks of anatase andrutile almost disap-
pearedinthe case of the Bi/Ti ≥75%, suggesting the presence of BiOI
could inhibit the crystal growth of TiO
2
. While on the other hand,
the intensity of (002) and (004) peaks decrease with increasing
relative amount of TiO
2
, implying that TiO
2
might inhibit the crys-
tallization of BiOI along (001) direction. Peaks indexed as (002),
(102), (110), and (004) gave small values for the crystallite sizes
according to Scherrer equation, and the crystallite sizes calculated
from the most three intensive peaks (102), (110), and (004) for
samples of pure BiOI and BiOI/TiO
2
composites were plotted vs.
R
m
(R
m
denotes half molar ratios of BiOI to TiO
2
, in case of pure
BiOI, R
m
=1.0) and presented in Fig. 2B. Since the low crystallinity
of TiO
2
, it can be deduced that the particle sizes of as-prepared
composites were mainly determined by crystallite sizes of BiOI if
the coupling particles were dispersed well. For all materials, the
crystallite sizes were increasing with increasing R
m
, hinting the
presence of TiO
2
could suppress the crystal growth of BiOI to some
extent, probably owing to the insulation effect of TiO
2
in BiOI/TiO
2
heterostructures.
3.2.3. FT-IR analysis
The FTIR transmittance spectra of all samples are presented in
Fig. 3. The main absorption peaks are located at 518, 1338, 1381,
1621, and 2345cm
−1
in all the samples. The sharp and strong peak
at 1621cm
−1
is ascribed to the bending vibration absorption of free
water molecules, and the peaks at 3000–3600cm
−1
are identified
as the stretching vibration absorption of hydroxyl function groups
which is often believed that such groups arise fromthe hydrolysis
reactions [29]. The absorption peak at 2343cm
−1
is characteris-
tic of surface adsorbed CO
2
. The band centered at 1338cm
−1
that
cannot be found in pure BiOI is assigned to bending vibrations of
C H bond in the species linking Ti O Ti structural network
[9], and the broad shoulder at around 739cm
−1
was ascribed to
absorption bands of Ti Oand O Ti Oflexion vibration, which was
often observed around 600cm
−1
[9]. The weak absorption band
present in the spectra at 692cm
−1
is assigned to the asymmetrical
stretching vibrations of Bi O bonds [30,31]. The intensities of the
absorption appear at 518 and 1554cm
−1
, which are absent in IR
spectrumof pure titania, increasing with BiOI content in BiOI/TiO
2
0.0 0.2 0.4 0.6 0.8 1.0
80
100
120
140
160
180
200
220
240
260
280
10 100
0.00
0.05
0.10
0.15
0.20
0.25
0.30
d
V
/
d
W

(
c
m
/
g
)
Porediameter (nm)
A
d
s
o
r
b
e
d

v
o
l
u
m
e

(
c
m
3
/
g
)
Relative pressure (p/p
0
)
Fig. 4. N
2
adsorption–desorptionisotherms andpore-sizedistribution(inset) of 75%
BiOI/TiO
2
powder.
composites might be associatedwiththe stretching vibrationof the
bonds in crystal tetragonal BiOI.
3.2.4. Nitrogen sorption
Fig. 4 shows typical nitrogen adsorption–desorption isotherms
and corresponding pore-size distribution curve (inset) of the 75%
BiOI/TiO
2
hybridparticles. Thecouplingstructureessentiallyshows
the type IV isotherms observed in the range of 0.5–1.0 P/P
0
with
type H1 hysteresis loops according to BDDT classification, suggest-
ing the presence of mesopores inthe composite. The corresponding
pore size distributions were monitored by using the BJH method
fromthe desorption branch of the isotherm(inset in Fig. 4), which
indicated a bimodal pore size distribution in the mesopores region
existed in the composite. The sample displayed small mesopores
and large mesopores with local maximum pore diameters of 3
and 37nm, respectively. It could be observed that the fine pores
have a narrower pore size distribution than the larger ones. Pre-
sumably, the finer pores might arise from the intra-aggregation
of nanoparticles of TiO
2
, whereas the large pores with a broad
pore size distribution from 7nm to 100nm could be attributed
to inter-aggregation between amorphous TiO
2
and crystalline BiOI
(crystallites size of 50–75nm derived from XRD results), and also
intra-aggregation of crystalline BiOI with various particle sizes.
However, pure BiOI powders did not possess such porous struc-
tures. Fang et al. [32] observed that a bimodal pore size distribution
of N TiO
2
powder and that might be caused by hard aggregates
of two kinds of particles with different average sizes prepared by
employing two kinds of titanium dioxide precursor. Table 1 sum-
marizes the BET surface area, pore volume, and average pore size
of as-synthesized samples calculated on the basis of isotherms. It is
found that pure BiOI has a poor BET surface area of 12.2m
2
g
−1
,
while the surface areas of 25% BiOI/TiO
2
, 50% BiOI/TiO
2
, 75%
BiOI/TiO
2
, and100%BiOI/TiO
2
are145.3, 101.1, 69.9and40.7m
2
g
−1
respectively, which decreased with increasing BiOI content in the
composites, much higher than that of BiOI. Correspondingly, it is
revealed that the average pore sizes showan increasing tendency.
3.2.5. TEMand HRTEManalysis
In order to investigate the detailed crystal structure of as-
prepared samples, TEM and HRTEM images for 75% BiOI/TiO
2
heterostructure without or with post-thermal treatment (300

C,
3h) were measured and shown in Fig. 5. It can be observed from
Fig. 5a that the particles display inorganized slice-like morphology
with size of about 100nmand thickness of about 8nm. Fig. 5b and
c show typical HRTEM images of 75% BiOI/TiO
2
composite from
Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778 3775
Table 1
Textural properties of BiOI/TiO
2
particles, and photocatalytic degradation rate constants of MO.
Photocatalysts ABET
a
(m
2
g
−1
) VBJH
b
(cm
3
g
−1
) Average pore size
b
(
˚
A) k (h
−1
)
TiO
2
193.7 0.3612 4.4 0.0052
25%BiOI/TiO
2
145.3 0.2768 15.5 0.3923
50%BiOI/TiO
2
101.1 0.2169 31.7 0.6550
75%BiOI/TiO
2
69.9 0.1815 48.6 0.8699
100%BiOI/TiO
2
40.7 0.1361 59.2 0.1460
BiOI 12.2 0.0359 89.6 0.0176
75%BiOI/TiO
2
(300

C) – – – 0.5254
BiOI +TiO
2
– – – 0.0962
a
The BET surface area was calculated fromthe linear part of the BET plot (P/P
0
=0.1–0.25).
b
Pore volume and average pore size were determined by nitrogen adsorption volume at P/P
0
=0.994.
the original region in Fig. 5a, the rough surface suggests porous
structures and large specific surface area, as evidenced by nitro-
gen sorption above. Fig. 5c reveals the fringes with an interval
of 0.2974 and 0.2283nm, which are in good agreement with the
(102) and (004) lattice planes of the tetragonal BiOI. The insert in
Fig. 5c shows the selected area electron diffraction pattern (SAED)
of 75% BiOI/TiO
2
composite, the first four diffraction rings corre-
spondto the interplanar distances (innm) of 0.2889, 0.2321, 0.1976
and 0.1679, which are consistent with (110), (004), (200) and
(204) Bragg reflections fromBiOI. To study the distribution of TiO
2
Fig. 5. TEM, HRTEM, and EDX images of 75% BiOI/TiO
2
heterostructure. (a) Morphology study and crystallite size survey of aggregated particles, (b) and (c) high-resolution
electron micrographs showing (102) and (004) planes of BiOI crystallite, inset of (b) exhibits the selected area electron diffraction (SAED) patterns of the heterostructure,
(d) and (e) high-resolution electron micrographs of BiOI/TiO
2
composites with post-thermal treatment showing (101) planes of BiOI and (101) planes of TiO
2
, and (f) the
TEM-EDX result for 75% BiOI/TiO
2
sample at higher sensitivity.
3776 Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778
Fig. 6. SEMimages of 75% BiOI/TiO
2
hybrid particles.
in BiOI/TiO
2
heterostructures, sample of 75% BiOI/TiO
2
calcined at
300

C for 3h was performed on a HRTEM and the typical images
are presented in Fig. 5d and e, two main sets of mixed fringes with
d-spacing of 0.357 (anatase, 101) and 0.366 (BiOI, 101) nm are
found, indicating the presence of the mixed phases of TiO
2
and
BiOI. It could also be observed that the TiO
2
are mainly dispersed
on the surface of BiOI. It is noteworthy that the BiOI in BiOI/TiO
2
composite after calcination show abundant of lattice fringes from
the reflections of (101) plane which was not observed obviously
in the sample without calcination according to XRD results. The
phenomenon might be interpreted as follows. It was believed the
obtained images were so numerable that it might be occasional
examples. Otherwise, thermal treatment played an intensive role
in the crystallization of BiOI in BiOI/TiO
2
heterostructures, which
suggested that a high temperature (300

C) would facilitate the
growth of BiOI along the (101) direction. Fig. 5f shows EDX analyt-
ical results of 75% BiOI/TiO
2
composite, the molar ratio of Bi/Ti was
calculated as 79%, which are in agreement with the nominal molar
ratio of BiOI to TiO
2
.
3.2.6. Morphology measurement
The surface morphology of 75%BiOI/TiO
2
coupling particles was
investigated and the typical SEMimages are given in Fig. 6. As illus-
tratedinFig. 6atheparticles displaychipping-likemorphologywith
serious agglomeration. The sizes of these agglomerates are not uni-
form and their diameters are in the range of several micrometers
300 400 500 600 700 800
0.0
0.5
1.0
25%BiOI/TiO2
75%BiOI/TiO2
50%BiOI/TiO2
100%BiOI/TiO2
TiO2
BiOI
A
b
s
o
r
b
a
n
c
e

/

a
.
u
.
wavelength/nm
Fig. 7. UV–vis absorptionspectra for pure TiO
2
, BiOI, and75%BiOI/TiO
2
heterostruc-
tures.
to more than 100␮m. The drastic aggregation of particles might
be caused by incomplete removal of surfactants existing in the
interstices of crystalline BiOI/TiO
2
coupling particles, which would
be dispersed well in ethanol (ultrasonication), as demonstrated in
TEMimages. Higher magnification SEMimage (Fig. 6b) reveals that
the particles have rough surface structure with woolly cloudlike
morphology, which conveys high adsorption abilities.
3.2.7. UV–vis spectroscope
Fig. 7 displays the UV–vis diffuse reflectance spectra (DRS) of
pure BiOI, TiO
2
and the 75% BiOI/TiO
2
composites. It is found that
the absorbance of TiO
2
in the visible light region is negligible, while
BiOI and 75% BiOI/TiO
2
show significant optical response in the
visible region. The absorption edge of 75%BiOI/TiO
2
shift blue com-
pared with that of pure BiOI sample, implying that the sizes of BiOI
in the BiOI/TiO
2
samples are smaller than the corresponding value
of pure BiOI [33], which accords with the XRD results. Approx-
imately, the absorption edges of as-synthesized TiO
2
, BiOI and
representative 75% BiOI/TiO
2
are located at 394, 646 and 714nmin
the near-UVandvisible light regions, respectively, andthese results
are consistent with the white, red, and carmine red colors of TiO
2
,
75% BiOI/TiO
2
and BiOI powders, respectively. The reduction in the
band gap energy of the as-prepared sample was determined by the
following equation [34]:
Eg =
1239.8

(4)
where Eg is the band gap energy (eV) and is the wavelength (nm)
of the absorption edge in the spectrum. Accordingly, the band gap
of BiOI and heterostructured 75% BiOI/TiO
2
are evaluated to be
1.74eV and 1.83eV, whereas the band gap of TiO
2
is found to be
about 3.15eV. The broadening in band width of heterostructured
75% BiOI/TiO
2
compared with that of pure BiOI is believed to the
formation of intermediate level between BiOI and TiO
2
.
3.3. Measurement of photocatalytic activity
Owing to chemical stable and lightfast character, azo dye MO
was chosen as a representative model pollutant to investigate
the adsorption and photocatalytic performance of the as-prepared
powders under visible light (>420nm) irradiation and the results
are shown in Fig. 8. The adsorption amounts were mainly deter-
mined by TiO
2
amounts in the composites. The direct photolysis
of MO upon visible light irradiation is negligible under our exper-
imental conditions. It can be observed that pure TiO
2
and BiOI
Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778 3777
-30 30 0 60 90 120 150 180
0.0
0.2
0.4
0.6
0.8
1.0
Bi/Ti=25%
Bi/Ti=50%
Bi/Ti=75%
Bi/Ti=75%(300
O
C)
Bi/Ti=100%
TiO2
BiOI
TiO2+BiOI
Time(min)
C
/
C
0
dark
Fig. 8. Comparisonof adsorptionandphotocatalytic performance of pure TiO
2
, BiOI,
and BiOI/TiO
2
hybrid nanoparticles on the degradation of methyl orange under vis-
ible light irradiation. (For interpretation of the references to color in the text, the
reader is referred to the web version of the article.)
exhibited inefficient photocatalytic degradation with MO decom-
position rate of 2% and 9%, respectively, in 3h illumination. In
contrast, heterostructured BiOI/TiO
2
revealed high photocatalytic
activities with the MO degradation efficiencies of 64, 85, 92, and
54% respectively as the loading amounts of BiOI increased from
25% to 100%. Obviously, the 75% BiOI/TiO
2
exhibited the high-
est photocatalytic degradation efficiency among those coupling
particles. To test whether an improved crystallinity in TiO
2
in
heterostructures would be beneficial for enhancing the photocat-
alytic activity of the samples, 75 BiOI/TiO
2
calcined at 300

C was
conducted to degrade MO in the same experiment condition, how-
ever, boththe adsorptionandphotocatalytic degradationefficiency
decreasedwithun-calcinedsample, webelievetheharmof theseri-
ous aggregationandreducedBETsurface area causedby calcination
contributed more than the benefit of improved crystallinity in TiO
2
in heterostructures for the decreased photocatalytic activity. To
examine whether formed between BiOI and TiO
2
, mechanically
mixed counterpart of the 75% BiOI +TiO
2
sample was conducted
to degrade MO aqueous solution under the same condition and it
was found that only 26% of MO was removed (Fig. 8, yellowcurve),
which was lower than that of BiOI/TiO
2
composites, indicating het-
erojunction might form between BiOI and TiO
2
and thus enhance
photocatalytic activity effectually.
To quantitatively understand the photocatalytic reaction kinet-
ics of the MO degradationinexperiments, the degradationdata was
analyzed with the pseudo-first-order model as expressed by Eq. (5)
as followed, which is generally used for the photocatalytic degra-
dation process when the initial concentration of pollutant is low
(and KC1) [35]:
ln
C
0
C
= kt (5)
where C
0
and C represent MO concentrations at time zero and t,
respectively, and k is the pseudo first-order rate constant.
The rate constants basically obtained fromthe data in Fig. 8 are
summarized in Table 1. Rather good correlation to the pseudo-first
order reaction kinetics was found (date not shown). The rate con-
stant of 75% BiOI/TiO
2
(0.8673h
−1
) was 49.4 times higher than that
of BiOI (0.0176h
−1
), manifesting that BiOI coupling with TiO
2
is
apparently an effective way to improve the visible-light-induced
photocatalytic efficiency.
The highest photocatalytic activity of 75% BiOI/TiO
2
semi-
conductor heterostructure may be first directly related to their
Fig. 9. Schematic diagramof the band levels of BiOI/TiO
2
composites and the pos-
sible reaction mechanismof the photocatalytic procedure.
heterojunction, which improved the separation efficiency of pho-
togenerated electrons and holes. Furthermore, the relative high
specific surface area and bimodal mesoporous structures, which
allows more efficient transport for the reactant molecules to get
to the active sites on the framework walls, meanwhile, enhances
the adsorption of light and reduce reflection of light, would be also
beneficial to enhance the photocatalytic activity [36].
3.4. Possible photocatalytic mechanism
To the best of our knowledge, efficient photoinduced
electron–holeseparationandtransfer arethekeyfactors toaphoto-
catalytic reaction, hence it is important and necessary to inhibit the
recombination of photoinduced carriers. On the basis of the above
experimental studies, a schematic diagramof the band levels of the
BiOI/TiO
2
composites and the possible reaction mechanism of the
photocatalytic procedure are proposedandillustratedinFig. 9. BiOI
has so narrow band gap energy (1.74eV) that it could be irritated
easily by visible light (>420nm, energy less than 2.95eV) and
consequently induce the generation of photoelectrons and holes.
In fact, pure BiOI has poor photoactivity because that the narrow
band gap energy results in rapidly recombined photoelectrons and
holes and big sizes in shape are detrimental to transfer of photo-
generatedelectrons inthe conductionbandontothe surface of BiOI.
Meanwhile, TiO
2
possesses both strong electron affinity and high
electron conductivity but with a wide energy gap of 3.15eV, thus it
could not be excited by the visible-light irradiation in our experi-
ments. However, in the case of BiOI/TiO
2
heterostructures, we can
observe that when BiOI is illuminated by photon energy less than
2.95eV (>420nm), the photoinduced electrons in the reformed
conduction band (CB) potential edge on the surface of BiOI [24]
could easily flow to a lower CB potential edge of TiO
2
[37], thus
the recombination of photogenerated electron–hole pairs could be
effectively inhibited and the corresponding photocatalytic proper-
ties would be greatly improved, as clarified by following equations:
BiOI +h (> 420nm) → BiOI (e
cb

+h
vb
+
) (6)
e
cb

(BiOI) → e
cb

(TiO
2
) (7)
e
cb

(TiO
2
) + O
2
→ TiO
2
+

O
2−
(8)

O
2−
+MO → degradationproducts (9)
h
vb
+
(BiOI) + MO → degradationproducts (10)
Furthermore, the formed heterojunction between BiOI and TiO
2
in the heterostructured BiOI/TiO
2
could prevent the recombina-
tion of photogenerated carriers of BiOI. As a result, the BiOI/TiO
2
composites showed much better activities over BiOI as well as
TiO
2
. It should be noted that there was a saturation value of the
3778 Z. Liu et al. / Applied Surface Science 258 (2012) 3771–3778
BiOI content in the BiOI/TiO
2
composites over which the excessive
photoinduced electrons and holes would recombine inevitably and
thus decrease the photoactivity. The optimized BiOI amount in the
heterostructures was fitted at 75% (BiOI/TiO
2
), which showed the
best photocatalytic performance in our experiments.
4. Conclusion
In summary, a two-microemulsion approach was demonstrated
to be mild and efficient method for preparation of hybrid BiOI/TiO
2
nanoparticles with enhanced visible-light-driven photocatalytic
performance. The photocatalytic activities against methyl orange
of all the as-prepared BiOI/TiO
2
particles displayed better photo-
catalytic performance than pure TiO
2
and BiOI under visible light
irradiation. It was also found that the BiOI amount in the BiOI/TiO
2
heterostructures played a pivotal role in the photocatalytic prop-
erty and the optimized ratio was 75%. The great improvement
in the visible light photocatalytic activity of the composites was
attributed to high degree of crystallization, the bimodal porous
structure, relative large specific surface area, appropriate energy
bandgapandthe junctionformedbetweenBiOI andTiO
2
. The study
provided a simple way to prepare visible-light-driven photocat-
alytic materials for more potential application.
Acknowledgments
The authors would like to gratefully acknowledge the finan-
cial supports from the Ministry of Education, and the Ministry
of Science and Technology of Guangdong, China (Project No.
20110B090400177).
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